Outer packaging material for electricity storage device, method for producing same, and electricity storage device

Abstract

The present invention relates to an outer packaging material for an electricity storage device, the outer packaging material comprising a laminate comprising at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order from the outside, the outer packaging material having a strength of 35 N / 15 mm or more when stretched by 20% in the MD direction in a tensile test in a 120 DEG C environment. Lt; carrying out tensile test gt; and a tensile testing device is adopted for measurement according to a method specified by JIS K7127: 1999. The measurement conditions are as follows: the sample is a rectangle with the width of 15mm, the distance between the marked lines is 30mm, the stretching speed is 0.5 mm / min, the test environment is 120 DEG C, and the average value of three times of measurement is taken.

Description

TECHNICAL FIELD

[0001] The present application relates to an outer packaging material for an electricity storage device, a manufacturing method thereof, and an electricity storage device. BACKGROUND

[0002] At present, various types of electricity storage devices have been developed, and in all of these electricity storage devices, an outer packaging material is an indispensable member in order to package electricity storage device elements such as electrodes, electrolytes, and the like. In the past, as an outer packaging material for an electricity storage device, a metal outer packaging material has been used.

[0003] On the other hand, in recent years, with the high performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, cell phones, and the like, not only is a variety of shapes required for electricity storage devices, but also thinness and lightness are required. However, the metal outer packaging material for an electricity storage device that is currently commonly used has the disadvantage that it is difficult to conform to the variety of shapes, and there are limitations in lightness.

[0004] For this reason, in recent years, as an outer packaging material for an electricity storage device that is easy to process into a variety of shapes and enables thinness and lightness, a film-shaped laminate in which a base material layer / barrier layer / heat-fusible resin layer are sequentially laminated has been proposed (for example, refer to Patent Document 1).

[0005] In such an outer packaging material for an electricity storage device, a recess is generally formed by cold roll forming, and an electricity storage device element such as an electrode, an electrolyte, and the like is disposed in a space formed by the recess, and an electricity storage device in which the electricity storage device element is accommodated inside the outer packaging material for an electricity storage device is obtained by heat-fusing the heat-fusible resin layer.

[0006] PRIOR ART DOCUMENTS PATENT DOCUMENTS Patent Document 1: Japanese Patent Application Laid-Open No. 2008-287971 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION Lithium ion batteries and all-solid-state batteries and the like expand and contract during charging and discharging in a high temperature environment of 120°C or the like. When the electricity storage device expands, the outer packaging material for an electricity storage device also expands, and thus there is a possibility that it will break in a high temperature environment.

[0008] Furthermore, since no liquid is used as an electrolyte in, for example, all-solid-state batteries, it is expected that the temperature of the battery will rise to 100°C or more during charging, and the thickness of the heat-fusible resin layer of the outer packaging material for an electricity storage device that has been elongated by molding will be reduced in a high temperature environment, and there is a possibility that the insulation performance will be reduced.

[0009] In this case, the primary object of the present application is to provide an outer packaging material for an electrical storage device composed of a laminate having, in order from the outside, a base material layer, a barrier layer, and a heat-fusible resin layer, which has high strength after being elongated in a high-temperature environment of 120°C and has high puncture strength. The object of the present application is also to provide a manufacturing method of such an outer packaging material for an electrical storage device and an electrical storage device using such an outer packaging material for an electrical storage device.

[0010] Technical solution for solving the technical problem The inventors of the present application have conducted intensive studies to solve the above technical problem. As a result, it has been found that, in an outer packaging material for an electrical storage device composed of a laminate having, in order from the outside, at least a base material layer, a barrier layer, and a heat-fusible resin layer, by making the strength at the time of elongation by 20% in the MD direction in a prescribed tensile test in an environment of 120°C be above a set value, the outer packaging material for an electrical storage device has high strength after being elongated and has high puncture strength.

[0011] The present application is based on the above new findings and has been completed through further repeated studies. That is, the present application provides the invention shown below.

[0012] An outer packaging material for an electrical storage device composed of a laminate having, in order from the outside, at least a base material layer, a barrier layer, and a heat-fusible resin layer, The outer packaging material for an electrical storage device has a strength at the time of elongation by 20% in the MD direction in a prescribed tensile test in an environment of 120°C of 35 N / 15 mm or more.

[0013] < Tensile test > Measurement is performed using a tensile testing device in accordance with the method prescribed in JIS K7127: 1999. The measurement conditions are that the sample is in the form of a rectangle having a width of 15 mm, the gauge length is set to 30 mm, the tensile speed is set to 0.5 mm / minute, the test environment is set to 120°C, and the average of three measurements is taken. Measurement is performed after two minutes have elapsed in a constant-temperature bath to reach 120°C.

[0014] Effect of the invention According to the present application, an outer packaging material for an electrical storage device composed of a laminate having, in order from the outside, at least a base material layer, a barrier layer, and a heat-fusible resin layer has high strength after being elongated in a high-temperature environment of 120°C and has high puncture strength. In addition, according to the present application, a manufacturing method of such an outer packaging material for an electrical storage device and an electrical storage device using such an outer packaging material for an electrical storage device can also be provided. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1A schematic view for showing an example of a cross-sectional structure of the outer packaging material for the power storage device according to the present application.

[0016] Figure 2 A schematic view for showing an example of a cross-sectional structure of the outer packaging material for the power storage device according to the present application.

[0017] Figure 3 A schematic view for showing an example of a cross-sectional structure of the outer packaging material for the power storage device according to the present application.

[0018] Figure 4 A schematic view for showing an example of a cross-sectional structure of the outer packaging material for the power storage device according to the present application.

[0019] Figure 5 A schematic view for showing a method of housing a power storage device element in a package formed of the outer packaging material for the power storage device according to the present application. DETAILED DESCRIPTION

[0020] The outer packaging material for the power storage device according to the present application is characterized in that it is composed of a laminate including, at least in the order from the outside, a base material layer, a barrier layer, and a heat-fusible resin layer, and in a tensile test in an environment at 120°C, the strength at 20% elongation in the MD direction is 35 N / 15 mm or more. The outer packaging material for the power storage device according to the present application has this characteristic, and thus can exhibit excellent performance in which the strength of the outer packaging material for the power storage device after elongation is high and the puncture strength is high in a high-temperature environment such as 120°C.

[0021] < Tensile test > Measurement was performed using a tensile tester in accordance with the method prescribed in JIS K7127: 1999. The measurement conditions were: the sample was in the form of a rectangle having a width of 15 mm, the gauge length was set to 30 mm, the tensile speed was set to 0.5 mm / minute, the test environment was set to 120°C, and the average of three measurements was taken.

[0022] The outer packaging material for the power storage device according to the present application will be described in detail below. Note that in the present application, a numerical range indicated by "to" means "from... or more to... or less". For example, the expression "2 to 15 mm" means "2 mm or more and 15 mm or less". In the present application, the upper limit value or the lower limit value in a certain numerical range can be replaced with the upper limit value or the lower limit value of another numerical range indicated in segments. In addition, the upper limit value and the upper limit value, the upper limit value and the lower limit value, or the lower limit value and the lower limit value, which are independently described, can be combined to form a numerical range, respectively. In addition, in the numerical range described in the present specification, the upper limit value or the lower limit value in a certain numerical range can be replaced with the value shown in the examples.

[0023] Further, in the outer packaging material for electrical storage devices, with respect to the barrier layer 3 described later, the MD (Machine Direction: processing direction / longitudinal direction) and the TD (Transverse Direction: lateral direction) in the manufacturing process thereof can be generally discriminated. For example, when the barrier layer 3 is made of a metal foil such as an aluminum alloy foil or a stainless steel foil, linear streaks called rolling marks are formed on the surface of the metal foil in the rolling direction (RD: Rolling Direction) of the metal foil. Since the rolling marks extend along the rolling direction, by observing the surface of the metal foil, the rolling direction of the metal foil can be determined. In addition, in the manufacturing process of the laminate, generally, the MD of the laminate coincides with the RD of the metal foil, and thus by determining the rolling direction (RD) of the metal foil by observing the surface of the metal foil of the laminate, the MD of the laminate can be determined. Also, since the TD of the laminate is in the perpendicular direction to the MD of the laminate, the TD of the laminate can be determined.

[0024] In addition, when the MD of the outer packaging material for electrical storage devices cannot be confirmed by the rolling marks of the metal foil such as an aluminum alloy foil or a stainless steel foil, it can be determined by the following method. As a method for confirming the MD of the outer packaging material for electrical storage devices, there is a method for observing the cross section of the heat-fusible resin layer of the outer packaging material for electrical storage devices with an electron microscope to confirm the island structure. In this method, the direction parallel to the cross section in which the average value of the diameters of the island shapes in the direction perpendicular to the thickness direction of the heat-fusible resin layer is the largest can be determined as the MD. Specifically, the cross section in the length direction of the heat-fusible resin layer, and each cross section (total of 10 cross sections) in which the angle is changed every 10 degrees from the direction parallel to the length direction cross section until the direction perpendicular to the length direction cross section is observed with an electron micrograph to confirm the island structure. Then, the shape of each island in each cross section is observed. The shape of each island is the distance of the straight line connecting the leftmost end in the perpendicular direction perpendicular to the thickness direction of the heat-fusible resin layer and the rightmost end in the perpendicular direction as the island diameter y, and in each cross section, the average value of the island diameters y of the first 20 island diameters y in descending order of the island diameter y values is calculated, and the direction parallel to the cross section in which the average value of the island diameter y of the island shape is the largest is determined as the MD.

[0025] 1. Laminated structure and physical properties of outer packaging material for electrical storage devices The outer packaging material for electrical storage devices 10 of the present application is, for example, as shown in Figures 1-4As shown, the laminate body having at least the substrate layer 1, the barrier layer 3, and the heat-fusible resin layer 4 in this order is formed. In the power storage device outer packaging material 10, the substrate layer 1 is on the outermost layer side, and the heat-fusible resin layer 4 is on the innermost layer. When a power storage device is assembled using the power storage device outer packaging material 10 and a power storage device element, the power storage device element is housed in a space formed by heat-fusing the peripheral edge portions in a state where the heat-fusible resin layers 4 of the power storage device outer packaging material 10 face each other. In the laminate body constituting the power storage device outer packaging material 10 of the present application, with the barrier layer 3 as a reference, the side of the heat-fusible resin layer 4 closer to the barrier layer 3 is the inner side, and the side of the substrate layer 1 closer to the barrier layer 3 is the outer side.

[0026] As shown, the power storage device outer packaging material 10 may, for example, have an adhesive layer 2 between the substrate layer 1 and the barrier layer 3, as needed, for the purpose of improving the interlayer adhesion between the substrate layer 1 and the barrier layer 3, or the like. Figures 2-4 Figure 3 As shown, the power storage device outer packaging material 10 may, for example, have an adhesive layer 2 between the substrate layer 1 and the barrier layer 3, as needed, for the purpose of improving the interlayer adhesion between the substrate layer 1 and the barrier layer 3, or the like. Figure 4 As shown, the power storage device outer packaging material 10 may, for example, have an adhesive layer 2 between the substrate layer 1 and the barrier layer 3, as needed, for the purpose of improving the interlayer adhesion between the substrate layer 1 and the barrier layer 3, or the like. Figure 4 As shown, the power storage device outer packaging material 10 may, for example, have an adhesive layer 2 between the substrate layer 1 and the barrier layer 3, as needed, for the purpose of improving the interlayer adhesion between the substrate layer 1 and the barrier layer 3, or the like.

[0027] ​From the viewpoint of reducing costs, improving energy density, and the like, the thickness of the laminate constituting the power storage device exterior material 10 can be, but is not particularly limited to, for example, about 300 μm or less, about 280 μm or less, about 210 μm or less, preferably about 190 μm or less, about 180 μm or less, about 155 μm or less, about 120 μm or less. In addition, from the viewpoint of maintaining the function of the power storage device exterior material for protecting the power storage device element, the thickness of the laminate constituting the power storage device exterior material 10 can preferably be about 35 μm or more, about 45 μm or more, about 60 μm or more. In addition, as a preferable range of the thickness of the laminate constituting the power storage device exterior material 10, for example, about 35 to 300 μm, about 35 to 280 μm, about 35 to 210 μm, about 35 to 190 μm, about 35 to 180 μm, about 35 to 155 μm, about 35 to 120 μm, about 45 to 210 μm, about 45 to 190 μm, about 45 to 180 μm, about 45 to 300 μm, about 45 to 280 μm, about 45 to 155 μm, about 45 to 120 μm, about 60 to 300 μm, about 60 to 280 μm, about 60 to 210 μm, about 60 to 190 μm, about 60 to 180 μm, about 60 to 155 μm, about 60 to 120 μm can be mentioned, particularly in the case of making the power storage device light and thin, about 60 to 155 μm is preferable, and in the case of improving moldability, about 155 to 190 μm is preferable.

[0028] In addition, the power storage device exterior material 10 can be favorably applied to an all-solid-state battery. In this case, the thickness of the laminate constituting the power storage device exterior material 10 is not particularly limited, but from the viewpoint of reducing costs, improving energy density, and the like, about 10,000 μm or less, about 8,000 μm or less, about 5,000 μm or less can be mentioned, and from the viewpoint of maintaining the function of the all-solid-state battery exterior material for protecting the power storage device element, about 10 μm or more, about 15 μm or more, about 20 μm or more can be mentioned, and a preferable range can be, for example, about 10 to 10,000 μm, about 10 to 8,000 μm, about 10 to 5,000 μm, about 15 to 10,000 μm, about 15 to 8,000 μm, about 15 to 5,000 μm, about 20 to 10,000 μm, about 20 to 8,000 μm, about 20 to 5,000 μm, particularly about 20 to 5,000 μm is preferable.

[0029] In the outer packaging material 10 for electrical storage devices, the proportion of the total thickness of the base material layer 1, the adhesive layer 2 provided as necessary, the barrier layer 3, the adhesive layer 5 provided as necessary, the heat-fusible resin layer 4, and the surface cover layer 6 provided as necessary, with respect to the thickness of the laminate constituting the outer packaging material 10 for electrical storage devices (total thickness), is preferably 90% or more, more preferably 95% or more, and further preferably 98% or more. As a specific example, in the case where the outer packaging material 10 for electrical storage devices of the present application 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 proportion of the total thickness of the above-mentioned layers with respect to the thickness of the laminate constituting the outer packaging material 10 for electrical storage devices (total thickness) is preferably 90% or more, more preferably 95% or more, and further preferably 98% or more. In addition, in the case where the outer packaging material 10 for electrical storage devices of the present application is a laminate including the base material layer 1, the adhesive layer 2, the barrier layer 3, and the heat-fusible resin layer 4, the proportion of the total thickness of the above-mentioned layers with respect to the thickness of the laminate constituting the outer packaging material 10 for electrical storage devices (total thickness) can also be, for example, 80% or more, preferably 90% or more, more preferably 95% or more, and further preferably 98% or more.

[0030] The outer packaging material 10 for electrical storage devices of the present application has a strength of 35 N / 15 mm or more at the time of elongation of 20% in the MD direction in the following tensile test in an environment of 120°C. From the viewpoint of more preferably exerting the effects of the present application, the strength is preferably about 40 N / 15 mm or more, more preferably about 50 N / 15 mm or more, and further preferably about 60 N / 15 mm or more, and is preferably about 200 N / 15 mm or less, more preferably about 180 N / 15 mm or less, and further preferably about 160 N / 15 mm or less, and as a preferable range, about 35 to 200 N / 15 mm, about 35 to 180 N / 15 mm, about 35 to 160 N / 15 mm, about 40 to 200 N / 15 mm, about 40 to 180 N / 15 mm, about 40 to 160 N / 15 mm, about 50 to 200 N / 15 mm, about 50 to 180 N / 15 mm, about 50 to 160 N / 15 mm, about 60 to 200 N / 15 mm, about 60 to 180 N / 15 mm, and about 60 to 160 N / 15 mm can be mentioned.

[0031] <120°C environment tensile test> The measurement was performed with a tensile tester in accordance with the method prescribed in JIS K7127: 1999. The measurement conditions were: the sample was in the form of a rectangle having a width of 15 mm, the gauge length was set to 30 mm, the tensile speed was set to 0.5 mm / minute, the test environment was set to 120°C, and the average of three measurements was taken. Note that the constant temperature bath was started from room temperature (25°C), and after reaching 120°C in two minutes, measurement was performed two minutes later.

[0032] Further, from the viewpoint of more effectively exerting the effects of the present application, the thickness reduction ratio of the heat-fusible resin layer 4 at the time of elongation of 20% in the MD direction in the above-described tensile test of the power storage device outer packaging material 10 under an environment of 120°C is preferably 15% or less, more preferably 10% or less, and even more preferably 8% or less. In other words, the residual ratio of the thickness of the heat-fusible resin layer 4 at the time of elongation of 20% in the MD direction in the above-described tensile test of the power storage device outer packaging material 10 under an environment of 120°C (i.e., the ratio (%) of the thickness of the heat-fusible resin layer after the tensile test to the thickness of the heat-fusible resin layer before the tensile test, which is taken as 100%) is preferably 85% or more, more preferably 90% or more, and even more preferably 92% or more.

[0033] Further, from the viewpoint of more effectively exerting the effects of the present application, the volume resistivity at the time of elongation of 20% in the MD direction in the above-described tensile test of the power storage device outer packaging material 10 under an environment of 120°C is preferably 1 x 10 13 Ω or more, more preferably 1 x 10 14 Ω or more, even more preferably 1 x 10 15 Ω or more, and an upper limit can be cited, for example, 1 x 10 20 Ω, 1 x 10 19 Ω, and as a preferable range, 1 x 10 13 Ω or so, 1 x 10 20 Ω or so, 1 x 10 13 Ω or so, 1 x 10 19 Ω or so, 1 x 10 14 Ω or so, 1 x 10 20 Ω or so, 1 x 10 14 Ω or so, 1 x 10 19 Ω or so, 1 x 10 15 Ω or so, 1 x 10 20 Ω or so, 1 x 10 15 Ω or so, 1 x 10 19 Ω or so.

