JP2005056729A - Aluminum laminate material for battery packing - Google Patents
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 67
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002648 laminated material Substances 0.000 title claims abstract description 52
- 238000012856 packing Methods 0.000 title abstract 3
- -1 polypropylene Polymers 0.000 claims abstract description 52
- 239000004743 Polypropylene Substances 0.000 claims abstract description 49
- 229920001155 polypropylene Polymers 0.000 claims abstract description 48
- 239000011888 foil Substances 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 28
- 238000010030 laminating Methods 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 9
- 239000000057 synthetic resin Substances 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000853 adhesive Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 238000009820 dry lamination Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 120
- 230000004888 barrier function Effects 0.000 abstract description 14
- 239000012790 adhesive layer Substances 0.000 abstract description 11
- 239000011247 coating layer Substances 0.000 abstract description 9
- 238000007739 conversion coating Methods 0.000 abstract description 8
- 206010033546 Pallor Diseases 0.000 abstract 1
- 239000005026 oriented polypropylene Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 238000011282 treatment Methods 0.000 description 19
- 230000002087 whitening effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000000465 moulding Methods 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZVYSYCLZXICWLH-UHFFFAOYSA-N 1,3-dioxetan-2-one Chemical compound O=C1OCO1 ZVYSYCLZXICWLH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000012793 heat-sealing layer Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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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
Abstract
Description
本発明は、電子機器、電子部品、特に携帯電話、ノートパソコンなどに用いられるポリマー二次電池用の包装材としての、成形性、バリヤー性、耐内容物性および白化性に優れたアルミラミネート材料に関する。 The present invention relates to an aluminum laminate material excellent in moldability, barrier properties, content resistance and whitening properties as a packaging material for polymer secondary batteries used in electronic devices, electronic components, particularly mobile phones, laptop computers and the like. .
従来、電池の外装材には、金属製の容器が使用される場合が多かった。しかし、携帯電話やノート型パソコン等の電子機器の高性能化や軽量化が進められ、それらに使用される電池の重量も軽量化し、また、スペースを可能な限り小さくするための薄型化、軽量化が求められている。このような要望に応えるため、電解液をゲル状ポリマー電界質としたリチウムイオンポリマー二次電池が開発され、その外装材にアルミラミネート材料を使用し、薄型化する方法が採られている。 Conventionally, metal containers have often been used for battery exterior materials. However, electronic devices such as mobile phones and notebook computers have been improved in performance and weight, the weight of batteries used in them has also been reduced, and the thickness and weight have been reduced to make the space as small as possible. Is required. In order to meet such a demand, a lithium ion polymer secondary battery using an electrolytic solution as a gel polymer electrolyte has been developed, and an aluminum laminate material is used as an outer packaging material to reduce the thickness.
電池の外装材は、その用途により種々の大きさに絞り成形され、この中に電極、セパレータ等が収容され、三方をシールする方法などが用いられている。この様なアルミラミネート材料には、成形性、強度、水蒸気バリヤー性や耐内容物性などが必要であり、絞り成形の際に外装材のフィルムや金属箔に亀裂が生じた場合には、水分や空気を透過し、また、電解液により金属箔が腐食し、電池性能に悪影響を与えるという問題点があり、種々の工夫がなされてきた。 Battery exterior materials are drawn into various sizes depending on the application, and electrodes, separators, and the like are accommodated therein, and a method of sealing three sides is used. Such an aluminum laminate material requires moldability, strength, water vapor barrier properties, content resistance, and the like. If cracks occur in the film or metal foil of the exterior material during drawing, moisture and There have been problems that air permeates and the metal foil is corroded by the electrolytic solution and adversely affects battery performance, and various devices have been made.
例えば、従来の電池用の外装材としては、アルミニウム箔表面をベーマイト処理したもの（特許文献１）、フィルムに紫外線照射処理したもの（特許文献２）、最内層のフィルムに酸変性ポリオレフィン粒子とスリップ剤を含有するオルガノゾルを塗布したもの（特許文献３）、最内層のフィルム表面にシリコーンオイル等の滑剤を塗布したもの（特許文献４）などがある。
しかしながら、上記従来の技術においては、いずれも、成形性、バリヤー性、耐内容物性および白化性のすべてを満足するものではなかった。そして、内容物形状の多様化、および高品質化に対応可能な電池包装用アルミラミネート材料が求められていた。
However, none of the above conventional techniques satisfy all of moldability, barrier properties, content resistance and whitening properties. And the aluminum laminate material for battery packaging which can respond to diversification of the contents shape and quality improvement was calculated | required.
本発明は，かかる従来の問題点に鑑みてなされたもので，成形性、バリヤー性、耐内容物性および白化性のすべてを満足し、内容物形状の多様化および高品質化にも対応可能な電池包装用アルミラミネート材料を提供しようとするものである。 The present invention has been made in view of such conventional problems, satisfying all of moldability, barrier properties, content resistance and whitening properties, and can cope with diversification of content shapes and high quality. It is intended to provide an aluminum laminate material for battery packaging.
