JP6936093B2 - Exterior material for power storage device, exterior case for power storage device and power storage device - Google Patents

Exterior material for power storage device, exterior case for power storage device and power storage device Download PDF

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JP6936093B2
JP6936093B2 JP2017187923A JP2017187923A JP6936093B2 JP 6936093 B2 JP6936093 B2 JP 6936093B2 JP 2017187923 A JP2017187923 A JP 2017187923A JP 2017187923 A JP2017187923 A JP 2017187923A JP 6936093 B2 JP6936093 B2 JP 6936093B2
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heat
sealing resin
resin layer
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power storage
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JP2019061938A (en
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大介 中嶋
大介 中嶋
誠 唐津
誠 唐津
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Resonac Packaging Corp
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Showa Denko Packaging Co Ltd
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Priority to CN202211500956.9A priority patent/CN115863861A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/18Layered products comprising a layer of metal comprising iron or steel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78Cases; Housings; Encapsulations; Mountings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/116Primary casings; Jackets or wrappings characterised by the material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/116Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117Inorganic material
    • H01M50/119Metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/116Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121Organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/116Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/116Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/10Batteries
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/16Capacitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Description

本発明は、スマートフォン、タブレット等の携帯機器に使用される電池やコンデンサ、ハイブリッド自動車、電気自動車、風力発電、太陽光発電、夜間電気の蓄電用に使用される電池やコンデンサ等の蓄電デバイス用の外装材および該外装材で外装された蓄電デバイスに関する。 The present invention is for power storage devices such as batteries and capacitors used in portable devices such as smartphones and tablets, hybrid vehicles, electric vehicles, wind power generation, solar power generation, and nighttime electricity storage. The present invention relates to an exterior material and a power storage device exteriorized by the exterior material.

なお、本明細書および特許請求の範囲において、「算術平均高さSa」の語は、ISO25178に準拠して測定される算術平均高さSaを意味する。 In the present specification and claims, the term "arithmetic mean height Sa" means the arithmetic mean height Sa measured in accordance with ISO25178.

近年、スマートフォン、タブレット端末等のモバイル電気機器の薄型化、軽量化に伴い、これらに搭載されるリチウムイオン二次電池、リチウムポリマー二次電池、リチウムイオンキャパシタ、電気2重層コンデンサ等の蓄電デバイスの外装材としては、従来の金属缶に代えて、耐熱性樹脂層/接着剤層/金属箔層/接着剤層/熱可塑性樹脂層(内側シーラント層)からなる積層体が用いられている。また、電気自動車等の電源、蓄電用途の大型電源、キャパシタ等も上記構成の積層体(外装材)で外装されることも増えてきている。前記積層体に対して張り出し成形や深絞り成形が行われることによって、略直方体形状等の立体形状に成形される。このような立体形状に成形することにより、蓄電デバイス本体部を収容するための収容空間を確保することができる。 In recent years, as mobile electric devices such as smartphones and tablet terminals have become thinner and lighter, storage devices such as lithium ion secondary batteries, lithium polymer secondary batteries, lithium ion capacitors, and electric double-layer capacitors mounted on these devices have become thinner and lighter. As the exterior material, a laminate composed of a heat-resistant resin layer / adhesive layer / metal foil layer / adhesive layer / thermoplastic resin layer (inner sealant layer) is used instead of the conventional metal can. In addition, power supplies for electric vehicles, large power supplies for power storage, capacitors, and the like are increasingly being exteriorized with a laminate (exterior material) having the above configuration. By performing overhang molding or deep drawing molding on the laminated body, it is molded into a three-dimensional shape such as a substantially rectangular parallelepiped shape. By molding into such a three-dimensional shape, it is possible to secure an accommodation space for accommodating the main body of the power storage device.

このような立体形状にピンホールや破断等なく良好状態に成形するには内側シーラント層の表面の滑り性を向上させることが求められる。内側シーラント層の表面の滑り性を向上させて良好な成形性を確保するものとして、内側シーラント層にアンチブロッキング剤(AB剤)を含有せしめた構成のものが公知である(特許文献1参照)。 In order to form such a three-dimensional shape in a good state without pinholes or breakage, it is required to improve the slipperiness of the surface of the inner sealant layer. As a substance for improving the slipperiness of the surface of the inner sealant layer and ensuring good moldability, a structure in which the inner sealant layer contains an anti-blocking agent (AB agent) is known (see Patent Document 1). ..

また、同様に滑り性を向上させて良好な成形性を確保するものとして、基材層の一方の面に最外層として耐酸性付与層が設けられ、該基材層の他方の面に、第1接着層、少なくとも片面に腐食防止処理層を設けたアルミニウム箔層、第2接着層、シーラント層が順次積層されたリチウムイオン電池用外装材であって、前記シーラント層の外側の表面にスリップ剤(脂肪酸アミド等)およびアンチブロッキング剤(シリカ粒子等)の少なくとも一方が塗布されるか、または前記シーラント層にスリップ剤(脂肪酸アミド等)およびアンチブロッキング剤(シリカ粒子等)の少なくとも一方が配合された構成のリチウムイオン電池用外装材が知られている(特許文献2参照)。 Similarly, in order to improve slipperiness and ensure good moldability, an acid resistance imparting layer is provided as an outermost layer on one surface of the base material layer, and an acid resistance imparting layer is provided on the other surface of the base material layer. An exterior material for a lithium ion battery in which one adhesive layer, an aluminum foil layer provided with a corrosion prevention treatment layer on at least one surface, a second adhesive layer, and a sealant layer are sequentially laminated, and a slip agent is applied to the outer surface of the sealant layer. At least one of (fatty acid amide, etc.) and anti-blocking agent (silica particles, etc.) is applied, or at least one of slip agent (fatty acid amide, etc.) and anti-blocking agent (silica particles, etc.) is blended in the sealant layer. An exterior material for a lithium ion battery having a different configuration is known (see Patent Document 2).

上記いずれの技術においても、内側シーラント層の表面の滑り性を向上させることができて良好な成形性を確保できる。 In any of the above techniques, the slipperiness of the surface of the inner sealant layer can be improved and good moldability can be ensured.

特開2001−266811号公報Japanese Unexamined Patent Publication No. 2001-266811 特開2015−53289号公報Japanese Unexamined Patent Publication No. 2015-53289

しかしながら、内側シーラント層の表面の滑り性を向上させるべく、内側シーラント層に過剰にアンチブロッキング剤を添加すると、内側シーラント層が白濁化しやすく、該シーラント層の白濁化により、外装材中に層間剥離(デラミネーション)が発生していても品質検査で見落としを生じやすいという問題があった。 However, if an excessive anti-blocking agent is added to the inner sealant layer in order to improve the slipperiness of the surface of the inner sealant layer, the inner sealant layer tends to become cloudy, and the whitening of the sealant layer causes delamination in the exterior material. There was a problem that even if (delamination) occurred, it was easy to overlook in the quality inspection.

勿論、アンチブロッキング剤の添加量を減少させれば、シーラント層の白濁化の問題は解消できるものの、シーラント層の表面の滑り性が低下して良好な成形を行うことができない。従来では、このように良好な成形性確保と、白濁化の抑制とを両立させることが困難であった。 Of course, if the amount of the anti-blocking agent added is reduced, the problem of white turbidity of the sealant layer can be solved, but the slipperiness of the surface of the sealant layer is lowered, and good molding cannot be performed. Conventionally, it has been difficult to achieve both good moldability and suppression of white turbidity.

また、前記シーラント層にスリップ剤(脂肪酸アミド等)を含有せしめた構成では、外装材(積層材)の生産工程での加温保持時間や保管期間によって表面滑剤析出量のコントロールが難しく、成形時のすべり性は良いものの、滑剤が表面に過度に析出するために、外装材の成形時に成形金型の成形面に滑剤が付着堆積していって白粉(滑剤による白粉)が発生する。このような白粉が成形金型の成形面に付着堆積した状態になると、良好な成形を行い難くなることから、白粉が付着堆積する毎に清掃して白粉の除去を行う必要が生じるが、このような白粉の清掃除去を行うことで外装材の生産性が低下するという問題があった。 Further, in the configuration in which the sealant layer contains a slip agent (fatty acid amide, etc.), it is difficult to control the amount of surface lubricant deposited depending on the heating retention time and the storage period in the production process of the exterior material (laminated material), and during molding. Although the slipperiness is good, the lubricant is excessively deposited on the surface, so that the lubricant adheres and accumulates on the molding surface of the molding die during molding of the exterior material, and white powder (white powder due to the lubricant) is generated. If such white powder adheres and accumulates on the molding surface of the molding die, it becomes difficult to perform good molding. Therefore, it is necessary to clean and remove the white powder every time the white powder adheres and accumulates. There is a problem that the productivity of the exterior material is lowered by cleaning and removing the white powder.

本発明は、かかる技術的背景に鑑みてなされたものであって、成形時に良好なすべり性を確保できて良好な成形性を確保できると共に、外装材における白濁を抑制することができ、且つ表面に白粉が表出し難い、蓄電デバイス用外装材、蓄電デバイス用外装ケース及び蓄電デバイスを提供することを目的とする。 The present invention has been made in view of such a technical background, and it is possible to secure good slipperiness at the time of molding, secure good moldability, suppress white turbidity in the exterior material, and surface. It is an object of the present invention to provide an exterior material for a power storage device, an exterior case for a power storage device, and a power storage device in which white powder is hard to be exposed.

前記目的を達成するために、本発明は以下の手段を提供する。 In order to achieve the above object, the present invention provides the following means.

[1]外側層としての基材層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層と、を含む蓄電デバイス用外装材であって、
前記熱融着性樹脂層は、外装材の最内層を形成する第1熱融着性樹脂層と、該第1熱融着性樹脂層における前記金属箔層側の面に積層された第2熱融着性樹脂層と、該第2熱融着性樹脂層における前記金属箔層側の面に積層された又は前記金属箔層側に配置された第3熱融着性樹脂層と、を含む3層以上の積層体からなり、
前記第1熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体と、滑剤と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有する第1樹脂組成物からなり、前記第1樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であり、前記第1樹脂組成物における前記非相溶粒子の含有率が1000ppm〜6000ppmの範囲であり、
前記第2熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するブロック共重合体と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有する第2樹脂組成物からなり、前記第2樹脂組成物における前記ブロック共重合体の含有率が50質量%以上であり、前記第2樹脂組成物における前記非相溶粒子の含有率が0ppmを超えて100ppm以下であり、
前記第3熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体を含有する第3樹脂組成物からなり、前記第3樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であることを特徴とする蓄電デバイス用外装材。
[1] An exterior material for a power storage device including a base material layer as an outer layer, a heat-sealing resin layer as an inner layer, and a metal foil layer arranged between both layers.
The heat-sealing resin layer is formed by laminating a first heat-sealing resin layer forming the innermost layer of the exterior material and a second surface of the first heat-sealing resin layer on the metal leaf layer side. The heat-sealing resin layer and the third heat-sealing resin layer laminated on the surface of the second heat-sealing resin layer on the metal leaf layer side or arranged on the metal leaf layer side are provided. Consists of three or more layers including
The first heat-sealing resin layer is incompatible with a random copolymer containing propylene and other copolymerization components other than propylene as copolymerization components, a lubricant, and an average particle size of 0.5 μm to 4 μm. The first resin composition containing particles, the content of the random copolymer in the first resin composition is 50% by mass or more, and the incompatible particles in the first resin composition. The content is in the range of 1000 ppm to 6000 ppm and
The second heat-sealing resin layer comprises a block copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene, and incompatible particles having an average particle size of 0.5 μm to 4 μm. The content of the block copolymer in the second resin composition is 50% by mass or more, and the content of the incompatible particles in the second resin composition is 50% by mass or more. More than 0 ppm and less than 100 ppm,
The third heat-sealing resin layer comprises a third resin composition containing a random copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene, and the third resin composition. An exterior material for a power storage device, characterized in that the content of the random copolymer is 50% by mass or more.

[2]外側層としての基材層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層と、を含む蓄電デバイス用外装材であって、
前記熱融着性樹脂層は、外装材の最内層を形成する第1熱融着性樹脂層と、該第1熱融着性樹脂層における前記金属箔層側の面に積層された第2熱融着性樹脂層と、該第2熱融着性樹脂層における前記金属箔層側の面に積層された又は前記金属箔層側に配置された第3熱融着性樹脂層と、を含む3層以上の積層体からなり、
前記第1熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体と、滑剤と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有する第1樹脂組成物からなり、前記第1樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であり、前記第1樹脂組成物における前記非相溶粒子の含有率が1000ppm〜6000ppmの範囲であり、
前記第2熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するブロック共重合体を含有し、非相溶粒子を含有しない第2樹脂組成物からなり、前記第2樹脂組成物における前記ブロック共重合体の含有率が50質量%以上であり、
前記第3熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体を含有する第3樹脂組成物からなり、前記第3樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であることを特徴とする蓄電デバイス用外装材。
[2] An exterior material for a power storage device including a base material layer as an outer layer, a heat-sealing resin layer as an inner layer, and a metal foil layer arranged between both layers.
The heat-sealing resin layer is formed by laminating a first heat-sealing resin layer forming the innermost layer of the exterior material and a second surface of the first heat-sealing resin layer on the metal leaf layer side. The heat-sealing resin layer and the third heat-sealing resin layer laminated on the surface of the second heat-sealing resin layer on the metal leaf layer side or arranged on the metal leaf layer side are provided. Consists of three or more layers including
The first heat-sealing resin layer is incompatible with a random copolymer containing propylene and other copolymerization components other than propylene as copolymerization components, a lubricant, and an average particle size of 0.5 μm to 4 μm. The first resin composition containing particles, the content of the random copolymer in the first resin composition is 50% by mass or more, and the incompatible particles in the first resin composition. The content is in the range of 1000 ppm to 6000 ppm and
The second heat-sealing resin layer comprises a second resin composition containing a block copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene, and not containing incompatible particles. , The content of the block copolymer in the second resin composition is 50% by mass or more.
The third heat-sealing resin layer comprises a third resin composition containing a random copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene, and the third resin composition. An exterior material for a power storage device, characterized in that the content of the random copolymer is 50% by mass or more.

