JP4665400B2 - Exterior materials for lithium-ion batteries - Google Patents
Exterior materials for lithium-ion batteries Download PDFInfo
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- JP4665400B2 JP4665400B2 JP2004022856A JP2004022856A JP4665400B2 JP 4665400 B2 JP4665400 B2 JP 4665400B2 JP 2004022856 A JP2004022856 A JP 2004022856A JP 2004022856 A JP2004022856 A JP 2004022856A JP 4665400 B2 JP4665400 B2 JP 4665400B2
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- 239000000463 material Substances 0.000 title claims description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 26
- 239000010410 layer Substances 0.000 claims description 91
- 239000011888 foil Substances 0.000 claims description 52
- 229910052782 aluminium Inorganic materials 0.000 claims description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 47
- 239000000565 sealant Substances 0.000 claims description 40
- -1 polypropylene Polymers 0.000 claims description 35
- 239000004743 Polypropylene Substances 0.000 claims description 33
- 229920001155 polypropylene Polymers 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 239000004840 adhesive resin Substances 0.000 claims description 21
- 229920006223 adhesive resin Polymers 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000005022 packaging material Substances 0.000 claims description 16
- 229910001593 boehmite Inorganic materials 0.000 claims description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 10
- 238000003475 lamination Methods 0.000 claims description 8
- 229920006284 nylon film Polymers 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 230000032798 delamination Effects 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002648 laminated material Substances 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- UQOULBWSWCWZJC-UHFFFAOYSA-N ethene;methyl hydrogen carbonate Chemical compound C=C.COC(O)=O UQOULBWSWCWZJC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
Description
本発明は、工業製品等の包装分野でガスバリアー材としてアルミニウム箔を積層した多層構成からなる積層体に関し、さらに詳しくは、強浸透性物質等を含む内容物を包装した場合であっても、内容物の影響を受けてデラミネーションなどを生じない積層体に関するものである。 The present invention relates to a laminate having a multilayer structure in which aluminum foil is laminated as a gas barrier material in the packaging field of industrial products and the like, more specifically, even when a content containing a strongly permeable substance is packaged, The present invention relates to a laminate that does not cause delamination under the influence of contents.
医薬品や工業製品などの包装材料においては、主にガスバリアー材としてアルミニウム箔が使用され、このアルミニウム箔を基材フィルムとシーラント層の中間に積層した積層材料が多く用いられている。これらの積層材料のアルミニウム箔とシーラント層の積層方法は、アルミニウム箔にポリエチレンイミン系や有機チタン系等のアンカーコート剤を介してシーラント層の樹脂を溶融押出してフィルムを形成し積層する溶融押出ラミネーション法や、アルミニウム箔にポリウレタン系接着剤を介してあらかじめ成膜された樹脂フィルムを積層するドライラミネーション法、あるいはアルミニウム箔に積層されたアンカーコート剤上に高温で押し出された接着樹脂層を介して、あらかじめ成膜された樹脂フィルムを積層するサンドイッチラミネーション法等が一般的である。前記アンカーコート剤やポリウレタン系接着剤を使用して積層した積層材料からなる包装材にリチウムイオン電池を包装した場合、ＬｉＰＦ6 を含んだ強浸透性の電解液がシーラント層を通過し、バリアー性のあるアルミニウム箔の表面で行き止まり、そこの接着剤やアンカーコート剤を膨潤させ、アルミニウム箔とシーラント層間のラミネート強度が低下し、最後にはデラミネーションが生じてしまい、電解液が漏れ出す等の問題があった。前記問題を改善する為に、無延伸フィルムからなるシーラント層がサンドイッチラミネーション法で、アルミニウム箔に積層されたイソシアネート化合物からなるアンカーコート層上に、高温で押し出されたポリエチレン樹脂からなる接着樹脂層を介して積層された積層材料が提案されている（例えば、特許文献１参照。）。
しかし、前記提案されている積層材料では接着樹脂層の樹脂としてポリエチレン樹脂が使用されているので、積層体全体の耐熱性が劣り、高温状態に保存された時にシーラント層同士のヒートシール強度が低下してしまい、強浸透性の電解液等を含む内容物の包装材料としては不十分であった。 However, since the proposed laminated material uses polyethylene resin as the resin for the adhesive resin layer, the heat resistance of the entire laminate is inferior, and the heat seal strength between the sealant layers decreases when stored in a high temperature state. Therefore, it is insufficient as a packaging material for contents containing a strong permeable electrolyte or the like.