本発明は、電池の包装に用いられる電池包装用アルミラミネート材料であって、
内側表面から、厚さ１０μｍ超え６０μｍ以下の無延伸ポリプロピレン層、厚さ１〜５μｍの酸変性ポリプロピレン層、皮膜付着量が５〜３０ｍｇ／ｍ2の第１化成皮膜層、および厚さ１０〜１００μｍのアルミニウム箔層を順次積層してなる内側積層部と、
上記アルミニウム箔層の外側に配設された、合成樹脂よりなる最外層を含む複数の層を積層してなる外側積層部とよりなることを特徴とする電池包装用アルミラミネート材料にある（請求項１）。
The present invention is an aluminum laminate material for battery packaging used for battery packaging,
From the inner surface, an unstretched polypropylene layer having a thickness of more than 10 μm and not more than 60 μm, an acid-modified polypropylene layer having a thickness of 1 to 5 μm, a first chemical conversion film layer having a coating amount of 5 to 30 mg / m 2 , and a thickness of 10 to 100 μm An inner laminated portion formed by sequentially laminating aluminum foil layers,
An aluminum laminate material for battery packaging, comprising: an outer laminated portion formed by laminating a plurality of layers including an outermost layer made of a synthetic resin, disposed outside the aluminum foil layer. 1).
本発明の電池包装用アルミラミネート材料（以下、適宜、単にラミネート材料という）は、上記のごとく、上記アルミニウム箔層の内側に配される上記内側積層部を、上記無延伸ポリプロピレン層、上記酸変性ポリプロピレン層、及び上記第１化成皮膜層より構成してある。そのため、上記ラミネート材料は、上記内側積層部の存在によって、電池包装用として非常に優れた特性を発揮する。
すなわち、上記アルミニウム箔層、上記第１化成皮膜層、酸変性ポリプロピレン、及び無延伸ポリプロピレンの積層の組み合わせによって、非常に優れた成形性、耐内容物性、及び白化性を発揮しうるのである。
As described above, the aluminum laminate material for battery packaging of the present invention (hereinafter, simply referred to as “laminate material”) includes the above-mentioned inner laminate portion disposed inside the aluminum foil layer, the unstretched polypropylene layer, and the acid-modified material. It comprises a polypropylene layer and the first chemical conversion film layer. Therefore, the laminate material exhibits very excellent characteristics for battery packaging due to the presence of the inner laminated portion.
That is, very excellent moldability, content resistance, and whitening can be exhibited by a combination of the aluminum foil layer, the first chemical conversion film layer, the acid-modified polypropylene, and the unstretched polypropylene.
最内層（内側表面）に位置する無延伸ポリプロピレン層の厚さは、成形性、耐内容物性および白化性の観点から１０μｍ超え６０μｍ以下の範囲とすることが最良である。この厚さが１０μｍ以下の場合には、成形性が低下して亀裂が発生しやすいという問題があり、一方、６０μｍを超える厚さは、ラミネート材料全体の厚さを薄くしたいという薄型化の要請に逆行するという問題がある。 The thickness of the unstretched polypropylene layer located in the innermost layer (inner surface) is best in the range of more than 10 μm and not more than 60 μm from the viewpoints of moldability, content resistance and whitening properties. If this thickness is 10 μm or less, there is a problem that the moldability is deteriorated and cracks are liable to occur. On the other hand, if the thickness exceeds 60 μm, the thickness of the laminate material is required to be reduced. There is a problem of going backwards.
また、上記酸変性ポリプロピレン層の厚さは、耐内容物性を向上させるために１〜５μｍの範囲とすることが最良である。この厚さが１μｍ未満の場合には、耐内容物性が低下するという問題があり、一方、５μｍを超える場合には、上記と同様に薄型化の観点から問題がある。 In addition, the thickness of the acid-modified polypropylene layer is best in the range of 1 to 5 μm in order to improve the content resistance. When the thickness is less than 1 μm, there is a problem that the content resistance is deteriorated. On the other hand, when the thickness exceeds 5 μm, there is a problem from the viewpoint of reducing the thickness as described above.
また、上記第１化成皮膜層の皮膜付着量は、アルミニウム箔層と酸変性ポリプロピレン層との間の密着性、および耐内容物性の間点から、５〜３０ｍｇ／ｍ2の範囲とすることが最良である。５ｍｇ／ｍ2未満の場合には、電解液の影響によりアルミニウム箔層に腐食が生じるおそれがあり、一方３０ｍｇ／ｍ2を超える場合には、成形時に皮膜の凝集破壊が発生しやすくなるという問題がある。 Moreover, the coating amount of the first chemical conversion coating layer should be in the range of 5 to 30 mg / m 2 from the point of adhesion between the aluminum foil layer and the acid-modified polypropylene layer and the resistance to content. Is the best. If it is less than 5 mg / m 2 , the aluminum foil layer may be corroded due to the influence of the electrolytic solution. On the other hand, if it exceeds 30 mg / m 2 , the film tends to cause cohesive failure during molding. There is.
