JP2002050325A - Laminate for battery outer package and its manufacturing method - Google Patents
Laminate for battery outer package and its manufacturing methodInfo
- Publication number
- JP2002050325A JP2002050325A JP2000233262A JP2000233262A JP2002050325A JP 2002050325 A JP2002050325 A JP 2002050325A JP 2000233262 A JP2000233262 A JP 2000233262A JP 2000233262 A JP2000233262 A JP 2000233262A JP 2002050325 A JP2002050325 A JP 2002050325A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- laminate
- lubricating
- aluminum foil
- inducing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子機器、電子部
品、特に携帯電話、ノート型パソコン、ビデオカメラ、
衛星などに用いられるリチウムイオン等の二次電池、と
りわけ固体電解質を用いているリチウムイオンポリマー
二次電池用の包装材として電解液耐性、密封性、成形性
に優れた電池外装用積層体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electronic devices and electronic components, particularly mobile phones, notebook computers, video cameras,
Related to battery exterior laminates with excellent electrolyte resistance, sealing properties, and moldability as a packaging material for lithium-ion and other secondary batteries used in satellites, especially lithium-ion polymer secondary batteries using solid electrolytes It is.
【０００２】[0002]
【従来の技術】リチウムイオン二次電池は、その高い体
積効率、重量効率から電子機器、電子部品、特に携帯電
話、ノート型パソコン、ビデオカメラ、衛星、電気自動
車などに広く用いられている。リチウムイオン二次電池
の中でも特にリチウムイオンポリマー二次電池は導電性
ポリマーなどのゲル状電解質を用いていることを特徴と
し、非水電解液を用いているリチウムイオン電池と比較
して電解液漏れの危険性が小さく安全性に優れると共
に、小型化や軽量化が可能であることから今後市場での
発展性が期待されている電池の一つである。2. Description of the Related Art Lithium-ion secondary batteries are widely used in electronic devices and electronic components, particularly mobile phones, notebook computers, video cameras, satellites, electric vehicles, etc. due to their high volume efficiency and weight efficiency. Among lithium ion secondary batteries, lithium ion polymer secondary batteries are particularly characterized by the use of a gel electrolyte such as a conductive polymer, and electrolyte leakage compared to lithium ion batteries using nonaqueous electrolytes. It is one of the batteries that are expected to be developed in the market in the future because of its small danger, excellent safety, and the ability to be reduced in size and weight.
【０００３】リチウムイオンポリマー二次電池の外装体
としては、金属板や金属箔などをプレス成形加工し、円
柱状や直方体状とした金属製の缶が生産性や品質の安定
性から一般的に用いられているが、金属製の缶を用いた
場合には、電池自体の形状や意匠性において制約が多い
上に、この金属製の缶からなる電池を搭載する電子機
器、電子部品内の該電池収納部の形状や意匠性にも制約
が課せられ、結果として電子機器や電子部品自体の形状
が意図する形状にできないといった問題があった。[0003] As an exterior body of a lithium-ion polymer secondary battery, a metal can or a metal foil is press-formed and formed into a cylindrical or rectangular parallelepiped metal can in general from the standpoint of productivity and quality stability. However, when a metal can is used, there are many restrictions on the shape and design of the battery itself, and in addition, the electronic device and the electronic component in which the battery made of the metal can is mounted are used. Restrictions are also imposed on the shape and design of the battery housing, and as a result, there has been a problem that the shape of the electronic device or the electronic component itself cannot be made the intended shape.
【０００４】そこで、電子機器、電子部品内の適当な空
間を電池収納部とすることができれば、すなわち、前記
適当な空間に合わせて色々な形状とすることが容易な外
装体であれば、電子機器や電子部品自体の形状を意図す
る形状にすることができ、より一層小型化、軽量化を図
ることができる。特に、生産性の観点から真空成形等の
絞り成形により色々な形状とすることができる外装体が
要望されていた。[0004] Therefore, if an appropriate space in an electronic device or electronic component can be used as a battery housing, that is, if an exterior body can be easily formed into various shapes in accordance with the appropriate space, an electronic device is required. The shape of the device or the electronic component itself can be made an intended shape, and the size and weight can be further reduced. In particular, from the viewpoint of productivity, there has been a demand for an exterior body that can be formed into various shapes by draw forming such as vacuum forming.
【０００５】また、前記外装体には、当然のことながら
次のような特性、物性、機能が求められる。すなわち、 ポリマー二次電池本体の基幹部と電極の一部を外気
（特に水蒸気ガス）と遮断した密封系に保持できる（外
部から水蒸気ガスが浸入すると電解質が加水分解してフ
ッ酸が生成してアルミニウム箔を腐食する）と共に前記
電極は金属により構成されているため、前記外装材の最
内層は、最内層同士の熱接着性と前記電極との接着性、
特に熱接着性を有すること。 ポリマー二次電池は充電／放電による内容物である電
池の温度上昇による熱接着の安定性と密封系の確保や、
使用される環境温度、具体的には夏期における自動車内
や冬期における寒冷地での使用などに耐える耐熱性や耐
寒性が求められ、前記のような厳しい環境下においても
包材として熱接着の安定性と密封系を確保できること。 ポリマー二次電池のゲル状電解質はリチウム塩と少量
のカーボネート系溶剤からなり、これらの電解質により
包材の層間接着強度が低下しないこと。 ゲル状電解質（電解液）の劣化、加水分解により発生
するフッ酸に対する耐腐食性を有すること。 などの特性、物性、機能である。[0005] Further, the following characteristics, physical properties, and functions are naturally required of the exterior body. That is, the main part of the polymer secondary battery main body and a part of the electrodes can be held in a sealed system that is shielded from outside air (especially steam gas). (When steam gas enters from the outside, the electrolyte is hydrolyzed and hydrofluoric acid is generated. (Corrosion of the aluminum foil) and the electrodes are made of metal, so that the innermost layer of the exterior material has thermal adhesiveness between innermost layers and adhesiveness with the electrodes,
In particular, it must have thermal adhesion. Polymer secondary batteries ensure the stability of thermal bonding and the sealing system by increasing the temperature of the battery, the content of which is charged / discharged.
The environment temperature used, specifically, heat resistance and cold resistance that can withstand the use in automobiles in the summer and in cold regions in the winter are required, and the stability of thermal bonding as a packaging material even under such harsh environment is required To ensure the integrity and sealing system. The gel electrolyte of the polymer secondary battery is composed of a lithium salt and a small amount of a carbonate-based solvent, and the electrolyte does not reduce the interlayer adhesive strength of the packaging material. It has corrosion resistance to hydrofluoric acid generated by the deterioration and hydrolysis of the gel electrolyte (electrolyte solution). Such as characteristics, physical properties, and functions.
【０００６】[0006]
【発明が解決しようとする課題】そこで本発明は、絞り
成形性に優れると共に、水蒸気ガスやその他のガスバリ
ア性に優れ、さらに電解液の影響を受けてもアルミニウ
ム箔と内層との層間接着強度の経時的低下の起こり難い
密封性に優れた電池外装用積層体を提供することにあ
る。Accordingly, the present invention is not only excellent in drawability, but also excellent in water vapor gas and other gas barrier properties, and furthermore, even under the influence of an electrolytic solution, the interlayer adhesion strength between an aluminum foil and an inner layer. It is an object of the present invention to provide a laminate for a battery exterior which is excellent in hermeticity and hardly deteriorates with time.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、上記目的
を達成するために、請求項１記載の発明は、外層、アル
ミニウム箔、内層の順に積層された電池外装用積層体に
おいて、前記外層の最表層に第１滑性層を備え、前記内
層の最表層に第２滑性層を備えたことを特徴とするもの
である。Means for Solving the Problems In order to achieve the above object, the present inventors have set forth the invention as set forth in claim 1, wherein the outer layer, the aluminum foil, and the inner layer are laminated in this order in a battery exterior laminate. A first slip layer is provided on the outermost layer of the outer layer, and a second slip layer is provided on the outermost layer of the inner layer.
