JP2014195910A - Resin-covered aluminum alloy foil and method for producing the same - Google Patents
Resin-covered aluminum alloy foil and method for producing the same Download PDFInfo
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- JP2014195910A JP2014195910A JP2013071658A JP2013071658A JP2014195910A JP 2014195910 A JP2014195910 A JP 2014195910A JP 2013071658 A JP2013071658 A JP 2013071658A JP 2013071658 A JP2013071658 A JP 2013071658A JP 2014195910 A JP2014195910 A JP 2014195910A
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- 239000011888 foil Substances 0.000 title claims abstract description 52
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920005989 resin Polymers 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 55
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 41
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims description 68
- 239000011248 coating agent Substances 0.000 claims description 66
- 239000003822 epoxy resin Substances 0.000 claims description 55
- 229920000647 polyepoxide Polymers 0.000 claims description 55
- 238000004070 electrodeposition Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 abstract description 15
- 239000011651 chromium Substances 0.000 abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 229910052804 chromium Inorganic materials 0.000 abstract description 7
- 239000005022 packaging material Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 229920000877 Melamine resin Polymers 0.000 abstract 1
- 229920002678 cellulose Polymers 0.000 abstract 1
- 239000001913 cellulose Substances 0.000 abstract 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract 1
- 229920005672 polyolefin resin Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 123
- 239000000463 material Substances 0.000 description 43
- 239000012790 adhesive layer Substances 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 239000008151 electrolyte solution Substances 0.000 description 12
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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
- Laminated Bodies (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
本発明は、クロムを使用しない環境での製造が可能で、耐電解液特性とヒートシール強度に優れ、特にリチウムイオン電池等のソフトパック型電池用外装材として好適な樹脂被覆アルミニウム合金箔及びその製造方法に関する。 The present invention can be produced in an environment not using chromium, has excellent anti-electrolytic solution characteristics and heat seal strength, and is particularly suitable as a resin-coated aluminum alloy foil suitable as an outer packaging material for soft pack type batteries such as lithium ion batteries and the like. It relates to a manufacturing method.
近年、パソコンや携帯電話等の携帯端末装置に用いられる電池として、薄型化、小型化が可能なリチウムイオン電池が開発され、その使用量も増加している。このようなリチウムイオン電池に用いる外装材（外装材）としては、従来から電池用外装材として用いられている金属製缶の他、軽量で電池の形状を自由に変更、選択できるという利点から、多層フィルム型、一般的に言うところのソフトパック型電池外装材が多く用いられるようになってきた。一般に用いられる外装材として、アルミニウム合金箔にＣＰＰフィルムを貼着したもの等が知られている。 In recent years, lithium-ion batteries that can be thinned and miniaturized have been developed as batteries used in portable terminal devices such as personal computers and mobile phones, and the amount of use thereof is increasing. As an exterior material (exterior material) used for such a lithium ion battery, from the advantage that the shape of the battery can be freely changed and selected in addition to a metal can conventionally used as a battery exterior material, A multi-layer film type, generally called soft pack type battery exterior material, has come to be widely used. As a generally used exterior material, an aluminum alloy foil having a CPP film attached thereto is known.
リチウムイオン電池には、電池内容物として正極材、負極材と共に、電解液が含まれている。電解液には強い浸透力を有する非プロトン型の溶媒、例えば炭酸エチレン、炭酸ジメチル、炭酸ジエチルと、電解質であるところのリチウム塩が含まれている。従って、このような強い浸透力を持った溶媒が外装材のＣＰＰフィルムを通過してしまうと、アルミニウム合金箔に対するフィルムのラミネート強度が著しく低下して剥がれる。ここで、電解質のリチウム塩として用いられるＬｉＰＦ６、ＬｉＢＦ４等は、水との加水分解によりフッ酸を発生させるためアルミニウム表面で腐食を引き起こし、最終的にはアルミニウム合金箔を腐食させ、穴が開き、電解液が外に漏れ出す危険がある。また、ヒートシール端部から水分が浸入し、加水分解を引き起こすことが懸念される。 Lithium ion batteries contain electrolyte as well as positive and negative electrode materials. The electrolytic solution contains an aprotic solvent having strong penetrating power, for example, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and a lithium salt as an electrolyte. Therefore, when the solvent having such strong penetrating power passes through the CPP film of the exterior material, the laminate strength of the film with respect to the aluminum alloy foil is remarkably lowered and peeled off. Here, LiPF6, LiBF4, etc. used as the lithium salt of the electrolyte cause corrosion on the aluminum surface because hydrofluoric acid is generated by hydrolysis with water, eventually corroding the aluminum alloy foil, opening a hole, There is a risk of electrolyte leaking out. Further, there is a concern that moisture may enter from the end of the heat seal and cause hydrolysis.
このため、アルミニウム合金箔とフィルム層との層間密着性を向上させ、内容物（電解液や発生したフッ酸）から守ることが必要で、電解液や発生したフッ酸の影響によるフィルム層の剥がれやアルミニウム合金箔の腐食を抑制するため、下記特許文献１〜５のように各種手段が提案されている。 For this reason, it is necessary to improve the interlayer adhesion between the aluminum alloy foil and the film layer and protect it from the contents (electrolytic solution and generated hydrofluoric acid). The film layer is peeled off due to the influence of the electrolytic solution and generated hydrofluoric acid. In order to prevent corrosion of aluminum alloy foil, various means have been proposed as in Patent Documents 1 to 5 below.
アルミニウム合金箔の下地処理として塗布型クロメート処理や、反応型クロメート処理など、多くのクロメート処理方法が開示されている。しかしながら、クロメート処理においては、６価クロムを主成分としているものは環境有害物質に指定されており、機能としては良好であっても、環境面で好ましくない。そのため、３価のクロムが用いられるようになってきたが６価クロムと比較すると、その機能で劣ることが知られている。また、クロムを使用している以上、環境的には好ましくないことは変わらない。 Many chromate treatment methods, such as coating chromate treatment and reactive chromate treatment, have been disclosed as ground treatment for aluminum alloy foils. However, in the chromate treatment, those containing hexavalent chromium as a main component are designated as environmentally hazardous substances, and even if they have good functions, they are not preferable in terms of the environment. For this reason, trivalent chromium has been used, but it is known that its function is inferior to that of hexavalent chromium. Moreover, as long as chromium is used, it is not environmentally undesirable.