本発明の課題は、シーラント層がサンドイッチラミネーション法で積層されたもので、アンカーコート層がなくてもアルミニウム箔とシーラント層の接着が強固で、耐熱性があり、高温状態で保存されてもシーラント層同士のヒートシール強度が低下せず、かつ強浸透性物質を含む内容物を長期間包装した場合でもアルミニウム箔とシーラント層間のデラミネーションがないリチウムイオン電池用外装材を提供することにある。 An object of the present invention is that a sealant layer is laminated by a sandwich lamination method, and even without an anchor coat layer, the adhesion between the aluminum foil and the sealant layer is strong, heat-resistant, and sealant even when stored at a high temperature. An object of the present invention is to provide an outer packaging material for a lithium ion battery in which the heat seal strength between layers does not decrease, and even when a content containing a strong permeable substance is packaged for a long period of time, there is no delamination between the aluminum foil and the sealant layer.
本発明の請求項１に係る発明は、基材層の一方の面にアルミニウム箔、接着樹脂層、シーラント層が順次積層されてなるリチウムイオン電池用外装材において、基材層がインフレーション法で成膜された延伸ナイロンフィルムからなり、アルミニウム箔の少なくとも接着樹脂層側がベーマイト処理されており、接着樹脂層が融点１５０℃以上のホモタイプポリプロピレン樹脂に対し３〜５重量％の無水マレイン酸をグラフト重合させた無水マレイン酸変性ポリプロピレン樹脂からなり、シーラント層が単層若しくは多層の無延伸ポリプロピレンフィルムからなり、前記シーラント層の無延伸ポリプロピレンフィルムが、基材層に積層されたアルミニウム箔上に、サンドイッチラミネーション法により、接着樹脂層を介して積層された後に、該無延伸ポリプロピレンフィルムの表面温度が１５０〜２００℃になるように加熱処理されており、前記リチウムイオン電池用外装材のシーラント層同士をヒートシールした時の１００℃環境下におけるヒートシール強度が３０Ｎ／１５ｍｍ幅以上であることを特徴とするリチウムイオン電池用外装材である。 The invention according to claim 1 of the present invention is an exterior material for a lithium ion battery in which an aluminum foil, an adhesive resin layer, and a sealant layer are sequentially laminated on one surface of a base material layer, and the base material layer is formed by an inflation method. Made of stretched nylon film, at least the adhesive resin layer side of aluminum foil is boehmite-treated, and the adhesive resin layer is graft-polymerized with 3-5% by weight of maleic anhydride to a homotype polypropylene resin with a melting point of 150 ° C or higher The laminate layer is made of a maleic anhydride-modified polypropylene resin, the sealant layer is made of a single-layer or multilayer unstretched polypropylene film, and the unstretched polypropylene film of the sealant layer is laminated on the aluminum foil laminated on the base material layer. After being laminated through the adhesive resin layer by the method, The surface temperature of the stretched polypropylene film has been heat treated to be 150 to 200 ° C., the heat seal strength is 30 N / 15 mm under 100 ° C. environment when the sealant layers to each other of the outer package for the lithium-ion battery and heat sealed It is the exterior material for lithium ion batteries characterized by being more than width.