[3]前記第3樹脂組成物は、非相溶粒子を含有しない組成である、又は平均粒子径が0.5μm〜4μmの非相溶粒子を0ppmを超えて6000ppm以下含有する組成である前項1または2に記載の蓄電デバイス用外装材。 [3] The third resin composition has a composition that does not contain incompatible particles, or a composition that contains incompatible particles having an average particle size of 0.5 μm to 4 μm in an amount of more than 0 ppm and 6000 ppm or less. The exterior material for a power storage device according to 1 or 2.

[4]前記第1熱融着性樹脂層の内側の表面の算術平均高さ(Sa)が50nm〜200nmである前項1〜3のいずれか1項に記載の蓄電デバイス用外装材。 [4] The exterior material for a power storage device according to any one of items 1 to 3 above, wherein the arithmetic mean height (Sa) of the inner surface of the first heat-sealing resin layer is 50 nm to 200 nm.

[5]前記第1樹脂組成物における前記滑剤の含有率が100ppm〜2000ppmであり、前記第2樹脂組成物は、さらに滑剤を含有し、該第2樹脂組成物における滑剤の含有率が500ppm〜5000ppmである前項1〜4のいずれか1項に記載の蓄電デバイス用外装材。 [5] The content of the lubricant in the first resin composition is 100 ppm to 2000 ppm, the second resin composition further contains a lubricant, and the content of the lubricant in the second resin composition is 500 ppm to 2000 ppm. The exterior material for a power storage device according to any one of items 1 to 4 above, which is 5000 ppm.

[6]前記熱融着性樹脂層は、前記第1熱融着性樹脂層、前記第2熱融着性樹脂層および前記第3熱融着性樹脂層からなり、
前記第1熱融着性樹脂層の厚さは、前記熱融着性樹脂層の全体厚さの5%〜30%である前項1〜5のいずれか1項に記載の蓄電デバイス用外装材。
[6] The heat-sealing resin layer comprises the first heat-sealing resin layer, the second heat-sealing resin layer, and the third heat-sealing resin layer.
The exterior material for a power storage device according to any one of the above items 1 to 5, wherein the thickness of the first heat-sealing resin layer is 5% to 30% of the total thickness of the heat-sealing resin layer. ..

[7]前項1〜6のいずれか1項に記載の蓄電デバイス用外装材の成形体からなる蓄電デバイス用外装ケース。 [7] An exterior case for a power storage device made of a molded body of the exterior material for the power storage device according to any one of the above items 1 to 6.

[8]蓄電デバイス本体部と、
前項1〜6のいずれか1項に記載の蓄電デバイス用外装材および前項7に記載の蓄電デバイス用外装ケースからなる群より選ばれる1種または2種の外装部材とを備え、
前記蓄電デバイス本体部が、前記外装部材で外装されていることを特徴とする蓄電デバイス。
[8] The main body of the power storage device and
It is provided with one or two types of exterior members selected from the group consisting of the exterior material for a power storage device according to any one of the above items 1 to 6 and the exterior case for a power storage device according to the above item 7.
A power storage device characterized in that the power storage device main body is covered with the exterior member.

[1]及び[2]の発明では、外装材の最内層を形成する第1熱融着性樹脂層は、前記ランダム共重合体と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有するので、最内層の表面(内面)に適度な凹凸を付与できて成形時の接触面積を低減できて、添加する滑剤量を少なくしても良好な滑り性を確保できて良好な成形性を確保できる。添加する滑剤量を少なくできることにより、滑剤のブリード量を低減でき、これにより外装材の表面に白粉が表出し難く、成形型表面への滑剤の付着汚染を抑制できる。 In the inventions of [1] and [2], the first heat-sealing resin layer forming the innermost layer of the exterior material is the random copolymer and incompatible particles having an average particle diameter of 0.5 μm to 4 μm. Since it contains, it is possible to impart appropriate unevenness to the surface (inner surface) of the innermost layer, reduce the contact area during molding, and secure good slipperiness even if the amount of lubricant added is small. Good moldability can be ensured. By reducing the amount of lubricant added, the amount of bleeding of the lubricant can be reduced, so that white powder is less likely to appear on the surface of the exterior material, and adhesion contamination of the lubricant on the surface of the molding die can be suppressed.

また、第2熱融着性樹脂層は、[1]の発明では平均粒子径が0.5μm〜4μmの非相溶粒子の含有率が0ppmを超えて100ppm以下であり、[2]の発明では非相溶粒子(いかなる平均粒子径のものも)を含有しない構成であるので、この第2熱融着性樹脂層においては白濁の発生を防止できる(第2熱融着性樹脂層のヘイズ率を極めて小さくできて透明性に優れている)。従って、このような第2熱融着性樹脂層を含む本発明の蓄電デバイス用外装材は、白濁化を抑制できたものとなり、これにより、外装材中に層間剥離(デラミネーション)が発生していたら品質検査等で発見することができ、製品としての品質を格段に向上させることができる。 Further, in the second heat-sealing resin layer, in the invention of [1], the content of incompatible particles having an average particle diameter of 0.5 μm to 4 μm exceeds 0 ppm and is 100 ppm or less, and the invention of [2] Since the structure does not contain incompatible particles (any average particle size), white turbidity can be prevented in the second heat-sealing resin layer (haze of the second heat-sealing resin layer). The rate can be extremely small and the transparency is excellent). Therefore, the exterior material for a power storage device of the present invention containing such a second heat-sealing resin layer can suppress white turbidity, which causes delamination in the exterior material. If so, it can be found by quality inspection, etc., and the quality of the product can be significantly improved.

また、第2熱融着性樹脂層において、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するブロック共重合体の含有率が50質量%以上であるから、熱融着性樹脂層(シーラント層)の耐熱性、耐久性を向上できると共に、熱シール後の液漏れを十分に防止できる。 Further, since the content of the block copolymer containing propylene and other copolymerization components other than propylene as the copolymerization component in the second heat-sealing resin layer is 50% by mass or more, the heat-bondable resin. The heat resistance and durability of the layer (sealant layer) can be improved, and liquid leakage after heat sealing can be sufficiently prevented.

更に、金属箔側に配置される第3熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体の含有率が50質量%以上であるから、金属箔層との接着性を向上させることができる。 Further, the third heat-sealing resin layer arranged on the metal foil side has a content of 50% by mass or more of a random copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene. Therefore, the adhesiveness with the metal foil layer can be improved.

加えて、外装材の最内層を形成する第1熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体の含有率が50質量%以上であるから、シール時のヒートシール温度を下げることができる(より低いヒートシール温度でのシールにより良好なシールを実現できる)。 In addition, the first heat-sealing resin layer forming the innermost layer of the exterior material has a content of 50% by mass or more of a random copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene. Therefore, the heat-sealing temperature at the time of sealing can be lowered (good sealing can be achieved by sealing at a lower heat-sealing temperature).

[3]の発明では、第3樹脂組成物は、平均粒子径が0.5μm〜4μmの非相溶粒子を0ppmを超えて6000ppm以下含有する組成である構成では、金属箔層との接着性をより向上させることができるし、第3樹脂組成物が非相溶粒子を含有しない組成である構成では、金属箔層との接着性をより一層向上させることができる。 In the invention of [3], the third resin composition has a composition containing incompatible particles having an average particle diameter of 0.5 μm to 4 μm in an average particle size of more than 0 ppm and 6000 ppm or less, and has adhesiveness to a metal foil layer. In a configuration in which the third resin composition does not contain incompatible particles, the adhesiveness to the metal foil layer can be further improved.

[4]の発明では、第1熱融着性樹脂層の内側の表面の算術平均高さ(Sa)が50nm〜200nmであるから、滑り性をより向上させることができてより良好な成形性を確保できると共に、第1熱融着性樹脂層における白濁化をより低減することができる。 In the invention of [4], since the arithmetic mean height (Sa) of the inner surface of the first heat-sealing resin layer is 50 nm to 200 nm, the slipperiness can be further improved and the moldability is improved. It is possible to further reduce white turbidity in the first heat-sealing resin layer.

[5]の発明では、十分な滑り性を維持しつつ、滑剤のブリード量をより一層抑制することができて成形型表面への滑剤の付着汚染をさらに低減できる。 In the invention of [5], the amount of bleeding of the lubricant can be further suppressed while maintaining sufficient slipperiness, and the adhesion and contamination of the lubricant on the surface of the mold can be further reduced.

[6]の発明では、第1熱融着性樹脂層の厚さは、前記熱融着性樹脂層の全体厚さの5%〜30%であるので、3層積層構成の熱融着性樹脂層における金属箔側の表面(第3熱融着性樹脂層の金属箔側の表面)が非相溶粒子の影響を受けがたいものとなり、該金属箔側の表面をより平滑面に形成することができ、積層時(接着時等)に気泡の混入を十分に防止できる。 In the invention of [6], the thickness of the first heat-sealing resin layer is 5% to 30% of the total thickness of the heat-sealing resin layer, so that the heat-sealing property of the three-layer laminated structure is obtained. The surface of the resin layer on the metal leaf side (the surface of the third heat-sealing resin layer on the metal leaf side) is less susceptible to the influence of incompatible particles, and the surface on the metal leaf side is formed to be a smoother surface. It is possible to sufficiently prevent air bubbles from being mixed during laminating (adhesion, etc.).

[7]の発明では、外装材の白濁化を抑制できるので、外装ケース中に層間剥離(デラミネーション)が発生していたら品質検査等で発見することができ、製品としての品質を格段に向上させることができる。また、良好な成形が行われた外装ケースを提供することができる。 In the invention of [7], since the white turbidity of the exterior material can be suppressed, if delamination occurs in the exterior case, it can be found by quality inspection or the like, and the quality as a product is remarkably improved. Can be made to. In addition, it is possible to provide an outer case that has been well molded.

[8]の発明では、良好な成形が行われた外装ケースを備えている上に、白濁化を抑制できているので、外装ケース中に層間剥離(デラミネーション)が発生していたら品質検査等で発見することができて、高品質の外装がなされた蓄電デバイスを提供できる。 In the invention of [8], since the outer case is provided with a well-formed outer case and the white turbidity can be suppressed, if delamination occurs in the outer case, a quality inspection or the like is performed. Can be found in, and can provide a power storage device with a high quality exterior.

本発明に係る蓄電デバイス用外装材の一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of the exterior material for a power storage device which concerns on this invention. 本発明に係る蓄電デバイスの一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of the power storage device which concerns on this invention. 図2の蓄電デバイスを構成する外装材(平面状のもの)、蓄電デバイス本体部及び外装ケース(立体形状に成形された成形体)をヒートシールする前の分離した状態で示す斜視図である。FIG. 2 is a perspective view showing a separated state before heat-sealing the exterior material (planar shape), the power storage device main body, and the exterior case (molded body molded into a three-dimensional shape) constituting the power storage device of FIG.

本発明に係る蓄電デバイス用外装材1は、外側層としての基材層2と、内側層としての熱融着性樹脂層3と、これら両層間に配置された金属箔層4と、を含み、前記熱融着性樹脂層3は、外装材1の最内層を形成する第1熱融着性樹脂層7と、該第1熱融着性樹脂層7における前記金属箔層側の面に積層された第2熱融着性樹脂層8と、該第2熱融着性樹脂層8における前記金属箔層側の面に積層された又は前記金属箔層側に配置された第3熱融着性樹脂層9と、を含む3層以上の積層体からなる構成である(図1参照)。 The exterior material 1 for a power storage device according to the present invention includes a base material layer 2 as an outer layer, a heat-sealing resin layer 3 as an inner layer, and a metal foil layer 4 arranged between both layers. The heat-sealing resin layer 3 is formed on the first heat-sealing resin layer 7 forming the innermost layer of the exterior material 1 and the surface of the first heat-sealing resin layer 7 on the metal leaf layer side. The laminated second heat-sealing resin layer 8 and the third heat-melting laminated on the surface of the second heat-sealing resin layer 8 on the metal leaf layer side or arranged on the metal leaf layer side. It is composed of a laminated body containing three or more layers including the adhesive resin layer 9 (see FIG. 1).

本発明において、前記第1熱融着性樹脂層7は、共重合成分として「プロピレン」及び「プロピレンを除く他の共重合成分」を含有するランダム共重合体と、滑剤と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有する第1樹脂組成物からなり、前記第1樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であり、前記第1樹脂組成物における前記平均粒子径が0.5μm〜4μmの非相溶粒子の含有率が1000ppm〜6000ppmの範囲に設定される。 In the present invention, the first heat-sealing resin layer 7 has a random copolymer containing "propylene" and "other copolymerization components other than propylene" as copolymerization components, a lubricant, and an average particle size. It is composed of a first resin composition containing 0.5 μm to 4 μm incompatible particles, and the content of the random copolymer in the first resin composition is 50% by mass or more, and the first resin. The content of the incompatible particles having an average particle size of 0.5 μm to 4 μm in the composition is set in the range of 1000 ppm to 6000 ppm.