クロムを使用しない方法として、特許文献５に、エポキシ樹脂を骨格とし、スルホニウム基を水和官能基として含有する樹脂を基体樹脂とする電解活性型電着塗料組成物を電池ケース缶に電着塗装することが提案されている。 As a method that does not use chromium, Patent Document 5 discloses an electrodeposition coating of an electrolytically active electrodeposition coating composition that uses a resin containing an epoxy resin as a skeleton and a sulfonium group as a hydrated functional group as a base resin. It has been proposed to do.
しかしながら、特許文献５の方法は、電池ケース缶においては有効であるものの、ＣＰＰ等のフィルム層を持つ、多層フィルム型（ソフトパック型電池外装材）にただちに適用できるものとはいえない。即ち、ここで用いられる外装材に対しては缶材と異なる条件、例えば厚さ、成形方法、加工等が施されることから、電池として使用した場合、耐食性のみならず、フィルム層及び接着剤層との十分な密着性はこれら条件に合わせて調整する必要があるためである。 However, although the method of Patent Document 5 is effective in a battery case can, it cannot be immediately applied to a multilayer film type (soft pack type battery exterior material) having a film layer such as CPP. That is, since the exterior material used here is subjected to conditions different from those of the can material, such as thickness, molding method, processing, etc., when used as a battery, not only corrosion resistance but also a film layer and an adhesive This is because sufficient adhesion with the layer needs to be adjusted according to these conditions.
また、近年、リチウム電池に対するニーズは、従来からのパソコンや携帯電話等の携帯端末装置等のいわゆる民生用途の薄型・小型化に加え、自動車用途として大容量・大型化も求められるようになってきた。このため、民生用途以上の極めて高い耐食性と安全性が以前にも増して求められるようになっている。 In addition, in recent years, the need for lithium batteries has come to require large capacity and large size for automobile applications in addition to conventional thin and small consumer applications such as portable terminal devices such as personal computers and mobile phones. It was. For this reason, the extremely high corrosion resistance and safety more than a consumer use are demanded more than before.
従って、強い浸透力を持った溶媒が、ＣＰＰ等のフィルム層を通過して、アルミニウム箔層とフィルム層間のラミネート強度を著しく低下させることや、フィルムが剥がれを起こし、電解液が漏れ出すといった問題発生を避ける重要性が高まっており、アルミニウム合金箔材とフィルム層間の層間密着性を高度に向上させ、内容物（電解液や発生したフッ酸）の漏れを確実に防ぐことが急務である。 Therefore, there is a problem that a solvent having a strong penetrating power passes through a film layer such as CPP to significantly reduce the laminate strength between the aluminum foil layer and the film layer, or the film peels off and the electrolyte leaks out. The importance of avoiding the occurrence is increasing, and there is an urgent need to improve the interlayer adhesion between the aluminum alloy foil material and the film layer to prevent leakage of the contents (electrolytic solution and generated hydrofluoric acid).
本発明は、上記事情に鑑みなされたもので、従来から電池用外装材として用いられてきた金属製缶とは異なり、軽量で電池の形状を自由に変更、選択できる多層フィルム型、一般的に言うところのソフトパック型電池外装材として好適に用いることができ、上記問題点の解消を図り、電解液や発生するフッ酸に対する耐性（耐食性）に優れるとともに、ＣＰＰ等の密着性にも優れた電池用外装材を、ノンクロムといった環境に配慮した方法で提供することを目的とする。 The present invention has been made in view of the above circumstances, and unlike a metal can conventionally used as a battery outer packaging material, it is a multilayer film type that is lightweight and can freely change and select the shape of the battery. It can be suitably used as the so-called soft pack type battery exterior material, solves the above-mentioned problems, has excellent resistance (corrosion resistance) to the electrolytic solution and generated hydrofluoric acid, and excellent adhesion to CPP and the like. The object is to provide an outer packaging material for a battery by an environmentally friendly method such as non-chrome.
本発明は上記の目的を達成するためになされたもので、以下の（１）と（２）からなる。
（１）アルミニウム合金箔と、該アルミニウム合金箔の少なくとも片面に樹脂層を有する樹脂被覆アルミニウム合金箔であって、該樹脂層はアルミニウム合金箔と接する面が電着塗装によるエポキシ系樹脂を主成分とする厚みが１〜２０μmのエポキシ系樹脂層を具備しかつ該エポキシ系樹脂層の表面にアクリル系樹脂を主成分とする厚みが０．５〜１０μmアクリル系樹脂層を具備し、エポキシ系樹脂層とアクリル系樹脂層とが同時焼付された樹脂層であることを特徴とする樹脂被覆アルミニウム合金箔。
（２）アルミニウム合金箔の少なくとも片面に樹脂層を有する樹脂被覆アルミニウム合金箔の製造方法であって、アルミニウム合金箔にエポキシ系樹脂を主成分とする厚みが１〜２０μmのエポキシ系樹脂層を電着塗装し、該エポキシ系樹脂層の上にアクリル系樹脂を主成分とする厚みが０．５〜１０μmアクリル系樹脂層を形成し、エポキシ系樹脂層とアクリル系樹脂層とを同時焼付して該樹脂層を形成することを特徴とする樹脂被覆アルミニウム合金箔の製造方法。
The present invention has been made to achieve the above object, and comprises the following (1) and (2).
(1) An aluminum alloy foil and a resin-coated aluminum alloy foil having a resin layer on at least one surface of the aluminum alloy foil, the surface of the resin layer being in contact with the aluminum alloy foil is mainly composed of an epoxy resin by electrodeposition coating An epoxy resin layer having a thickness of 1 to 20 μm, and an acrylic resin layer having a thickness of 0.5 to 10 μm mainly composed of an acrylic resin on the surface of the epoxy resin layer. A resin-coated aluminum alloy foil, wherein the layer and the acrylic resin layer are simultaneously baked resin layers.
(2) A method for producing a resin-coated aluminum alloy foil having a resin layer on at least one surface of an aluminum alloy foil, wherein an epoxy resin layer having a thickness of 1 to 20 μm mainly composed of an epoxy resin is applied to the aluminum alloy foil. After coating, an acrylic resin layer having a thickness of 0.5 to 10 μm mainly composed of an acrylic resin is formed on the epoxy resin layer, and the epoxy resin layer and the acrylic resin layer are baked simultaneously. A method for producing a resin-coated aluminum alloy foil, wherein the resin layer is formed.