また、上記アルミニウム箔層の厚さは、成形性、バリヤー性の観点から１０〜１００μｍの範囲が最良である。この厚さが１０μｍ未満の場合には、アルミニウム箔層自身を作製する際にピンホールが発生し易くなるという問題があり、一方、１００μｍを超える場合には、上記と同様に薄肉化の間点から問題がある。 The thickness of the aluminum foil layer is best in the range of 10 to 100 μm from the viewpoints of moldability and barrier properties. When this thickness is less than 10 μm, there is a problem that pinholes are likely to occur when the aluminum foil layer itself is produced. On the other hand, when it exceeds 100 μm, the point of thinning is the same as above. There is a problem.
本発明のラミネート材料における最内層は、上記のごとく無延伸ポリプロピレンを用いる。すなわち、いわゆる延伸処理を施していないものを用いる。これにより、上述した優れた成形性、耐内容物性、および白化性を得ることができる。
また、上記酸変性ポリプロピレン層における酸としては、例えば、アクリル酸、メタアクリル酸、マレイン酸、無水マレイン酸、無水シトラコン酸、イタコン酸、無水イタコン酸などの不飽和カルボン酸などを使用することができる。
The innermost layer in the laminate material of the present invention uses unstretched polypropylene as described above. That is, a material not subjected to so-called stretching treatment is used. Thereby, the outstanding moldability, content resistance property, and whitening property which were mentioned above can be obtained.
In addition, as the acid in the acid-modified polypropylene layer, for example, an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic anhydride, itaconic acid, itaconic anhydride, or the like may be used. it can.
上記第１化成皮膜層としては、リン酸クロメート処理又はクロム酸クロメート処理等の反応型クロメート処理、ジルコニウム処理等の反応型ノンクロメート処理、塗布型クロメート処理、塗布型ノンクロメート処理などの様々な処理方法により形成した化成皮膜層を適用することができる。 As the first chemical conversion coating layer, various treatments such as reactive chromate treatment such as phosphoric acid chromate treatment or chromate chromate treatment, reactive nonchromate treatment such as zirconium treatment, coating type chromate treatment, coating type nonchromate treatment, etc. The chemical conversion film layer formed by the method can be applied.
また、上記アルミニウム箔層の外側に配置された上記外側積層部は、皮膜付着量が５〜３０ｍｇ／ｍ2の第２化成皮膜層、厚さ１〜５μｍの接着剤層、および厚さ１０〜４０μｍの合成樹脂よりなる上記最外層を順次積層してなることが好ましい（請求項２）。
上記外側積層部としては、様々な合成樹脂を用いた積層構造を適用することができるが、特に上記のように、アルミニウム箔層の外側面に上記第２化成皮膜層を設け、さらにその上に上記特定の厚さの接着剤層を設けてから、上記特定の厚さの最外層を設けることが好ましい。これにより、合成樹脂よりなる最外層とアルミニウム箔層との密着性を高めることができ、優れた成形性を確保することができる。
Moreover, the said outer side laminated part arrange | positioned on the outer side of the said aluminum foil layer is the 2nd chemical conversion film layer whose film adhesion amount is 5-30 mg / m < 2 >, the adhesive agent layer of thickness 1-5 micrometers, and thickness 10- It is preferable that the outermost layers made of a synthetic resin of 40 μm are sequentially laminated (Claim 2).
As the outer laminated portion, a laminated structure using various synthetic resins can be applied. In particular, as described above, the second chemical conversion film layer is provided on the outer surface of the aluminum foil layer, and further thereon. It is preferable to provide the outermost layer with the specific thickness after providing the adhesive layer with the specific thickness. Thereby, the adhesiveness of the outermost layer which consists of synthetic resins, and an aluminum foil layer can be improved, and the outstanding moldability can be ensured.
上記第２化成皮膜層としては、上記第１化成皮膜層と同様に、反応型クロメート処理、反応型ノンクロメート処理、塗布型クロメート処理、塗布型ノンクロメート処理などの様々な処理方法により形成した化成皮膜層を適用することができる。また、第２化成皮膜層の皮膜付着量が５ｍｇ／ｍ2未満の場合には、アルミニウム箔層と接着剤層との間の密着性が低下するおそれがあり、一方３０ｍｇ／ｍ2を超える場合には、成形時に皮膜の凝集破壊が発生しやすくなるという問題がある。 As with the first chemical conversion film layer, the second chemical conversion film layer is formed by various treatment methods such as reactive chromate treatment, reactive nonchromate treatment, coating chromate treatment, and coating nonchromate treatment. A coating layer can be applied. Moreover, when the coating amount of the second chemical conversion coating layer is less than 5 mg / m 2 , there is a risk that the adhesiveness between the aluminum foil layer and the adhesive layer may be lowered, while when it exceeds 30 mg / m 2. However, there is a problem that cohesive failure of the film is likely to occur during molding.