また、前記第2熱融着性樹脂層8は、共重合成分として「プロピレン」及び「プロピレンを除く他の共重合成分」を含有するブロック共重合体と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有する第2樹脂組成物からなり、前記第2樹脂組成物における前記ブロック共重合体の含有率が50質量%以上であり、前記第2樹脂組成物における前記平均粒子径が0.5μm〜4μmの非相溶粒子の含有率が0ppmを超えて100ppm以下に設定される。或いは、前記第2樹脂組成物に、いかなる平均粒子径の非相溶粒子を含有せしめない構成としてもよい。 Further, the second heat-sealing resin layer 8 is a block copolymer containing "propylene" and "other copolymerization components other than propylene" as copolymerization components, and has an average particle size of 0.5 μm to 4 μm. The block copolymer is composed of a second resin composition containing the incompatible particles of the above, and the content of the block copolymer in the second resin composition is 50% by mass or more, and the average in the second resin composition. The content of incompatible particles having a particle size of 0.5 μm to 4 μm is set to be more than 0 ppm and 100 ppm or less. Alternatively, the second resin composition may be configured so as not to contain incompatible particles having any average particle size.

また、前記第3熱融着性樹脂層9は、共重合成分として「プロピレン」及び「プロピレンを除く他の共重合成分」を含有するランダム共重合体を含有する第3樹脂組成物からなり、前記第3樹脂組成物における前記ランダム共重合体の含有率が50質量%以上に設定される。 Further, the third heat-sealing resin layer 9 is composed of a third resin composition containing a random copolymer containing "propylene" and "other copolymerization components other than propylene" as copolymerization components. The content of the random copolymer in the third resin composition is set to 50% by mass or more.

図1は、本発明に係る蓄電デバイス用外装材1の一実施形態を示したものである。本実施形態の蓄電デバイス用外装材1は、前記金属箔層4の一方の面に内側接着剤層6を介して前記熱融着性樹脂層(内側層)3が積層一体化されると共に、前記金属箔層4の他方の面に外側接着剤層5を介して前記基材層(外側層)2が積層一体化された構成からなる。そして、図1に示す本実施形態では、前記熱融着性樹脂層(内側層)3は、該内側層3の最内層7を構成する第1熱融着性樹脂層と、該第1熱融着性樹脂層7における前記金属箔層4側の面に積層された第2熱融着性樹脂層8と、該第2熱融着性樹脂層8における前記金属箔層4側の面に積層された第3熱融着性樹脂層9と、からなる3層積層構成である。前記第1熱融着性樹脂層(最内層)7が蓄電デバイス用外装材1の内側の表面に露出している(図1参照)。また、前記第3熱融着性樹脂層9と前記金属箔層4の一方の面とが前記内側接着剤層6で接着一体化されている(図1参照)。 FIG. 1 shows an embodiment of the exterior material 1 for a power storage device according to the present invention. In the exterior material 1 for a power storage device of the present embodiment, the heat-sealing resin layer (inner layer) 3 is laminated and integrated on one surface of the metal foil layer 4 via an inner adhesive layer 6. The base material layer (outer layer) 2 is laminated and integrated on the other surface of the metal foil layer 4 via the outer adhesive layer 5. Then, in the present embodiment shown in FIG. 1, the heat-sealing resin layer (inner layer) 3 includes a first heat-sealing resin layer constituting the innermost layer 7 of the inner layer 3 and the first heat. On the surface of the second heat-sealing resin layer 7 on the side of the metal leaf layer 4 and the surface of the second heat-sealing resin layer 8 on the side of the metal leaf layer 4. It is a three-layer laminated structure composed of a laminated third heat-sealing resin layer 9. The first heat-sealing resin layer (innermost layer) 7 is exposed on the inner surface of the exterior material 1 for a power storage device (see FIG. 1). Further, the third heat-sealing resin layer 9 and one surface of the metal foil layer 4 are bonded and integrated by the inner adhesive layer 6 (see FIG. 1).

図1に示す本実施形態の蓄電デバイス用外装材1は、リチウムイオン2次電池ケース用として用いられるものである。前記蓄電デバイス用外装材1は、例えば、深絞り成形、張り出し成形等の成形に供されて2次電池のケース等として使用できる。 The exterior material 1 for a power storage device shown in FIG. 1 is used for a lithium ion secondary battery case. The exterior material 1 for a power storage device can be used as a case for a secondary battery or the like by being subjected to molding such as deep drawing molding and overhang molding.

本発明において、前記熱融着性樹脂層(内側層;シーラント層)3は、リチウムイオン二次電池等で用いられる腐食性の強い電解液等に対しても優れた耐薬品性を具備させると共に、外装材にヒートシール性を付与する役割を担うものである。 In the present invention, the heat-sealing resin layer (inner layer; sealant layer) 3 is provided with excellent chemical resistance to a highly corrosive electrolytic solution or the like used in a lithium ion secondary battery or the like. , It plays a role of imparting heat sealability to the exterior material.

前記第1熱融着性樹脂層7および前記第3熱融着性樹脂層9は、いずれも、共重合成分として「プロピレン」及び「プロピレンを除く他の共重合成分」を含有するランダム共重合体を含有する。前記ランダム共重合体に関して、前記「プロピレンを除く他の共重合成分」としては、特に限定されるものではないが、例えば、エチレン、1−ブテン、1−ヘキセン、1−ペンテン、4メチル−1−ペンテン等のオレフィン成分の他、ブタジエン等が挙げられる。 The first heat-sealing resin layer 7 and the third heat-sealing resin layer 9 both contain "propylene" and "other copolymerization components other than propylene" as copolymerization components at random co-weights. Contains coalescence. Regarding the random copolymer, the "other copolymerization component other than propylene" is not particularly limited, but for example, ethylene, 1-butane, 1-hexene, 1-pentene, 4methyl-1. -In addition to olefin components such as pentene, butadiene and the like can be mentioned.

前記第2熱融着性樹脂層8は、共重合成分として「プロピレン」及び「プロピレンを除く他の共重合成分」を含有するブロック共重合体を含有する。前記ブロック共重合体に関して、前記「プロピレンを除く他の共重合成分」としては、特に限定されるものではないが、例えば、エチレン、1−ブテン、1−ヘキセン、1−ペンテン、4メチル−1−ペンテン等のオレフィン成分の他、ブタジエン等が挙げられる。 The second heat-sealing resin layer 8 contains a block copolymer containing "propylene" and "other copolymerization components other than propylene" as copolymerization components. Regarding the block copolymer, the "other copolymer components other than propylene" are not particularly limited, but for example, ethylene, 1-butane, 1-hexene, 1-pentene, 4methyl-1. -In addition to olefin components such as penten, butadiene and the like can be mentioned.

本発明において、前記非相溶粒子としては、それが添加される第1熱融着性樹脂層7、第2熱融着性樹脂層8、第3熱融着性樹脂層9等を構成する樹脂(共重合体)に対して非相溶性の粒子であれば、特に限定されない。中でも、前記非相溶粒子としては、アンチブロッキング剤(AB剤)を用いるのが好ましい。 In the present invention, the incompatible particles constitute a first heat-sealing resin layer 7, a second heat-sealing resin layer 8, a third heat-sealing resin layer 9, and the like to which the particles are added. The particles are not particularly limited as long as they are incompatible with the resin (copolymer). Above all, it is preferable to use an anti-blocking agent (AB agent) as the incompatible particles.

前記アンチブロッキング剤としては、特に限定されるものではないが、例えば、無機粒子、樹脂粒子等が挙げられる。前記無機粒子としては、特に限定されるものではないが、例えば、無機酸化物粒子(シリカ粒子、アルミナ粒子、酸化チタン粒子等)、無機炭酸塩粒子(炭酸カルシウム粒子、炭酸バリウム粒子等)、無機ケイ酸塩粒子(ケイ酸アルミニウム粒子、タルク粒子、カオリン粒子等)などが挙げられる。前記樹脂粒子としては、特に限定されるものではないが、例えば、アクリル樹脂粒子、ポリオレフィン樹脂粒子(ポリエチレン樹脂粒子、ポリプロピレン樹脂粒子)、ポリスチレン樹脂粒子などが挙げられる。 The antiblocking agent is not particularly limited, and examples thereof include inorganic particles and resin particles. The inorganic particles are not particularly limited, but are, for example, inorganic oxide particles (silica particles, alumina particles, titanium oxide particles, etc.), inorganic carbonate particles (calcium carbonate particles, barium carbonate particles, etc.), and inorganic particles. Examples thereof include silicate particles (aluminum silicate particles, talc particles, kaolin particles, etc.). The resin particles are not particularly limited, and examples thereof include acrylic resin particles, polyolefin resin particles (polyethylene resin particles, polypropylene resin particles), and polystyrene resin particles.

前記非相溶粒子としては、1種のみを用いてもよいし、2種以上を併用してもよい。2種以上を併用する場合には平均粒子径の異なる2種以上の非相溶粒子を用いるのが好ましく、この場合には最内層(第1熱融着性樹脂層)7の表面(内面)7aの全体の粗さの分布を均一にできるという効果が得られる。また、前記非相溶粒子としては、比重が3以下であるものを用いるのが好ましく、この場合には非相溶粒子を層内で均一に分散できるという効果が得られる。 As the incompatible particles, only one type may be used, or two or more types may be used in combination. When two or more types are used in combination, it is preferable to use two or more types of incompatible particles having different average particle diameters. In this case, the surface (inner surface) of the innermost layer (first heat-sealing resin layer) 7 is used. The effect that the distribution of the overall roughness of 7a can be made uniform can be obtained. Further, as the incompatible particles, those having a specific gravity of 3 or less are preferably used, and in this case, the effect that the incompatible particles can be uniformly dispersed in the layer can be obtained.

前記非相溶粒子としては、平均粒子径が0.5μm〜4μmの非相溶粒子を用いる。平均粒子径が0.5μm未満の非相溶粒子を用いると外装材のブロッキング防止に必要な表面凹凸をうまく形成できないし、平均粒子径が4μm以上の非相溶粒子を用いると、非相溶粒子による型付きや非相溶粒子の脱落という問題を生じる。前記非相溶粒子としては、平均粒子径が0.7μm〜2.5μmの非相溶粒子を用いるのが好ましい。 As the incompatible particles, incompatible particles having an average particle diameter of 0.5 μm to 4 μm are used. If incompatible particles with an average particle size of less than 0.5 μm are used, the surface irregularities required to prevent blocking of the exterior material cannot be formed well, and if incompatible particles with an average particle size of 4 μm or more are used, incompatible particles are used. It causes problems of typed particles and shedding of incompatible particles. As the incompatible particles, it is preferable to use incompatible particles having an average particle diameter of 0.7 μm to 2.5 μm.

前記第1熱融着性樹脂層7における「平均粒子径が0.5μm〜4μmの非相溶粒子」の含有率(濃度)は1000ppm〜6000ppmの範囲に設定される。1000ppm未満では最内層(第1熱融着性樹脂層)7の表面(内面)7aの全体にわたって凹凸を形成することが難しくなるし、6000ppmを超えると、第1熱融着性樹脂層7の白濁化の程度が大きくなるし、熱シールを十分に行うことができなかったり、非相溶粒子の脱落という問題を生じる。前記第1熱融着性樹脂層7における「平均粒子径が0.5μm〜4μmの非相溶粒子」の含有率(濃度)は、2000ppm〜5000ppmの範囲に設定されるのが好ましい。 The content (concentration) of "incompatible particles having an average particle size of 0.5 μm to 4 μm" in the first heat-sealing resin layer 7 is set in the range of 1000 ppm to 6000 ppm. If it is less than 1000 ppm, it becomes difficult to form irregularities over the entire surface (inner surface) 7a of the innermost layer (first heat-sealing resin layer) 7, and if it exceeds 6000 ppm, it becomes difficult for the first heat-sealing resin layer 7 to form irregularities. The degree of white turbidity increases, heat sealing cannot be performed sufficiently, and incompatible particles fall off. The content (concentration) of "incompatible particles having an average particle size of 0.5 μm to 4 μm" in the first heat-sealing resin layer 7 is preferably set in the range of 2000 ppm to 5000 ppm.

前記第2熱融着性樹脂層8における「平均粒子径が0.5μm〜4μmの非相溶粒子」の含有率(濃度)は、0ppmを超えて100ppm以下に設定される構成とする、又は、前記第2熱融着性樹脂層8には非相溶粒子(平均粒子径を問わず)を含有せしめない構成とする。このような構成とすることで、第2熱融着性樹脂層8の白濁化を防止できる。即ち100ppmを超えて含有せしめると、金属箔層4と熱融着性樹脂層3の間でデラミネーション(剥離)が生じていても、品質検査等で発見することができない又は発見が困難になる。 The content (concentration) of the "incompatible particles having an average particle size of 0.5 μm to 4 μm" in the second heat-sealing resin layer 8 is set to be more than 0 ppm and 100 ppm or less, or The second heat-sealing resin layer 8 does not contain incompatible particles (regardless of the average particle size). With such a configuration, it is possible to prevent the second heat-sealing resin layer 8 from becoming cloudy. That is, if the content exceeds 100 ppm, even if delamination (peeling) occurs between the metal foil layer 4 and the heat-sealing resin layer 3, it cannot be found by quality inspection or the like, or it becomes difficult to find it. ..

