JP2023153770A - Exterior material for power storage device, manufacturing method thereof, film, and power storage device - Google Patents

Abstract

To provide an exterior material for a power storage device that can exhibit high sealing strength in a wide range of temperature environment from low to high temperatures.SOLUTION: An exterior material for a power storage device is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order, the heat-fusible resin layer includes a film, the film has a glass transition temperature of 67°C or less, and the resin forming the film has at least a polyester structure A.SELECTED DRAWING: None

Description

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

Conventionally, various types of power storage devices have been developed, and in all power storage devices, an exterior material has become an essential component for sealing power storage device elements such as electrodes and electrolytes. Conventionally, metal exterior materials have been frequently used as exterior materials for power storage devices.

On the other hand, in recent years, as electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, and the like have become more sophisticated, power storage devices are required to have a variety of shapes, as well as to be thinner and lighter. However, metal exterior materials for power storage devices, which have been widely used in the past, have the disadvantage that it is difficult to keep up with the diversification of shapes, and there is also a limit to the reduction in weight.

Therefore, in recent years, film-like materials in which a base material layer, a barrier layer, and a heat-fusible resin layer are sequentially laminated have been developed as exterior materials for power storage devices that can be easily processed into various shapes and can be made thinner and lighter. A laminate has been proposed (see, for example, Patent Document 1).

In such exterior materials for power storage devices, generally, a recess is formed by cold forming, power storage device elements such as electrodes and electrolyte are arranged in the space formed by the recess, and heat-sealable resin is placed in the space formed by the recess. By heat-sealing the layers, a power storage device in which power storage device elements are housed inside the power storage device exterior material is obtained.

JP2008-287971A

With the recent progress in IoT, various types of IoT devices are on the market. Depending on the type of IoT device, it is assumed that it will be used in a wide range of temperature environments from low to high temperatures. Therefore, power storage devices installed in IoT devices are also required to have durability over a wide temperature range. For example, among in-vehicle electronic devices, an IoT device that acquires data from an engine room or the like may be required to have durability in a high-temperature environment of 125 degrees Celsius.

Among power storage devices, for example, lithium ion batteries use an electrolyte containing an organic solvent, and therefore are not expected to be used at temperatures above the boiling point of the electrolyte solvent. On the other hand, all-solid-state batteries have a solid electrolyte, so they can be used in higher temperature environments than current lithium-ion batteries, making them ideal for IoT devices used in a wide range of temperature environments as mentioned above. can meet the demands of

For example, it is thought that high-speed charging will be possible by using an all-solid-state battery as a driving battery for an electric vehicle and heating the all-solid-state battery during charging. The high temperature environment caused by such heating is also a high temperature environment that is not applicable to current lithium ion batteries. Therefore, the exterior material for all-solid-state batteries is also required to have durability in a wide range of temperature environments.

Conventionally, in electrolyte solution lithium ion batteries containing organic solvents, the laminate film used for the heat-fusible resin layer of the exterior material is made of polypropylene film, etc., and has poor durability ( seal strength) will decrease significantly. Furthermore, since batteries for driving electric vehicles and the like are exposed not only to high temperatures but also to low temperature environments, it is necessary to maintain the airtightness of the battery even at low temperatures, that is, to maintain a seal strength above a certain level. However, exterior materials for power storage devices that use a polypropylene film or the like as a heat-fusible resin layer have insufficient durability in high-temperature environments. Furthermore, for example, instead of a polypropylene film, a polyester film, which has high durability in a high temperature environment, has insufficient durability in a low temperature environment (for example, about -30° C.). In this way, the films conventionally used for heat-adhesive resin layers are insufficient for power storage devices used in a wide range of temperature environments from low to high temperatures (for example, in the range of -30°C to 150°C). It is not applicable.

Under such circumstances, the main objective of the present disclosure is to provide an exterior material for a power storage device that can exhibit high sealing strength in a wide range of temperature environments from low to high temperatures. Another object of the present disclosure is to provide a method for manufacturing the exterior material for a power storage device and an energy storage device using the exterior material for a power storage device. Furthermore, the present disclosure also aims to provide a film that can exhibit high sealing strength in a wide range of temperature environments from low to high temperatures.

The inventors of the present disclosure have conducted extensive studies to solve the above problems. As a result, an exterior material for a power storage device is constructed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order, and the heat-fusible resin layer includes a film. , the film has a glass transition temperature of 67°C or less, and the resin forming the film contains polyester structure A, so that it has a high glass transition temperature in a wide range of temperature environments from low to high temperatures (for example, in the range of -30°C to 150°C). It has been found that the seal strength is exhibited.

The present disclosure was completed through further studies based on such new findings. That is, the present disclosure provides inventions of the following aspects.
It is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
The heat-fusible resin layer includes a film,
The film has a glass transition temperature of 67°C or less,
The resin forming the film includes a polyester structure A, an exterior material for a power storage device.

According to the present disclosure, it is possible to provide an exterior material for a power storage device that can exhibit high sealing strength in a wide range of temperature environments from low to high temperatures. Further, according to the present disclosure, it is also possible to provide a method for manufacturing the exterior material for a power storage device and an energy storage device using the exterior material for a power storage device. Furthermore, according to the present disclosure, it is also possible to provide a film that can exhibit high sealing strength in a wide range of temperature environments from low to high temperatures.

It is a schematic diagram showing an example of the cross-sectional structure of the exterior material for electricity storage devices of this indication. FIG. 2 is a schematic diagram showing an example of a cross-sectional structure of an exterior material for a power storage device according to the present disclosure. It is a schematic diagram showing an example of the cross-sectional structure of the exterior material for electricity storage devices of this indication. It is a schematic diagram showing an example of the cross-sectional structure of the exterior material for electricity storage devices of this indication. FIG. 2 is a schematic diagram showing an example of a cross-sectional structure of a heat-fusible resin layer (film) of the exterior material for a power storage device of the present disclosure. FIG. 2 is a schematic diagram showing an example of a cross-sectional structure of a heat-fusible resin layer (including a film) of an exterior material for an electricity storage device according to the present disclosure. FIG. 2 is a schematic diagram showing an example of a cross-sectional structure of a heat-fusible resin layer (including a film) of an exterior material for an electricity storage device according to the present disclosure. FIG. 2 is a schematic diagram for explaining a method of accommodating a power storage device element in a package formed of the exterior material for a power storage device according to the present disclosure. FIG. 3 is a schematic diagram for explaining a method of measuring seal strength. FIG. 3 is a schematic diagram for explaining a method for measuring seal strength.

The exterior material for a power storage device of the present disclosure is composed of a laminate including at least a base layer, a barrier layer, and a heat-fusible resin layer in this order, and the heat-fusible resin layer includes a film. The film is characterized in that the glass transition temperature is 67° C. or lower, and the resin forming the film includes a polyester structure A. The exterior material for a power storage device of the present disclosure can exhibit high sealing strength in a wide range of temperature environments from low to high temperatures.

Hereinafter, the exterior material for a power storage device of the present disclosure will be described in detail. In this specification, the numerical range indicated by "~" means "more than" or "less than". For example, the expression 2 to 15 mm means 2 mm or more and 15 mm or less.

1. Laminated structure of exterior material for power storage device The exterior material 10 for power storage device of the present disclosure is a laminate including a base material layer 1, a barrier layer 3, and a heat-fusible resin layer 4 in this order, for example, as shown in FIG. It consists of In the exterior material 10 for a power storage device, the base layer 1 is the outermost layer, and the heat-fusible resin layer 4 is the innermost layer. When assembling a power storage device using the power storage device exterior material 10 and the power storage device element, heat-seal the peripheral edges with the heat-sealable resin layers 4 of the power storage device exterior material 10 facing each other. A power storage device element is accommodated in the space formed by. In the laminate forming the exterior material 10 for a power storage device according to the present disclosure, with the barrier layer 3 as a reference, the heat-fusible resin layer 4 side is on the inner side than the barrier layer 3, and the base material layer 1 side is on the inner side than the barrier layer 3. It is outside.

For example, as shown in FIGS. 2 to 4, the exterior material 10 for a power storage device includes a layer between the base layer 1 and the barrier layer 3, as necessary, for the purpose of increasing the adhesiveness between these layers. It may also have an adhesive layer 2. Further, as shown in FIGS. 3 and 4, for example, an adhesive layer 5 may be provided between the barrier layer 3 and the heat-fusible resin layer 4 for the purpose of increasing the adhesion between these layers. It may have. Further, as shown in FIG. 4, a surface coating layer 6 or the like may be provided on the outside of the base material layer 1 (on the side opposite to the heat-fusible resin layer 4 side), if necessary.

The exterior material 10 for a power storage device of the present disclosure includes a film in the heat-fusible resin layer 4 . When the heat-fusible resin layer 4 is composed of a single layer, the heat-fusible resin layer 4 is composed of a film, and the heat-fusible resin layer 4 is composed of two or more layers. In this case, at least one layer among the layers included in the heat-fusible resin layer 4 is constituted by a film. As described later, when the heat-fusible resin layer 4 is composed of two or more layers, the surface of the heat-fusible resin layer 4 on the side opposite to the barrier layer 3 (i.e., the outermost surface of the exterior material 10 for an electricity storage device) It is preferable that the inner layer surface) is formed of a film.

The thickness of the laminate constituting the exterior material 10 for power storage devices is not particularly limited, but from the viewpoint of cost reduction, energy density improvement, etc., it is, for example, 190 μm or less, preferably about 180 μm or less, about 155 μm or less, about 120 μm or less can be mentioned. In addition, from the viewpoint of maintaining the function of the exterior material for an energy storage device to protect the energy storage device elements, the thickness of the laminate constituting the exterior material 10 for an energy storage device is preferably about 35 μm or more, about 45 μm or more, or about 45 μm or more. Examples include 60 μm or more. Further, preferred ranges of the laminate forming the exterior material 10 for power storage devices include, for example, approximately 35 to 190 μm, approximately 35 to 180 μm, approximately 35 to 155 μm, approximately 35 to 120 μm, approximately 45 to 190 μm, and approximately 45 to 180 μm. , about 45 to 155 μm, about 45 to 120 μm, about 60 to 190 μm, about 60 to 180 μm, about 60 to 155 μm, and about 60 to 120 μm, and particularly preferably about 60 to 155 μm.