【０００８】また、請求項２記載の発明は、請求項１記
載の電池外装用積層体において、前記第１滑性層が前記
外層表面に形成された滑性誘起層に添加された滑剤の該
滑性誘起層表面への染み出しにより形成されたものであ
ることを特徴とするものである。[0008] The invention according to claim 2 is the battery exterior laminate according to claim 1, wherein the first lubricating layer is a lubricant added to a lubricity-inducing layer formed on the outer layer surface. It is characterized by being formed by exuding on the surface of the slip-inducing layer.
【０００９】また、請求項３記載の発明は、請求項１記
載の電池外装用積層体において、前記第２滑性層が前記
内層の表面への前記第１滑性層の転移により形成された
ものであることを特徴とするのである。According to a third aspect of the present invention, in the battery exterior laminate of the first aspect, the second slip layer is formed by transferring the first slip layer to a surface of the inner layer. It is characterized by being something.
【００１０】請求項１〜３のいずれかに記載の構成とす
ることにより、水蒸気やその他のガスバリア性に優れ、
また、絞り成形時に第１滑性層、及び／ないし、第２滑
性層により金型に対して電池外装用積層体が部分的に密
着するのを防止することができ、厚みムラ（厚みバラツ
キ）のない均一な絞り成形品を得ることができる。[0010] By adopting the constitution according to any one of claims 1 to 3, it is excellent in water vapor and other gas barrier properties,
In addition, the first slip layer and / or the second slip layer can prevent the laminated body for battery exterior from being partially adhered to the mold at the time of drawing, and the thickness unevenness (thickness variation) can be prevented. ) Can be obtained.
【００１１】また、請求項４記載の発明は、請求項１、
３のいずれかに記載の電池外装用積層体において、前記
内層の前記第２滑性層と隣接する層がオレフィン系熱接
着性樹脂層からなり、その厚さが10〜100 μｍであるこ
とを特徴とするものである。[0011] The invention described in claim 4 is based on claim 1,
3. The laminate for a battery package according to any one of 3, wherein the inner layer adjacent to the second lubricating layer is formed of an olefin-based thermo-adhesive resin layer, and has a thickness of 10 to 100 μm. It is a feature.
【００１２】また、請求項５記載の発明は、請求項１、
２のいずれかに記載の電池外装用積層体において、前記
外層の少なくとも一つの層がポリエステルフィルムない
しポリアミドフィルムからなり、前記外層の厚さが６〜
25μｍであることを特徴とするものである。[0012] The invention according to claim 5 is based on claim 1,
2. In the laminate for battery packaging according to any one of (2), at least one of the outer layers is made of a polyester film or a polyamide film, and the thickness of the outer layer is 6 to
The thickness is 25 μm.
【００１３】また、請求項６記載の発明は、請求項１記
載の電池外装用積層体において、前記アルミニウム箔が
厚さ20〜80μｍの軟質アルミニウム箔からなることを特
徴とするものである。According to a sixth aspect of the present invention, in the laminate for a battery package according to the first aspect, the aluminum foil is made of a soft aluminum foil having a thickness of 20 to 80 μm.
【００１４】また、請求項７記載の発明は、請求項１〜
６のいずれかに記載の電池外装用積層体において、前記
アルミニウム箔の両方の面に耐腐食性及び易接着性処理
が施されていることを特徴とするものである。[0014] The invention according to claim 7 provides the invention according to claims 1 to
6. The laminate for battery exterior according to any one of the above 6, wherein both surfaces of the aluminum foil are subjected to corrosion resistance and easy adhesion treatment.
【００１５】請求項５〜７のいずれかに記載の構成とす
ることにより、絞り成形を施してもアルミニウム箔と外
層との層間接着強度の低下のない、また、電解液の影響
を受けてもアルミニウム箔と内層との層間接着強度の経
時的低下の起こり難い密封性に優れた電池外装用積層体
とすることができる。According to the structure of any one of claims 5 to 7, even if the drawing is performed, the interlayer adhesion strength between the aluminum foil and the outer layer does not decrease, and even if it is affected by the electrolytic solution. A battery exterior laminate excellent in hermeticity, in which the interlayer adhesive strength between the aluminum foil and the inner layer hardly decreases over time, can be obtained.
【００１６】また、請求項８記載の発明の電池外装用積
層体の製造方法は、アルミニウム箔の一方の面に外層、
他方の面に内層を設けて積層体とする工程と、該積層体
の前記外層上に滑剤を添加した滑性誘起層を設けると共
に該滑性誘起層と前記内層が接触するように巻き取って
巻取物とする工程と、該巻取物の前記滑性誘起層から前
記滑剤を前記滑性誘起層の表面に染み出させて第１滑性
層を形成すると共に前記第１滑性層を前記内層表面に転
移させて前記内層上に第２滑性層を形成する工程とから
なることを特徴とするものである。このような製造方法
を採ることにより、滑性誘起層を積層体の外層上に設け
ると共に巻き取って巻取物とすることにより第１滑性層
と第２滑性層とが自動的に形成されるために、別工程で
第１滑性層と第２滑性層を形成する必要がなく、それだ
け安価に製造することができる。Further, in the method for manufacturing a laminate for a battery exterior according to the present invention, an outer layer is provided on one surface of the aluminum foil.
A step of providing an inner layer on the other surface to form a laminate, and providing a lubricity-inducing layer to which a lubricant has been added on the outer layer of the laminate and winding the lubrication-inducing layer and the inner layer so that they contact each other. Forming a first lubricating layer by forming the first lubricating layer by leaching the lubricant from the lubricating layer of the reel to the surface of the lubricating layer; Forming a second lubricating layer on the inner layer by transferring to the inner layer surface. By adopting such a manufacturing method, the first lubricating layer and the second lubricating layer are automatically formed by providing the lubricity-inducing layer on the outer layer of the laminate and winding it into a roll. Therefore, it is not necessary to form the first lubricating layer and the second lubricating layer in a separate step, and it is possible to manufacture at a lower cost.
【００１７】[0017]
【発明の実施の形態】上記の本発明について、以下に更
に詳しく説明する。本発明の電池外装用積層体に用いる
アルミニウム箔は、外部から電池内部に水蒸気ガスや酸
素ガスの浸入することを防止するためのガスバリア層で
あり、ガスバリア性の確保、あるいは、加工適性（ラミ
ネート加工、絞り成形加工等）を考慮すると20〜80μｍ
の厚さのものが適当である。20μｍより厚さが薄い場合
は、アルミニウム箔単体のピンホールが危惧されると共
に、絞り成形時にアルミニウム箔に破断やピンホールが
発生し易く、水蒸気ガスや酸素ガスの侵入の危険性が高
くなり、80μｍより厚さが厚い場合は、ガスバリア性や
絞り成形時のアルミニウム箔の破断やピンホールに顕著
な効果が認められず、体積及び重量エネルギー密度を低
下させると共に費用対効果の面からも使用しない方が望
ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The aluminum foil used for the battery exterior laminate of the present invention is a gas barrier layer for preventing the invasion of water vapor gas or oxygen gas from the outside into the inside of the battery, and ensures gas barrier properties or suitability for processing (lamination processing). , Draw forming, etc.) 20-80μm
Is appropriate. If the thickness is less than 20 μm, pinholes of the aluminum foil alone may be feared, and the aluminum foil is liable to break or pinholes at the time of drawing, increasing the risk of intrusion of water vapor gas or oxygen gas. If the thickness is larger, there is no noticeable effect on gas barrier properties, breakage of aluminum foil during drawing, or pinholes, which reduces the volume and weight energy density and is not used in terms of cost effectiveness. Is desirable.