[0034] <Measurement of Volume Resistivity> A test piece was produced by elongating a 100 mm x 100 mm power storage device outer packaging material by 20% at 120°C at a rate of 0.5 mm / min in accordance with the above-described "Tensile test at 120°C". The volume resistivity was measured in accordance with the following method. The insulation resistance was measured at an applied voltage of 100 V using a digital ultra-high resistance / microammeter. The measurement was performed using a φ 50 electrode in a state in which the test piece was sandwiched with silicone rubber on both sides in accordance with the provisions of JIS K6911-1995. The measurement sample was a 100 mm x 100 mm laminate, and the measurement was performed from the hot melt layer side. The average value of the measurement number of 5 was taken under the measurement temperature condition of 23°C.

[0035] In addition, from the viewpoint of more effectively exerting the effects of the present application, the puncture strength of the power storage device outer packaging material 10 of the present application is preferably 30 N or greater, more preferably 31 N or greater, further preferably 35 N or greater, more further preferably 40 N or greater, and still further preferably 45 N or greater, and the upper limit can be, for example, 200 N or less, preferably 150 N or less, and as a preferable range, 30 to 200 N or so, 30 to 150 N or so, 31 to 200 N or so, 31 to 150 N or so, 35 to 200 N or so, 35 to 150 N or so, 40 to 200 N or so, 40 to 150 N or so, 45 to 200 N or so, and 45 to 150 N or so can be mentioned.

[0036] < Puncture strength > The puncture strength of the laminate constituting the power storage device outer packaging material was measured in accordance with the method prescribed by JIS Z1707: 1997 from the hot melt resin layer side. Each power storage device outer packaging material was cut into a 10 mm x 300 mm oblong shape to produce a test sample. Specifically, in a measurement environment of 23 ± 2°C and a relative humidity of 50 ± 5%, a test piece was fixed with a 115 mm diameter stage having a 15 mm diameter opening in the center and a pressing plate, and a puncture needle having a diameter of 1.0 mm and a needle tip shape of a semicircle with a radius of 0.5 mm was punctured at a rate of 10 ± 5 mm per minute, and the maximum stress until the needle penetrated was measured. The number of test pieces was 5, and the average value was taken. Note that when the number of test pieces was insufficient and 5 samples could not be measured, the number that could be measured was measured, and the average value was taken.

[0037] 2. Each layer forming the power storage device outer packaging material [Substrate layer 1] In the present application, the substrate layer 1 is a layer provided for the purpose of exhibiting the function as a substrate of the power storage device outer packaging material and the like. The substrate layer 1 is located on the outer layer side of the power storage device outer packaging material.

[0038] The material forming the base material layer 1 is not particularly limited, and is limited only to have a function as a base material, i.e., to have at least insulating properties. The base material layer 1 can be formed by, for example, using a resin, and the resin can also contain an additive described later.

[0039] In the case where the base material layer 1 is formed of a resin, the base material layer 1 can be formed of, for example, a resin film. In the case where the base material layer 1 is formed of a resin film, when the base material layer 1 is stacked with the barrier layer 3 or the like to produce the exterior material 10 for the power storage device of the present application, a resin film formed in advance can be used as the base material layer 1. Alternatively, a resin forming the base material layer 1 can be formed into a film on the surface of the barrier layer 3 or the like by extrusion molding, coating or the like, as the base material layer 1 formed of a resin film. The resin film can be an unstretched film or a stretched film. As the stretched film, a uniaxially stretched film, a biaxially stretched film, and preferably a biaxially stretched film can be given. As a stretching method for forming a biaxially stretched film, for example, a sequential (sequential) biaxial stretching method, a blow molding method, a simultaneous biaxial stretching method, or the like can be given. As a method of coating a resin, a roll coating method, a gravure coating method, an extrusion coating method, or the like can be given.

[0040] As the resin forming the base material layer 1, for example, a polyester, a polyamide, a polyolefin, an epoxy resin, an acrylic resin, a fluororesin, a polyurethane, a silicone resin, a phenol resin, or the like, and a modified product of these resins can be given. Alternatively, the resin forming the base material layer 1 can be a copolymer of these resins, and can also be a modified product of the copolymer. Alternatively, a mixture of these resins can be given.

[0041] The base material layer 1 preferably contains these resins as a main component, and more preferably contains a polyester or a polyamide as a main component. Here, the main component means that the content ratio of the resin component contained in the base material layer 1 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, still further preferably 90% by mass or more, yet further preferably 95% by mass or more, yet further preferably 98% by mass or more, and yet further preferably 99% by mass or more. For example, the base material layer 1 containing a polyester or a polyamide as a main component means that the content ratio of the polyester or the polyamide in the resin component contained in the base material layer 1 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, still further preferably 90% by mass or more, yet further preferably 95% by mass or more, yet further preferably 98% by mass or more, and yet further preferably 99% by mass or more, respectively.

[0042] As the resin forming the base material layer 1, a polyester and a polyamide can be given as preferable examples.

[0043] As the polyester, specifically, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, copolyester, and the like can be given. In addition, as the copolyester, copolyester having ethylene terephthalate as a main repeating unit, and the like can be given. Specifically, copolyester having ethylene terephthalate as a main repeating unit and polymerized with ethylene isophthalate (hereinafter, referred to as poly(ethylene terephthalate / ethylene isophthalate)), poly(ethylene terephthalate / hexamethylene adipate), poly(ethylene terephthalate / sodium sulfonate isophthalate), poly(ethylene terephthalate / sodium isophthalate), poly(ethylene terephthalate / benzene dicarboxylic acid), poly(ethylene terephthalate / decane dicarboxylic acid), and the like can be given. These polyesters can be used singly or in combination of two or more.

[0044] In addition, as the polyamide, specifically, aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, copolymer of nylon 6 and nylon 66, and the like; hexamethylene-isophthalic acid-terephthalic acid copolyamides such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I represents isophthalic acid and T represents terephthalic acid), and the like; aromatic-containing polyamides such as polyamide MXD6 (poly-m-xylylene adipamide), and the like; alicyclic polyamides such as polyamide PACM6 (polybis(4-aminocyclohexyl)methane adipamide), and the like; and polyamides obtained by copolymerizing a lactam component and / or an isocyanate component such as 4,4'-diphenylmethane-diisocyanate, and the like, copolyester-polyamide copolymers as copolyamides with copolymerization of polyester or polyalkylene ether glycol, and the like; and copolymers of the above compounds, and the like can be given. These polyamides can be used singly or in combination of two or more.

[0045] The substrate layer 1 preferably contains at least one of a polyester film, a polyamide film, and a polyolefin film, more preferably at least one of a stretched polyester film, a stretched polyamide film, and a stretched polyolefin film, further preferably at least one of a stretched polyethylene terephthalate film, a stretched polybutylene terephthalate film, a stretched nylon film, a stretched polypropylene film, and more further preferably at least one of a biaxially stretched polyethylene terephthalate film, a biaxially stretched polybutylene terephthalate film, a biaxially stretched nylon film, and a biaxially stretched polypropylene film.

[0046] The base material layer 1 can be a single layer or can be composed of two or more layers. In the case where the base material layer 1 is composed of two or more layers, the base material layer 1 can be a laminate of resin films stacked using an adhesive or the like, or can be a laminate of resin films formed by co-extrusion of two or more layers of resin. In addition, the laminate of resin films formed by co-extrusion of two or more layers of resin can be directly used as the base material layer 1 without stretching, or can be formed into the base material layer 1 by uniaxial stretching or biaxial stretching.

[0047] In the base material layer 1, as a specific example of a laminate of two or more layers of resin films, a laminate of a polyester film and a nylon film, a laminate of two or more layers of nylon films, a laminate of two or more layers of polyester films, and the like can be given, and a laminate of a stretched nylon film and a stretched polyester film, a laminate of two or more layers of stretched nylon films, and a laminate of two or more layers of stretched polyester films are preferable. In the case where, for example, the base material layer 1 is a laminate of two layers of resin films, a laminate of a polyester resin film and a polyester resin film, a laminate of a polyamide resin film and a polyamide resin film, or a laminate of a polyester resin film and a polyamide resin film is preferable, and a laminate of a polyethylene terephthalate film and a polyethylene terephthalate film, a laminate of a nylon film and a nylon film, or a laminate of a polyethylene terephthalate film and a nylon film is more preferable. In addition, since a polyester resin is less likely to discolor and the like when, for example, an electrolyte solution is attached to the surface, in the case where the base material layer 1 is a laminate of two or more layers of resin films, it is preferable that a polyester resin film be positioned at the outermost layer of the base material layer 1.

[0048] In the case where the base material layer 1 is a laminate of two or more layers of resin films, the two or more layers of resin films can be laminated with the aid of an adhesive. As a preferable adhesive, the same products as those exemplified for the adhesive layer 2 described later can be given. Note that the method of laminating the two or more layers of resin films is not particularly limited, and known methods can be employed, and for example, dry lamination, sandwich lamination, extrusion lamination, heat lamination, and the like can be given, and dry lamination is preferable. In the case where lamination is performed using dry lamination, a polyurethane adhesive is preferably used as the adhesive. In this case, the thickness of the adhesive can be, for example, about 2 to 5 μm. In addition, an anchor coat layer can be formed on the resin film. The anchor coat layer can be the same products as those exemplified for the adhesive layer 2 described later. In this case, the thickness of the anchor coat layer can be, for example, about 0.01 to 1.0 μm.

[0049] In addition, at least one of the surface and the interior of the base material layer 1 can be provided with an additive such as a lubricant, a flame retardant, an anti-blocking agent, an antioxidant, a light stabilizer, a tackifier, an antistatic agent, a coloring agent, and the like. The additive can be used singly or two or more kinds can be used in combination.

[0050] In the present application, from the viewpoint of improving the moldability of the outer packaging material for power storage devices, it is preferable that a lubricant be present at least one of the surface and the interior of the base material layer 1. As the lubricant, an amide-based lubricant is preferable, but is not particularly limited. As specific examples of the amide-based lubricant, saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, hydroxymethyl amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides, and the like can be given. As specific examples of the saturated fatty acid amides, lauramide, palmitamide, stearamide, behenamide, hydroxystearamide, and the like can be given. As specific examples of the unsaturated fatty acid amides, oleamide, erucamide, and the like can be given. As specific examples of the substituted amides, N-oleyl palmitamide, N-stearyl stearamide, N-stearyl oleamide, N-oleyl stearamide, N-stearyl erucamide, and the like can be given. In addition, as specific examples of the hydroxymethyl amides, hydroxymethyl stearamide, and the like can be given. As specific examples of the saturated fatty acid bisamides, methylene bisstearamide, ethylene bisdecanoamide, ethylene bislauramide, ethylene bisstearamide, ethylene bis hydroxystearamide, ethylene bisbehenamide, hexamethylene bisstearamide, hexamethylene bisbehenamide, hexamethylene bis hydroxystearamide, N,N'-distearyladipamide, N,N'-distearyl sebacic amide, and the like can be given. As specific examples of the unsaturated fatty acid bisamides, ethylene bisoleamide, ethylene biserucamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, N,N'-dioleyl sebacic amide, and the like can be given. As specific examples of the fatty acid ester amides, stearamide stearyl stearate, and the like can be given. In addition, as specific examples of the aromatic bisamides, m-xylyl bisstearamide, m-xylyl bis hydroxystearamide, N,N'-distearyl isophthalamide, and the like can be given. The lubricant can be used alone or in combination with two or more, and it is preferable to use two or more in combination.

[0051] In the case where the lubricant is present on the surface of the base material layer 1, as the amount of presence thereof, about 3 mg / m 2 or more, preferably about 4 mg / m 2 or more, about 5 mg / m 2 or more. Furthermore, as the amount of presence of the lubricant on the surface of the base material layer 1, about 15 mg / m 2 or less, preferably about 14 mg / m 2 or less, about 10 mg / m 2 or less. In addition, as the preferable range of the amount of presence of the lubricant on the surface of the base material layer 1, 3 to 15 mg / m 2 or so, 3 to 14 mg / m 2 or so, 3 to 10 mg / m 2 or so, 4 to 15 mg / m2 4-14 mg / m 2 4-10 mg / m 2 About 5-15 mg / m 2 5-14 mg / m 2 About 5-10 mg / m 2 about.

[0052] The lubricant present on the surface of the base layer 1 may be a lubricant exuded from the resin constituting the base layer 1 or a lubricant applied to the surface of the base layer 1 .

[0053] The thickness of the substrate layer 1 is not particularly limited, as long as it can function as a substrate. For example, it can be approximately 3 μm or greater, preferably approximately 10 μm or greater. Furthermore, the thickness of the substrate layer 1 can be approximately 50 μm or less, preferably approximately 35 μm or less, 13 μm or less, 11 μm or less, 8 μm or less, 7 μm or less, or 6 μm or less. Preferred thickness ranges for the substrate layer 1 include approximately 3 to 50 μm, approximately 3 to 35 μm, approximately 3 to 13 μm, approximately 3 to 11 μm, approximately 3 to 8 μm, approximately 3 to 7 μm, approximately 3 to 6 μm, approximately 10 to 50 μm, approximately 10 to 35 μm, and approximately 10 to 13 μm. In particular, when the electricity storage device is formed into a lightweight thin film, the thickness is preferably approximately 3 to 35 μm, approximately 3 to 11 μm, approximately 3 to 8 μm, approximately 3 to 7 μm, or approximately 3 to 6 μm. To improve formability, the thickness is preferably approximately 35 to 50 μm. When the substrate layer 1 is a laminate of two or more resin films, the thickness of the resin films constituting each layer can be, but is not particularly limited to, approximately 2 μm or greater, preferably approximately 10 μm or greater, or approximately 18 μm or greater. The thickness of the resin film constituting each layer may be, for example, about 33 μm or less, preferably about 28 μm or less, about 23 μm or less, about 18 μm or less, 11 μm or less, or 8 μm or less. Preferred ranges of the thickness of the resin film constituting each layer include approximately 2 to 33 μm, approximately 2 to 28 μm, approximately 2 to 23 μm, approximately 2 to 18 μm, approximately 2 to 11 μm, approximately 2 to 8 μm, approximately 10 to 33 μm, approximately 10 to 28 μm, approximately 10 to 23 μm, approximately 10 to 18 μm, approximately 18 to 33 μm, approximately 18 to 28 μm, or approximately 18 to 23 μm.

[0054] By including a colorant in the base material layer 1, the outer packaging material for the storage device can be colored. As the colorant, known materials such as pigments and dyes can be used. In addition, the colorant can be used alone or in combination of two or more.

[0055] The kind of the pigment is not particularly limited as long as it does not impair the function of the base material layer 1 as a base material within a range not impairing the function. As the organic pigment, pigments such as azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo sulfur indigo-based, pyrenone-perylene-based, isoindole-based, benzimidazolone-based, and the like can be given, and as the inorganic pigment, pigments such as carbon black-based, titanium oxide-based, cadmium-based, lead-based, chromium oxide-based, iron-based, and the like can be given, and in addition to these, fine powder of mica, fish scale foil, and the like can be given.

[0056] In the colorant, for example, in order to make the appearance of the outer packaging material for electrical storage devices black, carbon black is also preferable. In addition, from the viewpoint of releasing the heat generated by the electrical storage devices, mica is preferably used.

[0057] As the average particle diameter of the pigment, for example, about 0.03 to 5 μm, preferably about 0.05 to 2 μm can be given, but is not particularly limited thereto. Note that the average particle diameter of the pigment is the median particle diameter measured by a laser diffraction / scattering type particle size distribution measuring device.

[0058] The content of the colorant in the base material layer 1 is not particularly limited as long as it can color the outer packaging material for electrical storage devices, and for example, about 5 to 60 mass%, preferably about 10 to 40 mass% can be given.

[0059] [Adhesive layer 2] In the outer packaging material for electrical storage devices of the present application, the adhesive layer 2 is a layer provided as necessary between the base material layer 1 and the barrier layer 3 for the purpose of improving the adhesion therebetween.

[0060] The adhesive layer 2 is formed by an adhesive capable of adhering the base material layer 1 and the barrier layer 3. The adhesive used in the formation of the adhesive layer 2 can be, but is not particularly limited to, any of chemical reaction type, solvent evaporation type, hot melting type, heat press type, and the like. In addition, it can be a two-liquid curing type adhesive (two-liquid adhesive), can be a one-liquid curing type adhesive (one-liquid adhesive), or can be a resin that does not undergo a curing reaction. In addition, the adhesive layer 2 can be a single layer, or can be a plurality of layers.

[0061] As the adhesive component contained in the adhesive, specifically, there can be mentioned polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, copolyester, etc.; polyether; polyurethane; epoxy resin; phenol resin; polyamide such as nylon 6, nylon 66, nylon 12, copolyamide, etc.; polyolefin-based resin such as polyolefin, cyclic polyolefin, acid-modified polyolefin, acid-modified cyclic polyolefin, etc.; polyvinyl acetate; cellulose; (meth)acrylic resin; polycarbonate; amino resin such as urea resin, melamine resin, etc.; rubber such as chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc.; silicone resin, etc. These adhesive components can be used singly or in combination of two or more. Among these adhesive components, polyurethane adhesive is preferable. In addition, the resin forming these adhesive components can be used in combination with a proper curing agent to improve the adhesive strength. The above curing agent can be selected from a proper compound among polyisocyanate, polyfunctional epoxy resin, polymer containing oxazoline group, polyamine resin, acid anhydride, etc. according to the functional group possessed by the adhesive component.