本発明の電池用外装材及びその製造方法は、ノンクロムで製造可能という環境問題に好適に対応し、リチウム電池等のソフトパック型の外装材として、電解液や発生するフッ酸に対する耐性（耐食性）に優れるとともに、ＣＰＰ等のフィルム層との密着性に優れ、自動車材としての安全が求められる用途に好適に採用し得、リチウムイオン電池に求められる様々な用途に用いることができる。 The battery outer packaging material and the manufacturing method thereof according to the present invention are suitable for the environmental problem of being able to be produced with non-chromium, and as a soft pack type outer packaging material such as a lithium battery, resistance to electrolytic solution and generated hydrofluoric acid (corrosion resistance). In addition, it is excellent in adhesion to a film layer such as CPP, can be suitably used for applications requiring safety as an automobile material, and can be used in various applications required for lithium ion batteries.
以下、本発明を各要素に分けて詳述する。
本発明の製造方法で基材（箔板）となるアルミニウム合金箔は、従来から外装材の用途として使用されているものであれば良く、特に限定されるものではない。例えば、ＪＩＳ規格の８０２１合金、８０７９合金などを用いることができる。またアルミニウム合金の基材自体の形状は、特に、形状は板、シートやコイル等のいずれでも良い。
Hereinafter, the present invention will be described in detail for each element.
The aluminum alloy foil used as the base material (foil plate) in the production method of the present invention is not particularly limited as long as it has been conventionally used as an application for an exterior material. For example, JIS standard 8021 alloy, 8079 alloy or the like can be used. The shape of the aluminum alloy substrate itself may be any of a plate, a sheet, a coil, and the like.
本発明の樹脂被覆アルミニウム合金箔は、上記アルミニウム合金基材に樹脂層が形成されたものである。本発明において樹脂層は、アルミニウム合金箔と接する面が電着塗装によるエポキシ系樹脂を主成分とするエポキシ系樹脂層を具備しかつアルミニウム合金箔と接しない面がアクリル系樹脂を主成分とするアクリル系樹脂層の構成であることが必要である。 The resin-coated aluminum alloy foil of the present invention is obtained by forming a resin layer on the aluminum alloy base material. In the present invention, the resin layer has an epoxy resin layer mainly composed of an epoxy resin by electrodeposition coating on the surface in contact with the aluminum alloy foil, and the surface not in contact with the aluminum alloy foil has an acrylic resin as a main component. It is necessary to have a configuration of an acrylic resin layer.
なお、本願発明でいう、樹脂層のエポキシ系樹脂層、アクリル系樹脂層は樹脂層成分中のエポキシ成分とアクリル成分とのバランスで定義され、アクリル成分に対してエポキシ成分が多い層をエポキシ系樹脂層、エポキシ成分に対してアクリル成分が多い層をアクリル系樹脂層と呼ぶものとする。後述する厚さ等の測定でもエポキシ系樹脂層と、アクリル系樹脂層を同様に定義するものとする。 The epoxy resin layer of the resin layer and the acrylic resin layer in the present invention are defined by the balance between the epoxy component and the acrylic component in the resin layer component. The resin layer and a layer having a larger amount of acrylic component than the epoxy component are referred to as an acrylic resin layer. The epoxy resin layer and the acrylic resin layer are similarly defined in the measurement of thickness and the like described later.
本発明の樹脂層は、エポキシ系樹脂層と、アクリル系樹脂層とは夫々の層を形成して多層構造にした後、同時焼付したものであり、その製造方法については後述する。 In the resin layer of the present invention, the epoxy resin layer and the acrylic resin layer are formed by forming respective layers to form a multilayer structure and then co-baking, and the manufacturing method thereof will be described later.
本願発明のエポキシ系樹脂層は、電着塗料として調整することが必要で、水溶性高分子、エマルション、コロイド状分散体などのいずれかから誘導されたエポキシ系樹脂を用いることができる。具体的には、カチオン化されたカチオン性エポキシ樹脂であれば用いることが出来るが、特にエポキシ樹脂にアミン変性したアミン変性エポキシ樹脂が好ましい。なお、これらエポキシ系樹脂に対しては、更に目的に応じ、中和剤（有機酸）、溶剤、各種添加剤（分散剤、消泡剤、レべリング剤）を添加したものでも良い。 The epoxy resin layer of the present invention needs to be adjusted as an electrodeposition paint, and an epoxy resin derived from any one of a water-soluble polymer, an emulsion, a colloidal dispersion and the like can be used. Specifically, any cationic cationic epoxy resin can be used, but an amine-modified epoxy resin that is amine-modified to an epoxy resin is particularly preferable. These epoxy resins may be further added with a neutralizing agent (organic acid), a solvent, and various additives (dispersant, antifoaming agent, leveling agent) depending on the purpose.
本発明のエポキシ系樹脂層は、電着塗装を施して製造されたものである。ここで電着塗装とは、水溶液中でイオン化した塗料樹脂を電極である被塗装物上に電気泳動的に析出させて不溶性の塗膜を形成させる方式である。本発明においては、上記電着塗装を採用することにより、アルミニウム合金箔との密着性が強固な塗膜になっている。電着塗装以外では、局部的な膜厚の増減、塗膜のピンホールが発生し、非常に緻密で均一な塗膜を得ることができない。またエポキシ系樹脂の厚さは、電解条件の変更で任意に選択できるが、本発明においては、通常１．０μm〜２０．０μmであることが好ましい。１．０μm未満では、塗膜が薄くて、その耐食性能を発揮できない。一方、２０．０μmを越えてもそれ以上の耐食性能向は期待できず、塗膜が厚すぎて、加工に対し、追従できなくなり、クラックの発生などを招くことになる。 The epoxy resin layer of the present invention is produced by electrodeposition coating. Here, electrodeposition coating is a method in which a coating resin ionized in an aqueous solution is electrophoretically deposited on an object to be coated as an electrode to form an insoluble coating film. In the present invention, by adopting the above-mentioned electrodeposition coating, a coating film having strong adhesion to the aluminum alloy foil is formed. Other than electrodeposition coating, local increase / decrease in film thickness and pinholes of the coating film occur, and a very dense and uniform coating film cannot be obtained. The thickness of the epoxy resin can be arbitrarily selected by changing the electrolysis conditions, but in the present invention, it is usually preferably 1.0 μm to 20.0 μm. If it is less than 1.0 μm, the coating film is thin and its corrosion resistance cannot be exhibited. On the other hand, even if it exceeds 20.0 μm, no further anticorrosion performance can be expected, and the coating film is too thick to follow the processing, resulting in the generation of cracks.