【００１８】次に、本発明の電池外装用積層体に用いる
内層は、単層でも複層でも構わないのであって、後述す
る第２滑性層と隣接する層、すなわち、前記内層として
電解液側に最も位置する層が少なくとも熱接着性を有す
る熱接着性樹脂層であればよい。この理由としては、前
記電池外装用積層体を用いて電池とする時に、熱接着す
ることにより、確実に外気（特に水蒸気ガス）と遮断し
た密封系に保持できる必要性があるからである。さらに
加えて、長期に亘って電解液と接触しても接着強度が低
下することがなく、また、電池の高温保存試験（安全試
験）において電解液の洩れや破裂等の不具合の発生を防
止する必要性から前記熱接着性樹脂層に供することがで
きる樹脂としては、融点が80℃以上であるものを使用す
る必要性がある。以上のことを勘案すると、前記熱接着
性樹脂層に用いる樹脂としてはオレフィン系熱接着性樹
脂が好ましい。Next, the inner layer used in the battery exterior laminate of the present invention may be a single layer or a multi-layer, and may be a layer adjacent to a second lubricating layer described later, that is, The layer located closest to the side only needs to be a thermo-adhesive resin layer having at least thermo-adhesive properties. The reason for this is that when a battery is formed using the battery exterior laminate, it is necessary to be able to reliably hold the battery in a sealed system that is shielded from outside air (particularly water vapor gas) by heat bonding. In addition, even when the battery is in contact with the electrolyte for a long period of time, the adhesive strength is not reduced, and problems such as leakage and rupture of the electrolyte in a high temperature storage test (safety test) of the battery are prevented. From the necessity, it is necessary to use a resin having a melting point of 80 ° C. or more as a resin that can be provided to the heat-adhesive resin layer. In consideration of the above, an olefin-based heat-adhesive resin is preferable as the resin used for the heat-adhesive resin layer.
【００１９】前記オレフィン系熱接着性樹脂としては、
たとえば、低密度ポリエチレン樹脂、中密度ポリエチレ
ン樹脂、高密度ポリエチレン樹脂、線状低密度ポリエチ
レン樹脂、エチレン−酢酸ビニル共重合体樹脂、エチレ
ン−アクリル酸共重合体樹脂、エチレン−メタクリル酸
共重合体樹脂、エチレン−プロピレン共重合体樹脂、ポ
リプロピレン樹脂、酸変性ポリプロピレン樹脂等の１種
ないしこれらの樹脂を適宜積層して複層構成とした積層
体等を挙げることができる。The olefin-based thermoadhesive resin includes:
For example, low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-methacrylic acid copolymer resin , An ethylene-propylene copolymer resin, a polypropylene resin, an acid-modified polypropylene resin, and the like, or a laminate having a multilayer structure formed by appropriately laminating these resins.
【００２０】また、前記内層としては、前記熱接着性樹
脂層のみで構成したものであってもよいし、また、前記
熱接着性樹脂層とアルミニウム箔との間に、単層ないし
複層からなる各種の合成樹脂層を設けることができる。
この合成樹脂層はＴダイ押出機等を用いて押し出し形成
してもよいし、また、フィルム化したシート（未延伸あ
るいは一軸方向ないし二軸方向に延伸したフィルムのい
ずれであってもよい）をドライラミネーション、サンド
ラミネーション等の周知の積層法で形成してもよい。な
お、参考までに好ましい態様を例示するならば、たとえ
ば、アルミニウム箔面に酸変性ポリプロピレン樹脂が当
接するように、酸変性ポリプロピレン樹脂／ポリプロピ
レン樹脂とを共押出しして積層した仕様、酸変性ポリプ
ロピレン樹脂（の溶液）を塗工した後に未延伸ポリプロ
ピレンフィルムを熱ラミネートして積層した仕様、ま
た、アルミニウム箔面と未延伸ポリプロピレンフィルム
をポリプロピレン樹脂にて押出しラミネートして積層し
た仕様、或いは片面にコロナ放電処理を施した未延伸ポ
リプロピレンフィルムを周知のドライラミネート用接着
剤にて接着積層した仕様等を挙げることができる。なお
上記内層を形成する樹脂層をフィルム化したシートで形
成する場合、必要に応じて、フィルム表面に濡れ性を付
与する目的で、必要な面にコロナ放電処理及び／ないし
大気圧プラズマ処理等の易接着処理を施すことができ
る。Further, the inner layer may be constituted by only the heat-adhesive resin layer, or may be formed between a single layer or a plurality of layers between the heat-adhesive resin layer and the aluminum foil. Various synthetic resin layers can be provided.
This synthetic resin layer may be formed by extrusion using a T-die extruder or the like. Alternatively, a sheet formed into a film (which may be unstretched or a film stretched uniaxially or biaxially) may be used. It may be formed by a known lamination method such as dry lamination and sand lamination. Incidentally, if a preferred embodiment is exemplified for reference, for example, a specification in which an acid-modified polypropylene resin / polypropylene resin is coextruded and laminated so that the acid-modified polypropylene resin is in contact with the aluminum foil surface, an acid-modified polypropylene resin (Specification of (solution of)) and then unlaminated polypropylene film is heat laminated and laminated, or aluminum foil surface and unoriented polypropylene film are extruded and laminated with polypropylene resin and laminated, or corona discharge on one side Examples include a specification in which a treated unstretched polypropylene film is bonded and laminated with a well-known dry laminating adhesive. When the resin layer for forming the inner layer is formed of a sheet formed into a film, if necessary, a corona discharge treatment and / or an atmospheric pressure plasma treatment or the like may be applied to a necessary surface for the purpose of imparting wettability to the film surface. An easy adhesion treatment can be performed.
【００２１】また、前記内層を構成する前記熱接着性樹
脂層は、電池に設けられる電極を隙間ができないように
密封固着する必要があり、その厚さとしては10〜100 μ
ｍが好ましい。10μｍより薄い場合は、絞り成形時にピ
ンホールが発生し易く、電解液に対する耐性が低下する
危険性があり、100 μｍより厚い場合は、絞り成形時の
ピンホールの発生や電極を隙間なく密封固着するなどの
点で顕著な効果が認められず、体積及び重量エネルギー
密度を低下させると共に費用対効果の面からも使用しな
い方が望ましい。Further, it is necessary that the heat-adhesive resin layer constituting the inner layer is hermetically fixed so that no gap is formed between electrodes provided in the battery, and has a thickness of 10 to 100 μm.
m is preferred. If the thickness is less than 10 μm, pinholes are likely to occur during drawing, and there is a risk that the resistance to the electrolyte will decrease.If the thickness is more than 100 μm, pinholes will occur during drawing and the electrodes will be tightly sealed without gaps. No remarkable effect is observed in terms of, for example, reducing the volume and weight energy density, and it is desirable not to use it from the viewpoint of cost effectiveness.
【００２２】次に、本発明の電池外装用積層体に用いる
外層は、アルミニウム箔を保護し、特に突き刺しのよう
な外力に対する耐性を向上させて、突き刺しによる穴開
きを防止すると共に、絞り成形時にアルミニウム箔が破
断するのを防止することを目的に設けられるものであっ
て、単層でも複層でも構わないが、特に単層である場合
はそれ自体で上記目的を達成する必要があり、機械的強
度に優れると共に、少なくとも熱接着時の熱に対する熱
寸法安定性が要求され、これらを考慮すると二軸方向に
延伸した、たとえば、ポリエチレンテレフタレート、ポ
リブチレンテレフタレート、ポリエチレンナフタレー
ト、ポリブチレンナフタレート、ポリカーボネート等の
ポリエステルフィルム（二軸延伸ポリエステルフィル
ム）、ないし、二軸方向に延伸した、たとえば、ナイロ
ン６、ナイロン66等のポリアミドフィルム（二軸延伸ポ
リアミドフィルム）が好ましいが、絞り深さの深い絞り
成形品を製造する場合は二軸延伸ポリエステルフィルム
に比べて伸びが大きい二軸延伸ポリアミドフィルムが好
適である。このように前記外層を二軸延伸ポリエステル
フィルムないし二軸延伸ポリアミドフィルムの単層で形
成する場合、少なくともその厚さは６μｍ以上が好まし
い、この理由としては、６μｍより薄い場合は絞り成形
時にアルミニウム箔にピンホールや破断が発生し易く、
成形不良を起こし易いからである。また、前記外層が単
層であれ複層であれ、25μｍより厚い場合は絞り成形時
のアルミニウム箔のピンホールや破断などの点で顕著な
効果が認められず、体積及び重量エネルギー密度を低下
させると共に費用対効果の面からも使用しない方が望ま
しい。Next, the outer layer used for the battery exterior laminate of the present invention protects the aluminum foil, improves the resistance to external force such as piercing, and prevents perforation caused by piercing. It is provided for the purpose of preventing the aluminum foil from being broken, and may be a single layer or a multi-layer. In addition to excellent mechanical strength, at least thermal dimensional stability to heat at the time of thermal bonding is required, and in consideration of these, biaxially stretched, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, Polyester film such as polycarbonate (biaxially stretched polyester film) or biaxial For example, a polyamide film (biaxially stretched polyamide film) such as nylon 6, nylon 66 or the like is preferable, but when a drawn product having a large drawing depth is manufactured, the elongation is larger than that of the biaxially stretched polyester film. Biaxially stretched polyamide films are preferred. When the outer layer is formed as a single layer of a biaxially stretched polyester film or a biaxially stretched polyamide film as described above, the thickness is preferably at least 6 μm. Pinholes and breaks easily occur on
This is because molding defects are likely to occur. Further, when the outer layer is a single layer or a multi-layer, if it is thicker than 25 μm, a remarkable effect such as pinhole or breakage of the aluminum foil at the time of drawing is not recognized, and the volume and the weight energy density are reduced. It is also desirable not to use it from the viewpoint of cost-effectiveness.