Moreover, the exterior material 10 for a power storage device can be suitably applied to an all-solid-state battery. In this case, the thickness of the laminate constituting the exterior material 10 for power storage devices is not particularly limited, but from the viewpoint of cost reduction, improvement of energy density, etc., it is preferably about 10,000 μm or less, about 8,000 μm or less, or about 5,000 μm or less. From the viewpoint of maintaining the function of the exterior material for all-solid-state batteries to protect battery elements, the thickness is preferably about 10 μm or more, about 15 μm or more, and about 20 μm or more, and the preferable range is, for example, 10 to Examples include about 10,000 μm, about 15 to 8,000 μm, about 20 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, and about 20 to 5,000 μm, especially 20 to 5,000 μm. degree is preferred.

In the exterior material 10 for power storage devices, the base material layer 1, the adhesive layer 2 provided as necessary, the barrier layer 3, and the The ratio of the total thickness of the adhesive layer 5 provided, the heat-fusible resin layer 4, and the surface coating layer 6 provided as necessary is preferably 90% or more, more preferably 95% or more, More preferably, it is 98% or more. As a specific example, when the exterior material 10 for a power storage device of the present disclosure includes a base layer 1, an adhesive layer 2, a barrier layer 3, an adhesive layer 5, and a heat-fusible resin layer 4, the exterior material for a power storage device The ratio of the total thickness of each of these layers to the thickness (total thickness) of the laminate constituting the material 10 is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. Further, even when the exterior material 10 for an energy storage device of the present disclosure is a laminate including a base layer 1, an adhesive layer 2, a barrier layer 3, and a heat-fusible resin layer 4, the exterior material for an energy storage device The ratio of the total thickness of each of these layers to the thickness (total thickness) of the laminate constituting 10 is, for example, 80% or more, preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. Can be done.

Furthermore, the exterior material 10 for a power storage device of the present disclosure has a seal strength in a −30° C. environment measured by the following measuring method, preferably 40 N/15 mm or more, more preferably 80 N/15 mm or more. Note that the upper limit of the seal strength is, for example, 200 N/15 mm or less, preferably 180 N/15 mm or less. Preferred ranges of the seal strength include approximately 40 to 200 N/15 mm, approximately 40 to 180 N/15 mm, approximately 80 to 200 N/15 mm, and approximately 80 to 180 N/15 mm.

Moreover, the exterior material 10 for an electricity storage device of the present disclosure has a seal strength in a 23° C. environment measured by the following measuring method, preferably 40 N/15 mm or more, more preferably 80 N/15 mm or more. Note that the upper limit of the seal strength is, for example, 200 N/15 mm or less, preferably 180 N/15 mm or less. Preferred ranges of the seal strength include approximately 40 to 200 N/15 mm, approximately 40 to 180 N/15 mm, approximately 80 to 200 N/15 mm, and approximately 80 to 180 N/15 mm.

Moreover, the exterior material 10 for an electricity storage device of the present disclosure has a seal strength in a 120° C. environment measured by the following measurement method, preferably 30 N/15 mm or more, more preferably 50 N/15 mm or more. Note that the upper limit of the seal strength is, for example, 150 N/15 mm or less, preferably 120 N/15 mm or less. Preferred ranges of the seal strength include approximately 30 to 150 N/15 mm, approximately 30 to 120 N/15 mm, approximately 50 to 150 N/15 mm, and approximately 50 to 120 N/15 mm.

Moreover, the exterior material 10 for an electricity storage device of the present disclosure has a seal strength of preferably 30 N/15 mm or more, more preferably 50 N/15 mm or more in a 150° C. environment, as measured by the following measurement method. Note that the upper limit of the seal strength is, for example, 150 N/15 mm or less, preferably 120 N/15 mm or less. Preferred ranges of the seal strength include approximately 30 to 150 N/15 mm, approximately 30 to 120 N/15 mm, approximately 50 to 150 N/15 mm, and approximately 50 to 120 N/15 mm.

<Measurement of seal strength (-30°C, 23°C, 120°C, or 150°C environment)>
In accordance with the provisions of JIS K7127:1999, the seal strength of the exterior material at each measurement temperature of -30°C, 23°C, 120°C, or 150°C is measured as follows. A test sample is prepared by cutting the exterior material into a strip having a width of 15 mm in the TD direction. Specifically, as shown in FIG. 9, each exterior material is first cut into 60 mm (TD direction) x 200 mm (MD direction) (FIG. 9a). Next, the exterior material is folded in half in the MD direction at the crease P (midway in the MD direction) so that the heat-fusible resin layers face each other (FIG. 9b). About 10 mm inward from the crease P in the MD direction, heat is applied under conditions such as a seal width of 7 mm, a temperature of 240°C, a surface pressure and a sealing time such that the thickness of the heat-sealing resin layer is 80 ± 5% of the thickness before sealing. Heat seal the fusible resin layers together (FIG. 9c). In FIG. 9c, the shaded portion S is the heat-sealed portion. Next, the test piece 13 is obtained by cutting in the MD direction (cutting at the position of the two-dot chain line in FIG. 9d) so that the width in the TD direction is 15 mm (FIG. 9e). Next, the test piece 13 was left for 2 minutes at each measurement temperature, and the heat-fusible resin layer at the heat-sealed portion was peeled off at a rate of 300 mm/min using a tensile testing machine in each measurement temperature environment (Figure 10). . The maximum strength at the time of peeling is defined as the seal strength (N/15 mm). The distance between chucks is 50 mm.

2. Each layer forming the exterior material for power storage device [base material layer 1]
In the present disclosure, the base material layer 1 is a layer provided for the purpose of exhibiting a function as a base material of an exterior material for a power storage device. Base material layer 1 is located on the outer layer side of the exterior material for a power storage device.

The material forming the base material layer 1 is not particularly limited as long as it has a function as a base material, that is, it has at least insulation properties. The base material layer 1 can be formed using, for example, a resin, and the resin may contain additives described below.

When the base material layer 1 is formed of resin, the base material layer 1 can be formed of a resin film, for example. When the base material layer 1 is formed of a resin film, when the base material layer 1 is laminated with the barrier layer 3 and the like to produce the exterior material 10 for an electricity storage device of the present disclosure, the preformed resin film is used as the base material layer. It may be used as 1. Alternatively, the resin forming the base layer 1 may be formed into a film on the surface of the barrier layer 3 or the like by extrusion molding, coating, etc., so that the base layer 1 is formed of a resin film. The resin film may be an unstretched film or a stretched film. Examples of the stretched film include uniaxially stretched film and biaxially stretched film, with biaxially stretched film being preferred. Examples of the stretching method for forming a biaxially stretched film include a sequential biaxial stretching method, an inflation method, and a simultaneous biaxial stretching method. Examples of methods for applying the resin include roll coating, gravure coating, and extrusion coating.

Examples of the resin forming the base layer 1 include resins such as polyester, polyamide, polyolefin, epoxy resin, acrylic resin, fluororesin, polyurethane, silicone resin, and phenol resin, and modified products of these resins. Moreover, the resin forming the base material layer 1 may be a copolymer of these resins, or a modified product of the copolymer. Furthermore, a mixture of these resins may be used.

The base layer 1 preferably contains these resins as a main component, and more preferably contains polyester or polyamide as a main component. Here, the main component refers to a resin component whose content is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass. % or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, even more preferably 99% by mass or more. For example, the expression that the base layer 1 contains polyester or polyamide as a main component means that the content of polyester or polyamide in the resin components contained in the base layer 1 is, for example, 50% by mass or more, preferably 60% by mass. % or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, even more preferably 99% by mass or more. It means that.

Among these, the resin forming the base layer 1 is preferably polyester or polyamide, and more preferably polyester (especially preferably polyethylene terephthalate).

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, copolymerized polyester, and the like. Examples of the copolyester include copolyesters containing ethylene terephthalate as a main repeating unit. Specifically, copolymer polyester polymerized with ethylene isophthalate with ethylene terephthalate as the main repeating unit (hereinafter abbreviated as polyethylene (terephthalate/isophthalate)), polyethylene (terephthalate/adipate), polyethylene (terephthalate/adipate), etc. Examples include sodium sulfoisophthalate), polyethylene (terephthalate/sodium isophthalate), polyethylene (terephthalate/phenyl-dicarboxylate), and polyethylene (terephthalate/decanedicarboxylate). These polyesters may be used alone or in combination of two or more.

Specific examples of polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; terephthalic acid and/or isophthalic acid; Hexamethylene diamine-isophthalic acid-terephthalic acid copolymer polyamides, polyamide MXD6 (polymethacrylic acid), etc. containing structural units derived from nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid), etc. Aromatic polyamides such as silylene adipamide); alicyclic polyamides such as polyamide PACM6 (polybis(4-aminocyclohexyl)methaneadipamide); and lactam components and isocyanate components such as 4,4'-diphenylmethane-diisocyanate. Polyamides such as copolymerized polyamides, polyesteramide copolymers and polyetheresteramide copolymers which are copolymers of copolymerized polyamides and polyesters or polyalkylene ether glycols; and copolymers of these are exemplified. These polyamides may be used alone or in combination of two or more.

The base layer 1 preferably contains at least one of a polyester film, a polyamide film, and a polyolefin film, and preferably contains at least one of a stretched polyester film, a stretched polyamide film, and a stretched polyolefin film, It is more preferable to include at least one of a stretched polyethylene terephthalate film, a stretched polybutylene terephthalate film, a stretched nylon film, and a stretched polypropylene film, and the film preferably includes a biaxially stretched polyethylene terephthalate film, a biaxially stretched polybutylene terephthalate film, and a biaxially stretched nylon film. , a biaxially oriented polypropylene film.