本発明において、アクリル系樹脂層としてはアクリル酸あるいはメタクリル酸およびそれらの誘導体を主成分とする樹脂、また、これらのモノマを含むアクリル共重合体を用いることができ、具体的には、ポリアクリル酸、ポリアクリル酸エステル、ポリメタクリル酸、ポリメタクリル酸エステル及びそれらの共重合体などが好適に用いられる。加えて、アンモニア、アミン類にてｐＨ調整したアクリル樹脂も好適であるが、特にアミン類でｐＨ調整したものが好ましい。 In the present invention, as the acrylic resin layer, a resin mainly composed of acrylic acid or methacrylic acid and derivatives thereof, or an acrylic copolymer containing these monomers can be used. Acid, polyacrylic acid ester, polymethacrylic acid, polymethacrylic acid ester, and copolymers thereof are preferably used. In addition, acrylic resins whose pH is adjusted with ammonia or amines are also suitable, but those whose pH is adjusted with amines are particularly preferred.
本発明のアクリル系樹脂層は、上記電着塗装にて製造されたエポキシ系樹脂層の上に種々の方法で形成される。アクリル系樹脂の膜厚は特に制限されるものではなく、電解条件の変更で任意に選択できるが、通常５μm〜１０．０μmであることが必要である。５μm未満では、塗膜が薄すぎて、その性能である密着性能を十分に発揮できない。一方、１０．０μmを超えるとそれ以上の性能向上は期待できず製造コストに問題が生じる上、塗膜が厚すぎて、外装材の加工に追従できなくなり、クラックの発生などを招く場合がある。 The acrylic resin layer of the present invention is formed by various methods on the epoxy resin layer produced by the above electrodeposition coating. The film thickness of the acrylic resin is not particularly limited, and can be arbitrarily selected by changing the electrolysis conditions, but usually needs to be 5 μm to 10.0 μm. If the thickness is less than 5 μm, the coating film is too thin and the adhesion performance as the performance cannot be sufficiently exhibited. On the other hand, if it exceeds 10.0 μm, no further improvement in performance can be expected, causing problems in manufacturing cost, and the coating film is too thick to follow the processing of the exterior material, which may lead to the occurrence of cracks, etc. .
本発明の樹脂層は、上記アクリル系樹脂層を形成した後、更にエポキシ系樹脂層とアクリル系樹脂層とを同時焼付けにより一体成形することが好ましい。焼付処理の温度及び時間は、各層の成分の種類や組成によって変わるが、通常は、焼付温度を１５０℃〜２５０℃、好ましくは180℃〜250℃の範囲で、焼付時間を２０秒〜１０分、好ましくは20秒〜8分とすることが推奨される。１５０℃未満では硬化不足や二層の一体型塗膜への変化が不十分になり易い。また２５０℃を超えると樹脂の分解が起こり易くなり、共に十分な性能を確保できなくなる場合がある。焼付時間が２０秒未満では硬化不足が生じやすく、また１０分を超えると長時間焼付しても塗膜性能は変化せず、十分な効果を期待できない場合がある。 It is preferable that the resin layer of the present invention is integrally formed by co-baking an epoxy resin layer and an acrylic resin layer after the acrylic resin layer is formed. The temperature and time of the baking treatment vary depending on the type and composition of the components of each layer, but usually the baking temperature is 150 ° C. to 250 ° C., preferably 180 ° C. to 250 ° C., and the baking time is 20 seconds to 10 minutes. It is recommended that 20 seconds to 8 minutes be used. If it is less than 150 degreeC, it will be easy to become inadequate hardening and the change to a two-layer integrated coating film. If the temperature exceeds 250 ° C., the resin tends to decompose, and sufficient performance may not be ensured. If the baking time is less than 20 seconds, insufficient curing tends to occur, and if it exceeds 10 minutes, the coating film performance does not change even if baking is performed for a long time, and a sufficient effect may not be expected.
本発明の樹脂層は、アルミニウム合金に直接密着するエポキシ系樹脂層の持つ耐食性とその上層に形成されるアクリル系樹脂層による相乗効果でリチウムイオン電池用外装材を形成した場合、CPP等のフィルム層や接着剤層との更なる密着性により、より優れた耐電解液特性とヒートシール強度とが確保されている。従って、安全面で信頼性が求められている自動車等の車載用外装材に好適に採用でき、厳しい環境化での電池性能が要求される分野への使用も可能となる。 The resin layer of the present invention is a film such as CPP when the exterior material for lithium ion battery is formed by the synergistic effect of the corrosion resistance of the epoxy resin layer directly adhered to the aluminum alloy and the acrylic resin layer formed thereon. Due to the further adhesiveness with the layer and the adhesive layer, more excellent electrolytic solution resistance and heat seal strength are ensured. Therefore, it can be suitably used for a vehicle exterior material such as an automobile that requires reliability in terms of safety, and can be used in a field where battery performance is required in a severe environment.
本発明の樹脂被覆アルミニウム合金箔を得るには、エポキシ系樹脂層は、電着塗装を施す必要がある。ここで電着塗装とは、上述したように、水溶液中でイオン化した塗料樹脂を電極である被塗装物上に電気泳動的に析出させて不溶性の塗膜を形成させる方式である。本発明においては、上記電着塗装を採用することにより、エポキシ系樹脂層とアルミニウム合金箔との密着性を強固にするだけでなく、通常の外装材の製造方法として用いられるロールコート法に比べて、塗膜厚さのコントロールが容易であり、局部的な膜厚の増減が無く、塗膜のピンホール発生を抑制でき、非常に緻密で均一な塗膜を得ることができ、塗装時に異物等を巻き込むなどの塗膜欠陥の発生する要因がなく、塗料の無駄を省ける等、有利な条件で製造を行うことができる。 In order to obtain the resin-coated aluminum alloy foil of the present invention, the epoxy resin layer needs to be subjected to electrodeposition coating. Here, the electrodeposition coating is a system in which a coating resin ionized in an aqueous solution is electrophoretically deposited on an object to be coated as an electrode to form an insoluble coating film as described above. In the present invention, by adopting the above-mentioned electrodeposition coating, not only the adhesion between the epoxy resin layer and the aluminum alloy foil is strengthened, but also compared with a roll coating method used as a manufacturing method of a normal exterior material. The coating thickness is easy to control, there is no local increase or decrease in film thickness, pinhole generation in the coating can be suppressed, and a very dense and uniform coating can be obtained. There are no factors that cause coating film defects such as entrainment, and the like, and the production can be performed under advantageous conditions such as the waste of paint.
なお、本発明において、電着塗装は、アルミニウム箔板を陰極とし、対極にステンレス板を用いて行うことができ、例えば、２０〜１００Ｖで電解し、塗膜の厚さは通電時間でコントロールして公知の方法で行うことができる。 In the present invention, electrodeposition coating can be performed using an aluminum foil plate as a cathode and a stainless plate as a counter electrode. For example, electrolysis is performed at 20 to 100 V, and the thickness of the coating film is controlled by energization time. Can be carried out by a known method.