前記第3熱融着性樹脂層9は、平均粒子径が0.5μm〜4μmの非相溶粒子を0ppmを超えて6000ppm以下含有する組成であるのが好ましい。このような構成を採用した場合には、金属箔層4との接着性をより向上させることができるし、第3熱融着性樹脂層9の白濁化を抑制できて、金属箔層4と熱融着性樹脂層3の間でデラミネーション(剥離)が生じていたら、品質検査等で発見することができる。或いは、前記第3熱融着性樹脂層9は、非相溶粒子(平均粒子径を問わず)を含有しない組成とするのが好ましく、この場合には金属箔層4との接着性をより一層向上できるし、第3熱融着性樹脂層9の白濁化を生じないので、金属箔層4と熱融着性樹脂層3の間でデラミネーション(剥離)が生じていたら、品質検査等で容易に発見することができる。 The third heat-sealing resin layer 9 preferably contains incompatible particles having an average particle size of 0.5 μm to 4 μm in an amount of more than 0 ppm and 6000 ppm or less. When such a configuration is adopted, the adhesiveness with the metal foil layer 4 can be further improved, and the white turbidity of the third heat-sealing resin layer 9 can be suppressed, so that the metal foil layer 4 and the metal foil layer 4 can be combined with each other. If delamination (peeling) occurs between the heat-sealing resin layers 3, it can be found by quality inspection or the like. Alternatively, the third heat-sealing resin layer 9 preferably has a composition that does not contain incompatible particles (regardless of the average particle size), and in this case, the adhesiveness to the metal foil layer 4 is improved. Since it can be further improved and the third heat-sealing resin layer 9 does not become cloudy, if delamination (peeling) occurs between the metal foil layer 4 and the heat-sealing resin layer 3, a quality inspection or the like is performed. Can be easily found at.

前記熱融着性樹脂層3として図1の3層積層構成を採用する場合において、3層の厚さの比率は、第1熱融着性樹脂層7の厚さ/第2熱融着性樹脂層8の厚さ/第3熱融着性樹脂層9の厚さ=5〜20/90〜60/5〜20の範囲に設定されるのが好ましい。 When the three-layer laminated structure of FIG. 1 is adopted as the heat-sealing resin layer 3, the ratio of the thickness of the three layers is the thickness of the first heat-sealing resin layer 7 / the second heat-sealing property. It is preferable that the thickness of the resin layer 8 / the thickness of the third heat-sealing resin layer 9 is set in the range of 5 to 20/90 to 60/5 to 20.

本発明において、前記滑剤としては、特に限定されるものではないが、脂肪酸アミドが好適に用いられる。前記脂肪酸アミドとしては、特に限定されるものではないが、例えば、飽和脂肪酸アミド、不飽和脂肪酸アミド、置換アミド、メチロールアミド、飽和脂肪酸ビスアミド、不飽和脂肪酸ビスアミド、脂肪酸エステルアミド、芳香族系ビスアミド等が挙げられる。 In the present invention, the lubricant is not particularly limited, but a fatty acid amide is preferably used. The fatty acid amide is not particularly limited, but for example, saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylol amide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, fatty acid ester amide, aromatic bisamide and the like. Can be mentioned.

前記飽和脂肪酸アミドとしては、特に限定されるものではないが、例えば、ラウリン酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベヘン酸アミド、ヒドロキシステアリン酸アミド等が挙げられる。前記不飽和脂肪酸アミドとしては、特に限定されるものではないが、例えば、オレイン酸アミド、エルカ酸アミド等が挙げられる。 The saturated fatty acid amide is not particularly limited, and examples thereof include lauric acid amide, palmitic acid amide, stearic acid amide, bechenic acid amide, and hydroxystearic acid amide. The unsaturated fatty acid amide is not particularly limited, and examples thereof include oleic acid amide and erucic acid amide.

前記置換アミドとしては、特に限定されるものではないが、例えば、N−オレイルパルミチン酸アミド、N−ステアリルステアリン酸アミド、N−ステアリルオレイン酸アミド、N−オレイルステアリン酸アミド、N−ステアリルエルカ酸アミド等が挙げられる。また、前記メチロールアミドとしては、特に限定されるものではないが、例えば、メチロールステアリン酸アミド等が挙げられる。 The substituted amide is not particularly limited, but is, for example, N-oleyl palmitate amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid. Examples include amides. The methylolamide is not particularly limited, and examples thereof include methylolstearic amide.

前記飽和脂肪酸ビスアミドとしては、特に限定されるものではないが、例えば、メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスステアリン酸アミド、エチレンビスヒドロキシステアリン酸アミド、エチレンビスベヘン酸アミド、ヘキサメチレンビスステアリン酸アミド、ヘキサメチレンビスベヘン酸アミド、ヘキサメチレンヒドロキシステアリン酸アミド、N,N’−ジステアリルアジピン酸アミド、N,N’−ジステアリルセバシン酸アミド等が挙げられる。 The saturated fatty acid bisamide is not particularly limited, but for example, methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene. Bisbechenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbechenic acid amide, hexamethylene hydroxystearic acid amide, N, N'-distearyl adipate amide, N, N'-distearyl sebacic acid amide and the like. Be done.

前記不飽和脂肪酸ビスアミドとしては、特に限定されるものではないが、例えば、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド、ヘキサメチレンビスオレイン酸アミド、N,N’−ジオレイルセバシン酸アミド等が挙げられる。 The unsaturated fatty acid bisamide is not particularly limited, and examples thereof include ethylene bisoleic acid amide, ethylene biserucate amide, hexamethylene bisoleic acid amide, and N, N'-diorail sebacic acid amide. Can be mentioned.

前記脂肪酸エステルアミドとしては、特に限定されるものではないが、例えば、ステアロアミドエチルステアレート等が挙げられる。前記芳香族系ビスアミドとしては、特に限定されるものではないが、例えば、m−キシリレンビスステアリン酸アミド、m−キシリレンビスヒドロキシステアリン酸アミド、N,N’−システアリルイソフタル酸アミド等が挙げられる。 The fatty acid ester amide is not particularly limited, and examples thereof include stearoamide ethyl stearate and the like. The aromatic bisamide is not particularly limited, and examples thereof include m-xylylene bisstearic acid amide, m-xylylene bishydroxystearic acid amide, and N, N'-cystelyl isophthalic acid amide. Can be mentioned.

前記第1熱融着性樹脂層7における滑剤の含有率は、100ppm〜2000ppmに設定されるのが好ましい。100ppm以上であることで第1熱融着性樹脂層7内にある滑剤が適度に表面7aに析出して滑り性をより向上させることができるし、2000ppm以下であることで前記表面7aに滑剤が過剰に析出することがなくて前記表面7aに白粉がより表出し難いものとなる。中でも、前記第1熱融着性樹脂層7における滑剤の含有率は、100ppm〜1000ppmに設定されるのがより好ましい。 The content of the lubricant in the first heat-sealing resin layer 7 is preferably set to 100 ppm to 2000 ppm. When it is 100 ppm or more, the lubricant in the first heat-sealing resin layer 7 can be appropriately precipitated on the surface 7a to further improve the slipperiness, and when it is 2000 ppm or less, the lubricant is on the surface 7a. Is not excessively deposited, and white powder is less likely to appear on the surface 7a. Above all, the content of the lubricant in the first heat-sealing resin layer 7 is more preferably set to 100 ppm to 1000 ppm.

前記第2熱融着性樹脂層8には滑剤を含有せしめるのが好ましい。前記第2熱融着性樹脂層8における滑剤の含有率は、500ppm〜5000ppmに設定されるのが好ましい。500ppm以上であることで、第1熱融着性樹脂層7に存在する滑剤が第2熱融着性樹脂層8に浸透することで生じる第1熱融着性樹脂層7内での滑剤の欠乏状態を防止できるし、5000ppm以下であることでブリードアウトした滑剤による、外装材表面の白粉汚染や周辺装置の白粉汚染を防止できる。 It is preferable that the second heat-sealing resin layer 8 contains a lubricant. The content of the lubricant in the second heat-sealing resin layer 8 is preferably set to 500 ppm to 5000 ppm. When the content is 500 ppm or more, the lubricant existing in the first heat-sealing resin layer 7 permeates the second heat-sealing resin layer 8 to cause the lubricant in the first heat-sealing resin layer 7. It is possible to prevent a deficiency state, and it is possible to prevent white powder contamination on the surface of the exterior material and white powder contamination of peripheral devices due to the lubricant bleeding out when the amount is 5000 ppm or less.

なお、前記第3熱融着性樹脂層9にも滑剤を含有せしめるのが好ましいが、ラミネート強度が低下する懸念があるので、前記第3熱融着性樹脂層9には滑剤を0ppmを超えて250ppm以下含有せしめるのが好ましい。勿論、前記第3熱融着性樹脂層9に滑剤を含有せしめない構成としてもよい。 It is preferable that the third heat-sealing resin layer 9 also contains a lubricant, but since there is a concern that the lamination strength may decrease, the lubricant exceeds 0 ppm in the third heat-sealing resin layer 9. It is preferable to contain 250 ppm or less. Of course, the third heat-sealing resin layer 9 may be configured so as not to contain a lubricant.

本発明において、前記第1熱融着性樹脂層7の厚さは、前記熱融着性樹脂層3の全体厚さの5%〜30%に設定されるのが好ましい。5%以上に設定されることで、滑り性を向上させるに十分な表面粗さが得られると共に、熱シール時に十分なシール強度を確保できる。また、30%以下に設定されることで、熱シール後の熱融着性樹脂層3の耐久性をより向上させることができると共に、熱融着性樹脂層3における金属箔側の表面が非相溶粒子の影響を受けがたいものとなり、該金属箔側の表面をより平滑面に形成することができて積層時(接着時等)に気泡の混入を十分に防止できる。中でも、前記第1熱融着性樹脂層7の厚さは、前記熱融着性樹脂層3の全体厚さの10%〜20%に設定されるのが特に好ましい。 In the present invention, the thickness of the first heat-sealing resin layer 7 is preferably set to 5% to 30% of the total thickness of the heat-sealing resin layer 3. By setting it to 5% or more, sufficient surface roughness can be obtained to improve slipperiness, and sufficient sealing strength can be ensured at the time of thermal sealing. Further, by setting it to 30% or less, the durability of the heat-sealing resin layer 3 after heat sealing can be further improved, and the surface of the heat-sealing resin layer 3 on the metal leaf side is not formed. It becomes less susceptible to the influence of compatible particles, and the surface on the metal foil side can be formed into a smoother surface, so that air bubbles can be sufficiently prevented from being mixed during lamination (adhesion, etc.). Above all, the thickness of the first heat-sealing resin layer 7 is particularly preferably set to 10% to 20% of the total thickness of the heat-sealing resin layer 3.

本発明では、前記熱融着性樹脂層3の最内層(第1熱融着性樹脂層)7の表面7aに、前記滑剤の一部が表出して(ブリードして)付着しているが、前記最内層(第1熱融着性樹脂層)7の表面7aにおける滑剤の付着量は、0.1μg/cm2〜1.0μg/cm2の範囲であるのが好ましい。 In the present invention, a part of the lubricant is exposed (bleed) and adheres to the surface 7a of the innermost layer (first heat-sealing resin layer) 7 of the heat-sealing resin layer 3. the innermost layer adhesion amount of the lubricant at the surface 7a of the (first heat fusion resin layer) 7 is preferably in the range of 0.1μg / cm 2 ~1.0μg / cm 2 .

なお、図1に示す実施形態では、熱融着性樹脂層(内側層)3は、外装材1の最内層7を構成する第1熱融着性樹脂層/第2熱融着性樹脂層8/第3熱融着性樹脂層9の3層積層構成が採用されているが、特にこのような構成に限定されるものではなく、第2熱融着性樹脂層8と第3熱融着性樹脂層9の間に「他の熱融着性樹脂層」が1ないし複数層積層配置された構成を採用することもできる。即ち、前記[1]及び[2]の発明で規定している「…第2熱融着性樹脂層8における…(略)…前記金属箔層側に配置された第3熱融着性樹脂層9と、を含む3層以上の積層体からなる」における「前記金属箔層側に配置された」の語は、第2熱融着性樹脂層8と第3熱融着性樹脂層9の間に他の熱融着性樹脂層が1ないし複数層積層配置された構成を規定したものである。なお、前記「他の熱融着性樹脂層」としては、例えば、エラストマー成分や滑剤量を変えた前記ランダム共重合体(共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体)、エラストマー成分や滑剤量を変えた前記ブロック共重合体(共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するブロック共重合体)、ホモポリプロピレン樹脂等が挙げられる。 In the embodiment shown in FIG. 1, the heat-sealing resin layer (inner layer) 3 is a first heat-sealing resin layer / second heat-sealing resin layer constituting the innermost layer 7 of the exterior material 1. Although a three-layer laminated structure of the 8 / third heat-sealing resin layer 9 is adopted, the structure is not particularly limited to such a structure, and the second heat-sealing resin layer 8 and the third heat-sealing resin layer 8 are not particularly limited to such a structure. It is also possible to adopt a configuration in which one or a plurality of "other heat-sealing resin layers" are laminated and arranged between the adhesive resin layers 9. That is, the "... in the second heat-sealing resin layer 8 ... (omitted) ... the third heat-sealing resin arranged on the metal leaf layer side" defined in the inventions of the above [1] and [2]. The term "arranged on the metal leaf layer side " in "consisting of a laminated body containing three or more layers including the layer 9" refers to the second heat-sealing resin layer 8 and the third heat-sealing resin layer 9. It defines a structure in which one or a plurality of other heat-sealing resin layers are laminated and arranged between the two layers. The "other heat-sealing resin layer" includes, for example, the random copolymer having an elastomer component or a different amount of lubricant (random containing propylene and other copolymer components other than propylene as copolymer components). Copolymers), the block copolymers having different elastomer components and lubricant amounts (block copolymers containing propylene and other copolymerization components other than propylene as copolymerization components), homopolypropylene resins and the like.