The base material layer 1 may be a single layer or may be composed of two or more layers. When the base material layer 1 is composed of two or more layers, the base material layer 1 may be a laminate in which resin films are laminated with an adhesive or the like, or a resin film may be coextruded to form two or more layers. It may also be a laminate of resin films. Further, a laminate of resin films formed into two or more layers by coextrusion of resin may be used as the base layer 1 without being stretched, or may be uniaxially or biaxially stretched as the base layer 1.

In the base material layer 1, specific examples of a laminate of two or more resin films include a laminate of a polyester film and a nylon film, a laminate of two or more nylon films, and a laminate of two or more polyester films. Preferably, 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 preferred. For example, when the base material layer 1 is a laminate of two resin films, it may be 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. A laminate is preferred, 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 preferred. In addition, since polyester resin is difficult to discolor when an electrolyte adheres to the surface, for example, when the base layer 1 is a laminate of two or more resin films, the polyester resin film is the same as the base layer 1. Preferably, it is located in the outermost layer.

When the base material layer 1 is a laminate of two or more layers of resin films, the two or more layers of resin films may be laminated via an adhesive. Preferred adhesives include those similar to the adhesives exemplified in adhesive layer 2 described below. The method for laminating two or more layers of resin films is not particularly limited and any known method can be used, such as a dry lamination method, a sandwich lamination method, an extrusion lamination method, a thermal lamination method, etc., and preferably a dry lamination method. One example is the lamination method. When laminating by dry lamination, it is preferable to use a polyurethane adhesive as the adhesive. At this time, the thickness of the adhesive is, for example, about 2 to 5 μm. Alternatively, an anchor coat layer may be formed on a resin film and laminated thereon. Examples of the anchor coat layer include the same adhesive as the adhesive layer 2 described below. At this time, the thickness of the anchor coat layer is, for example, about 0.01 to 1.0 μm.

Further, even if additives such as lubricants, flame retardants, anti-blocking agents, antioxidants, light stabilizers, tackifiers, and antistatic agents are present on at least one of the surface and inside of the base layer 1, good. Only one type of additive may be used, or a mixture of two or more types may be used.

In the present disclosure, from the viewpoint of improving the moldability of the exterior material for a power storage device, it is preferable that a lubricant be present on at least one of the surface and inside of the base layer 1. The lubricant is not particularly limited, but preferably includes an amide lubricant. Specific examples of amide lubricants include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides, and the like. Specific examples of saturated fatty acid amides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, and the like. Specific examples of unsaturated fatty acid amides include oleic acid amide and erucic acid amide. Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, and the like. Furthermore, specific examples of methylolamide include methylolstearamide and the like. Specific examples of saturated fatty acid bisamides include methylene bisstearamide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, and hexamethylene bis stearic acid amide. Examples include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N,N'-distearyl adipic acid amide, N,N'-distearyl sebacic acid amide, and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyladipic acid amide, and N,N'-dioleyl sebacic acid amide. Examples include. Specific examples of fatty acid ester amides include stearamide ethyl stearate. Specific examples of aromatic bisamides include m-xylylene bisstearamide, m-xylylene bishydroxystearamide, and N,N'-distearylisophthalic acid amide. One type of lubricant may be used alone or two or more types may be used in combination, and a combination of two or more types is preferably used.

When a lubricant is present on the surface of the base layer 1, its amount is not particularly limited, but is preferably about 3 mg/m ² or more, more preferably about 4 to 15 mg/m ² , and even more preferably 5 to 14 mg. / ^m2 .

The lubricant present on the surface of the base layer 1 may be one obtained by exuding a lubricant contained in the resin constituting the base layer 1, or a lubricant coated on the surface of the base layer 1. It's okay.

The thickness of the base material layer 1 is not particularly limited as long as it functions as a base material, but may be, for example, about 3 to 50 μm, preferably about 10 to 35 μm. When the base layer 1 is a laminate of two or more layers of resin films, the thickness of the resin films constituting each layer is preferably about 2 to 25 μm.

[Adhesive layer 2]
In the exterior material for a power storage device according to the present disclosure, the adhesive layer 2 is a layer provided between the base material layer 1 and the barrier layer 3 as necessary for the purpose of increasing the adhesiveness between the two.

The adhesive layer 2 is formed of an adhesive capable of bonding the base material layer 1 and the barrier layer 3 together. The adhesive used to form the adhesive layer 2 is not limited, but may be any one of a chemical reaction type, a solvent volatilization type, a heat melt type, a heat pressure type, and the like. Further, it may be a two-component curing adhesive (two-component adhesive), a one-component curing adhesive (one-component adhesive), or a resin that does not involve a curing reaction. Furthermore, the adhesive layer 2 may be a single layer or a multilayer.

Specifically, the adhesive components contained in the adhesive include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymerized polyester; polyether; polyurethane; epoxy resin; Phenol resins; polyamides such as nylon 6, nylon 66, nylon 12, and copolyamide; polyolefin resins such as polyolefins, cyclic polyolefins, acid-modified polyolefins, and acid-modified cyclic polyolefins; polyvinyl acetate; cellulose; (meth)acrylic resins; Examples include polyimide; polycarbonate; amino resins such as urea resin and melamine resin; rubbers such as chloroprene rubber, nitrile rubber, and styrene-butadiene rubber; and silicone resins. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, polyurethane adhesives are preferred. Further, the adhesive strength of these adhesive component resins can be increased by using an appropriate curing agent in combination. The curing agent is selected from among polyisocyanates, polyfunctional epoxy resins, oxazoline group-containing polymers, polyamine resins, acid anhydrides, etc., depending on the functional groups of the adhesive component.

Examples of the polyurethane adhesive include a polyurethane adhesive that includes a first part containing a polyol compound and a second part containing an isocyanate compound. Preferred examples include two-component curing polyurethane adhesives in which a polyol such as a polyester polyol, a polyether polyol, or an acrylic polyol is used as a first part and an aromatic or aliphatic polyisocyanate is used as a second part. Further, examples of the polyurethane adhesive include a polyurethane adhesive containing a polyurethane compound prepared by reacting a polyol compound and an isocyanate compound in advance, and an isocyanate compound. Further, examples of the polyurethane adhesive include a polyurethane adhesive containing a polyurethane compound prepared by reacting a polyol compound and an isocyanate compound in advance, and a polyol compound. Further, examples of the polyurethane adhesive include, for example, a polyurethane adhesive obtained by curing a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance with moisture in the air or the like. As the polyol compound, it is preferable to use a polyester polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the end of the repeating unit. Examples of the second agent include aliphatic, alicyclic, aromatic, and araliphatic isocyanate compounds. Examples of isocyanate compounds include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate. (MDI), naphthalene diisocyanate (NDI), and the like. Also included are polyfunctional isocyanate modified products of one or more of these diisocyanates. It is also possible to use multimers (for example trimers) as the polyisocyanate compound. Such multimers include adducts, biurets, nurates, and the like. Since the adhesive layer 2 is formed of a polyurethane adhesive, the exterior material for the power storage device has excellent electrolyte resistance, and peeling of the base material layer 1 is suppressed even if the electrolyte adheres to the side surface. .

Further, the adhesive layer 2 may include other components as long as they do not impair adhesiveness, and may contain colorants, thermoplastic elastomers, tackifiers, fillers, and the like. Since the adhesive layer 2 contains the coloring agent, the exterior material for the electricity storage device can be colored. As the colorant, known colorants such as pigments and dyes can be used. Moreover, only one type of coloring agent may be used, or two or more types of coloring agents may be used in combination.

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

Among the colorants, carbon black is preferable, for example, in order to make the exterior of the power storage device exterior black.

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

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

The thickness of the adhesive layer 2 is not particularly limited as long as the base layer 1 and the barrier layer 3 can be bonded together, but is, for example, about 1 μm or more and about 2 μm or more. Further, the thickness of the adhesive layer 2 is, for example, about 10 μm or less, about 5 μm or less. Further, preferable ranges for the thickness of the adhesive layer 2 include about 1 to 10 μm, about 1 to 5 μm, about 2 to 10 μm, and about 2 to 5 μm.

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

The colored layer can be formed, for example, by applying ink containing a coloring agent to the surface of the base layer 1 or the surface of the barrier layer 3. As the colorant, known colorants such as pigments and dyes can be used. Moreover, only one type of coloring agent may be used, or two or more types of coloring agents may be used in combination.

As specific examples of the coloring agent contained in the colored layer, the same ones as those exemplified in the column of [Adhesive layer 2] are exemplified.

[Barrier layer 3]
In the exterior material for a power storage device, the barrier layer 3 is a layer that prevents at least moisture from entering.

Examples of the barrier layer 3 include a metal foil, a vapor deposited film, and a resin layer having barrier properties. Examples of the vapor-deposited film include a metal vapor-deposited film, an inorganic oxide vapor-deposited film, and a carbon-containing inorganic oxide vapor-deposited film, and examples of the resin layer include polyvinylidene chloride, polymers mainly composed of chlorotrifluoroethylene (CTFE), and tetrafluoroethylene. Examples include fluorine-containing resins such as polymers containing fluoroethylene (TFE) as a main component, polymers having a fluoroalkyl group, and polymers containing fluoroalkyl units as a main component, and ethylene vinyl alcohol copolymers. Further, examples of the barrier layer 3 include a resin film provided with at least one of these vapor-deposited films and a resin layer. A plurality of barrier layers 3 may be provided. It is preferable that the barrier layer 3 includes a layer made of a metal material. Specific examples of the metal material constituting the barrier layer 3 include aluminum alloy, stainless steel, titanium steel, steel plate, etc. When used as metal foil, it includes at least one of aluminum alloy foil and stainless steel foil. It is preferable.