[0062] As the polyurethane adhesive, for example, a polyurethane adhesive including a first agent containing a polyol compound and a second agent containing an isocyanate compound can be given. As the polyurethane adhesive, a two-liquid curing type polyurethane adhesive in which a polyol such as a polyester polyol, a polyether polyol, and an acrylic polyol is used as the first agent and a polyisocyanate of an aromatic or aliphatic series is used as the second agent can be given. In addition, as the polyurethane adhesive, for example, a polyurethane adhesive containing a polyurethane compound obtained by previously reacting a polyol compound with an isocyanate compound and an isocyanate compound can be given. In addition, as the polyurethane adhesive, for example, a polyurethane adhesive containing a polyurethane compound obtained by previously reacting a polyol compound with an isocyanate compound and a polyol compound can be given. In addition, as the polyurethane adhesive, for example, a polyurethane adhesive cured by reacting a polyurethane compound obtained by previously reacting a polyol compound with an isocyanate compound with moisture in the air can be given. As the polyol compound, a polyester polyol having a hydroxyl group in a side chain in addition to a hydroxyl group at a terminal of a repeating unit is preferably used. As the second agent, an isocyanate compound of an aliphatic, alicyclic, aromatic, or aromatic aliphatic series can be given. As the isocyanate compound, for example, hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), and the like can be given. In addition, a polyfunctional isocyanate-modified product and the like derived from one or two or more of these diisocyanates can also be given. In addition, as the polyisocyanate compound, a multimer (for example, a trimer) can also be used. Such a multimer can include an adduct, a biuret, a urethane, and the like. By forming the adhesive layer 2 from a polyurethane adhesive, the exterior material for electrical storage devices can have excellent electrolyte resistance, and peeling of the base material layer 1 can be suppressed even if electrolyte adheres to the side surface.

[0063] In addition, the adhesive layer 2 can also allow addition of other components as long as adhesion is not hindered, and can contain a colorant, a thermoplastic elastomer, an adhesion promoter, a filler, and the like. By containing a colorant in the adhesive layer 2, the exterior material for electrical storage devices can be colored. As the colorant, known materials such as pigments and dyes can be used. In addition, the colorant can be used alone or two or more kinds can be mixed and used.

[0064] The kind of the pigment is not particularly limited as long as it does not impair the adhesion of the adhesive layer 2. As the organic pigment, pigments such as azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo sulfur indigo-based, pyrenone-perylene-based, iso- pseudoindole-based, benzimidazolone-based pigments can be given, as the inorganic pigment, pigments such as carbon black-based, titanium oxide-based, cadmium-based, lead-based, chromium oxide-based, iron-based pigments can be given, in addition to these, fine powder of mica, fish scale foil, and the like can be given.

[0065] In the colorant, for example, in order to make the appearance of the outer packaging material for electrical storage devices black, carbon black is also preferable.

[0066] As the average particle diameter of the pigment, for example, about 0.03 to 5 μm, preferably about 0.05 to 2 μm can be given, but is not particularly limited. Note that the average particle diameter of the pigment is the median particle diameter measured by a laser diffraction / scattering type particle size distribution measuring device.

[0067] As the content of the colorant in the adhesive layer 2, there is no particular limitation as long as it can color the outer packaging material for electrical storage devices, for example, about 5 to 60 mass%, preferably about 10 to 40 mass% can be given.

[0068] The thickness of the adhesive layer 2 is not particularly limited as long as it can adhere the substrate layer 1 and the barrier layer 3, for example, about 1 μm or more, about 2 μm or more. Also, the thickness of the adhesive layer 2 is, for example, about 10 μm or less, about 5 μm or less. In addition, as for the preferable range of the thickness of the adhesive layer 2, about 1 to 10 μm, about 1 to 5 μm, about 2 to 10 μm, about 2 to 5 μm can be given.

[0069] [Coloring layer] The coloring layer is a layer provided between the substrate layer 1 and the barrier layer 3 as needed (omitted from the drawing). In the case of having the adhesive layer 2, the coloring layer can be provided between the substrate layer 1 and the adhesive layer 2, between the adhesive layer 2 and the barrier layer 3. In addition, the coloring layer can be provided on the outside of the substrate layer 1. By providing the coloring layer, the outer packaging material for electrical storage devices can be colored.

[0070] The coloring layer can be formed by, for example, applying an ink containing a colorant to the surface of the substrate layer 1 or the surface of the barrier layer 3. As the colorant, known materials such as pigments, dyes, and the like can be used. In addition, the colorant can be used alone or two or more kinds can be mixedly used.

[0071] As a specific example of the colorant contained in the coloring layer, the same colorants as exemplified in the [adhesive layer 2] section can be given.

[0072] [Barrier layer 3] In the outer packaging material for the power storage device, the barrier layer 3 is a layer that at least suppresses the penetration of moisture.

[0073] As the barrier layer 3, for example, a metal foil, an evaporation film, a resin layer, or the like having barrier properties can be given. As the evaporation film, a metal evaporation film, an inorganic oxide evaporation film, a carbon-containing inorganic oxide evaporation film, or the like can be given; as the resin layer, a polyvinylidene chloride, a polymer having chlorotrifluoroethylene (CTFE) as a main component, a polymer having tetrafluoroethylene (TFE) as a main component, a polymer having a fluoroalkyl group, and a polymer having a fluoroalkyl unit as a main component, a fluororesin, an ethylene-vinyl alcohol copolymer, or the like can be given. In addition, as the barrier layer 3, a resin film provided with at least one of these evaporation films and resin layers, or the like can be given. The barrier layer 3 can also be provided in multiple layers. The barrier layer 3 preferably includes a layer composed of a metal material. As the metal material constituting the barrier layer 3, specifically, an aluminum alloy, stainless steel, titanium steel, a steel sheet, or the like can be given, and in the case of being used in the form of a metal foil, at least one of an aluminum alloy foil and a stainless steel foil is preferably included.

[0074] In the barrier layer 3, the above-described layer composed of a metal material can also contain a recycled material of a metal material. As the recycled material of a metal material, for example, a recycled material of an aluminum alloy, stainless steel, titanium steel, or a steel sheet can be given. Each of these recycled materials can be obtained by a known method. For example, the recycled material of an aluminum alloy can be obtained by a manufacturing method described in, for example, International Publication No. 2022 / 092231. The barrier layer 3 can be composed only of a recycled material, or can be composed of a mixed material of a recycled material and a virgin material. The recycled material of a metal material refers to a metal material that is formed in a state that can be reused by performing recycling, separation, purification, or the like of various products used on the market, waste produced in a manufacturing process, or the like. In addition, the virgin material of a metal material refers to a new metal material that is refined from a natural resource (raw material) of a metal, and is not a recycled material.

[0075] From the viewpoint of improving the moldability of the exterior material for the electrical storage device, the aluminum alloy foil is more preferably a soft aluminum alloy foil composed of, for example, an aluminum alloy in which annealing treatment is completed, and from the viewpoint of further improving the moldability, an aluminum alloy foil containing iron is preferred. In the aluminum alloy foil containing iron (100 mass%), the content of iron is preferably 0.1 to 9.0 mass%, and more preferably 0.5 to 2.0 mass%. By making the content of iron 0.1 mass% or more, an exterior material for an electrical storage device having more excellent moldability can be obtained. By making the content of iron 9.0 mass% or less, an exterior material for an electrical storage device having more excellent flexibility can be obtained. As the soft aluminum alloy foil, for example, an aluminum alloy foil having a composition specified in JIS H4160:1994 A8021H-O, JIS H4160:1994 A8079H-O, JIS H4000:2014 A8021P-O, or JIS H4000:2014 A8079P-O can be given. In addition, silicon, magnesium, copper, manganese, and the like can be added as needed. And the softening can be achieved by annealing treatment or the like.

[0076] In addition, as the stainless steel foil, an austenitic type, a ferritic type, an austenitic / ferritic type, a martensitic type, a precipitation hardening type, and the like can be given. From the viewpoint of providing an exterior material for an electrical storage device having more excellent moldability, the stainless steel foil is preferably composed of an austenitic type stainless steel.

[0077] As a specific example of the austenitic type stainless steel constituting the stainless steel foil, SUS304, SUS301, SUS316L, and the like can be given, and among them, SUS304 is particularly preferred.

[0078] In the case of a metal foil, the thickness of the barrier layer 3 is only required to be at least capable of exhibiting the function as a barrier layer of suppressing the penetration of moisture, and can be, for example, about 9 to 200 μm. The thickness of the barrier layer 3 is preferably about 100 μm or less, more preferably about 90 μm or less, further preferably about 85 μm or less, particularly preferably about 80 μm or less. Also, the thickness of the barrier layer 3 is preferably about 40 μm or more, more preferably about 50 μm or more, further preferably about 55 μm or more. In addition, as a preferable range of the thickness of the barrier layer 3, about 40 to 100 μm, about 40 to 90 μm, about 40 to 85 μm, about 40 to 80 μm, about 50 to 100 μm, about 50 to 90 μm, about 50 to 85 μm, about 50 to 80 μm, about 55 to 100 μm, about 55 to 90 μm, about 55 to 85 μm, about 55 to 80 μm can be mentioned. In the case where the barrier layer 3 is composed of an aluminum alloy foil, the above ranges are particularly preferable. In addition, from the viewpoint of imparting high formability and high rigidity to the power storage device exterior material 10, the thickness of the barrier layer 3 is preferably about 35 μm or more, more preferably about 45 μm or more, further preferably about 50 μm or more, more further preferably about 55 μm or more, and is preferably about 200 μm or less, about 100 μm or less, more preferably about 90 μm or less, further preferably about 85 μm or less, and as a preferable range, about 35 to 200 μm, about 35 to 100 μm, about 35 to 90 μm, about 35 to 85 μm, about 45 to 200 μm, about 45 to 100 μm, about 45 to 90 μm, about 45 to 85 μm, about 50 to 200 μm, about 50 to 100 μm, about 50 to 90 μm, about 50 to 85 μm, about 55 to 200 μm, about 55 to 100 μm, about 55 to 90 μm, about 55 to 85 μm. By imparting high formability to the power storage device exterior material 10, deep draw molding can be easily achieved, and high capacity of the power storage device is expected. In addition, once the power storage device is made high capacity, the weight of the power storage device will increase, but by increasing the rigidity of the power storage device exterior material 10, high sealing property of the power storage device is expected. In addition, particularly when the barrier layer 3 is composed of a stainless steel foil, the thickness of the stainless steel foil is preferably about 90 μm or less, more preferably about 80 μm or less, further preferably about 75 μm or less, more further preferably about 70 μm or less, particularly preferably about 65 μm or less. Also, the thickness of the stainless steel foil is preferably about 10 μm or more, more preferably about 15 μm or more.In addition, as a preferable range of the thickness of the stainless steel foil, 10 to 90 μm or so, 10 to 80 μm or so, 10 to 75 μm or so, 10 to 70 μm or so, 10 to 65 μm or so, 15 to 90 μm or so, 15 to 80 μm or so, 15 to 75 μm or so, 15 to 70 μm or so, and 15 to 65 μm or so can be mentioned.

[0079] In addition, in the case where the barrier layer 3 is a metal foil, in order to prevent dissolution and corrosion and the like, it is preferable to have a corrosion-resistant film on at least the side opposite to the base material layer. The barrier layer 3 can have a corrosion-resistant film on both sides thereof. In the present application, the corrosion-resistant film refers to a film that imparts corrosion resistance (e.g., acid resistance, alkali resistance, and the like) to the barrier layer by performing, for example, a hot water modification treatment such as boehmite treatment, a chemical surface treatment, an anodization treatment, a plating treatment with nickel or chromium, or a corrosion-resistant treatment by applying a coating agent. The corrosion-resistant film specifically refers to a film that improves the acid resistance of the barrier layer (acid-resistant film), a film that improves the alkali resistance of the barrier layer (alkali-resistant film), and the like. The treatment for forming the corrosion-resistant film can be performed in one type or in two or more types in combination. In addition, it can be provided in one layer or in multiple layers. In these treatments, the hot water modification treatment and the anodization treatment are treatments that dissolve the surface of the metal foil by a treatment agent and form a metal compound having excellent corrosion resistance. Note that these treatments can also be included in the definition of the chemical surface treatment. In addition, in the case where the barrier layer 3 has a corrosion-resistant film, the barrier layer 3 including the corrosion-resistant film is formed.

[0080] The corrosion-resistant film exhibits the following effects at the time of molding of the outer packaging material for the power storage device: prevention of delamination between the barrier layer (e.g., aluminum alloy foil) and the base material layer; prevention of dissolution and corrosion of the surface of the barrier layer due to hydrogen fluoride generated by the reaction of the electrolyte with moisture, particularly in the case where the barrier layer is an aluminum alloy foil, prevention of dissolution and corrosion of aluminum oxide present on the surface of the barrier layer, and improvement of the adhesion (wettability) of the surface of the barrier layer; prevention of delamination between the base material layer and the barrier layer at the time of heat sealing; and prevention of delamination between the base material layer and the barrier layer at the time of molding.

[0081] As a corrosion resistant film formed by chemical surface treatment, various corrosion resistant films are known, and examples of the corrosion resistant film mainly include a corrosion resistant film containing at least one of a phosphate, a chromate, a fluoride, a triazine thiol compound, and a rare earth oxide. As a chemical surface treatment using a phosphate, a chromate, examples of the chemical surface treatment can include chromic acid-chromate treatment, phosphoric acid-chromate treatment, phosphoric acid-chromate treatment, chromate treatment, and the like, and as a chromium compound used for these treatments, examples of the chromium compound can include chromic nitrate, chromic fluoride, chromic sulfate, chromic acetate, chromic oxalate, chromic dihydrogen phosphate, chromic acetoacetate, chromic chloride, potassium chromic sulfate, and the like. Further, as a phosphorus compound used for these treatments, examples of the phosphorus compound can include sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid, and the like. Further, as the chromate treatment, examples of the chromate treatment can include etching chromate treatment, electrolytic chromate treatment, coating type chromate treatment, and the like, and the coating type chromate treatment is preferable. The coating type chromate treatment is a treatment in which, first, a surface of at least an inner layer side of a barrier layer (for example, an aluminum alloy foil) is subjected to degreasing treatment by a known treatment method such as an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid activation method, and the like, and then, a treatment liquid in which a phosphoric acid metal salt such as a phosphoric acid Cr (chromium) salt, a phosphoric acid Ti (titanium) salt, a phosphoric acid Zr (zirconium) salt, a phosphoric acid Zn (zinc) salt, or a mixture of these metal salts, or a treatment liquid in which a phosphoric acid nonmetal salt or a mixture of these nonmetal salts is used as a main component, or a treatment liquid in which a mixture of the above-mentioned salt or the mixture thereof and a synthetic resin or the like is formed is applied to the degreasing treatment surface by a known coating method such as a roll coating method, a gravure coating method, an immersion method, and the like, and then, drying is performed. The treatment liquid can use various solvents such as water, an alcohol-based solvent, a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an ether-based solvent, and the like, and water is preferable. Further, as a resin component used at this time, examples of the resin component can include a phenolic resin, an acrylic resin, a high molecular compound, and the like, and examples of the chromate treatment using an amino phenol polymer having a repeating unit represented by the following general formulae (1) to (4) can be mentioned. Note that, in the amino phenol polymer, the repeating unit represented by the following general formulae (1) to (4) can be contained alone as one kind, or can be two or more kinds in any combination. The acrylic resin is preferably polyacrylic acid, an acrylic-methacrylic acid ester copolymer, an acrylic-maleic acid copolymer, an acrylic-styrene copolymer, or a derivative thereof such as a sodium salt, an ammonium salt, an amine salt, or the like. Particularly preferably, a derivative of polyacrylic acid such as an ammonium salt, a sodium salt, or an amine salt of polyacrylic acid is used. In the present application, polyacrylic acid refers to a polymer of acrylic acid. Further, the acrylic resin is preferably a copolymer of acrylic acid and a dibasic acid or a dibasic acid anhydride, and further preferably an ammonium salt, a sodium salt, or an amine salt of the copolymer of acrylic acid and the dibasic acid or the dibasic acid anhydride. The acrylic resin can be used alone or in combination of two or more kinds. In General Formulae (1) to (4), X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group, or a benzyl group. In addition, R 1 and R 2 each independently represent a hydroxyl group, an alkyl group, or a hydroxyalkyl group. In General Formulae (1) to (4), as the alkyl group represented by X, R 1 and R 2 may be mentioned, for example, a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and the like. In addition, as the hydroxyalkyl group represented by X, R 1 and R 2 may be mentioned, for example, a linear or branched alkyl group having 1 to 4 carbon atoms substituted with one hydroxyl group such as a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and the like. In General Formulae (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 General Formulae (1) to (4), X is preferably a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. The number average molecular weight of the aminophenol polymer having the repeating unit represented by General Formulae (1) to (4) is, for example, preferably about 500 to 10 million, more preferably about 1,000 to 2 million. The aminophenol polymer can be produced, for example, by subjecting a phenol compound or a naphthol compound to polycondensation with formaldehyde to produce a polymer having the repeating unit represented by General Formula (1) or General Formula (3), and then introducing a functional group (-CH2NR 1 R 2 NH) into the obtained polymer using formaldehyde and an amine (R 1 R 2 ). The aminophenol polymer can be used alone or in combination of two or more kinds.