【００２３】また、前記外層とアルミニウム箔とを積層
する方法としては、周知のドライラミネート用接着剤を
用いて周知のドライラミネーション法で積層することが
できる。なお、前記外層を構成する、たとえば、二軸延
伸ポリエステルフィルムや二軸延伸ポリアミドフィルム
は、必要に応じて、フィルム表面に濡れ性を付与する目
的で、必要な面にコロナ放電処理及び／ないし大気圧プ
ラズマ処理等の易接着処理を施すことができる。The outer layer and the aluminum foil may be laminated by a known dry lamination method using a known dry laminating adhesive. The outer layer, for example, a biaxially stretched polyester film or a biaxially stretched polyamide film may be provided with a corona discharge treatment and / or a large surface if necessary for the purpose of imparting wettability to the film surface. An easy adhesion treatment such as a pressure plasma treatment can be performed.
【００２４】次に、本発明の電池外装用積層体のアルミ
ニウム箔の両面に施す耐腐食性及び易接着性処理につい
て説明する。この耐腐食性及び易接着性処理は、アルミ
ニウム箔と前記外層、及び、前記内層を強固に接着させ
ると共に、アルミニウム箔の前記内層側の面を電解液、
あるいは、電解液の加水分解により発生するフッ酸から
保護するために施す処理である。本発明で使用する耐腐
食性及び易接着性処理は、クロム酸クロメート処理、リ
ン酸クロメート処理、塗布型クロメート処理などのクロ
ム系化成処理、あるいは、ジルコニウム、チタン、リン
酸亜鉛などの非クロム系（塗布型）化成処理などであっ
て、これらの化成処理を用いてアルミニウム箔表面に耐
腐食性及び易接着性の皮膜を形成させるものである。こ
れらの化成処理のうち、連続処理が可能であり水洗工程
が不要となり、処理コストを安価にすることができると
いう点から塗布型化成処理が最も好ましい。この塗布型
化成処理は、たとえば、ポリアクリル酸などの水溶性高
分子と３価クロム化合物とフッ化物とリン酸とからなる
クロム系水性処理液、あるいは、ポリアクリル酸などの
水溶性高分子とジルコニウム塩とからなる非クロム系水
性処理液などを用いて、ロールコート法、グラビアコー
ト法、浸漬法などの周知の塗工法でアルミニウム箔表面
に塗工し乾燥する処理である。なお、前記塗布型化成処
理の前に、予めアルミニウム箔表面を、たとえば、アル
カリ浸漬法、電解洗浄法、酸洗浄法、電解酸洗浄法、酸
活性化法などの周知の脱脂処理法で処理しておく方が、
前記塗布型化成処理の機能を最大限に発現させると共
に、長期間維持することができる点から望ましい。Next, a description will be given of the corrosion resistance and easy adhesion treatment applied to both surfaces of the aluminum foil of the battery exterior laminate of the present invention. This corrosion resistance and easy adhesion treatment, the aluminum foil and the outer layer, and, while firmly bonding the inner layer, the inner layer side surface of the aluminum foil electrolytic solution,
Alternatively, it is a treatment performed to protect from hydrofluoric acid generated by hydrolysis of the electrolytic solution. Corrosion resistance and easy adhesion treatments used in the present invention are chromium conversion treatments such as chromate chromate treatment, phosphate chromate treatment, and coating type chromate treatment, or non-chromium-based treatments such as zirconium, titanium, and zinc phosphate. (Coating type) chemical conversion treatment, etc., in which a corrosion-resistant and easily-adhesive film is formed on the aluminum foil surface by using these chemical conversion treatments. Among these chemical conversion treatments, a coating type chemical conversion treatment is most preferable in that a continuous treatment is possible, a washing step is not required, and the treatment cost can be reduced. This coating-type chemical conversion treatment includes, for example, a chromium-based aqueous treatment solution comprising a water-soluble polymer such as polyacrylic acid and a trivalent chromium compound, fluoride and phosphoric acid, or a water-soluble polymer such as polyacrylic acid. This is a process of applying and drying a surface of an aluminum foil by a well-known coating method such as a roll coating method, a gravure coating method, and a dipping method using a non-chromium-based aqueous processing solution containing a zirconium salt. Before the coating chemical conversion treatment, the surface of the aluminum foil is previously treated by a known degreasing method such as an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, and an acid activation method. It is better to keep
It is desirable because the function of the coating type chemical conversion treatment is maximized and can be maintained for a long time.
【００２５】次に、本発明の電池外装用積層体の最表層
（前記外層の最表層）に設ける第１滑性層及び本発明の
電池外装用積層体の前記内層の表面に設ける第２滑性層
について、本発明の電池外装用積層体の製造方法も含め
て説明する。この第１滑性層及び第２滑性層は、絞り成
形時に金型に対して電池外装用積層体が部分的に密着す
るのを防止して、厚みムラ（厚みバラツキ）のない均一
な絞り成形品を得る目的（絞り成形時の成形性を向上さ
せる目的）で設けるものである。前記第１滑性層及び前
記第２滑性層は滑剤からなる層であって、たとえば、流
動パラフィンなどの炭化水素系、ステアリン酸などの脂
肪酸系、ステアリルアミドなどの脂肪酸アミド系、金属
石鹸、天然ワックス、シリコーンなどの滑剤を適当な溶
媒で溶液化するなどの塗工可能な状態として、たとえ
ば、グラビアコート法、ロールコート法、あるいは、パ
ターン状に形成する場合にはグラビア印刷法等の周知の
塗工法で形成することができるが、本発明の電池外装用
積層体においては、次に記す方法で形成する。Next, a first lubricating layer provided on the outermost layer (outermost layer of the outer layer) of the laminate for battery exterior of the present invention and a second slip layer provided on the surface of the inner layer of the laminate for battery exterior of the present invention. The conductive layer will be described, including the method for producing the battery exterior laminate of the present invention. The first lubricating layer and the second lubricating layer prevent the laminated body for battery exterior from being partially adhered to the mold at the time of drawing, and have a uniform drawing without thickness unevenness (thickness variation). It is provided for the purpose of obtaining a molded product (for the purpose of improving the formability during drawing). The first lubricating layer and the second lubricating layer are layers composed of a lubricant, for example, hydrocarbons such as liquid paraffin, fatty acids such as stearic acid, fatty acid amides such as stearylamide, metal soaps, Well-known conditions such as gravure coating, roll coating, or gravure printing when forming in a pattern form, as a coatable state such as a solution of a lubricant such as natural wax or silicone in a suitable solvent. Can be formed by the following coating method, but in the laminate for battery exterior of the present invention, it is formed by the following method.