From the perspective of improving the formability of the exterior material for power storage devices, the aluminum alloy foil is preferably a soft aluminum alloy foil made of, for example, annealed aluminum alloy, and from the perspective of further improving the formability. Therefore, an aluminum alloy foil containing iron is preferable. In the aluminum alloy foil containing iron (100% by mass), the iron content is preferably 0.1 to 9.0% by mass, more preferably 0.5 to 2.0% by mass. When the iron content is 0.1% by mass or more, it is possible to obtain an exterior material for a power storage device that has better formability. By setting the iron content to 9.0% by mass or less, it is possible to obtain an exterior material for an electricity storage device that has more excellent flexibility. Examples of the soft aluminum alloy foil include an aluminum alloy having a composition specified by JIS H4160:1994 A8021H-O, JIS H4160:1994 A8079H-O, JIS H4000:2014 A8021P-O, or JIS H4000:2014 A8079P-O. One example is foil. Further, silicon, magnesium, copper, manganese, etc. may be added as necessary. Further, softening can be performed by annealing treatment or the like.

Examples of the stainless steel foil include austenitic, ferritic, austenite-ferritic, martensitic, and precipitation hardening stainless steel foils. Furthermore, from the viewpoint of providing an exterior material for a power storage device with excellent formability, the stainless steel foil is preferably made of austenitic stainless steel.

Specific examples of the austenitic stainless steel constituting the stainless steel foil include SUS304, SUS301, SUS316L, etc. Among these, SUS304 is particularly preferred.

In the case of metal foil, the thickness of the barrier layer 3 may be about 9 to 200 μm, as long as it can at least function as a barrier layer to prevent moisture from entering. The thickness of the barrier layer 3 is preferably about 85 μm or less, more preferably about 50 μm or less, even more preferably about 40 μm or less, particularly preferably about 35 μm or less. Further, the thickness of the barrier layer 3 is preferably about 10 μm or more, more preferably about 20 μm or more, and even more preferably about 25 μm or more. Further, the preferable range of the thickness of the barrier layer 3 is about 10 to 85 μm, about 10 to 50 μm, about 10 to 40 μm, about 10 to 35 μm, about 20 to 85 μm, about 20 to 50 μm, about 20 to 40 μm, and about 20 to 40 μm. Examples include about 35 μm, about 25 to 85 μm, about 25 to 50 μm, about 25 to 40 μm, and about 25 to 35 μm. When the barrier layer 3 is made of aluminum alloy foil, the above-mentioned range is particularly preferable. In addition, in the case where the barrier layer 3 is made of aluminum alloy foil, the thickness of the barrier layer 3 is preferably about 45 μm or more, from the viewpoint of imparting high formability and high rigidity to the exterior material 10 for an electricity storage device. More preferably about 50 μm or more, more preferably about 55 μm or more, preferably about 85 μm or less, more preferably 75 μm or less, even more preferably 70 μm or less, and the preferable range is about 45 to 85 μm, about 45 to 75 μm. , about 45-70 μm, about 50-85 μm, about 50-75 μm, about 50-70 μm, about 55-85 μm, about 55-75 μm, and about 55-70 μm. When the exterior material 10 for an electricity storage device has high formability, deep drawing becomes easy, which can contribute to increasing the capacity of the electricity storage device. Further, when the capacity of the power storage device is increased, the weight of the power storage device increases, but the increased rigidity of the exterior material 10 for the power storage device can contribute to high sealing performance of the power storage device. Further, in particular, when the barrier layer 3 is made of stainless steel foil, the thickness of the stainless steel foil is preferably about 60 μm or less, more preferably about 50 μm or less, still more preferably about 40 μm or less, and even more preferably about 30 μm. It is particularly preferably about 25 μm or less. Further, the thickness of the stainless steel foil is preferably about 10 μm or more, more preferably about 15 μm or more. Further, the preferable range of the thickness of the stainless steel foil is about 10 to 60 μm, about 10 to 50 μm, about 10 to 40 μm, about 10 to 30 μm, about 10 to 25 μm, about 15 to 60 μm, about 15 to 50 μm, and about 15 to 50 μm. Examples include about 40 μm, about 15 to 30 μm, and about 15 to 25 μm.

Moreover, when the barrier layer 3 is a metal foil, it is preferable that at least the surface opposite to the base material layer is provided with a corrosion-resistant film in order to prevent dissolution and corrosion. The barrier layer 3 may be provided with a corrosion-resistant coating on both sides. Here, the corrosion-resistant film refers to, for example, hydrothermal conversion treatment such as boehmite treatment, chemical conversion treatment, anodizing treatment, plating treatment with nickel or chromium, or corrosion prevention treatment such as applying a coating agent to the surface of the barrier layer. A thin film that provides corrosion resistance (for example, acid resistance, alkali resistance, etc.) to the barrier layer. Specifically, the corrosion-resistant film 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. As the treatment for forming a corrosion-resistant film, one type of treatment may be performed or a combination of two or more types may be performed. Furthermore, it is possible to have not only one layer but also multiple layers. Furthermore, among these treatments, hydrothermal conversion treatment and anodization treatment are treatments in which the surface of the metal foil is dissolved with a treatment agent to form a metal compound with excellent corrosion resistance. Note that these treatments may be included in the definition of chemical conversion treatment. Further, when the barrier layer 3 includes a corrosion-resistant film, the barrier layer 3 includes the corrosion-resistant film.

Corrosion-resistant coatings are used to prevent delamination between the barrier layer (for example, aluminum alloy foil) and the base material layer during the molding of exterior materials for power storage devices, and to prevent delamination by hydrogen fluoride generated by the reaction between electrolyte and moisture. , prevents the dissolution and corrosion of the barrier layer surface, especially when the barrier layer is an aluminum alloy foil, and prevents the aluminum oxide present on the barrier layer surface from dissolving and corroding, and the adhesion (wettability) of the barrier layer surface. It shows the effect of preventing delamination between the base material layer and the barrier layer during heat sealing and the delamination between the base material layer and the barrier layer during molding.

Various types of corrosion-resistant coatings are known that are formed by chemical conversion treatment, and mainly include at least one of phosphates, chromates, fluorides, triazinethiol compounds, and rare earth oxides. Examples include corrosion-resistant coatings containing. Examples of chemical conversion treatments using phosphates and chromates include chromic acid chromate treatment, phosphoric acid chromate treatment, phosphoric acid-chromate treatment, and chromate treatment. Examples of the compound include chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium diphosphate, chromic acid acetylacetate, chromium chloride, potassium chromium sulfate, and the like. Further, examples of phosphorus compounds used in these treatments include sodium phosphate, potassium phosphate, ammonium phosphate, and polyphosphoric acid. Examples of the chromate treatment include etching chromate treatment, electrolytic chromate treatment, coating type chromate treatment, and coating type chromate treatment is preferred. In this coating-type chromate treatment, at least the inner layer side of the barrier layer (for example, aluminum alloy foil) is first coated using a well-known method such as an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid activation method, etc. Degrease treatment is performed using a treatment method, and then metal phosphates such as Cr (chromium) phosphate, Ti (titanium) phosphate, Zr (zirconium) phosphate, and Zn (zinc) phosphate are applied to the degreased surface. Treatment liquids whose main components are salts and mixtures of these metal salts, treatment liquids whose main components are nonmetallic phosphoric acid salts and mixtures of these nonmetallic salts, or combinations of these with synthetic resins, etc. This is a process in which a treatment liquid consisting of a mixture is applied by a well-known coating method such as a roll coating method, a gravure printing method, or a dipping method, and then dried. Various solvents such as water, alcohol solvents, hydrocarbon solvents, ketone solvents, ester solvents, and ether solvents can be used as the treatment liquid, and water is preferable. In addition, the resin component used at this time includes polymers such as phenolic resins and acrylic resins, and aminated phenol polymers having repeating units represented by the following general formulas (1) to (4) are used. Examples include chromate treatment. In addition, in the aminated phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be contained alone or in any combination of two or more. Good too. The acrylic resin must be polyacrylic acid, acrylic acid methacrylate copolymer, acrylic acid maleic acid copolymer, acrylic acid styrene copolymer, or derivatives thereof such as sodium salt, ammonium salt, or amine salt. is preferred. Particularly preferred are polyacrylic acid derivatives such as ammonium salts, sodium salts, or amine salts of polyacrylic acid. In the present disclosure, polyacrylic acid refers to a polymer of acrylic acid. Further, the acrylic resin is also preferably a copolymer of acrylic acid and dicarboxylic acid or dicarboxylic anhydride, such as ammonium salt, sodium salt, Or it is also preferable that it is an amine salt. Only one type of acrylic resin may be used, or a mixture of two or more types may be used.

In the general formulas (1) to (4), X represents a hydrogen atom, a hydroxy group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. Further, R ¹ and R ² are each the same or different and represent a hydroxy group, an alkyl group, or a hydroxyalkyl group. In general formulas (1) to ( ⁴ ), ^the alkyl group represented by Examples include straight chain or branched alkyl groups having 1 to 4 carbon atoms such as tert-butyl group. Furthermore, examples of the hydroxyalkyl group represented by X, R ¹ and R ² include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, Straight chain or branched chain with 1 to 4 carbon atoms substituted with one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group Examples include alkyl groups. In the general formulas (1) to (4), the alkyl groups and hydroxyalkyl groups represented by X, R ¹ and R ² may be the same or different. In general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having repeating units represented by general formulas (1) to (4) is preferably about 500 to 1,000,000, and preferably about 1,000 to 20,000, for example. More preferred. Aminated phenol polymers can be produced, for example, by polycondensing a phenol compound or a naphthol compound with formaldehyde to produce a polymer consisting of repeating units represented by the above general formula (1) or general formula (3), and then adding formaldehyde to the polymer. and amine (R ¹ R ² NH) to introduce a functional group (-CH ₂ NR ¹ R ² ) into the polymer obtained above. Aminated phenol polymers may be used alone or in combination of two or more.