[0082] As other examples of the corrosion-resistant film, a film formed by applying a coating-type corrosion-resistant treatment using a coating agent containing at least one selected from the group consisting of a rare earth element oxide sol, a cationic polymer, and an anionic polymer can be given. The coating agent can further contain phosphoric acid or a phosphoric acid salt, and a cross-linking agent that cross-links the polymer. In the rare earth element oxide sol, fine particles of a rare earth element oxide (for example, particles having an average particle diameter of 100 nm or less) are dispersed in a liquid dispersion medium. As the rare earth element oxide, cerium oxide, yttrium oxide, neodymium oxide, lanthanum oxide, or the like can be given, and from the viewpoint of further improving adhesion, cerium oxide is preferred. The rare earth element oxide contained in the corrosion-resistant film can be used alone or in combination with two or more. As the liquid dispersion medium of the rare earth element oxide sol, various solvents such as water, an alcohol-based solvent, a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an ether-based solvent, or the like can be used, and water is preferred. As the cationic polymer, polyethyleneimine, an ionomer complex of polyethyleneimine and a polymer having a carboxylic acid, a primary amine-grafted acrylic acid resin in which a primary amine is grafted to an acrylic acid main skeleton, a polyallylamine or a derivative thereof, an amino phenol, or the like are preferred. In addition, as the anionic polymer, poly(meth)acrylic acid or a salt thereof, or a copolymer in which (meth)acrylic acid or a salt thereof is a main component is preferred. In addition, the cross-linking agent is preferably at least one selected from the group consisting of a compound having an isocyanate group, a glycidyl group, a carboxyl group, an oxazoline group, and a silane coupling agent. In addition, the above-described phosphoric acid or phosphoric acid salt is preferably condensed phosphoric acid or a condensed phosphoric acid salt.

[0083] As an example of the corrosion-resistant film, a corrosion-resistant film formed by applying a dispersion liquid in which fine particles of a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate are dispersed in phosphoric acid to the surface of the barrier layer, and performing a baking treatment at a temperature of 150°C or higher can be given.

[0084] As needed, the corrosion-resistant film can also be formed in a layered structure further layered with at least one of a cationic polymer and an anionic polymer. As the cationic polymer and the anionic polymer, the above-described polymers can be given.

[0085] Note that the composition analysis of the corrosion-resistant film formed on the surface of the barrier layer 3 in the chemical surface treatment can be performed using, for example, time-of-flight secondary ion mass spectrometry.

[0086] The amount of the corrosion-resistant film formed on the surface of the barrier layer 3 in the chemical surface treatment is not particularly limited, and for example, in the case of performing a coating-type chromic acid treatment, 0.1 to 10 mg / cm2, preferably 0.5 to 5 mg / cm2, is required per 1 m2of the barrier layer 3. 2The surface contains a chromium compound in an amount of, for example, about 0.5 to 50 mg, preferably about 1.0 to 40 mg, in terms of chromium; a phosphorus compound in an amount of, for example, about 0.5 to 50 mg, preferably about 1.0 to 40 mg, in terms of phosphorus; and an aminophenol polymer in an amount of, for example, about 1.0 to 200 mg, preferably about 5.0 to 150 mg.

[0087] The thickness of the corrosion-resistant film can be preferably selected from, but is not particularly limited to, about 1 nm to 20 μm, more preferably about 1 nm to 100 nm, and further preferably about 1 nm to 50 nm, from the viewpoints of the cohesion of the film and the adhesion to the barrier layer or the heat-fusible resin layer. Note that the thickness of the corrosion-resistant film can be measured by transmission electron microscope observation, or a combination of transmission electron microscope observation and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy. By analyzing the composition of the corrosion-resistant film using a time-of-flight secondary ion mass spectrometry method, a peak of, for example, at least one of secondary ions derived from Ce, P, and O (for example, Ce2PO4 ﹢ , CePO4 ﹣ , etc.), or a peak of, for example, at least one of secondary ions derived from Cr, P, and O (for example, CrPO2 ﹢ , CrPO4 ﹣ , etc.), or the like can be detected.

[0088] The chemical surface treatment is performed by applying a solution containing a compound used for forming the corrosion-resistant film to the surface of the barrier layer using a bar coating method, a roll coating method, a gravure coating method, an immersion method, or the like, and then heating the barrier layer so that the temperature of the barrier layer reaches about 70 to 200°C. Alternatively, the barrier layer can be subjected to degreasing treatment using an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like, before the chemical surface treatment is performed on the barrier layer. By performing the degreasing treatment, the chemical surface treatment of the surface of the barrier layer can be performed more efficiently. In addition, by using an acid degreasing agent in which a fluorine-containing compound is dissolved in an inorganic acid in the degreasing treatment, not only the degreasing effect of the metal foil but also a passive metal fluoride can be formed, and in this case, only the degreasing treatment can be performed.

[0089] [Heat-fusible resin layer 4] In the outer packaging material for electrical storage devices of the present application, the heat-fusible resin layer 4 contains the innermost layer, and is a layer (sealing layer) in which the heat-fusible resin layers are heat-fused to each other to function to seal the elements of the electrical storage device when the electrical storage device is assembled.

[0090] In the present application, the hot-melt adhesive resin contained in the hot-melt adhesive resin layer 4 is not particularly limited, and examples of a resin having hot-melt adhesiveness, such as a thermoplastic resin, can be given, provided that the effect of the present application is not impaired. From the viewpoint of more preferably exerting the effect of the present application, the hot-melt adhesive resin layer 4 preferably contains polybutylene terephthalate, and more preferably contains at least one of homopolybutylene terephthalate and copolybutylene terephthalate.

[0091] The hot-melt adhesive resin layer 4 is preferably formed of, for example, a homopolybutylene terephthalate film, and the content ratio of the homopolybutylene terephthalate is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 85% by mass or more.

[0092] In the case where the hot-melt adhesive resin layer 4 is a resin layer formed of a homopolybutylene terephthalate film, the resin contained in the hot-melt adhesive resin layer 4 is substantially only homopolybutylene terephthalate (for example, 99% by mass or more, and further 100% by mass or more). That is, the hot-melt adhesive resin layer 4 in this case is formed of a homopolybutylene terephthalate film substantially not containing a resin other than homopolybutylene terephthalate. For example, the hot-melt adhesive resin layer 4 in this case is a layer formed of a homopolybutylene terephthalate film not containing an elastomer and a resin other than copolybutylene terephthalate.

[0093] Further, the homopolybutylene terephthalate contained in the hot-melt adhesive resin layer 4 can be subjected to acid modification or can not be subjected to acid modification. In the case where the homopolybutylene terephthalate is an acid-modified homopolybutylene terephthalate, the acid modification of the homopolybutylene terephthalate can be performed using an acid component such as maleic anhydride or acrylic acid.

[0094] The hot-melt adhesive resin layer 4 formed of homopolybutylene terephthalate has, for example, a melting peak temperature of 220 to 230°C. Note that, in the present application, the melting peak temperature of the resin constituting a layer is an endothermic peak measured by a differential scanning calorimeter (DSC), and is measured by the following method.

[0095] <Measurement of Melting Peak Temperature> The melting peak temperature of the resin forming the layer was measured in accordance with the provisions of JIS K7121 : 2012 (Method of Measuring Glass Transition Temperature of Plastics (Supplement 1 to JIS K7121 : 1987)). The measurement was performed using a differential scanning calorimeter. After the test sample was held at a temperature of -50°C for 15 minutes, the temperature was raised from -50°C to 300°C at a temperature increase rate of 10°C / min, and the first melting peak temperature P (°C) was measured, after which the temperature was held at 300°C for 2 minutes. Next, the temperature was lowered from 300°C to -50°C at a temperature decrease rate of 10°C / min, and held at -50°C for 15 minutes. Then, the temperature was raised from -50°C to 300°C at a temperature increase rate of 10°C / min, and the second melting peak temperature Q (°C) was measured. Note that the nitrogen flow rate was set to 50 ml / min. The first melting peak temperature P (°C) and the second melting peak temperature Q (°C) were obtained in accordance with the above procedure, and the first melting peak temperature was taken as the melting peak temperature.

[0096] In addition, the heat-adhesive resin layer 4 is preferably a layer containing copolymerized polybutylene terephthalate. In the case where the heat-adhesive resin layer 4 is formed of a copolymerized polybutylene terephthalate film, the content of the copolymerized polybutylene terephthalate contained in the heat-adhesive resin layer 4 is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.

[0097] In the case where the heat-adhesive resin layer 4 is a resin layer formed of a copolymerized polybutylene terephthalate film, the resin contained in the heat-adhesive resin layer 4 is substantially only copolymerized polybutylene terephthalate (e.g., 99% by mass or more, and further 100% by mass or more). That is, the heat-adhesive resin layer 4 in this case is formed of a copolymerized polybutylene terephthalate film substantially containing no resin other than copolymerized polybutylene terephthalate. For example, the heat-adhesive resin layer 4 in this case is a layer formed of a copolymerized polybutylene terephthalate film containing no elastomer and no resin other than copolymerized polybutylene terephthalate.

[0098] From the viewpoint of more preferably exerting the effects of the present application, the melting peak temperature of the hot melt adhesive resin layer 4 containing the copolymerized polybutylene terephthalate is preferably 170°C or higher, more preferably 190°C or higher, further preferably 200°C or higher, and is preferably 350°C or lower, more preferably 300°C or lower, further preferably 270°C or lower, more further preferably 230°C or lower, still further preferably 220°C or lower, yet further preferably 217°C or lower. As the preferable range, there can be mentioned around 170 to 350°C, around 170 to 300°C, around 170 to 270°C, around 170 to 230°C, around 170 to 220°C, around 170 to 217°C, around 190 to 350°C, around 190 to 300°C, around 190 to 270°C, around 190 to 230°C, around 190 to 220°C, around 190 to 217°C, around 200 to 350°C, around 200 to 300°C, around 200 to 270°C, around 200 to 230°C, around 200 to 220°C, around 200 to 217°C, and the like. The measurement method of the melting peak temperature is as described above.

[0099] In the present application, the copolymerized polybutylene terephthalate contained in the hot melt adhesive resin layer 4 preferably includes at least one selected from a polyether structure and a polyester structure B in addition to the polybutylene terephthalate structure. Among them, the polyester structure B has a structure different from that of the polybutylene terephthalate.

[0100] The polyether structure can be introduced into the resin by subjecting the polybasic acid (i.e., terephthalic acid) of the polybutylene terephthalate structure to a polycondensation reaction with a compound (monomer) having a polyether structure. The polyether structure preferably constitutes a soft segment of the resin in the hot melt adhesive resin layer 4. As the compound (monomer) subjected to the polycondensation reaction with the polybasic acid (i.e., terephthalic acid) of the polybutylene terephthalate structure to constitute such a soft segment, there can be mentioned dihydric alcohols such as polytetramethylene ether glycol and neopentyl glycol, which can exhibit stretchability. The polyether structure is preferably a polyether structure derived from at least one selected from polytetramethylene ether glycol and neopentyl glycol. Polytetramethylene ether glycol, neopentyl glycol, and the like form a structural unit in the polyether structure of the resin. By introducing the polyether structure as a soft segment into the resin, the rubber elasticity of the resin is enhanced, and the resin is less likely to be broken, thereby exerting a high sealing strength in a low-temperature environment.

[0101] Furthermore, the polyester structure B can be incorporated into the resin by using a compound (monomer) that forms a polyester structure through a polycondensation reaction with the butanediol used in the polybutylene terephthalate structure. The polyester structure B preferably constitutes the soft segment of the resin in the heat-adhesive resin layer 4. Examples of compounds (monomers) that form this soft segment through a polycondensation reaction with the butanediol used in the polybutylene terephthalate structure include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; and aliphatic dicarboxylic acids (preferably those with 4 to 20 carbon atoms) such as adipic acid, sebacic acid, dodecanedioic acid, and cyclohexane dicarboxylic acid. Aromatic and aliphatic dicarboxylic acids form structural units in the polyester structure B of the resin. The polyester structure B is particularly preferably a polyester structure formed by the polycondensation of a polyol and at least one dicarboxylic acid selected from isophthalic acid, sebacic acid, and dodecanedioic acid. By introducing the polyester structure B as a soft segment into the resin, the rubber elasticity of the resin is enhanced, making the resin less likely to break, thereby better exerting high sealing strength in a low-temperature environment.

[0102] To better demonstrate the effects of the present invention, the resin forming the heat-adhesive resin layer 4 preferably includes a polyether structure in addition to a polybutylene terephthalate structure. The polyether structure is particularly preferably a condensation-polymerized structure of terephthalic acid having a polybutylene terephthalate structure and at least one of polytetramethylene ether glycol and neopentyl glycol. Furthermore, the resin forming the heat-adhesive resin layer 4 preferably includes a polyester structure B in addition to a polybutylene terephthalate structure. The polyester structure B is a condensation-polymerized structure of 1,4-butanediol having a polybutylene terephthalate structure and at least one selected from isophthalic acid, dodecanedioic acid, and sebacic acid.

[0103] Furthermore, to better demonstrate the effects of the present invention, the copolymerized polybutylene terephthalate forming the thermally adhesive resin layer 4 preferably has a polybutylene terephthalate structure as its main component. The term "main component" means a proportion of 50% by mass or greater, preferably 60% by mass or greater, more preferably 70% by mass or greater, and even more preferably 80% by mass or greater, relative to 100% by mass of all components constituting the resin. Furthermore, the proportion of at least one of the polyether structure and the dicarboxylic acid structure in the resin forming the thermally adhesive resin layer 4 relative to 100% by mass of all components (total structural units) constituting the resin is preferably approximately 2 to 30% by mass, more preferably approximately 3 to 25% by mass, and even more preferably approximately 3 to 20% by mass.

[0104] The hot-melt resin layer 4 can be a layer containing at least one of homopolybutylene terephthalate and copolybutylene terephthalate, or can be a layer not containing homopolybutylene terephthalate and copolybutylene terephthalate. Resins other than polybutylene terephthalate are not particularly limited as long as they do not hinder the effects of the present application, and for example, polyethylene terephthalate, ETFE, and the like, which are thermoplastic resins having higher heat resistance than polypropylene, can be given.

[0105] In addition, the hot-melt resin layer 4 can contain a resin having a polyolefin skeleton as a main component, can contain a polyolefin as a main component, and further preferably contains homopolypropylene as a main component. The main component means that the content ratio of the resin component in the resin component contained in the hot-melt resin layer 4 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, more further preferably 90% by mass or more, still further preferably 95% by mass or more, yet further preferably 98% by mass or more, and yet more further preferably 99% by mass or more. For example, the hot-melt resin layer 4 containing polypropylene as a main component means that the content ratio of polypropylene in the resin component contained in the hot-melt resin layer 4 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, more further preferably 90% by mass or more, still further preferably 95% by mass or more, yet further preferably 98% by mass or more, and yet more further preferably 99% by mass or more.

[0106] As the polyolefin, specifically, polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and the like; ethylene / α-olefin copolymer; polypropylene such as homopolypropylene, polypropylene block copolymer (for example, block copolymer of propylene and ethylene), polypropylene random copolymer (for example, random copolymer of propylene and ethylene), and the like; propylene / α-olefin copolymer; and terpolymer of ethylene / butylene / propylene, and the like can be given. Among them, polypropylene is preferred. In the case of a copolymer, the polyolefin resin can be a block copolymer or a random copolymer. These polyolefin-based resins can be used singly or in combination of two or more.

[0107] In addition, the polyolefin can also be a cyclic polyolefin. The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and as the olefin of the structural monomer of the cyclic polyolefin, for example, ethylene, propylene, 4-methyl-l-pentene, styrene, butadiene, isoprene, and the like can be given. In addition, as the cyclic monomer of the structural monomer of the cyclic polyolefin, for example, cyclic olefins such as norbornene, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like can be given. Among them, cyclic olefins are preferred, and norbornene is more preferred.

[0108] In addition, the polyolefin can be an acid-modified polyolefin. The acid-modified polyolefin refers to a polymer modified by block polymerization or graft polymerization of a polyolefin with an acid component. As the polyolefin that can be acid-modified, the above-described polyolefin, or a copolymer of a polar molecule such as acrylic acid or methacrylic acid with the above-described polyolefin, or a crosslinked polyolefin, or the like can be used. In addition, as the acid component used for the acid modification, a carboxylic acid such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or the like, or an anhydride thereof can be exemplified.

[0109] The acid-modified polyolefin can be an acid-modified cyclic polyolefin. The acid-modified cyclic polyolefin refers to a polymer obtained by replacing a part of the monomer constituting the cyclic polyolefin with an acid component and copolymerizing, or block polymerizing or graft polymerizing the acid component with the cyclic polyolefin. The cyclic polyolefin that can be acid-modified is the same as described above. In addition, as the acid component used in the acid modification, the acid component used in the modification of the above-described polyolefin is the same.

[0110] As the preferred acid-modified polyolefin, a carboxylic acid or an anhydride thereof-modified polyolefin, a carboxylic acid or an anhydride thereof-modified polypropylene, a maleic anhydride-modified polyolefin, a maleic anhydride-modified polypropylene can be exemplified.

[0111] The hot melt adhesive resin layer 4 can be formed of only one resin, or can be formed of a blended polymer of two or more resins combined. Further, the hot melt adhesive resin layer 4 can be formed of only one layer, or can be formed of two or more layers of the same or different resins.

[0112] A lubricant or the like can be contained in the hot melt adhesive resin layer 4 as needed. In the case where the hot melt adhesive resin layer 4 contains a lubricant, the moldability of the power storage device outer packaging material can be improved. As the lubricant, there is no particular limitation, and a known lubricant can be used.

[0113] As the lubricant, an amide-based lubricant is preferred, but not particularly limited. As specific examples of the lubricant, the compounds exemplified in the base material layer 1 can be exemplified. The lubricant can be used alone, or two or more can be used in combination, and two or more are preferably used in combination.

