JP6690800B1 - Power storage device exterior material, manufacturing method thereof, and power storage device - Google Patents

Abstract

Provided is a technique in which a base material layer has a polyamide film, has a predetermined thickness, and suppresses curling due to molding of an exterior material for an electricity storage device having excellent insulating properties. The exterior material for an electricity storage device according to the first disclosure is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order, and the base material layer is at least a polyamide film. The polyamide film layer has a thickness of 10 μm or more and 17 μm or less, the barrier layer has a thickness of 36 μm or more and 44 μm or less, and the laminate has a thickness of 83 μm or more and 93 μm or less.

Description

  The present disclosure relates to an exterior material for an electricity storage device, a method for manufacturing the same, and an electricity storage device.

  Conventionally, various types of power storage devices have been developed, but in all power storage devices, a packaging material (exterior material) is an indispensable member for sealing the power storage device elements such as electrodes and electrolytes. Conventionally, metal exterior materials have been often used as exterior materials for power storage devices.

  On the other hand, in recent years, as electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, and the like have become more sophisticated, power storage devices have been required to have various shapes, and to be thin and lightweight. However, it has been difficult to follow the diversification of the shape with the metal outer casing material for an electricity storage device, which has been widely used in the past, and there is a limitation in weight reduction.

  Therefore, in recent years, as a packaging material for an electricity storage device that can be easily processed into various shapes and can be made thin and lightweight, a film-like material in which a base material / aluminum foil layer / heat-fusible resin layer is sequentially laminated An exterior material has been proposed (for example, see Patent Document 1).

  In such a film-like exterior material, generally, a recess is formed by cold molding, and an electric storage device element such as an electrode or an electrolytic solution is arranged in the space formed by the recess, and a heat-fusible resin is used. By heat-sealing the layers to each other, an electricity storage device in which the electricity storage device element is housed inside the exterior material is obtained.

JP, 2008-287971, A

  In recent years, film-shaped exterior materials have been required to be thinner. Further, from the viewpoint of further increasing the energy density of the electricity storage device, it is also required to form deep recesses in the exterior material.

  In order to improve the moldability of the film-shaped exterior material, it is conceivable to use, for example, a polyamide film having excellent moldability as the base material layer.

  However, as a result of investigations by the present inventors, a polyamide film was used as a base material layer, and a base material layer, a barrier layer, and a heat-fusible resin layer were sequentially laminated to form an exterior material for an electricity storage device, which was molded. When a recess for accommodating an electricity storage device element is formed by reducing the thickness of the exterior material for an electricity storage device, the peripheral portion of the recess is curled (curved) by molding to accommodate the electricity storage device element or heat fusion. It was found that the heat fusion of the conductive resin layer may be hindered and the production efficiency of the electricity storage device may be reduced.

  In particular, for power storage devices used in small equipment such as personal computers, cameras, and mobile phones, it is required to form a deep recess with a small area in a thin exterior material, and curling due to molding is remarkable. Can be.

  Under such circumstances, the present disclosure provides a technique for suppressing curling due to molding of an exterior material for an electricity storage device having a polyamide film as a base material layer, having a predetermined thickness, and having excellent insulating properties. The main purpose is to do.

  In order to solve the above-described problems, the present disclosure focuses on reducing the molding curl by focusing on the laminated structure of the exterior material for an electricity storage device in the exterior material for an electricity storage device using a base material layer having at least a polyamide film. Diligently studied. As a result, they have found that it is possible to provide a packaging material for an electricity storage device in which molding curl is significantly suppressed as compared with a conventional packaging material for an electricity storage device. Specifically, after setting the total thickness of the laminate constituting the exterior material for an electricity storage device to a specific range of 83 μm or more and 93 μm or less, the thickness of the polyamide film layer is set to a range of 10 μm or more and 17 μm or less, and the barrier By setting the layer thickness to be in the range of 36 μm or more and 44 μm or less, the power storage device in which curling due to molding is effectively suppressed although the thickness of the power storage device exterior material is relatively thin and has excellent insulating properties It has been found that it can be used as an exterior material for automobiles.

  Further, the present inventors set the total thickness of the laminate constituting the exterior material for an electricity storage device to a specific range of 83.1 μm or more and 98 μm or less, and then set the thickness of the surface coating layer to 0.1 μm or more and 5 μm or less. By setting the thickness of the polyamide film layer in the range of 10 μm or more and 17 μm or less and the thickness of the barrier layer in the range of 36 μm or more and 44 μm or less, the outer packaging material for an electricity storage device has a relatively small thickness. However, they have found that the curling due to molding is effectively suppressed to provide an exterior material for an electricity storage device.

The present disclosure has been completed by further studies based on these findings. That is, the present disclosure provides the inventions of the following aspects.
Item 1. At least, a base layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate including in this order,
The base material layer has at least a polyamide film layer,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminate is 83 μm or more and 93 μm or less.
Item 2. An adhesive layer is provided between the barrier layer and the heat-fusible resin layer,
The adhesive layer has a thickness of 8 μm or more and 22 μm or less,
Item 2. The outer casing material for an electricity storage device according to Item 1, wherein the heat-fusible resin layer has a thickness of 8 μm or more and 22 μm or less.
Item 3. An adhesive layer is provided between the barrier layer and the heat-fusible resin layer,
The thickness of the adhesive layer is 1 μm or more and 5 μm or less,
Item 2. The outer casing material for an electricity storage device according to Item 1, wherein the heat-fusible resin layer has a thickness of 18 μm or more and 34 μm or less.
Item 4. The laminate has a breaking energy per 1 m unit width in MD and a breaking energy per 1 m unit width in TD, which is calculated from a curve of “measured load (N / 15 mm) -displacement amount” measured by a tensile test. The outer packaging material for an electricity storage device according to any one of Items 1 to 3, wherein the total is 100 J or more.
Item 5. An electricity storage device, wherein an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte is contained in a package formed of the exterior material for an electricity storage device according to any one of Items 1 to 4.
Item 6. At least, a step of obtaining a laminate by laminating the base material layer, the barrier layer, and the heat-fusible resin layer in this order,
The base material layer has at least a polyamide film layer,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The thickness of the said laminated body is 83 micrometers or more and 93 micrometers or less, The manufacturing method of the exterior material for an electrical storage device.
Item 7. At least a surface coating layer, a base material layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate provided in this order,
The base material layer has at least a polyamide film layer,
The thickness of the surface coating layer is 0.1 μm or more and 5 μm or less,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminated body is 83.1 μm or more and 98 μm or less.

  According to the present disclosure, it is possible to provide a technique in which a base material layer has a polyamide film, has a predetermined thickness, and suppresses curling due to molding of a packaging material for an electricity storage device having excellent insulating properties. . Further, according to the present disclosure, it is also possible to provide a method for manufacturing an exterior material for an electricity storage device and an electricity storage device.

FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure. FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure. FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure. FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure. FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure. FIG. 3 is a schematic diagram showing an example of a cross-sectional structure of a power storage device exterior material of the present disclosure. FIG. 3 is a schematic diagram for explaining a curl evaluation method by molding an outer casing for an electricity storage device. FIG. 3 is a schematic diagram for explaining a curl evaluation method by molding an outer casing for an electricity storage device. It is a schematic diagram of the barrier layer of the test sample after shaping | molding in an Example. It is a schematic diagram of the curve (MD) of the measurement load (N / 15 mm) -displacement amount obtained by the tensile test of the exterior material for an electricity storage device. It is a schematic diagram which showed the part which integrated the data of the curve of a measurement load (N / 15mm) -displacement amount.

  This disclosure includes the following first disclosure and second disclosure. In the following description, it is clearly stated which of the disclosures is the description regarding the different matters between the first disclosure and the second disclosure, and regarding the matters common to the first disclosure and the second disclosure, The first disclosure and the second disclosure will be described without distinction.

  The exterior material for an electricity storage device according to the first disclosure is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order, and the base material layer is at least a polyamide film. And a thickness of the polyamide film layer is 10 μm or more and 17 μm or less, a thickness of the barrier layer is 36 μm or more and 44 μm or less, and a thickness of the laminate is 83 μm or more and 93 μm or less. Is characterized by.

  The exterior material for an electricity storage device according to the second disclosure is composed of a laminate including at least a surface coating layer, a base material layer, a barrier layer, and a heat-fusible resin layer in this order. Has at least a polyamide film layer, the thickness of the surface coating layer is 0.1 μm or more and 5 μm or less, the thickness of the polyamide film layer is 10 μm or more and 17 μm or less, and the thickness of the barrier layer is Is 36 μm or more and 44 μm or less, and the thickness of the laminated body is 83.1 μm or more and 98 μm or less.

  Hereinafter, the exterior material for an electricity storage device of the present disclosure will be described in detail. In addition, in this specification, the numerical range shown by "-" means "more than" and "less than". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. In addition, in the present specification, the thickness of each layer constituting the laminate is a value rounded off to one decimal place.

1. Laminated Structure of Exterior Material for Energy Storage Device The exterior material 10 for an energy storage device according to the first disclosure includes a base material layer 1, a barrier layer 3, and a heat-fusible resin layer 4 in this order, as shown in FIG. It is composed of a laminate. Further, the exterior material 10 for an electricity storage device of the second disclosure is, for example, as shown in FIG. 6, a laminate including a surface coating layer 6, a base material layer 1, a barrier layer 3, and a heat-fusible resin layer 4 in this order. It is composed of the body. In the exterior material for an electricity storage device of the present disclosure, the base material layer 1 is the outermost layer side, and the heat-fusible resin layer 4 is the innermost layer. When assembling an electricity storage device using the electricity storage device exterior material 10 and the electricity storage device element, the peripheral edges are heat-sealed with the heat-fusible resin layers 4 of the electricity storage device exterior material 10 facing each other. The electricity storage device element is housed in the space formed by.

  The base material layer 1 only needs to have at least the polyamide film layer 11, and may be composed of only the polyamide film layer 11 as shown in FIG. 1, or as shown in FIGS. For example, you may have the polyamide film layer 11 and the polyester film layer 12. From the viewpoint of more effectively suppressing curling due to the molding of the exterior material for an electricity storage device of the present disclosure, the base material layer 1 is preferably composed of only the polyamide film layer 11.

  In addition, when the base material layer 1 has the polyamide film layer 11 and the polyester film layer 12 as described below, either the polyamide film layer 11 or the polyester film layer 12 may be located on the outermost layer side, but the electricity storage From the viewpoint of improving the electrolytic solution resistance on the outer surface of the device exterior material, it is preferable that the polyamide film layer 11 and the polyester film layer 12 are laminated in order from the barrier layer 3 side.

  For example, as shown in FIG. 2, the polyamide film layer 11 and the polyester film layer 12 may be laminated so as to be in contact with each other. For example, as shown in FIG. 3, the polyamide film layer 11 and the polyester film layer 12 may be laminated. The film layer 12 is adhered to the film layer 12 with an adhesive, and the adhesive layer 13 may be provided between these layers.

  For example, as shown in FIGS. 4 to 6, the exterior material for an electricity storage device of the present disclosure may include an adhesive layer 2 between the base material layer 1 and the barrier layer 3 for the purpose of enhancing the adhesiveness thereof. May have. Further, as shown in FIGS. 5 and 6, an adhesive layer 5 may be provided between the barrier layer 3 and the heat-fusible resin layer 4 as needed for the purpose of enhancing the adhesiveness between them. Further, also in the first disclosure, as in the second disclosure, as shown in FIG. 6, the surface of the base material layer 1 (on the side opposite to the heat-fusible resin layer 4) may have a surface if necessary. The coating layer 6 and the like may be provided.

  The thickness of the laminate that constitutes the exterior material for an electricity storage device according to the first disclosure is set to a specific range of 83 to 93 μm. In the exterior material for an electricity storage device of the first disclosure, by setting the thickness of the laminated body in the range, and by setting the thicknesses of the polyamide film layer 11 and the barrier layer 3 described below in respective specific ranges, Curling due to molding is suppressed even though the thickness of the exterior material for an electricity storage device is relatively thin. From the viewpoint of effectively suppressing curling due to molding while making the thickness of the laminate as thin as possible, the lower limit of the thickness of the laminate is preferably 85 μm or more, more preferably 86 μm or more, and further preferably 87 μm. The above is mentioned, and the upper limit is preferably 91 μm or less, more preferably about 90 μm or less, further preferably about 89 μm or less, and the preferable range is about 83 to 91 μm, about 83 to 90 μm, about 83 to 89 μm. , About 85 to 93 μm, about 85 to 91 μm, about 85 to 90 μm, about 85 to 89 μm, about 86 to 93 μm, about 86 to 91 μm, about 86 to 90 μm, about 86 to 89 μm, about 87 to 93 μm, about 87 to 91 μm , 87 to 90 μm, and 87 to 89 μm. When the thickness of the laminate is not less than the above lower limit, moldability and insulating properties can be improved, and curling due to molding can be more effectively suppressed. In addition, when the thickness of the laminate is not more than these upper limit values, curling due to molding of the exterior material for an electricity storage device is suppressed, and the exterior material for an electricity storage device is thinned while improving the insulating property, and the volume of the electricity storage device element is increased. Can be increased to increase the energy density.

