TWI752039B - Sealing film for exterior material of electric storage device, exterior material for electric storage device, and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a sealing film for an exterior material of a power storage device, wherein the sealing film 3 comprises at least one non-stretching film layer, and the non-stretching film layer contains: propylene-based polymer; selected from saturated fatty acid amides and at least one first lubricant selected from the group consisting of unsaturated fatty acid diamides; and at least one second lubricant selected from the group consisting of fatty acid diamides and aromatic diamides. With this configuration, it is possible to provide a sealing film for an exterior material of an electrical storage device, which can suppress the decrease in the amount of lubricant due to precipitation on the surface of the exterior material, has excellent formability, and is less likely to have white powder on the surface.

Description

Sealing film for exterior material of electrical storage device, exterior material for electrical storage device, and method for producing the same

The present invention relates to batteries or capacitors used in portable devices such as smartphones and touch panels, batteries or capacitors used in hybrid vehicles, electric vehicles, wind power generation, solar power generation, and night-time power storage, etc., and constitute power storage devices thereof. A sealing film used for an exterior material, an exterior material for a power storage device using the sealing film, and a method for producing the same.

In addition, the term "fatty acid amide" in the scope of the present application and this specification is used without including "fatty acid bisamide".

In recent years, with the thinning and weight reduction of portable devices such as smartphones and touch panel terminals, the external packaging of power storage devices such as lithium-ion batteries, lithium-polymer batteries, lithium-ion capacitors, and electric double-layer capacitors has been carried out. In place of traditional metal cans, a laminate consisting of a heat-resistant resin layer/adhesive layer/metal foil layer/adhesive layer/thermoplastic resin layer (inside sealing layer) is used. In addition, the number of power sources for electric vehicles and the like, large-scale power sources for power storage, capacitors, and the like are also increased by the laminates (exterior materials) configured as described above. The above-mentioned laminated body is formed into a three-dimensional shape such as a roughly rectangular parallelepiped shape by bulging or deep drawing. By forming such a three-dimensional shape, an accommodation space for accommodating the main body of the power storage device can be secured.

In order to form such a three-dimensional shape into a good shape without pinholes or cracks, it is required to improve the surface smoothness of the inner sealing layer. In order to improve the surface smoothness of the inner sealing layer and ensure good formability, a laminated material for a battery container is proposed, wherein an exterior resin film, a first adhesive layer, a chemical conversion-treated aluminum foil, and a second adhesive layer are laminated in this order. , Sealing film; the sealing film is composed of a random copolymer of propylene and α-olefin containing 2 to 10% by weight of α-olefin, and contains 1000 to 5000 ppm of lubricant (refer to Patent Document 1).

【Prior technical literature】 【Patent Literature】

[Patent Document 1] Japanese Patent Laid-Open No. 2003-288865

However, in the above-mentioned conventional technology, it is difficult to control the precipitation amount of the surface lubricant during the heating and holding time or during the storage period in the production process of the exterior material (laminated material). Although the smoothness during molding is good, the lubricant is excessive on the surface. When the exterior material is formed, the lubricant adheres and accumulates on the molding surface of the molding die to generate white powder (white powder generated from the lubricant). In such a state that the white powder adheres and accumulates on the molding surface, it is difficult to perform good molding. Therefore, it is necessary to clean and remove the white powder every time the white powder adheres and accumulates. This cleaning and removal of the white powder increases the productivity of the exterior material. lowering problem.

Of course, if the amount of lubricant added (lubricant content) is reduced, the adhesion and accumulation of white powder can be suppressed, but in this case, there is a problem that the amount of precipitation of the surface lubricant is insufficient and the formability is deteriorated. With such a conventional technique, it is difficult to achieve both excellent formability and suppression of the occurrence of white powder on the surface of the exterior material.

The present invention has been made in view of the background of the related art, and an object of the present invention is to provide a sealing film for an exterior material of an electrical storage device, an exterior material for an electrical storage device, and a method for producing the same, which can suppress the slippage deposited on the surface of the exterior material. The dosage is reduced, and while ensuring good smoothness and excellent formability, white powder is difficult to appear on the surface.

In order to achieve the aforementioned objects, the present invention provides the following technical means.

[1] A sealing film for an exterior material of a power storage device, which is characterized by comprising at least one non-stretching film layer, and the non-stretching film layer contains: a propylene-based polymer; At least one first lubricant selected from the group consisting of saturated fatty acid amides; and at least one second lubricant selected from the group consisting of fatty acid diamides and aromatic diamides.

[2] A sealing film for an exterior material of a power storage device, characterized in that it is formed of a non-stretchable film layer, and the non-stretchable film layer contains: a propylene-based polymer; selected from saturated fatty acid amides and unsaturated fatty acid amides The first moisturizing agent of at least one of the group of amines A lubricant; and at least one second lubricant selected from the group consisting of fatty acid bisamide and aromatic bisamide.

[3] A sealing film for an exterior material of a power storage device, characterized by being formed of a laminate of two or more layers, and the laminate system comprising a first non-stretching film layer, and a layer laminated on the first non-stretching film layer; The second non-stretch film layer on one side; the first non-stretch film layer, which forms the innermost layer of the exterior material; the first non-stretch film layer, which contains: propylene containing copolymer components and excluding propylene A random copolymer of other copolymer components, and a lubricant; the second non-stretched film layer contains: a block copolymer containing propylene as a copolymer component and a block copolymer of other copolymer components other than propylene, and a lubricant; and The lubricant in the first unstretched film layer and/or the lubricant in the second unstretched film layer contains: at least one selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides 1. A lubricant, and at least one second lubricant selected from the group consisting of fatty acid bisamide and aromatic bisamide.

[4] A sealing film for an exterior material of an electrical storage device, characterized by being formed of a laminate of three or more layers, and the laminate system comprising a second non-stretching film layer laminated on one of the second non-stretching film layers The first unstretched film layer on the side surface, and the first unstretched film layer laminated on the other side of the second unstretched film layer; The innermost layer of the packaging material; the aforementioned first non-stretched film layer contains: a random copolymer of propylene containing a copolymer component and other copolymer components other than propylene, and a lubricant; The second unstretched film layer comprises: a block copolymer containing propylene as a copolymer component and a copolymer component other than propylene, and a lubricant; and the first unstretched layer forming the innermost layer of the exterior material The lubricant in the film layer and/or the lubricant in the second non-stretched film layer contains: at least one first lubricant selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides, and At least one second lubricant selected from the group consisting of fatty acid bisamide and aromatic bisamide.

[5] The sealing film for an exterior material of a power storage device as described in the preceding paragraph 3 or 4, wherein the total concentration of the lubricant contained in the first non-stretched film layer is 200 ppm to 7000 ppm, and the second The total value of the content concentration of all the lubricants contained in the unstretched film layer is 500 ppm to 7000 ppm.

[6] The sealing film for an exterior material of an electrical storage device as described in any one of the preceding paragraphs 1 to 5, wherein the layer containing the second lubricant is based on the total concentration of the lubricant in the layer. value, the ratio of the concentration of the second lubricant is 5% to 90%.

[7] An exterior material for a power storage device, characterized by comprising: an inner sealing layer formed of the sealing film described in any one of 1 to 6 above, and a metal foil layer laminated on one side of the inner sealing layer .

[8] An exterior material for a power storage device, characterized by comprising: a heat-resistant resin layer as an outer layer, an inner sealing layer formed of the sealing film described in any one of the preceding paragraphs 1 to 6, and an inner sealing layer disposed between these two layers the metal foil layer.

[9] The exterior material for an electricity storage device as described in the preceding paragraph 7 or 8, wherein the amount of lubricant present in the surface of the first non-stretched thin film layer forming the innermost layer of the exterior material is 0.1 μg/ cm ² ~1.0μg/cm ^{2 in} the range.

[10] An exterior case for a power storage device, comprising a molded body of the exterior material according to any one of the items 7 to 9 above.

[11] A method of manufacturing an exterior material for an electrical storage device, comprising: a preparation step of preparing a laminate, wherein the laminate system includes the sealing film according to any one of the preceding items 1 to 6 via a first adhesive and a laminate. It is obtained by laminating metal foils; in the aging step, the above-mentioned laminated body is heat-treated to obtain an exterior material for an electrical storage device.

[12] The method for producing an exterior material for an electrical storage device according to the above item 11, wherein the first adhesive is a thermosetting adhesive.

[13] A method of manufacturing an exterior material for an electrical storage device, comprising: a preparation step of preparing a laminate, wherein one side of the laminate system metal foil is laminated via a second adhesive and a heat-resistant resin film, The other side surface of the metal foil is composed of a laminate of the first adhesive and the sealing film described in any one of 1 to 6 above; in the aging step, the laminate is heat-treated to obtain an outer casing for an electrical storage device material.

[14] The method for producing an exterior material for an electrical storage device according to the above item 13, wherein the first adhesive is a thermosetting adhesive, and the second adhesive is a thermosetting adhesive.

[15] The method for producing an exterior material for an electrical storage device according to any one of Items 11 to 14 above, wherein the first unstretched thin film layer is obtained by heat treatment to form the innermost part of the exterior material for an electrical storage device layer, and the amount of lubricant present on its surface is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .

According to the invention of [1], since the non-stretchable film layer includes at least one non-stretchable film layer, and the non-stretched film layer contains the above-mentioned specific first lubricant and the above-mentioned specific second lubricant, it exists in the outer casing material. The reduction in the amount of (precipitated) lubricant on the surface (surface of the inner seal layer) can be suppressed, thereby ensuring good sliding properties during molding, excellent formability, and less white powder on the surface of the exterior material. In addition, since the amount of lubricant existing on the surface of the exterior material does not change due to the thermal history during transportation or storage, it is possible to provide the exterior material with excellent formability and stability.

According to the invention of [2], since the sealing film is composed of the non-stretching film layer containing the above-mentioned specific first lubricant and the above-mentioned specific second lubricant, it exists on the surface of the exterior material (the inner sealing layer). The reduction in the amount of (precipitated) lubricant on the surface can be suppressed, thereby ensuring good sliding properties during molding, excellent moldability, and less white powder on the surface of the exterior material. In addition, since the amount of lubricant existing on the surface of the exterior material does not change due to the thermal history during transportation or storage, it is possible to provide the exterior material with excellent formability and stability.