[0114] In the present application, from the viewpoint of improving the moldability of the outer packaging material for electrical storage devices, it is preferable that a lubricant be present at least one of the surface and the interior of the heat-sealable resin layer 4. As the lubricant, an amide-based lubricant is preferable, but is not particularly limited. As specific examples of the amide-based lubricant, saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, hydroxymethyl amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides, and the like can be given. As specific examples of the saturated fatty acid amides, lauramide, palmitamide, stearamide, behenamide, hydroxystearamide, and the like can be given. As specific examples of the unsaturated fatty acid amides, oleamide, erucamide, and the like can be given. As specific examples of the substituted amides, N-oleyl palmitamide, N-stearyl stearamide, N-stearyl oleamide, N-oleyl stearamide, N-stearyl erucamide, and the like can be given. In addition, as specific examples of the hydroxymethyl amides, hydroxymethyl stearamide, and the like can be given. As specific examples of the saturated fatty acid bisamides, methylene bisstearamide, ethylene bisdecanoamide, ethylene bislauramide, ethylene bisstearamide, ethylene bis hydroxystearamide, ethylene bisbehenamide, hexamethylene bisstearamide, hexamethylene bisbehenamide, hexamethylene bis hydroxystearamide, N,N'-distearyladipamide, N,N'-distearyl sebacamide, and the like can be given. As specific examples of the unsaturated fatty acid bisamides, ethylene bisoleamide, ethylene biserucamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, N,N'-dioleyl sebacamide, and the like can be given. As specific examples of the fatty acid ester amides, stearamide stearyl stearate, and the like can be given. In addition, as specific examples of the aromatic bisamides, m-xylyl bisstearamide, m-xylyl bis hydroxystearamide, N,N'-distearyl isophthalamide, and the like can be given. The lubricant can be used alone as one kind, or two or more kinds in combination, and it is preferable to use two or more kinds in combination.

[0115] In the case where the lubricant is present on the surface of the heat-sealable resin layer 4, there is no particular limitation on the amount present, and from the viewpoint of improving the moldability of the outer packaging material for electrical storage devices, it is preferable that the amount present be about 1 mg / m 2 More preferably, about 3 mg / m 2 Further preferably, about 5 mg / m 2 Still more preferably, about 10 mg / m 2 Still further preferably, about 15 mg / m 2 Still further preferably, about 15 mg / m 2 More preferably, about 40 mg / m 2 More preferably, about 40 mg / m 2 More preferably, about 40 mg / m 2about 3 to 50 mg / m 2 about 3 to 40 mg / m 2 about 5 to 50 mg / m 2 about 5 to 40 mg / m 2 about 10 to 50 mg / m 2 about 10 to 40 mg / m 2 about 15 to 50 mg / m 2 about 15 to 40 mg / m 2 about 20 to 50 mg / m

[0116] In the case where a lubricant is present inside the hot-melt adhesive resin layer 4, there is no particular limitation on the amount present, and from the viewpoint of improving the moldability of the outer packaging material for electrical storage devices, it is preferably about 100 ppm or greater, more preferably about 300 ppm or greater, and further preferably about 500 ppm or greater, and it is preferably about 3000 ppm or less, more preferably about 2000 ppm or less, and as a preferable range, about 100 to 3000 ppm, about 100 to 2000 ppm, about 300 to 3000 ppm, about 300 to 2000 ppm, about 500 to 3000 ppm, and about 500 to 2000 ppm can be given. In the case where two or more kinds of lubricants are present inside the hot-melt adhesive resin layer 4, the above-mentioned amount of lubricant is the total amount of the lubricants. Also, in the case where two or more kinds of lubricants are present inside the hot-melt adhesive resin layer 4, there is no particular limitation on the amount of the first lubricant present, and from the viewpoint of improving the moldability of the outer packaging material for electrical storage devices, it is preferably about 100 ppm or greater, more preferably about 300 ppm or greater, and further preferably about 500 ppm or less, and it is preferably about 3000 ppm or less, more preferably about 2000 ppm or less, and as a preferable range, about 100 to 3000 ppm, about 100 to 2000 ppm, about 300 to 3000 ppm, about 300 to 2000 ppm, about 500 to 3000 ppm, and about 500 to 2000 ppm can be given. There is no particular limitation on the amount of the second lubricant present, and from the viewpoint of improving the moldability of the outer packaging material for electrical storage devices, it is preferably about 50 ppm or greater, more preferably about 100 ppm or greater, and further preferably about 200 ppm or greater, and it is preferably about 1500 ppm or less, more preferably about 1000 ppm or less, and as a preferable range, about 50 to 1500 ppm, about 50 to 1000 ppm, about 100 to 1500 ppm, about 100 to 1000 ppm, about 200 to 1500 ppm, and about 200 to 1000 ppm can be given.

[0117] The lubricant present on the surface of the thermally adhesive resin layer 4 may be a lubricant exudate from the resin constituting the thermally adhesive resin layer 4 or a lubricant applied to the surface of the thermally adhesive resin layer 4 .

[0118] The thickness of the heat-fusible resin layer 4 is not particularly limited, as long as the heat-fusible resin layers can be heat-fused together and function as a sealant for the electrical storage device. To achieve the best effects of the present invention, the thickness is preferably approximately 25 μm or greater, more preferably approximately 30 μm or greater, and even more preferably approximately 40 μm or greater. It is preferably approximately 100 μm or less, more preferably approximately 90 μm or less, and even more preferably approximately 80 μm or less. Preferred ranges include approximately 25 to 100 μm, approximately 25 to 90 μm, approximately 25 to 80 μm, approximately 30 to 100 μm, approximately 30 to 90 μm, approximately 30 to 80 μm, approximately 40 to 100 μm, approximately 40 to 90 μm, and approximately 40 to 80 μm.

[0119] (Method for Manufacturing Thermally Adhesive Resin Layer 4) The method for producing the heat-fusible resin layer 4 is not particularly limited, as long as the heat-fusible resin layer 4 of the present invention can be obtained. Known or conventional film-forming methods and lamination methods can be used. The film can be produced by known film-forming methods and / or lamination methods, such as extrusion or co-extrusion, cast molding, T-die method, cutting method, inflation method, etc. For example, a pre-prepared film constituting the heat-fusible resin layer 4 can be laminated with an adhesive layer, or a molten resin composition can be laminated onto a pre-prepared layer by extrusion or co-extrusion. Multiple layers can also be prepared simultaneously and laminated by melt-compression bonding, or one or more resins can be applied to other layers and dried to form a coating.

[0120] The heat-adhesive resin layer 4 can also be formed by extruding or co-extruding the layers comprising the heat-adhesive resin layer 4 and laminating them using an extrusion coating method, or by forming a film using an inflation method, casting method, or the like, followed by lamination with an adhesive layer. In the case of extrusion coating, lamination with an adhesive layer can also be performed as needed. Alternatively, a film for the water-absorbing layer (or sulfur-containing gas absorbing layer) previously formed can be laminated and bonded with an adhesive layer laminated using extrusion coating, dry lamination, solventless lamination, or the like. An aging treatment can then be performed as needed.

[0121] For example, in the case of laminating a film or the like by an extrusion coating method, first, a resin for forming a film is heated and melted, and (co)extruded in a curtain shape by stretching in a desired width direction using a T-shaped die, and the melted resin is caused to flow onto a surface to be laminated, and the laminating and adhesion of the layer to the surface to be laminated can be simultaneously performed by sandwiching the resin with a rubber roll and a cooled metal roll. The melt flow rate (MFR) of each resin component at the time of lamination by the extrusion coating method is preferably 0.2 to 50 g / 10 minutes, and more preferably 0.5 to 30 g / 10 minutes. When the MFR is less than or greater than the above range, the processability easily becomes poor. Note that, in the present specification, the MFR is a value measured according to the method of JIS K7210.

[0122] The melt flow rate (MFR) of each resin component at the time of lamination by the extrusion coating method is preferably 0.2 to 50 g / 10 minutes, and more preferably 0.5 to 30 g / 10 minutes. When the MFR is less than or greater than the above range, the processability easily becomes poor. Note that, in the present specification, the MFR is a value measured according to the method of JIS K7210.

[0123] In addition, in order to improve the adhesion, the surface of the hot-melt adhesive resin layer 4 can be subjected to a desired surface treatment as needed in advance. For example, a pre-treatment such as a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment using oxygen or nitrogen or the like, a glow discharge treatment, an oxidation treatment using a chemical agent or the like, a corona-treated layer, an ozone-treated layer, a plasma-treated layer, an oxidation-treated layer or the like can be formed and provided arbitrarily. Alternatively, various coating agent layers such as a primer coat agent layer, an under coat agent layer, an anchor coat agent layer, an adhesive agent layer, an evaporation anchor agent layer or the like can be formed arbitrarily on the surface to form a surface-treated layer. The above various coating agent layers can use, for example, a resin composition in which a resin having a main component such as a polyester-based resin, a polyamide-based resin, a polyurethane-based resin, an epoxy-based resin, a phenolic-based resin, a (meth)acrylic-based resin, a polyvinyl acetate-based resin, a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, a cellulose-based resin or the like is used as a medium.

[0124] The layer contained in the hot-melt adhesive resin layer 4 can also be uniaxially stretched or biaxially stretched by a tenter method, a tubular method or the like, using a conventional known method as needed.

[0125] [Adhesive layer 5] In the outer packaging material for power storage devices of the present application, the adhesive layer 5 is a layer provided between the barrier layer 3 (or the corrosion-resistant film) and the hot-melt adhesive resin layer 4 as needed in order to firmly adhere them.

[0126] The adhesive layer 5 is formed of a resin capable of adhering the barrier layer 3 to the heat-fusible resin layer 4. As the resin used for forming the adhesive layer 5, the same resin as the adhesives exemplified in the adhesive layer 2 can be used.

[0127] In addition, from the viewpoint of firmly adhering the adhesive layer 5 to the heat-fusible resin layer 4, as the resin used for forming the adhesive layer 5, it is preferable to contain a polyolefin skeleton, and the polyolefin exemplified in the above heat-fusible resin layer 4, acid-modified polyolefin, cyclic polyolefin, acid-modified cyclic polyolefin can be cited. On the other hand, from the viewpoint of firmly adhering the barrier layer 3 and the adhesive layer 5, the adhesive layer 5 preferably contains an acid-modified polyolefin. As the acid-modifying component, dicarboxylic acids such as maleic acid, itaconic acid, succinic acid, adipic acid or anhydrides thereof, acrylic acid, methacrylic acid, etc. can be cited. From the viewpoints of easiness of modification and versatility, maleic anhydride is most preferable. In addition, from the viewpoint of heat resistance of the exterior material for power storage devices, it is preferable that the polyolefin component be a polypropylene-based resin, and it is most preferable that the adhesive layer 5 contain maleic anhydride-modified polypropylene.

[0128] In the case where the resin used for forming the adhesive layer 5 contains a polyolefin skeleton, the adhesive layer 5 preferably contains a resin containing a polyolefin skeleton as a main component, more preferably contains an acid-modified polyolefin as a main component, and further preferably contains an acid-modified polypropylene as a main component. Here, the main component means a resin component contained in the adhesive layer 5 at a content rate of, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, more further preferably 90% by mass or more, still more further preferably 95% by mass or more, yet more further preferably 98% by mass or more, and yet more further preferably 99% by mass or more. For example, the fact that the adhesive layer 5 contains an acid-modified polypropylene as a main component means that the acid-modified polypropylene is contained in the resin component contained in the adhesive layer 5 at a content rate of, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, more further preferably 90% by mass or more, still more further preferably 95% by mass or more, yet more further preferably 98% by mass or more, and yet more further preferably 99% by mass or more.

[0129] 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. In addition, the fact that the resin constituting the adhesive layer 5 contains an acid-modified polyolefin can be confirmed, for example, when a maleic anhydride-modified polyolefin is measured by infrared spectroscopy, in the vicinity of a wave number of 1760 cm ﹣1 and a wave number of 1780 cm ﹣1A peak from maleic anhydride is detected in the vicinity. However, when the acid modification degree is low, the peak becomes small and can not be detected. In this case, analysis by nuclear magnetic resonance spectroscopy can be performed.

[0130] Further, from the viewpoint of heat resistance, content resistance, and the like of the outer packaging material for the power storage device, and the viewpoint of being able to make the thickness thin while ensuring moldability, the adhesive layer 5 is more preferably a cured product of a resin composition containing an acid-modified polyolefin and a curing agent. As the acid-modified polyolefin, the above-described exemplified substances are preferably selected.

[0131] Further, the adhesive layer 5 is preferably 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, and particularly preferably 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 and a compound having an epoxy group. In addition, the adhesive layer 5 preferably contains at least one selected from the group consisting of a polyurethane, a polyester, and an epoxy resin, and more preferably contains a polyurethane and an epoxy resin. As the polyester, for example, an ester resin generated by the reaction of an epoxy group with a maleic anhydride group, an amide ester resin generated by the reaction of an oxazoline group with a maleic anhydride group are preferable. Note that in the case where unreacted substances of the curing agent such as a compound having an isocyanate group, a compound having an oxazoline group, an epoxy resin, and the like remain in the adhesive layer 5, the presence of the unreacted substances can be confirmed by a method selected from, for example, infrared spectroscopy, Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like.

[0132] Further, from the viewpoint of further enhancing the adhesion of the barrier layer 3 to the adhesive layer 5, the adhesive layer 5 is preferably a cured product of a resin composition containing a curing agent having at least one selected from the group consisting of an oxygen atom, a heterocycle, a C=N bond, and a C-O-C bond. As the curing agent having a heterocycle, for example, a curing agent having an oxazoline group, a curing agent having an epoxy group, and the like can be given. In addition, as the curing agent having a C=N bond, a curing agent having an oxazoline group, a curing agent having an isocyanate group, and the like can be given. In addition, as the curing agent having a C-O-C bond, a curing agent having an oxazoline group, a curing agent having an epoxy group, and the like can be given. The fact that the adhesive layer 5 is a cured product of a resin composition containing these curing agents can be confirmed by a method such as 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.

[0133] As the compound having an isocyanate group, there is no particular limitation, but from the viewpoint of effectively improving the adhesion between the barrier layer 3 and the adhesive layer 5, a multifunctional isocyanate compound can be cited as preferable. The multifunctional isocyanate compound is not particularly limited, but is a compound having two or more isocyanate groups. As specific examples of the multifunctional isocyanate-based curing agent, pentamethylene diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymers or urethane bodies of these isocyanates, mixtures thereof, or copolymers with other polymers, and the like can be cited. In addition, adducts, biuret bodies, isocyanurate bodies, and the like can also be cited.

[0134] As the content of the compound having an isocyanate group in the adhesive layer 5, it is preferable to be in the range of 0.1 to 50% by mass in the resin composition constituting the adhesive layer 5, and more preferably in the range of 0.5 to 40% by mass. Thereby, the adhesion between the barrier layer 3 and the adhesive layer 5 can be effectively improved.

[0135] The compound having an oxazoline group is not particularly limited, but is a compound having an oxazoline skeleton. As specific examples of the compound having an oxazoline group, a compound having a polystyrene backbone, a compound having an acrylic acid backbone, and the like can be cited. In addition, as a commercial product, for example, the Epocros series manufactured by Nippon Shokubai Co., Ltd., and the like can be cited.

[0136] As the proportion of the compound having an oxazoline group in the adhesive layer 5, it is preferable to be in the range of 0.1 to 50% by mass in the resin composition constituting the adhesive layer 5, and more preferably in the range of 0.5 to 40% by mass. Thereby, the adhesion between the barrier layer 3 and the adhesive layer 5 can be effectively improved.

[0137] As the compound having an oxazoline group, there is no particular limitation, but from the viewpoint of effectively improving the adhesion between the barrier layer 3 and the adhesive layer 5, a multifunctional isocyanate compound can be cited as preferable. The multifunctional isocyanate compound is not particularly limited, but is a compound having two or more isocyanate groups. As specific examples of the multifunctional isocyanate-based curing agent, pentamethylene diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymers or urethane bodies of these isocyanates, mixtures thereof, or copolymers with other polymers, and the like can be cited. In addition, adducts, biuret bodies, isocyanurate bodies, and the like can also be cited.

[0138] As specific examples of the epoxy resin, glycidyl ether derivatives of trimethylolpropane, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, bisphenol F type diglycidyl ether, linear phenol aldehyde diglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and the like can be given. The epoxy resin can be used alone or in combination of two or more kinds.

[0139] The proportion of the epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, in the resin composition constituting the adhesive layer 5. This can effectively improve the adhesion of the barrier layer 3 to the adhesive layer 5.

[0140] As the polyurethane, there is no particular limitation, and known polyurethanes can be used. The adhesive layer 5 can be, for example, a cured product of a two-liquid curable polyurethane.

[0141] The proportion of the polyurethane in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, in the resin composition constituting the adhesive layer 5. This can effectively improve the adhesion of the barrier layer 3 to the adhesive layer 5 in the environment where components that easily induce corrosion of the barrier layer, such as electrolyte, are present.

[0142] Note that, in the case where the adhesive layer 5 is a cured product of 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 described above, the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the compound having an epoxy group each function as a curing agent.

[0143] The adhesive layer 5 can further contain a modifier having a carbodiimide group.

[0144] In the process of manufacturing the power storage device exterior material 10 of the present application by stacking the adhesive layer 5, the barrier layer 3, the heat-fusible resin layer 4, and the like, a resin film formed in advance can be used as the adhesive layer 5. Further, the heat-fusible resin forming the adhesive layer 5 can be formed into a film on the surface of the barrier layer 3 or the heat-fusible resin layer 4, or the like, by extrusion molding, coating, or the like, as the adhesive layer 5 formed of a resin film.