  Further, the thickness of the laminated body that constitutes the exterior material for an electricity storage device of the second disclosure is set to a specific range of 83.1 to 98 μm. In the exterior material for an electricity storage device according to the second disclosure, after setting the thickness of the laminate within the range, the thicknesses of the surface coating layer 6, the polyamide film layer 11 and the barrier layer 3 described below are set within specific ranges. By setting, although the outer casing material for an electricity storage device is relatively thin, it has excellent insulating properties and curling due to molding is suppressed. From the viewpoint of exhibiting excellent insulating properties and effectively suppressing curling due to molding while making the thickness of the laminate as thin as possible, the lower limit of the thickness of the laminate is preferably about 85.1 μm or more. , More preferably 87 μm or more, further preferably 89 μm or more, and the upper limit is preferably about 96 μm or less, more preferably about 94 μm or less, further preferably about 92 μm or less, and the preferable range is 83. 1 to 96 μm, 83.1 to 94 μm, 83.1 to 92 μm, 85.1 to 96 μm, 85.1 to 94 μm, 85.1 to 92 μm, 87 to 98 μm, 87 to 96 μm, 87-94 μm, 87-92 μm, 89-98 μm, 89-96 μm, 89-94 μm, 89-92 μm. Be done. When the thickness of the laminate is not less than the above lower limit, moldability and insulating properties can be improved, and curling due to molding can be more effectively suppressed. Further, when the thickness of the laminated body is equal to or less than these upper limit values, the curl due to the molding of the exterior material for an electricity storage device is suppressed, the exterior material for an electricity storage device is thinned, and the volume of the electricity storage device element is increased, The energy density can be increased.

  In the exterior material for an electricity storage device according to the first disclosure and the second disclosure, the base material layer 1 and the adhesive layer 2 provided as necessary with respect to the thickness (total thickness) of the laminate constituting the exterior material for the electricity storage device. The ratio of the total thickness of the barrier layer 3, the adhesive layer 5 optionally provided, the heat-fusible resin layer 4, and the surface coating layer 6 optionally provided is preferably 90% or more, and more preferably Is 95% or more, and more preferably 98% or more. As a specific example, when the packaging material for an electricity storage device of the present disclosure includes the base material layer 1, the adhesive layer 2, the barrier layer 3, the adhesive layer 5, and the heat-fusible resin layer 4, the packaging material for the electricity storage device. The ratio of the total thickness of these layers to the thickness (total thickness) of the laminate constituting 10 is preferably 90% or more, more preferably 95% or more, and further preferably 98% or more. In addition, even when the packaging material for an electricity storage device of the present disclosure includes the base material layer 1, the adhesive layer 2, the barrier layer 3, and the heat-fusible resin layer 4, a laminate forming the packaging material 10 for the electricity storage device. The ratio of the total thickness of these layers to the body thickness (total thickness) is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more.

  Further, in the outer casing material for an electricity storage device according to the first and second disclosures, the total thickness of layers located inside the barrier layer 3 (on the side of the heat-fusible resin layer 4) is preferably about 16 μm or more, It is more preferably about 19 μm or more, still more preferably about 25 μm or more. The total thickness is preferably about 44 μm or less, more preferably about 39 μm or less, and further preferably about 33 μm or less. The preferable range of the total thickness is about 16 to 44 μm, about 16 to 39 μm, about 16 to 33 μm, about 19 to 44 μm, about 19 to 39 μm, about 19 to 33 μm, about 25 to 44 μm, about 25 to 39 μm, 25. About 33 μm.

  The thickness of each layer or the thickness of the laminate of the exterior material for an electricity storage device of the present disclosure is cut in the thickness direction of the exterior material for an electricity storage device using, for example, a microtome (manufactured by Daiwa Koki Kogyo: REM-710 Retoratome). Then, the exterior material for the electricity storage device is divided into two, and the obtained cross section can be observed and measured with, for example, a laser microscope (manufactured by KEYENCE: VK-9700).

  Further, the exterior material for an electricity storage device according to the present disclosure has a molding depth such that the thickness of the barrier layer 3 described later is 20 μm (that is, when the exterior material for an electricity storage device according to the present disclosure is used for molding, the exterior material for an electricity storage device). The molding depth when the thickness of the barrier layer 3 becomes 20 μm) is preferably 4.5 mm or more, more preferably 5.0 mm or more as the lower limit, and preferably 10.0 mm or less, more preferably as the upper limit. Is 8.0 mm or less, and preferable ranges are about 4.5 to 10.0 mm, about 4.5 to 8.0 mm, about 5.0 to 10.0 mm, and about 5.0 to 8.0 mm. . With respect to the molding depth, the exterior material for an electricity storage device was sequentially molded under the condition that the molding depth was increased from 2.0 mm by 0.5 mm by the cold molding method, and the barrier layer of the test sample after molding was formed. The relationship between the thickness a of the corner P (see FIG. 9) and the molding depth is plotted, and an approximate straight line is drawn to create a graph. From the graph, the thickness a of the corner P of the barrier layer 3 is 20 μm. The molding depth is calculated as follows. Specifically, it is a value measured by the method described in the examples. When the molding depth is equal to or more than the lower limit value described above, curling due to molding of the exterior material for an electricity storage device can be suppressed and pinholes due to molding can be reduced.

  Further, the limit forming depth of the exterior material for an electricity storage device of the present disclosure is preferably 4.0 mm or more, more preferably 5.5 mm or more as a lower limit, and preferably 12.0 mm or less, more preferably as an upper limit. The thickness is 10.0 mm or less, and a preferable range is about 4.0 to 12.0 mm, about 4.0 to 10.0 mm, about 5.5 to 12.0 mm, and about 5.5 to 10.0 mm. The limit forming depth is determined by using a rectangular forming die for the exterior material for the electricity storage device, and changing the forming depth in 0.5 mm units from the forming depth of 0.5 mm at a pressing pressure (contact pressure) of 0.25 MPa. Instead, cold forming (pull-in one-step forming) is performed on 20 samples each, and pinholes in the barrier layer, the deepest forming depth where cracks do not occur in all 20 samples is Amm, and pinholes in the barrier layer. The number of samples in which pinholes and the like were generated at the shallowest molding depth at which the above occurred was B, and the value calculated by the following formula was defined as the critical molding depth of the exterior material for the electricity storage device. Limit forming depth = Amm + (0.5 mm / 20 pieces) × (20 pieces−B pieces). Specifically, it is a value measured by the method described in the examples. When the limit forming depth is equal to or more than the above lower limit value, the exterior material for an electricity storage device can be applied to a high capacity electricity storage device.

  The laminate constituting the exterior material for an electricity storage device of the present disclosure has a breaking energy (MD (Machine) per unit width 1 m calculated from a curve of “measured load (N / 15 mm) -displacement amount” measured by a tensile test. The sum of the breaking energy per 1 m unit width in Direction) and the breaking energy per 1 m unit width in TD (Transverse Direction) is preferably 100 J or more, more preferably 150 J or more as the lower limit, and from the viewpoint of superior moldability. It is more preferably 260 J or more, further preferably 280 J or more, and the upper limit is preferably 650 J or less, more preferably 450 J or less, further preferably 400 J or less, further preferably 380 J or less, and the preferable range is 100 to 650. J degree, 100-450J degree, 100-400J degree, 100-380J degree, 150-650J degree, 150-450J degree, 150-400J degree, 150-380J degree, 260-650J degree, 260-450J degree, 260-260. 400 J, about 260 to 380 J, about 280 to 650 J, about 280 to 450 J, about 280 to 400 J, about 280 to 380 J. The breaking energy is specifically a value measured by the method described in the examples. In the present disclosure, the tensile test means a test of tensile properties. When the breaking energy is equal to or higher than the lower limit value described above, it is possible to improve the formability and the insulating property while suppressing the curl due to the molding of the exterior material for an electricity storage device. Further, when the breaking energy is equal to or less than the upper limit value, it is possible to more effectively suppress the curl due to the molding of the exterior material for an electricity storage device.

  As a method of setting the breaking energy to the above value, the materials and thicknesses of the base material layer 1, the barrier layer 3, and the heat-fusible resin layer 4 which form the laminate are adjusted. The base material layer 1 is mentioned as a layer which contributes most to the magnitude of the breaking energy. As the material constituting the base material layer 1, the following materials are used, and in the manufacturing process of the base material layer 1, for example, the type of film forming method and the conditions during film formation (for example, film forming temperature, stretching ratio, The cooling temperature, cooling rate, and heat setting temperature after stretching) are adjusted appropriately. Examples of the film forming method include T-die method, calender method, tubular method and the like. In addition, a heating step of the laminated body after laminating each layer (for example, a heating step after obtaining a laminated body of a base material layer / adhesive layer / barrier layer, or an adhesive layer / In a heating step after laminating the heat-fusible resin layer), it is preferable to heat under a condition of an appropriate temperature and an appropriate time. By adopting an appropriate temperature and time, it is possible to improve the adhesion of each layer while suppressing damage to the laminate, especially to the base material layer. The upper limit of the heating temperature in the heating step is preferably about 185 ° C. or lower, more preferably about 180 ° C. or lower, further preferably 178 ° C. or lower, and the lower limit of the heating temperature is preferably 150 ° C. or higher, more preferably Is 160 ° C. or higher, more preferably 165 ° C. or higher. The preferable heating temperature range in the heating step is about 150 to 185 ° C, about 150 to 180 ° C, about 150 to 178 ° C, about 160 to 185 ° C, about 160 to 180 ° C, about 160 to 178 ° C, about 165 to 185. C., about 160 to 180.degree. C., and about 160 to 178.degree. Further, the upper limit of the heating time in the heating step is preferably 30 minutes or less, more preferably 15 minutes or less, further preferably 10 minutes or less, and the lower limit is preferably 0.1 minutes or more, more preferably 0.5 minutes or more, more preferably 1 minute or more. The heating temperature and heating time in the heating step are preferably combined from these.

  Regarding the barrier layer 3 described below in the exterior material for an electricity storage device, normally, MD (Machine Direction) and TD (Transverse Direction) in the manufacturing process can be distinguished. For example, when the barrier layer 3 is made of aluminum foil, linear streaks called so-called rolling marks are formed on the surface of the aluminum foil in the rolling direction (RD: Rolling Direction) of the aluminum foil. Since the rolling mark extends along the rolling direction, the rolling direction of the aluminum foil can be grasped by observing the surface of the aluminum foil. In addition, in the manufacturing process of the laminated body, since the MD of the laminated body and the RD of the aluminum foil generally match, the surface of the aluminum foil of the laminated body is observed and the rolling direction (RD) of the aluminum foil is specified. Thus, the MD of the laminated body can be specified. Since the TD of the laminated body is in the direction perpendicular to the MD of the laminated body, the TD of the laminated body can be specified.

2. Each layer forming the exterior material for a power storage device [base material layer 1]
In the present disclosure, the base material layer 1 is a layer provided for the purpose of exerting a function as a base material of the exterior material for an electricity storage device. The base material layer 1 is located on the outer layer side of the exterior material for an electricity storage device. The base material layer 1 has at least a polyamide film layer 11. As described above, the base material layer 1 may be composed of only the polyamide film layer 11 or may have the polyamide film layer 11 and the polyester film layer 12.

  In the base material layer 1, each of the polyamide film layer 11 and the polyester film layer 12 may be a resin film or may be formed by applying a resin. The resin may contain the additives described below.

  The resin film may be an unstretched film or a stretched film. Examples of the stretched film include a uniaxially stretched film and a biaxially stretched film, and a biaxially stretched film is preferable. Examples of the stretching method for forming the biaxially stretched film include a sequential biaxial stretching method, an inflation method and a simultaneous biaxial stretching method. Examples of the method for applying the resin include a roll coating method, a gravure coating method and an extrusion coating method.

  Specific examples of the polyamide forming the polyamide film layer 11 include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; terephthalate. Hexamethylenediamine-isophthalic acid-terephthalic acid copolymerization such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) containing a structural unit derived from acid and / or isophthalic acid Aromatic polyamides such as polyamide and polyamide MXD6 (polymethaxylylene adipamide); alicyclic polyamides such as polyamide PACM6 (polybis (4-aminocyclohexyl) methane adipamide); lactam components and 4,4′-diphenylmethane -Diiso Such as a polyamide obtained by copolymerizing an isocyanate component such as a nate or the like, a polyesteramide copolymer or a polyetheresteramide copolymer which is a copolymer of the copolymerized polyamide and polyester or polyalkylene ether glycol; Examples include polyamides. These polyamides may be used alone or in combination of two or more.

  The polyamide film layer 11 is preferably composed of a stretched polyamide film, more preferably a biaxially stretched polyamide film, especially a biaxially stretched nylon film.

  The base material layer 1 may be a single layer or may be composed of two or more layers. When the base material layer 1 is composed of two or more layers, the base material layer 1 may be a laminate in which resin films are laminated with an adhesive or the like, or a resin is coextruded into two or more layers. It may be a laminate of the above resin films. Further, a resin film laminate obtained by coextruding a resin into two or more layers may be the unstretched base material layer 1 or may be uniaxially or biaxially stretched to form the base material layer 1.