本発明のリチウムイオン用外装材は、基材層の一方の面にアルミニウム箔、接着樹脂層、シーラント層が順次積層されてなるリチウムイオン電池用外装材において、基材層がインフレーション法で成膜された延伸ナイロンフィルムからなり、アルミニウム箔の少なくとも接着樹脂層側がベーマイト処理されており、接着樹脂層が融点１５０℃以上のホモタイプポリプロピレン樹脂に対し３〜５重量％の無水マレイン酸をグラフト重合させた無水マレイン酸変性ポリプロピレン樹脂からなり、シーラント層が単層若しくは多層の無延伸ポリプロピレンフィルムからなると共に、基材層に積層されたアルミニウム箔上に、サンドイッチラミネーション法により、接着樹脂層を介して積層された後に、該無延伸ポリプロピレンフィルムの表面温度が１５０〜２００℃になるように加熱処理されているので、アンカーコート層がなくてもアルミニウム箔とシーラント層の接着が非常に強固であり、積層体の耐熱性も良好で、高温状態に保存された時もシーラント層同士のヒートシール強度が低下せず、この積層体を用いて、内容物として強浸透性物質である電解液等を含む内容物を長期間包装しても、アルミニウム箔とシーラント層のデラミネーションが発生しない。従って、強浸透性物質を含有するその他の工業製品（例えば殺菌剤、発布剤）等の包装材料としても使用可能である。 The lithium ion exterior material of the present invention is a lithium ion battery exterior material in which an aluminum foil, an adhesive resin layer, and a sealant layer are sequentially laminated on one surface of a base material layer. The base material layer is formed by an inflation method. Made of stretched nylon film, and at least the adhesive resin layer side of the aluminum foil is boehmite-treated, and the adhesive resin layer is graft-polymerized with 3 to 5% by weight of maleic anhydride to a homotype polypropylene resin having a melting point of 150 ° C. or higher. It is made of a maleic anhydride-modified polypropylene resin, and the sealant layer is made of a single-layer or multilayer unstretched polypropylene film, and is laminated on the aluminum foil laminated on the base material layer via the adhesive resin layer by the sandwich lamination method. The surface temperature of the unstretched polypropylene film is Since it is heat-treated at 50 to 200 ° C., the adhesion between the aluminum foil and the sealant layer is very strong even without an anchor coat layer, the heat resistance of the laminate is good, and it is stored in a high temperature state. The heat seal strength between the sealant layers does not decrease even when the aluminum foil and the sealant are used, even if the laminate is used to wrap the contents containing the electrolyte, which is a strong permeable substance, for a long period of time. No layer delamination occurs. Therefore, it can also be used as a packaging material for other industrial products (for example, bactericides and foaming agents) containing strong penetrating substances.
本発明のリチウムイオン電池用外装材を、実施の形態に沿って以下に詳細に説明する。 The outer packaging material for a lithium ion battery of the present invention will be described in detail below along the embodiment.
図１は本発明の一実施の形態を示す側断面図であり、厚み方向の順に、基材層（１）、接着剤層（２）、アルミニウム箔（３）、接着樹脂層（４）、シーラント層（５）が積層されている。 FIG. 1 is a side sectional view showing an embodiment of the present invention, and in the order of thickness, a base material layer (1), an adhesive layer (2), an aluminum foil (3), an adhesive resin layer (4), A sealant layer (5) is laminated.
前記基材層（１）は、インフレーション法で成膜された延伸ナイロンフィルム（ＯＮｙフィルム）からなっている。フィルムの厚みは、１５〜２５μｍの範囲のものが利用できる。前記の如く基材層に延伸ナイロンフィルムを使用しているので、積層体の突き刺し強度他の各種機械的強度も強く、この積層体を用いて冷間成形する場合でも成形性が良い。 The base material layer (1) is made of a stretched nylon film (ONy film) formed by an inflation method. A film having a thickness in the range of 15 to 25 μm can be used. Since the stretched nylon film is used for the base material layer as described above, the piercing strength of the laminate and other various mechanical strengths are also strong, and the moldability is good even when cold forming using this laminate.
前記接着剤層（２）には、一般的に水酸基を持った主剤とイソシアネート基を持った硬化剤とを混合した二液混合型接着剤を主に使用し、塗布方法としてはグラビアコート法、ロールコート法などで塗布する。接着剤の塗布量は１〜５ｇ／ｍ2（ 乾燥状態）である。 For the adhesive layer (2), a two-component mixed adhesive in which a main agent having a hydroxyl group and a curing agent having an isocyanate group are generally used is mainly used. As a coating method, a gravure coating method, Apply by roll coating. The application amount of the adhesive is 1 to 5 g / m 2 (dry state).
前記アルミニウム箔（３）は、少なくともアンカーコート層側の面がベーマイト処理されている軟質のアルミニウム合金箔で、種類としてはＪＩＳ−Ｈ−４１６０に規定されている合金番号８０２１若しくは合金番号８０７９の軟質のアルミニウム合金箔が好ましく、厚みとしては７〜１００μｍの範囲のものが利用できる。 The aluminum foil (3) is a soft aluminum alloy foil in which at least the surface on the anchor coat layer side is boehmite-treated, and the type is a soft alloy of alloy number 8021 or alloy number 8079 defined in JIS-H-4160. An aluminum alloy foil is preferable, and a thickness in the range of 7 to 100 μm can be used.