本発明において、前記基材層(外側層)2は、耐熱性樹脂層で形成されているのが好ましい。前記耐熱性樹脂層2を構成する耐熱性樹脂としては、外装材1をヒートシールする際のヒートシール温度で溶融しない耐熱性樹脂を用いる。前記耐熱性樹脂としては、熱融着性樹脂層3の融点(第1〜3熱融着性樹脂層のうち最も高い融点を有する層の融点)より10℃以上高い融点を有する耐熱性樹脂を用いるのが好ましく、熱融着性樹脂層3の融点(第1〜3熱融着性樹脂層のうち最も高い融点を有する層の融点より20℃以上高い融点を有する耐熱性樹脂を用いるのが特に好ましい。 In the present invention, the base material layer (outer layer) 2 is preferably formed of a heat-resistant resin layer. As the heat-resistant resin constituting the heat-resistant resin layer 2, a heat-resistant resin that does not melt at the heat-sealing temperature when the exterior material 1 is heat-sealed is used. As the heat-resistant resin, a heat-resistant resin having a melting point higher than the melting point of the heat-sealing resin layer 3 (the melting point of the layer having the highest melting point among the first to third heat-sealing resin layers) by 10 ° C. or more is used. It is preferable to use a heat-resistant resin having a melting point of 20 ° C. or more higher than the melting point of the heat-sealing resin layer 3 (the melting point of the layer having the highest melting point among the first to third heat-sealing resin layers). Especially preferable.

前記耐熱性樹脂層(外側層)2としては、特に限定されるものではないが、例えば、ナイロンフィルム等のポリアミドフィルム、ポリエステルフィルム等が挙げられ、これらの延伸フィルムが好ましく用いられる。中でも、前記耐熱性樹脂層2としては、二軸延伸ナイロンフィルム等の二軸延伸ポリアミドフィルム、二軸延伸ポリブチレンテレフタレート(PBT)フィルム、二軸延伸ポリエチレンテレフタレート(PET)フィルム又は二軸延伸ポリエチレンナフタレート(PEN)フィルムを用いるのが特に好ましい。前記ナイロンフィルムとしては、特に限定されるものではないが、例えば、6ナイロンフィルム、6,6ナイロンフィルム、MXDナイロンフィルム等が挙げられる。なお、前記耐熱性樹脂層2は、単層で形成されていても良いし、或いは、例えばポリエステルフィルム/ポリアミドフィルムからなる複層(PETフィルム/ナイロンフィルムからなる複層等)で形成されていても良い。 The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include a polyamide film such as a nylon film and a polyester film, and these stretched films are preferably used. Among them, the heat-resistant resin layer 2 includes a biaxially stretched polyamide film such as a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film, or a biaxially stretched polyethylene film. It is particularly preferable to use a phthalate (PEN) film. The nylon film is not particularly limited, and examples thereof include a 6-nylon film, a 6,6 nylon film, and an MXD nylon film. The heat-resistant resin layer 2 may be formed of a single layer, or may be formed of, for example, a multi-layer made of a polyester film / polyamide film (a multi-layer made of a PET film / nylon film, etc.). Is also good.

前記耐熱性樹脂層(外側層)2の厚さは、2μm〜50μmであるのが好ましい。ポリエステルフィルムを用いる場合には厚さは2μm〜50μmであるのが好ましく、ナイロンフィルムを用いる場合には厚さは7μm〜50μmであるのが好ましい。上記好適下限値以上に設定することで包装材として十分な強度を確保できると共に、上記好適上限値以下に設定することで張り出し成形、絞り成形等の成形時の応力を小さくできて成形性を向上させることができる。 The thickness of the heat-resistant resin layer (outer layer) 2 is preferably 2 μm to 50 μm. When a polyester film is used, the thickness is preferably 2 μm to 50 μm, and when a nylon film is used, the thickness is preferably 7 μm to 50 μm. Sufficient strength as a packaging material can be ensured by setting it to the above-mentioned preferable lower limit value or more, and stress during molding such as overhang molding and draw forming can be reduced and formability is improved by setting it to the above-mentioned preferable upper limit value or less. Can be made to.

前記金属箔層4は、外装材1に酸素や水分の侵入を阻止するガスバリア性を付与する役割を担うものである。前記金属箔層4としては、特に限定されるものではないが、例えば、アルミニウム箔、SUS箔(ステンレス箔)、Cu箔、Ni箔、Ti箔等が挙げられ、中でも、アルミニウム箔、SUS箔(ステンレス箔)を用いるのが好ましい。前記金属箔層4の厚さは、5μm〜120μmであるのが好ましい。5μm以上であることで金属箔を製造する際の圧延時のピンホール発生を防止できると共に、120μm以下であることで張り出し成形、絞り成形等の成形時の応力を小さくできて成形性を向上させることができる。中でも、前記金属箔層4の厚さは10μm〜80μmであるのがより好ましい。 The metal leaf layer 4 plays a role of imparting a gas barrier property to prevent the invasion of oxygen and moisture to the exterior material 1. The metal foil layer 4 is not particularly limited, and examples thereof include an aluminum foil, a SUS foil (stainless steel foil), a Cu foil, a Ni foil, a Ti foil, and the like. Among them, an aluminum foil and a SUS foil ( (Stainless foil) is preferably used. The thickness of the metal foil layer 4 is preferably 5 μm to 120 μm. When it is 5 μm or more, it is possible to prevent the occurrence of pinholes during rolling when manufacturing a metal foil, and when it is 120 μm or less, the stress during molding such as overhang molding and draw forming can be reduced and the formability is improved. be able to. Above all, the thickness of the metal foil layer 4 is more preferably 10 μm to 80 μm.

前記金属箔層4は、少なくとも内側の面(内側層3側の面)に、化成処理が施されているのが好ましい。このような化成処理が施されていることによって内容物(電池の電解液等)による金属箔表面の腐食を十分に防止できる。例えば次のような処理をすることによって金属箔に化成処理を施す。即ち、例えば、脱脂処理を行った金属箔の表面に、
1)リン酸と、
クロム酸と、
フッ化物の金属塩及びフッ化物の非金属塩からなる群より選ばれる少なくとも1種の化合物と、を含む混合物の水溶液
2)リン酸と、
アクリル系樹脂、キトサン誘導体樹脂及びフェノール系樹脂からなる群より選ばれる少なくとも1種の樹脂と、
クロム酸及びクロム(III)塩からなる群より選ばれる少なくとも1種の化合物と、を含む混合物の水溶液
3)リン酸と、
アクリル系樹脂、キトサン誘導体樹脂及びフェノール系樹脂からなる群より選ばれる少なくとも1種の樹脂と、
クロム酸及びクロム(III)塩からなる群より選ばれる少なくとも1種の化合物と、
フッ化物の金属塩及びフッ化物の非金属塩からなる群より選ばれる少なくとも1種の化合物と、を含む混合物の水溶液
上記1)〜3)のうちのいずれかの水溶液を塗工した後、乾燥することにより、化成処理を施す。
It is preferable that at least the inner surface (the surface on the inner layer 3 side) of the metal foil layer 4 is subjected to chemical conversion treatment. By performing such a chemical conversion treatment, it is possible to sufficiently prevent the metal foil surface from being corroded by the contents (electrolyte solution of the battery, etc.). For example, the metal foil is subjected to chemical conversion treatment by performing the following treatment. That is, for example, on the surface of the metal leaf that has been degreased,
1) Phosphoric acid and
With chromic acid
An aqueous solution of a mixture containing at least one compound selected from the group consisting of a metal salt of fluoride and a non-metal salt of fluoride 2) Phosphoric acid.
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins, and
An aqueous solution of a mixture containing at least one compound selected from the group consisting of chromic acid and a chromium (III) salt 3) phosphoric acid.
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins, and
At least one compound selected from the group consisting of chromic acid and chromium (III) salt, and
An aqueous solution of a mixture containing at least one compound selected from the group consisting of a metal salt of fluoride and a non-metal salt of fluoride An aqueous solution of any one of 1) to 3) above is applied and then dried. By doing so, the chemical conversion process is performed.

前記化成皮膜は、クロム付着量(片面当たり)として0.1mg/m2〜50mg/m2が好ましく、特に2mg/m2〜20mg/m2が好ましい。 The conversion coating, chromium coating weight preferably is 0.1mg / m 2 ~50mg / m 2 as a (per one surface), in particular 2mg / m 2 ~20mg / m 2 preferred.

前記外側接着剤5としては、特に限定されるものではないが、例えば、熱硬化性接着剤等が挙げられる。前記熱硬化性接着剤としては、特に限定されるものではないが、例えば、オレフィン系接着剤、エポキシ系接着剤、アクリル系接着剤等が挙げられる。前記外側接着剤層5の厚さは、1μm〜5μmに設定されるのが好ましい。中でも、包装材1の薄膜化、軽量化の観点から、前記外側接着剤層5の厚さは、1μm〜3μmに設定されるのが特に好ましい。 The outer adhesive 5 is not particularly limited, and examples thereof include a thermosetting adhesive. The thermosetting adhesive is not particularly limited, and examples thereof include an olefin-based adhesive, an epoxy-based adhesive, and an acrylic-based adhesive. The thickness of the outer adhesive layer 5 is preferably set to 1 μm to 5 μm. Above all, from the viewpoint of thinning and weight reduction of the packaging material 1, the thickness of the outer adhesive layer 5 is particularly preferably set to 1 μm to 3 μm.

前記内側接着剤6としては、特に限定されるものではないが、例えば、前記熱硬化性接着剤等が挙げられる。前記内側接着剤層6の厚さは、1μm〜5μmに設定されるのが好ましい。中でも、包装材1の薄膜化、軽量化の観点から、前記内側接着剤層6の厚さは、1μm〜3μmに設定されるのが特に好ましい。 The inner adhesive 6 is not particularly limited, and examples thereof include the thermosetting adhesive. The thickness of the inner adhesive layer 6 is preferably set to 1 μm to 5 μm. Above all, from the viewpoint of thinning and weight reduction of the packaging material 1, the thickness of the inner adhesive layer 6 is particularly preferably set to 1 μm to 3 μm.

前記蓄電デバイス用外装材1を構成する基材層2、熱融着性樹脂層3(最内層7を含む)中に、本発明の効果を阻害しない範囲で、次のような添加剤を添加してもよい。前記添加剤としては、特に限定されるものではないが、例えば、酸化防止剤、可塑剤、紫外線吸収剤、防かび剤、着色剤(顔料、染料等)、帯電防止剤、防さび剤、吸湿剤、酸素吸収剤等が挙げられる。前記可塑剤としては、特に限定されるものではないが、例えば、グリセリン脂肪酸エステルモノグリセライド、グリセリン脂肪酸エステルアセチル化モノグリセライド、グリセリン脂肪酸エステル有機酸モノグリセライド、グリセリン脂肪酸エステル中鎖脂肪酸トリグリセライド、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、特殊脂肪酸エステル、高級アルコール脂肪酸エステルなどが挙げられる。 The following additives are added to the base material layer 2 and the heat-sealing resin layer 3 (including the innermost layer 7) constituting the exterior material 1 for the power storage device, as long as the effects of the present invention are not impaired. You may. The additive is not particularly limited, but is, for example, an antioxidant, a plasticizer, an ultraviolet absorber, a fungicide, a colorant (pigment, dye, etc.), an antistatic agent, a rust preventive, and a moisture absorbing agent. Agents, oxygen absorbers and the like. The plasticizer is not particularly limited, but is, for example, glycerin fatty acid ester monoglyceride, glycerin fatty acid ester acetylated monoglyceride, glycerin fatty acid ester organic acid monoglyceride, glycerin fatty acid ester medium chain fatty acid triglyceride, polyglycerin fatty acid ester, sorbitan. Examples thereof include fatty acid esters, propylene glycol fatty acid esters, special fatty acid esters, and higher alcohol fatty acid esters.

本発明の蓄電デバイス用外装材1を成形(深絞り成形、張り出し成形等)することにより、外装ケース(電池ケース等)10を得ることができる(図3参照)。なお、本発明の外装材1は、成形に供されずにそのまま使用することもできる(図3参照)。 The exterior case (battery case, etc.) 10 can be obtained by molding (deep drawing molding, overhang molding, etc.) the exterior material 1 for a power storage device of the present invention (see FIG. 3). The exterior material 1 of the present invention can be used as it is without being subjected to molding (see FIG. 3).