【００２６】まず最初に、アルミニウム箔の一方の面に
外層、他方の面に内層を設けて積層体とし、次に前記積
層体の前記外層上に滑剤を添加した滑性誘起層を設ける
と共に該滑性誘起層と前記内層が接触するように巻き取
って巻取物とし、その後に前記巻取物の前記滑性誘起層
から前記滑剤を前記滑性誘起層の表面に染み出させて第
１滑性層を形成すると共に前記第１滑性層を前記内層表
面に転移させて前記内層上に第２滑性層を形成するとい
うものである。このような製造方法を採ることにより、
滑性誘起層を設ける工程のみで前記第１滑性層と前記第
２滑性層とを形成することができ、極めて効率的であ
る。さらに、前記滑性誘起層を滑剤を添加した電解液に
対する耐性に優れた樹脂を用いて形成することにより、
前記外層の最表面が前記滑性誘起層で被覆されることに
なり、電解液が電池製造中に電池外装用積層体の表面に
付着したとしても前記外層を形成する、たとえば、上記
で説明した二軸延伸ポリエステルフィルムないし二軸延
伸ポリアミドフィルムが電解液で侵食されて、耐突き刺
し性が低下したり、穴が開く（極端な場合）といったこ
とを防止することができる。First, an aluminum foil is provided with an outer layer on one side and an inner layer on the other side to form a laminate, and then a lubricity-inducing layer to which a lubricant is added is provided on the outer layer of the laminate. Winding is performed so that the slip-inducing layer and the inner layer are in contact with each other, and then the lubricant is oozed out of the slip-inducing layer of the wound-into the surface of the slip-inducing layer to form a first roll. Forming a lubricating layer and transferring the first lubricating layer to the inner layer surface to form a second lubricating layer on the inner layer. By adopting such a manufacturing method,
The first lubricating layer and the second lubricating layer can be formed only by providing the lubricity inducing layer, which is extremely efficient. Furthermore, by forming the lubricity inducing layer using a resin having excellent resistance to an electrolyte solution containing a lubricant,
The outermost surface of the outer layer will be covered with the lubricity-inducing layer, forming the outer layer even if the electrolyte adheres to the surface of the battery exterior laminate during battery production, for example, as described above. It is possible to prevent the biaxially stretched polyester film or the biaxially stretched polyamide film from being eroded by the electrolytic solution to lower the piercing resistance and to form a hole (in an extreme case).
【００２７】次に、前記滑性誘起層について説明する。
この滑性誘起層は、上記したように第１滑性層と第２滑
性層を形成すると共に、外層が電解液により侵食される
のを防止するために設けるものであり、前記外層表面に
ロールコート法、グラビアコート法等の周知の塗工法で
形成することができる。この滑性誘起層を形成する樹脂
としては、電解液に対する耐性に優れた樹脂であれば、
特に限定するものではないが、塗工適性や電解液に対す
る耐性を考慮すると、（メタ）アクリル樹脂が最も好ま
しい。Next, the slip-inducing layer will be described.
The slip-inducing layer forms the first slip layer and the second slip layer as described above, and is provided to prevent the outer layer from being eroded by the electrolytic solution. It can be formed by a well-known coating method such as a roll coating method and a gravure coating method. As the resin forming the slip-inducing layer, if the resin has excellent resistance to the electrolyte,
Although not particularly limited, a (meth) acrylic resin is most preferable in consideration of coating suitability and resistance to an electrolytic solution.
【００２８】そして、滑剤が添加された滑性誘起層とす
るために、前記滑性誘起層を形成する前記樹脂に添加す
る滑剤としては、上記で説明した滑剤、すなわち、流動
パラフィンなどの炭化水素系、ステアリン酸などの脂肪
酸系、ステアリルアミドなどの脂肪酸アミド系、金属石
鹸、天然ワックス、シリコーンなどの周知の滑剤を用い
ることができる。また、滑剤の添加量としては、樹脂10
0 重量部に対して５〜30重量部とすることが好ましい。
滑剤の添加量が樹脂100 重量部に対して５重量部未満に
なると、第１滑性層及び第２滑性層の形成が不十分とな
り、滑剤の添加量が樹脂100 重量部に対して30重量部を
越えると、第１滑性層及び第２滑性層の滑剤が飽和状態
となり、費用対効果を考慮すると望ましくない。また、
前記滑性誘起層の塗工量としては、ピンホールのない均
一な皮膜を形成することと、費用対効果を考慮すると、
乾燥後に0.2 〜２ｇ／ｍ2 とすることが適当である。こ
のようにして形成された滑性誘起層は、絞り成形時の金
型に対する滑り性が良好な第１滑性層及び第２滑性層を
形成することができ、厚みムラ（厚みバラツキ）のない
均一な成形品を得ることができる。The lubricant to be added to the resin forming the slip-inducing layer in order to form the slip-inducing layer to which the lubricant is added may be the lubricant described above, that is, a hydrocarbon such as liquid paraffin. Well-known lubricants such as fatty acids such as stearic acid, fatty acid amides such as stearylamide, metal soaps, natural waxes and silicones can be used. In addition, the amount of the lubricant to be added, resin 10
It is preferably 5 to 30 parts by weight based on 0 parts by weight.
If the amount of the lubricant is less than 5 parts by weight with respect to 100 parts by weight of the resin, the formation of the first lubricating layer and the second lubricating layer becomes insufficient, and the amount of the lubricant added is 30 parts by weight based on 100 parts by weight of the resin. If the amount exceeds the weight parts, the lubricants of the first lubricating layer and the second lubricating layer become saturated, which is not desirable in view of cost effectiveness. Also,
As the coating amount of the lubricity-inducing layer, to form a uniform film without pinholes, considering the cost-effectiveness,
After drying, it is suitably 0.2 to 2 g / m 2 . The thus formed slip-inducing layer can form the first slip layer and the second slip layer having good slipperiness with respect to the mold at the time of drawing, and have uneven thickness (thickness variation). No uniform molded product can be obtained.
【００２９】[0029]
【実施例】上記の本発明について、以下に実施例をあげ
て、さらに詳しく説明する。実施例に用いるアルミニウ
ム箔は、予め50℃の10％水酸化ナトリウム溶液に４分間
浸漬して後に水洗し、さらに脱イオン水で洗浄して温風
乾燥することにより脱脂処理を施した後、塗布型クロメ
ート処理により耐腐食性及び易接着性皮膜を両面に形成
した40μｍの処理済軟質アルミニウム箔である。 実施例１ 〔アルミニウム箔と外層との貼り合わせ〕前記処理済軟
質アルミニウム箔の一方の面に、ウレタン系ドライラミ
ネート用接着剤〔東洋モートン（株）製：AD122/CAT10
〕を乾燥後に３ｇ／ｍ2 となるように塗工して接着剤
層を形成すると共に、該接着剤層と25μｍの二軸延伸ナ
イロンフィルム〔出光石油化学（株）製：U-100 〕のコ
ロナ放電処理面を貼り合わせて第１積層体を作製した。 〔アルミニウム箔と内層との貼り合わせ〕前記第１積層
体のアルミニウム箔面に、ウレタン系ドライラミネート
用接着剤〔東洋モートン（株）製：AD503/CAT10 〕を乾
燥後に３ｇ／ｍ2 となるように塗工して接着剤層を形成
すると共に、該接着剤層と30μｍの無延伸ポリプロピレ
ンフィルム〔二村化学工業（株）製：FCZK〕のコロナ放
電処理面を貼り合わせて第２積層体を作製した。 〔滑性誘起層の形成〕前記第２積層体の二軸延伸ナイロ
ンフィルム面に滑剤としてシリコーンが添加されたアク
リル系樹脂〔大日精化工業（株）製：PTCU-103メジウム
(NS)／PTCP-6滑剤／PTCBK 硬化剤＝100 （固形分40％）
／６／30（樹脂と滑剤の含有重量比100:15）〕を乾燥後
の塗工量が１ｇ／ｍ2 となるように塗工して滑性誘起層
を形成し、該滑性誘起層と前記無延伸ポリプロピレンフ
ィルムが接触するように巻き取って巻取物を作製した。 〔第１滑性層及び第２滑性層の形成〕前記巻取物を一定
時間放置（条件：60℃24時間）して、第１滑性層及び第
２滑性層の形成を確認して、本発明の電池外装用積層体
を作製した。なお、第１滑性層及び第２滑性層の形成
は、二軸延伸ナイロンフィルム及び無延伸ポリプロピレ
ンフィルムの動摩擦係数を前記第２積層体と前記巻取物
で測定して、二軸延伸ナイロンフィルムの動摩擦係数が
0.15から0.06に、そして、無延伸ポリプロピレンフィル
ムの動摩擦係数が0.95から0.35に低下したことから確認
した。The present invention will be described in more detail with reference to the following examples. The aluminum foil used in the examples was previously immersed in a 10% sodium hydroxide solution at 50 ° C. for 4 minutes, washed with water, further washed with deionized water, dried with warm air, and degreased. This is a 40 µm treated soft aluminum foil with a corrosion resistant and easily adhesive film formed on both sides by mold chromate treatment. Example 1 [Lamination of Aluminum Foil and Outer Layer] An adhesive for urethane-based dry lamination [AD122 / CAT10 manufactured by Toyo Morton Co., Ltd.] was applied to one surface of the treated soft aluminum foil.