本発明においては、エポキシ系樹脂層の膜厚は特に制限されるものではなく、電解条件の変更で任意に選択できるが、本発明においては、通常１．０μm〜２０．０μmの範囲が好適である。１．０μm未満では、塗膜が薄くて、その耐食性能を発揮できない。一方、２０．０μmを越えてもそれ以上の耐食性能向は期待できず、塗膜が厚すぎて、加工に対し、追従できなくなり、クラックの発生などを招くことになる。このような条件及び厚さで製造されたエポキシ系樹脂層は、製造後、塗膜中に水分をほとんど含んでおらず、塗膜中に残ったわずかな水分を除去する程度で良く、ベトツキが無い程度の簡単な乾燥で製造できるので工業的に有利である。 In the present invention, the thickness of the epoxy resin layer is not particularly limited and can be arbitrarily selected by changing electrolysis conditions. However, in the present invention, a range of 1.0 μm to 20.0 μm is usually preferable. is there. If it is less than 1.0 μm, the coating film is thin and its corrosion resistance cannot be exhibited. On the other hand, even if it exceeds 20.0 μm, no further anticorrosion performance can be expected, and the coating film is too thick to follow the processing, resulting in the generation of cracks. The epoxy resin layer produced under such conditions and thickness contains little moisture in the coating film after production, and only needs to remove the slight moisture remaining in the coating film. This is industrially advantageous because it can be produced with as little dryness as possible.
次に本発明のアクリル系樹脂層は、上記電着塗装にて製造されたエポキシ系樹脂層の上に製造するものである。アクリル系樹脂の膜厚は特に制限されるものではなく、電解条件の変更で任意に選択できるが、通常５μm〜１０．０μmの範囲が好適である。５μm未満では、塗膜が薄すぎて、その性能である密着性能を十分に発揮できない。一方、１０．０μmを超えるとそれ以上の性能向上は期待できず製造コストに問題が生じる上、塗膜が厚すぎて、外装材の加工に追従できなくなり、クラックの発生などを招く場合がある。 Next, the acrylic resin layer of this invention is manufactured on the epoxy resin layer manufactured by the said electrodeposition coating. The film thickness of the acrylic resin is not particularly limited and can be arbitrarily selected by changing the electrolysis conditions, but a range of usually 5 μm to 10.0 μm is suitable. If the thickness is less than 5 μm, the coating film is too thin and the adhesion performance as the performance cannot be sufficiently exhibited. On the other hand, if it exceeds 10.0 μm, no further improvement in performance can be expected, causing problems in manufacturing cost, and the coating film is too thick to follow the processing of the exterior material, which may lead to the occurrence of cracks, etc. .
本発明の樹脂層は、上記アクリル系樹脂層を形成した後、更にエポキシ系樹脂層とアクリル系樹脂層とを一体成形することが好ましい。これは、二層を同時に焼付処理すればよい。焼付処理の温度及び時間は、各層の成分の種類や組成によって変わるが、通常は、焼付温度を１５０℃〜２５０℃、好ましくは180℃〜250℃の範囲で、焼付時間を２０秒〜１０分、好ましくは20秒〜8分とすることが好ましい。１５０℃未満では硬化不足や二層の一体型塗膜への変化が不十分になり易い。また２５０℃を超えると樹脂の分解が起こり易くなり、共に十分な性能を確保できなくなる。焼付時間が２０秒未満では硬化不足が生じやすく、また１０分を超えると長時間焼付しても塗膜性能は変化せず、十分な効果を期待できない場合がある。焼付には熱風炉および赤外炉が利用できる。この焼付処理によれば、電着塗装によるエポキシ系樹脂皮膜に対しては実質的に行わないことになるため、アクリル系樹脂層同時に焼付処理するといった２コート１ベーク方式が出来るため、製造的に非常に効率がよく、工業的に有利である。 The resin layer of the present invention is preferably formed by integrally molding an epoxy resin layer and an acrylic resin layer after forming the acrylic resin layer. This can be done by baking the two layers simultaneously. The temperature and time of the baking treatment vary depending on the type and composition of the components of each layer, but usually the baking temperature is 150 ° C. to 250 ° C., preferably 180 ° C. to 250 ° C., and the baking time is 20 seconds to 10 minutes. Preferably, it is 20 seconds to 8 minutes. If it is less than 150 degreeC, it will be easy to become inadequate hardening and the change to a two-layer integrated coating film. If the temperature exceeds 250 ° C., the resin is likely to be decomposed, and sufficient performance cannot be secured. If the baking time is less than 20 seconds, insufficient curing tends to occur, and if it exceeds 10 minutes, the coating film performance does not change even if baking is performed for a long time, and a sufficient effect may not be expected. Hot stove and infrared furnace can be used for baking. According to this baking treatment, since the epoxy resin film by electrodeposition coating is not substantially performed, a two-coat one-bake method of simultaneously baking the acrylic resin layer can be performed. It is very efficient and industrially advantageous.
本発明の樹脂被覆アルミニウム合金箔は、上述したように良好な耐電解液特性とヒートシール強度とをかね添えたものであるが、本発明の必須構成要件以外には、種々の製造方法を採用することができる。従って、例えば、即ち、外装材は、通常はアルミニウム箔層にフィルム層を設けて多層化することで、多層化する層が増えるに従い、層間での密着性の問題が解決できる。即ち、従来のようなエポキシ系樹脂にて、塗装―焼付処理して樹脂層を設け、（この場合は電着塗装でもロールコートでも同様である）その後、アクリル系樹脂にて塗装―焼付処理することで二層よりなる樹脂層構造を得た場合（一般的な２コート２ベーク方式）、柔軟性を持ったエポキシ系樹脂層と、比較的硬く、伸びの少ないアクリル系樹脂層間で樹脂層同士のズレ（スベリ）が生じたり、また、素材（アルミニウム箔）の変形に追従できなくなり割れを起こし、結果的に剥がれを生んでしまうことがなく、優れた耐電解液特性とヒートシール強度が確保される。 As described above, the resin-coated aluminum alloy foil of the present invention combines good electrolytic solution characteristics and heat seal strength, but adopts various manufacturing methods other than the essential constituent requirements of the present invention. can do. Therefore, for example, the exterior material is usually formed by providing a film layer on an aluminum foil layer to be multilayered, so that the problem of adhesion between layers can be solved as the number of multilayered layers increases. That is, a resin layer is formed by painting-baking treatment with a conventional epoxy resin (in this case, it is the same with electrodeposition coating or roll coating), and then painting-baking treatment with acrylic resin is performed. When a two-layered resin layer structure is obtained (general two-coat two-bake method), the resin layers are formed between a flexible epoxy resin layer and a relatively hard acrylic resin layer with little elongation. No slippage (slip) occurs, and it is impossible to follow the deformation of the material (aluminum foil), causing cracks, resulting in no peeling, ensuring excellent electrolytic solution resistance and heat seal strength Is done.