[0145] The thickness of the adhesive layer 5 is preferably about 50 μm or less, about 40 μm or less, about 30 μm or less, about 20 μm or less, about 5 μm or less, and the thickness of the adhesive layer 5 is preferably about 0.1 μm or more, about 0.5 μm or more. In addition, as the thickness range of the adhesive layer 5, 0.1 to 50 μm or so, 0.1 to 40 μm or so, 0.1 to 30 μm or so, 0.1 to 20 μm or so, 0.1 to 5 μm or so, 0.5 to 50 μm or so, 0.5 to 40 μm or so, 0.5 to 30 μm or so, 0.5 to 20 μm or so, 0.5 to 5 μm or so can be preferably cited. More specifically, in the case of the cured product of the adhesive or acid-modified polyolefin and curing agent cited in the adhesive layer 2, or the like, 1 to 10 μm or so is preferably cited, and more preferably 1 to 5 μm or so. Further, in the case of using the resin cited in the hot-melt adhesive resin layer 4, 2 to 50 μm or so is preferably cited, and more preferably 10 to 40 μm or so. Note that in the case where the adhesive layer 5 is a cured product of a resin composition containing the adhesive, acid-modified polyolefin, and curing agent cited in the adhesive layer 2, the adhesive layer 5 can be formed by, for example, applying the resin composition and curing by heating or the like. Further, in the case of using the resin cited in the hot-melt adhesive resin layer 4, the adhesive layer 5 can be formed by, for example, extrusion molding of the hot-melt adhesive resin layer 4 and the adhesive layer 5.

[0146] In the outer packaging material for power storage devices of the present application, at least one of the layers (the hot-melt adhesive resin layer 4, the adhesive layer 5, or the like provided as needed) inside the barrier layer 3 can contain at least one of a water absorbing agent and a sulfur-containing gas absorbing agent. In the present application, the layer containing the water absorbing agent is sometimes referred to as a "water absorbing layer". In addition, in the present application, the layer containing the sulfur-containing gas absorbing agent is sometimes referred to as a "sulfur-containing gas absorbing layer". In the case where the layer inside the barrier layer 3 contains the water absorbing agent and the sulfur-containing gas absorbing agent, the water absorbing agent and the sulfur-containing gas absorbing agent can be contained in the same layer or in different layers. In the case where the layer inside the barrier layer 3 is composed of two or more layers, it is preferable that the sulfur-containing gas absorbing agent be contained in the layer not containing the water absorbing agent, which constitutes the sulfur-containing gas absorbing layer.

[0147] The moisture to be absorbed as the water absorbing agent is moisture in a gaseous state and / or a liquid state. When the moisture to be absorbed is absorbed by, for example, a solid electrolyte-type lithium ion battery, various gases are generated. In addition, the sulfur-containing gas to be absorbed as the sulfur-containing gas absorbing agent can cite hydrogen sulfide, dimethyl sulfide, methyl mercaptan, SO x sulfur oxides represented by SOx (x = 1 to 3), or the like. The sulfur-containing gas is a component of the generated gas (in the case where, for example, the power storage device is an all-solid-state battery using a sulfide-based inorganic solid electrolyte, or a lithium secondary battery using lithium-sulfur at the positive electrode, or the like).

[0148] The water-absorbing agent contained in the water-absorbing layer is not particularly limited, as long as it is a substance dispersed in the resin and exhibits water-absorbing properties. For example, from the perspective of aging stability in the storage device, inorganic water-absorbing agents can be appropriately used. Preferred specific examples of inorganic water-absorbing agents include calcium oxide, anhydrous magnesium sulfate, magnesium oxide, calcium chloride, zeolite, aluminum oxide, silica gel, aluminum oxide gel, and calcined alum. Generally, among inorganic water-absorbing agents, inorganic chemical water-absorbing agents have better water-absorbing properties than inorganic physical water-absorbing agents, can be reduced in content, and easily achieve sufficient water absorption and thermal weldability in a single layer. Moreover, among inorganic chemical water-absorbing agents, calcium oxide, anhydrous magnesium sulfate, and magnesium oxide are particularly preferred because they have low water re-release, high aging stability under low humidity conditions within the package, and a dry-through effect. It should be noted that the dry-through effect refers to the effect of continuously absorbing water until the relative humidity reaches near 0%, while the humidity control effect refers to the effect of absorbing water when the humidity is high and releasing water when the humidity is low to maintain a constant humidity.

[0149] The content of the resin contained in the water-absorbing layer is, for example, 50 mass % or more, preferably 55 mass % or more, and more preferably 60 mass % or more.

[0150] The content of the water-absorbing agent contained in the water-absorbing layer is not particularly limited, as long as the effects of the present invention can be achieved. For example, the content is preferably about 0.5 parts by mass or more, more preferably about 2 parts by mass or more, and even more preferably about 3 parts by mass or more, and is preferably about 50 parts by mass or less, more preferably about 45 parts by mass or less, and even more preferably 40 parts by mass or less, relative to 100 parts by mass of the resin contained in the water-absorbing layer. Preferred ranges of this content include about 0.5 to 50 parts by mass, about 0.5 to 45 parts by mass, about 0.5 to 40 parts by mass, about 2 to 50 parts by mass, about 2 to 45 parts by mass, about 2 to 40 parts by mass, about 3 to 50 parts by mass, about 3 to 45 parts by mass, and about 3 to 40 parts by mass.

[0151] The sulfur-containing gas absorbent preferably contains a sulfur-containing gas physical absorbent and / or a sulfur-containing gas chemical absorbent. By using various sulfur-containing gas absorbents in combination, such as a sulfur-containing gas physical absorbent and a sulfur-containing gas chemical absorbent in combination, it is possible to easily absorb a variety of sulfur-containing gases. The sulfur-containing gas absorbent is used in the form of, for example, a powder. The maximum particle diameter of the sulfur-containing gas absorbent is preferably 20 μm or less, and the number average particle diameter of the powder is preferably 0.1 μm or more, 1.0 μm or more, or the like, and is preferably 15 μm or less, 10 μm or less, 8 μm or less, or the like, and as a preferable range, 0.1 to 15 μm or so, 0.1 to 10 μm or so, 0.1 to 8 μm or so, 1 to 15 μm or so, 1 to 10 μm or so, 1 to 8 μm or so can be given. When the number average particle diameter is less than the above range, the sulfur-containing gas absorbent is easily aggregated; when the number average particle diameter is greater than the above range, the uniformity of the sulfur-containing gas absorbing film can be poor, the surface area of the sulfur-containing gas absorbent is reduced, and the absorption of the sulfur-containing gas can be poor.

[0152] (Sulfur-containing gas physical absorbent) The sulfur-containing gas physical absorbent is a gas absorbent having a function of physically absorbing a sulfur-containing gas as an absorption object. The sulfur-containing gas physical absorbent preferably contains one or two or more selected from a hydrophobic zeolite having a molar ratio of SiO2 / Al2O3 of 1 / 1 to 2000 / 1, bentonite, and sepiolite.

[0153] The hydrophobic zeolite is a zeolite having excellent absorption performance for low-polarity molecules such as a sulfur-containing gas, and has a porous structure. In general, the higher the molar ratio of the constituent SiO2 / Al2O3 of the zeolite, the higher the hydrophobicity. Furthermore, by increasing the hydrophobicity, the absorption of low-polarity molecules such as a sulfur-containing gas becomes easier; conversely, the affinity for high-polarity molecules such as water becomes low, and it becomes difficult to absorb these molecules. The molar ratio of SiO2 / Al2O3 of the hydrophobic zeolite is preferably 30 / 1 to 10000 / 1, more preferably 35 / 1 to 9000 / 1, and further preferably 40 / 1 to 8500 / 1. In addition, the hydrophobic zeolite has high heat resistance, and can maintain the absorption effect even when exposed to a high-temperature environment of 230°C or higher. In the present application, based on the balance between the absorption capacity for a sulfur-containing gas and the easiness of availability, it is preferable to use a hydrophobic zeolite having a molar ratio within the above range.

[0154] Bentonite is an inorganic substance containing a large amount of layered phyllosilicate of aluminum as a main component of a clay mineral, montmorillonite, and containing minerals such as quartz, feldspar, and the like as impurities. Bentonite includes, for example, Na-type bentonite containing a large amount of Na ﹢ ions, Ca-type bentonite containing a large amount of Ca 2﹢ ions, and activated bentonite of artificial Na-type in which a certain weight% of sodium carbonate is added to Ca-type bentonite, and the like.

[0155] Sepiolite is a clay mineral with hydrous magnesium silicate as its main component. Its chemical composition is usually Mg8Si 12 O 30 (OH2)4(OH)4·6-8H2O represents a porous structure. From the perspective of availability, the pH value (3% suspension) is preferably 8.0-9.0, more preferably 8.9-9.3.

[0156] (Sulfur-containing gas chemical absorbent) A sulfur-containing gas chemical absorbent is a gas absorbent that chemically absorbs or decomposes the sulfur-containing gas being absorbed. Furthermore, because it is a chemical absorption or decomposition agent, it is not easily affected by water, etc. Once absorbed, the sulfur-containing gas molecules are not easily desorbed, enabling efficient absorption. Furthermore, the decomposition products are absorbed by the sulfur-containing gas physical absorbent or the sulfur-containing gas chemical absorbent. The sulfur-containing gas chemical absorbent preferably contains one or more selected from inorganic materials containing metal oxides, glass mixed with metals, and glass mixed with metal ions. The metal oxide in the inorganic material containing metal oxides preferably contains one or more selected from CuO, ZnO, and AgO. Furthermore, the supporting inorganic material is preferably an inorganic porous material such as zeolite. The metal species in the metal mixed glass and the metal ions in the metal ion mixed glass preferably contain one or more selected from Ca, Mg, Na, Cu, Zn, Ag, Pt, Au, Fe, Al, and Ni.

[0157] The content of the sulfur-containing gas absorbent contained in the sulfur-containing gas absorbing layer is not particularly limited. However, the content is preferably about 5 parts by mass or more, more preferably about 6 parts by mass or more, and even more preferably about 7 parts by mass or more, relative to 100 parts by mass of the resin contained in the sulfur-containing gas absorbing layer, so long as the sulfur-containing gas is absorbed. The content is preferably about 60 parts by mass or less, more preferably about 55 parts by mass or less, even more preferably about 50 parts by mass or less, or about 30 parts by mass or less. Preferred ranges of the content include about 5 to 60 parts by mass, about 5 to 55 parts by mass, about 5 to 50 parts by mass, about 5 to 30 parts by mass, about 6 to 60 parts by mass, about 6 to 55 parts by mass, about 6 to 50 parts by mass, about 6 to 30 parts by mass, about 7 to 60 parts by mass, about 7 to 55 parts by mass, about 7 to 50 parts by mass, and about 7 to 30 parts by mass.

[0158] [Surface coating layer 6] The outer packaging material for electrical storage devices of the present application can have a surface covering layer 6 on the substrate layer 1 (on the side of the substrate layer 1 opposite the barrier layer 3) as needed for the purpose of improving at least one of the design, electrolyte resistance, scratch resistance, moldability, and the like. The surface covering layer 6 is a layer that is on the outermost side of the outer packaging material for electrical storage devices after the outer packaging material for electrical storage devices is assembled into an electrical storage device.

[0159] The surface covering layer 6 can be exemplified by resins such as polyvinylidene chloride, polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicone resin, phenol resin, and the like, and modifications of these resins. In addition, it can also be a copolymer of these resins, and can also be a modification of the copolymer. Furthermore, it can also be a mixture of these resins. The resin is preferably a curable resin. That is, the surface covering layer 6 is preferably composed of a cured product of a resin composition containing a curable resin.

[0160] In the case where the resin that forms the surface covering layer 6 is a curable resin, the resin can be either one of a one-liquid curable type and a two-liquid curable type, and is preferably a two-liquid curable type. As a two-liquid curable type resin, there can be exemplified, for example, a two-liquid curable type polyurethane, a two-liquid curable type polyester, a two-liquid curable type epoxy resin, and the like. Of these, a two-liquid curable type polyurethane is preferred.

[0161] As the two-liquid curing type polyurethane, for example, a polyurethane including a first agent containing a polyol compound and a second agent containing an isocyanate compound can be given. A two-liquid curing type polyurethane in which a polyol such as a polyester polyol, a polyether polyol, and an acrylic polyol is used as the first agent and a polyisocyanate of an aromatic or aliphatic series is used as the second agent is preferable. In addition, as the polyurethane, for example, a polyurethane including a polyurethane compound obtained by previously reacting a polyol compound with an isocyanate compound and an isocyanate compound can be given. As the polyurethane, for example, a polyurethane including a polyurethane compound obtained by previously reacting a polyol compound with an isocyanate compound and a polyol compound can be given. As the polyurethane, for example, a polyurethane compound obtained by previously reacting a polyol compound with an isocyanate compound, and a polyurethane cured by reacting the polyurethane compound with moisture in the air or the like can be given. As the polyol compound, a polyester polyol having a hydroxyl group in a side chain in addition to a hydroxyl group at a terminal of a repeating unit is preferable. As the second agent, an isocyanate compound of an aliphatic, alicyclic, aromatic, or aromatic-aliphatic series can be given. As the isocyanate compound, for example, hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), or the like can be given. In addition, a polyfunctional isocyanate-modified product or the like derived from one or two or more of these diisocyanates can be given. Furthermore, as the polyisocyanate compound, a multimer (for example, a trimer) can be used. Such a multimer can be given as an adduct, a biuret, a urethane, or the like. Note that the aliphatic isocyanate compound refers to an isocyanate having an aliphatic group but no aromatic ring, the alicyclic isocyanate compound refers to an isocyanate having an alicyclic hydrocarbon group, and the aromatic isocyanate compound refers to an isocyanate having an aromatic ring. By forming the surface cover layer 6 of the polyurethane, the outer packaging material for the power storage device can have excellent electrolyte resistance.

[0162] In the surface cover layer 6, at least one of the surface and the inside of the surface cover layer 6 can contain an additive such as a lubricant, a flame retardant, an antiblocking agent, an antioxidant, a light stabilizer, an adhesion-improving agent, an antistatic agent, a pigment, or the like, as necessary, in accordance with the functionality or the like that the surface cover layer 6 or the surface thereof should have. As the additive, for example, a fine particle having an average particle diameter of about 0.5 nm to 5 μm can be given. The average particle diameter of the additive is a median particle diameter measured by a laser diffraction / scattering type particle size distribution measuring device.

[0163] The additive can be either of inorganic and organic substances. In addition, examples of the shape of the additive include, but are not particularly limited to, a spherical shape, a fibrous shape, a plate shape, an irregular shape, a scale shape, and the like.

[0164] Specific examples of the additive include talc, silica, graphite, kaolin, montmorillonite, mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, 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 nanotube, high-melting-point nylon, acrylate resin, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel, and the like. The additive can be used singly or in combination of two or more. Of these additives, from the viewpoints of dispersion stability, cost, and the like, silica, barium sulfate, and titanium oxide can be preferably exemplified. In addition, various surface treatments such as insulation treatment and high dispersibility treatment can be applied to the surface of the additive.

[0165] As the method of forming the surface cover layer 6, a method of coating the surface cover layer 6-forming resin can be exemplified, but is not particularly limited. In the case where the additive is incorporated in the surface cover layer 6, it is only necessary to coat the resin mixed with the additive.

[0166] In the present application, at least one of the surface and the inside of the surface covering layer 6 preferably has a lubricant from the viewpoint of improving the moldability of the outer packaging material for power storage devices. As the lubricant, an amide-based lubricant can be given as an example, but is not particularly limited thereto. As specific examples of the amide-based lubricant, saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, hydroxymethyl amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides, and the like can be given. As specific examples of the saturated fatty acid amides, lauramide, palmitamide, stearamide, behenamide, hydroxystearamide, and the like can be given. As specific examples of the unsaturated fatty acid amides, oleamide, erucamide, and the like can be given. As specific examples of the substituted amides, N-oleyl palmitamide, N-stearyl stearamide, N-stearyl oleamide, N-oleyl stearamide, N-stearyl erucamide, and the like can be given. In addition, as specific examples of the hydroxymethyl amides, hydroxymethyl stearamide, and the like can be given. As specific examples of the saturated fatty acid bisamides, methylene bisstearamide, ethylene bisdecanoamide, ethylene bislauramide, ethylene bisstearamide, ethylene bis hydroxystearamide, ethylene bisbehenamide, hexamethylene bisstearamide, hexamethylene bisbehenamide, hexamethylene bis hydroxystearamide, N,N'-distearyladipamide, N,N'-distearyl sebacamide, and the like can be given. As specific examples of the unsaturated fatty acid bisamides, ethylene bisoleamide, ethylene biserucamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, N,N'-dioleyl sebacamide, and the like can be given. As specific examples of the fatty acid ester amides, stearamide stearyl stearate, and the like can be given. In addition, as specific examples of the aromatic bisamides, m-xylyl bisstearamide, m-xylyl bis hydroxystearamide, N,N'-distearyl isophthalamide, and the like can be given. The lubricant can be used alone or in combination with two or more kinds, and preferably two or more kinds are combined.

[0167] In the case where the lubricant is present on the surface of the surface covering layer 6, the amount of the lubricant present can be given as an example, but is not particularly limited to, for example, about 3 mg / m 2 or less, about 4 mg / m 2 or less, about 5 mg / m 2 or less. Furthermore, the amount of the lubricant present on the surface of the surface covering layer 6 can be given as an example, for example, about 15 mg / m 2 or less, preferably about 14 mg / m 2 or less, about 10 mg / m 2 or less. In addition, the preferable range of the amount of the lubricant present on the surface of the surface covering layer 6 can be given as an example, for example, 3 to 15 mg / m 2 or less, 3 to 14 mg / m 2 or less, 3 to 10 mg / m 2Left and right, 4 to 15 mg / m 2 Left and right, 4 to 14 mg / m 2 Left and right, 4 to 10 mg / m 2 Left and right, 5 to 15 mg / m 2 Left and right, 5 to 14 mg / m 2 Left and right, 5 to 10 mg / m 2 Left and right.