  One feature of the exterior material for an electricity storage device of the present disclosure is that the thickness of the polyamide film layer 11 is set in a specific range of 10 to 17 μm. From the viewpoint of more appropriately suppressing curling due to molding of the exterior material for an electricity storage device and improving moldability and insulating properties, the lower limit of the thickness of the polyamide film layer 11 is preferably about 11 μm or more, more preferably about 12 μm or more. , Or about 13 μm or more, and the upper limit value is preferably about 17 μm or less, more preferably 16 μm or less, further preferably 15 μm or less, and a preferable range is about 10 to 16 μm, about 10 to 15 μm, 11 to 17 μm, 11 to 16 μm, 11 to 15 μm, 12 to 17 μm, 12 to 16 μm, 12 to 15 μm, 13 to 17 μm, 13 to 16 μm, and 13 to 15 μm. When the thickness of the polyamide film layer 11 is at least the above lower limit, curl due to the molding of the exterior material for an electricity storage device can be suppressed and moldability can be improved. Curling due to molding can be effectively suppressed while reducing the thickness of the device exterior material.

  Specific examples of the polyester forming the polyester film layer 12 include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester. Further, examples of the copolyester include a copolyester having ethylene terephthalate as a main repeating unit. Specifically, a copolymer polyester in which ethylene terephthalate is a main repeating unit and is polymerized with ethylene isophthalate (hereinafter abbreviated to polyethylene (terephthalate / isophthalate)), polyethylene (terephthalate / adipate), polyethylene (terephthalate / Sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate), polyethylene (terephthalate / decanedicarboxylate), and the like. These polyesters may be used alone or in combination of two or more.

  The polyester film layer 12 is preferably composed of a biaxially stretched polyester film, particularly a biaxially stretched polyethylene terephthalate film.

  When the base material layer 1 further has the polyester film layer 12, the thickness of the polyester film layer 12 is the thickness of the laminate constituting the exterior material for an electricity storage device, the thickness of the polyamide film layer 11, and the barrier layer 3 The thickness is not particularly limited as long as it is set in the predetermined range of the present disclosure, and for example, is about 17 μm or less, preferably about 17 to 8 μm, and more preferably about 17 to 10 μm. When the thickness of the polyester film layer 12 is equal to or more than the above lower limit, it is possible to suppress the curling due to the molding of the exterior material for an electricity storage device and improve the insulating property. Further, when the thickness of the polyester film layer 12 is equal to or less than the above upper limit value, curling due to molding can be effectively suppressed while making the exterior material for an electricity storage device thin.

  In the base material layer 1, the lamination order of the polyamide film layer 11 and the polyester film layer 12 is not particularly limited, but from the viewpoint of improving the electrolytic solution resistance of the exterior material for an electricity storage device, the barrier layer 3 will be described later. It is preferable that the polyamide film layer 11 and the polyester film layer 12 are laminated in this order.

  As described above, for example, as shown in FIG. 2, the polyamide film layer 11 and the polyester film layer 12 may be laminated so as to be in contact with each other. For example, as shown in FIG. The adhesive layer 13 may be provided between these layers. In the case of adhering without an adhesive, for example, a coextrusion method, a sand laminating method, a thermal laminating method or the like may be used. When the adhesive is used for the adhesion, the adhesive used may be a two-component curable adhesive or a one-component curable adhesive. Further, the adhesive is not particularly limited, and may be any of chemical reaction type, solvent volatilization type, heat melting type, heat pressure type, ultraviolet ray curing type, electron beam curing type and the like.

  The thickness of the adhesive layer 13 located between the polyamide film layer 11 and the polyester film layer 12 is preferably about 0.1 to 5 μm, more preferably about 0.5 to 3 μm.

  The adhesive layer 13 may include the same colorant as that of the adhesive layer 2 described later.

  The base material layer 1 may further include other layers in addition to the polyamide film layer 11 and the polyester film layer 12 provided as necessary. The materials forming the other layers are not particularly limited as long as they have insulating properties. Examples of the material for forming the other layer include polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, and mixtures and copolymers thereof. Etc. When the other layer is provided, the thickness of the other layer is preferably about 1 to 20 μm, more preferably about 1 to 10 μm.

  Further, even if additives such as a lubricant, a flame retardant, an antiblocking agent, an antioxidant, a light stabilizer, a tackifier, and an antistatic agent are present on at least one of the surface and the inside of the base material layer 1. Good. As the additive, only one kind may be used, or two or more kinds may be mixed and used.

  In the present disclosure, it is preferable that a lubricant is present on the surface of the base material layer 1 from the viewpoint of enhancing the moldability of the exterior material for an electricity storage device. The lubricant is not particularly limited, but preferably includes the amide lubricants exemplified in the heat-fusible resin layer 4 described below.

If a lubricant on the surface of the base material layer 1 is present, as it is its abundance is not particularly limited, preferably about 3 mg / m ² or more, more preferably 4~15mg / m ² approximately, more preferably 5~14mg / M ² is included.

  The lubricant present on the surface of the base material layer 1 may be one in which the lubricant contained in the resin forming the base material layer 1 is exuded, or the one coated with the lubricant on the surface of the base material layer 1. May be.

  As for the total thickness of the base material layer 1, while reducing the total thickness of the exterior material for an electricity storage device, curling due to molding is suppressed, moldability and insulation properties are improved, and an exterior for an electricity storage device having excellent insulation properties is further provided. From the viewpoint of the material, the lower limit is preferably 10 μm or more, more preferably 12 μm or more or 13 μm or more, and the upper limit is preferably about 20 μm or less, more preferably 19 μm or less, further preferably 17 μm or less. Examples of preferable ranges include 10 to 20 μm, 10 to 19 μm, 10 to 17 μm, 12 to 20 μm, 12 to 19 μm, 12 to 17 μm, 13 to 20 μm, 13 to 19 μm, and 13 to The thickness is about 17 μm. When the total thickness of the base material layer 1 is equal to or more than the lower limit value described above, it is possible to improve the insulating property while suppressing curling due to the molding of the exterior material for an electricity storage device. In addition, when the entire thickness of the base material layer 1 is equal to or less than the above upper limit value, curling due to molding can be effectively suppressed while making the exterior material for an electricity storage device thin. In the present disclosure, when the base material layer 1 is composed of two or more layers and these layers are adhered by an adhesive layer such as the adhesive layer 13, the total thickness of the base material layer 1 Does not include the thickness of the layer of the adhesive.

[Adhesive layer 2]
In the exterior material for an electricity storage device of the present disclosure, the adhesive layer 2 is a layer provided between the base material layer 1 and the barrier layer 3 as needed for the purpose of enhancing the adhesiveness between the base material layer 1 and the barrier layer 3. .

  The adhesive layer 2 is formed of an adhesive that can bond the base material layer 1 and the barrier layer 3 together. The adhesive used for forming the adhesive layer 2 is not limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type and the like. Further, it may be a two-component curing type adhesive (two-component adhesive), a one-component curing type adhesive (one-component adhesive), or a resin that does not undergo a curing reaction. Further, the adhesive used for forming the adhesive layer 2 may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type and the like. The adhesive layer 2 may be a single layer or a multilayer.

  Specific examples of the adhesive component contained in the adhesive include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polyesters such as copolyester; polyether; polyurethane; epoxy resin; Phenol resin; nylon 6, nylon 66, nylon 12, polyamide such as copolyamide; polyolefin resin such as polyolefin, cyclic polyolefin, acid modified polyolefin, acid modified cyclic polyolefin; polyvinyl acetate; cellulose; (meth) acrylic resin; Polyimide; Polycarbonate; Amino resin such as urea resin and melamine resin; Rubber such as chloroprene rubber, nitrile rubber and styrene-butadiene rubber; Silicone resin and the like. That. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, a polyurethane adhesive is preferable. Further, the resin serving as the adhesive component may be used in combination with an appropriate curing agent to enhance the adhesive strength. The curing agent is selected from polyisocyanates, polyfunctional epoxy resins, oxazoline group-containing polymers, polyamine resins, acid anhydrides, etc. depending on the functional groups of the adhesive component.

  Examples of polyurethane adhesives include polyurethane adhesives containing a base compound containing a polyol compound and a curing agent containing an isocyanate compound. Preferred is a two-component curing type polyurethane adhesive containing a polyol such as a polyester polyol, a polyether polyol and an acrylic polyol as a main component and an aromatic or aliphatic polyisocyanate as a curing agent. Further, as the polyol compound, it is preferable to use a polyester polyol having a hydroxyl group at the side chain in addition to the hydroxyl group at the terminal of the repeating unit. Since the adhesive layer 2 is made of a polyurethane adhesive, excellent resistance to the electrolytic solution is imparted to the exterior material for an electricity storage device, and the base layer 1 is prevented from peeling off even when the electrolytic solution adheres to the side surface. .

  Further, the adhesive layer 2 may contain other components as long as it does not impair the adhesiveness, and may contain a colorant, a thermoplastic elastomer, a tackifier, a filler, and the like. Since the adhesive layer 2 contains the coloring agent, the exterior material for the electricity storage device can be colored. Known colorants such as pigments and dyes can be used as the colorant. Moreover, only one type of colorant may be used, or two or more types may be mixed and used.

  The type of pigment is not particularly limited as long as it does not impair the adhesiveness of the adhesive layer 2. Examples of organic pigments include azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigothioindigo-based, perinone-perylene-based, isoindolenine-based, benzimidazolone-based pigments, etc. Examples of the pigment include carbon black-based pigments, titanium oxide-based pigments, cadmium-based pigments, lead-based pigments, chromium oxide-based pigments, iron-based pigments, and other fine particles of mica (mica) and fish scale foil.

  Among the colorants, for example, carbon black is preferable in order to make the outer appearance of the electricity storage device black in appearance.

  The average particle diameter of the pigment is not particularly limited and is, for example, about 0.05 to 5 μm, preferably about 0.08 to 2 μm. The average particle size of the pigment is the median size measured by a laser diffraction / scattering particle size distribution measuring device.

  The content of the pigment in the adhesive layer 2 is not particularly limited as long as the exterior material for an electricity storage device is colored, and is, for example, about 5 to 60% by mass, preferably 10 to 40% by mass.

  The thickness of the adhesive layer 2 is such that the base material layer 1 and the barrier layer 3 are adhered to each other, and further the thickness of the laminate constituting the exterior material for an electricity storage device, the thickness of the polyamide film layer 11, and the thickness of the barrier layer 3 are the same. Is not particularly limited as long as it is set to the predetermined range of the present disclosure, and the lower limit includes, for example, about 1 μm or more and about 2 μm or more, and the upper limit includes about 10 μm or less and about 5 μm or less, The preferable range is about 1 to 10 μm, about 1 to 5 μm, about 2 to 10 μm, and about 2 to 5 μm. When the thickness of the adhesive layer 2 is at least the above lower limit, the adhesiveness between the base material layer 1 and the barrier layer 3 can be effectively enhanced. Further, when the thickness of the adhesive layer 2 is equal to or less than the above upper limit value, curl due to molding is suppressed while the outer casing material for an electricity storage device is thinned, and drying and curing can be performed in a shorter time, which results in productivity. Excel. Further, it is possible to effectively suppress the deterioration of the adhesiveness due to the thickness of the adhesive layer 2 becoming too thick and cracking.

[Colored layer]
The colored layer is a layer provided between the base material layer 1 and the barrier layer 3 as needed (not shown). When the adhesive layer 2 is provided, a coloring layer may be provided between the base material layer 1 and the adhesive layer 2 and between the adhesive layer 2 and the barrier layer 3. Further, a colored layer may be provided outside the base material layer 1. By providing the colored layer, the exterior material for the electricity storage device can be colored.

  The coloring layer can be formed, for example, by applying an ink containing a coloring agent to the surface of the base material layer 1, the surface of the adhesive layer 2, or the surface of the barrier layer 3. Known colorants such as pigments and dyes can be used as the colorant. Moreover, only one type of colorant may be used, or two or more types may be mixed and used.

  Specific examples of the coloring agent contained in the coloring layer are the same as those exemplified in the section of [Adhesive layer 2].

[Barrier layer 3]
In the exterior material for an electricity storage device, the barrier layer 3 is a layer that suppresses at least entry of moisture.

  Examples of the barrier layer 3 include a metal foil having a barrier property, a vapor deposition film, a resin layer, and the like. Examples of the vapor deposition film include a metal vapor deposition film, an inorganic oxide vapor deposition film, and a carbon-containing inorganic oxide vapor deposition film, and the resin layer includes polyvinylidene chloride. Moreover, as the barrier layer 3, a resin film provided with at least one of the vapor deposition film and the resin layer may be used. A plurality of barrier layers 3 may be provided. The barrier layer 3 preferably includes a layer made of a metal material. Specific examples of the metal material forming the barrier layer 3 include aluminum alloy, stainless steel, and titanium steel. When used as a metal foil, at least one of an aluminum alloy foil and a stainless steel foil may be included. preferable.