According to the inventions of [3] and [4], since the lubricant in the first unstretched film layer and/or the lubricant in the second unstretched film layer which forms the innermost layer of the exterior material contains the above-mentioned specific first 1. The composition of the lubricant and the above-specified second lubricant can suppress the decrease in the amount of (precipitated) lubricant existing on the surface of the exterior material (the surface 7a of the innermost innermost layer of the inner seal layer), so that the molding process can be ensured. It has good sliding property and excellent formability, and it is difficult for white powder to appear on the surface of the exterior material (surface 7a of the innermost layer of the inner sealing layer). In addition, since the amount of lubricant existing on the surface of the exterior material does not change due to the thermal history during transportation or storage, it is possible to provide the exterior material with excellent formability and stability.

According to the invention of [5], since the total concentration of all lubricants in the first unstretched film layer is 200 ppm to 7000 ppm, and the sum of the concentrations of all lubricants in the second unstretched film layer is 500 ppm to 500 ppm 7000ppm, so even if it is subjected to thermal history during transportation or storage, the amount of lubricant deposited on the surface of the exterior material can be controlled within the range of ^{0.1μg/cm 2} ~1.0μg/cm ^{2 .}

According to the invention of [6], in the layer containing the second lubricant, the ratio of the concentration of the second lubricant to the total concentration of the lubricants in the layer is 5% to 90%. The movement of the first lubricant that is easily spilled can be restricted, so that the amount of lubricant deposited on the surface of the exterior material can be controlled within the range of ^{0.1 μg/cm 2} to 1.0 μg/cm ^{2 .}

According to the inventions of [7] and [8], it is possible to provide an exterior material for an electrical storage device, which can reduce the amount of (precipitated) lubricant present on the surface of the exterior material (surface 7a of the innermost layer of the inner sealing layer). This is suppressed, thereby ensuring good sliding properties during molding, excellent moldability, and less white powder on the surface of the exterior material (surface 7a of the innermost layer of the inner sealing layer). In addition, since the amount of lubricant existing on the surface of the exterior material does not change due to the thermal history during transportation or storage, it is possible to provide the exterior material with excellent formability and stability.

In addition, according to the invention of [8], since the outer layer is further provided with the heat-resistant resin layer, the insulating properties of the metal foil layer on the opposite side to the inner sealing layer can be sufficiently ensured, and the physical strength and impact resistance of the exterior material can be improved. sex.

According to the invention of [9], since the amount of lubricant present on the surface of the innermost layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² , it can be found that it has further good sliding properties during molding , thereby ensuring better formability, and fully suppressing the appearance of white powder on the surface of the exterior material, preventing contamination of the processing equipment.

According to the invention of [10], it is possible to provide an outer casing for a power storage device, which is a well-shaped outer casing, and the surface of the outer casing (the surface of the innermost layer of the inner sealing layer) is less likely to have white powder.

According to the inventions of [11] to [14], the exterior material for an electrical storage device can be manufactured, and the reduction in the amount of (precipitated) lubricant existing on the surface of the exterior material (the surface 7a of the innermost innermost layer of the inner sealing layer) can be suppressed, Therefore, good sliding properties can be ensured during molding, excellent formability, and white powder is unlikely to appear on the surface of the exterior material (surface 7a of the innermost layer of the inner sealing layer).

In addition, according to the inventions of [13] and [14], since the heat-resistant resin layer of the outer layer is further provided, the insulating properties of the metal foil layer on the opposite side to the inner sealing layer can be sufficiently ensured, and the physical properties of the exterior material can be improved. Strength and shock resistance.

According to the invention of [15], since the amount of lubricant present on the surface of the innermost layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² , it can be found that it has further good sliding properties during molding , so that an exterior material for a power storage device can be produced, which can ensure further good formability and prevent the occurrence of white powder. ^{In addition, the amount of lubricant (0.1 μg/cm 2} to 1.0 μg/cm ² ) present on the surface of the obtained exterior material for electrical storage devices did not change even when subjected to thermal history during transportation or storage. Exterior materials with excellent formability and stability can be provided.

1: Exterior materials for power storage devices

2: Heat-resistant resin layer (outer layer)

3: Inner sealing layer (sealing film) (inner layer)

4: Metal foil layer

5: Second adhesive layer (outer adhesive layer)

6: 1st adhesive layer (inner adhesive layer)

7: 1st non-stretch film layer (innermost layer)

7a: The surface of the first unstretched film layer (the surface of the innermost layer of the exterior material)

8: The second non-stretching film layer

9: 1st unstretched film layer (metal foil layer side)

10: Outer case (molded body) for power storage device

15: Exterior parts

30: Power storage device

31: Power storage device body

Fig. 1 is a cross-sectional view showing a first embodiment of the exterior material for an electrical storage device according to the present invention.

Fig. 2 is a cross-sectional view showing a second embodiment of the exterior material for an electrical storage device according to the present invention.

[ Fig. 3] Fig. 3 is a cross-sectional view showing a third embodiment of the exterior material for an electrical storage device according to the present invention.

Fig. 4 is a cross-sectional view showing an embodiment of the power storage device of the present invention.

Fig. 5 is a perspective view showing a separated state before heat-sealing the main body of the electric storage device and the outer casing (molded body in a three-dimensional shape) constituting the exterior material (planar) of the electric storage device of Fig. 4 .

The sealing film 3 for an exterior material of a power storage device according to the present invention comprises at least one unstretched film layer, and the unstretched film layer contains: a propylene-based polymer, selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides One or more first lubricants selected from the group consisting of amines, and one or more second lubricants selected from the group consisting of fatty acid diamides and aromatic diamides.

The above-mentioned propylene-based polymer is not particularly limited, and examples thereof include random copolymers containing "propylene" as a copolymer component and "copolymer components other than propylene", "propylene" and "propylene" containing a copolymer component. block copolymers, homopolypropylene, etc.

Three embodiments of the sealing film 3 for an exterior material of an electrical storage device according to the present invention are shown in FIGS. 1 to 3 , respectively. These three kinds of embodiments are only representative embodiments, and are not particularly limited to such a configuration.

The sealing film 3 for exterior materials of the first embodiment shown in FIG. 1 is composed of only a first unstretched film layer 7 and a second unstretched film layer 8 laminated on one side of the first unstretched film layer (2-layer laminated structure). In the exterior material 1 constituted using this sealing film 3, the above-mentioned The first unstretched film layer 7 is disposed on the innermost layer side (see FIG. 1 ), the second unstretched film layer 8 is disposed on the metal foil layer 4 side, and the first unstretched film layer 7 is exposed on the outer covering material 1 . the inner surface (see Figure 1).

In addition, the sealing film 3 for exterior materials of the second embodiment shown in FIG. 2 is composed of a second unstretched film layer 8 and a first unstretched film layer laminated on one side of the second unstretched film layer. 7. The first non-stretch film layer 9 which is laminated on the other side of the second non-stretch film layer 8 is constituted by a three-layer lamination. In the exterior material 1 constituted using this sealing film 3, the first non-stretched film layer 7 on one side is arranged on the innermost layer side of the exterior material 1 (see FIG. 2 ), and the first non-stretched film on the other side The layer 9 is arranged on the metal foil layer 4 side, and the first non-stretched film layer 7 on the one side is exposed to the inner surface of the exterior material 1 (see FIG. 2 ).

In the sealing film 3 for exterior materials of the first and second embodiments, the first non-stretched film layers 7 and 9 contain a random copolymer and a lubricant, and the random copolymer contains a copolymer component. propylene and other copolymer components other than propylene, the aforementioned second non-stretch film layer 8 contains a block copolymer and a lubricant, and the block copolymer contains propylene and other copolymer components other than propylene . Further, the lubricant in the first unstretched film layer 7 and/or the lubricant in the second unstretched film layer 8 that form the innermost layer of the exterior material 1 contain saturated fatty acid amides and unsaturated fatty acids. A configuration of at least one first lubricant selected from the group consisting of fatty acid diamides and at least one second lubricant selected from the group consisting of fatty acid diamides and aromatic diamides. With regard to the content of the lubricant, by adopting such a specific configuration, the decrease in the amount of (precipitated) lubricant existing on the surface of the exterior material 1 (the surface 7a of the innermost innermost layer of the inner seal layer) can be suppressed, so that the molding can be ensured. It has good sliding properties, excellent formability, and the surface of the exterior material 1 (the surface 7a of the innermost innermost layer of the inner sealing layer) is difficult to appear white. pink.

In addition, the sealing film 3 for exterior materials of 3rd Embodiment shown in FIG. 3 consists of only the 1st unstretched film layer 7. As shown in FIG. In the exterior material 1 constituted using the sealing film 3, the first non-stretch film layer 7 is disposed on the innermost layer side (see FIG. 3 ), and the first non-stretch film layer 7 is exposed to the inside of the exterior material 1 surface (see Figure 3). In the sealing film 3 for exterior materials of the third embodiment, the first non-stretched film layer 7 is composed of a propylene-based polymer selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides At least one type of first lubricant, and at least one type of second lubricant from the group consisting of fatty acid diamide and aromatic diamide. With regard to the content of the lubricant, by adopting such a specific configuration, the decrease in the amount of (precipitated) lubricant existing on the surface of the exterior material 1 (the surface of the inner seal layer) can be suppressed, thereby ensuring good sliding during molding. It has excellent formability and excellent formability, and it is difficult for white powder to appear on the surface of the exterior material 1 .

In the present invention, the above-mentioned specific first lubricant and the above-mentioned specific second lubricant are jointly contained, and the combined size of the lubricants can be increased (the combined size is increased) compared to only containing the specific second lubricant. As a result, it is considered that it can sufficiently suppress excessive movement of the lubricant to the surface, excessive movement of the lubricant to the phosphorus layer, and the like.

In the sealing film 3 of the present invention, when the sealing film 3 is composed of two or more layers (FIGS. 1 and 2), it is preferable to adopt the following structure. That is, the propylene-based polymer constituting the first non-stretched film layers 7 and 9 is preferably a random copolymer containing "propylene" as a copolymer component and "other copolymer components other than propylene". Regarding the above-mentioned random copolymer, the above-mentioned "other copolymer components other than propylene" is not particularly limited, and examples thereof include ethylene, 1-butene, 1-hexene, 1-pentene, and 4methyl-1-pentene. Olefin components such as olefins, and butyl Diene etc.