前記アルミニウム箔（３）に施されるベーマイト処理は、アンモニアあるいはトリエタノールアミンなどの添加剤を蒸留水中に０．０１〜１．０重量％、好ましくは０．１〜０．５重量％の範囲で添加した処理液を作成し、その処理液を７５〜１００℃の範囲、好ま
しくは８５〜１００℃の範囲、更に好ましくは９０〜１００℃の範囲で加熱し、アルミニウム箔の片面又は両面を１分以上、好ましくは２分以上、更に好ましくは３分以上処理することで、ベーマイト処理を行ったアルミニウム箔を得ることが出来る。片面を処理する場合は公知のロールコート法等で処理液を片面に塗布し処理する方法で実施し、両面を処理する場合は処理液を入れた処理槽にアルミニウム箔をウエブ方式等で通して処理する方法などで実施する。
In the boehmite treatment applied to the aluminum foil (3), an additive such as ammonia or triethanolamine is added in distilled water in the range of 0.01 to 1.0% by weight, preferably in the range of 0.1 to 0.5% by weight. The treatment liquid added in step 1 is prepared, and the treatment liquid is heated in the range of 75 to 100 ° C., preferably in the range of 85 to 100 ° C., more preferably in the range of 90 to 100 ° C., and one side or both sides of the aluminum foil is 1 The aluminum foil which performed the boehmite process can be obtained by processing for more than minutes, Preferably it is 2 minutes or more, More preferably, it is 3 minutes or more. When processing one side, it is carried out by applying a processing solution to one side by a known roll coating method or the like, and when processing both sides, an aluminum foil is passed through a processing tank containing the processing solution by a web method or the like. Implement by the method of processing.
このベーマイト処理を行うことにより、アルミニウム箔の表面は針状構造になり、またその表面に−ＯＨ基を多く存在させることができ、その上に積層する層の樹脂表面の−Ｏ−基と水素結合を形成することなどにより、より密着強度を向上させることができる。 By performing this boehmite treatment, the surface of the aluminum foil has a needle-like structure, and a large amount of —OH groups can be present on the surface, and —O— groups and hydrogen on the resin surface of the layer laminated thereon can be present. The adhesion strength can be further improved by forming a bond.
前記接着樹脂層（４）は、融点１５０℃以上のホモタイプポリプロピレン樹脂に対し３〜５重量％の無水マレイン酸をグラフト重合させた無水マレイン酸ポリプロピレン樹脂からなり、該無水マレイン酸ポリプロピレン樹脂が樹脂温度２５０〜３００℃で溶融押出され、積層されている。前記樹脂は耐熱性があり、アルミニウム箔などの金属との接着も良好で、アルミニウム箔にアンカーコート層を積層しないで直接積層しても強い接着力が得られる。厚さ１５〜２０μｍが好ましい。 The adhesive resin layer (4) is composed of a maleic anhydride polypropylene resin obtained by graft polymerization of 3 to 5% by weight of maleic anhydride to a homotype polypropylene resin having a melting point of 150 ° C. or higher, and the maleic anhydride polypropylene resin is a resin. It is melt extruded and laminated at a temperature of 250 to 300 ° C. The resin has heat resistance and good adhesion to a metal such as an aluminum foil, and a strong adhesive force can be obtained even when directly laminated without an anchor coat layer being laminated on the aluminum foil. A thickness of 15 to 20 μm is preferable.
前記シーラント層（５）は、単層あるいは多層の無延伸ポリプロピレンフィルムからなっており、基材層（１）に接着剤層（２）を介して積層されたアルミニウム箔（３）上に、サンドイッチラミネーション法で前記接着樹脂層（４）を介して積層された後に、該無延伸ポリプロピレンフィルムの表面温度が１５０〜２００℃になるように加熱ロールで、加熱処理されている。従って、シーラント層の接着が強固であり、内容物耐性が良い。厚さは３５〜５０μｍが好ましい。 The sealant layer (5) is made of a single layer or multilayer unstretched polypropylene film, and sandwiched on an aluminum foil (3) laminated on a base material layer (1) via an adhesive layer (2). After being laminated via the adhesive resin layer (4) by a lamination method, the unstretched polypropylene film is heat-treated with a heating roll so that the surface temperature of the unstretched polypropylene film is 150 to 200 ° C. Accordingly, the adhesion of the sealant layer is strong and the content resistance is good. The thickness is preferably 35 to 50 μm.