特に、エポキシ系樹脂層とアクリル系樹脂層の二層を同時に焼付処理された層は、一体型の樹脂層のため、更に強固な密着性を確保できる。 In particular, since the two layers of the epoxy resin layer and the acrylic resin layer that have been baked at the same time are an integral resin layer, stronger adhesion can be secured.
なお、それぞれの樹脂層の厚みは、最初に形成されるエポキシ樹脂においては、直接測定することも可能であるが、（例えば脱膜による重量法や渦電流による測定）電着塗装条件と被膜厚みを事前に測定しておくと、より効率的である。(例えば電圧を一定にし、通電時間で制御する。)2層目としてのアクリル樹脂は、既に被膜量が既知であるところの1層目（エポキシ樹脂）上に形成されるので、総被膜量が知れれば、その値は既知となる。総被膜量は、例えば脱膜による重量法や渦電流によって直接測定することが可能である。 In addition, although the thickness of each resin layer can be directly measured in the epoxy resin initially formed, the electrodeposition coating conditions and the film thickness (for example, a gravimetric method by film removal or eddy current measurement) It is more efficient to measure in advance. (For example, the voltage is fixed and controlled by the energization time.) Since the acrylic resin as the second layer is formed on the first layer (epoxy resin) where the coating amount is already known, the total coating amount is If known, its value is known. The total coating amount can be directly measured by, for example, a gravimetric method based on film removal or eddy current.
以下、本発明の実施例及び比較例を示し、本発明の好適な実施の形態を具体的に説明するが、本発明は下記実施例に制限されるものではない。 EXAMPLES Examples and comparative examples of the present invention will be described below, and preferred embodiments of the present invention will be specifically described. However, the present invention is not limited to the following examples.
本発明の好適な実施の形態を具体的に説明する。基材であるアルミニウム材は８０７９合金相当のアルミニウム合金箔（板厚４０μｍ）を用いた。
カチオン型の電着塗装方式を用いて、エポキシ系樹脂層をアルミニウム合金箔の両面に形成した。樹脂層の厚さは処理時の電圧及び処理時間で調整した。樹脂層形成後、冷風にて乾燥した。
乾燥後、電池用外装材とした場合の内面側になる片面のエポキシ系樹脂皮膜上に、アクリル系樹脂塗料をバーコーターにて均一に塗布した。塗膜量は事前に調査し、バーコーターの種類及び塗料濃度で調整した。塗膜を形成後、所定の温度、所定の時間で二層を同時に焼付処理した。
焼付処理には熱風炉を用いて、風速は１５m／秒で行った。得られた材料に対して、電池用外装材の外面側にウレタン系接着剤を塗布後、１００℃、１５秒の乾燥焼付を行い、３．０ｇ／ｍ２の接着層を設けた。その上に、厚さ２５μmのコロナ処理したＯＮｙフィルムのコロナ処理面を接着層に貼り合わせ、４０℃雰囲気中で１６８時間のエージング処理を施した。
その後、電池用外装材の内面側に変性ポリオレフィンから成る接着剤をバーコーターにて均一に塗布し、２００℃、２０秒で乾燥焼付けを行い、１．０ｇ／ｍ２の接着層を形成させた。厚さ３０μmのＣＰＰフィルムのコロナ処理面を接着層側に貼り合わせ、熱溶融ラミネートを温度１１０℃、１ｍ／ｍｉｎの速度で行った。以上のようにして、〔ＣＰＰフィルム層／接着層／アクリル系樹脂層／電着塗装でのエポキシ系樹脂層／アルミニウム箔材／電着塗装でのエポキシ系樹脂層／接着層／ＯＮｙフィルム層〕と積層貼着された二次電池外装用材料を得た。
A preferred embodiment of the present invention will be specifically described. As an aluminum material as a base material, an aluminum alloy foil (plate thickness: 40 μm) corresponding to 8079 alloy was used.
An epoxy resin layer was formed on both surfaces of the aluminum alloy foil using a cationic electrodeposition coating method. The thickness of the resin layer was adjusted by the voltage during the treatment and the treatment time. After forming the resin layer, it was dried with cold air.
After drying, an acrylic resin coating was uniformly applied with a bar coater on one side of the epoxy resin film that would be the inner surface when the battery was made into an exterior material. The coating amount was investigated in advance and adjusted with the type of bar coater and paint concentration. After forming the coating film, the two layers were simultaneously baked at a predetermined temperature for a predetermined time.
A baking furnace was used for the baking treatment, and the wind speed was 15 m / sec. A urethane adhesive was applied to the outer surface of the battery outer packaging material, and then subjected to dry baking at 100 ° C. for 15 seconds to provide a 3.0 g / m 2 adhesive layer. On top of that, the corona-treated surface of a corona-treated ONy film with a thickness of 25 μm was bonded to the adhesive layer, and an aging treatment was performed for 168 hours in a 40 ° C. atmosphere.
Thereafter, an adhesive made of a modified polyolefin was uniformly applied to the inner surface side of the battery exterior material with a bar coater, followed by drying and baking at 200 ° C. for 20 seconds to form a 1.0 g / m 2 adhesive layer. The corona-treated surface of a 30 μm thick CPP film was bonded to the adhesive layer side, and hot melt lamination was performed at a temperature of 110 ° C. and a speed of 1 m / min. As described above, [CPP film layer / adhesive layer / acrylic resin layer / epoxy resin layer in electrodeposition coating / aluminum foil material / epoxy resin layer in electrodeposition coating / adhesion layer / ONy film layer] A secondary battery exterior material laminated and adhered was obtained.