In addition, as the propylene-based polymer constituting the second non-stretched film layer 8, it is preferable to use a block copolymer containing "propylene" as a copolymer component and "other copolymer components other than propylene". Regarding the above-mentioned block copolymer, the above-mentioned "other copolymer components other than propylene" are not particularly limited, and examples thereof include ethylene, 1-butene, 1-hexene, 1-pentene, and 4methyl-1- Olefin components such as pentene, and butadiene, etc.

In addition, when the sealing film 3 is composed of two or more layers (FIGS. 1 and 2), the total concentration of the lubricant contained in the first non-stretch film layer 7 is 200 ppm to 7000 ppm, and the second non-stretch film layer 7 It is preferable that the total value of the content concentration of all the lubricants contained in the stretched film layer 8 is in the range of 500 ppm to 7000 ppm. In addition, it is preferable that the total value of the content concentration of all the lubricants contained in the first non-stretched thin film layer 9 is 200 ppm to 7000 ppm. By satisfying such a condition, the lubricant existing in the first non-stretched film layer 7 can be suppressed from moving into the second non-stretched film layer 8 when the aging treatment for curing the adhesive is performed, so that it is possible to secure the coating material 1 . The amount of lubricant deposited on the surface (the surface 7a of the innermost first non-stretched film layer) can ensure that the outer material has good sliding properties during molding, thereby obtaining excellent moldability. If the concentration of the lubricant in the first non-stretched film layer 7 is less than 200 ppm, the amount of lubricant present on the surface 7a of the innermost layer decreases after the aging treatment to harden the adhesive, resulting in a decrease in formability. It is not good; if it exceeds 7000ppm, after the aging treatment to harden the adhesive, the surface 7a of the innermost layer is likely to produce white powder, which must be cleaned and removed to reduce productivity. In addition, it is also used as an exterior material. It is easy to reduce the adhesion with the metal foil layer or contaminate the electrolyte, so it is not good. In addition, if the content concentration of the lubricant in the second non-stretched film layer 8 is less than 500 ppm, During the aging treatment to harden the adhesive, the lubricant tends to move from the innermost first unstretched film layer 7 to the second unstretched film layer 8, so that the amount of lubricant on the surface 7a where the innermost layer exists is reduced, thereby reducing the amount of the lubricant. The formability is reduced, so it is not good; if it exceeds 7000ppm, the lubricant tends to move from the second unstretched film layer 8 to the first unstretched film layers 7 and 9 during the aging treatment to harden the adhesive, resulting in production It is easy to produce white powder pollution in the device, and when used as an exterior material, it is easy to reduce the adhesion force with the metal foil layer or the pollution of the electrolyte, so it is not good.

The concentration of the lubricant in the first non-stretched thin film layers 7 and 9 is preferably in the range of 300 ppm to 2000 ppm, and more preferably in the range of 800 ppm to 1500 ppm. In addition, the concentration of the lubricant in the second non-stretched thin film layer 8 is preferably in the range of 700 ppm to 3000 ppm, and more preferably in the range of 800 ppm to 2500 ppm.

In addition, when the sealing film 3 is composed of two or more layers ( FIGS. 1 and 2 ), the concentration of the lubricant in the second non-stretching film layer 8 is the concentration of the first non-stretching film forming the innermost layer of the exterior material 1 . The lubricant content in the stretched film layer 7 is preferably 0.1 to 10 times the concentration. By performing the aging treatment to harden the adhesive at 0.1 times or more, it is possible to suppress the lubricant from the innermost first unstretched film layer 7 to the second unstretched film layer due to the lubricant concentration gradient. The interface of 8 (the interface between the two thin film layers 7, 8) moves intensively, so that the amount of lubricant existing on the surface 7a of the innermost layer is sufficient, and excellent formability is obtained. The aging treatment can suppress the concentrated movement of the lubricant from the second unstretched film layer 8 to the interface of the innermost first unstretched film layer 7 (the interface between the two film layers 7 and 8) caused by the lubricant concentration gradient. Thus, the first unstretched film of the innermost layer can be sufficiently suppressed Variation in lubricant content of layer 7. The concentration of the lubricant in the second non-stretched thin film layer 8 is 0.5 to 5.0 times the concentration of the lubricant in the first non-stretched thin film layer 7 that forms the innermost layer of the exterior material 1 . The composition is good.

In the sealing film 3 of the present invention, in the layer containing the second lubricant, the ratio of the concentration of the second lubricant to the total value of the concentration of all lubricants in the layer is preferably 5% to 90%. Among them, 10%~50% is better.

As the first lubricant, one or more lubricants selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides are used. The above-mentioned saturated fatty acid amide is not particularly limited, and examples thereof include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, and the like. The unsaturated fatty acid amide is not particularly limited, and examples thereof include oleamide, erucamide, and the like. In addition, in this specification, the term "saturated fatty acid amide" does not include saturated fatty acid diamide, and the term "unsaturated fatty acid amide" does not include unsaturated fatty acid diamide.

As the second lubricant, one or more lubricants selected from the group consisting of fatty acid bisamide and aromatic bisamide are used. Examples of the aforementioned fatty acid diamide include saturated fatty acid diamide and unsaturated fatty acid diamide.

The aforementioned saturated fatty acid bisamide is not particularly limited, and examples thereof include methylenebisstearate, ethylenebiscaprate, ethylenebislaurate, and ethylenebisstearyl. Acid amide (EBSA), ethylene bishydroxystearic acid amide, ethylene bis-docosamide, hexamethylene bis-docosamide, hexamethylene bis-docosamide Amine, hexamethylene hydroxystearate amide, N,N'-distearyl adipate amide, N,N'-distearyl sebacate amide, etc. The above-mentioned unsaturated fatty acid bisamide is not particularly limited, for example: ethylene bisoleate Amine (EBOA), Ethylenebiserucamide, Hexamethylenebisoleamide, N,N'-dioleyladipic acid amide, N,N'-dioleylsebacic acid Amide, etc.

In addition, the above-mentioned aromatic bisamide is not particularly limited, and examples thereof include m-isophenyldistearate amide, m-isophenylbishydroxystearate amide, and N,N'-distearic acid. Isophthalic acid amide, etc.

The thickness of the aforementioned sealing film 3 is preferably set at 10 μm˜100 μm. 10 μm or more can sufficiently prevent the generation of pinholes, and setting it to 100 μm or less can reduce the amount of resin used and achieve cost reduction.

When the above-mentioned sealing film 3 is composed of two layers in FIG. 1, the ratio of the thickness of the two layers is set at the thickness of the first unstretched film layer 7/the thickness of the second unstretched film layer 8=5~90/95~ The range of 10 is preferred, and the thickness of the first non-stretch film layer 7 / the thickness of the second non-stretch thin film layer 8 = 5~40/95~60 is particularly preferred.

In addition, when the aforementioned sealing film 3 is constituted by the three-layer laminate shown in FIG. 2, the ratio of the thickness of the three layers is set at the thickness of the first unstretched film layer 7/the thickness of the second unstretched film layer 8/the first unstretched film layer 8 The thickness of the thin film layer 9 is preferably in the range of 5~45/90~10/5~45, wherein the thickness of the first non-stretching thin film layer 7 / the thickness of the second non-stretching thin film layer 8 / the first The thickness of the non-stretched film layer 9 is particularly preferred in the range of 5~20/90~60/5~20.

The first unstretched film layer 7 forming the innermost layer may further contain an anti-blocking agent. In addition, both the first unstretched film layer 7 forming the innermost layer and the first unstretched film layer 9 on the metal foil layer side may contain an anti-blocking agent. The aforementioned anti-blocking agent is not particularly limited Certain examples include silica particles, acrylic resin particles, aluminum silicate particles, and the like. The particle size of the aforementioned anti-blocking agent is preferably in the range of 0.1 μm to 10 μm in average particle size, and more preferably in the range of 1 μm to 5 μm in average particle size. When the first non-stretched film layers 7 and 9 contain the aforementioned anti-blocking agent, the concentration thereof is preferably set at 100 ppm to 5000 ppm.

By using the anti-blocking agent (particles) in the first non-stretched film layer 7 forming the innermost layer, microscopic protrusions can be formed on the surface 7a of the innermost layer 7, thereby reducing the contact area between the films and suppressing the sealing between the films. of mutual adhesion. In addition, by containing the lubricant and the anti-blocking agent (particles) together, the sliding property during the molding can be further improved.

The aforementioned sealing film 3 is preferably produced by a molding method such as multilayer extrusion molding, inflation molding, and T-die casting film molding.

The exterior material 1 for an electricity storage device of the present invention is produced by using the sealing film 3 having the above-described configuration. It is prepared that the surface on one side of the metal foil layer 4 is laminated with the heat-resistant resin film (outer layer) 2 via a second adhesive (outer adhesive) 5, and the other surface of the metal foil layer 4 is interposed. A layered product in which the first adhesive agent (inside adhesive agent) 6 and the sealing film 3 of the first embodiment described above are layered. At this time, the second unstretched film layer 8 of the sealing film 3 is connected to the first adhesive (inside adhesive) 6 (see FIG. 1 ). That is, the first unstretched film layer 7 of the sealing film 3 forms the innermost layer (see FIG. 1 ). Next, by subjecting the obtained laminated body to heat treatment (aging treatment), the exterior material 1 for an electrical storage device of the present invention having the configuration shown in FIG. 1 can be obtained.

In addition, a surface on one side of the metal foil layer 4 is prepared to be laminated with a heat-resistant resin film (outer layer) 2 via a second adhesive (outer adhesive) 5, and one of the aforementioned metal foil layers 4 is prepared. The side surface is a layered product in which the first adhesive agent (inside adhesive agent) 6 and the sealing film 3 of the second embodiment described above are layered. At this time, the first unstretched film layer 9 on one side of the sealing film 3 is connected to the first adhesive (inside adhesive) 6 (see FIG. 2 ). That is, the first unstretched film layer 7 on the other side of the sealing film 3 forms the innermost layer (see FIG. 2 ). Next, by subjecting the obtained layered body to a heat treatment (aging treatment), the exterior material 1 for an electrical storage device of the present invention having the configuration shown in FIG. 2 can be obtained.