本発明のリチウムイオン電池用外装材を、以下に具体的な実施例に従って説明する。本発明は、これらの実施例に限定されるものではない。 The outer packaging material for a lithium ion battery of the present invention will be described below according to specific examples. The present invention is not limited to these examples.
基材層（１）として、インフレーション法で成膜した厚さ２５μｍの延伸ナイロンフィルム（出光ユニテック（株）、商品名：ユニロンＧ−１００）を使用し、そのフィルムの片面にドライラミネート機を使用してグラビア法で、接着剤層（２）として二液反応型ポリウレタン系接着剤（東洋モートン（株）、商品名：ＴＭ−Ｋ５５／ＣＡＴ−１０Ｌ）を４ｇ／ｍ2（ 乾燥状態）塗布し、乾燥した後に、その上にアルミニウム箔（３）として、前もって別のコーター機でエタノールアミン０．５重量％含有の９５℃温水で箔を３分間表面処理し、両面ベーマイト処理した厚さ４０μｍのアルミニウム箔（東洋アルミニウム（株）、商品名：ＣＥ）を公知の方法で貼り合わせる。続いて、積層された前記アルミニウム箔上に、接着樹脂層（４）として、無水マレイン酸変性ポリプロピレン樹脂（三菱化学（株）、商品名：モディックＴＬ−０５）を樹脂温度２９０℃で厚さ１５μｍになるように押出して積層し、その上にシーラント層（５）として、厚さ３０μｍの三層構成の無延伸ポリプロピレンフィルム（昭和電工（株）、商品名：アロマーＥＴ２０）を積層した後に、前記無延伸ポリプロピレンフィルムの表面温度が１５０℃になるように、加熱ロールで加熱、処理して、本発明のリチウムイオン電池用外装材を作成した。 As the base material layer (1), a stretched nylon film (Idemitsu Unitech Co., Ltd., trade name: Unilon G-100) formed by an inflation method is used, and a dry laminating machine is used on one side of the film. Then, by the gravure method, 4 g / m 2 (dry state) of a two-component reactive polyurethane adhesive (Toyo Morton Co., Ltd., trade name: TM-K55 / CAT-10L) is applied as the adhesive layer (2). After drying, the surface of the aluminum foil (3) was further treated with 95% hot water containing 0.5% by weight of ethanolamine in another coater machine for 3 minutes in advance, and the thickness was 40 μm. Aluminum foil (Toyo Aluminum Co., Ltd., trade name: CE) is bonded by a known method. Subsequently, a maleic anhydride-modified polypropylene resin (Mitsubishi Chemical Corporation, trade name: Modic TL-05) is used as an adhesive resin layer (4) on the laminated aluminum foil, and the resin temperature is 290 ° C. and the thickness is 15 μm. After extruding and laminating to form a three-layer unstretched polypropylene film (Showa Denko Co., Ltd., trade name: Aroma ET20) having a thickness of 30 μm as the sealant layer (5), The exterior material for lithium ion batteries of the present invention was prepared by heating and treating with a heating roll so that the surface temperature of the unstretched polypropylene film was 150 ° C.
実施例１において、シーラント層（５）として、厚さ３０μｍの三層構成の無延伸ポリプロピレンフィルム（昭和電工（株）、商品名：アロマーＥＴ２０）を積層した後に、前記無延伸ポリプロピレンフィルムの表面温度が１８０℃になるように、加熱ロールで加熱、処理した以外は、同様にして本発明のリチウムイオン電池用外装材を作成した。 In Example 1, as a sealant layer (5), a non-stretched polypropylene film (Showa Denko Co., Ltd., trade name: Aroma ET20) having a three-layer structure having a thickness of 30 μm was laminated, and then the surface temperature of the unstretched polypropylene film. The outer packaging material for a lithium ion battery of the present invention was prepared in the same manner except that it was heated and treated with a heating roll so that the temperature became 180 ° C.