[0168] The lubricant present on the surface of the surface cover layer 6 can be exudate after exudation of a lubricant contained in the resin constituting the surface cover layer 6, or can be an application after application of a lubricant on the surface of the surface cover layer 6.

[0169] By causing the surface cover layer 6 to contain a colorant, the exterior material for electrical storage devices can be colored. As the colorant, known materials such as pigments, dyes, and the like can be used. In addition, the colorant can be used by only one kind, or two or more kinds can be mixed and used.

[0170] The kind of the pigment is not particularly limited, and as the organic pigment, pigments such as azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo sulfur indigo-based, pyrenone-perylene-based, iso- pseudoindole-based, benzimidazolone-based, and the like can be given, and as the inorganic pigment, pigments such as carbon black-based, titanium oxide-based, cadmium-based, lead-based, chromium oxide-based, iron-based, and the like can be given, and in addition thereto, fine powder of mica, fish scale foil, and the like can be given.

[0171] In the colorant, for example, in order to make the appearance of the exterior material for electrical storage devices black, carbon black is also preferable. In addition, from the viewpoint of releasing heat generated by the electrical storage device, mica is preferably used.

[0172] As the average particle diameter of the pigment, for example, 0.03 to 5 μm or so, preferably 0.05 to 2 μm or so can be given, but is not particularly limited thereto. Note that the average particle diameter of the pigment is the median particle diameter measured by a laser diffraction / scattering type particle diameter distribution measuring device.

[0173] As the content of the colorant in the surface cover layer 6, there is no particular limitation as long as the exterior material for electrical storage devices can be colored, and for example, 5 to 60 mass% or so, preferably 10 to 40 mass% or so can be given.

[0174] As the thickness of the surface cover layer 6, there is no particular limitation as long as the above-described functions as the surface cover layer 6 can be exerted, and for example, 0.5 to 10 μm or so, preferably 1 to 5 μm or so can be given.

[0175] 3. Method for manufacturing an exterior material for electrical storage devices The method for producing the exterior material for electrical storage devices is not particularly limited as long as a laminated body in which the layers of the exterior material for electrical storage devices of the present application are laminated can be obtained, and a method including a lamination step in which at least the base material layer 1, the barrier layer 3, and the hot-melt adhesive layer 4 are sequentially laminated can be cited.

[0176] One example of the method for producing the exterior material for electrical storage devices of the present application is described below. First, a laminated body in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are sequentially laminated (hereinafter also referred to as "laminated body A") is formed. The formation of the laminated body A can be specifically performed by a dry lamination method in which, on the base material layer 1 or the barrier layer 3 on which a chemical surface treatment has been performed on the surface as necessary, an adhesive used in the formation of the adhesive layer 2 is applied by a coating method such as a gravure coating method, a roll coating method, and the like, and dried, and then the barrier layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured.

[0177] Next, the hot-melt adhesive layer 4 is laminated on the barrier layer 3 of the laminated body A. In the case where the hot-melt adhesive layer 4 is directly laminated on the barrier layer 3, the hot-melt adhesive layer 4 can be laminated on the barrier layer 3 of the laminated body A by a hot lamination method, an extrusion lamination method, or the like. In the case where the adhesive layer 5 is provided between the barrier layer 3 and the hot-melt adhesive layer 4, the adhesive layer 5 and the hot-melt adhesive layer 4 can be laminated by, for example, (1) an extrusion lamination method, (2) a hot lamination method, (3) a sandwich lamination method, (4) a dry lamination method, or the like. As the (1) extrusion lamination method, a method in which the adhesive layer 5 and the hot-melt adhesive layer 4 are extruded on the barrier layer 3 of the laminated body A to be laminated (co-extrusion lamination method, series lamination method), or the like can be cited. In addition, as the (2) hot lamination method, a method in which a laminated body in which the adhesive layer 5 and the hot-melt adhesive layer 4 are laminated is separately formed, and the laminated body is laminated on the barrier layer 3 of the laminated body A, or a method in which a laminated body in which the adhesive layer 5 is laminated on the barrier layer 3 of the laminated body A is formed, and the laminated body is laminated with the hot-melt adhesive layer 4, or the like can be cited. In addition, as the (3) sandwich lamination method, a method in which the laminated body A and the hot-melt adhesive layer 4 are adhered with the adhesive layer 5 while the adhesive layer 5 is injected in a molten state between the barrier layer 3 of the laminated body A and the hot-melt adhesive layer 4 that is formed in advance as a sheet-shaped film, or the like can be cited. In addition, as the (4) dry lamination method, a method in which an adhesive solution for forming the adhesive layer 5 is applied on the barrier layer 3 of the laminated body A and dried, and a method in which baking is further performed to achieve lamination, a method in which a hot-melt adhesive layer 4 that is formed in advance as a sheet-shaped film is laminated on the adhesive layer 5, or the like can be cited.

[0178] In the case of providing the surface cover layer 6, the surface cover layer 6 is laminated on the surface of the base material layer 1 on the opposite side to the barrier layer 3. The surface cover layer 6 can be formed by, for example, applying the above-mentioned resin forming the surface cover layer 6 to the surface of the base material layer 1. Note that the order of the process of laminating the barrier layer 3 on the surface of the base material layer 1 and the process of laminating the surface cover layer 6 on the surface of the base material layer 1 is not particularly limited. For example, the barrier layer 3 can be formed on the surface of the base material layer 1 on the opposite side to the surface cover layer 6 after the surface cover layer 6 is formed on the surface of the base material layer 1.

[0179] As described above, the laminate having the surface cover layer 6 / base material layer 1 / adhesive layer 2 / barrier layer 3 / adhesive layer 5 / heat-fusible resin layer 4 provided as needed in this order can be formed, but in order to reinforce the adhesion of the adhesive layer 2 and the adhesive layer 5 provided as needed, further heat treatment can be performed.

[0180] In the case of the outer packaging material for power storage devices, surface activation treatment such as corona treatment, sandblasting treatment, oxidation treatment, ozone treatment, and the like can be performed on each layer constituting the laminate as needed to improve workability. For example, the surface of the base material layer 1 on the opposite side to the barrier layer 3 can be subjected to corona treatment to improve the workability of the surface of the base material layer 1 to ink printing.

[0181] 4. Use of the outer packaging material for power storage devices The outer packaging material for power storage devices of the present application is used in a packaging body for sealing and housing power storage device elements such as a positive electrode, a negative electrode, and an electrolyte. That is, a power storage device can be produced by housing power storage device elements having at least a positive electrode, a negative electrode, and an electrolyte in a packaging body formed of the outer packaging material for power storage devices of the present application. In other words, a power storage device can be formed by packaging power storage device elements with the outer packaging material for power storage devices of the present application.

[0182] Specifically, the outer packaging material for an electrical storage device of the present invention is used to wrap an electrical storage device element having at least the positive electrode, negative electrode and electrolyte in a manner that allows a flange portion (an area where the heat-fusible resin layers are in contact with each other) to be formed on the periphery of the electrical storage device element, with the metal terminals respectively connected to the positive electrode and the negative electrode protruding to the outside. The heat-fusible resin layers of the flange portion are heat-sealed to each other to achieve sealing, thereby providing an electrical storage device using the outer packaging material for an electrical storage device. It should be noted that when the electrical storage device element is accommodated in a packaging body formed by the outer packaging material for an electrical storage device of the present invention, the packaging body is formed in a manner that the heat-fusible resin portion of the outer packaging material for an electrical storage device of the present invention becomes the inner side (the surface in contact with the electrical storage device element). The heat-fusible resin layers of two outer packaging materials for an electrical storage device may be placed opposite to each other and stacked, and the peripheral portions of the stacked outer packaging materials for an electrical storage device may be heat-fused to form a packaging body, or as Figure 5 As shown in the example, a storage device is folded and overlapped with an outer packaging material, and the peripheral edge is heat-welded to form a package. Figure 5 As in the example shown, the sides other than the folded side are heat-fused to form a three-sided package. Alternatively, the package can be folded so as to form a flange portion and sealed on all four sides. It should be noted that when the innermost and outermost layers of the outer packaging material for a storage battery device are heat-fusible resin layers, the package can also be formed by heat-fusion bonding the innermost heat-fusible resin layer to the outermost heat-fusible resin layer.

[0183] In addition to the outer packaging material for the electrical storage device, the electrical storage device element may also be encapsulated by a cover. That is, the outer packaging material for the electrical storage device and the cover constitute an outer packaging body (electricity storage device outer packaging body) that seals the electrical storage device element. For example, the electrical storage device element may be housed within a cylindrical outer packaging material for the electrical storage device, with the opening sealed by the cover. In another example, the electrical storage device element, in contact with the cover, may be housed within a cylindrical outer packaging material for the electrical storage device with an opening formed therein, with the opening sealed by the cover. Preferably, the cover and the electrical storage device outer packaging material are joined in any manner. To increase the volumetric energy density of the electrical storage device and reduce the dead space between the electrical storage device element and the outer packaging material for the electrical storage device, it is preferred that the outer packaging material for the electrical storage device be wrapped around the electrical storage device element and the cover.

[0184] The cover can be formed, for example, from a resin molded part, a metal molded part, an outer packaging material for a storage device, or a combination thereof. In the present invention, when the cover is a resin molded part, it does not include a cover composed solely of a film as defined in JIS K6900-1994 [Plastic Terminology]. When the cover is a metal molded part, the metal terminals may be omitted because the cover also functions as a metal terminal. The cover can be constructed from a resin material and a conductive material.

[0185] The outer packaging material for storage devices of the present invention can be applied to storage devices such as batteries (including capacitors, capacitors, etc.). In addition, the outer packaging material for storage devices of the present invention can also be used in any type of primary batteries or secondary batteries, and is preferably used in secondary batteries. There is no particular limitation on the type of secondary battery to which the outer packaging material for storage devices of the present invention is applied, and examples thereof include lithium-ion batteries, lithium-ion polymer batteries, all-solid-state batteries, semi-solid-state batteries, quasi-solid-state batteries, polymer batteries, all-resin batteries, lead-acid batteries, nickel-hydrogen batteries, nickel-cadmium batteries, nickel-iron batteries, nickel-zinc batteries, silver oxide-zinc batteries, metal-air batteries, multivalent cation batteries, capacitors, capacitors, etc. Among these secondary batteries, lithium-ion batteries, lithium-ion polymer batteries, and all-solid-state batteries are preferred as the outer packaging material for storage devices of the present invention.

[0186] Example Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples.

[0187] <Manufacturing of Outer Packaging Materials for Electricity Storage Devices> (Example 1) A polyethylene terephthalate film (25μm thick) with the laminating surface corona-treated was prepared as the base layer. An aluminum alloy foil (JIS H4160: 1994 A8021H-O, 60μm thick) was also prepared as the barrier layer. Furthermore, a homopolymer polybutylene terephthalate film (homopolymer PBT: (structural units are terephthalic acid and 1,4-butanediol)) was used as the heat-fusible resin layer (40μm thick). The base layer and barrier layer were then bonded together using a two-component curing polyurethane adhesive (polyester polyol and alicyclic isocyanate compound) via dry lamination, creating a laminate consisting of base layer, adhesive layer, and barrier layer in this order.

[0188] Then, a film was bonded on the barrier layer side of the obtained laminate by dry lamination using a two-liquid curing type polyurethane adhesive (polyester polyol and alicyclic isocyanate compound), thereby laminating an adhesive layer (4 μm) / hot-melt adhesive layer on the barrier layer. Next, by subjecting the obtained laminate to aging treatment and heating, an exterior material for power storage devices formed of a laminate in which a substrate layer / adhesive layer / barrier layer / adhesive layer / hot-melt adhesive layer were sequentially laminated was obtained.

[0189] (Example 2) The same as in Example 1 was carried out except that an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) was used as the barrier layer and a copolymerized polybutylene terephthalate film described below was used as the hot-melt adhesive layer (thickness 40 μm), thereby obtaining an exterior material for power storage devices formed of a laminate in which a substrate layer / adhesive layer / barrier layer / adhesive layer / hot-melt adhesive layer were sequentially laminated.

[0190] The hot-melt adhesive layer in Example 2 was formed of a copolymerized polybutylene terephthalate film (copolymerized PBT). The copolymerized polybutylene terephthalate film is a product in which terephthalic acid and 1,4-butanediol that form a polybutylene terephthalate structure are two structural units, and further, a polyester structure B that is an auxiliary component with respect to the polybutylene terephthalate structure is block-polymerized with the polybutylene terephthalate structure. The polyester structure B is a structure that is introduced into the resin by copolymerization with the above-described 1,4-butanediol with dodecanedioic acid (dodecanedioic acid) as a third structural unit. Therefore, the resin that forms the film contains the polybutylene terephthalate structure (terephthalic acid and 1,4-butanediol as monomer units are two structural units) and the polyester structure B (dodecanedioic acid as a monomer unit is one structural unit), and has a structure in which three kinds of structural units are copolymerized in total. In the copolymerized polybutylene terephthalate film of the hot-melt adhesive layer, the content of the polyester structure B is 10 mass% (the ratio of the mole ratio of terephthalic acid, 1,4-butanediol, and dodecanedioic acid (terephthalic acid residue: 1,4-butanediol residue: dodecanedioic acid residue) is 100:112:13 as monomer units).

[0191] (Example 3) A laminated film of a polyethylene terephthalate film (thickness 12 μm) and a nylon film (thickness 12 μm) bonded by a two-liquid curing type polyurethane adhesive (polyester polyol and aromatic isocyanate compound, thickness after curing 3 μm) was prepared as a base material layer. An aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 80 μm) was prepared as a barrier layer. Then, the nylon film side of the base material layer was bonded to the barrier layer by dry lamination using a two-liquid curing type polyurethane adhesive (polyester polyol and aromatic isocyanate compound) to produce a laminate in which the base material layer / adhesive layer / barrier layer were sequentially laminated.

[0192] Then, a maleic anhydride-modified polypropylene as a bonding layer and a polypropylene as a heat-fusible resin layer were co-extrusion molded to laminate the bonding layer (40 μm) / heat-fusible resin layer (40 μm) on the barrier layer. Next, by subjecting the obtained laminate to aging treatment and heating, an exterior material for power storage devices formed of a laminate in which the base material layer / adhesive layer / barrier layer / bonding layer / heat-fusible resin layer were sequentially laminated was obtained.

[0193] (Example 4) Except that an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 60 μm) was used as the barrier layer, the same procedure as in Example 2 was carried out to produce an exterior material for power storage devices formed of a laminate in which the base material layer / adhesive layer / barrier layer / bonding layer / heat-fusible resin layer were sequentially laminated.

[0194] (Example 5) Except that a polyethylene terephthalate film (thickness 38 μm) whose adherend side was subjected to a corona treatment was used as the base material layer, the same procedure as in Example 1 was carried out to produce an exterior material for power storage devices formed of a laminate in which the base material layer / adhesive layer / barrier layer / bonding layer / heat-fusible resin layer were sequentially laminated.

[0195] (Example 6) As the base material layer, a polyethylene terephthalate film (thickness 25 μm) whose adherend side was subjected to a corona treatment was prepared. In addition, an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 60 μm) was prepared as the barrier layer. Furthermore, as the heat-fusible resin layer (thickness 50 μm), an ethylene-tetrafluoroethylene copolymer (ETFE) was subjected to nitrogen plasma treatment, and a two-liquid curing type polyurethane adhesive (polyester polyol and aromatic isocyanate compound) was used to bond the inside to the base material layer and the barrier layer by dry lamination to produce a laminate in which the base material layer / adhesive layer / barrier layer were sequentially laminated.

[0196] Then, a film was adhered to the barrier layer side of the obtained laminate by dry lamination using a two-liquid curing type polyurethane adhesive (polyester polyol and alicyclic isocyanate compound), thereby laminating an adhesive layer (4 μm) / hot-melt adhesive layer on the barrier layer. Next, by subjecting the obtained laminate to aging treatment and heating, an exterior material for power storage devices formed of a laminate in which a substrate layer / adhesive layer / barrier layer / adhesive layer / hot-melt adhesive layer were sequentially laminated was obtained.

[0197] (Example 7) The same as in Example 2 was carried out except that a product in which the adhering surface side of a polyethylene terephthalate film (thickness 6 μm) was subjected to a corona treatment was used as the substrate layer and an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 60 μm) was used as the barrier layer, and an exterior material for power storage devices formed of a laminate in which a substrate layer / adhesive layer / barrier layer / adhesive layer / hot-melt adhesive layer were sequentially laminated was obtained.

[0198] (Example 8) The same as in Example 2 was carried out except that a product in which the adhering surface side of a polyethylene terephthalate film (thickness 12 μm) was subjected to a corona treatment was used as the substrate layer and an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 60 μm) was used as the barrier layer, and an exterior material for power storage devices formed of a laminate in which a substrate layer / adhesive layer / barrier layer / adhesive layer / hot-melt adhesive layer were sequentially laminated was obtained.

[0199] (Example 9) As the substrate layer, a product in which the adhering surface side of a polyethylene terephthalate film (thickness 6 μm) was subjected to a corona treatment was prepared. In addition, as the barrier layer, an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 80 μm) was prepared. Then, the nylon film side of the substrate layer was adhered to the barrier layer by dry lamination using a two-liquid curing type polyurethane adhesive (polyester polyol and aromatic isocyanate compound), and a laminate in which a substrate layer / adhesive layer / barrier layer were sequentially laminated was prepared.