Is dried and coated to 3 g / m 2 to form an adhesive layer, and the adhesive layer and a 25 μm biaxially stretched nylon film [U-100 manufactured by Idemitsu Petrochemical Co., Ltd.] The first laminate was produced by bonding the corona discharge treated surfaces. [Lamination of Aluminum Foil and Inner Layer] A urethane-based adhesive for dry lamination (AD503 / CAT10, manufactured by Toyo Morton Co., Ltd.) is dried on the aluminum foil surface of the first laminate to 3 g / m 2 after drying. To form an adhesive layer, and the adhesive layer and a corona-discharge treated surface of a 30 μm non-stretched polypropylene film [FCZK manufactured by Nimura Chemical Industry Co., Ltd.] are bonded to form a second laminate. did. [Formation of lubricity-inducing layer] Acrylic resin obtained by adding silicone as a lubricant to the surface of the biaxially stretched nylon film of the second laminate [manufactured by Dainichi Seika Kogyo Co., Ltd .: PTCU-103 Medium]
(NS) / PTCP-6 lubricant / PTCBK hardener = 100 (solid content 40%)
/ 6/30 (weight ratio of resin to lubricant: 100: 15)], so that the coating amount after drying is 1 g / m 2 to form a slip-inducing layer. And the unstretched polypropylene film were wound so as to be in contact with each other to produce a roll. [Formation of first and second lubricating layers] The above-mentioned roll was left for a certain period of time (condition: 60 ° C for 24 hours) to confirm the formation of the first and second lubricating layers. Thus, a battery exterior laminate of the present invention was produced. The formation of the first lubricating layer and the second lubricating layer was performed by measuring the kinetic friction coefficient of a biaxially stretched nylon film and a non-stretched polypropylene film with the second laminate and the rolled product. The dynamic friction coefficient of the film
It was confirmed from 0.15 to 0.06 and that the coefficient of kinetic friction of the unstretched polypropylene film was reduced from 0.95 to 0.35.
【００３０】実施例２ 実施例１で作製した第１積層体のアルミニウム箔面に、
無水マレイン酸変性ポリプロピレンを膜厚が15μｍとな
るようにＴダイ押出機で押し出すと共に、押し出した無
水マレイン酸変性ポリプロピレン面に30μｍの無延伸ポ
リプロピレンフィルム〔二村化学工業（株）製：FCZK〕
のコロナ放電処理面を貼り合わせて第３積層体を作製し
た。該第３積層体の二軸延伸ナイロンフィルム面に実施
例１と同じように滑性誘起層を形成すると共に、該滑性
誘起層と前記無延伸ポリプロピレンフィルムが接触する
ように巻き取って巻取物となし、一定時間放置（条件：
60℃24時間）して第１滑性層及び第２滑性層の形成を実
施例１と同じ方法で確認して、本発明の電池外装用積層
体を作製した。Example 2 On the aluminum foil surface of the first laminate produced in Example 1,
The maleic anhydride-modified polypropylene was extruded with a T-die extruder to a thickness of 15 μm, and a 30 μm unstretched polypropylene film was applied to the extruded maleic anhydride-modified polypropylene surface (FCZK, manufactured by Nimura Chemical Industry Co., Ltd.).
Were laminated to produce a third laminate. A slip-inducing layer is formed on the biaxially stretched nylon film surface of the third laminate in the same manner as in Example 1, and the slip-inducing layer and the unstretched polypropylene film are wound and wound so as to be in contact with each other. With nothing, leave for a certain time (Conditions:
At 60 ° C. for 24 hours), the formation of the first lubricating layer and the second lubricating layer was confirmed by the same method as in Example 1, and a laminate for battery exterior of the present invention was produced.
【００３１】比較例１ 実施例１の第２積層体を比較例とする電池外装用積層体
とした。Comparative Example 1 The second laminate of Example 1 was used as a comparative example for a battery exterior laminate.
【００３２】比較例２ 実施例２の第３積層体を比較例とする電池外装用積層体
とした。Comparative Example 2 The third laminate of Example 2 was used as a comparative example for a battery exterior laminate.
【００３３】比較例３ 実施例１の第２積層体の二軸延伸ナイロンフィルム面に
滑剤を含まないアクリル系樹脂〔大日精化工業（株）
製：PTCU-103メジウム(NS)／PTCBK 硬化剤＝100（固形
分40％）／30〕を乾燥後の塗工量が１ｇ／ｍ2 となるよ
うに塗工して、比較例とする電池外装用積層体を作製し
た。Comparative Example 3 Acrylic resin containing no lubricant on the surface of the biaxially stretched nylon film of the second laminate of Example 1 [Dainichi Seika Kogyo Co., Ltd.
Manufactured by: PTCU-103 Medium (NS) / PTCBK curing agent = 100 (solid content 40%) / 30] so that the coating amount after drying is 1 g / m 2 , and a battery as a comparative example An exterior laminate was produced.
【００３４】比較例４ 実施例１の第２積層体の二軸延伸ナイロンフィルム面に
滑剤としてシリコーンが添加されたアクリル系樹脂〔大
日精化工業（株）製：PTCU-103メジウム(NS)／PTCP-6滑
剤／PTCBK 硬化剤＝100 （固形分40％）／６／30（樹脂
と滑剤の含有重量比100:15）〕を乾燥後の塗工量が３ｇ
／ｍ2 となるように塗工して滑性誘起層を形成し、該滑
性誘起層と前記無延伸ポリプロピレンフィルムが接触す
るように巻き取って巻取物となし、一定時間放置（条
件：60℃24時間）して第１滑性層及び第２滑性層の形成
を実施例１と同じ方法で確認して、比較例とする電池外
装用積層体を作製した。Comparative Example 4 Acrylic resin obtained by adding silicone as a lubricant to the biaxially stretched nylon film surface of the second laminate of Example 1 [manufactured by Dainichi Seika Kogyo Co., Ltd .: PTCU-103 Medium (NS) / PTCP-6 lubricant / PTCBK hardener = 100 (solid content 40%) / 6/30 (weight ratio of resin to lubricant 100: 15)] and the coated amount after drying is 3 g
/ M by applying to 2 become to form a slip-inducing layer,該滑resistance-inducing layer and the unstretched polypropylene film wound in contact taken winding Tobutsu and without a fixed time left (conditions: At 60 ° C. for 24 hours), the formation of the first lubricating layer and the second lubricating layer was confirmed by the same method as in Example 1, and a laminate for battery exterior as a comparative example was produced.
【００３５】比較例５ 実施例１の第２積層体の二軸延伸ナイロンフィルム面に
滑剤としてシリコーンが添加されたアクリル系樹脂〔大
日精化工業（株）製：PTCU-103メジウム(NS)／PTCP-6滑
剤／PTCBK 硬化剤＝100 （固形分40％）／６／30（樹脂
と滑剤の含有重量比100:15）〕を乾燥後の塗工量が１ｇ
／ｍ2 となるように塗工して滑性誘起層を形成し、該滑
性誘起層と前記無延伸ポリプロピレンフィルムとの間に
離型紙を挟み込んで前記滑性誘起層の滑剤が前記無延伸
ポリプロピレンフィルムに転移しないようにして巻き取
って、比較例とする電池外装用積層体を作製した。Comparative Example 5 Acrylic resin obtained by adding silicone as a lubricant to the biaxially stretched nylon film surface of the second laminate of Example 1 [manufactured by Dainichi Seika Kogyo Co., Ltd .: PTCU-103 Medium (NS) / PTCP-6 lubricant / PTCBK curing agent = 100 (solid content 40%) / 6/30 (weight ratio of resin to lubricant 100: 15)] and the coating amount after drying is 1 g
/ M 2 and was coated so as to form a slip-inducing layer,該滑resistance-inducing layer and the lubricant is the unstretched of sandwich the release paper the slip inducing layer between the non-oriented polypropylene film The film was wound so as not to transfer to a polypropylene film, and a laminate for battery exterior as a comparative example was produced.