また、上記接着剤層としては、例えば、ポリウレタン系接着剤、あるいはエポキシ系接着剤等を適用することができる。そして、その厚さは１〜５μｍとする。厚さが１μｍ未満の場合には優れた接着強度を得ることができないおそれがある。一方、５μｍを超える場合には、凝集破壊の発生を招くおそれがある。
また、上記最外層の厚さは、成形性の観点から１０〜４０μｍの範囲とすることが好ましい。この厚さが１０μｍ未満の場合には亀裂が発生しやすいという問題があり、一方、４０μｍを超える場合には薄型化の要請に逆行するという問題がある。
Moreover, as said adhesive bond layer, a polyurethane-type adhesive agent or an epoxy-type adhesive agent etc. are applicable, for example. And the thickness shall be 1-5 micrometers. When the thickness is less than 1 μm, there is a possibility that excellent adhesive strength cannot be obtained. On the other hand, if it exceeds 5 μm, there is a risk of causing cohesive failure.
The thickness of the outermost layer is preferably in the range of 10 to 40 μm from the viewpoint of moldability. If this thickness is less than 10 μm, there is a problem that cracks are likely to occur, whereas if it exceeds 40 μm, there is a problem that it goes against the demand for thinning.
また、上記電池包装用アルミラミネート材料は、総厚みが５０〜２００μｍであることが好ましい（請求項３）。この範囲に総厚みを収めることによって、成形性、バリヤー性、耐内容物性及び白化性をバランスよく得ることができる。上記総厚みが５０μｍ未満の場合には、亀裂が発生しやすく、バリヤー性も低下するおそれがある。一方、２００μｍを超える場合には、薄型化の観点から好ましくない。 Moreover, it is preferable that the total thickness of the said aluminum laminated material for battery packaging is 50-200 micrometers. By keeping the total thickness within this range, the moldability, barrier property, content resistance and whitening property can be obtained in a balanced manner. If the total thickness is less than 50 μm, cracks are likely to occur and the barrier properties may be reduced. On the other hand, when it exceeds 200 μm, it is not preferable from the viewpoint of thinning.
また、上記電池包装用アルミラミネート材料は、引張強度が１２０〜１８０Ｎ／１５ｍｍ、伸びが４０〜１５０％であることが好ましい（請求項４）。なお、１２０〜１８０Ｎ／１５ｍｍとは、１５ｍｍ幅の短冊形状の試験片を引張試験したときの最大荷重（Ｎ）が１２０〜１８０Ｎであることを意味する。このような機械的性質を得ることによって、優れた成形性を確保することができる。
引張強度が１８０Ｎ／１５ｍｍを超える場合、及び伸びが４０％以下の場合には、成形性が低下して、成形時に亀裂が発生しやすくなるおそれがある。一方、上記引張強度が１２０Ｎ／１５ｍｍ未満の場合、及び上記伸びが１５０％を超える場合には、成形後の剛性が不足するおそれがある。
Further, the aluminum laminate material for battery packaging preferably has a tensile strength of 120 to 180 N / 15 mm and an elongation of 40 to 150%. In addition, 120-180N / 15mm means that the maximum load (N) when carrying out the tension test of the strip-shaped test piece of 15 mm width is 120-180N. By obtaining such mechanical properties, excellent moldability can be ensured.
When the tensile strength exceeds 180 N / 15 mm and when the elongation is 40% or less, the moldability is lowered, and cracks are likely to occur during molding. On the other hand, when the tensile strength is less than 120 N / 15 mm and when the elongation exceeds 150%, the rigidity after molding may be insufficient.
また、上記アルミニウム箔層は、Ｆｅが１．２〜１．７重量％、Ｓｉが０．２重量％以下、Ｍｎが０．１重量％以下、および残部が不可避的不純物およびＡｌからなるアルミニウム合金よりなることが好ましい（請求項５）。
Ｆｅが１．２重量％未満、Ｓｉが０．２重量％超え、あるいはＭｎが０．１重量％超えの場合には、機械的性質における引張強さ及び伸びが低下するおそれがある。一方、Ｆｅが１．７重量％を超える場合には、粗大な金属間化合物が発生し、割れやすくなるという問題が生じるおそれがある。
The aluminum foil layer is made of an aluminum alloy comprising Fe of 1.2 to 1.7% by weight, Si of 0.2% by weight or less, Mn of 0.1% by weight or less, and the balance of inevitable impurities and Al. (Claim 5).
If Fe is less than 1.2% by weight, Si is more than 0.2% by weight, or Mn is more than 0.1% by weight, the tensile strength and elongation in mechanical properties may be reduced. On the other hand, when Fe exceeds 1.7% by weight, a coarse intermetallic compound is generated, which may cause a problem that it is easily cracked.