本発明の蓄電デバイス用外装材1を用いて構成された蓄電デバイス30の一実施形態を図2に示す。この蓄電デバイス30は、リチウムイオン2次電池である。本実施形態では、図2、3に示すように、外装材1を成形して得られた外装ケース10と、平面状の外装材1とにより外装部材15が構成されている。しかして、本発明の外装材1を成形して得られた外装ケース10の収容凹部内に、略直方体形状の蓄電デバイス本体部(電気化学素子等)31が収容され、該蓄電デバイス本体部31の上に、本発明の外装材1が成形されることなくその熱融着性樹脂層3側を内方(下側)にして配置され、該平面状外装材1の熱融着性樹脂層3(第1熱融着性樹脂層7)の周縁部と、前記外装ケース10のフランジ部(封止用周縁部)29の熱融着性樹脂層3(第1熱融着性樹脂層7)とがヒートシールによりシール接合されて封止されることによって、本発明の蓄電デバイス30が構成されている(図2、3参照)。なお、前記外装ケース10の収容凹部の内側の表面は、熱融着性樹脂層3(第1熱融着性樹脂層7)になっており、収容凹部の外面が基材層(外側層)2になっている(図3参照)。 FIG. 2 shows an embodiment of the power storage device 30 configured by using the exterior material 1 for the power storage device of the present invention. The power storage device 30 is a lithium ion secondary battery. In the present embodiment, as shown in FIGS. 2 and 3, the exterior member 15 is composed of the exterior case 10 obtained by molding the exterior material 1 and the flat exterior material 1. Thus, a substantially square-shaped power storage device main body (electrochemical element or the like) 31 is housed in the storage recess of the exterior case 10 obtained by molding the exterior material 1 of the present invention, and the power storage device main body 31 is housed. The exterior material 1 of the present invention is arranged on the surface with the heat-sealing resin layer 3 side facing inward (lower side) without being molded, and the heat-sealing resin layer of the planar exterior material 1 is arranged. 3 (1st heat-sealing resin layer 7) and the heat-sealing resin layer 3 (1st heat-sealing resin layer 7) of the flange portion (sealing peripheral portion) 29 of the outer case 10 ) Is sealed by heat sealing to form the power storage device 30 of the present invention (see FIGS. 2 and 3). The inner surface of the housing recess of the exterior case 10 is a heat-sealing resin layer 3 (first heat-sealing resin layer 7), and the outer surface of the housing recess is a base material layer (outer layer). It is 2 (see FIG. 3).

図2において、39は、前記外装材1の周縁部と、前記外装ケース10のフランジ部(封止用周縁部)29とが接合(溶着)されたヒートシール部である。なお、前記蓄電デバイス30において、蓄電デバイス本体部31に接続されたタブリードの先端部が、外装部材15の外部に導出されているが、図示は省略している。 In FIG. 2, 39 is a heat-sealed portion in which the peripheral edge portion of the exterior material 1 and the flange portion (sealing peripheral edge portion) 29 of the exterior case 10 are joined (welded). In the power storage device 30, the tip of the tab lead connected to the power storage device main body 31 is led out to the outside of the exterior member 15, but the illustration is omitted.

前記蓄電デバイス本体部31としては、特に限定されるものではないが、例えば、電池本体部、キャパシタ本体部、コンデンサ本体部等が挙げられる。 The power storage device main body 31 is not particularly limited, and examples thereof include a battery main body, a capacitor main body, and a capacitor main body.

前記ヒートシール部39の幅は、0.5mm以上に設定するのが好ましい。0.5mm以上とすることで封止を確実に行うことができる。中でも、前記ヒートシール部39の幅は、3mm〜15mmに設定するのが好ましい。 The width of the heat seal portion 39 is preferably set to 0.5 mm or more. Sealing can be reliably performed by setting the thickness to 0.5 mm or more. Above all, the width of the heat seal portion 39 is preferably set to 3 mm to 15 mm.

なお、上記実施形態では、外装部材15が、外装材1を成形して得られた外装ケース10と、平面状の外装材1と、からなる構成であったが(図2、3参照)、特にこのような組み合わせに限定されるものではなく、例えば、外装部材15が、一対の平面状の外装材1からなる構成であってもよいし、或いは、一対の外装ケース10からなる構成であってもよい。 In the above embodiment, the exterior member 15 is composed of an exterior case 10 obtained by molding the exterior material 1 and a flat exterior material 1 (see FIGS. 2 and 3). The combination is not particularly limited, and for example, the exterior member 15 may be composed of a pair of flat exterior materials 1, or may be composed of a pair of exterior cases 10. You may.

次に、本発明の具体的実施例について説明するが、本発明はこれら実施例のものに特に限定されるものではない。 Next, specific examples of the present invention will be described, but the present invention is not particularly limited to those of these examples.

<実施例1>
厚さ35μmのアルミニウム箔4の両面に、リン酸、ポリアクリル酸(アクリル系樹脂)、クロム(III)塩化合物、水、アルコールからなる化成処理液を塗布した後、180℃で乾燥を行って、化成皮膜を形成した。この化成皮膜のクロム付着量は片面当たり10mg/m2であった。
<Example 1>
A chemical conversion treatment solution consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol was applied to both sides of a 35 μm-thick aluminum foil 4, and then dried at 180 ° C. , A chemical conversion film was formed. The amount of chromium adhered to this chemical conversion film was 10 mg / m 2 per side.

次に、前記化成処理済みアルミニウム箔4の一方の面に、2液硬化型のウレタン系接着剤5を介して厚さ5μmの二軸延伸6ナイロンフィルム2をドライラミネートした(貼り合わせた)。 Next, a biaxially stretched 6 nylon film 2 having a thickness of 5 μm was dry-laminated (bonded) on one surface of the chemical conversion-treated aluminum foil 4 via a two-component curable urethane adhesive 5.

次に、エチレン−プロピレンランダム共重合体、1000ppmのエルカ酸アミド(滑剤)、2000ppmのシリカ粒子(平均粒子径1.0μm;非相溶粒子)を含有してなる厚さ4.5μmの第1熱融着性樹脂無延伸フィルム7、エチレン−プロピレンブロック共重合体、1000ppmのエルカ酸アミド(滑剤)、50ppmのシリカ粒子(平均粒子径1.0μm;非相溶粒子)を含有してなる厚さ21μmの第2熱融着性樹脂無延伸フィルム8、エチレン−プロピレンランダム共重合体、1000ppmのエルカ酸アミド(滑剤)、2000ppmのシリカ粒子(平均粒子径1.0μm;非相溶粒子)を含有してなる厚さ4.5μmの第3熱融着性樹脂無延伸フィルム9がこの順で3層積層されるようにTダイを用いて共押出することにより、これら3層が積層されてなる厚さ30μmのシーラントフィルム(第1熱融着性樹脂無延伸フィルム層7/第2熱融着性樹脂無延伸フィルム層8/第3熱融着性樹脂無延伸フィルム層9)3を得た後、該シーラントフィルム3の第3熱融着性樹脂無延伸フィルム層9面を、2液硬化型のマレイン酸変性ポリプロピレン接着剤6を介して、前記ドライラミネート後のアルミニウム箔4の他方の面に重ね合わせて、ゴムニップロールと、100℃に加熱されたラミネートロールとの間に挟み込んで圧着することによりドライラミネートし、ロール軸に巻き取り、しかる後、40℃で10日間エージングした(加熱した)後、ロール軸から引き出すことによって、図1に示す構成の蓄電デバイス用外装材1を得た。 Next, a first 4.5 μm thick containing an ethylene-propylene random copolymer, 1000 ppm erucic acid amide (lubricant), and 2000 ppm silica particles (average particle size 1.0 μm; incompatible particles). Thickness containing heat-sealing resin non-stretched film 7, ethylene-propylene block copolymer, 1000 ppm erucic acid amide (lubricant), 50 ppm silica particles (average particle size 1.0 μm; incompatible particles) 21 μm second heat-sealing resin non-stretched film 8, ethylene-propylene random copolymer, 1000 ppm erucic acid amide (lubricant), 2000 ppm silica particles (average particle size 1.0 μm; incompatible particles). These three layers are laminated by co-extruding using a T-die so that the contained third heat-sealing resin non-stretched film 9 having a thickness of 4.5 μm is laminated in this order. A sealant film having a thickness of 30 μm (first heat-sealing resin non-stretched film layer 7 / second heat-sealing resin non-stretched film layer 8 / third heat-sealing resin non-stretched film layer 9) 3 is obtained. After that, the 9 surfaces of the third heat-sealing resin non-stretched film layer of the sealant film 3 are passed through a two-component curable maleic acid-modified polypropylene adhesive 6 to the other of the aluminum foil 4 after the dry lamination. It was overlapped on the surface, sandwiched between a rubber nip roll and a laminate roll heated to 100 ° C, crimped to dry laminate, wound around a roll shaft, and then aged at 40 ° C for 10 days (heating). After that, the exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained by pulling it out from the roll shaft.

なお、前記2液硬化型マレイン酸変性ポリプロピレン接着剤として、主剤としてのマレイン酸変性ポリプロピレン(融点80℃、酸価10mgKOH/g)100質量部、硬化剤としてのヘキサメチレンジイソシアナートのイソシアヌレート体(NCO含有率:20質量%)8質量部、さらに溶剤が混合されてなる接着剤溶液を用い、該接着剤溶液を固形分塗布量が2g/m2になるように、前記アルミニウム箔4の他方の面に塗布して、加熱乾燥させた後、前記シーラントフィルム3の第3無延伸フィルム層9面に重ね合わせた。 As the two-component curable maleic acid-modified polypropylene adhesive, 100 parts by mass of maleic acid-modified polypropylene (melting point 80 ° C., acid value 10 mgKOH / g) as a main agent, and an isocyanurate of hexamethylene diisocyanate as a curing agent. (NCO content: 20% by mass) Using an adhesive solution prepared by mixing 8 parts by mass and a solvent, the adhesive solution was applied to the aluminum foil 4 so that the solid content coating amount was 2 g / m 2. It was applied to the other surface, dried by heating, and then laminated on the 9th surface of the third non-stretched film layer of the sealant film 3.

<実施例2>
第1熱融着性樹脂層(最内層)7および第3熱融着性樹脂層9におけるシリカ粒子(非相溶粒子)の含有率2000ppmを1000ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 2>
The same as in Example 1 except that the content of silica particles (incompatible particles) in the first heat-sealing resin layer (innermost layer) 7 and the third heat-sealing resin layer 9 was changed to 1000 ppm. Therefore, an exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained.

<実施例3>
第1熱融着性樹脂層(最内層)7および第3熱融着性樹脂層9におけるシリカ粒子(非相溶粒子)の含有率2000ppmを6000ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 3>
The same as in Example 1 except that the content of silica particles (incompatible particles) in the first heat-sealing resin layer (innermost layer) 7 and the third heat-sealing resin layer 9 was changed from 2000 ppm to 6000 ppm. Therefore, an exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained.

<実施例4>
非相溶粒子として、平均粒子径1.0μmのシリカ粒子に代えて、平均粒子径3.0μmのシリカ粒子を用いた以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 4>
As the incompatible particles, the power storage device having the configuration shown in FIG. 1 is the same as in Example 1 except that silica particles having an average particle diameter of 3.0 μm are used instead of silica particles having an average particle diameter of 1.0 μm. Exterior material 1 was obtained.

<実施例5>
非相溶粒子として、平均粒子径1.0μmのシリカ粒子に代えて、平均粒子径4.0μmのシリカ粒子を用いた以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 5>
A power storage device having the configuration shown in FIG. 1 in the same manner as in Example 1 except that silica particles having an average particle diameter of 4.0 μm were used instead of silica particles having an average particle diameter of 1.0 μm as incompatible particles. Exterior material 1 was obtained.

<実施例6>
非相溶粒子として、平均粒子径1.0μmのシリカ粒子に代えて、平均粒子径0.5μmのシリカ粒子を用いた以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 6>
As the incompatible particles, the power storage device having the configuration shown in FIG. 1 is the same as in Example 1 except that silica particles having an average particle diameter of 0.5 μm are used instead of silica particles having an average particle diameter of 1.0 μm. Exterior material 1 was obtained.

<実施例7>
第2熱融着性樹脂層8におけるエルカ酸アミド含有率1000ppmを6000ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 7>
An exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1 except that the erucic acid amide content in the second heat-sealing resin layer 8 was changed from 1000 ppm to 6000 ppm.

<実施例8>
第2熱融着性樹脂層8におけるエルカ酸アミド含有率1000ppmを400ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 8>
An exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1 except that the erucic acid amide content of 1000 ppm in the second heat-sealing resin layer 8 was changed to 400 ppm.

<実施例9>
第1熱融着性樹脂層7および第3熱融着性樹脂層9におけるエルカ酸アミド含有率1000ppmを3000ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 9>
A power storage device having the configuration shown in FIG. 1 in the same manner as in Example 1 except that the erucic acid amide content of 1000 ppm in the first heat-sealing resin layer 7 and the third heat-sealing resin layer 9 was changed to 3000 ppm. Exterior material 1 was obtained.

<実施例10>
第1熱融着性樹脂層7および第3熱融着性樹脂層9におけるエルカ酸アミド含有率1000ppmを50ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 10>
A power storage device having the configuration shown in FIG. 1 in the same manner as in Example 1 except that the erucic acid amide content of 1000 ppm in the first heat-sealing resin layer 7 and the third heat-sealing resin layer 9 was changed to 50 ppm. Exterior material 1 was obtained.

<実施例11>
第1熱融着性樹脂層7の厚さ4.5μmを1.0μmに変更し、第3熱融着性樹脂層9の厚さ4.5μmを8.0μmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 11>
Examples except that the thickness of the first heat-sealing resin layer 7 was changed from 4.5 μm to 1.0 μm and the thickness of the third heat-sealing resin layer 9 was changed to 8.0 μm. In the same manner as in No. 1, an exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained.