In addition, the surface on one side of the metal foil layer 4 is prepared to be laminated with the heat-resistant resin film (outer layer) 2 via a second adhesive (outer adhesive) 5, and the other surface of the metal foil layer 4 is interposed. A laminated body in which the first adhesive agent (inside adhesive agent) 6 and the sealing film 3 of the third embodiment described above are laminated. At this time, the first unstretched film layer 7 of the sealing film 3 is connected to the first adhesive agent (inside adhesive agent) 6 (see FIG. 3 ). Moreover, the 1st non-stretching film layer 7 of the said sealing film 3 forms the innermost layer (refer FIG. 3). Next, by subjecting the obtained laminated body to heat treatment (aging treatment), the exterior material 1 for an electrical storage device of the present invention having the configuration shown in FIG. 3 can be obtained.

The said 1st adhesive agent (inner side adhesive agent) 6 is not specifically limited, For example, a thermosetting adhesive agent etc. are mentioned. In addition, the said 2nd adhesive agent (outer side adhesive agent) 5 is not specifically limited, For example, a thermosetting adhesive agent etc. are mentioned. The said thermosetting adhesive agent is not specifically limited, For example, an olefin type adhesive agent, an epoxy resin type adhesive agent, an acrylic type adhesive agent, etc. are mentioned.

The heating temperature of the above-mentioned aging treatment is preferably set below 65°C, among which, it is set at 35°C to 45°C from the viewpoint of the degree of hardening of the adhesive and the appropriate amount of lubricant to maintain the amount of lubricant present on the surface 7a of the exterior material. ℃ is better. In addition, regarding the aforementioned aging treatment The heating time varies depending on the type of adhesive, so it is sufficient to match the type of adhesive so as to obtain sufficient bonding strength. However, considering the pre-step time and heating time, it can be It is preferable to obtain sufficient bonding strength for as short a time as possible.

In the exterior material 1 for an electrical storage device of the present invention obtained by such an aging treatment, the surface on one side of the metal foil layer 4 is interposed between the second adhesive layer (outer adhesive layer) 5 and the heat-resistant resin layer (outer side). layer) 2 is laminated and integrated, and the other side of the metal foil layer 4 is laminated and integrated through the first adhesive layer (inner adhesive layer) 6 and the inner sealing layer (sealing film) (inner layer) 3 structure (refer to Figures 1 to 3). When a thermosetting adhesive is used as the first and second adhesives, the first adhesive layer 6 is made of a cured product of the thermosetting adhesive, and the second adhesive layer 5 is made of a thermosetting adhesive. of hardening.

Since the sealing film 3 used in the production of the exterior material 1 for a power storage device obtained by the above-mentioned aging treatment has the above-mentioned specific structure, it exists in the innermost part of the exterior material 1 for a power storage device after the aging treatment is formed. The amount of lubricant on the surface '7a of the first non-stretched thin film layer 7 can be controlled within the range of ^{0.1 μg/cm 2} to 1.0 μg/cm ^{2 .} Therefore, in the obtained exterior material 1 for a power storage device, the amount of lubricant existing (precipitated) on the surface (the surface 7a of the innermost layer of the inner sealing layer) can be suppressed from being reduced, so that good sliding properties during molding can be ensured. The formability is excellent, and the surface of the exterior material (surface 7a of the innermost layer of the inner sealing layer) hardly appears white powder.

In the exterior material 1 for a power storage device, the coefficient of kinetic friction of the surface 7a of the first non-stretched film layer (innermost layer) 7 is preferably in the range of 0.10 to 0.50. When it is less than 0.50, the sliding property can be improved to ensure good formability, and when it is more than 0.10, the outflow amount of lubricant to the innermost surface 7a can be reduced.

The exterior material 1 for a power storage device of the present invention can be used, for example, as an exterior material for a lithium ion battery. The aforementioned exterior material 1 for a power storage device can be used as an exterior material without molding (see FIG. 5 ), or it can be used as an exterior case 10 by deep drawing, bulging, or the like (see FIG. 5 ). 5).

In the exterior material 1 for a power storage device of the present invention, the inner sealing layer (inner layer) 3 has excellent chemical resistance against highly corrosive electrolytes and the like used in lithium ion batteries and the like, and is responsible for imparting the exterior The function of material heat sealing.

In addition, the heat-resistant resin layer (base material layer; outer layer) 2 is not an essential constituent layer, but the other surface of the metal foil layer 4 (the surface opposite to the inner sealing layer) is used through the first 2. The structure in which the adhesive layer (outer adhesive layer) 5 and the heat-resistant resin layer 2 are laminated is preferable (see FIGS. 1 to 3 ). By providing the heat-resistant resin layer 2 in this way, the insulating properties of the other surface (the surface opposite to the inner sealing layer) side of the metal foil layer 4 can be sufficiently ensured, and the physical strength and the physical strength of the exterior material 1 can be improved. Impact resistance.

As the heat-resistant resin constituting the above-mentioned heat-resistant resin layer (substrate layer; outer layer) 2, a heat-resistant resin that does not melt at the heat-sealing temperature when heat-sealing the exterior material is used. The above-mentioned heat-resistant resin is preferably a heat-resistant resin having a melting point higher than the melting point of the block copolymer constituting the first non-stretching film layer 7 by 10°C or more. A heat-resistant resin whose melting point of the segment copolymer is higher than the melting point of 20°C or more is particularly preferred.

The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include polyamide films such as nylon films, polyester films, and polyolefin films, and these stretched films can be suitably used. Among them, the above-mentioned heat-resistant resin layer 2 is a biaxially stretched polyamide film such as a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, Biaxially stretched polyethylene terephthalate (PET) film or biaxially stretched polyethylene naphthalate (PEN) are particularly preferred. The said nylon film is not specifically limited, For example, a 6 nylon film, a 6,6 nylon film, a MXD nylon film, etc. are mentioned. In addition, the above-mentioned heat-resistant resin layer 2 may be formed as a single layer, or may be formed as a multi-layer of polyester film/polyamide film (multilayer of PET film/nylon film, etc.), for example.

The thickness of the heat-resistant resin layer (outer layer) 2 is preferably 2 μm to 50 μm. When using polyester film, the thickness is preferably 2μm~50μm; when using nylon film, the thickness is preferably 7μm~50μm. By setting it to the above-mentioned suitable lower limit value or more, sufficient strength of the exterior material can be ensured, and by setting it to the above-mentioned suitable upper limit value or less, the stress at the time of forming such as bulging molding and stretch forming can be reduced, thereby reducing the stress. Formability can be improved.

In the exterior material 1 for a power storage device of the present invention, it is preferable that the surface on the opposite side of the metal foil layer 4 of the heat-resistant resin layer (outer layer) 2 is adhered with a lubricant, and the lubricant is formed by What is contained in the 1st non-stretched film layer 7 of the innermost layer of the exterior material 1 for electrical storage devices. This adhesion lubricant is transferred from the inner layer 3 by contacting the surface 7a of the inner sealing layer 3 in the curled state when the exterior material 1 for an electric storage device obtained by lamination is aged in a curled state. Of deposit after the transfer, based at 0.1μg / cm ² ~ 0.8μg / cm ² of the preferred range. When the adhesion amount is within such a range, the formability of the exterior material 1 for an electrical storage device can be improved. Wherein, after the deposition amount of the write transfer, at 0.1μg / cm ² ~ 0.6μg preferable range / cm ² of at 0.15μg / cm ² ~ 0.45μg / cm ² and that of the particularly good. The transfer lubricant may be removed, retained, or left to disappear naturally after forming the exterior material 1 for an electrical storage device by deep drawing or the like.

The above-mentioned metal foil layer 4 is used to provide the exterior material 1 with a gas that prevents the intrusion of oxygen or moisture. The role of body barrier. The metal foil layer 4 is not particularly limited, and examples thereof include aluminum foil, SUS foil (stainless steel foil), and copper foil. Among them, aluminum foil and SUS foil (stainless steel foil) are preferably used. The thickness of the aforementioned metal foil layer 4 is preferably 5 μm˜120 μm. A thickness of 5 μm or more can prevent pinholes during rolling in the production of metal foils, and a thickness of 120 μm or less can reduce the stress at the time of forming such as bulging and deep-cut forming, and improve the formability. Among them, the thickness of the aforementioned metal foil layer 4 is preferably 10 μm˜80 μm.

Preferably, at least the inner side surface (the side surface of the inner sealing layer 3 side) of the aforementioned metal foil layer 4 is subjected to chemical conversion treatment. By performing such a chemical conversion treatment, the corrosion of the surface of the metal foil due to the contents (electrolyte of the battery, etc.) can be sufficiently prevented. For example, the metal foil can be subjected to chemical conversion treatment by the following treatment. That is, for example, on the surface of the metal foil subjected to the degreasing treatment, the chemical conversion treatment is applied by applying the aqueous solution of any one of the following 1) to 3) and drying:

1) An aqueous mixture solution containing phosphoric acid, chromic acid, and at least one compound selected from the group consisting of metal salts of fluorides and non-metallic salts of fluorides;

2) Phosphoric acid, at least one resin selected from the group consisting of acrylic resins, chitosan derivative resins, and phenol-based resins, and at least one resin selected from the group consisting of chromic acid and chromium (III) salts Aqueous solutions of mixtures of compounds.

3) A resin containing phosphoric acid, at least one selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins, An aqueous solution of a mixture of at least one compound selected from the group consisting of chromic acid and chromium(III) salts, and at least one compound selected from the group consisting of metal salts of fluorides and non-metallic salts of fluorides.

For the aforementioned chemical film, the amount of chromium adhesion (one side) is ^{preferably 0.1 mg/m 2} to 50 mg/m ^{2 , and particularly} preferably 2 mg/m ² to 20 mg/m ² .

The thickness of the second adhesive layer (outer adhesive layer) 5 is preferably set to 1 μm to 5 μm. Among them, from the viewpoint of thinning and weight reduction of the exterior material 1 , the thickness of the outer adhesive layer 5 is particularly preferably set to 1 μm to 3 μm.