Another example of a corrosion-resistant film is a film formed by a coating-type corrosion-preventing treatment in which a coating agent containing at least one selected from the group consisting of a rare earth element oxide sol, an anionic polymer, and a cationic polymer is applied. Examples include thin films that are The coating agent may further contain phosphoric acid or a phosphate salt, a crosslinking agent for crosslinking the polymer. The rare earth element oxide sol includes rare earth element oxide fine particles (for example, particles with an average particle size of 100 nm or less) dispersed in a liquid dispersion medium. Examples of rare earth element oxides include cerium oxide, yttrium oxide, neodymium oxide, and lanthanum oxide, with cerium oxide being preferred from the viewpoint of further improving adhesion. The rare earth element oxides contained in the corrosion-resistant film can be used alone or in combination of two or more. As the liquid dispersion medium for the rare earth element oxide sol, various solvents such as water, alcohol solvents, hydrocarbon solvents, ketone solvents, ester solvents, and ether solvents can be used, with water being preferred. Examples of the cationic polymer include polyethyleneimine, an ionic polymer complex consisting of a polymer containing polyethyleneimine and a carboxylic acid, a primary amine-grafted acrylic resin in which a primary amine is graft-polymerized onto an acrylic main skeleton, polyallylamine or its derivatives. , aminated phenol, etc. are preferred. The anionic polymer is preferably poly(meth)acrylic acid or a salt thereof, or a copolymer containing (meth)acrylic acid or a salt thereof as a main component. Further, it is preferable that the crosslinking agent is at least one selected from the group consisting of a compound having a functional group such as an isocyanate group, a glycidyl group, a carboxyl group, or an oxazoline group, and a silane coupling agent. Moreover, it is preferable that the phosphoric acid or phosphate is a condensed phosphoric acid or a condensed phosphate.

As an example of a corrosion-resistant film, fine particles of metal oxides such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate are dispersed in phosphoric acid and then applied to the surface of the barrier layer. Examples include those formed by performing baking treatment at temperatures above .degree.

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

Note that the composition of the corrosion-resistant film can be analyzed using, for example, time-of-flight secondary ion mass spectrometry.

The amount of the corrosion-resistant film formed on the surface of the barrier layer 3 in the chemical conversion treatment ^is not particularly limited. is, for example, about 0.5 to 50 mg, preferably about 1.0 to 40 mg, in terms of chromium, the phosphorus compound is, for example, about 0.5 to 50 mg, preferably about 1.0 to 40 mg, in terms of phosphorus, and the aminated phenol polymer. It is desirable that the content is, for example, about 1.0 to 200 mg, preferably about 5.0 to 150 mg.

The thickness of the corrosion-resistant film is not particularly limited, but from the viewpoint of the cohesive force of the film and the adhesion with the barrier layer and the heat-fusible resin layer, it is preferably about 1 nm to 20 μm, more preferably 1 nm to 100 nm. More preferably, it is about 1 nm to 50 nm. The thickness of the corrosion-resistant film can be measured by observation using a transmission electron microscope, or by a combination of observation using a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy. Analysis of the composition of the corrosion-resistant film using time-of-flight secondary ion mass spectrometry reveals that, for example, secondary ions consisting of Ce, P, and O (for example, at least one of Ce ₂ PO ₄ ⁺ , CePO ₄ ^- , etc.) peaks derived from secondary ions (for example, at least one of CrPO ₂ ⁺ and CrPO ₄ ^- ) made of Cr, P, and O are detected.

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

[Thermofusible resin layer 4]
In the exterior material for a power storage device of the present disclosure, the heat-fusible resin layer 4 corresponds to the innermost layer, and has a function of thermally fusing the heat-fusible resin layers to each other and sealing the power storage device element during assembly of the power storage device. This is a layer (sealant layer) that exhibits the following properties. The heat-fusible resin layer 4 includes a film. The film can function as a sealant film in the heat-fusible resin layer 4.

In the present disclosure, the heat-fusible resin layer 4 includes a film having a glass transition temperature (Tg) of 67° C. or lower. From the viewpoint of more suitably exhibiting the effects of the invention of the present disclosure, the glass transition temperature (Tg) is preferably 60°C or lower, more preferably 50°C or lower, and preferably 0°C or higher, more preferably The temperature is 10°C or higher, and preferable ranges include about 0 to 67°C, about 0 to 60°C, about 0 to 50°C, about 10 to 67°C, about 10 to 60°C, and about 10 to 50°C. The glass transition temperature (Tg) is a value measured by DMA (dynamic viscoelasticity measurement). Specifically, the glass transition temperature of the resin forming the film is measured by DMA (dynamic mechanical measurement). Measurements are made using commercially available equipment. The distance between the chucks was 10 mm, and a film cut out to a width of 5 mm and a length of 20 mm was installed.The measurement conditions were: heating from -30 to 250 °C at a heating rate of 5 °C/min, frequency: 10 Hz, static load of 70 g, The peak temperature of the loss sine (tan δ) obtained by dividing the loss modulus by the storage modulus when the strain is 5 μm is defined as the glass transition temperature. In addition, when the heat-fusible resin layer is formed of multiple layers containing different resins, the barrier layer and the heat-fusible resin layer are separated, and the glass transition temperature (Tg) of the heat-fusible resin layer is adjusted. When measured, the peak value of tan δ is obtained for each resin. For each layer included in the heat-fusible resin layer, it is possible to separately measure the infrared absorption spectrum or the like to correlate the type of resin included in each layer and its glass transition temperature (Tg).

In the present disclosure, since the heat-fusible resin layer 4 has a polyester structure with a relatively high melting point, deformation when a load such as tension is applied to the exterior material 10 for an electricity storage device in a high-temperature environment is suppressed. Ru. Furthermore, since the glass transition temperature (Tg) of the film included in the heat-fusible resin layer 4 is set to 67°C or lower, the flexibility of the film in low-temperature environments is good, and when a load is applied to the film, damage and breakage of the film can be suppressed. As a result, it can be considered that the exterior material for a power storage device of the present disclosure can exhibit high sealing strength in a wide range of temperature environments from low to high temperatures.

The glass transition temperature (Tg) of a film can be adjusted, for example, by increasing the proportion of copolymerized components (particularly parts that are not polyester structure A (polyester structure B, soft segments such as polyether structure)) of the resin that makes up the film. can be lowered.

Further, from the viewpoint of more suitably exhibiting the effects of the invention of the present disclosure, the melting peak temperature of the film is preferably 170°C or higher, more preferably 190°C or higher, even more preferably 200°C or higher, and preferably The temperature is 350°C or lower, more preferably 300°C or lower, even more preferably 270°C or lower, even more preferably 217°C, and the preferred ranges are about 170 to 350°C, 170 to 300°C, 170 to 270°C, 170 to About 217℃, about 190-350℃, about 190-300℃, about 190-270℃, about 190-217℃, about 200-350℃, about 200-300℃, about 200-270℃, 200-217℃ Examples include degree. The method for measuring the melting peak temperature is as follows.

<Measurement of melting peak temperature>
The melting peak temperature of the resin forming the film is measured in accordance with the provisions of JIS K7121:2012 (Plastic transition temperature measurement method (JIS K7121:1987 Supplement 1)). The measurement is performed using a differential scanning calorimeter (DSC, Differential Scanning Calorimeter Q200 manufactured by TA Instruments). After holding the measurement sample at -50 ° C. for 15 minutes, raising the temperature from -50 ° C. to 300 ° C. at a heating rate of 10 ° C./min, and measuring the first melting peak temperature P (° C.), Hold at 300°C for 2 minutes. Next, the temperature was lowered from 300°C to -50°C at a rate of 10°C/min and held for 15 minutes. Furthermore, the temperature is raised from -50°C to 300°C at a heating rate of 10°C/min, and the second melting peak temperature Q (°C) is measured. Note that the flow rate of nitrogen gas is 50 ml/min. By the above procedure, the melting peak temperature P (°C) measured at the first time and the melting peak temperature Q (°C) measured at the second time are determined, and the melting peak temperature measured at the first time is defined as the melting peak temperature. do.

From the viewpoint of more preferably exhibiting the effects of the invention of the present disclosure, the film preferably has a tensile elongation at break in a -30°C environment of 5% or more, more preferably 150% or more, and still more preferably 200% or more. , is also preferably 2000% or less, more preferably 1600% or less, even more preferably 500% or less, and the preferable ranges are about 5 to 2000%, about 5 to 1600%, about 5 to 500%, and 150 to 2000%. %, about 150-1600%, about 150-500%, about 200-2000%, about 200-1600%, about 200-500%, etc. The method for measuring the tensile elongation at break is as described below.

From the viewpoint of more preferably exhibiting the effects of the invention of the present disclosure, the film preferably has a tensile elongation at break in a 23°C environment of 5% or more, more preferably 400% or more, and still more preferably 500% or more, Further, it is preferably 2000% or less, more preferably 1600% or less, and even more preferably 850% or less, and the preferable ranges are about 5 to 2000%, about 5 to 1600%, about 5 to 850%, and 400 to 2000%. %, about 400-1600%, about 400-850%, about 500-2000%, about 500-1600%, about 500-850%, etc. The method for measuring the tensile elongation at break is as described below.

Further, from the viewpoint of more preferably exhibiting the effects of the invention of the present disclosure, the tensile elongation at break of the film in a 120°C environment is preferably 650% or more, more preferably 700% or more, still more preferably 750% or more, and It is preferably 800% or more, more preferably 850% or more, and preferably 2000% or less, more preferably 1600% or less, and the preferable ranges are about 650 to 2000%, 650 to 1600%, and 700 to They are about 2000%, about 700-1600%, about 750-2000%, about 750-1600%, about 800-2000%, about 800-1600%, about 850-2000%, about 850-1600%, etc. The method for measuring the tensile elongation at break is as described below.