また、上記無延伸ポリプロピレン層は、静摩擦係数が０．３５以下であり、かつ、上記最外層は、静摩擦係数が０．４以下であることが好ましい（請求項６）。上記無延伸ポリプロピレン層の静摩擦係数が０．３５を超える場合、あるいは上記最外層の静摩擦係数が０．４を超える場合には、電池包装用アルミラミネート材料を成形する際にその加工工具との間の抵抗が大きくなるため亀裂が発生するおそれがある。そして、上記摩擦係数の下限値を上記最外層よりも最内層である無延伸ポリプロピレン層を小さくすることによって、成形性、バリヤー性、耐内容物性および白化性にきわめて重要な内側積層部への成形時のダメージを、外側積層部よりもより小さくすることができ、上記の優れた性質を確実に発現させることができる。 The unstretched polypropylene layer preferably has a static friction coefficient of 0.35 or less, and the outermost layer preferably has a static friction coefficient of 0.4 or less. When the static friction coefficient of the unstretched polypropylene layer exceeds 0.35, or when the static friction coefficient of the outermost layer exceeds 0.4, a gap is formed between the processing tool and the aluminum laminate material for battery packaging. There is a risk that cracks may occur because of an increase in resistance. Then, by forming the lower limit of the coefficient of friction of the unstretched polypropylene layer that is the innermost layer rather than the outermost layer, molding into the inner laminated portion that is extremely important for moldability, barrier properties, content resistance and whitening properties The damage at the time can be made smaller than that of the outer laminated portion, and the above excellent properties can be surely expressed.
また、上記最外層は、ポリプロピレン、ポリエチレン、ポリ塩化ビニル、ポリエステル、ナイロン（Ｒ）のいずれかよりなることが好ましい（請求項７）。これらの材料を上記最外層として適用することにより、上述した優れた特性を有する電池包装用アルミラミネート材料を確実に構成することができる。 The outermost layer is preferably made of any one of polypropylene, polyethylene, polyvinyl chloride, polyester, and nylon (R). By applying these materials as the outermost layer, an aluminum laminate material for battery packaging having the above-described excellent characteristics can be reliably configured.
また、上記無延伸ポリプロピレン層は、押出ラミネート処理により配設された押出層と、該押出層の表面に熱融着により配設された熱融着フィルム層の二層により構成されていることが好ましい（請求項８）。すなわち、上記内側積層部としては、上記酸変性ポリプロピレン層の上に溶融状態のポリプロピレンを押出してこれを貼り付け、さらに、その上に、予めフィルム状態で作製した無延伸ポリプロピレンフィルムを熱融着させて形成したものであることが好ましい。
これにより、上記無延伸ポリプロピレン層は、より成形性、バリヤー性、耐内容物性、白化性を向上させることができる。
The unstretched polypropylene layer may be composed of two layers, an extruded layer disposed by an extrusion laminating process and a heat fusion film layer disposed on the surface of the extruded layer by thermal fusion. Preferred (claim 8). That is, as the inner laminated portion, a melted polypropylene is extruded onto the acid-modified polypropylene layer, and this is pasted, and further, an unstretched polypropylene film previously prepared in a film state is heat-sealed thereon. It is preferable that they are formed.
Thereby, the said unstretched polypropylene layer can improve a moldability, barrier property, content resistance property, and whitening property more.
また、上記最外層は、ドライラミネート処理により配設されていることが好ましい（請求項９）。
上記ドライラミネート処理は、基材の上に接着剤層を配設すると共にこれをある程度乾燥させ、その接着剤層の上にフィルム状の層を重ねて圧着する方法である。上記基材として、化成皮膜層を設けたアルミニウム箔層を用い、その上に接着剤層を配設して乾燥させ、その後、上記最外層を構成する合成樹脂よりなるフィルム状の層を重ね、ローラ等を用いた圧着を行うことにより電池包装用アルミラミネート材料の外側積層部を形成することができる。
The outermost layer is preferably disposed by a dry laminating process (claim 9).
The dry laminating process is a method in which an adhesive layer is disposed on a substrate and dried to some extent, and a film-like layer is stacked on the adhesive layer and pressure-bonded. As the base material, using an aluminum foil layer provided with a chemical conversion film layer, an adhesive layer is disposed thereon and dried, and then a film-like layer made of a synthetic resin constituting the outermost layer is overlaid, By performing pressure bonding using a roller or the like, the outer laminated portion of the aluminum laminate material for battery packaging can be formed.
（実施例１）
本発明の実施例に係る電池包装用アルミラミネート材料につき、図１〜図３を用いて説明する。
本例では、本発明の実施例として２９種類のラミネート材料（実施例１〜２９）を作製し、また、比較例として１６種類のラミネート材料（比較例１〜１６）を作製し、その特性を評価する試験を複数行った。
(Example 1)
An aluminum laminate material for battery packaging according to an embodiment of the present invention will be described with reference to FIGS.
In this example, 29 types of laminate materials (Examples 1 to 29) were produced as examples of the present invention, and 16 types of laminate materials (Comparative Examples 1 to 16) were produced as comparative examples. Several tests to evaluate were conducted.