[0200] Then, a maleic anhydride-modified polypropylene as the adhesive layer and a polypropylene as the hot-melt adhesive layer were co-extruded, thereby laminating an adhesive layer (40 μm) / hot-melt adhesive layer (40 μm) on the barrier layer. Next, by subjecting the obtained laminate to aging treatment and heating, an exterior material for power storage devices formed of a laminate in which a substrate layer / adhesive layer / barrier layer / adhesive layer / hot-melt adhesive layer were sequentially laminated was obtained.

[0201] (Example 10) The same procedure as in Example 9 was conducted except that a product in which the adhering surface side of a polyethylene terephthalate film (thickness 12 μm) as a base material layer was subjected to a corona treatment was used, to obtain an exterior material for power storage devices formed of a laminate in which a base material layer / adhesive layer / barrier layer / adhesive layer / heat-fusible resin layer were sequentially layered.

[0202] (Comparative Example 1) The same procedure as in Example 5 was conducted except that a product in which the adhering surface side of a polyethylene terephthalate film (thickness 25 μm) as a base material layer was subjected to a corona treatment and an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) as a barrier layer was used, to obtain an exterior material for power storage devices formed of a laminate in which a base material layer / adhesive layer / barrier layer / adhesive layer / heat-fusible resin layer were sequentially layered.

[0203] (Comparative Example 2) As a base material layer, a laminated film in which a polyethylene terephthalate film (thickness 12 μm) and a nylon film (thickness 12 μm) were adhered by a two-liquid curing type polyurethane adhesive (polyester polyol and aromatic isocyanate compound, thickness after curing 3 μm) was prepared. An aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 40 μm) was prepared as a barrier layer. Then, the nylon film side of the base material layer was adhered to the barrier layer by a dry lamination method using a two-liquid curing type polyurethane adhesive (polyester polyol and aromatic isocyanate compound), to produce a laminate in which a base material layer / adhesive layer / barrier layer were sequentially layered.

[0204] Then, maleic anhydride-modified polypropylene as an adhesive layer and polypropylene as a heat-fusible resin layer were co-extruded, to layer an adhesive layer (40 μm) / heat-fusible resin layer (40 μm) on the barrier layer. Subsequently, by subjecting the obtained laminate to aging treatment and heating, an exterior material for power storage devices formed of a laminate in which a base material layer / adhesive layer / barrier layer / adhesive layer / heat-fusible resin layer were sequentially layered was obtained.

[0205] (Comparative Example 3) As the base material layer, a laminated film in which a polyethylene terephthalate film (thickness 12 μm) and a nylon film (thickness 12 μm) were bonded by a two-liquid curing type polyurethane adhesive (polyester polyol and aromatic isocyanate compound, thickness after curing 3 μm) was prepared. An aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 60 μm) was prepared as the barrier layer. Then, the base material layer and the barrier layer were bonded by a two-liquid curing type polyurethane adhesive (polyester polyol and alicyclic isocyanate compound) by dry lamination to produce a laminate in which the base material layer / adhesive layer / barrier layer were sequentially laminated.

[0206] Then, the maleic anhydride-modified polypropylene as the adhesive layer and the polypropylene as the heat-fusible resin layer were co-extruded to laminate the adhesive layer (15 μm) / heat-fusible resin layer (20 μm) on the barrier layer. Subsequently, by subjecting the obtained laminate to aging treatment and heating, an exterior material for power storage devices formed of a laminate in which the base material layer / adhesive layer / barrier layer / adhesive layer / heat-fusible resin layer were sequentially laminated was obtained.

[0207] <Stretching test in 120°C environment> The exterior material for power storage devices was subjected to a stretching test in a 120°C environment, and the strength (N) at the time of elongation by 20% in the MD direction was measured. The measurement was performed using a stretching tester in accordance with the method prescribed in JIS K7127: 1999. The measurement conditions were: sample width 15 mm, sample length 100 mm, gauge length 30 mm, stretching speed 0.5 mm / minute, test environment 120°C, and the average of three measurements was taken. The measurement was performed in a thermostat, starting from room temperature (25°C), reaching 120°C in two minutes, and then, after two minutes, the measurement was performed. The results are shown in Table 1.

[0208] The thickness reduction ratio of the heat-fusible resin layer 4 at the time of elongation by 20% in the MD direction in the above-mentioned <stretching test in 120°C environment> was 0% for the exterior material for power storage devices of Examples 1 to 10. That is, the residual rate of the thickness of the heat-fusible resin layer at the time of elongation by 20% in the MD direction in the above-mentioned stretching test in a 120°C environment for the exterior material for power storage devices of Examples 1 to 10 (i.e., the ratio (%) of the thickness of the heat-fusible resin layer after the stretching test to the thickness of the heat-fusible resin layer before the stretching test, which was taken as 100%) was 100%. The thickness was 100% for Comparative Example 1, and in comparison thereto, the thickness was 72% for Comparative Example 2, and the thickness was 86% for Comparative Example 3.

[0209] <Stretching test in 120°C environment> The penetration strength of the laminate constituting the outer packaging material for electrical storage devices was measured by the method prescribed in JIS Z1707: 1997 using ZP-50N (dynamometer) and MX2-500N (measuring stand) manufactured by IMADA Co., Ltd. from the side of the heat-fusible resin layer. Each outer packaging material for electrical storage devices was cut into a rectangle of 10 mm x 300 mm as a test sample. Specifically, in a measuring environment of 23 ± 2°C, relative humidity 50 ± 5%, the test piece was fixed with a stage of 115 mm in diameter having an opening of 15 mm in diameter and a pressing plate, and a needle of 1.0 mm in diameter, a needle tip shape of a semicircle of 0.5 mm in radius was penetrated at a speed of 10 ± 5 mm per minute, and the maximum stress until the needle penetrated through was measured. The number of test pieces was 5, and the average was taken. Note that when the number of test pieces was insufficient and 5 samples could not be measured, the number that could be measured was measured, and the average was taken.

[0210] <Formation Evaluation> Each of the power storage devices was cut into a rectangular shape of 90 mm in length (MD direction) x 150 mm in width (TD direction) with an outer packaging material as a test sample. The MD of the outer packaging material for the power storage device corresponded to the rolling direction of the aluminum alloy foil, and the TD of the outer packaging material for the power storage device corresponded to the TD of the aluminum alloy foil. In an environment at 25°C, a rectangular die (female die, the surface of which had a maximum height roughness (Rz nominal value) of 3.2 μm as specified in Table 2 of JIS B 0659-1:2002 Appendix 1 (Reference Comparative Surface Roughness Standard Plate), chamfer R 2.0 mm, land R 1.0 mm) having a caliber of 30.6 mm (MD direction) x 54.5 mm (TD direction) and a corresponding molding die (male die, the land surface of which had a maximum height roughness (Rz nominal value) of 1.6 μm as specified in Table 2 of JIS B 0659-1:2002 Appendix 1 (Reference Comparative Surface Roughness Standard Plate), and the surface other than the land had a maximum height roughness (Rz nominal value) of 3.2 μm as specified in Table 2 of JIS B 0659-1:2002 Appendix 1 (Reference Comparative Surface Roughness Standard Plate), chamfer R 2.0 mm, land R 1.0 mm) were used, and the sample was subjected to a pressing pressure (surface pressure) of 0.4 MPa, and the molding depth was changed in units of 0.5 mm from a molding depth of 0.5 mm, and cold-rolling molding (one-step drawing) was performed on 10 samples each. In this case, the test sample was placed on the female die with the side of the heat-fusible resin layer positioned on the side of the male die, and molding was performed. In addition, the clearance between the male die and the female die was set to 0.3 mm. The sample after cold-rolling molding was irradiated with light from a penlight in a dark room, and the presence or absence of pinholes or cracks and the like on the aluminum foil was confirmed by the transmission of light. The deepest molding depth at which pinholes or cracks were not present on the aluminum foil of 10 samples was recorded as Hmm. The evaluation criteria for the moldability are shown below.

[0211] (Moldability Evaluation Criteria) A: Hmm is 7 mm or more B: Hmm is more than 6 mm and less than 7 mm C: Hmm is less than 6 mm <Measurement of Volume Resistivity> According to the above <Tensile Test at 120°C Environment>, a test piece was prepared by elongating the outer packaging material for the power storage device of 100 mm x 100 mm by 20% at a speed of 0.5 mm / minute in an environment at 120°C. The volume resistivity was measured by the following method. The results are shown in Table 1.

[0212] A digital megohmmeter / microammeter using a 5450 manufactured by ADCMT was used to measure the insulation resistance at an applied voltage of 100 V. The measurement was performed in accordance with JIS K6911-1995 using a φ50 electrode under the condition that the test piece was sandwiched with silicone rubber. The measurement sample was a 100 mm x 100 mm laminate, and the measurement was performed from the hot melt layer side. The average of five measurements was taken under the measurement temperature condition of 23°C.

[0213] A: Volume resistivity is 1 x 10 15 Ω or more B: Volume resistivity is 1 x 10 13 Ω or more and volume resistivity is less than 1 x 10 15 Ω C: Volume resistivity is less than 1 x 10 13 Ω [Table 1] In the laminate constitution of the outer packaging material for the power storage device of Table 1, PET means polyethylene terephthalate, Ny means nylon, PPa means maleic anhydride-modified polypropylene, PP means polypropylene, DL means a layer formed of an adhesive (adhesive layer or adhesive layer) using a dry lamination method, and PBT means polybutylene terephthalate. The values in parentheses are thicknesses (μm), and " / " represents the division between layers.

[0214] As described above, the present application provides the invention in the manner shown below.

[0215] Item 1: An outer packaging material for a power storage device, wherein the outer packaging material for the power storage device is constituted by a laminate including, in order from the outside, a base material layer, a barrier layer, and a hot melt resin layer, The outer packaging material for the power storage device has a strength of 35 N / 15 mm or more when elongated by 20% in the MD direction in the following tensile test under an environment of 120°C.

[0216] < Tensile Test > The measurement was performed using a tensile tester in accordance with the method prescribed by JIS K7127:1999. The measurement conditions were: the sample was in the form of a rectangle having a width of 15 mm, the gauge length was set to 30 mm, the tensile speed was set to 0.5 mm / minute, the test environment was set to 120°C, and the average of three measurements was taken.

[0217] Item 2: The outer packaging material for the power storage device according to Item 1, wherein the reduction ratio of the thickness of the hot melt resin layer is 15% or less when elongated by 20% in the MD direction in the tensile test under an environment of 120°C.

[0218] Item 3: The outer packaging material for electrical storage devices according to item 1 or 2, wherein the volume resistivity at the time of elongation of 20% in the MD direction in the aforementioned tensile test in an environment of 120°C is 1 x 10 13 Ω or more.

[0219] Item 4: The outer packaging material for electrical storage devices according to any one of items 1 to 3, wherein the heat-fusible resin layer contains polybutylene terephthalate.

[0220] Item 5: The outer packaging material for electrical storage devices according to any one of items 1 to 3, wherein the heat-fusible resin layer contains at least one of homopolymer polybutylene terephthalate and copolymer polybutylene terephthalate.

[0221] Item 6: The outer packaging material for electrical storage devices according to item 5, wherein the copolymer polybutylene terephthalate includes at least one selected from a polyether structure and a polyester structure B other than the polybutylene terephthalate structure, the polyester structure B having a structure different from that of the polybutylene terephthalate.

[0222] Item 7: The outer packaging material for electrical storage devices according to item 6, wherein the polyester structure B has a polycondensation structure of at least one selected from isophthalic acid, dodecanedioic acid, and sebacic acid and 1,4-butanediol.

[0223] Item 8: The outer packaging material for electrical storage devices according to any one of items 1 to 7, wherein the thickness of the barrier layer is 40 μm or more.

[0224] Item 9: The outer packaging material for electrical storage devices according to any one of items 1 to 8, wherein the thickness of the heat-fusible resin layer is 30 μm or more.

[0225] Item 10: The outer packaging material for electrical storage devices according to any one of items 1 to 9, wherein an adhesive layer is further provided between the barrier layer and the heat-fusible resin layer.

[0226] Item 11: The outer packaging material for electrical storage devices according to any one of items 1 to 10, wherein an adhesive layer is further provided between the substrate layer and the barrier layer.

[0227] Item 12: The outer packaging material for electrical storage devices according to any one of items 1 to 11, wherein the outer packaging material for electrical storage devices is an outer packaging material for a full solid-state battery, a semi-solid-state battery, a quasi-solid-state battery, a polymer battery, or a full-resin battery.

[0228] Item 13: A method for manufacturing an outer packaging material for electrical storage devices, comprising: a step of obtaining a laminate in which at least a base material layer, a barrier layer, and a hot melt resin layer are sequentially stacked from the outside, The above-mentioned outer packaging material for electrical storage devices has a strength of 35 N / 15 mm or more at the time of elongation of 20% in the MD direction in the following tensile test in an environment of 120°C.

[0229] < Tensile Test > Measurement was performed using a tensile testing device in accordance with the method prescribed in JIS K7127: 1999. The measurement conditions were: the sample was in the form of a rectangle with a width of 15 mm, the gauge length was set to 30 mm, the tensile speed was set to 0.5 mm / min, the test environment was set to 120°C, and the average of three measurements was taken.

[0230] Item 14: The manufacturing method of the outer packaging material for electrical storage devices according to item 13, wherein the outer packaging material for electrical storage devices is an outer packaging material for all-solid-state batteries, semi-solid-state batteries, quasi-solid-state batteries, polymer batteries, or all-resin batteries.

[0231] Item 15: An electrical storage device, wherein an electrical storage device element having at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed from the outer packaging material for electrical storage devices according to any one of items 1 to 12.

[0232] Item 16: An all-solid-state battery, wherein an electrical storage device element having at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed from the outer packaging material for electrical storage devices according to any one of items 1 to 12.

[0233] Explanation of Symbols 1. Base material layer 2. Adhesive layer 3. Barrier layer 4. Hot melt resin layer 5. Adhesive layer 6. Surface covering layer 10. Outer packaging material for electrical storage devices.

Claims

1. An outer packaging material for an electrical storage device, characterized by: comprising a laminate of at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order from the outside, the outer packaging material for the electrical storage device has a strength of 35 N / 15 mm or more at the time of elongation of 20% in the MD direction in a tensile test under an environment of 120°C, Tensile test: measured using a tensile tester in a method prescribed in JIS K7127: 1999, measurement conditions being: a sample in a rectangular shape with a width of 15 mm, a gauge length of 30 mm, a tensile speed of 0.5 mm / minute, a test environment of 120°C, and an average of 3 measurements.

2. The outer packaging material for the electrical storage device according to claim 1, characterized by: a reduction ratio of the thickness of the heat-fusible resin layer is 15% or less at the time of elongation of 20% in the MD direction in the tensile test under an environment of 120°C.

3. The outer packaging material for the electrical storage device according to claim 1 or 2, characterized by:

4. The outer packaging material for the electrical storage device according to claim 1 or 2, characterized by: The volume resistivity at 20% elongation in the MD direction in the tensile test in an environment at 120°C was 1 x 10 13 Ω or more. the heat-fusible resin layer contains polybutylene terephthalate.

5. The outer packaging material for the electrical storage device according to claim 1 or 2, characterized by: the heat-fusible resin layer contains at least one of a homopolymer polybutylene terephthalate and a copolymer polybutylene terephthalate.

6. The outer packaging material for the electrical storage device according to claim 5, characterized by: the copolymer polybutylene terephthalate includes at least one selected from a polyether structure and a polyester structure B in addition to a polybutylene terephthalate structure, the polyester structure B has a structure different from that of the polybutylene terephthalate.

7. The outer packaging material for the electrical storage device according to claim 6, characterized by: the polyester structure B has a polycondensation structure of at least one selected from isophthalic acid, dodecanedioic acid, and sebacic acid and 1,4-butanediol.

8. The outer packaging material for the electrical storage device according to claim 1 or 2, characterized by: the thickness of the barrier layer is 40 μm or more.

9. The outer packaging material for the electrical storage device according to claim 1 or 2, characterized by: the thickness of the heat-fusible resin layer is 30 μm or more.

10. The outer packaging material for the electrical storage device according to claim 1 or 2, characterized by: further having an adhesive layer between the barrier layer and the heat-fusible resin layer.

11. The outer packaging material for the electrical storage device according to claim 1 or 2, characterized by: further having an adhesive layer between the base material layer and the barrier layer.

12. The outer packaging material for the electrical storage device according to claim 1 or 2, characterized by: the outer packaging material for the electrical storage device is an outer packaging material for a full solid-state battery, a semi-solid-state battery, a quasi-solid-state battery, a polymer battery, or a full resin battery. comprising:

13. A method for producing an outer packaging material for an electrical storage device, characterized by a step of obtaining a laminate of at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order from the outside, ​ The strength of the power storage device outer packaging material at the time when the elongation in the MD direction is 20% in the following tensile test in an environment at 120°C is 35 N / 15 mm or more, Tensile test: Measurement was performed using a tensile tester in accordance with the method prescribed by JIS K7127:1999, with the measurement conditions being: the sample was in the form of a rectangle with a width of 15 mm, the gauge length was set to 30 mm, the tensile speed was set to 0.5 mm / minute, the test environment was set to 120°C, and the average of three measurements was taken.

14. The manufacturing method of the power storage device outer packaging material according to claim 13, characterized by: The power storage device outer packaging material is an outer packaging material for a full-solid-state battery, a semi-solid-state battery, a quasi-solid-state battery, a polymer battery, or a full-resin battery.

15. A power storage device, characterized by: A power storage device element having at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the power storage device outer packaging material according to claim 1 or 2.

16. A full-solid-state battery, characterized by: A power storage device element having at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the power storage device outer packaging material according to claim 1 or 2.

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