実施例１と同様の方法でエポキシ系樹脂層を設けた後、所定温度及び所定時間で焼付処理を行った。その後アクリル系樹脂層をバーコーターにて均一に塗布した。塗膜量は事前に調査し、バーコーターの種類及び塗料濃度で調整した。次いで、アクリル系樹脂層を塗布後、所定温度、所定時間で焼付処理した。また、比較例には、エポキシ系樹脂層のみを形成したものも作製した。その後は実施例１と同様の方法で、〔ＣＰＰフィルム層／接着層／アクリル系樹脂層／電着塗装でのエポキシ系樹脂層／アルミニウム箔材／電着塗装でのエポキシ系樹脂層／接着層／ＯＮｙフィルム層〕と積層貼着された二次電池外装用材料を得た。 After the epoxy resin layer was provided by the same method as in Example 1, baking treatment was performed at a predetermined temperature and a predetermined time. Thereafter, an acrylic resin layer was uniformly applied with a bar coater. The coating amount was investigated in advance and adjusted with the type of bar coater and paint concentration. Next, after the acrylic resin layer was applied, it was baked at a predetermined temperature for a predetermined time. Moreover, what formed only the epoxy resin layer was also produced for the comparative example. Thereafter, in the same manner as in Example 1, [CPP film layer / adhesive layer / acrylic resin layer / epoxy resin layer in electrodeposition coating / aluminum foil material / epoxy resin layer in electrodeposition coating / adhesion layer] / ONy film layer] and a secondary battery exterior material laminated and adhered were obtained.
アルミニウム合金の下地処理として、従来から利用されている、クロメート処理により試験材を作製した。なお、比較例の一部は下地処理を行わず、そのまま使用した。
基材であるアルミニウム材は８０７９合金相当のアルミニウム合金箔（板厚４０μｍ）を用いた。
塗布型クロメート処理の場合、電池容器の内面側塗布型クロメート処理液をバーコーターにて塗装し、１５０℃の熱風炉で２０秒の焼付処理を実施した。樹脂層量はＣｒ量として２０ｍｇ／ｍ２を得た。
反応型クロメート処理の場合には、反応型クロメート処理液を使用し、４０℃の温度で浸漬することにより、Ｃｒ量として２０ｍｇ／ｍ２の皮膜量を得た。皮膜量の調整は浸漬時間で行った。さらに水洗後、温風で乾燥させた。その後、外装材の外面側になる片側にウレタン系接着剤を塗布後、１００℃、１５秒の乾燥焼付を行い、３．０ｇ／ｍ２の接着層を設けた。その上に、厚さ２５μmのコロナ処理したＯＮｙフィルムのコロナ処理面を接着層に貼り合わせ、４０℃雰囲気中で１６８時間のエージング処理を施した。その後、電池容器の内面側になるツヤ面側に、変性ポリオレフィンから成る接着剤をバーコーターにて均一に塗布し、２００℃、２０秒で乾燥焼付けを行い、１．０ｇ／ｍ２の接着層を形成させた。厚さ３０μmのＣＰＰフィルムのコロナ処理面を接着層側に貼り合わせ、熱溶融ラミネートを温度１１０℃、１ｍ／ｍｉｎの速度で行った。以上のようにして、〔ＣＰＰフィルム層／接着層／クロメート皮膜層／アルミニウム箔材／（クロメート皮膜層）／接着層／ＯＮｙフィルム層〕と積層貼着された二次電池外装用材料を得た。
A test material was prepared by chromate treatment, which has been conventionally used as a base treatment for an aluminum alloy. In addition, a part of the comparative example was used as it was without performing the ground treatment.
As an aluminum material as a base material, an aluminum alloy foil (plate thickness: 40 μm) corresponding to 8079 alloy was used.
In the case of the coating type chromate treatment, the inner side coating type chromate treatment liquid of the battery container was coated with a bar coater, and the baking treatment was carried out in a hot air oven at 150 ° C. for 20 seconds. The resin layer amount was 20 mg / m 2 as the Cr amount.
In the case of reactive chromate treatment, a reactive chromate treatment solution was used and immersed at a temperature of 40 ° C. to obtain a coating amount of 20 mg / m 2 as the Cr amount. The coating amount was adjusted by the immersion time. Further, after washing with water, it was dried with warm air. Then, after applying a urethane adhesive on one side which becomes the outer surface side of the exterior material, it was dried and baked at 100 ° C. for 15 seconds to provide a 3.0 g / m 2 adhesive layer. On top of that, the corona-treated surface of a corona-treated ONy film with a thickness of 25 μm was bonded to the adhesive layer, and an aging treatment was performed for 168 hours in a 40 ° C. atmosphere. Thereafter, an adhesive made of a modified polyolefin is uniformly applied to the glossy surface side, which is the inner surface side of the battery container, with a bar coater and dried and baked at 200 ° C. for 20 seconds to form a 1.0 g / m 2 adhesive layer. Formed. The corona-treated surface of a 30 μm thick CPP film was bonded to the adhesive layer side, and hot melt lamination was performed at a temperature of 110 ° C. and a speed of 1 m / min. As described above, a secondary battery exterior material laminated and adhered as [CPP film layer / adhesive layer / chromate film layer / aluminum foil material / (chromate film layer) / adhesive layer / ONy film layer] was obtained. .
上記実施例、比較例を以下の方法で評価した。結果を表１に示す。
《評価方法》
評価は、電池外装材として重要視される、電池内面側であるところのＣＰＰフィルム層側を評価した。
The said Example and the comparative example were evaluated with the following method. The results are shown in Table 1.
"Evaluation method"
The evaluation evaluated the CPP film layer side, which is the battery inner surface side, which is regarded as important as a battery exterior material.
１．耐電解液特性試験
安田精機製作所製ヒートシーラーを使用し、シーリング条件として温度１８０℃、圧力２．４ｋｇ／Ｇ圧、時間２秒。で三方をヒートシールして密閉した、内部には電解液として、ＥＣ／ＤＥＣ／ＤＭＣ＝１／１／１（ｗｔ％） ＬｉＰＦ６＝１．５Ｍを使用した。その後、８５℃雰囲気中に１週間放置した。 放置した後、水洗を十分に行ない、ＣＰＰの白化及びはがれ状態（デラミ）を目視にて観察した。
白化○：白化なし
△：一部の白化
×：全面白化
デラミ ○：発生なし
△：一部発生
×：全面的に発生
1. Electrolytic solution characteristic test A heat sealer manufactured by Yasuda Seiki Seisakusho was used. Sealing conditions were a temperature of 180 ° C., a pressure of 2.4 kg / G pressure, and a time of 2 seconds. In the inside, EC / DEC / DMC = 1/1/1 (wt%) LiPF6 = 1.5M was used as the electrolyte. Thereafter, it was left in an atmosphere at 85 ° C. for 1 week. After leaving it to stand, it was thoroughly washed with water, and the whitening and peeling state (delamination) of CPP was visually observed.