The thickness of the first adhesive layer (inside adhesive layer) 6 is preferably set to 1 μm to 5 μm. Among them, from the viewpoint of thinning and weight reduction of the exterior material 1 , the thickness of the inner adhesive layer 6 is particularly preferably set to 1 μm to 3 μm.

By forming the exterior material 1 of the present invention (deep drawing, bulging, etc.), an exterior case (battery case, etc.) 10 can be obtained (see FIGS. 4 and 5 ). In addition, the exterior material 1 of this invention can also be used without shaping|molding (refer FIG. 4, 5).

FIG. 4 shows an embodiment of the power storage device 30 constructed using the exterior material 1 of the present invention. This power storage device 30 is a lithium-ion storage battery. In this embodiment, as shown in FIGS. 4 and 5 , the exterior case 10 obtained by molding the exterior material 1 and the planar exterior material 1 constitute the exterior member 15 . Therefore, by accommodating a substantially rectangular parallelepiped-shaped power storage device body portion (electrochemical element, etc.) 31 in the housing recess of the exterior casing 10 obtained by molding the exterior material 1 of the present invention, and in the power storage device body portion Above 31, the unmolded exterior material 1 of the present invention is arranged so that the inner side of the sealing layer 3 becomes the inner side (lower side), and the inner sealing layer 3 of the flat exterior material 1 (No. 1 The peripheral portion of the non-stretched film layer 7), and The inner sealing layer 3 (the first non-stretching film layer 7 ) of the flange portion (peripheral portion for sealing) 29 of the outer casing 10 is hermetically bonded and sealed, thereby constituting the power storage device 30 of the present invention (see FIGS. 4 and 5 ) . In addition, the surface of the inner side of the accommodating recess of the outer casing 10 is the inner sealing layer 3 (the first non-stretch film layer 7), and the outer surface of the accommodating recess is the heat-resistant resin layer (outer layer) 2 (refer to FIG. 5). .

In FIG. 4, the code|symbol 39 is a heat-sealing part which joins (fuses) the peripheral part of the said exterior material 1, and the flange part (peripheral edge part for sealing) 29 of the said exterior case 10. In addition, in the power storage device 30 described above, the leading end portion of the tab connecting the power storage device main body portion 31 is led out to the outside of the exterior member 15, but the illustration is omitted.

The power storage device body portion 31 is not particularly limited, and examples thereof include a battery body portion, a capacitor body portion, a capacitor body portion, and the like.

The width of the heat-sealed portion 39 is preferably set to 0.5 mm or more. When the thickness is more than 0.5mm, the sealing can be performed reliably. Wherein, the width of the aforementioned heat-sealing portion 39 is preferably set at 3 mm to 15 mm.

Moreover, in the above-mentioned embodiment, the exterior member 15 is constituted by the exterior case 10 obtained by molding the exterior material 1 and the planar exterior material 1 (see FIGS. 4 and 5 ), but it is not In particular, it is limited to such a combination. For example, the exterior member 15 may be constituted by a pair of planar exterior materials 1 or may be constituted by a pair of exterior casings 10 .

【Example】

Next, specific embodiments of the present invention are described, but the present invention is not limited to these embodiments.

<Reference example 1>

A chemical conversion treatment liquid composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and ethanol was applied to both sides of an aluminum foil with a thickness of 40 μm, and then dried at 180° C. to form a chemical conversion film. The chromium adhesion amount of this chemical film is 10 mg/m ^{2 on} one side.

Next, dry lamination (lamination) with a biaxially stretched 6 nylon film with a thickness of 25 μm is carried out on the surface of the one side of the aluminum foil that has completed the chemical conversion treatment through a two-component curable urethane adhesive. .

Next, the first non-stretching film layer 7 and the second non-stretching film layer 8 are sequentially laminated and co-extruded using a T-shape, and the first non-stretching film layer 7 contains ethylene-propylene random copolymer and 1000ppm of mustard The first non-stretching film layer 7 with a thickness of 4.5 μm is composed of amide acid and silica particles (anti-blocking agent); the aforementioned second non-stretching film layer 8 contains ethylene-propylene block copolymer, 300ppm of A second non-stretch film layer 8 with a thickness of 25.5 μm formed of erucamide and 200 ppm of ethylene bisoleate, thereby obtaining a sealing film with a thickness of 30 μm formed by laminating these two layers (the first After the non-stretching film layer 7/the second non-stretching film layer 8) 3, the second non-stretching film layer 8 of the sealing film 3 is interposed with the above-mentioned dry-type adhesive through a 2-liquid curing type maleic acid modified polypropylene adhesive. After lamination, the other side of the aluminum foil is superimposed, and dry laminated by sandwiching between a rubber nip roll and a laminating roll heated to 100°C and pressing, and then aging at 40°C. (heating) for 10 days, and the exterior material 1 for electric storage devices of the structure shown in FIG. 1 was obtained.

In addition, the maleic acid-modified polypropylene adhesive of the above-mentioned 2-component curing type used maleic acid-modified polypropylene (melting point 80° C., acid value 10 mgKOH/g) as the main agent 100 parts by mass, and hexamethylene was used as the main agent. An adhesive solution obtained by mixing the isocyanurate body of diisocyanate (NCO content: 20 mass %) as 8 parts by mass of the curing agent and further with a solvent. It was coated on the other side of the aluminum foil so that the solid coating amount of the adhesive solution was 2 g/m ² , and after heating and drying, it was overlapped with the second non-stretched film layer 8 of the sealing film 3 .

<Reference example 2>

Except that the first unstretched film layer 7 which is the innermost layer contains 250 ppm of erucamide and 750 ppm of ethylene bisoleamide as lubricants, and the second unstretched film layer 8 contains 500 ppm of erucamide Except for the configuration of the lubricant (refer to Table 1), the rest was the same as that of Reference Example 1, and an exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained.

<Reference example 3>

Except that the first unstretched film layer 7 which is the innermost layer contains 2000 ppm of erucamide and 2000 ppm of ethylene bisoleamide as lubricants, and the second unstretched film layer 8 contains 300 ppm of erucamide Except that 200 ppm of ethylenebisoleamide was used as a lubricant (refer to Table 1), the rest was the same as that of Reference Example 1, and an exterior material 1 for a power storage device having the structure shown in FIG. 1 was obtained.

<Reference Example 4>

A chemical conversion treatment liquid composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and ethanol was applied to both surfaces of an aluminum foil with a thickness of 40 μm, and then dried at 180° C. to form a chemical conversion film. The chromium adhesion amount of this chemical film is 10 mg/m ^{2 on} one side.

Next, on the surface of the aluminum foil on which the chemical conversion treatment has been completed, a dry-type biaxially stretched 6 nylon film with a thickness of 25 μm is interposed through a 2-component curable urethane-based adhesive. Laminate (fit).

Next, a first non-stretching film layer with a thickness of 30 μm containing ethylene-propylene random copolymer, 1000 ppm of erucamide, 500 ppm of ethylene bisoleamide and silica particles (anti-blocking agent) was obtained 7 After the sealing film 3 is formed, the sealing film 3 is superimposed on the other side of the aluminum foil after the dry lamination through a 2-liquid hardening type maleic acid modified polypropylene adhesive, and is sandwiched between A rubber nip roll and a lamination roll heated to 100°C were pressed and dry-laminated, and then aged (heated) at 40°C for 10 days to obtain an external device for a power storage device having the configuration shown in FIG. 3 . Loading 1.

In addition, the maleic acid-modified polypropylene adhesive of the above-mentioned 2-component curing type is made of maleic acid-modified polypropylene (melting point 80° C., acid value 10 mgKOH/g) as the main agent 100 parts by mass, and hexamethylene dimethicone The adhesive solution which the isocyanurate body (NCO content: 20 mass %) of isocyanate was mixed with a solvent as 8 mass parts of hardeners. This was applied to the other side of the aluminum foil so that the adhesive solution had a solid coating amount of 2 g/m ² , and after heating and drying, it was superimposed on the sealing film 3 .

<Example 5>

A chemical conversion treatment liquid composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and ethanol was applied to both surfaces of an aluminum foil with a thickness of 40 μm, and then dried at 180° C. to form a chemical conversion film. The chromium adhesion amount of this chemical film is 10 mg/m ^{2 on} one side.

Next, on the one side of the aluminum foil after the chemical conversion treatment, it was dry-laminated (bonded) with a biaxially stretched 6 nylon film with a thickness of 25 μm through a two-component curable urethane adhesive.

Next, the first unstretched film layer 7, the second unstretched film layer 8 and the first unstretched film layer 9 are sequentially laminated and coextruded in three layers using a T-shape, and the first unstretched film layer 7 contains ethylene- The first non-stretching film layer 7 with a thickness of 4.5 μm is composed of propylene random copolymer, 1000ppm erucamide and silica particles (anti-blocking agent); the aforementioned second non-stretching film layer 8 contains ethylene- A second non-stretch film layer 8 with a thickness of 21 μm, which is composed of propylene block copolymer, 300ppm of erucamide and 200ppm of ethylene bisoleate; the first non-stretch film layer 9 contains ethylene-propylene random A first non-stretching film layer 9 with a thickness of 4.5 μm formed of a copolymer, 1000 ppm of erucamide and 2000 ppm of silicon dioxide particles (anti-blocking agent), thereby obtaining these three-layer laminates After the sealing film with a thickness of 30 μm (the first non-stretching film layer 7 / the second non-stretching film layer 8 / the first non-stretching film layer 9) 3, the first non-stretching film layer 9 surface of the sealing film 3, through 2 The liquid-curable maleic acid-modified polypropylene adhesive is overlapped with the other side of the aluminum foil after dry lamination, and is sandwiched between a rubber nip roll and a lamination roll heated to 100°C. After being pressed and dry-laminated, it was aged (heated) at 40° C. for 10 days to obtain an exterior material 1 for an electrical storage device having the configuration shown in FIG. 2 .