実施例１において、シーラント層（５）として、厚さ３０μｍの三層構成の無延伸ポリプロピレンフィルム（昭和電工（株）、商品名：アロマーＥＴ２０）を積層した後に、前記無延伸ポリプロピレンフィルムの表面温度が２００℃になるように、加熱ロールで加熱、処理した以外は、同様にして本発明のリチウムイオン電池用外装材を作成した。 In Example 1, as a sealant layer (5), a non-stretched polypropylene film (Showa Denko Co., Ltd., trade name: Aroma ET20) having a three-layer structure having a thickness of 30 μm was laminated, and then the surface temperature of the unstretched polypropylene film. The outer packaging material for a lithium ion battery of the present invention was prepared in the same manner except that it was heated and treated with a heating roll so that the temperature became 200 ° C.
以下に、本発明の比較用の実施例を説明する。 In the following, comparative examples of the present invention will be described.
アルミニウム箔として、表面をベーマイト処理していない厚さ４０μｍのアルミニウム箔（東洋アルミ（株））を使用し、シーラント層として厚さ３０μｍの三層構成の無延伸ポリプロピレンフィルム（昭和電工（株）、商品名：アロマーＥＴ２０）を積層した後に、加熱ロールで加熱、処理しなかった以外は、実施例１と同様にして比較用のリチウムイオン電池用外装材を作成した。 As the aluminum foil, a 40 μm thick aluminum foil (Toyo Aluminum Co., Ltd.) whose surface is not boehmite-treated is used, and a 30 μm thick unstretched polypropylene film (Showa Denko Co., Ltd.) After laminating the product name: Aroma ET20), a comparative lithium ion battery exterior material was prepared in the same manner as in Example 1 except that the product was not heated and processed with a heating roll.
アルミニウム箔として、表面をベーマイト処理していない厚さ４０μｍのアルミニウム箔（東洋アルミ（株））を使用し、シーラント層として厚さ３０μｍの三層構成の無延伸ポリプロピレンフィルム（昭和電工（株）、商品名：アロマーＥＴ２０）を積層した後に、該無延伸ポリプロピレンフィルムの表面温度が１８０℃になるように加熱ロールで加熱、処理した以外は、実施例１と同様にして比較用のリチウムイオン電池用外装材を作成した。 As the aluminum foil, a 40 μm thick aluminum foil (Toyo Aluminum Co., Ltd.) whose surface is not boehmite-treated is used, and a 30 μm thick unstretched polypropylene film (Showa Denko Co., Ltd.) Product name: Allomer ET20) was laminated, and then heated and processed with a heating roll so that the surface temperature of the unstretched polypropylene film was 180 ° C. An exterior material was created.
シーラント層として、厚さ３０μｍの三層構成の無延伸ポリプロピレンフィルム（昭和電工（株）、商品名：アロマーＥＴ２０）を積層した後に、加熱ロールで加熱、処理しなかった以外は、実施例１と同様にして比較用のリチウムイオン電池用外装材を作成した。 As the sealant layer, Example 1 was used except that a three-layer unstretched polypropylene film (Showa Denko Co., Ltd., trade name: Aroma ET20) having a thickness of 30 μm was laminated and then heated and processed with a heating roll. Similarly, a packaging material for a lithium ion battery for comparison was prepared.