  The aluminum alloy foil is, from the viewpoint of improving the formability of the exterior material for an electricity storage device, for example, more preferably a soft aluminum alloy foil composed of an annealed aluminum alloy or the like, and from the viewpoint of further improving the formability. Therefore, the aluminum alloy foil containing iron is preferable. In the aluminum alloy foil containing iron (100% by mass), the content of iron is preferably 0.1 to 9.0% by mass, and more preferably 0.5 to 2.0% by mass. When the content of iron is 0.1% by mass or more, it is possible to obtain the exterior material for an electricity storage device having more excellent moldability. When the content of iron is 9.0% by mass or less, a more flexible outer packaging material for an electricity storage device can be obtained. As the soft aluminum alloy foil, for example, an aluminum alloy having a composition defined by JIS H4160: 1994 A8021H-O, JIS H4160: 1994 A8079H-O, JIS H4000: 2014 A8021P-O, or JIS H4000: 2014 A8079P-O. Foil can be mentioned.

  Examples of the stainless steel foil include austenite-based, ferrite-based, austenite-ferrite-based, martensite-based, and precipitation hardening-based stainless steel foils. Further, from the viewpoint of providing an exterior material for an electricity storage device having excellent moldability, the stainless steel foil is preferably made of austenitic stainless steel.

  Specific examples of the austenitic stainless steel forming the stainless steel foil include SUS304, SUS301, and SUS316L, and among these, SUS304 is particularly preferable.

  One feature of the exterior material for an electricity storage device of the present disclosure is that the thickness of the barrier layer 3 is set in a specific range of 36 to 44 μm. From the viewpoint of more suitably suppressing curling due to the molding of the exterior material for an electricity storage device, the lower limit of the thickness of the barrier layer 3 is preferably 38 μm or more, more preferably about 39 μm or more, and the upper limit is preferably. Is 42 μm or less, more preferably 41 μm or less, and the preferable range is about 36 to 42 μm, about 36 to 41 μm, about 38 to 44 μm, about 38 to 42 μm, about 38 to 41 μm, about 39 to 44 μm, 39 to 44 μm. It is about 42 μm or about 39 to 41 μm. When the thickness of the barrier layer 3 is equal to or more than the above lower limit value, the moldability of the exterior material for an electricity storage device can be improved. In addition, when the thickness of the barrier layer 3 is equal to or less than the above upper limit value, curling due to molding can be effectively suppressed while making the exterior material for an electricity storage device thin.

  Further, when the barrier layer 3 is a metal foil, it is preferable that at least the surface opposite to the base material layer 1 is provided with a corrosion-resistant coating in order to prevent dissolution and corrosion. The barrier layer 3 may have a corrosion resistant coating on both sides. The term "corrosion resistant film" as used herein means, for example, hot water conversion treatment such as boehmite treatment, chemical conversion treatment, anodic oxidation treatment, or corrosion prevention treatment for coating a coating agent on the surface of the barrier layer 3 so that A thin film that provides corrosion resistance. As the treatment for forming the corrosion resistant film, one type may be performed, or two or more types may be combined and performed. Among these treatments, the hot water conversion treatment and the anodic oxidation treatment are treatments for dissolving the metal foil surface with a treatment agent to form a metal compound having excellent corrosion resistance. Note that these processes may be included in the definition of the chemical conversion process. In addition, when the barrier layer 3 has a corrosion resistant film, the barrier layer 3 includes the corrosion resistant film.

  The corrosion-resistant film is a fluoride that is generated by preventing delamination between the barrier layer 3 (for example, an aluminum alloy foil) and the base material layer 1 and reacting with the electrolyte and moisture during the molding of the exterior material for an electricity storage device. The hydrogen prevents the surface of the barrier layer 3 from being dissolved and corroded, and particularly prevents the aluminum oxide existing on the surface of the barrier layer 3 from being dissolved and corroded when the barrier layer 3 is an aluminum alloy foil. The effect of improving the adhesiveness (wettability), preventing delamination between the base material layer 1 and the barrier layer 3 during heat sealing, and preventing delamination between the base material layer 1 and the barrier layer 3 during molding is shown.

  Various types of corrosion-resistant films formed by chemical conversion treatment are known, and are mainly at least one of phosphates, chromates, fluorides, triazine thiol compounds, and rare earth oxides. And a corrosion resistant film containing the like. As the rare earth oxide, a cerium compound is preferable, and cerium oxide is particularly preferable. Examples of the chemical conversion treatment using a phosphate or a chromate include a chromate chromate treatment, a phosphoric acid chromate treatment, a phosphoric acid-chromate treatment, a chromate treatment, and the like. Examples of the compound include chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium diphosphate, acetyl acetate chromate, chromium chloride, potassium chromium sulfate and the like. Further, examples of the phosphorus compound used for these treatments include sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid, and the like. Further, examples of the chromate treatment include etching chromate treatment, electrolytic chromate treatment, coating type chromate treatment and the like, and coating type chromate treatment is preferable. In this coating type chromate treatment, at least the surface of the barrier layer 3 (for example, aluminum alloy foil) on the inner layer side is firstly known by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid activation method, or the like. Degreasing treatment is performed on the degreasing surface, and thereafter, phosphoric acid such as Cr (chromium) phosphate, Ti (titanium) phosphate, Zr (zirconium) phosphate, Zn (zinc) phosphate, etc. A treatment liquid containing a metal salt and a mixture of these metal salts as a main component, or a treatment liquid containing a non-metallic phosphate and a mixture of these non-metal salts as a main component, or a synthetic resin with these. This is a treatment in which a treatment liquid consisting of the mixture is applied by a well-known coating method such as a roll coating method, a gravure printing method, or a dipping method and then dried. As the treatment liquid, various solvents such as water, alcohol solvents, hydrocarbon solvents, ketone solvents, ester solvents, ether solvents can be used, and water is preferable. In addition, examples of the resin component used at this time include polymers such as phenolic resins and acrylic resins, and aminated phenolic polymers having repeating units represented by the following general formulas (1) to (4) are used. Examples include the chromate treatment used. In the aminated phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be contained alone or in any combination of two or more. Good. Acrylic resin must be polyacrylic acid, acrylic acid methacrylic acid ester copolymer, acrylic acid maleic acid copolymer, acrylic acid styrene copolymer, or their derivatives such as sodium salt, ammonium salt, amine salt, etc. Is preferred. Particularly preferred are polyacrylic acid derivatives such as ammonium salt, sodium salt, or amine salt of polyacrylic acid. In the present disclosure, polyacrylic acid means a polymer of acrylic acid. Further, the acrylic resin is also preferably a copolymer of acrylic acid and a dicarboxylic acid or a dicarboxylic acid anhydride, an ammonium salt of a copolymer of acrylic acid and a dicarboxylic acid or a dicarboxylic acid anhydride, a sodium salt, Alternatively, it is also preferably an amine salt. Only one type of acrylic resin may be used, or two or more types may be mixed and used.

In formulas (1) to (4), X represents a hydrogen atom, a hydroxy group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. R ¹ and R ² are the same or different and each represents a hydroxy group, an alkyl group, or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, A linear or branched alkyl group having 1 to 4 carbon atoms such as a tert-butyl group can be mentioned. Examples of the hydroxyalkyl group represented by X, R ¹ and R ² include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group and a 3-hydroxypropyl group. A straight or branched chain having 1 to 4 carbon atoms in which one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group is substituted. An alkyl group is mentioned. In the general formulas (1) to (4), the alkyl group and the hydroxyalkyl group represented by X, R ¹ and R ² may be the same or different. In the general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having the repeating units represented by the general formulas (1) to (4) is, for example, preferably about 500 to 1,000,000, and more preferably about 1,000 to 20,000. More preferable. The aminated phenol polymer is produced by, for example, polycondensing a phenol compound or a naphthol compound with formaldehyde to produce a polymer having a repeating unit represented by the above general formula (I) or general formula (III), and then forming formaldehyde. And an amine (R ¹ R ² NH) to introduce a water-soluble functional group (—CH ₂ NR ¹ R ² ) into the polymer obtained above. The aminated phenol polymer is used alone or in combination of two or more.

  Another example of the corrosion resistant film is formed by a coating type corrosion prevention treatment in which a coating agent containing at least one selected from the group consisting of rare earth element oxide sols, anionic polymers and cationic polymers is applied. A thin film is used. The coating agent may further contain phosphoric acid or phosphate, and a cross-linking agent that cross-links the polymer. In the rare earth element oxide sol, fine particles of rare earth element oxide (for example, particles having an average particle diameter of 100 nm or less) are dispersed in a liquid dispersion medium. Examples of the rare earth element oxide include cerium oxide, yttrium oxide, neodymium oxide, and lanthanum oxide, and cerium oxide is preferable from the viewpoint of further improving the adhesiveness. The rare earth element oxides contained in the corrosion resistant coating may be used alone or in combination of two or more. As the liquid dispersion medium of the rare earth element oxide sol, various solvents such as water, alcohol solvents, hydrocarbon solvents, ketone solvents, ester solvents, ether solvents can be used, and water is preferable. Examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine-grafted acrylic resin obtained by graft-polymerizing a primary amine on an acrylic main skeleton, polyallylamine or a derivative thereof. , Aminated phenol and the like are preferable. The anionic polymer is preferably poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component. Further, it is preferable that the cross-linking agent is at least one selected from the group consisting of a compound having any one of an isocyanate group, a glycidyl group, a carboxyl group and an oxazoline group, and a silane coupling agent. The phosphoric acid or phosphate is preferably condensed phosphoric acid or condensed phosphate.

  As an example of the corrosion-resistant film, a dispersion of metal oxides such as aluminum oxide, titanium oxide, cerium oxide, and tin oxide or fine particles of barium sulfate in phosphoric acid is applied to the surface of the barrier layer 3, The thing formed by baking at 150 degreeC or more is mentioned.

  The corrosion resistant film may have a laminated structure in which at least one of a cationic polymer and an anionic polymer is further laminated, if necessary. Examples of the cationic polymer and the anionic polymer include those mentioned above.

  The composition of the corrosion-resistant coating can be analyzed by, for example, the time-of-flight secondary ion mass spectrometry.

The amount of the corrosion resistant film formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, but, for example, when the coating type chromate treatment is performed, the chromic acid compound per 1 m ² of the surface of the barrier layer 3 is used. Is about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of chromium, and the phosphorus compound is about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and aminated phenol polymer. Is contained in a ratio of, for example, about 1.0 to 200 mg, preferably about 5.0 to 150 mg.

As the thickness of the corrosion resistant film, if the thickness of the laminate constituting the exterior material for the electricity storage device, the thickness of the polyamide film layer 11, and the thickness of the barrier layer 3 are set within the predetermined range of the present disclosure, Although not particularly limited, from the viewpoint of the cohesive force of the film and the adhesive force with the barrier layer and the heat-fusible resin layer, preferably about 1 nm to 20 μm, more preferably about 1 nm to 100 nm, further preferably about 1 nm to 50 nm. Is mentioned. The thickness of the corrosion-resistant coating can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy. By analysis of the composition of the corrosion-resistant coating using time-of-flight secondary ion mass spectrometry, for example, at least one secondary ion consisting of Ce, P, and O (eg, Ce ₂ PO ₄ ⁺ , CePO ₄ ^−, etc. Species) or, for example, a peak derived from a secondary ion of Cr, P, and O (for example, at least one of CrPO ₂ ⁺ , CrPO ₄ ⁻ ).

  The chemical conversion treatment is carried out by applying a solution containing a compound used for forming a corrosion resistant film to the surface of the barrier layer 3 by a bar coating method, a roll coating method, a gravure coating method, a dipping method or the like, and then applying the barrier layer 3 It is carried out by heating so that the temperature becomes about 70 to 200 ° C. Further, the barrier layer 3 may be previously subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like before the barrier layer 3 is subjected to the chemical conversion treatment. By performing the degreasing treatment in this manner, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the barrier layer 3. In addition, by using an acid degreasing agent in which a fluorine-containing compound is dissolved in an inorganic acid for degreasing treatment, it is possible to form not only the degreasing effect of the metal foil but also a passive metal fluoride. In such cases, only degreasing treatment may be performed.

[The heat-fusible resin layer 4]
In the exterior material for an electricity storage device of the present disclosure, the heat-fusible resin layer 4 corresponds to the innermost layer, and the heat-fusible resin layers are heat-fused to each other during assembly of the electricity storage device to seal the electricity storage device element. It is a layer (sealant layer) that exhibits the above.

The resin constituting the heat-fusible resin layer 4 is not particularly limited as long as it is heat-fusible, but a resin containing a polyolefin skeleton such as polyolefin or acid-modified polyolefin is preferable. The fact that the resin constituting the heat-fusible resin layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, or the like. Further, when the resin forming the heat-fusible resin layer 4 is analyzed by infrared spectroscopy, it is preferable that a peak derived from maleic anhydride is detected. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. When the heat-fusible resin layer 4 is a layer composed of a maleic anhydride-modified polyolefin, a peak derived from maleic anhydride is detected when measured by infrared spectroscopy. However, if the degree of acid modification is low, the peak may be too small to be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

  Specific examples of the polyolefin include polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; ethylene-α-olefin copolymers; homopolypropylene, polypropylene block copolymers (for example, propylene and Examples thereof include polypropylene block copolymers) and polypropylene random copolymers (eg, propylene and ethylene random copolymers); propylene-α-olefin copolymers; ethylene-butene-propylene terpolymers. Of these, polypropylene is preferred. When the polyolefin resin is a copolymer, it may be a block copolymer or a random copolymer. These polyolefin resins may be used alone or in combination of two or more.