【００３６】比較例６ 前記処理済軟質アルミニウム箔に代えて何も処理をしな
い普通の40μｍの軟質アルミニウム箔を用いた以外は、
実施例１と同じ方法で比較例とする電池外装用積層体を
作製した。COMPARATIVE EXAMPLE 6 A normal 40 μm soft aluminum foil without any treatment was used instead of the treated soft aluminum foil.
A laminate for battery exterior as a comparative example was produced in the same manner as in Example 1.
【００３７】上記で作製した実施例１、２、および、比
較例１〜６の電池外装用積層体を、120mm ×150mm の矩
形状シートとし、成形高さフリーのストレート金型にて
張り出し１段成形を行い、各積層体の成形深さにより成
形性の良否を評価して、その結果を表１に示した。評価
基準として、成形深さ５mm以上を良好として○印で、成
形深さ５mm未満を不良として×印で示した。また、各積
層体の最外層の耐電解性について評価し、その結果を表
１に示した。評価基準としては、各積層体の最外層表面
に電解液（６フッ化リンリチウムをエチレンカーボネー
トに溶解し、１モルの６フッ化リンリチウム溶液とした
もの）を１ml滴下し、30分後に最外層表面の状態を目視
評価し、表面が白濁しなかったものを良好として○印
で、白濁したものを不良として×印で示した。また、各
積層体を85℃の電解液（６フッ化リンリチウムをエチレ
ンカーボネートに溶解し、１モルの６フッ化リンリチウ
ム溶液としたもの）に浸漬し、アルミニウム箔と無延伸
ポリプロピレンフィルムとの間の接着強度を時系列的に
評価して、その結果を表１に示した。評価基準として
は、アルミニウム箔と無延伸ポリプロピレンフィルムと
の間が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×印で示した。The battery exterior laminates of Examples 1 and 2 and Comparative Examples 1 to 6 were formed into a rectangular sheet of 120 mm × 150 mm, and overhanged by a straight mold having a free molding height of one step. The molding was performed, and the quality of the moldability was evaluated based on the molding depth of each laminate. The results are shown in Table 1. As evaluation criteria, a molding depth of 5 mm or more was evaluated as good, and a molding depth of less than 5 mm was evaluated as defective, as indicated by x. In addition, the outermost layer of each laminate was evaluated for electrolysis resistance, and the results are shown in Table 1. As an evaluation standard, 1 ml of an electrolytic solution (a solution of lithium phosphate hexafluoride in ethylene carbonate to make a 1 mol solution of lithium phosphate hexafluoride) was dropped on the outermost layer surface of each laminate, and 30 minutes later, The state of the surface of the outer layer was visually evaluated, and those having no surface turbidity were indicated by "O" as good, and those having white turbidity were indicated by "X" as defective. Further, each laminate was immersed in an electrolyte solution of 85 ° C. (a solution of lithium phosphate hexafluoride dissolved in ethylene carbonate to form a 1 mol solution of lithium phosphate hexafluoride), and an aluminum foil and a non-stretched polypropylene film were immersed. The adhesive strength between them was evaluated in chronological order, and the results are shown in Table 1. As the evaluation criteria, those in which the aluminum foil and the non-stretched polypropylene film were not peeled were indicated by a mark と し て as good, and those that were peeled were indicated by a mark x inferior.
【００３８】 [0038]
【００３９】表１からも明らかなように、本発明の電池
外装用積層体は、第１滑性層及び第２滑性層を設けたこ
とにより成形性に優れると共に、また、前記第１滑性層
及び前記第２滑性層を形成するために設ける滑性誘起層
に電解液に対する耐性のある樹脂を用いることにより、
外層側についても電解液に対する耐性を持たせることが
できる。さらに、アルミニウム箔表面に耐腐食性及び易
接着性処理を施すことにより、アルミニウム箔と無延伸
ポリプロピレンフィルムとの間の接着強度を強固なもの
とすることができると共に、電解液に対してもアルミニ
ウム箔と無延伸ポリプロピレンフィルムとの間の接着強
度が経時的に低下を来すことがない。As is clear from Table 1, the laminate for battery exterior of the present invention has excellent moldability due to the provision of the first lubricating layer and the second lubricating layer. By using a resin having resistance to an electrolytic solution for a slip-inducing layer provided for forming the slippery layer and the second slip layer,
The outer layer side can also have resistance to the electrolytic solution. Furthermore, by subjecting the aluminum foil surface to corrosion resistance and easy adhesion treatment, the adhesive strength between the aluminum foil and the unstretched polypropylene film can be strengthened, and the aluminum foil is also resistant to the electrolytic solution. The adhesive strength between the foil and the unstretched polypropylene film does not decrease over time.
【００４０】なお、今まで、本発明の電池外装用積層体
を絞り成形に供することを前提に説明してきたが、本発
明の電池外装用積層体は絞り成形のあるタイプの電池外
装体のみならず、成形のないタイプの電池外装体にも十
分対応することができるものである。Although the description has been made so far on the premise that the laminate for battery exterior of the present invention is subjected to drawing, the laminate for battery exterior of the present invention can be used only if the battery exterior of the type having the draw molding is used. Therefore, it is possible to sufficiently cope with a battery outer casing without molding.
【００４１】[0041]
【発明の効果】本発明は、今まで縷々説明してきたよう
に、絞り成形性に優れ、水蒸気やその他のガスバリア性
においても優れると共に、長期に亘ってアルミニウム箔
と内層との間の接着強度の低下がないという優れた効果
を奏する電池外装用積層体を提供することができる。ま
た、第１滑性層及び第２滑性層を形成するために設ける
滑性誘起層に電解液に対する耐性のある樹脂を用いるこ
とにより、外層側についても電解液に対する耐性を持た
せ電池外装用積層体を提供することができる。また、本
発明は、アルミニウム箔の一方の面に外層、他方の面に
内層を設けて積層体とする工程と、該積層体の前記外層
上に滑剤を添加した滑性誘起層を設けると共に該滑性誘
起層と前記内層が接触するように巻き取って巻取物とす
る工程と、該巻取物の前記滑性誘起層から前記滑剤を前
記滑性誘起層の表面に染み出させて第１滑性層を形成す
ると共に前記第１滑性層を前記内層表面に転移させて前
記内層上に第２滑性層を形成する工程とからなる製造方
法を採ることにより、滑性誘起層を設ける工程のみで前
記第１滑性層と前記第２滑性層とを効率的に形成するこ
とができるために、それだけ安価に製造することができ
る。As has been described so far, the present invention is excellent in drawability, excellent in water vapor and other gas barrier properties, and has a long bond strength between the aluminum foil and the inner layer for a long time. It is possible to provide a laminate for a battery exterior which has an excellent effect of no reduction. Further, by using a resin having resistance to an electrolyte for the slip-inducing layer provided for forming the first slip layer and the second slip layer, the outer layer side is also made to have resistance to the electrolyte, so that the outer layer side can be formed. A laminate can be provided. In addition, the present invention provides an aluminum foil having an outer layer on one surface and an inner layer on the other surface to form a laminate, and providing a lubricity-inducing layer to which a lubricant is added on the outer layer of the laminate. Winding the slip-inducing layer and the inner layer so as to be in contact with each other to form a roll; and extruding the lubricant from the slip-inducing layer of the roll onto the surface of the slip-inducing layer. Forming a second lubricating layer on the inner layer by transferring the first lubricating layer to the inner layer surface and forming the second lubricating layer on the inner layer. Since the first lubricating layer and the second lubricating layer can be efficiently formed only by the providing step, it can be manufactured at a lower cost.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮原 美穂 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 (72)発明者 弘光 礼 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 (72)発明者 中川 博喜 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 (72)発明者 小幡 洋治 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 (72)発明者 後藤 貴和 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 (72)発明者 岡 素裕 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 Ｆターム(参考） 5H011 AA01 AA17 CC02 CC06 DD00 KK01 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Miho Miyahara 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Rei Hiromitsu 1-chome, Ichigaga-cho, Shinjuku-ku, Tokyo No. 1 Dai Nippon Printing Co., Ltd. (72) Hiroki Nakagawa 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo Dainippon Printing Co., Ltd. (72) Yoji Obata Inventor Yoji Ichigaya, Shinjuku-ku, Tokyo 1-1, Dai Nippon Printing Co., Ltd. (72) Inventor Takakazu Goto 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo (72) Inventor Motohiro Oka Ichigaya, Shinjuku-ku, Tokyo 1-1-1 Kagacho Dai Nippon Printing Co., Ltd. F term (reference) 5H011 AA01 AA17 CC02 CC06 DD00 KK01
Claims (8)
された電池外装用積層体において、前記外層の最表層に
第１滑性層を備え、前記内層の最表層に第２滑性層を備
えたことを特徴とする電池外装用積層体。1. A battery exterior laminate in which an outer layer, an aluminum foil, and an inner layer are laminated in this order, the outermost layer of the outer layer includes a first slip layer, and the outermost layer of the inner layer includes a second slip layer. A laminate for a battery exterior, comprising:
れた滑性誘起層に添加された滑剤の該滑性誘起層表面へ
の染み出しにより形成されたものであることを特徴とす
る請求項１記載の電池外装用積層体。2. The method according to claim 1, wherein the first lubricating layer is formed by exuding a lubricant added to the lubricating inducing layer formed on the outer layer surface onto the lubricating inducing layer surface. The battery exterior laminate according to claim 1.