In addition, the maleic acid-modified polypropylene adhesive of the above-mentioned 2-component curing type is made of maleic acid-modified polypropylene (melting point 80° C., acid value 10 mgKOH/g) as the main agent 100 parts by mass, and hexamethylene dimethicone The adhesive solution which the isocyanurate body (NCO content: 20 mass %) of isocyanate was mixed with a solvent as 8 mass parts of hardeners. It was coated on the other side of the aluminum foil so that the adhesive solution had a solid coating weight of 2 g/m ² , and after heating and drying, it was overlapped with the first non-stretched film layer 9 of the sealing film 3 .

<Example 6>

Except that the first unstretched film layer 7 of the innermost layer contains 200 ppm of erucamide as a lubricant, the first unstretched film layer 9 on the metal foil layer side contains 200 ppm of erucamide as a lubricant, and the second The non-stretched film layer 8 contains 400 ppm of erucamide and 400 ppm of ethylene bisoleamide as lubricants (refer to Table 1), the rest is the same as that of Example 5, and the structure shown in FIG. 2 is obtained. Exterior material 1 for electric storage device.

<Example 7>

Except that the first unstretched film layer 7 of the innermost layer contains 1000 ppm of erucamide as a lubricant, the first unstretched film layer 9 of the metal foil layer side contains 1000 ppm of erucamide as a lubricant, and the second The non-stretched film layer 8 contains 2000 ppm of erucamide and 500 ppm of ethylene bisoleamide as lubricants (refer to Table 1), the rest is the same as that of Example 5, and the structure shown in FIG. 2 is obtained. Exterior material 1 for electric storage device.

<Example 8>

Except that the first unstretched film layer 7 of the innermost layer contains 3000 ppm of erucamide as a lubricant, the first unstretched film layer 9 of the metal foil layer side contains 3000 ppm of erucamide as a lubricant, and the second The non-stretched film layer 8 contains 2000 ppm of erucamide and 500 ppm of ethylene bisoleamide as lubricants (refer to Table 1), the rest is the same as that of Example 5, and the structure shown in FIG. 2 is obtained. Exterior material 1 for electric storage device.

<Example 9>

Except that the first unstretched film layer 7 which is the innermost layer contains 200 ppm of docosamide as a lubricant, the first unstretched film layer 9 on the side of the metal foil layer contains 200 ppm In addition to the composition (refer to Table 1) that pm of docosamide is used as a lubricant, and the second non-stretched film layer 8 contains 400 ppm of docosamide and 400 ppm of ethylenebisoleamide as lubricants, Others were the same as in Example 5, and the exterior material 1 for a power storage device having the structure shown in FIG. 2 was obtained.

<Example 10>

Except that the first unstretched film layer 7 which is the innermost layer contains 800 ppm of erucamide and 200 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 800 ppm of The composition of erucamide and 200ppm of ethylenebisoleate as lubricants, and the second non-stretched film layer 8 containing 2000ppm of erucamide and 200ppm of ethylenebisoleate as lubricants Except (refer to Table 1), it was the same as that of Example 5, and the exterior material 1 for electric storage devices of the structure shown in FIG. 2 was obtained.

<Example 11>

Except that the first unstretched film layer 7 which is the innermost layer contains 2500 ppm of erucamide and 500 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 2500 ppm of The composition of erucamide and 500ppm of ethylene bisoleate as lubricants, and the second non-stretch film layer 8 containing 300ppm of erucamide and 500ppm of ethylene bisoleate as lubricants Except (refer to Table 1), it was the same as that of Example 5, and the exterior material 1 for electrical storage devices of the structure shown in FIG. 2 was obtained.

<Example 12>

Except that oleic acid amide is used instead of erucic acid amide, others are the same as those in Example 1. In the same manner as 1, an exterior material 1 for a power storage device having the configuration shown in FIG. 2 was obtained (see Table 1).

<Example 13>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 200 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 1000 ppm of Except that erucamide and 200 ppm of ethylene bisoleamide are used as lubricants, and the second non-stretched film layer 8 contains 2000 ppm of erucamide as lubricants (refer to Table 1), the rest are the same as the implementation In the same manner as in Example 5, the exterior material 1 for a power storage device having the structure shown in FIG. 2 was obtained.

<Example 14>

Except that the first unstretched film layer 7 which is the innermost layer contains 2500 ppm of erucamide and 500 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 2500 ppm of Except that erucamide and 500 ppm of ethylene bisoleamide are used as lubricants, and the second non-stretched film layer 8 contains 800 ppm of erucamide as lubricants (refer to Table 1), the rest is the same as the implementation In the same manner as in Example 5, the exterior material 1 for a power storage device having the structure shown in FIG. 2 was obtained.

<Example 15>

Except for using docosamide instead of erucamide (refer to Table 1), the same procedure as in Example 11 was carried out to obtain an exterior material 1 for a power storage device (refer to Table 1) having the configuration shown in FIG. 2 .

<Example 16>

Except for using ethylenebisstearylamine instead of ethylenebisoleamide (refer to Table 1), the rest is the same as that of Example 6, to obtain a power storage device with the configuration shown in FIG. 2 . 1 for the exterior material.

<Example 17>

Except having used ethylenebisstearylamine instead of ethylenebisoleamide (refer to Table 1), it was the same as that of Example 14, and the exterior material 1 for electric storage devices of the structure shown in FIG. 2 was obtained.

<Example 18>

Except that the second unstretched film layer 8 contains 300 ppm of erucamide and 500 ppm of ethylene bis-stearylamine as lubricants (see Table 1), the rest is the same as that of Example 17, and the result shown in FIG. 2 is obtained. The exterior material 1 for an electric storage device is constructed.

<Example 19>

Except that the first unstretched film layer 7 of the innermost layer contains 3000 ppm of erucamide as a lubricant, the first unstretched film layer 9 of the metal foil layer side contains 3000 ppm of erucamide as a lubricant, and the second The non-stretched film layer 8 contains 400 ppm of erucamide and 400 ppm of ethylene bisoleamide as lubricants (refer to Table 2), the rest is the same as that of Example 5, and the structure shown in FIG. 2 is obtained. Exterior material 1 for electric storage device.

<Example 20>

Except that the first unstretched film layer 7 which is the innermost layer contains 200 ppm of stearylamine as a lubricant, the first unstretched film layer 9 on the side of the metal foil layer contains 200 ppm of stearylamine as a lubricant, and the second The non-stretched film layer 8 contains 400 ppm of stearylamine and 400 ppm of ethylene bisoleamide as lubricants (refer to Table 2), the rest is the same as that of Example 5, and the composition shown in FIG. 2 is obtained. Exterior material 1 for electric storage device.

<Example 21>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 100 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 1000 ppm of Except that erucamide and 100 ppm of ethylene bisoleamide are used as lubricants, and the second non-stretched film layer 8 contains 2000 ppm of erucamide as lubricants (refer to Table 2), the rest is the same as the implementation In the same manner as in Example 5, the exterior material 1 for a power storage device having the structure shown in FIG. 2 was obtained.

<Example 22>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 2000 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 1000 ppm of Except that erucamide and 2000 ppm of ethylene bisoleamide are used as lubricants, and the second non-stretched film layer 8 contains 800 ppm of erucamide as lubricants (refer to Table 2), the rest is the same as the implementation In the same manner as in Example 5, the exterior material 1 for a power storage device having the structure shown in FIG. 2 was obtained.

<Example 23>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 100 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 1000 ppm of The composition of erucamide and 100ppm of ethylene bisoleate as lubricants, and the second non-stretch film layer 8 containing 2000ppm of erucamide and 100ppm of ethylene bisoleate as lubricants Except (refer to Table 2), it was the same as that of Example 5, and the exterior material 1 for electrical storage devices of the structure shown in FIG. 2 was obtained.

<Example 24>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 1500 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 1000 ppm of The composition of erucamide and 1500ppm of ethylene bisoleate as lubricants, and the second non-stretched film layer 8 containing 2000ppm of erucamide and 1000ppm of ethylene bisoleate as lubricants Except (refer to Table 2), it was the same as that of Example 5, and the exterior material 1 for electrical storage devices of the structure shown in FIG. 2 was obtained.

<Reference Example 25>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide as a lubricant, and the second unstretched film layer 8 contains 2000 ppm of erucamide and 100 ppm of ethylene bisoleate Except for the configuration of the lubricant (refer to Table 2), the rest was the same as that of Reference Example 1, and an exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained.

<Reference Example 26>

Except that the first non-stretch film layer 7 which is the innermost layer contains 1000 ppm of docosamide as a lubricant, and the second non-stretched film layer 8 contains 300 ppm of docosamide and 200 ppm of ethylene bisoleic acid Except for the configuration of amide as a lubricant (see Table 2), the rest was the same as that of Reference Example 1, and an exterior material 1 for an electrical storage device having the configuration shown in FIG. 1 was obtained.

<Reference Example 27>

Except that the first non-stretching film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 100 ppm of ethylene bisoleamide as lubricants, and the second non-stretching Except that the stretched film layer 8 contained 2000 ppm of erucamide as a lubricant (refer to Table 2), the rest was the same as that of Reference Example 1, and an exterior material 1 for a power storage device having the structure shown in FIG. 1 was obtained.

<Reference Example 28>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 1500 ppm of ethylene bisoleate as lubricants, and the second unstretched film layer 8 contains 2000 ppm of erucamide Except for the configuration of the lubricant (refer to Table 2), the rest was the same as that of Reference Example 1, and an exterior material 1 for a power storage device having the configuration shown in FIG. 1 was obtained.

<Example 29>

Except that the first unstretched film layer 7 which is the innermost layer contains 2000 ppm of erucamide and 2000 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 2000 ppm of Except that erucamide and 2000ppm of ethylene bisoleamide are used as lubricants, and the second non-stretched film layer 8 contains 500ppm of erucamides as lubricants (refer to Table 2), the rest is the same as the implementation In the same manner as in Example 5, the exterior material 1 for a power storage device having the structure shown in FIG. 2 was obtained.

<Example 30>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 100 ppm of m-xylylene bisstearylamine as lubricants, the first unstretched film layer 9 on the side of the metal foil layer Contains 1000ppm of erucamide and 100ppm of m-xylylenedistearylamine as lubricants, and the second non-stretch film layer 8 contains 2000ppm of erucamide and 100ppm of m-xylylenebis Except for the composition of stearylamine as the lubricant (refer to Table 2), the rest are the same as in Example 5, and the results shown in Figure 2 are obtained. The exterior material 1 for a power storage device is shown.