  Further, the polyolefin may be a cyclic polyolefin. The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene and isoprene. To be Examples of the cyclic monomer which is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene and norbornadiene. Among these, cyclic alkenes are preferable, and norbornene is more preferable.

  The acid-modified polyolefin is a polymer modified by block-polymerizing or graft-polymerizing a polyolefin with an acid component. As the acid-modified polyolefin, the above-mentioned polyolefin, a copolymer obtained by copolymerizing the above-mentioned polyolefin with a polar molecule such as acrylic acid or methacrylic acid, or a polymer such as a cross-linked polyolefin can be used. Examples of the acid component used for acid modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof.

  The acid-modified polyolefin may be an acid-modified cyclic polyolefin. The acid-modified cyclic polyolefin is a polymer obtained by copolymerizing some of the monomers constituting the cyclic polyolefin instead of the acid component, or by block-polymerizing or graft-polymerizing the acid component with respect to the cyclic polyolefin. is there. The acid-modified cyclic polyolefin is the same as described above. The acid component used for the acid modification is the same as the acid component used for the modification of the polyolefin.

  Preferred acid-modified polyolefins include polyolefins modified with carboxylic acids or their anhydrides, polypropylenes modified with carboxylic acids or their anhydrides, maleic anhydride-modified polyolefins, maleic anhydride-modified polypropylenes.

  The heat-fusible resin layer 4 may be formed of one type of resin alone, or may be formed of a blend polymer in which two or more types of resins are combined. Furthermore, the heat-fusible resin layer 4 may be formed of only one layer, but may be formed of two or more layers of the same or different resin.

  In the present disclosure, a lubricant is preferably present on the surface of the heat-fusible resin layer 4 from the viewpoint of enhancing the moldability of the exterior material for an electricity storage device. Since a lubricant is present on the surface of the heat-fusible resin layer 4 and forms the lubricant layer, curling due to the molding of the exterior material for an electricity storage device is suppressed and the formability of the exterior material for an electricity storage device is improved. You can The lubricant is not particularly limited, and known lubricants can be used. The lubricant may be used alone or in combination of two or more. The thickness of the lubricant layer is also included in the thickness of the laminate that constitutes the exterior material for the electricity storage device of the present disclosure.

  The lubricant is not particularly limited, but preferably an amide lubricant is used. Specific examples of the amide-based lubricant include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides, and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. Specific examples of unsaturated fatty acid amides include oleic acid amide and erucic acid amide. Specific examples of the substituted amide include N-oleylpalmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, and N-stearyl erucic acid amide. Specific examples of the methylolamide include methylolstearic acid amide. Specific examples of the saturated fatty acid bisamide include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, and hexamethylenebisstearic acid amide. Examples thereof include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide, and N, N′-distearyl sebacic acid amide. Specific examples of the unsaturated fatty acid bisamide include ethylenebisoleic acid amide, ethylenebiserucic acid amide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipamide, N, N′-dioleyl sebacic acid amide. And so on. Specific examples of the fatty acid ester amide include stearoamide ethyl stearate. Further, specific examples of the aromatic bisamide include m-xylylenebisstearic acid amide, m-xylylenebishydroxystearic acid amide, N, N'-distearylisophthalic acid amide and the like. The lubricant may be used alone or in combination of two or more.

When the lubricant is present on the surface of the heat-fusible resin layer 4, the amount of the lubricant is not particularly limited, but from the viewpoint of enhancing the moldability of the exterior material for an electricity storage device, it is preferably about 10 to 50 mg / m ^2. And more preferably about 15 to 40 mg / m ² .

  The lubricant present on the surface of the heat-fusible resin layer 4 may be one in which the lubricant contained in the resin constituting the heat-fusible resin layer 4 is exuded, or the lubricant of the heat-fusible resin layer 4 The surface may be coated with a lubricant.

  Further, as the thickness of the heat-fusible resin layer 4, the thickness of the laminate constituting the exterior material for the electricity storage device, the thickness of the polyamide film layer 11, and the thickness of the barrier layer 3 are set within the predetermined range of the present disclosure. While setting, it can be set according to the presence or absence of the adhesive layer 5, the thickness of the adhesive layer 5, and the like. The upper limit of the thickness of the heat-fusible resin layer 4 is, for example, about 34 μm or less, preferably about 33 μm or less, more preferably 32 μm or less, and the lower limit is, for example, about 8 μm or more, preferably 10 μm or more, more preferably Is 12 μm or more, and a preferable range is about 8 to 34 μm, about 8 to 33 μm, about 8 to 32 μm, about 10 to 34 μm, about 10 to 33 μm, about 10 to 32 μm, about 12 to 34 μm, 12 to 33 μm. And about 12 to 32 μm.

  In particular, when the thickness of the adhesive layer 5 described later is in the range of 8 to 22 μm, the upper limit of the thickness of the heat-fusible resin layer 4 is preferably about 22 μm or less, more preferably about 21 μm or less. , More preferably about 20 μm or less, and the lower limit is preferably about 8 μm or more, more preferably about 9 μm or more, further preferably about 10 μm or more, and the preferable range is about 8 to 22 μm, 8 to It is about 21 μm, about 8 to 20 μm, about 9 to 22 μm, about 9 to 21 μm, about 9 to 20 μm, about 10 to 22 μm, about 10 to 21 μm, and about 10 to 20 μm. Further, when the thickness of the adhesive layer 5 described later is in the range of 1 to 5 μm, the upper limit of the thickness of the heat-fusible resin layer 4 is preferably about 34 μm or less, more preferably about 33 μm or less. , More preferably about 32 μm or less, and the lower limit is preferably about 18 μm or more, more preferably about 19 μm or more, still more preferably about 20 μm or more, and the preferable range is about 18 to 34 μm, 18 to 34 μm. Examples include about 33 μm, about 18 to 32 μm, about 19 to 34 μm, about 19 to 33 μm, about 19 to 32 μm, about 20 to 34 μm, about 20 to 33 μm, and about 20 to 32 μm.

[Adhesive layer 5]
In the exterior material for an electricity storage device of the present disclosure, the adhesive layer 5 is a layer provided between the barrier layer 3 and the heat-fusible resin layer 4 as needed in order to firmly bond them.

  The adhesive layer 5 is formed of a resin that can bond the barrier layer 3 and the heat-fusible resin layer 4. As the resin used for forming the adhesive layer 5, polyolefin resins such as the polyolefin, the cyclic polyolefin, the acid-modified polyolefin, and the acid-modified cyclic polyolefin exemplified in the heat-fusible resin layer 4 can be preferably used. As the polyolefin-based resin, polypropylene-based resins such as polypropylene, cyclic polypropylene, acid-modified polypropylene, acid-modified cyclic polypropylene can be preferably used. In this case, the heat-fusible resin layer 4 and the adhesive layer 5 can be suitably formed by extrusion molding.

  Further, as the resin used for forming the adhesive layer 5, the same adhesives as those exemplified for the adhesive layer 2 can be used.

From the viewpoint of excellent adhesion between the barrier layer 3 and the heat-fusible resin layer 4, the polyolefin resin is preferably polyolefin and acid-modified polyolefin, and polypropylene and acid-modified polypropylene are particularly preferable. That is, the resin forming the adhesive layer 5 may or may not include a polyolefin skeleton, and preferably includes a polyolefin skeleton. The fact that the resin constituting the adhesive layer 5 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited. Further, when the resin constituting the adhesive layer 5 is analyzed by infrared spectroscopy, it is preferable to detect a peak derived from maleic anhydride. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the degree of acid modification is low, the peak may be too small to be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

  From the viewpoint of improving the adhesion between the barrier layer 3 (or the acid resistant film (corrosion resistant film)) and the heat-fusible resin layer 4, the adhesive layer 5 preferably contains an acid-modified polyolefin. The acid-modified polyolefin is a polymer modified by block-polymerizing or graft-polymerizing a polyolefin with an acid component such as carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof. Examples of the modified polyolefin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and other polyethylene; homopolypropylene, polypropylene block copolymer (for example, propylene-ethylene block copolymer), and polypropylene. Examples include polypropylene such as random copolymers (for example, random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene, and the like. Among these polyolefins, polyethylene and polypropylene are preferable.

  Among the acid-modified polyolefins, maleic anhydride-modified polyolefin, and maleic anhydride-modified polypropylene are particularly preferable for the adhesive layer 5.

  Further, from the viewpoint of making the exterior material for an electricity storage device thinner while also providing an exterior material for an electricity storage device excellent in shape stability after molding, the adhesive layer 5 is a resin composition containing an acid-modified polyolefin and a curing agent. It is more preferable that the cured product is. Preferred examples of the acid-modified polyolefin include those mentioned above.

  The adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group. It is preferable that the cured product is a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group. The adhesive layer 5 preferably contains at least one selected from the group consisting of urethane resin, ester resin, and epoxy resin, and more preferably contains urethane resin and epoxy resin. As the ester resin, for example, an amide ester resin is preferable. The amide ester resin is generally produced by the reaction of a carboxyl group and an oxazoline group. The adhesive layer 5 is more preferably a cured product of a resin composition containing at least one of these resins and the acid-modified polyolefin. When the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing it by heating or the like. When unreacted compounds such as a compound having an isocyanate group, a compound having an oxazoline group, and a curing agent such as an epoxy resin remain in the adhesive layer 5, the presence of the unreacted substance is determined by, for example, infrared spectroscopy, It can be confirmed by a method selected from Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like.

  Further, from the viewpoint of further enhancing the adhesion between the barrier layer 3 (or the acid resistant film (corrosion resistant film)) and the heat-fusible resin layer 4 and the adhesive layer 5, the adhesive layer 5 includes an oxygen atom, a heterocycle, It is preferably a cured product of a resin composition containing a curing agent having at least one selected from the group consisting of a C = N bond and a C-O-C bond. Examples of the curing agent having a heterocycle include a curing agent having an oxazoline group and a curing agent having an epoxy group. Examples of the curing agent having a C = N bond include a curing agent having an oxazoline group and a curing agent having an isocyanate group. Further, examples of the curing agent having a C—O—C bond include a curing agent having an oxazoline group, a curing agent having an epoxy group, and a urethane resin. The fact that the adhesive layer 5 is a cured product of a resin composition containing these curing agents means, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF). -SIMS), X-ray photoelectron spectroscopy (XPS) and the like.

  The compound having an isocyanate group is not particularly limited, but from the viewpoint of effectively enhancing the adhesion between the acid resistant coating (corrosion resistant coating) and the adhesive layer 5, a polyfunctional isocyanate compound is preferably used. The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and polymerization or nurate thereof. And the like, and their mixtures and copolymers with other polymers.

  The content of the compound having an isocyanate group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. It is more preferable to be in the range.

  The compound having an oxazoline group is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the compound having an oxazoline group include those having a polystyrene main chain and those having an acrylic main chain. Examples of commercially available products include Epocros series manufactured by Nippon Shokubai Co., Ltd.

  The ratio of the compound having an oxazoline group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. Is more preferable. Thereby, the adhesion between the barrier layer 3 (or the acid resistant film (corrosion resistant film)) and the adhesive layer 5 can be effectively enhanced.

  The epoxy resin is not particularly limited as long as it is a resin that can form a crosslinked structure by an epoxy group existing in the molecule, and a known epoxy resin can be used. The weight average molecular weight of the epoxy resin is preferably about 50 to 2000, more preferably about 100 to 1000, and further preferably about 200 to 800. In the present disclosure, the weight average molecular weight of the epoxy resin is a value measured by gel permeation chromatography (GPC), which is measured under the condition that polystyrene is used as a standard sample.

  Specific examples of the epoxy resin include glycidyl ether derivatives of trimethylolpropane, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether. The epoxy resin may be used alone or in combination of two or more.

  The ratio of the epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass% in the resin composition constituting the adhesive layer 5, and in the range of 0.5 to 40 mass%. Is more preferable. Thereby, the adhesion between the barrier layer 3 (or the acid resistant film (corrosion resistant film)) and the adhesive layer 5 can be effectively enhanced.

  In the present disclosure, the adhesive layer 5 cures a resin composition containing at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and an epoxy resin, and the acid-modified polyolefin. When it is a substance, the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the epoxy resin each function as a curing agent.

  The carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (-N = C = N-). The carbodiimide-based curing agent is preferably a polycarbodiimide compound having at least two carbodiimide groups.

  From the viewpoint of enhancing the adhesion between the barrier layer 3 and the heat-fusible resin layer 4 by the adhesive layer 5, the curing agent may be composed of two or more kinds of compounds.

  The content of the curing agent in the resin composition forming the adhesive layer 5 is preferably in the range of about 0.1 to 50% by mass, more preferably in the range of about 0.1 to 30% by mass, More preferably, it is in the range of about 0.1 to 10% by mass.