実施例１の電池包装用アルミラミネート材料１は、図１に示すごとく、内側表面から、無延伸ポリプロピレン層２、酸変性ポリプロピレン層３、第１化成皮膜層４１、およびアルミニウム箔層１０を順次積層してなる内側積層部１１を有している。また、その外側には、第２化成皮膜層４２、接着剤層５、および最外層６を順次積層した外側積層部１２を有している。そして、この実施例１においては、上記無延伸ポリプロピレン層２として押出ラミネート処理により配設された押出層２１と、該押出層２１の表面に熱融着により配設された熱融着フィルム層２２の二層により構成されている。
As shown in FIG. 1, an
実施例２〜１２，１６〜２９、および比較例１〜１０，１３、１４，１６は、基本的に実施例１と同様の積層構造を有するラミネート材料である。
実施例１３，１５，および比較例１１は、上記無延伸ポリプロピレン層２を熱融着フィルム層２２のみにより構成し、押出層を用いなかった点が実施例１と異なっている。
実施例１４，および比較例１２は、上記無延伸ポリプロピレン層２を押出層２１のみにより構成し、熱融着フィルム層を用いなかった点が実施例１と異なっている。
比較例１５は、酸変性ポリプロピレン層３を用いずに、その代わりにドライ接着剤層を用いた点が実施例１と異なっている。
Examples 2 to 12, 16 to 29 and Comparative Examples 1 to 10, 13, 14, and 16 are basically laminate materials having the same laminated structure as that of Example 1.
Examples 13 and 15 and Comparative Example 11 differ from Example 1 in that the
Example 14 and Comparative Example 12 differ from Example 1 in that the
Comparative Example 15 differs from Example 1 in that the acid-modified polypropylene layer 3 was not used and a dry adhesive layer was used instead.
上記比較例１〜５は、ラミネート材料の構成のうち外側積層部が本発明における好ましい範囲から外れる部分があるものであり、比較例６〜１２は内側積層部が本発明の範囲から外れる部分があるものである。また、比較例１３、１４はラミネート材料全体の機械的性質が好ましい範囲から外れるもの、比較例１５は内側積層部の構成が本発明の範囲と異なるもの、比較例１６は静摩擦係数が好ましい範囲から外れるものである。 In Comparative Examples 1 to 5, there are portions in which the outer laminated portion deviates from the preferred range in the present invention in the configuration of the laminate material, and Comparative Examples 6 to 12 have portions in which the inner laminated portion deviates from the scope of the present invention. There is something. Further, Comparative Examples 13 and 14 are those in which the mechanical properties of the entire laminate material deviate from the preferred range, Comparative Example 15 is different from the scope of the present invention in the configuration of the inner laminated portion, and Comparative Example 16 from the preferred range of the static friction coefficient. It is something that comes off.
各実施例１〜２９，比較例１〜１６を構成する各層の材質および厚さについては、表１、表２に示す。
簡単に補足説明すると、最外層６としては、Ｎｙ：ナイロン（Ｒ）フィルム，ＰＥ：ポリエチレンフィルム、ＰＶＣ：ポリ塩化ビニルフィルム、ＰＥＴ：ポリエステルフィルムのいずれかを採用した。
接着剤層５（ドライ接着剤）としては、Ａ系：ポリウレタン系接着剤、あるいはＢ系：エポキシ系接着剤を用いた。
第１化成皮膜層４１および第２化成皮膜層４２としては、ＰＣｒ：リン酸クロメート処理、Ｚｒ：ジルコニウム処理、Ｔｉ：チタン処理、ＰＺｎ：リン酸亜鉛処理により作製した化成被膜を用いた。
アルミニウム箔層１０としては、Ｆｅ：１．０重量％、Ｓｉ：０．１重量％、Ｍｎ：０．０５重量％を含有するＡ材、あるいはＦｅ：１．５重量％、Ｓｉ：０．１重量％、Ｍｎ：０．０５重量％を含有するＢ材のいずれかを用いた。
酸変性ポリプロピレン層３としては、いずれもマレイン酸を用いた。
押出層および熱融着層は、いずれも無延伸ポリプロピレンでありＰＰと表した。
Tables 1 and 2 show the material and thickness of each layer constituting each of Examples 1 to 29 and Comparative Examples 1 to 16.
Briefly, as the
As the adhesive layer 5 (dry adhesive), A-based: polyurethane-based adhesive or B-based: epoxy-based adhesive was used.
As the first chemical conversion film layer 41 and the second chemical conversion film layer 42, chemical conversion films prepared by PCr: phosphate chromate treatment, Zr: zirconium treatment, Ti: titanium treatment, PZn: zinc phosphate treatment were used.
As the aluminum foil layer 10, an A material containing Fe: 1.0 wt%, Si: 0.1 wt%, Mn: 0.05 wt%, or Fe: 1.5 wt%, Si: 0.1 One of the B materials containing wt% and Mn: 0.05 wt% was used.
As the acid-modified polypropylene layer 3, maleic acid was used for all.
The extruded layer and the heat-sealing layer were both unstretched polypropylene and represented as PP.