<Reference Example 9>

Except that the first unstretched film layer 7 which is the innermost layer contains 2000 ppm of stearylamine and 1000 ppm of m-xylylene bisstearylamine as lubricants, the first unstretched film layer 9 on the side of the metal foil layer The composition containing 2000ppm of stearylamine as lubricant, and the second non-stretched film layer 8 containing 500ppm of stearylamine and 1000ppm of m-xylylenebisstearylamine as lubricant (refer to Table 2) Others were the same as in Example 5, and the exterior material 1 for a power storage device having the structure shown in FIG. 2 was obtained.

<Example 32>

Except that the first unstretched film layer 7 which is the innermost layer contains 6000 ppm of erucamide and 500 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 6000 ppm of The composition of erucamide and 500ppm of ethylene bisoleate as lubricants, and the second non-stretch film layer 8 containing 300ppm of erucamide and 500ppm of ethylene bisoleate as lubricants Except (refer to Table 2), it was the same as that of Example 5, and the exterior material 1 for electrical storage devices of the structure shown in FIG. 2 was obtained.

<Example 33>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide and 500 ppm of ethylene bisoleamide as lubricants, the first unstretched film layer 9 on the side of the metal foil layer contains 1000 ppm of The composition of erucamide and 500ppm of ethylene bisoleate as lubricants, and the second non-stretch film layer 8 containing 5000ppm of erucamide and 500ppm of ethylene bisoleate as lubricants (see Except according to Table 2), the other is the same as that of Example 5, and the exterior material 1 for electric storage devices of the structure shown in FIG. 2 was obtained.

<Comparative Example 1>

Except that the innermost first unstretched film layer 7 contains 1000 ppm of erucamide as a lubricant, and the second unstretched film layer 8 contains 500 ppm of erucamide as a lubricant (refer to Table 3) , and the rest were the same as in Reference Example 1, and an exterior material for a power storage device was obtained.

<Comparative Example 2>

Except that the first unstretched film layer 7 which is the innermost layer contains 1000 ppm of erucamide as a lubricant, the first unstretched film layer 9 on the metal foil layer side contains 1000 ppm of erucamide, and the second unstretched film contains 1000 ppm of erucamide. Except that the layer 8 contained 500 ppm of erucamide as a lubricant (refer to Table 3), it was the same as that of Example 5, and an exterior material for a power storage device was obtained.

<Comparative Example 3>

Except that the first unstretched film layer 7 of the innermost layer contains 200 ppm of erucamide as a lubricant, the first unstretched film layer 9 on the metal foil layer side contains 200 ppm of erucamide as a lubricant, and the second Except that the non-stretched film layer 8 contained 800 ppm of erucamide as a lubricant (refer to Table 3), it was the same as that of Example 5, to obtain an exterior material for a power storage device.

<Comparative Example 4>

Except that the first unstretched film layer 7 which is the innermost layer contains 3000 ppm of erucamide as a lubricant, the first unstretched film layer 9 on the side of the metal foil layer contains 3000 ppm of erucamide as a lubricant. ppm of erucamide was used as a lubricant, and the second non-stretched film layer 8 contained 800 ppm of erucamide as a lubricant (refer to Table 3), the rest was the same as that of Example 5. Loading material.

<Comparative Example 5>

Except that the first unstretched film layer 7 of the innermost layer contains 200 ppm of erucamide as a lubricant, the first unstretched film layer 9 on the metal foil layer side contains 200 ppm of erucamide as a lubricant, and the second Except that the non-stretched film layer 8 contained 1500 ppm of erucamide as a lubricant (refer to Table 3), it was the same as that of Example 5, and the exterior material for electric storage devices was obtained.

<Comparative Example 6>

Except that the innermost first non-stretch film layer 7 contains 250 ppm of erucamide as a lubricant, and the second non-stretched film layer 8 contains 100 ppm of erucamide as a lubricant (refer to Table 3) , and the rest were the same as in Reference Example 1, and an exterior material for a power storage device was obtained.

<Comparative Example 7>

Except that the first unstretched film layer 7 which is the innermost layer contains 250 ppm of erucamide as a lubricant, the first unstretched film layer 9 on the metal foil layer side contains 250 ppm of erucamide, and the second unstretched film contains 250 ppm of erucamide. Except that the layer 8 contained 100 ppm of erucamide as a lubricant (refer to Table 3), it was the same as that of Example 5, and an exterior material for an electrical storage device was obtained.

<Comparative Example 8>

Except that the first non-stretched film layer 7 which is the innermost layer contains 200 ppm of Erucamide is used as a lubricant, the first unstretched film layer 9 on the side of the metal foil layer contains 200 ppm of erucamide, and the second unstretched film layer 8 contains 7000 ppm of erucamide as a lubricant. Except for Table 3), it was the same as that of Example 5, and the exterior material for electrical storage devices was obtained.

<Comparative Example 9>

Except that the innermost first non-stretch film layer 7 contains 3500 ppm of erucamide as a lubricant, the first non-stretched film layer 9 on the metal foil layer side contains 3500 ppm of erucamide, and the second non-stretched film Except that the layer 8 contained 21,000 ppm of erucamide as a lubricant (see Table 3), it was the same as that of Example 5, to obtain an exterior material for an electrical storage device.

<Comparative Example 10>

Except that the first unstretched film layer 7 of the innermost layer contains 3500 ppm of erucamide as a lubricant, the first unstretched film layer 9 on the metal foil layer side contains 3500 ppm of erucamide as a lubricant, and the second Except that the non-stretched film layer 8 contained 100 ppm of erucamide as a lubricant (refer to Table 3), it was the same as that of Example 5, and an exterior material for an electrical storage device was obtained.

<Comparative Example 11>

Except that the innermost first unstretched film layer 7 contains 4000 ppm of erucamide as a lubricant, and the second unstretched film layer 8 contains 500 ppm of erucamide as a lubricant (refer to Table 3) , and the rest were the same as in Reference Example 1, and an exterior material for a power storage device was obtained.

<Comparative Example 12>

Except that the first unstretched film layer 7 which is the innermost layer contains 4000 ppm of erucamide as a lubricant, the first unstretched film layer 9 on the side of the metal foil layer contains 4000 ppm of erucamide, and the second unstretched film contains 4000 ppm of erucamide. Except that the layer 8 contained 500 ppm of erucamide as a lubricant (refer to Table 3), it was the same as that of Example 5, and an exterior material for a power storage device was obtained.

<Comparative Example 13>

Except that the first unstretched film layer 7 which is the innermost layer contains 4000 ppm of amide oleate as a lubricant, the first unstretched film layer 9 on the side of the metal foil layer contains 4000 ppm of oleic acid amide, and the second unstretched film Except that the layer 8 contained 500 ppm of amide oleate as a lubricant (refer to Table 3), it was the same as that of Example 5, and an exterior material for an electrical storage device was obtained.

<Comparative Example 14>

Except that the first unstretched film layer 7 which is the innermost layer contains 4000 ppm of docosamide as a lubricant, the first unstretched film layer 9 on the metal foil layer side contains 4000 ppm of docosamide, and the second unstretched film layer 9 contains 4000 ppm of docosamide. Except that the stretched film layer 8 contained 500 ppm of docosamide as a lubricant (refer to Table 3), it was the same as that of Example 5, and an exterior material for an electrical storage device was obtained.

<Comparative Example 15>

Except that the innermost first non-stretched film layer 7 contains 1000 ppm of erucamide as a lubricant (see Table 3), the same procedure as in Reference Example 4 was carried out to obtain an exterior material for a power storage device.

Each of the exterior materials for electrical storage devices obtained as described above was evaluated based on the following evaluation method. The results are shown in Table 4. In addition, the coefficient of kinetic friction described in Table 4 is the coefficient of kinetic friction measured on the innermost grease surface 7a of each exterior material based on JIS K7125-1995. In addition, in Tables 1 to 3, "EBOA" is an abbreviation for ethylenebisoleamide, "EBSA" is an abbreviation for ethylenebisstearylamide, and "KBSA" is m-xylylenebis Abbreviation for stearylamine.

<Method for evaluating the amount of lubricant present on the surface of the innermost layer of the exterior material>

Two rectangular test pieces of 100 mm in length x 100 mm in width were cut out from each of the exterior materials for electrical storage devices, and the two test pieces were superimposed, and the periphery of the sealing layers of both were sealed at a heat-sealing temperature of 200°C. Heat-sealed to each other to make a bag body. 1 mL of acetone was injected into the inner space of the bag body using a syringe, and the surface 7a of the innermost layer 7 of the sealing layer was placed in contact with acetone for 3 minutes, and then the acetone in the bag body was withdrawn. The amount of lubricant contained in the extracted liquid was measured and analyzed using a gas chromatograph, thereby obtaining the amount of lubricant (μg/cm ² ) present on the surface of the innermost layer of the exterior material. That is, the amount of lubricant ^{per 1 cm 2} of the surface of the innermost layer was obtained.

<Formability evaluation method>

Using a straight die with a free forming depth, the exterior material was deep-stretched in one stage under the following forming conditions, and the formability of each forming depth (9mm, 8mm, 7mm, 6mm, 5mm, 4mm, 3mm, 2mm) was evaluated. The maximum forming depth (mm) that can be formed well without generating pinholes at the corners was investigated. Judgment: Those with a maximum molding depth of 5 mm or more are "○", those with a maximum molding depth of 2 mm or more and less than 5 mm are "△", and those with a maximum molding depth of less than 2 mm are "×". The results are shown in Table 4. In addition, the presence or absence of pinholes was investigated by visually observing the presence or absence of light transmitted through the pinholes.

(forming conditions)

Forming die...Punch: 33.3mm×53.9mm, Die: 80mm×120mm, Corner R: 2mm, Punch R: 1.3mm, Die R: 1mm

Anti-crease pressure... gauge pressure: 0.475MPa, actual pressure (calculated value): 0.7MPa

Material...SC (carbon steel) material, only punch R is chrome plated.