  Furthermore, the adhesive layer 5 can also be suitably formed using, for example, an adhesive. Examples of the adhesive include a non-crystalline polyolefin resin (A) having a carboxyl group, a polyfunctional isocyanate compound (B), and a tertiary amine having no functional group that reacts with the polyfunctional isocyanate compound (B) ( C), the polyfunctional isocyanate compound (B) is contained in an amount of 0.3 to 10 moles of isocyanate groups per 1 mole of carboxyl groups, and 1 mole of total carboxyl groups is contained. Then, the thing formed from the adhesive composition which contains the tertiary amine (C) in the range used as 1-10 mol is mentioned. The adhesive contains a styrene-based thermoplastic elastomer (A), a tackifier (B), and a polyisocyanate (C), and contains a styrene-based thermoplastic elastomer (A) and a tackifier (B). ), The styrene-based thermoplastic elastomer (A) is contained in an amount of 20 to 90% by weight, the tackifier (B) is included in an amount of 10 to 80% by weight, and the styrene-based thermoplastic elastomer (A) is , 0.003 to 0.04 mmol / g of active hydrogen derived from an amino group or a hydroxyl group, and the tackifier (B) with respect to 1 mol of the active hydrogen derived from the styrene-based thermoplastic elastomer (A). The active hydrogen derived from the functional group is 0 to 15 mol, and the polyisocyanate (C) is derived from the active hydrogen derived from the styrene-based thermoplastic elastomer (A) and the tackifier (B). The total one mole of the sexual hydrogen, an isocyanate group also such as those formed by the adhesive composition consisting of those that are included within an amount of 3-150 mol.

  Further, as the thickness of the adhesive layer 5, while setting the thickness of the laminate constituting the exterior material for an electricity storage device, the thickness of the polyamide film layer 11, and the thickness of the barrier layer 3 within the predetermined range of the present disclosure, It can be set according to the thickness of the heat-fusible resin layer 4 and the like. The upper limit of the thickness of the adhesive layer 5 is, for example, about 22 μm or less, preferably about 21 μm or less, more preferably 20 μm or less, and the lower limit thereof is, for example, about 1 μm or more, preferably 2 μm or more. Is about 1 to 22 μm, about 1 to 21 μm, about 1 to 20 μm, about 2 to 22 μm, about 2 to 21 μm, about 2 to 20 μm.

  In particular, when the thickness of the heat-fusible resin layer 4 is 8 to 22 μm, the lower limit of the thickness of the adhesive layer 5 is preferably about 8 μm or more, more preferably about 9 μm or more, The upper limit is preferably about 22 μm or less, more preferably about 21 μm or less, and the preferable range is about 8 to 22 μm, about 8 to 21 μm, about 9 to 22 μm, about 9 to 21 μm. In this case, as the adhesive layer 5, it is preferable to use a polyolefin resin such as the polyolefin resin and the acid-modified polyolefin resin exemplified in the heat-fusible resin layer 4. When the thickness of the heat-fusible resin layer 4 is 18 to 34 μm, the lower limit of the thickness of the adhesive layer 5 is preferably about 1 μm or more, more preferably about 2 μm or more. The upper limit is preferably about 5 μm or less, more preferably about 4 μm or less, and the preferred range is about 1 to 5 μm, about 1 to 4 μm, about 2 to 5 μm, about 2 to 4 μm. In this case, as the adhesive layer 5, it is preferable to use a cured product of an acid-modified polyolefin and a curing agent, or the same one as the adhesive exemplified in the adhesive layer 2.

[Surface coating layer 6]
The exterior material for an electricity storage device of the first disclosure is, if necessary, on the base material layer 1 (of the base material layer 1) for the purpose of improving designability, electrolytic solution resistance, abrasion resistance, moldability, and the like. The surface coating layer 6 may be provided on the side opposite to the barrier layer 3). Further, the exterior material for an electricity storage device according to the second disclosure includes the surface coating layer 6. The surface coating layer 6 is a layer positioned on the outermost layer side of the electricity storage device when the electricity storage device is assembled using the electricity storage device exterior material.

  The surface coating layer 6 can be formed of a resin such as polyvinylidene chloride, polyester, polyurethane, acrylic resin, or epoxy resin.

  When the resin forming the surface coating layer 6 is a curable resin, the resin may be either a one-component curing type or a two-component curing type, but is preferably a two-component curing type. Examples of the two-component curing type resin include two-component curing type polyurethane, two-component curing type polyester, and two-component curing type epoxy resin.

  The surface coating layer 6 may contain an additive. Examples of the additive include fine particles having a particle size of about 0.5 nm to 5 μm.

  The material of the additive is not particularly limited, and may be an inorganic material or an organic material. Also, the shape of the additive is not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an amorphous shape, and a balloon shape.

  As for the thickness of the surface coating layer 6, the thickness of the laminate that exhibits the above-mentioned functions as the surface coating layer 6 and constitutes the exterior material for an electricity storage device, the thickness of the polyamide film layer 11, and the thickness of the barrier layer 3 Is not particularly limited as long as it is set within the predetermined range of the present disclosure, but preferable lower limits include about 0.1 μm or more, about 0.5 μm or more, about 1 μm or more, about 2 μm or more, and the preferable upper limit is The thickness may be about 5 μm or less, about 4 μm or less, about 3 μm or less, and a preferable range is about 0.1 to 5 μm, about 0.1 to 4 μm, about 0.1 to 3 μm, about 0.5 to 5 μm, and 0.1. It is about 5 to 4 μm, about 0.5 to 3 μm, about 1 to 5 μm, about 1 to 4 μm, about 1 to 3 μm, about 2 to 5 μm, about 2 to 4 μm, and about 2 to 3 μm.

  Specific examples of the additive include talc, silica, graphite, kaolin, montmorillonite, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, and oxidation. Neodymium, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high melting point nylon , Acrylate resin, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like. The additives may be used alone or in combination of two or more. Among these additives, silica, barium sulfate and titanium oxide are preferable from the viewpoint of dispersion stability and cost. Further, the surface of the additive may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment. In addition, a lubricant, an anti-blocking agent, a matting agent may be added to at least one of the surface and the inside of the surface coating layer 6 depending on the surface coating layer 6 and the functionality to be provided on the surface, if necessary. It may contain additives such as flame retardants, antioxidants, light stabilizers, tackifiers, antistatic agents, and elastomer resins. Specific examples of the lubricant include the above-mentioned lubricants. Further, the above-mentioned fine particles may function as a lubricant, an anti-blocking agent, and a matting agent.

  The method of forming the surface coating layer 6 is not particularly limited, and examples thereof include a method of applying a resin forming the surface coating layer 6. When the surface coating layer 6 contains an additive, a resin mixed with the additive may be applied.

3. For the manufacturing method of the outer package for a power storage device TECHNICAL FIELD The present disclosure of the outer package for a power storage device, as long as the laminate as a laminate of layers having a predetermined composition can be obtained, is not particularly limited. That is, in the method of manufacturing the exterior material for an electricity storage device according to the first disclosure, at least the base material layer 1, the barrier layer 3, and the heat-fusible resin layer 4 are laminated in this order to form a laminate. The substrate layer 1 has at least the polyamide film layer 11, the thickness of the polyamide film layer 11 is 10 to 17 μm, and the thickness of the barrier layer 3 is 36 to 44 μm. The thickness of the laminated body is 83 to 93 μm. Further, in the method for manufacturing the exterior material for an electricity storage device according to the second disclosure, at least the surface coating layer 6, the base material layer 1, the barrier layer 3, and the heat-fusible resin layer 4 are laminated in this order. To obtain a laminate, the base material layer 1 has at least the polyamide film layer 11, the thickness of the surface coating layer is 0.1 to 5 μm, and the thickness of the polyamide film layer 11 is Is 10 to 17 μm, the thickness of the barrier layer 3 is 36 to 44 μm, and the thickness of the laminate is 83.1 to 98 μm.

  The following is an example of a method for manufacturing the exterior material for an electricity storage device of the present disclosure. First, a laminated body in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are laminated in order (hereinafter, also referred to as “laminated body A”) is formed. Specifically, the laminate A is formed by applying an adhesive used for forming the adhesive layer 2 on the base material layer 1 or on the barrier layer 3 whose surface has been subjected to chemical conversion treatment, if necessary, by a gravure coating method. This can be performed by a dry laminating method in which the barrier layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a roll coating method.

  Next, the adhesive layer 5 and the heat-fusible resin layer 4 are laminated on the barrier layer 3 of the laminate A in this order. For example, (1) a method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 on the barrier layer 3 of the laminate A by co-extruding (co-extrusion laminating method), (2) a separate adhesive layer 5 And a heat-fusible resin layer 4 are laminated to form a laminated body, and the laminated body is laminated on the barrier layer 3 of the laminated body A by a thermal lamination method. (3) Adhesion on the barrier layer 3 of the laminated body A An adhesive for forming the layer 5 is laminated by an extrusion method, a solution coating method, a drying method at a high temperature, a baking method, or the like, and the heat-fusible resin layer 4 formed in a sheet shape in advance on the adhesive layer 5. A method of laminating by a thermal laminating method, (4) Adhesion while pouring a melted adhesive layer 5 between the barrier layer 3 of the laminate A and the heat-fusible resin layer 4 formed into a sheet in advance. Laminate the laminate A and the heat-fusible resin layer 4 via the layer 5 The method (sandwich lamination method), and the like to match.

  When the surface coating layer 6 is provided as in the second disclosure, the surface coating layer 6 is laminated on the surface of the base material layer 1 opposite to the barrier layer 3. The surface coating layer 6 can be formed, for example, by applying the above-mentioned resin forming the surface coating layer 6 to the surface of the base material layer 1. The order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer 6 on the surface of the base material layer 1 is not particularly limited. For example, after forming the surface coating layer 6 on the surface of the base material layer 1, the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer 6.

  As described above, in the first disclosure, it is provided as necessary, and in the second disclosure, the surface coating layer 6 / base material layer 1 / adhesive layer 2 / if necessary provided / as needed A layered body composed of the barrier layer 3 whose surface has been subjected to chemical conversion treatment / adhesive layer 5 optionally provided / heat-fusible resin layer 4 is formed, but the adhesiveness of the adhesive layer 2 or the adhesive layer 5 is strengthened. In order to achieve this, it may be further subjected to heat treatment such as hot roll contact type, hot air type, near infrared ray type or far infrared ray type. The conditions for such heat treatment are as described above.

  In the exterior material for an electricity storage device of the present disclosure, each layer constituting the laminate improves or stabilizes film forming properties, laminating processing, final product secondary processing (pouching, embossing molding) suitability, etc., if necessary. In order to do so, surface activation treatment such as corona treatment, blast treatment, oxidation treatment and ozone treatment may be performed.

4. Application of Exterior Material for Energy Storage Device The exterior material for an energy storage device according to the present disclosure is used for a package for hermetically housing an energy storage device element such as a positive electrode, a negative electrode, and an electrolyte. That is, an electricity storage device can be prepared by accommodating an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte in a package formed of the electricity storage device exterior material of the present disclosure.

  Specifically, in an electricity storage device element having at least a positive electrode, a negative electrode, and an electrolyte, in the exterior material for an electricity storage device of the present disclosure, in a state in which metal terminals connected to each of the positive electrode and the negative electrode are projected outward. To cover the periphery of the electricity storage device element so that a flange portion (a region where the heat-fusible resin layers are in contact with each other) can be formed, and heat-seal and seal the heat-fusible resin layers of the flange portion. Thus, an electricity storage device using the exterior material for an electricity storage device is provided. In the case where the electricity storage device element is housed in a package formed of the electricity storage device exterior material of the present disclosure, the heat-fusible resin portion of the electricity storage device exterior material of the present disclosure is inside (a surface that contacts the electricity storage device element). ), And a package is formed.

  The exterior material for an electricity storage device of the present disclosure can be suitably used for an electricity storage device such as a battery (including a capacitor and a capacitor). Further, the exterior material for an electricity storage device of the present disclosure may be used in either a primary battery or a secondary battery, but is preferably a secondary battery. The type of secondary battery to which the exterior material for an electricity storage device of the present disclosure is applied is not particularly limited, and examples thereof include a lithium ion battery, a lithium ion polymer battery, an all-solid-state battery, a lead storage battery, a nickel-hydrogen storage battery, and a nickel-hydrogen storage battery. Examples thereof include a cadmium storage battery, a nickel / iron storage battery, a nickel / zinc storage battery, a silver oxide / zinc storage battery, a metal-air battery, a polyvalent cation battery, a capacitor and a capacitor. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are mentioned as suitable targets to which the exterior material for an electricity storage device of the present disclosure is applied.

  Hereinafter, the present disclosure will be described in detail with reference to Examples and Comparative Examples. However, the present disclosure is not limited to the embodiments.