In addition, from the viewpoint of more suitably exhibiting the effects of the invention of the present disclosure, the film preferably has a tensile elongation at break in a 150°C environment of 750% or more, more preferably 800% or more, and even more preferably 850% or more. More preferably 900% or more, and preferably 2000% or less, more preferably 1700% or less, still more preferably 1600% or less, and preferable ranges are about 750 to 2000%, about 750 to 1700%, and about 750%. ～1600%, 800-2000%, 800-1700%, 800-1600%, 850-2000%, 850-1700%, 850-1600%, 900-2000%, 900-1700 %, about 900 to 1600%, etc. The method for measuring tensile elongation at break is as follows.

<Measurement of tensile elongation at break of film (-30°C, 23°C, 120°C or 150°C)>
The tensile elongation at break is measured using a tensile testing machine in accordance with the regulations of JIS K7127. The test sample width is a JIS-K 6251-7 dumbbell type, the distance between gauge lines is 15 mm, the tensile speed is 50 mm/min, and the test environments are -30°C, 23°C, 120°C, and 150°C, respectively. The measurement is carried out three times each, and the average value of the three measurements is taken as the tensile elongation at break.

The tensile elongation at break of a film can be increased, for example, by increasing the proportion of copolymerized components of the resin constituting the film (particularly parts that are not polyester structure A (soft segments such as polyester structure B and polyether structure)). .

From the viewpoint of more preferably exhibiting the effects of the invention of the present disclosure, the indentation modulus (indentation modulus of the film) from the heat-fusible resin layer 4 side of the laminate constituting the exterior material is preferably about 0. It is 3 GPa or more, more preferably about 0.4 GPa or more, even more preferably about 0.5 GPa or more. From the same point of view, the indentation modulus of the film is preferably about 5 GPa or less, more preferably about 4 GPa or less, even more preferably about 3 GPa or less, even more preferably about 2 GPa or less, even more preferably about 1.5 GPa or less. The preferable range of the indentation modulus of the film is about 0.3 to 5 GPa, about 0.3 to 4 GPa, about 0.3 to 3 GPa, about 0.3 to 2 GPa, about 0.3 to 1.5 GPa, and about 0.3 to 4 GPa. 4 to 5 GPa, 0.4 to 4 GPa, 0.4 to 3 GPa, 0.4 to 2 GPa, 0.4 to 1.5 GPa, 0.5 to 5 GPa, 0.5 to 4 GPa, 0 Examples include about .5 to 5 GPa, about 0.5 to 2 GPa, and about 0.5 to 1.5 GPa. The method for measuring the indentation modulus is as follows.

[Measurement of indentation modulus]
The indentation modulus is based on ISO 14577:2015, and is determined by applying a Vickers indenter (a square pyramid with a facing angle of 136°) to the surface of the heat-sealing resin layer side of the laminate in an environment of approximately 23°C and approximately 60% RH. A method is used to measure the indentation modulus using an ultra-microload hardness tester equipped with a diamond indenter. The measurement is performed at a pushing speed of 0.1 μm/sec, a pushing depth of 2 μm, a holding time of 5 seconds, and a pulling speed of 0.1 μm/sec. The ultra-microload hardness tester is preferably Picodenter HM500 (manufactured by Fisher Instruments). At least five samples are measured, and the average of the measured values is taken as the value of the indentation modulus under that condition. It is preferable to use a suction stand or instant adhesive to fix the sample. When measuring the indentation modulus of a single film, the measurement is performed at the center of the main surface of the film.

In the present disclosure, the resin forming the film includes polyester structure A. Polyester structure A is obtained by condensation polymerization of an acid component and a polyol component. The acid component is selected from phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and the like. Further, the polyol component is selected from ethylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, diethylene glycol, polytetramethylene glycol, cyclohexanedimethanol, propanediol, and the like. It is more preferable that the polyester structure A is a polybutylene terephthalate structure. Polybutylene terephthalate structure is a structure formed by polymerizing terephthalic acid and 1,4-butanediol, and has two types of structural units: a structure derived from terephthalic acid and a structure derived from 1,4-butanediol. Contains.

In the present disclosure, the film is preferably formed of a resin containing three or more types of structural units. Here, the structural unit of the resin means the structural unit that constitutes the resin. For example, if the resin is a copolymer, at least two types of monomer units are the structural units of the resin (multiple units formed in the resin due to polymerization). unit of structure to be introduced). For example, polyester structure A is a structure in which a polycarboxylic acid (monomer) and a polyol (monomer) are dehydrated and condensed to form an ester bond, and the structure derived from the polycarboxylic acid (monomer unit (also called repeating unit) )) and a structure derived from polyol (monomer unit (also referred to as repeating unit)). Polybutylene terephthalate structure is a structure formed by polymerizing terephthalic acid and 1,4-butanediol, and has two types of structural units: a structure derived from terephthalic acid and a structure derived from 1,4-butanediol. (monomer unit). Note that there is no particular upper limit to the types of structural units for the resin forming the film, but it is, for example, about six types.

In the present disclosure, the constituent units of the resin are typically monomer units contained in the copolymer. However, the constituent units of the resin are not limited to monomer units forming the main chain of the copolymer, but also monomer units forming side chains (for example, monomer units introduced by graft polymerization etc.) This concept also includes monomer units (units derived from crosslinkable monomers) that constitute a crosslinked structure between main chains.

As mentioned above, in conventional electrolyte lithium ion batteries containing organic solvents, the film used for the heat-fusible resin layer of the exterior material is made of polypropylene film, etc. Durability (seal strength) decreases significantly. For example, polypropylene film is generally formed from a copolymer of propylene and ethylene as structural units, and its melting peak temperature is also below 170°C. Further, polyethylene terephthalate generally has a glass transition temperature (as measured by the above-mentioned DMA) of about 110 to 145°C.

From the viewpoint of more preferably exhibiting the effects of the invention of the present disclosure, the resin forming the film further includes at least one selected from the group consisting of polyether structure and polyester structure B, in addition to polyester structure A. It is more preferable. Polyester structure B is a different polyester structure from polyester structure A.

A polyether structure can be introduced into a resin by performing a polycondensation reaction between a polycarboxylic acid of polyester structure A (for example, terephthalic acid in the case of a polybutylene terephthalate structure) and a compound (monomer) having a polyether structure. can. It is desirable that the polyether structure constitutes the soft segment of the resin in the film, and as a compound (monomer) that constitutes such a soft segment by polycondensation reaction with the polyhydric carboxylic acid of polyester structure A, polytetra Examples include diols that can exhibit stretchability, such as methylene ether glycol and neopentyl glycol. The polyether structure is preferably a polyether structure derived from at least one selected from the group consisting of polytetramethylene ether glycol and neopentyl glycol. Polytetramethylene ether glycol, neopentyl glycol, etc. form structural units in the polyether structure of the resin. By introducing a polyether structure into the resin as a soft segment, the rubber elasticity of the resin increases and the resin becomes difficult to break, allowing high sealing strength to be suitably demonstrated in a wide range of temperature environments from low to high temperatures.

In addition, polyester structure B undergoes a polycondensation reaction with the polyols used in polyester structure A, such as ethylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, diethylene glycol, polytetramethylene glycol, cyclohexanedimethanol, and propanediol. It can be introduced into the resin by using a compound (monomer) that forms a polyester structure. It is desirable that polyester structure B constitutes a soft segment of the resin in the film, and compounds (monomers) that undergo polycondensation reaction with the polyol of polyester structure A to constitute such a soft segment include phthalic acid and terephthalic acid. , aromatic dicarboxylic acids such as isophthalic acid and naphthalene dicarboxylic acid, and aliphatic dicarboxylic acids (preferably aliphatic dicarboxylic acids having 4 to 20 carbon atoms) such as adipic acid, sebacic acid, dodecanedioic acid, and cyclohexanedicarboxylic acid. Examples include dicarboxylic acids. Aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and the like form structural units in the polyester structure B of the resin. It is particularly preferable that the polyester structure B is a polyester structure formed by polycondensation of a polyol and at least one dicarboxylic acid selected from the group consisting of isophthalic acid, sebacic acid, and dodecanedioic acid. By introducing polyester structure B as a soft segment into the resin, the rubber elasticity of the resin increases and the resin becomes difficult to break, so that high sealing strength is suitably exhibited in a wide range of temperature environments from low to high temperatures.

From the viewpoint of more preferably exhibiting the effects of the invention of the present disclosure, the resin forming the film further includes a polyether structure in addition to the polybutylene terephthalate structure, and the polyether structure is composed of polytetramethylene ether glycol and It is particularly preferable to have a polycondensation structure of at least one of neopentyl glycol and terephthalic acid having a polybutylene terephthalate structure. In addition to the polybutylene terephthalate structure, the resin forming the film further includes a polyester structure B, and the polyester structure B is at least one member selected from the group consisting of isophthalic acid, dodecanedioic acid, and sebacic acid. It is particularly preferable to have a polycondensation structure of a seed and 1,4-butanediol having a polybutylene terephthalate structure.

Moreover, from the viewpoint of more suitably exhibiting the effects of the invention of the present disclosure, the resin forming the film preferably has a polyester structure A as a main component, and more preferably has a polybutylene terephthalate structure as a main component. In addition, the main component refers to a component whose proportion to 100 mol% (the same applies hereinafter) of all components constituting the resin is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. It means that. In addition, in the resin forming the sealant film, the proportion of at least one of the polyether structure and the dicarboxylic acid structure is preferably about 2 to 30 mol% with respect to 100 mol% of all components (all monomer units) constituting the resin. , more preferably about 3 to 25 mol%, still more preferably about 3 to 20 mol%.