<Assessment method for the presence or absence of white powder>

After cutting out a rectangular test piece with a length of 600 mm x 100 mm in width from each exterior material for an electrical storage device, the obtained test piece was placed with the three surfaces of the inner sealing layer (that is, the surface 7a of the innermost layer) on the upper side. On the test bench, a SUS hammer (mass 1.3 kg, size of contacting the ground: 55 mm × 50 mm) with a black surface wound with black cloth is placed on the top of the test piece, and the hammer is placed on the test piece. The horizontal direction parallel to the upper surface of the test piece was stretched at a tensile speed of 4 cm/sec, whereby the hammer was in contact with the upper surface of the test piece and was moved over a length of 400 mm. Visually observe the contact surface of the hammer after the stretching movement For the cloth (black), if there is white powder on the surface of the cloth (black), it is marked as “×”, if only a small amount of white powder is produced, it is “△”, and if there is little or no white powder is observed, it is “○”. In addition, as the above-mentioned black cloth, "Static Removal Sheet S SD2525 3100" manufactured by TRUSCO Co., Ltd. was used.

<Comprehensive Judgment>

If the evaluation of the formability is "○", and the evaluation of the presence or absence of white powder is also "○", the comprehensive judgment is judged as "○"; at least one of the evaluation of the formability and the evaluation of the presence or absence of white powder is "△", and the other is "△". Those with "○" were judged as "△" by the comprehensive judgment, and when at least one of the formability evaluation and the presence or absence of white powder was judged as "X", the comprehensive judgment was judged as "X". Those with a comprehensive judgment of "○" or "△" are considered acceptable.

As is apparent from Table 1, the exterior materials for electrical storage devices of Examples 5 to 33 of the present invention constituted by the sealing film of the present invention are excellent in formability, and white powder hardly appears on the surface of the exterior materials.

On the other hand, Comparative Examples 1 to 3, 5 to 8, and 10, which deviate from the scope of the present invention, have poor formability of the exterior material, and Comparative Examples 3, 4, 9, and 11 that deviate from the scope of the present invention. ~15, the surface of the exterior material produces white powder remarkably. That is, in Comparative Examples 1 to 15, which deviate from the prescribed range of the present invention, the comprehensive judgment of any one is "x".

【Industrial Availability】

Specific examples of the exterior material for an electrical storage device produced using the sealing film of the present invention and the exterior material for an electrical storage device of the present invention are, for example, as

‧Power storage devices such as lithium ion batteries (lithium ion batteries, lithium polymer batteries, etc.)

‧Lithium-ion capacitors

‧External materials for various electric storage devices such as electric double layer capacitors. In addition, the power storage device of the present invention also includes an all-solid-state battery in addition to the power storage device of the above example.

This application claims priority along with Japanese Patent Application No. 2016-120918 of the Japanese Patent Application filed on June 17, 2016, and the disclosure thereof directly constitutes a part of this application.

The terms and descriptions used herein are used to describe the embodiments of the present invention, but the present invention is not limited thereto. Any equivalents to the characteristic matters disclosed and recited in the present invention should not be excluded, and various modifications within the claimed scope of the present invention should also be understood to be acceptable.

1: Exterior materials for power storage devices

2: Heat-resistant resin layer (outer layer)

3: Inner sealing layer (sealing film) (inner layer)

4: Metal foil layer

5: Second adhesive layer (outer adhesive layer)

6: 1st adhesive layer (inner adhesive layer)

7: 1st non-stretch film layer (innermost layer)

7a: The surface of the first unstretched film layer (the surface of the innermost layer of the exterior material)

8: The second non-stretching film layer

9: 1st unstretched film layer (metal foil layer side)

Claims (14)

A sealing film for an exterior material of a power storage device, characterized in that it is formed of a laminate of three or more layers, and the laminate system includes a second non-stretching film layer and a surface laminated on one side of the second non-stretching film layer The first non-stretching film layer and the first non-stretching film layer laminated on the other side of the second non-stretching film layer; the above-mentioned first non-stretching film layer on either side forms the outermost material. The inner layer; the first non-stretched film layer, which contains: a random copolymer containing propylene as a copolymer component and other copolymer components other than propylene, and a lubricant; the second non-stretched film layer contains: Propylene as a copolymer component and block copolymers of other copolymer components other than propylene, and lubricants; and the lubricants and/or the second non-stretched film layers forming the innermost layer of the exterior material The lubricant in the non-stretchable film layer contains: at least one first lubricant selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides, and fatty acid diamides and aromatic diamides At least one second lubricant in the group; the lubricant in the first non-stretched film layer of the exterior material and the lubricant in the second non-stretched film layer, which contain: selected from saturated fatty acid amides and at least one first lubricant selected from the group consisting of unsaturated fatty acid amides, and at least one second lubricant selected from the group consisting of fatty acid bisamides and aromatic bisamides; the aforementioned first has no extension The lubricant and lubricant concentration contained in each of the thin film layers are the same. A sealing film for an exterior material of a power storage device, characterized in that it is formed by a laminate of three or more layers, and the laminate system includes a second non-stretching film layer laminated on one side of the second non-stretching film layer The first non-stretching film layer on the side of the second non-stretching film layer, and the first non-stretching film layer on the other side of the second non-stretching film layer; the first non-stretching film layer on either side forms the exterior The innermost layer of the material; the first non-stretch film layer, which contains: a random copolymer of propylene and other copolymer components other than propylene, and a lubricant; the second non-stretch film layer, which contains : a block copolymer containing propylene as a copolymer component and other copolymer components other than propylene, and a lubricant; and the lubricant and/or the aforementioned first non-stretch film layer forming the innermost layer of the exterior material The lubricant in the second unstretched film layer contains at least one first lubricant selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides, and fatty acid bisamides and aromatic bisamides At least one second lubricant in the group of amides; the lubricant in the first non-stretchable film layer of the exterior material, containing: selected from the group of saturated fatty acid amides and unsaturated fatty acid amides At least one first lubricant, and at least one second lubricant selected from the group consisting of fatty acid diamides and aromatic diamides; the lubricant in the second non-stretched film layer contains: At least one first lubricant selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides; the lubricants and lubricant concentrations contained in the first non-stretched film layers are the same. A sealing film for an exterior material of a power storage device, characterized in that it is formed of a laminate of three or more layers, and the laminate system includes a second non-stretching film layer and a surface laminated on one side of the second non-stretching film layer The first non-stretching film layer and the first non-stretching film layer laminated on the other side of the second non-stretching film layer; the above-mentioned first non-stretching film layer on either side forms the outermost material. inner layer; The first unstretched film layer contains: a random copolymer containing propylene as a copolymer component and other copolymer components other than propylene, and a lubricant; the second unstretched film layer contains: a copolymer component A block copolymer of propylene and other copolymer components other than propylene, and a lubricant; and the lubricant and/or the second unstretched film in the first unstretched film layer forming the innermost layer of the exterior material The lubricant in the layer contains at least one first lubricant selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides, and a group of fatty acid bisamides and aromatic bisamides At least one of the second lubricants; the lubricant in the first non-stretched film layer of the exterior material, which contains: at least one selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides. 1. Lubricant; the lubricant in the second non-stretching film layer, comprising: at least one first lubricant selected from the group consisting of saturated fatty acid amides and unsaturated fatty acid amides, and a first lubricant selected from fatty acid diamides The second lubricant of at least one of the group consisting of amine and aromatic bisamide; the lubricant and lubricant concentration contained in the first non-stretched film layers are the same. The sealing film for an exterior material of an electrical storage device according to any one of claims 1 to 3, wherein the total concentration of the lubricant contained in the first non-stretched film layer is 200 ppm to 200 ppm. 7000 ppm, the total value of the content concentration of all the lubricants contained in the second non-stretched film layer is 500 ppm to 7000 ppm. The sealing film for an exterior material of an electrical storage device according to any one of Claims 1 to 3, wherein in the layer containing the second lubricant, the concentration of the lubricant with respect to all the lubricants in the layer The total value, the ratio of the concentration of the second lubricant is 5% to 90%. An exterior material for a power storage device, which is characterized by including: any one of items 1 to 5 in the scope of the patent application An inner sealing layer formed of the sealing film described in the item 1, and a metal foil layer laminated on one side of the inner sealing layer. An exterior material for a power storage device, characterized by comprising: a heat-resistant resin layer for an outer layer, an inner sealing layer formed of the sealing film described in any one of the claims 1 to 5 of the scope of application, and two Metal foil layers between layers. The exterior material for an electricity storage device as described in claim 6 or 7 of the scope of the application, wherein the amount of lubricant present in the surface of the first non-stretched thin film layer forming the innermost layer of the exterior material is 0.1 μg /cm ² ~1.0μg/cm ^{2 in} the range. An outer casing for a power storage device is characterized by being formed of a molded body of the outer casing described in any one of the 6th to 8th claims. A method of manufacturing an exterior material for a power storage device, comprising: a preparation step, preparing a laminate, wherein the sealing film described in any one of claims 1 to 5 in the scope of the application for the laminate system is interposed with a first adhesive It is obtained by laminating with metal foil; in the aging step, the above-mentioned laminated body is heat-treated to obtain an exterior material for an electrical storage device. The manufacturing method of the exterior material for electrical storage devices as described in Claim 10 of Claim 1 whose said 1st adhesive agent is a thermosetting adhesive agent. A method of manufacturing an exterior material for an electrical storage device, comprising: a preparation step of preparing a laminate, wherein one side surface of the laminate system metal foil is laminated via a second adhesive and a heat-resistant resin film, the metal foil The other side of the surface is composed of the first adhesive and the sealing film layered as described in any one of the claims 1 to 5 of the scope of the application; in the aging step, the above layered body is subjected to heat treatment to obtain an outer shell for an electrical storage device. Loading material. The method for manufacturing an exterior material for an electrical storage device as described in Item 12 of the scope of the patent application, wherein, The said 1st adhesive agent is a thermosetting adhesive agent, and the said 2nd adhesive agent is a thermosetting adhesive agent. The method for producing an exterior material for an electrical storage device as described in any one of Claims 10 to 13, wherein the first non-stretched thin film layer is obtained by heat treatment to form the most important part of the exterior material for an electrical storage device. In the inner layer, the amount of lubricant present on its surface is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .

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