<実施例12>
第1熱融着性樹脂層7の厚さ4.5μmを10μmに変更し、第2熱融着性樹脂層8の厚さ21μmを16μmに変更し、第3熱融着性樹脂層9の厚さ4.5μmを4.0μmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 12>
The thickness of the first heat-sealing resin layer 7 was changed from 4.5 μm to 10 μm, the thickness of the second heat-sealing resin layer 8 was changed to 16 μm, and the thickness of the third heat-sealing resin layer 9 was changed to 16 μm. An exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1 except that the thickness of 4.5 μm was changed to 4.0 μm.

<実施例13>
第2熱融着性樹脂層8におけるシリカ粒子(非相溶粒子)の含有率50ppmを75ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 13>
Exterior material 1 for power storage device having the configuration shown in FIG. 1 in the same manner as in Example 1 except that the content of silica particles (incompatible particles) in the second heat-sealing resin layer 8 was changed from 50 ppm to 75 ppm. Got

<実施例14>
第2熱融着性樹脂層8におけるシリカ粒子(非相溶粒子)の含有率50ppmを25ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 14>
Exterior material 1 for power storage device having the configuration shown in FIG. 1 in the same manner as in Example 1 except that the content of silica particles (incompatible particles) in the second heat-sealing resin layer 8 was changed from 50 ppm to 25 ppm. Got

<実施例15>
第2熱融着性樹脂層8におけるシリカ粒子(非相溶粒子)の含有率50ppmを0ppmに変更した(非相溶粒子を非含有とした)以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 15>
The figure is the same as in Example 1 except that the content of silica particles (incompatible particles) in the second heat-sealing resin layer 8 is changed from 50 ppm to 0 ppm (incompatible particles are not contained). An exterior material 1 for a power storage device having the configuration shown in 1 was obtained.

<実施例16>
非相溶粒子として、平均粒子径1.0μmのシリカ粒子に代えて、平均粒子径2.0μmのシリカ粒子を用いた以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 16>
As the incompatible particles, the power storage device having the configuration shown in FIG. 1 is the same as in Example 1 except that silica particles having an average particle diameter of 2.0 μm are used instead of silica particles having an average particle diameter of 1.0 μm. Exterior material 1 was obtained.

<実施例17>
非相溶粒子として、平均粒子径1.0μmのシリカ粒子に代えて、平均粒子径1.0μmの炭酸バリウム粒子を用いた以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 17>
As the incompatible particles, the storage storage having the configuration shown in FIG. 1 is the same as in Example 1 except that barium carbonate particles having an average particle diameter of 1.0 μm are used instead of silica particles having an average particle diameter of 1.0 μm. The exterior material 1 for the device was obtained.

<実施例18>
非相溶粒子として、平均粒子径1.0μmのシリカ粒子に代えて、平均粒子径1.0μmのアクリル樹脂ビーズ(粒子)を用いた以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 18>
As the incompatible particles, FIG. 1 shows in the same manner as in Example 1 except that acrylic resin beads (particles) having an average particle diameter of 1.0 μm were used instead of silica particles having an average particle diameter of 1.0 μm. An exterior material 1 for a power storage device having a configuration was obtained.

<実施例19>
滑剤として、エルカ酸アミドに代えて、ベヘン酸アミドを用いた以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 19>
An exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1 except that bechenic acid amide was used as the lubricant instead of erucic acid amide.

<実施例20>
第3熱融着性樹脂層9におけるシリカ粒子(非相溶粒子)の含有率2000ppmを50ppmに変更した以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 20>
Exterior material 1 for power storage device having the configuration shown in FIG. 1 in the same manner as in Example 1 except that the content of silica particles (incompatible particles) in the third heat-sealing resin layer 9 was changed from 2000 ppm to 50 ppm. Got

<実施例21>
第3熱融着性樹脂層9におけるシリカ粒子(非相溶粒子)の含有率2000ppmを0ppmに変更した(非相溶粒子を非含有とした)以外は、実施例1と同様にして、図1に示す構成の蓄電デバイス用外装材1を得た。
<Example 21>
The figure is the same as in Example 1 except that the content of silica particles (incompatible particles) in the third heat-sealing resin layer 9 is changed from 2000 ppm to 0 ppm (incompatible particles are not contained). An exterior material 1 for a power storage device having the configuration shown in 1 was obtained.

<比較例1>
第2熱融着性樹脂層8におけるシリカ粒子(非相溶粒子)の含有率50ppmを150ppmに変更した以外は、実施例1と同様にして、蓄電デバイス用外装材を得た。
<Comparative example 1>
An exterior material for a power storage device was obtained in the same manner as in Example 1 except that the content of silica particles (incompatible particles) in the second heat-sealing resin layer 8 was changed from 50 ppm to 150 ppm.

<比較例2>
第1熱融着性樹脂層(最内層)7におけるシリカ粒子(非相溶粒子)の含有率2000ppmを800ppmに変更した以外は、実施例1と同様にして、蓄電デバイス用外装材を得た。
<Comparative example 2>
An exterior material for a power storage device was obtained in the same manner as in Example 1 except that the content of silica particles (incompatible particles) in the first heat-sealing resin layer (innermost layer) 7 was changed from 2000 ppm to 800 ppm. ..

<比較例3>
第1熱融着性樹脂層(最内層)7におけるシリカ粒子(非相溶粒子)の含有率2000ppmを6500ppmに変更した以外は、実施例1と同様にして、蓄電デバイス用外装材を得た。
<Comparative example 3>
An exterior material for a power storage device was obtained in the same manner as in Example 1 except that the content of silica particles (incompatible particles) in the first heat-sealing resin layer (innermost layer) 7 was changed from 2000 ppm to 6500 ppm. ..

<比較例4>
シーラントフィルム3として、エチレン−プロピレンランダム共重合体、1000ppmのエルカ酸アミド(滑剤)、2000ppmのシリカ粒子(平均粒子径1.0μm;非相溶粒子)を含有してなる厚さ30μmの熱融着性樹脂無延伸フィルム(単層)を用いた以外は、実施例1と同様にして、蓄電デバイス用外装材を得た。
<Comparative example 4>
The sealant film 3 contains an ethylene-propylene random copolymer, 1000 ppm of erucic acid amide (lubricant), and 2000 ppm of silica particles (average particle size 1.0 μm; incompatible particles), and has a thickness of 30 μm. An exterior material for a power storage device was obtained in the same manner as in Example 1 except that a non-stretched film (single layer) made of a resin was used.

<比較例5>
シーラントフィルム3として、エチレン−プロピレンブロック共重合体、1000ppmのエルカ酸アミド(滑剤)、50ppmのシリカ粒子(平均粒子径1.0μm;非相溶粒子)を含有してなる厚さ30μmの熱融着性樹脂無延伸フィルム(単層)を用いた以外は、実施例1と同様にして、蓄電デバイス用外装材を得た。
<Comparative example 5>
As the sealant film 3, a heat fusion having a thickness of 30 μm containing an ethylene-propylene block copolymer, 1000 ppm of erucic acid amide (lubricant), and 50 ppm of silica particles (average particle diameter 1.0 μm; incompatible particles). An exterior material for a power storage device was obtained in the same manner as in Example 1 except that a non-stretched film (single layer) was used.

<比較例6>
第1熱融着性樹脂層7の厚さ4.5μmを10μmに変更し、第2熱融着性樹脂層8の厚さ21μmを10μmに変更し、第3熱融着性樹脂層9の厚さ4.5μmを10μmに変更し、第2熱融着性樹脂層8を構成する樹脂として、エチレン−プロピレンブロック共重合体に代えて、エチレン−プロピレンランダム共重合体を用いた以外は、実施例1と同様にして、蓄電デバイス用外装材を得た。
<Comparative Example 6>
The thickness of the first heat-sealing resin layer 7 was changed from 4.5 μm to 10 μm, the thickness of the second heat-sealing resin layer 8 was changed to 10 μm, and the thickness of the third heat-sealing resin layer 9 was changed to 10 μm. Except that the thickness of 4.5 μm was changed to 10 μm and an ethylene-propylene random copolymer was used as the resin constituting the second heat-sealing resin layer 8 instead of the ethylene-propylene block copolymer. An exterior material for a power storage device was obtained in the same manner as in Example 1.

<比較例7>
非相溶粒子として、平均粒子径1.0μmのシリカ粒子に代えて、平均粒子径0.2μmのシリカ粒子を用いた以外は、実施例1と同様にして、蓄電デバイス用外装材を得た。
<Comparative Example 7>
As the incompatible particles, an exterior material for a power storage device was obtained in the same manner as in Example 1 except that silica particles having an average particle diameter of 0.2 μm were used instead of silica particles having an average particle diameter of 1.0 μm. ..

<比較例8>
非相溶粒子として、平均粒子径1.0μmのシリカ粒子に代えて、平均粒子径5.0μmのシリカ粒子を用いた以外は、実施例1と同様にして、蓄電デバイス用外装材を得た。
<Comparative Example 8>
As the incompatible particles, an exterior material for a power storage device was obtained in the same manner as in Example 1 except that silica particles having an average particle diameter of 5.0 μm were used instead of silica particles having an average particle diameter of 1.0 μm. ..

<算術平均高さの測定法>
上記のようにして得られた各蓄電デバイス用外装材の第1熱融着性樹脂層(最内層)7の表面7aの算術平均平均高さ(Sa)を次のようにして求めた。即ち、日立ハイテクノロジーズ株式会社製の走査型白色干渉顕微鏡VS1330を用いて、対物レンズ:5倍、中間レンズ:1倍、カメラ:1/3”の条件で5倍単視野(938mm×703mm)で、前記外装材1の最内層7の表面7aの算術平均高さ(Sa)を求めた。
<Measurement method of arithmetic mean height>
The arithmetic mean average height (Sa) of the surface 7a of the first heat-sealing resin layer (innermost layer) 7 of the exterior material for each power storage device obtained as described above was determined as follows. That is, using the scanning white interference microscope VS1330 manufactured by Hitachi High-Technologies Corporation, the objective lens: 5x, the intermediate lens: 1x, and the camera: 1/3 "with a 5x single field of view (938mm x 703mm). , The arithmetic average height (Sa) of the surface 7a of the innermost layer 7 of the exterior material 1 was determined.

Figure 0006936093
Figure 0006936093

Figure 0006936093
Figure 0006936093

Figure 0006936093
Figure 0006936093

上記のようにして得られた各蓄電デバイス用外装材について下記評価法に基づいて評価を行った。その結果を表3に示す。 The exterior materials for each power storage device obtained as described above were evaluated based on the following evaluation methods. The results are shown in Table 3.

<成形性評価法>
成形深さフリーのストレート金型を用いて外装材に対し下記成形条件で深絞り1段成形を行い、各成形深さ(9.0mm、8.5mm、8.0mm、7.5mm、7.0mm、6.5mm、6.0mm、5.5mm、5.0mm、4.5mm、4.0mm、3.5mm、3.0mm、2.5mm、2.0mm)毎に成形性を評価し、コーナー部にピンホールが全く発生しない良好な成形を行うことができる最大成形深さ(mm)を調べ、下記判定基準に基づいて成形性を評価した。なお、ピンホールの有無は、ピンホールを透過してくる透過光の有無を目視により観察することにより調べた。
(成形条件)
成形型…パンチ:33.3mm×53.9mm、ダイ:80mm×120mm、コーナーR:2mm、パンチR:1.3mm、ダイR:1mm
しわ押さえ圧…ゲージ圧:0.475MPa、実圧(計算値):0.7MPa
材質…SC(炭素鋼)材、パンチRのみクロムメッキ。
(判定基準)
「◎」…ピンホール及び割れが発生しない最大成形深さが7.0mm以上である
「○」…ピンホール及び割れが発生しない最大成形深さが5.0mm以上7.0mm未満である
「×」…ピンホール及び割れが発生しない最大成形深さが5.0mm未満である。
<Moldability evaluation method>
Using a straight mold with no molding depth, the exterior material was deep-drawn and one-stage molded under the following molding conditions, and each molding depth (9.0 mm, 8.5 mm, 8.0 mm, 7.5 mm, 7. Moldability was evaluated for each 0 mm, 6.5 mm, 6.0 mm, 5.5 mm, 5.0 mm, 4.5 mm, 4.0 mm, 3.5 mm, 3.0 mm, 2.5 mm, 2.0 mm). The maximum molding depth (mm) capable of performing good molding with no pinholes generated at the corners was investigated, and the moldability was evaluated based on the following criteria. The presence or absence of pinholes was examined by visually observing the presence or absence of transmitted light transmitted through the pinholes.
(Molding condition)
Molding mold: Punch: 33.3 mm x 53.9 mm, Die: 80 mm x 120 mm, Corner R: 2 mm, Punch R: 1.3 mm, Die R: 1 mm
Wrinkle pressing pressure: Gauge pressure: 0.475 MPa, actual pressure (calculated value): 0.7 MPa
Material: SC (carbon steel) material, punch R only chrome plated.
(criterion)
"◎" ... The maximum molding depth at which pinholes and cracks do not occur is 7.0 mm or more. "○" ... The maximum molding depth at which pinholes and cracks do not occur is 5.0 mm or more and less than 7.0 mm. The maximum molding depth at which pinholes and cracks do not occur is less than 5.0 mm.