The heat-fusible resin layer 4 may be composed of a single layer, as shown in FIG. 5, for example, or may be composed of two or more layers, as shown in FIGS. 6 and 7, for example. . FIG. 6 shows a heat-fusible resin layer 4 composed of a laminate in which a first layer 41 on the barrier layer 3 side and a second layer 42 on the innermost layer side are laminated, and FIG. The heat-fusible resin layer 4 is shown as a laminate in which a third layer 43 on the side, a first layer 41 located in the middle, and a second layer 42 on the innermost side are laminated in this order.

When the heat-fusible resin layer 4 is composed of two or more layers, at least one layer of the two or more layers is the film of the present disclosure (that is, the glass transition temperature is 67° C. or lower, and the film is It is preferable that the resin forming the polyester structure (containing a polyester structure A) is preferable. That is, when the heat-fusible resin layer 4 is composed of two or more layers, at least one of the two or more layers has a glass transition temperature of 67° C. or lower, and The resin forming the film has at least the polyester structure A, but the other layers do not need to have a glass transition temperature of 67° C. or lower or do not need to have the polyester structure A. When the heat-fusible resin layer 4 is composed of two or more layers, the surface of the heat-fusible resin layer 4 on the side opposite to the barrier layer 3 (i.e., the innermost layer surface of the exterior material 10 for an electricity storage device) is Preferably, the film is formed of the film of the present disclosure. In FIGS. 6 and 7, at least the second layer 42 is preferably the film of the present disclosure. When the heat-fusible resin layer 4 is composed of two or more layers, it is also preferable that all the layers are formed of the film of the present disclosure. Note that when the heat-fusible resin layer is formed of multiple layers containing different resins, each layer can be separated and the melting peak temperature of each layer can be measured.

Further, the heat-fusible resin layer 4 may contain a lubricant or the like as necessary. When the heat-fusible resin layer 4 contains a lubricant, the moldability of the exterior material for a power storage device can be improved. The lubricant is not particularly limited, and any known lubricant can be used. One type of lubricant may be used alone, or two or more types may be used in combination.

The lubricant is not particularly limited, but preferably includes an amide lubricant. Specific examples of the lubricant include those exemplified for the base layer 1. One type of lubricant may be used alone, or two or more types may be used in combination.

In the present disclosure, from the viewpoint of improving the moldability of the exterior material for a power storage device, it is preferable that a lubricant be present on at least one of the surface and inside of the heat-fusible resin layer 4. The lubricant is not particularly limited, but preferably includes an amide lubricant. Specific examples of amide lubricants include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides, and the like. Specific examples of saturated fatty acid amides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, and the like. Specific examples of unsaturated fatty acid amides include oleic acid amide and erucic acid amide. Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, and the like. Furthermore, specific examples of methylolamide include methylolstearamide and the like. Specific examples of saturated fatty acid bisamides include methylene bisstearamide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbehenic acid amide, and hexamethylene bis stearic acid amide. Examples include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N,N'-distearyl adipic acid amide, N,N'-distearyl sebacic acid amide, and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyladipic acid amide, and N,N'-dioleyl sebacic acid amide. Examples include. Specific examples of fatty acid ester amides include stearamide ethyl stearate. Specific examples of aromatic bisamides include m-xylylene bisstearamide, m-xylylene bishydroxystearamide, and N,N'-distearylisophthalic acid amide. One type of lubricant may be used alone or two or more types may be used in combination, and a combination of two or more types is preferably used.

When a lubricant is present on the surface of the heat-fusible resin layer 4, the amount thereof is not particularly limited, but from the viewpoint of improving the moldability of the exterior material for an electricity storage device, it is preferably about 1 mg/m ² or more, More preferably about 3 mg/m ² or more, still more preferably about 5 mg/m ² or more, even more preferably about 10 mg/m ² or more, even more preferably about 15 mg/m ² or more, and preferably about 50 mg/m 2 ² or less, more preferably about 40 mg/m ² or less, and preferred ranges are about 1 to 50 mg/m ² , about 1 to 40 mg/m ² , about 3 to 50 mg/m ² , and 3 to 40 mg/m ^{2 The degree of _ _ _} Can be mentioned.

When a lubricant is present inside the heat-fusible resin layer 4, its amount is not particularly limited, but from the viewpoint of improving the moldability of the exterior material for an electricity storage device, it is preferably about 100 ppm or more, more preferably about 100 ppm or more. It is about 300 ppm or more, more preferably about 500 ppm or more, and preferably about 3000 ppm or less, more preferably about 2000 ppm or less, and the preferable range is about 100 to 3000 ppm, about 100 to 2000 ppm, about 300 to 3000 ppm, Examples include about 300 to 2000 ppm, about 500 to 3000 ppm, and about 500 to 2000 ppm. When two or more types of lubricants are present inside the heat-fusible resin layer 4, the above amount of lubricant is the total amount of lubricant. In addition, when two or more types of lubricants are present inside the heat-fusible resin layer 4, the amount of the first type of lubricant is not particularly limited, but from the viewpoint of improving the moldability of the exterior material for power storage devices, It is preferably about 100 ppm or more, more preferably about 300 ppm or more, even more preferably about 500 ppm or more, and preferably about 3000 ppm or less, more preferably about 2000 ppm or less, and the preferable range is about 100 to 3000 ppm, 100 ppm or more. Examples include about ~2000 ppm, about 300 to 3000 ppm, about 300 to 2000 ppm, about 500 to 3000 ppm, and about 500 to 2000 ppm. The amount of the second type of lubricant is not particularly limited, but from the viewpoint of improving the moldability of the exterior material for power storage devices, it is preferably about 50 ppm or more, more preferably about 100 ppm or more, and still more preferably about 200 ppm or more. Also, preferably about 1,500 ppm or less, more preferably about 1,000 ppm or less, and preferable ranges include about 50 to 1,500 ppm, about 50 to 1,000 ppm, about 100 to 1,500 ppm, about 100 to 1,000 ppm, about 200 to 1,500 ppm, and about 200 to 1,500 ppm. An example is about 1000 ppm.

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

Further, the thickness of the heat-fusible resin layer 4 is not particularly limited as long as the heat-fusible resin layers exhibit the function of thermally fusing each other and sealing the electricity storage device element, but is preferably about 100 μm or less, for example. The thickness is about 85 μm or less, more preferably about 15 to 85 μm. Note that, for example, when the thickness of the adhesive layer 5 described below is 10 μm or more, the thickness of the heat-fusible resin layer 4 is preferably about 85 μm or less, more preferably about 15 to 45 μm, for example. When the thickness of the adhesive layer 5 described below is less than 10 μm or when the adhesive layer 5 is not provided, the thickness of the heat-fusible resin layer 4 is preferably about 20 μm or more, more preferably 35 to 85 μm. The degree is mentioned.

(Method for manufacturing film)
The method for producing the film included in the heat-fusible resin layer 4 is not particularly limited as long as the film of the present disclosure can be obtained, and any known or conventional film forming method or lamination method can be applied. The film can be produced by a known film forming method and/or lamination method, such as an extrusion method, a coextrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, and the like. When there are two or more films included in the heat-fusible resin layer 4, for example, the films constituting each layer prepared in advance may be laminated via an adhesive layer. A molten resin composition may be laminated on the layer by extrusion or coextrusion, a plurality of layers may be simultaneously produced and laminated by melt compression bonding, or one or two types of resin composition may be laminated on the other layer. The above resin may be applied and dried for coating.

The heat-fusible resin layer 4 including a film can be formed by laminating the layers contained in the heat-fusible resin layer 4 by extrusion or co-extrusion using an extrusion coating method, or by adhering the layers after film formation by an inflation method or a casting method. They can also be laminated with layers interposed therebetween. Even in the case of the extrusion coating method, lamination may be performed via an adhesive layer if necessary. Alternatively, pre-formed films for the water absorption layer (or sulfur-based gas absorption layer) are laminated and adhered via an adhesive layer laminated by an extrusion coating method, dry lamination method, non-solvent lamination method, etc. Good too. Then, aging processing may be performed as necessary.

For example, when laminating films etc. using the extrusion coating method, first, the resin forming the film is heated and melted, expanded and stretched in the required width direction with a T die, and (co)extruded into a curtain shape. By flowing the molten resin onto the surface to be laminated and sandwiching it between a rubber roll and a cooled metal roll, formation of the layer and lamination and adhesion to the surface to be laminated can be performed simultaneously. The melt flow rate (MFR) of each resin component when laminated by extrusion coating is preferably 0.2 to 50 g/10 minutes, more preferably 0.5 to 30 g/10 minutes. If the MFR is smaller or larger than the above range, processing suitability tends to be poor. Note that in this specification, MFR is a value measured using a method based on JIS K7210.

The melt flow rate (MFR) of the resin component when using the inflation method is preferably 0.2 to 10 g/10 minutes, more preferably 0.2 to 9.5 g/10 minutes. If the MFR is smaller or larger than the above range, processing suitability tends to be poor.

In addition, when the heat-fusible resin layer 4 is composed of two or more layers, in order to improve adhesion between each layer constituting the heat-fusible resin layer 4 including the film, the surface of each layer is If necessary, a desired surface treatment can be performed in advance. For example, pretreatment such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. is optionally performed to form a corona treatment layer, ozone treatment, etc. A layer, a plasma treatment layer, an oxidation treatment layer, etc. can be formed and provided. Alternatively, various coating agent layers such as a primer coating agent layer, an undercoating agent layer, an anchor coating agent layer, an adhesive layer, and a vapor-deposited anchor coating agent layer can be arbitrarily formed on the surface to form a surface treatment layer. . The various coating agent layers mentioned above include, for example, polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth)acrylic resins, polyvinyl acetate resins, and polyolefins such as polyethylene or polypropylene. A resin composition in which the main component of the vehicle is a resin, a copolymer or modified resin thereof, a cellulose resin, etc. can be used.

The layers included in the heat-fusible resin layer 4 can further be uniaxially or biaxially stretched by a conventionally known method using a tenter method, a tubular method, or the like, if necessary.