基材層として、インフレーション法で成膜した厚さ２５μｍの延伸ナイロンフィルム（出光ユニテック（株）、商品名：ユニロンＧ−１００）を使用し、そのフィルムの片面にドライラミネート機を使用してグラビア法で、接着剤層として二液反応型ポリウレタン系接着剤（東洋モートン（株）、商品名：ＴＭ−Ｋ５５／ＣＡＴ−１０Ｌ）を４ｇ／ｍ2（ 乾燥状態）塗布し、乾燥した後に、その上にアルミニウム箔として、前もって別のコーター機でエタノールアミン０．５重量％含有の９５℃温水で箔を３分間表面処理し、両面ベーマイト処理した厚さ４０μｍのアルミニウム箔（東洋アルミニウム（株）、商品名：ＣＥ）を公知の方法で貼り合わせる。続いて、積層された前記アルミニウム箔上に、アンカーコート層として、固形分５重量％のトリレンジイソシアネート化合物（東洋モートン（株）、商品名：ＣＡＴ−１０）溶液を、厚み０．３μｍ（乾燥状態）になるようにグラビア法で塗布、乾燥し、さらに、アンカーコート層上に接着樹脂層として、無水変性ポリプロピレン樹脂（三菱化学（株）、モディックＴＬ−０５）を樹脂温度２９０℃で厚さ１５μｍになるように押出して積層し、その上にシーラント層として、厚さ３０μｍの三層構成の無延伸ポリプロピレンフィルム（昭和電工（株）、商品名：アロマーＥＴ２０）を積層して、比較用のリチウムイオン電池用外装材を作成した。 As a base material layer, a 25 μm-thick stretched nylon film (Idemitsu Unitech Co., Ltd., trade name: Unilon G-100) formed by an inflation method is used, and a gravure is used on one side of the film using a dry laminating machine. In this method, a two-component reactive polyurethane adhesive (Toyo Morton Co., Ltd., trade name: TM-K55 / CAT-10L) is applied as an adhesive layer at 4 g / m 2 (dry state) and dried. As an aluminum foil, a 40 μm-thick aluminum foil (Toyo Aluminum Co., Ltd.) was prepared by subjecting the foil to surface treatment with 95 ° C. warm water containing 0.5% by weight of ethanolamine for 3 minutes in advance using another coater. A product name: CE) is bonded by a known method. Subsequently, a tolylene diisocyanate compound (Toyo Morton Co., Ltd., trade name: CAT-10) solution having a solid content of 5% by weight as an anchor coat layer was formed on the laminated aluminum foil with a thickness of 0.3 μm (dried). The coating is dried by a gravure method so as to become a state), and further, an anhydrous modified polypropylene resin (Mitsubishi Chemical Corporation, Modic TL-05) is formed as an adhesive resin layer on the anchor coat layer at a resin temperature of 290 ° C. An unstretched polypropylene film (Showa Denko Co., Ltd., trade name: Aroma ET20) with a three-layer structure having a thickness of 30 μm is laminated thereon as a sealant layer, and laminated for comparison. A packaging material for a lithium ion battery was prepared.
〈評価〉
実施例１〜３の本発明のリチウムイオン電池用外装材及び実施例４〜７の比較用のリチウムイオン電池用外装材を用いて、以下の試験方法によりヒートシール強度、電解液耐性を評価した。その結果を表１に示す。
（１）ヒートシール強度試験
作成した外装材を用いて、そのシーラント層同士を温度１９０℃、圧力０．２ＭＰａで３秒間シールした試験片を１５ｍｍ幅にスリットし、テンシロン型引張試験機で引張スピード３００ｍｍ／ｍｉｎでヒートシール強度を測定した。測定環境は室温環境下及び１００℃環境下で実施した。
（２）電解液耐性試験
エチレンカーボネート／エチレンメチルカーボネート＝１／１＋ＬｉＰＦ6（ １．５Ｎ）の電解液中に作成した外装材を１５ｍｍ×３０ｍｍのサイズにカットし、８５℃で２週間侵漬し、外装材のアルミニウム箔とシーラント層間のデラミネーションの有無を調査した。
<Evaluation>
Using the packaging materials for lithium ion batteries of Examples 1 to 3 of the present invention and the packaging materials for comparative lithium ion batteries of Examples 4 to 7, heat seal strength and electrolyte resistance were evaluated by the following test methods. . The results are shown in Table 1.
(1) Heat seal strength test Using the created exterior material, the sealant layers were sealed at a temperature of 190 ° C. and a pressure of 0.2 MPa for 3 seconds, and a test piece was slit to a width of 15 mm, and the tensile speed was measured with a Tensilon type tensile tester. The heat seal strength was measured at 300 mm / min. The measurement environment was a room temperature environment and a 100 ° C. environment.
(2) Electrolyte resistance test The exterior material made in the electrolyte solution of ethylene carbonate / ethylene methyl carbonate = 1/1 + LiPF 6 (1.5N) was cut into a size of 15mm x 30mm and immersed in at 85 ° C for 2 weeks. The presence or absence of delamination between the aluminum foil of the exterior material and the sealant layer was investigated.
１…基材層
２…接着剤層
３…アルミニウム箔
４…接着樹脂層
５…シーラント層
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