<白濁防止性評価法>
アルミニウム箔4に接着積層する前のシーラントフィルム3単体を準備し、JIS K7136−2000に準拠してヘーズメーター(株式会社村上色彩技術研究所製「HM−150」)を用いてヘーズ率(ヘイズ率)を測定し、下記判定基準に基づいて評価した。
(判定基準)
「◎」…ヘーズ率が3%未満である(デラミネーション等の欠陥有無検査の視認性に優れる)
「○」…ヘーズ率が3%以上10%未満である(デラミネーション等の欠陥有無検査の視認性が良好である)
「×」…ヘーズ率が10%以上である(デラミネーション等の欠陥有無検査の視認性が悪い)。
<Evaluation method for white turbidity prevention>
Prepare the sealant film 3 alone before adhesively laminating it on the aluminum foil 4, and use a haze meter (“HM-150” manufactured by Murakami Color Technology Research Institute Co., Ltd.) in accordance with JIS K7136-2000 to achieve the haze rate (haze rate). ) Was measured and evaluated based on the following criteria.
(criterion)
“◎”… Haze rate is less than 3% (excellent in visibility of defect inspection such as delamination)
“○”… Haze rate is 3% or more and less than 10% (good visibility of defect presence inspection such as delamination)
“X”: The haze rate is 10% or more (the visibility of defect inspection such as delamination is poor).

<白粉の有無(白粉表出防止性)評価法>
各蓄電デバイス用外装材から縦600mm×横100mmの矩形状の試験片を切り出した後、得られた試験片を内側層3面(即ち最内層の表面7a)を上側にして試験台の上に載置し、この試験片の上面に、黒色のウェスが巻き付けられて表面が黒色を呈しているSUS製錘(質量1.3kg、接地面の大きさが55mm×50mm)を載せた状態で、該錘を試験片の上面と平行な水平方向に引張速度4cm/秒で引っ張ることによって錘を試験片の上面に接触状態で長さ400mmにわたって引張移動させた。引張移動後の錘の接触面のウェス(黒色)を目視で観察し、ウェス(黒色)の表面に白粉が顕著に生じていたものを「×」とし、白粉が僅かに生じていたに過ぎないものを「○」とし、白粉が殆どないか又は白粉が認められなかったものを「◎」とした。なお、上記黒色のウェスとしては、TRUSCO社製「静電気除去シートS SD2525 3100」を使用した。
<Presence / absence of white powder (prevention of white powder appearance) evaluation method>
After cutting out a rectangular test piece of 600 mm in length × 100 mm in width from the exterior material for each power storage device, the obtained test piece is placed on a test table with the inner layer 3 surfaces (that is, the innermost layer surface 7a) facing up. A SUS weight (mass 1.3 kg, ground plane size 55 mm x 50 mm) with a black waste cloth wrapped around the test piece and having a black surface is placed on the upper surface of the test piece. By pulling the weight in the horizontal direction parallel to the upper surface of the test piece at a tensile speed of 4 cm / sec, the weight was pulled and moved over a length of 400 mm in contact with the upper surface of the test piece. The waste (black) on the contact surface of the weight after the tensile movement was visually observed, and the one where white powder was prominently generated on the surface of the waste (black) was marked with "x", and only a small amount of white powder was generated. Those with almost no white powder or no white powder were marked with "○". As the black waste cloth, TRUSCO's "Static electricity removal sheet S SD2525 3100" was used.

表から明らかなように、本発明の実施例1〜21の蓄電デバイス用外装材は、最大成形深さが5.0mm以上であり、良好な成形性を確保できると共に、外装材における白濁を抑制できてデラミネーション等の欠陥有無検査の視認性が良好であるし、外装材の表面に白粉が表出し難いものであった。 As is clear from the table, the exterior materials for power storage devices of Examples 1 to 21 of the present invention have a maximum molding depth of 5.0 mm or more, can ensure good moldability and suppress white turbidity in the exterior materials. As a result, the visibility of the inspection for defects such as delamination was good, and it was difficult for white powder to appear on the surface of the exterior material.

これに対し、本発明の規定範囲を逸脱する比較例1〜8では、成形性、白濁防止性、白粉表出防止性のいずれかの評価が悪かった。 On the other hand, in Comparative Examples 1 to 8 which deviated from the specified range of the present invention, any one of the moldability, the white turbidity prevention property, and the white powder expression prevention property was poorly evaluated.

本発明に係る蓄電デバイス用外装材は、具体例として、例えば、
・リチウム2次電池(リチウムイオン電池、リチウムポリマー電池等)などの蓄電デバイス
・リチウムイオンキャパシタ
・電気2重層コンデンサ
等の各種蓄電デバイスの外装材として用いられる。また、本発明に係る蓄電デバイスは、上記例示した蓄電デバイスの他、全固体電池も含む。
As a specific example, the exterior material for a power storage device according to the present invention is, for example,
-Used as an exterior material for various power storage devices such as power storage devices such as lithium secondary batteries (lithium ion batteries, lithium polymer batteries, etc.), lithium ion capacitors, and electric double-layer capacitors. Further, the power storage device according to the present invention includes an all-solid-state battery in addition to the power storage device exemplified above.

1…蓄電デバイス用外装材
2…基材層(外側層)
3…熱融着性樹脂層(内側層)
4…金属箔層
7…第1熱融着性樹脂層(最内層)
8…第2熱融着性樹脂層
9…第3熱融着性樹脂層
10…外装ケース
15…外装部材
30…蓄電デバイス
31…蓄電デバイス本体部
1 ... Exterior material for power storage device 2 ... Base material layer (outer layer)
3 ... Heat-sealing resin layer (inner layer)
4 ... Metal leaf layer 7 ... First heat-sealing resin layer (innermost layer)
8 ... 2nd heat-sealing resin layer 9 ... 3rd heat-sealing resin layer 10 ... Exterior case 15 ... Exterior member 30 ... Power storage device 31 ... Power storage device main body

Claims (8)

外側層としての基材層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層と、を含む蓄電デバイス用外装材であって、
前記熱融着性樹脂層は、外装材の最内層を形成する第1熱融着性樹脂層と、該第1熱融着性樹脂層における前記金属箔層側の面に積層された第2熱融着性樹脂層と、該第2熱融着性樹脂層における前記金属箔層側の面に積層された又は前記金属箔層側に配置された第3熱融着性樹脂層と、を含む3層以上の積層体からなり、
前記第1熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体と、滑剤と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有する第1樹脂組成物からなり、前記第1樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であり、前記第1樹脂組成物における前記非相溶粒子の含有率が1000ppm〜6000ppmの範囲であり、
前記第2熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するブロック共重合体と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有する第2樹脂組成物からなり、前記第2樹脂組成物における前記ブロック共重合体の含有率が50質量%以上であり、前記第2樹脂組成物における前記非相溶粒子の含有率が0ppmを超えて100ppm以下であり、
前記第3熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体を含有する第3樹脂組成物からなり、前記第3樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であることを特徴とする蓄電デバイス用外装材。
An exterior material for a power storage device including a base material layer as an outer layer, a heat-sealing resin layer as an inner layer, and a metal foil layer arranged between both layers.
The heat-sealing resin layer is formed by laminating a first heat-sealing resin layer forming the innermost layer of the exterior material and a second surface of the first heat-sealing resin layer on the metal leaf layer side. The heat-sealing resin layer and the third heat-sealing resin layer laminated on the surface of the second heat-sealing resin layer on the metal leaf layer side or arranged on the metal leaf layer side are provided. Consists of three or more layers including
The first heat-sealing resin layer is incompatible with a random copolymer containing propylene and other copolymerization components other than propylene as copolymerization components, a lubricant, and an average particle size of 0.5 μm to 4 μm. The first resin composition containing particles, the content of the random copolymer in the first resin composition is 50% by mass or more, and the incompatible particles in the first resin composition. The content is in the range of 1000 ppm to 6000 ppm and
The second heat-sealing resin layer comprises a block copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene, and incompatible particles having an average particle size of 0.5 μm to 4 μm. The content of the block copolymer in the second resin composition is 50% by mass or more, and the content of the incompatible particles in the second resin composition is 50% by mass or more. More than 0 ppm and less than 100 ppm,
The third heat-sealing resin layer comprises a third resin composition containing a random copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene, and the third resin composition. An exterior material for a power storage device, characterized in that the content of the random copolymer is 50% by mass or more.
外側層としての基材層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層と、を含む蓄電デバイス用外装材であって、
前記熱融着性樹脂層は、外装材の最内層を形成する第1熱融着性樹脂層と、該第1熱融着性樹脂層における前記金属箔層側の面に積層された第2熱融着性樹脂層と、該第2熱融着性樹脂層における前記金属箔層側の面に積層された又は前記金属箔層側に配置された第3熱融着性樹脂層と、を含む3層以上の積層体からなり、
前記第1熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体と、滑剤と、平均粒子径が0.5μm〜4μmの非相溶粒子と、を含有する第1樹脂組成物からなり、前記第1樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であり、前記第1樹脂組成物における前記非相溶粒子の含有率が1000ppm〜6000ppmの範囲であり、
前記第2熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するブロック共重合体を含有し、非相溶粒子を含有しない第2樹脂組成物からなり、前記第2樹脂組成物における前記ブロック共重合体の含有率が50質量%以上であり、
前記第3熱融着性樹脂層は、共重合成分としてプロピレン及びプロピレンを除く他の共重合成分を含有するランダム共重合体を含有する第3樹脂組成物からなり、前記第3樹脂組成物における前記ランダム共重合体の含有率が50質量%以上であることを特徴とする蓄電デバイス用外装材。
An exterior material for a power storage device including a base material layer as an outer layer, a heat-sealing resin layer as an inner layer, and a metal foil layer arranged between both layers.
The heat-sealing resin layer is formed by laminating a first heat-sealing resin layer forming the innermost layer of the exterior material and a second surface of the first heat-sealing resin layer on the metal leaf layer side. The heat-sealing resin layer and the third heat-sealing resin layer laminated on the surface of the second heat-sealing resin layer on the metal leaf layer side or arranged on the metal leaf layer side are provided. Consists of three or more layers including
The first heat-sealing resin layer is incompatible with a random copolymer containing propylene and other copolymerization components other than propylene as copolymerization components, a lubricant, and an average particle size of 0.5 μm to 4 μm. The first resin composition containing particles, the content of the random copolymer in the first resin composition is 50% by mass or more, and the incompatible particles in the first resin composition. The content is in the range of 1000 ppm to 6000 ppm and
The second heat-sealing resin layer comprises a second resin composition containing a block copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene, and not containing incompatible particles. , The content of the block copolymer in the second resin composition is 50% by mass or more.
The third heat-sealing resin layer comprises a third resin composition containing a random copolymer containing propylene as a copolymerization component and other copolymerization components other than propylene, and the third resin composition. An exterior material for a power storage device, characterized in that the content of the random copolymer is 50% by mass or more.
前記第3樹脂組成物は、非相溶粒子を含有しない組成である、又は平均粒子径が0.5μm〜4μmの非相溶粒子を0ppmを超えて6000ppm以下含有する組成である請求項1または2に記載の蓄電デバイス用外装材。 The third resin composition is a composition that does not contain incompatible particles, or a composition that contains incompatible particles having an average particle size of 0.5 μm to 4 μm in an amount of more than 0 ppm and 6000 ppm or less. 2. The exterior material for a power storage device according to 2. 前記第1熱融着性樹脂層の内側の表面の算術平均高さ(Sa)が50nm〜200nmである請求項1〜3のいずれか1項に記載の蓄電デバイス用外装材。 The exterior material for a power storage device according to any one of claims 1 to 3, wherein the arithmetic mean height (Sa) of the inner surface of the first heat-sealing resin layer is 50 nm to 200 nm. 前記第1樹脂組成物における前記滑剤の含有率が100ppm〜2000ppmであり、前記第2樹脂組成物は、さらに滑剤を含有し、該第2樹脂組成物における滑剤の含有率が500ppm〜5000ppmである請求項1〜4のいずれか1項に記載の蓄電デバイス用外装材。 The content of the lubricant in the first resin composition is 100 ppm to 2000 ppm, the second resin composition further contains a lubricant, and the content of the lubricant in the second resin composition is 500 ppm to 5000 ppm. The exterior material for a power storage device according to any one of claims 1 to 4. 前記熱融着性樹脂層は、前記第1熱融着性樹脂層、前記第2熱融着性樹脂層および前記第3熱融着性樹脂層からなり、
前記第1熱融着性樹脂層の厚さは、前記熱融着性樹脂層の全体厚さの5%〜30%である請求項1〜5のいずれか1項に記載の蓄電デバイス用外装材。
The heat-sealing resin layer comprises the first heat-sealing resin layer, the second heat-sealing resin layer, and the third heat-sealing resin layer.
The exterior for a power storage device according to any one of claims 1 to 5, wherein the thickness of the first heat-sealing resin layer is 5% to 30% of the total thickness of the heat-sealing resin layer. Material.
請求項1〜6のいずれか1項に記載の蓄電デバイス用外装材の成形体からなる蓄電デバイス用外装ケース。 An exterior case for a power storage device made of a molded body of the exterior material for the power storage device according to any one of claims 1 to 6. 蓄電デバイス本体部と、
請求項1〜6のいずれか1項に記載の蓄電デバイス用外装材および請求項7に記載の蓄電デバイス用外装ケースからなる群より選ばれる1種または2種の外装部材とを備え、
前記蓄電デバイス本体部が、前記外装部材で外装されていることを特徴とする蓄電デバイス。
Power storage device body and
It is provided with one or two types of exterior members selected from the group consisting of the exterior material for a power storage device according to any one of claims 1 to 6 and the exterior case for a power storage device according to claim 7.
A power storage device characterized in that the power storage device main body is covered with the exterior member.
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