次に、上記実施例１の電池包装用アルミラミネート材料１を製造する方法について簡単に説明する。まず、アルミニウム箔層１０の内側面および外側面に第１化成皮膜層４１および第２化成皮膜層４２を形成する化成処理工程を行い、その後、ドライラミネート処理によって最外層６を含む外側積層部１２を設ける。
ドライラミネート処理は、上記第２化成皮膜層４２の上に接着剤を塗布する接着剤塗工工程と、上記接着剤を乾燥させて接着剤層５を形成する乾燥工程と、接着剤層５上に最外層６を圧着するドライラミネート工程とを施すことにより行われる。
Next, a method for manufacturing the battery packaging
The dry laminating process includes: an adhesive coating process for applying an adhesive on the second chemical conversion film layer 42; a drying process for drying the adhesive to form the adhesive layer 5; Is performed by performing a dry laminating step of press-bonding the
また、上記アルミニウム箔層１０の内側面においては、上記第２化成皮膜４２上に、酸変性ポリプロピレンを塗布して酸変性ポリプロピレン層３を形成する工程と、酸変性ポリプロピレン層３上に、無延伸ポリプロピレンを順次押し出して上記押出層２１を形成する押出ラミネート工程とを行い、さらに、押出層２１の上に無延伸ポリプロピレンよりなるフィルムを配置して熱融着させて熱融着フィルム２２を配置する融着工程を行って、内側積層部１１を得る。
Further, on the inner surface of the aluminum foil layer 10, a step of forming an acid-modified polypropylene layer 3 by applying an acid-modified polypropylene on the second chemical film 42, and an unstretched layer on the acid-modified polypropylene layer 3. An extrusion laminating step of forming the extruded
その他の実施例および比較例については、実施例１とほぼ同様の製造方法によって作製するが、実施例１３，１５，および比較例１１は、押出ラミネート工程を削除し、実施例１４，および比較例１２は、押出ラミネート工程を削除し、比較例１５は、酸変性ポリプロピレン層を形成する工程を削除して、その代わりにドライ接着剤層形成する工程を追加した点が実施例１の場合と異なっている。 Other examples and comparative examples are produced by the manufacturing method almost the same as that of Example 1, but Examples 13 and 15 and Comparative Example 11 omit the extrusion laminating step, and Example 14 and Comparative Example. 12 is different from the case of Example 1 in that the extrusion laminating step is deleted, and in Comparative Example 15, the step of forming the acid-modified polypropylene layer is deleted and the step of forming the dry adhesive layer is added instead. ing.
本例では、上記各実施例および比較例のラミネート材料に対し、その機械的性質および両面の摩擦係数を測定する試験を行うと共に、成形性、バリヤー性、耐内容物性、白化性を評価する試験を行った。
＜機械的性質＞
上記各実施例および比較例のラミネート材料から引張試験用サンプルを切り出し、引張試験を行って引張強さおよび伸びを測定した。引張試験用サンプルは幅１５ｍｍ、長さ１５０ｍｍというサイズにした。測定結果は表３、表４に示す。
In this example, the laminate material of each of the above examples and comparative examples is subjected to a test for measuring its mechanical properties and friction coefficients on both sides, and a test for evaluating formability, barrier property, content resistance property, and whitening property. Went.
<Mechanical properties>
A sample for a tensile test was cut out from the laminate materials of the above Examples and Comparative Examples, and a tensile test and a tensile strength and elongation were measured. The tensile test sample was 15 mm wide and 150 mm long. The measurement results are shown in Tables 3 and 4.
＜摩擦係数＞
摩擦係数を測定するに当たっては、３点ボール式スリップテスター摩擦試験にて、荷重２００ｇを負荷した状態で直径φ１２ｍｍ鋼球を摺動させる方法によりにより行った。測定結果は表３、表４に示す。
<Friction coefficient>
The friction coefficient was measured by a method of sliding a steel ball having a diameter of 12 mm in a three-point ball type slip tester friction test under a load of 200 g. The measurement results are shown in Tables 3 and 4.
＜成形性＞
上記各実施例および比較例のラミネート材料から、１００ｍｍ×１５０ｍｍの矩形状シートを切り出し、成形高さフリーの角頭の金型を用いて張り出し加工を行った。成形後における成形深さにより成形性の良否を判断した。判断基準としては、成形深さ４ｍｍ以上の場合を良好として○印で、成形深さ４ｍｍ未満の場合を不良として×印で表３および表４に示した。
<Moldability>
A 100 mm × 150 mm rectangular sheet was cut out from the laminate material of each of the above Examples and Comparative Examples, and overhanging was performed using a square head mold having a molding height free. The quality of the moldability was judged by the molding depth after molding. As the judgment criteria, the case where the forming depth is 4 mm or more is shown as “Good” by ○, and the case where the forming depth is less than 4 mm is shown as “Poor” in Table 3 and Table 4.
＜バリヤー性＞
上記各実施例および比較例のラミネート材料を用いて三方をシールした袋を作製し、その中に炭酸エチル、炭酸ジエチル、炭酸メチレンを同一体積ずつ混合した溶液を３ｍｇ注入し、６０℃×９０％の雰囲気中で１週間保管し、保管前後の溶液中の水分量をカールフィッシャー法で測定した。そして、その水分量の増加量が５０ｐｐｍ以下の場合を良好として○印で、５０ｐｐｍ以上の場合を不良として×印で表３および表４に示した。
<Barrier properties>
A three-side sealed bag is prepared using the laminate material of each of the above examples and comparative examples, and 3 mg of a solution in which ethyl carbonate, diethyl carbonate, and methylene carbonate are mixed in the same volume is injected therein, and 60 ° C. × 90%. Was stored in the atmosphere for 1 week, and the water content in the solution before and after storage was measured by the Karl Fischer method. Table 3 and Table 4 show that the case where the amount of increase in the amount of water is 50 ppm or less is good as ◯, and the case where it is 50 ppm or more is bad as x.