<Manufacture of exterior materials for power storage devices>
Example 1
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) having acid-resistant coatings formed on both sides is formed on a biaxially stretched nylon film (thickness 15 μm) as a base material layer by a dry lamination method. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 3 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, maleic anhydride-modified polypropylene (thickness 15 μm) as an adhesive layer and polypropylene (thickness 15 μm) as a heat-fusible resin layer are coextruded on the barrier layer of the obtained laminate. Thus, the adhesive layer / heat-fusible resin layer was laminated on the barrier layer. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (15 μm) / adhesive layer (3 μm) / barrier layer (40 μm) / adhesive layer (15 μm) / heat-fusible resin. An outer casing material for electric storage devices (total thickness 88 μm) was obtained by stacking layers (15 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In addition, erucic acid amide was present as a lubricant on both surfaces of the obtained exterior material for an electricity storage device to form a lubricant layer.

Example 2
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) having acid-resistant coatings formed on both sides is formed on a biaxially stretched nylon film (thickness 12 μm) as a base material layer by a dry lamination method. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 3 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, maleic anhydride-modified polypropylene (thickness 18 μm) as an adhesive layer and polypropylene (thickness 15 μm) as a heat-fusible resin layer are coextruded on the barrier layer of the obtained laminate. Thus, the adhesive layer / heat-fusible resin layer was laminated on the barrier layer. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (12 μm) / adhesive layer (3 μm) / barrier layer (40 μm) / adhesive layer (18 μm) / heat-fusible resin. An outer casing material for electric storage devices (total thickness 88 μm) was obtained by stacking layers (15 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Example 3
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) having acid-resistant coatings formed on both sides is formed on a biaxially stretched nylon film (thickness 12 μm) as a base material layer by a dry lamination method. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 3 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, a two-component curable urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to the barrier layer side of the obtained laminate to form an adhesive layer (thickness after curing 3 μm) on the aluminum foil. . Further, an unstretched polypropylene film (CPP, thickness 30 μm) as a heat-fusible resin layer was laminated on the adhesive layer by a dry lamination method. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (12 μm) / adhesive layer (3 μm) / barrier layer (40 μm) / adhesive layer (3 μm) / heat-fusible resin. An outer packaging material for an electricity storage device (total thickness 88 μm) was obtained by stacking layers (30 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Example 4
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) having acid-resistant coatings formed on both sides is formed on a biaxially stretched nylon film (thickness 15 μm) as a base material layer by a dry lamination method. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 3 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, a two-component curable urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to the barrier layer side of the obtained laminate to form an adhesive layer (thickness after curing 3 μm) on the aluminum foil. . Further, an unstretched polypropylene film (CPP, thickness 30 μm) as a heat-fusible resin layer was laminated on the adhesive layer by a dry lamination method. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (15 μm) / adhesive layer (3 μm) / barrier layer (40 μm) / adhesive layer (3 μm) / heat-fusible resin. An outer casing material for electric storage devices (total thickness 91 μm) was obtained by stacking layers (30 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Example 5
In Example 1, instead of the two-component curing type urethane adhesive (polyol compound and aromatic isocyanate compound) for adhering the base layer and the barrier layer, a two-component curing type urethane adhesive containing a black pigment ( A biaxially stretched nylon film (15 μm) / adhesive layer (black, 3 μm) / barrier layer (40 μm) / in the same manner as in Example 1 except that a black pigment, a polyol compound and an aromatic isocyanate compound) were used. A laminate (total thickness 88 μm) in which the adhesive layer (15 μm) / heat-fusible resin layer (15 μm) was laminated in this order was obtained. Then, the surface of the biaxially stretched nylon film of the obtained laminate was gravure coated with a precipitating barium sulfate having an average particle diameter of 1 μm as a filler, erucic acid amide, and an acrylate resin having an average particle diameter of 2 μm. A resin composition containing the resin (having a thickness after curing of 3 μm) was applied to form a matte surface coating layer, to obtain an exterior material for an electricity storage device (total thickness 91 μm). The average particle size of the precipitated barium sulfate is the median size measured by a laser diffraction / scattering particle size distribution measuring device (“LA-950” manufactured by Horiba, Ltd.). Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Example 6
In Example 1, instead of the two-component curing type urethane adhesive (polyol compound and aromatic isocyanate compound) for adhering the base layer and the barrier layer, a two-component curing type urethane adhesive containing a black pigment ( A biaxially stretched nylon film (15 μm) / adhesive layer (black, 3 μm) / barrier layer (40 μm) / in the same manner as in Example 1 except that a black pigment, a polyol compound and an aromatic isocyanate compound) were used. A laminate (total thickness 88 μm) in which the adhesive layer (15 μm) / heat-fusible resin layer (15 μm) was laminated in this order was obtained. Next, the surface of the biaxially stretched nylon film of the obtained laminate was gravure coated with silica having an average particle diameter of 1.5 μm as a filler, erucic acid amide, and an acrylate resin having an average particle diameter of 2.5 μm. A resin composition containing (having a thickness after curing of 3 μm) was applied to form a matte surface coating layer, and an exterior material for an electricity storage device (total thickness 91 μm) was obtained. The average particle size of the precipitated barium sulfate is the median size measured by a laser diffraction / scattering particle size distribution measuring device (“LA-950” manufactured by Horiba, Ltd.). Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Comparative Example 1
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 35 μm) having acid-resistant coatings formed on both sides is formed on a biaxially stretched nylon film (thickness 15 μm) as a base material layer by a dry lamination method. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 3 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, maleic anhydride-modified polypropylene (thickness 20 μm) as an adhesive layer and polypropylene (thickness 15 μm) as a heat-fusible resin layer are coextruded on the barrier layer of the obtained laminate. Thus, the adhesive layer / heat-fusible resin layer was laminated on the barrier layer. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (15 μm) / adhesive layer (3 μm) / barrier layer (35 μm) / adhesive layer (20 μm) / heat-fusible resin. An outer casing material for electric storage devices (total thickness 88 μm) was obtained by stacking layers (15 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Comparative example 2
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 35 μm) on both sides of which a biaxially stretched nylon film (thickness 25 μm) as a base material layer was formed with an acid resistant film was dry laminated. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 3 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, maleic anhydride-modified polypropylene (thickness 14 μm) as an adhesive layer and polypropylene (thickness 10 μm) as a heat-fusible resin layer are coextruded on the barrier layer of the obtained laminate. Thus, the adhesive layer / heat-fusible resin layer was laminated on the barrier layer. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (25 μm) / adhesive layer (3 μm) / barrier layer (35 μm) / adhesive layer (14 μm) / heat-fusible resin. An outer casing material for an electricity storage device (total thickness 87 μm) was obtained by laminating layers (10 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Comparative Example 3
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) having an acid resistant film formed on both sides is formed on a biaxially stretched nylon film (thickness 25 μm) as a base material layer by a dry lamination method. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 3 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, on the barrier layer of the obtained laminate, maleic anhydride-modified polypropylene (thickness 22.5 μm) as an adhesive layer and polypropylene (thickness 22.5 μm) as a heat-fusible resin layer were formed. Was coextruded to laminate the adhesive layer / heat-fusible resin layer on the barrier layer. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (25 μm) / adhesive layer (3 μm) / barrier layer (40 μm) / adhesive layer (22.5 μm) / heat fusion. Thus, a packaging material for electric storage devices (total thickness: 113 μm) was obtained by laminating a conductive resin layer (22.5 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Comparative Example 4
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) having an acid resistant film formed on both sides is formed on a biaxially stretched nylon film (thickness 25 μm) as a base material layer by a dry lamination method. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 2 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, maleic anhydride-modified polypropylene (thickness 14 μm) as an adhesive layer and polypropylene (thickness 10 μm) as a heat-fusible resin layer are coextruded on the barrier layer of the obtained laminate. Thus, the adhesive layer / heat-fusible resin layer was laminated on the barrier layer. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (25 μm) / adhesive layer (2 μm) / barrier layer (40 μm) / adhesive layer (14 μm) / heat-fusible resin. An outer packaging material for an electricity storage device (total thickness 91 μm) was obtained by stacking layers (10 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Comparative Example 5
A barrier layer made of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) having acid-resistant coatings formed on both sides is formed on a biaxially stretched nylon film (thickness 15 μm) as a base material layer by a dry lamination method. Were laminated by. Specifically, a two-component curable urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil having an acid resistant film formed on both surfaces, and the adhesive layer (after curing) is applied on the aluminum foil. Thickness of 3 μm) was formed. Next, after laminating the adhesive layer on the aluminum foil and the biaxially stretched nylon film, aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer.

  Next, maleic anhydride-modified polypropylene (thickness 14 μm) as an adhesive layer and polypropylene (thickness 10 μm) as a heat-fusible resin layer are coextruded on the barrier layer of the obtained laminate. Thus, the adhesive layer / heat-fusible resin layer was laminated on the barrier layer. Next, the obtained laminate is aged and heated to give a biaxially stretched nylon film (15 μm) / adhesive layer (3 μm) / barrier layer (40 μm) / adhesive layer (14 μm) / heat-fusible resin. An outer casing material for electric storage devices (total thickness 82 μm) was obtained by stacking layers (10 μm) in this order. Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

Comparative Example 6
In Comparative Example 1, a two-component curable urethane adhesive containing a black pigment in place of the two-component curable urethane adhesive (polyol compound and aromatic isocyanate compound) for adhering the base layer and the barrier layer ( A biaxially stretched nylon film (15 μm) / adhesive layer (black, 3 μm) / barrier layer (35 μm) / in the same manner as in Comparative Example 1 except that a black pigment, a polyol compound and an aromatic isocyanate compound) were used. A laminate (total thickness 88 μm) in which the adhesive layer (20 μm) / heat-fusible resin layer (15 μm) was laminated in this order was obtained. Then, the surface of the biaxially stretched nylon film of the obtained laminate was gravure coated with a precipitating barium sulfate having an average particle diameter of 1 μm as a filler, erucic acid amide, and an acrylate resin having an average particle diameter of 2 μm. A resin composition containing the resin (having a thickness after curing of 3 μm) was applied to form a matte surface coating layer, to obtain an exterior material for an electricity storage device (total thickness 91 μm). The average particle size of the precipitated barium sulfate is the median size measured by a laser diffraction / scattering particle size distribution measuring device (“LA-950” manufactured by Horiba, Ltd.). Table 1 shows the laminated structure of the exterior material for an electricity storage device.

  In the same manner as in Example 1, erucic acid amide was present as a lubricant on both surfaces of the obtained electricity storage device exterior material to form a lubricant layer.

<Fracture energy of laminate>
The breaking energy per unit width 1 m in MD and TD of each of the exterior materials for an electricity storage device obtained above was evaluated by a tensile test under the following test conditions for MD and TD of the exterior material for an electricity storage device. The data of the "measured load (N / 15 mm) -displacement amount curve" measured when performing was acquired, the data was saved in a csv file format, and spreadsheet software (Excel (registered trademark) of Microsoft Corporation) Was calculated by integrating the data until the laminate was broken. At this time, it was calculated by converting (divided by 0.015) into the breaking energy per 1 m width of the exterior material for each electricity storage device by the spreadsheet software. Then, the breaking energy per 1 m unit width in MD and the breaking energy per 1 m unit width in TD were summed. In addition, five pieces of the exterior materials for the electricity storage device to be measured were prepared, and the average of three values excluding the maximum value and the minimum value out of the breaking energy values of the five samples was calculated as the breaking energy of the laminate. And The results are shown in Table 2. The breaking energy values of the laminates shown in Table 2 are values obtained by rounding off the second decimal point of the obtained average value.
(Test condition)
・ Tensile tester: Shimadzu's trade name AGS-XPlus
・ Test speed: 50 mm / min
・ Width of test piece: 15mm
・ Length of test piece: 100mm
・ Gage length: 30mm

  For reference, a schematic diagram of a curve of measured load (N / 15 mm) -displacement amount obtained in a tensile test (MD) of the exterior material for an electricity storage device is shown in FIG. The portion where the data of the curve of measured load (N / 15 mm) -displacement amount is integrated is, for example, as shown in the schematic diagram of FIG. 11, the integration from the start of the tensile test (displacement amount 0) to the break point of the laminate. This is a value and corresponds to the area of the hatched portion in FIG.

<Evaluation of curl by molding>
The exterior material for an electricity storage device obtained above was cut to prepare a strip of TD (Transverse Direction) 150 mm × MD (Machine Direction) 90 mm, which was used as a test sample. 31.6 mm x 54.5 mm rectangular male mold (the surface is JIS B 0659-1: 2002 Annex 1 (reference) The maximum height roughness defined in Table 2 of the surface roughness standard piece for comparison. (Rz nominal value) is 1.6 μm. Corner R2.0 mm, ridge R1.0 mm) and this male mold have a female mold with a clearance of 0.3 mm (the surface is JIS B 0659-1: 2002 Annex 1). (Reference) The maximum height roughness (nominal value of Rz) specified in Table 2 of the surface roughness standard piece for comparison is 3.2 μm, and a mold having a corner R2.0 mm and a ridge line R1.0 mm is used. Using the above test sample on a female mold so that the heat-fusible resin layer side is located on the male mold side, the molding depth is 31.6 mm (MD) x 54.5 mm (TD), and the molding depth is 6 mm. The test sample to 0.25 MPa holding pressure (contact pressure) Presser, and cold forming (draw-stage molding). The details of the position where the molding is performed are as shown in FIG. 7. As shown in FIG. 7, molding was performed at a position where the shortest distance d between the rectangular shaped molding portion M and the end portion P of the exterior material 10 for an electricity storage device was 70.5 mm. The molding portion M indicates the position where the concave portion is formed by the mold. Next, the molded electric storage device exterior material 10 is placed on the horizontal plane 20 as shown in FIG. 8, and the maximum value t of the distance in the vertical direction y from the horizontal plane 20 to the end P is curled. Maximum height The smaller the curl due to molding is, the smaller the curl is, which is excellent as an exterior material for an electricity storage device. The molding curl (mm) shown in Table 1 is a value obtained by rounding off the second decimal point of the maximum value t.