Whitening ○: No whitening
Δ: Partial whitening
×: Fully whitened Delami ○: No occurrence
Δ: Partial occurrence
×: Fully generated
ヒートシール強度
（１）剥離強度
安田精機製作所製ヒートシーラーを使用し、シーリング条件として温度１８０℃、圧力２．４ｋｇ／Ｇ圧、時間２秒。でヒートシールしたサンプルで耐電解液特性試験終了後に、島津製オートグラフＡＧ−Ｘプラスを使用してクロスヘッドスピード２００mm／minにて１８０度剥離試験を行い、剥離強度を測定した。 サンプルサイズは巾１５ｍｍで長さは適宜とした。
○：１０Ｎ／15mm以上
△：１０Ｎ／15mm未満、５Ｎ／15mm以上
×：５Ｎ／15mm未満
（２）剥離モード評価
ヒートシール強度測定後のサンプルの剥離面を目視にて確認した。
○：ＣＰＰの凝集剥離
△：ＣＰＰの凝集剥離と層間剥離の混在
×：ＣＰＰの層間剥離
Heat seal strength (1) Peel strength Using a heat sealer manufactured by Yasuda Seiki Seisakusho, the sealing conditions were a temperature of 180 ° C., a pressure of 2.4 kg / G pressure, and a time of 2 seconds. After the end of the electrolytic solution resistance test with the sample heat-sealed, a 180 ° peel test was performed at a crosshead speed of 200 mm / min using an autograph AG-X plus manufactured by Shimadzu, and the peel strength was measured. The sample size was 15 mm wide and the length was appropriate.
○: 10 N / 15 mm or more Δ: Less than 10 N / 15 mm, 5 N / 15 mm or more ×: Less than 5 N / 15 mm (2) Peeling mode evaluation The peeled surface of the sample after heat seal strength measurement was visually confirmed.
◯: CPP cohesive peeling Δ: CPP cohesive peeling and delamination ×: CPP delamination
ラミネート強度
耐電解液特性試験終了後のラミネート強度を、島津製オートグラフＡＧ−Ｘプラスを使用してクロスヘッドスピード２００mm／minにて１８０度剥離試験を行い、アルミニウム箔材との剥離強度を測定した。 サンプルサイズは巾１５ｍｍで長さは適宜とした。
○：１０Ｎ／15mm以上
△：１０Ｎ／15mm未満、５Ｎ／15mm以上
×：５Ｎ／15mm未満
Laminate strength After the end of the electrolyte resistance test, the laminate strength is measured at 180 ° using a Shimadzu autograph AG-X plus at a crosshead speed of 200 mm / min to measure the peel strength from the aluminum foil material. did. The sample size was 15 mm wide and the length was appropriate.
○: 10N / 15mm or more △: Less than 10N / 15mm, 5N / 15mm or more ×: Less than 5N / 15mm
基材であるアルミニウム材は８０７９合金相当のアルミニウム合金箔（板厚４０μｍ）を用いた。表２に示される電着塗料を用いて、エポキシ系樹脂層を両面に形成した。このときはカチオン電着方式で行った。樹脂層厚は処理時の電圧及び処理時間で調整した。樹脂層形成後、冷風にて乾燥した。 As an aluminum material as a base material, an aluminum alloy foil (plate thickness: 40 μm) corresponding to 8079 alloy was used. Using the electrodeposition paint shown in Table 2, an epoxy resin layer was formed on both sides. At this time, the cation electrodeposition was performed. The resin layer thickness was adjusted by the voltage and processing time during processing. After forming the resin layer, it was dried with cold air.
乾燥後、電池とした場合の内面側になる片面のエポキシ系樹脂皮膜上に、アクリル系樹脂塗料をバーコーターにて均一に塗布した。塗膜量は事前に調査し、バーコーターの種類及び塗料濃度で調整した。塗膜を形成後、所定の温度、所定の時間で焼付処理した。焼付処理には熱風炉を用いて、風速は１５m／秒で行った。 After drying, an acrylic resin coating was uniformly applied with a bar coater on one side of the epoxy resin film that would be the inner surface of the battery. The coating amount was investigated in advance and adjusted with the type of bar coater and paint concentration. After forming the coating film, it was baked at a predetermined temperature for a predetermined time. A baking furnace was used for the baking treatment, and the wind speed was 15 m / sec.
得られた材料に対して、電池容器の外面側にウレタン系接着剤を塗布後、１００℃、１５秒の乾燥焼付を行い、３．０ｇ／ｍ２の接着層を設けた。その上に、厚さ２５μmのコロナ処理したＯＮｙフィルムのコロナ処理面を接着層に貼り合わせ、４０℃雰囲気中で１６８時間のエージング処理を施した。 A urethane adhesive was applied to the outer surface side of the battery container on the obtained material, and then subjected to dry baking at 100 ° C. for 15 seconds to provide a 3.0 g / m 2 adhesive layer. On top of that, the corona-treated surface of a corona-treated ONy film with a thickness of 25 μm was bonded to the adhesive layer, and an aging treatment was performed for 168 hours in a 40 ° C. atmosphere.
その後、電池容器の内面側になるツヤ面に変性ポリオレフィンから成る接着剤をバーコーターにて均一に塗布し、２００℃、２０秒で乾燥焼付けを行い、１．０ｇ／ｍ２の接着層を形成させた。厚さ３０μmのＣＰＰフィルムのコロナ処理面を接着層側に貼り合わせ、熱溶融ラミネートを温度１１０℃、１ｍ／ｍｉｎの速度で行った。以上のようにして、〔ＣＰＰフィルム層／接着層／アクリル系樹脂層／電着塗装でのエポキシ系樹脂層／アルミニウム箔材／電着塗装でのエポキシ系樹脂層／接着層／ＯＮｙフィルム層〕と積層貼着された二次電池外装用材料を得、表１と同様の方法で評価した。結果を表２に示す。 Thereafter, an adhesive made of a modified polyolefin is uniformly applied to the glossy surface on the inner surface side of the battery container with a bar coater and dried and baked at 200 ° C. for 20 seconds to form a 1.0 g / m 2 adhesive layer. It was. The corona-treated surface of a 30 μm thick CPP film was bonded to the adhesive layer side, and hot melt lamination was performed at a temperature of 110 ° C. and a speed of 1 m / min. As described above, [CPP film layer / adhesive layer / acrylic resin layer / epoxy resin layer in electrodeposition coating / aluminum foil material / epoxy resin layer in electrodeposition coating / adhesion layer / ONy film layer] The secondary battery exterior material laminated and adhered was obtained and evaluated in the same manner as in Table 1. The results are shown in Table 2.
Claims (2)
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