＜耐内容物性＞
上記各実施例および比較例のラミネート材料を、６０℃の電解液（１モルの６フッ化リンリチウム溶液）に浸漬し、アルミニウム箔層１０と無延伸ポリプロピレン層２との間の接着強度を時系列的に評価した。評価基準としては、アルミニウム箔層１０と無延伸ポリプロピレン層２間で剥離していないものを良好として○印で、剥離しているものを不良として×印で表３および表４に示した。
<Content resistance>
The laminate materials of the above examples and comparative examples were immersed in an electrolytic solution (1 mol of lithium hexafluorophosphate solution) at 60 ° C., and the adhesive strength between the aluminum foil layer 10 and the
＜白化性＞
白化性については、上記成形性評価の際の張出し加工後の試料を用い、その最内層である無延伸ポリプロピレン層２を拡大観察し、アルミニウム箔層１０にまで至る亀裂が発生していないものを良好として○印で、亀裂が発生しているものを不良として×印で表３および表４に示した。
<Whitening>
For the whitening property, using the sample after the overhang processing at the time of the above-described moldability evaluation, the
表３から知られるように、本発明の実施例である実施例１〜２９については、いずれも機械的性質、摩擦係数が適正範囲内にあり、かつ、成形性、バリヤー性、耐内容物性、白化性についてもすべて良好であった。
一方、表３から知られるように、比較例１〜１６は、少なくとも１つの評価項目において基準値を下回り、電池包装用アルミラミネート材料としては不十分な性能しか有していないことがわかった。
As can be seen from Table 3, for Examples 1 to 29, which are examples of the present invention, the mechanical properties and the coefficient of friction are within appropriate ranges, and the moldability, barrier properties, content resistance properties, The whitening properties were all good.
On the other hand, as can be seen from Table 3, Comparative Examples 1 to 16 were below the reference value in at least one evaluation item, and it was found that the comparative examples 1 to 16 had insufficient performance as an aluminum laminate material for battery packaging.
次に、上記電池包装用アルミラミネート材料１を電池の包装に使用した使用例を示す。
図２には、上記電池包装用アルミラミネート材料１を用いて構成した電池８外観を３方向からみて示してある。電池８の外周面は、電池包装用アルミラミネート材料１により覆われ、２つの電極８１が一つの端部から飛び出している。
Next, the usage example which used the said aluminum laminated
FIG. 2 shows the appearance of the
図３には、電池８の断面図を示してある。同図より知られるように、セパレータ８５を一対の電極８１によって挟持して構成された積層体を、両面から電池包装用アルミラミネート材料１によって覆って電池８が構成されている。そして、電池包装用アルミラミネート材料１は、その内側に実施例１における無延伸ポリプロピレン層２が位置するように使用されている。
FIG. 3 shows a cross-sectional view of the
このような構成の電池８は、その包装であるラミネート材料１が上記のごとく優れた機械的性質、摩擦係数を有し、かつ、成形性、バリヤー性、耐内容物性、白化性についても優れているので、電池本来の性能をほとんど低下させることなく、耐久性の高いものとなる。
The
１ 電池包装用アルミラミネート材料
１０ アルミニウム箔層
１１ 内側積層部
１２ 外側積層部
２ 無延伸ポリプロピレン層
２１ 押出層
２２ 熱融着フィルム層
３ 酸変性ポリプロピレン層
４１ 第１化成皮膜層
４２ 第２化成皮膜層
５ 接着剤層
６ 最外層
DESCRIPTION OF
Claims (9)
内側表面から、厚さ１０μｍ超え６０μｍ以下の無延伸ポリプロピレン層、厚さ１〜５μｍの酸変性ポリプロピレン層、皮膜付着量が５〜３０ｍｇ／ｍ2の第１化成皮膜層、および厚さ１０〜１００μｍのアルミニウム箔層を順次積層してなる内側積層部と、
上記アルミニウム箔層の外側に配設された、合成樹脂よりなる最外層を含む複数の層を積層してなる外側積層部とよりなることを特徴とする電池包装用アルミラミネート材料。 An aluminum laminate material for battery packaging used for battery packaging,
From the inner surface, an unstretched polypropylene layer having a thickness of more than 10 μm and not more than 60 μm, an acid-modified polypropylene layer having a thickness of 1 to 5 μm, a first chemical conversion film layer having a coating amount of 5 to 30 mg / m 2 , and a thickness of 10 to 100 μm An inner laminated portion formed by sequentially laminating aluminum foil layers,
An aluminum laminate material for battery packaging, comprising: an outer laminated portion formed by laminating a plurality of layers including an outermost layer made of a synthetic resin, which is disposed outside the aluminum foil layer.
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