記第１滑性層の転移により形成されたものであることを
特徴とする請求項１記載の電池外装用積層体。3. The laminate according to claim 1, wherein the second lubricating layer is formed by transferring the first lubricating layer to a surface of the inner layer.
がオレフィン系熱接着性樹脂層からなり、その厚さが10
〜100 μｍであることを特徴とする請求項１、３のいず
れかに記載の電池外装用積層体。4. A layer of the inner layer adjacent to the second lubricating layer is made of an olefin-based heat-adhesive resin layer, and has a thickness of 10%.
The laminate for battery exterior according to any one of claims 1 and 3, wherein the thickness is from 100 to 100 µm.
ステルフィルムないしポリアミドフィルムからなり、前
記外層の厚さが６〜25μｍであることを特徴とする請求
項１、２のいずれかに記載の電池外装用積層体。5. The battery package according to claim 1, wherein at least one of the outer layers is made of a polyester film or a polyamide film, and the thickness of the outer layer is 6 to 25 μm. For laminate.
軟質アルミニウム箔からなることを特徴とする請求項１
記載の電池外装用積層体。6. The method according to claim 1, wherein said aluminum foil is made of a soft aluminum foil having a thickness of 20 to 80 μm.
The laminate for battery exterior as described in the above.
性及び易接着性処理が施されていることを特徴とする請
求項１〜６のいずれかに記載の電池外装用積層体。7. The battery package according to claim 1, wherein both surfaces of the aluminum foil are subjected to corrosion resistance and easy adhesion treatment.
の面に内層を設けて積層体とする工程と、該積層体の前
記外層上に滑剤を添加した滑性誘起層を設けると共に該
滑性誘起層と前記内層が接触するように巻き取って巻取
物とする工程と、該巻取物の前記滑性誘起層から前記滑
剤を前記滑性誘起層の表面に染み出させて第１滑性層を
形成すると共に前記第１滑性層を前記内層表面に転移さ
せて前記内層上に第２滑性層を形成する工程とからなる
ことを特徴とする電池外装用積層体の製造方法。8. A step of providing an aluminum foil with an outer layer on one surface and an inner layer on the other surface to form a laminate, and providing a lubricity-inducing layer to which a lubricant is added on the outer layer of the laminate, and A step of winding the lubricity-inducing layer and the inner layer so as to be in contact with each other to form a roll, and causing the lubricant to exude from the lubricity-inducing layer of the roll to the surface of the lubricity-inducing layer to form a first roll. Forming a lubricating layer and transferring the first lubricating layer to the inner layer surface to form a second lubricating layer on the inner layer. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000233262A JP4647756B2 (en) | 2000-08-01 | 2000-08-01 | Battery exterior laminate and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000233262A JP4647756B2 (en) | 2000-08-01 | 2000-08-01 | Battery exterior laminate and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2002050325A true JP2002050325A (en) | 2002-02-15 |
| JP4647756B2 JP4647756B2 (en) | 2011-03-09 |
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ID=18725806
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|---|---|---|---|
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Cited By (18)
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| JP2002075298A (en) * | 2000-09-04 | 2002-03-15 | Sumitomo Light Metal Ind Ltd | Complex packing material for polymer battery and its manufacturing method as well as polymer battery using said complex packing material |
| JP2007073402A (en) * | 2005-09-08 | 2007-03-22 | Sumitomo Light Metal Ind Ltd | Aluminum laminate structure for battery housing |
| JP2007073313A (en) * | 2005-09-06 | 2007-03-22 | Showa Denko Packaging Co Ltd | Wrapping material for electronic component case |
| JP2010192154A (en) * | 2009-02-16 | 2010-09-02 | Murata Mfg Co Ltd | Power storage device and method of manufacturing the same |
| WO2011132545A1 (en) * | 2010-04-23 | 2011-10-27 | 大倉工業株式会社 | Outer packaging material for battery or capacitor, and process for production thereof |
| KR101147242B1 (en) | 2010-04-01 | 2012-05-18 | 삼성에스디아이 주식회사 | Electrode assembly, and rechargeable battery using thereof |
| JP2012164676A (en) * | 2012-04-24 | 2012-08-30 | Sumitomo Light Metal Ind Ltd | Manufacturing method for polymer battery composite packaging material |
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| JP2019055498A (en) * | 2017-09-20 | 2019-04-11 | 昭和電工パッケージング株式会社 | Packaging material for molding, exterior case for power storage device, and power storage device |
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| JP2002075298A (en) * | 2000-09-04 | 2002-03-15 | Sumitomo Light Metal Ind Ltd | Complex packing material for polymer battery and its manufacturing method as well as polymer battery using said complex packing material |
| JP2007073313A (en) * | 2005-09-06 | 2007-03-22 | Showa Denko Packaging Co Ltd | Wrapping material for electronic component case |
| JP2007073402A (en) * | 2005-09-08 | 2007-03-22 | Sumitomo Light Metal Ind Ltd | Aluminum laminate structure for battery housing |
| JP2010192154A (en) * | 2009-02-16 | 2010-09-02 | Murata Mfg Co Ltd | Power storage device and method of manufacturing the same |
| US9356274B2 (en) | 2010-04-01 | 2016-05-31 | Samsung Sdi Co., Ltd. | Electrode assembly and rechargeable battery using the same |
| KR101147242B1 (en) | 2010-04-01 | 2012-05-18 | 삼성에스디아이 주식회사 | Electrode assembly, and rechargeable battery using thereof |
| WO2011132545A1 (en) * | 2010-04-23 | 2011-10-27 | 大倉工業株式会社 | Outer packaging material for battery or capacitor, and process for production thereof |
| JPWO2011132545A1 (en) * | 2010-04-23 | 2013-07-18 | 大倉工業株式会社 | Battery or capacitor outer packaging material and method for manufacturing the same |
| JP2013149397A (en) * | 2012-01-17 | 2013-08-01 | Showa Denko Packaging Co Ltd | Exterior material for battery, method for molding the same, and lithium secondary battery |
| JP2012164676A (en) * | 2012-04-24 | 2012-08-30 | Sumitomo Light Metal Ind Ltd | Manufacturing method for polymer battery composite packaging material |
| KR20150018385A (en) | 2013-08-09 | 2015-02-23 | 쇼와 덴코 패키징 가부시키가이샤 | Packaging material for molding |
| CN104340514A (en) * | 2013-08-09 | 2015-02-11 | 昭和电工包装株式会社 | Molding packaging material |
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| JP5725224B1 (en) * | 2014-03-20 | 2015-05-27 | 大日本印刷株式会社 | Battery packaging materials |
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| JP2015053289A (en) * | 2014-11-20 | 2015-03-19 | 凸版印刷株式会社 | Outer package material for lithium ion battery |
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