<Evaluation of moldability>
The exterior material for each electricity storage device was cut into a rectangle having a length (MD) of 90 mm and a width (TD) of 150 mm to obtain a test sample. This sample is a rectangular molding die having a diameter of 32 mm (MD) × 54 mm (TD) (female die, surface is JIS B 0659-1: 2002 Annex 1 (reference)) The maximum height roughness (nominal value of Rz) specified in Table 2 is 3.2 μm and the corresponding molding die (male, surface is JIS B 0659-1: 2002 Annex 1). (Reference) Using the maximum height roughness (nominal value of Rz) of 1.6 μm defined in Table 2 of the surface roughness standard piece for comparison, the pressing pressure (contact pressure) of 0.25 MPa was set to 0. The forming depth was changed in 0.5 mm units from the forming depth of 0.5 mm, and cold forming (pull-in one-stage forming) was performed on each of 20 samples. At this time, the test sample was placed on the female mold and molding was performed so that the heat-fusible resin layer side was located on the male mold side. The clearance between the male and female molds was 0.5 mm. The sample after cold forming was irradiated with light in a dark room with a penlight to confirm whether or not pinholes or cracks were formed in the barrier layer due to the light transmission. The deepest molding depth where pinholes and cracks do not occur in all the 20 samples is Amm, and the number of samples where pinholes occur in the shallowest molding depth where pinholes occur in the barrier layer is B The number of pieces was determined and the value calculated by the following formula was used as the limit forming depth of the exterior material for the electricity storage device. The results are shown in Table 1. The limit forming depth (mm) shown in Table 1 is a value obtained by rounding the calculated value to the second decimal place.
Limit forming depth = Amm + (0.5mm / 20 pieces) x (20 pieces-B pieces)

<Molding depth at which the barrier layer has a thickness of 20 μm>
The exterior material for each electricity storage device was cut into strips having a length (MD) of 90 mm and a width (TD) of 150 mm, which were used as test samples. A rectangular male mold having a length (MD) of 31.6 mm and a width (TD) of 54.5 mm (the surface is JIS B 0659-1: 2002 Annex 1 (reference) Table 2 of surface roughness standard pieces for comparison. The maximum height roughness (nominal value of Rz) specified is 1.6 μm, the corner R2.0 mm, the ridgeline R1.0 mm, and the female mold with a clearance of 0.3 mm between this male mold (the surface is JIS B 0659-1: 2002 Annex 1 (reference) The maximum height roughness (nominal value of Rz) specified in Table 2 of the surface roughness standard piece for comparison is 3.2 μm, and the corner R2.0 mm, Using a straight mold having a ridge line R1.0 mm), the test sample was placed on the female mold so that the heat-fusible resin layer side of the test sample was located on the male mold side, and Pressing with a pressing pressure (contact pressure) of 25 MPa, cold forming ( 1-stage molding) was included come.

  By this cold forming method, forming is sequentially performed under the condition that the forming depth is increased from 2.0 mm by 0.5 mm, and the thickness a of the corner portion P of the barrier layer of the test sample after forming (see FIG. 9). ) And the molding depth were plotted, and an approximate straight line was drawn to create a graph. From the graph, the molding depth at which the thickness a of the corner portion P of the barrier layer was 20 μm was obtained. The molding depth (mm) shown in Table 1 at which the thickness of the barrier layer is 20 μm is a value obtained by rounding off the second decimal place of the obtained value.

  The thickness a of the barrier layer of the test sample after molding is determined by measuring the microtome (Yamato) on the straight line connecting the mutually facing corner portions P of the substantially projecting portions when the test sample is viewed in plan from the base material layer side. Light machine industry: REM-710 retortome) was used to cut in the thickness direction to divide the exterior material for an electricity storage device into two, and the cross section of the corner P of one of the divided test samples was laser microscope (Keyence: VK). -9700) and observed. One of the divided test samples had two corners, and the thickness a of the barrier layer was the average value of the thickness a of the barrier layer at these corners. A schematic view of the barrier layer of the test sample after molding is shown in FIG. The position of the thickness of the corner portion P is where the radius of curvature is the smallest in the corner portion P (curved portion) formed by molding, and usually means the central portion from the start to the end of the bending.

<Evaluation of insulation (wire short circuit)>
The exterior material for each electricity storage device was cut into strips having a width of 40 mm and a length of 100 mm, which were used as test samples. On the surface of the heat-fusible resin layer of the test sample, a stainless wire having a diameter of 13 μm and a length of 70 mm was arranged at the center in the width direction. Further, an aluminum plate having a width of 30 mm, a length of 100 mm and a thickness of 100 μm was arranged from above. At this time, the center of the test sample in the width direction was made to coincide with the center of the aluminum plate in the width direction. Next, the positive electrode of the tester was connected to the aluminum plate, and the negative electrode was connected to the exterior material for the electricity storage device. Regarding the negative pole of the tester, the alligator clip was sandwiched so as to reach the barrier layer from the base material layer side of the exterior material for an electricity storage device, and the negative pole of the tester and the barrier layer were electrically connected. The tester was prepared to emit a conduction (short circuit) signal when the applied voltage was 100 V and the resistance was 200 MΩ or less. Next, a voltage of 100 V was applied between the testers, and in this state, with a stainless steel wire interposed between the aluminum plate and the exterior material for the electricity storage device, at 190 ° C., 1 MPa, and a width of 7 mm so as to be orthogonal to the wire. It heat-sealed and measured the time until a short circuit signal was generated. The time until the short circuit was taken as an average value of 3 points obtained by measuring 5 times and excluding the longest and shortest points. The case where the time to short circuit was 40.0 seconds or more was determined as A, the case where it was less than 40.0 seconds and 13.0 seconds or more was B, and the case where it was less than 13.0 seconds was determined as C. If the evaluation is A or B, the insulating property is excellent, and if the evaluation is A, the insulating property is particularly excellent.

  In Table 1, ONy is a biaxially stretched nylon film, DL is an adhesive layer or an adhesive layer formed by a dry lamination method, ALM is an aluminum foil, PPa is an adhesive layer formed by maleic anhydride modified polypropylene, and PP is polypropylene. The heat-fusible resin layer formed by CPP means the heat-fusible resin layer formed by unstretched polypropylene (CPP). SC means a surface coating layer. Further, the numerical value in the laminated constitution means the thickness (μm), and the expression “ONy15” means a biaxially stretched nylon film having a thickness of 15 μm.

  As is clear from the results shown in Table 1, in the exterior materials for electricity storage devices of Examples 1 to 6, the base material layer has a polyamide film layer, and the thickness of the polyamide film layer is 10 μm or more and 17 μm or less, The barrier layer has a thickness of 36 μm or more and 44 μm or less, and the thickness of the laminated body is set to 83 μm or more and 93 μm or less. It can be seen that the molding curl is effectively suppressed. Further, the outer layer materials for electricity storage devices of Examples 1 to 5 were also excellent in moldability. It can be seen that the outer layer materials for electricity storage devices of Examples 1, 4, and 5 have a large forming depth at which the barrier layer has a thickness of 20 μm and a limit forming depth, and are particularly high in formability.

  On the other hand, the outer packaging materials for electricity storage devices of Comparative Examples 1 to 4 and Comparative Example 6 had a large molding curl. Further, the exterior material for an electricity storage device of Comparative Example 5 had a thickness of less than 83 μm and had insufficient insulation, and was not suitable as an exterior material for an electricity storage device.

  Further, as shown in Table 2, it can be seen that the exterior materials for electricity storage devices of Examples 1 to 6 have large breaking energy per unit width of 1 m and are excellent in moldability.

DESCRIPTION OF SYMBOLS 1 Base material layer 11 Polyamide film layer 12 Polyester film layer 13 Adhesive layer 2 Adhesive layer 3 Barrier layer 4 Heat-fusible resin layer 5 Adhesive layer 6 Surface coating layer 10 Exterior material for power storage devices

Claims (14)

At least a base material layer which is the outermost layer, a barrier layer, and a heat-fusible resin layer is composed of a laminate provided in this order,
The base material layer has at least a polyamide film layer,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminate is 83 μm or more and 93 μm or less. At least, a base layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate including in this order,
  A lubricant layer is formed on the surface of the base material layer opposite to the barrier layer,
  The base material layer has at least a polyamide film layer,
  The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
  The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
  The thickness of the barrier layer is 36 μm or more and 44 μm or less,
  The packaging material for an electricity storage device, wherein the thickness of the laminate is 83 μm or more and 93 μm or less. At least a surface coating layer, a base material layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate provided in this order,
The surface coating layer is formed of at least one selected from the group consisting of polyester, two-component curing type polyurethane, acrylic resin, and epoxy resin,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
The base material layer has at least a polyamide film layer,
The thickness of the surface coating layer is 0.1 μm or more and 5 μm or less,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminated body is 83.1 μm or more and 98 μm or less. At least a surface coating layer (excluding those containing 100 parts by mass of acid-modified polyolefin resin, 5 to 1000 parts by mass of polyvinyl alcohol, and 0 to 50 parts by mass of a crosslinking agent), a base material layer, a barrier layer, and heat. It is composed of a laminate having a fusible resin layer in this order,
The base material layer has at least a polyamide film layer,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
The thickness of the surface coating layer is 0.1 μm or more and 5 μm or less,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminated body is 83.1 μm or more and 98 μm or less. At least a surface coating layer, a base material layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate provided in this order,
The base material layer has at least a polyamide film layer,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
The thickness of the surface coating layer is 1 μm or more and 5 μm or less,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminated body is 83.1 μm or more and 98 μm or less. At least a surface coating layer, a base material layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate provided in this order,
The base material layer has at least a polyamide film layer,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
Between the barrier layer and the heat-fusible resin layer, an adhesive layer having a polyolefin skeleton is provided,
The thickness of the surface coating layer is 0.1 μm or more and 5 μm or less,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminated body is 83.1 μm or more and 98 μm or less. At least a surface coating layer, a base material layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate provided in this order,
The base material layer has at least a polyamide film layer,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
Between the barrier layer and the heat-fusible resin layer, an adhesive layer formed of an acid-modified polyolefin is provided,
The thickness of the surface coating layer is 0.1 μm or more and 5 μm or less,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminated body is 83.1 μm or more and 98 μm or less. At least a surface coating layer, a base material layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate provided in this order,
The base material layer has at least a polyamide film layer,
An adhesive layer is provided between the barrier layer and the heat-fusible resin layer,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
The thickness of the surface coating layer is 0.1 μm or more and 5 μm or less,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The adhesive layer has a thickness of 8 μm or more and 22 μm or less,
The thickness of the heat-fusible resin layer is 8 μm or more and 22 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminated body is 83.1 μm or more and 98 μm or less. At least a surface coating layer, a base material layer, a barrier layer, and a heat-fusible resin layer, which is composed of a laminate provided in this order,
The base material layer has at least a polyamide film layer,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
The thickness of the surface coating layer is 0.1 μm or more and 5 μm or less,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The packaging material for an electricity storage device, wherein the thickness of the laminated body is 83.1 μm or more and 92 μm or less. An adhesive layer is provided between the barrier layer and the heat-fusible resin layer,
The adhesive layer has a thickness of 8 μm or more and 22 μm or less,
The exterior material for an electricity storage device according to claim 1, wherein the heat-fusible resin layer has a thickness of 8 μm or more and 22 μm or less. An adhesive layer is provided between the barrier layer and the heat-fusible resin layer,
The thickness of the adhesive layer is 1 μm or more and 5 μm or less,
The outer casing material for an electricity storage device according to claim 1, wherein the heat-fusible resin layer has a thickness of 18 μm or more and 34 μm or less.   The laminate has a breaking energy per 1 m unit width in MD and a breaking energy per 1 m unit width in TD, which is calculated from a curve of “measured load (N / 15 mm) -displacement amount” measured by a tensile test. Is 100 J or more, and the exterior material for an electricity storage device according to any one of claims 1 to 11.   An electricity storage device, wherein an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the exterior material for an electricity storage device according to claim 1. At least, the outermost base material layer, a barrier layer, and a heat-fusible resin layer are laminated in this order to obtain a laminate,
The base material layer has at least a polyamide film layer,
The barrier layer is made of aluminum alloy, stainless steel, or titanium steel,
The thickness of the polyamide film layer is 10 μm or more and 17 μm or less,
The thickness of the barrier layer is 36 μm or more and 44 μm or less,
The thickness of the said laminated body is 83 micrometers or more and 93 micrometers or less, The manufacturing method of the exterior material for an electrical storage device.

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