[Adhesive layer 5]
In the exterior material for a power storage device of the present disclosure, the adhesive layer 5 is provided between the barrier layer 3 (or corrosion-resistant film) and the heat-fusible resin layer 4 as necessary in order to firmly adhere them. This is the layer where

The adhesive layer 5 is formed of a resin that can bond the barrier layer 3 and the heat-fusible resin layer 4 together. As the resin used for forming the adhesive layer 5, for example, the same adhesive as the adhesive exemplified for the adhesive layer 2 can be used.

Further, from the viewpoint of further increasing the adhesion between the barrier layer 3 and the adhesive layer 5, the adhesive layer 5 is made of at least one selected from the group consisting of oxygen atoms, heterocycles, C=N bonds, and C-O-C bonds. It is preferable that it is a cured product of a resin composition containing one type of curing agent. Examples of the curing agent having a heterocycle include a curing agent having an oxazoline group, a curing agent having an epoxy group, and the like. Furthermore, examples of the curing agent having a C=N bond include a curing agent having an oxazoline group, a curing agent having an isocyanate group, and the like. Further, examples of the curing agent having a C--O--C bond include a curing agent having an oxazoline group, a curing agent having an epoxy group, and the like. The fact that the adhesive layer 5 is a cured product of a resin composition containing these curing agents can be achieved by, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF). -SIMS), X-ray photoelectron spectroscopy (XPS), and other methods.

The compound having an isocyanate group is not particularly limited, but from the viewpoint of effectively increasing the adhesion between the barrier layer 3 and the adhesive layer 5, polyfunctional isocyanate compounds are preferably used. The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of polyfunctional isocyanate curing agents include pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and these can be polymerized or nurated. Examples include polymers, mixtures thereof, and copolymers with other polymers. Further examples include adducts, biurets, isocyanurates, and the like.

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

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

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

Examples of compounds having epoxy groups include epoxy resins. The epoxy resin is not particularly limited as long as it is a resin that can form a crosslinked structure by the epoxy groups present in the molecule, and any known epoxy resin can be used. The weight average molecular weight of the epoxy resin is preferably about 50 to 2,000, more preferably about 100 to 1,000, and still more preferably about 200 to 800. In the present disclosure, the weight average molecular weight of the epoxy resin is a value measured by gel permeation chromatography (GPC) under conditions using polystyrene as a standard sample.

Specific examples of epoxy resins include trimethylolpropane glycidyl ether derivatives, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, bisphenol F type glycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, etc. can be mentioned. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The proportion of the epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and preferably in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. is more preferable. Thereby, the adhesion between the barrier layer 3 and the adhesive layer 5 can be effectively improved.

The polyurethane is not particularly limited, and any known polyurethane can be used. The adhesive layer 5 may be, for example, a cured product of two-part curable polyurethane.

The proportion of polyurethane in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and preferably in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. More preferred. Thereby, it is possible to effectively improve the adhesion between the barrier layer 3 and the adhesive layer 5 in an atmosphere where a component that induces corrosion of the barrier layer, such as an electrolytic solution, is present.

In addition, when 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. , 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.

The adhesive layer 5 may contain a modifier having a carbodiimide group.

Moreover, it is also preferable that the adhesive layer 5 is formed of a cured product of a resin composition containing at least one of polyester and polycarbonate, and at least one of an alicyclic isocyanate compound and an aromatic isocyanate compound.

Preferably, the polyester is a polyester polyol. The polyester polyol is not particularly limited as long as it has an ester bond in the polymer main chain and a plurality of hydroxyl groups at the terminal or side chain. Further, the polycarbonate is preferably a polycarbonate polyol. The polyester polyol is not particularly limited as long as it has a carbonate bond in the polymer main chain and a plurality of hydroxyl groups at the terminal or side chain. The number of polyesters and polycarbonates contained in the resin composition forming the adhesive layer 5 may be one, or two or more.

The alicyclic isocyanate compound is not particularly limited as long as it has an alicyclic structure and an isocyanate group. It is preferable that the alicyclic isocyanate compound has two or more isocyanate groups. Specific examples of alicyclic isocyanate compounds include isophorone diisocyanate (IPDI), polymerized or nurated compounds thereof, mixtures thereof, and copolymers with other polymers. Further examples include adduct bodies, bullet bodies, isocyanurate bodies, and the like. The number of alicyclic isocyanate compounds contained in the resin composition forming the adhesive layer 5 may be one type, or two or more types.

Further, the aromatic isocyanate compound is not particularly limited as long as it is a compound having an aromatic ring and an isocyanate group. It is preferable that the aromatic isocyanate compound has two or more isocyanate groups. Specific examples of aromatic isocyanate compounds include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymerized or nurated products thereof, mixtures thereof, and copolymers with other polymers. Further examples include adduct bodies, bullet bodies, isocyanurate bodies, and the like. The number of aromatic isocyanate compounds contained in the resin composition forming the adhesive layer 5 may be one type, or two or more types.

When the resin composition forming the adhesive layer 5 includes at least one of an alicyclic isocyanate compound and an aromatic isocyanate compound, for example, the alicyclic isocyanate compound may be included and the aromatic isocyanate compound may not be included. However, for example, an aromatic isocyanate compound may be included and an alicyclic isocyanate compound may not be included, or, for example, both an alicyclic isocyanate compound and an aromatic isocyanate compound may be included.

The content of the alicyclic isocyanate compound and the aromatic isocyanate compound in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass in the resin composition constituting the adhesive layer 5, and 0. More preferably, the content is in the range of .5 to 40% by mass. In addition, when the adhesive layer 5 contains both an alicyclic isocyanate compound and an aromatic isocyanate compound, the total content of these compounds is in the range of 0.1 to 50% by mass in the resin composition constituting the adhesive layer 5. It is preferably in the range of 0.5 to 40% by mass, and more preferably in the range of 0.5 to 40% by mass.

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. Further, the thickness of the adhesive layer 5 is preferably about 0.1 μm or more and about 0.5 μm or more. Further, the thickness range of the adhesive layer 5 is preferably about 0.1 to 50 μm, about 0.1 to 40 μm, about 0.1 to 30 μm, about 0.1 to 20 μm, and about 0.1 to 5 μm. , about 0.5 to 50 μm, about 0.5 to 40 μm, about 0.5 to 30 μm, about 0.5 to 20 μm, and about 0.5 to 5 μm. More specifically, in the case of the adhesive exemplified in adhesive layer 2, the thickness is preferably about 1 to 10 μm, more preferably about 1 to 5 μm. In addition, when the adhesive layer 5 is a cured product of a resin composition containing the adhesive exemplified in the adhesive layer 2, the adhesive layer 5 can be formed by, for example, applying the resin composition and curing it by heating or the like. can do.

[Surface coating layer 6]
The exterior material for a power storage device of the present disclosure is provided on the base material layer 1 (base material layer 1 A surface coating layer 6 may be provided on the opposite side of the barrier layer 3). The surface coating layer 6 is a layer located on the outermost layer side of the exterior material for a power storage device when the power storage device is assembled using the exterior material for a power storage device.

Examples of the surface coating layer 6 include resins such as polyvinylidene chloride, polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicone resin, and phenol resin, and modified products of these resins. Further, it may be a copolymer of these resins or a modified product of the copolymer. Furthermore, a mixture of these resins may be used. The resin is preferably a curable resin. That is, the surface coating layer 6 is preferably composed of a cured product of a resin composition containing a curable resin.

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

Examples of the two-part curable polyurethane include polyurethanes containing a first part containing a polyol compound and a second part containing an isocyanate compound. Preferred examples include two-component curing polyurethanes in which a polyol such as a polyester polyol, a polyether polyol, or an acrylic polyol is used as a first part and an aromatic or aliphatic polyisocyanate is used as a second part. Examples of the polyurethane include polyurethane containing a polyurethane compound prepared by reacting a polyol compound and an isocyanate compound in advance, and an isocyanate compound. Examples of the polyurethane include a polyurethane compound prepared by reacting a polyol compound and an isocyanate compound in advance, and a polyurethane containing a polyol compound. Examples of the polyurethane include polyurethane obtained by curing a polyurethane compound obtained by reacting a polyol compound and an isocyanate compound in advance with moisture in the air. As the polyol compound, it is preferable to use a polyester polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the end of the repeating unit. Examples of the second agent include aliphatic, alicyclic, aromatic, and araliphatic isocyanate compounds. Examples of isocyanate compounds include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), tolylene diisocyanate (TDI), and diphenylmethane diisocyanate. (MDI), naphthalene diisocyanate (NDI), and the like. Also included are polyfunctional isocyanate modified products of one or more of these diisocyanates. It is also possible to use multimers (for example trimers) as the polyisocyanate compound. Such multimers include adducts, biurets, nurates, and the like. In addition, an aliphatic isocyanate-based compound refers to an isocyanate that has an aliphatic group and does not have an aromatic ring, and an alicyclic isocyanate-based compound refers to an isocyanate that has an alicyclic hydrocarbon group. refers to an isocyanate having an aromatic ring. Since the surface coating layer 6 is made of polyurethane, the exterior material for the electricity storage device has excellent electrolyte resistance.

The surface coating layer 6 may contain the above-mentioned lubricant or anti-oxidant on at least one of the surface and inside of the surface coating layer 6, depending on the functionality to be provided to the surface coating layer 6 and its surface. It may contain additives such as blocking agents, matting agents, flame retardants, antioxidants, tackifiers, and antistatic agents. Examples of the additive include fine particles having an average particle diameter of about 0.5 nm to 5 μm. The average particle diameter of the additive is the median diameter measured by a laser diffraction/scattering particle size distribution measuring device.

The additive may be either inorganic or organic. Further, the shape of the additive is not particularly limited, and examples include spherical, fibrous, plate-like, amorphous, and scaly shapes.

Specific examples of additives 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 nanotubes, high melting point nylon, acrylate resin, Examples include crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, and nickel. The additives may be used alone or in combination of two or more. Among these additives, silica, barium sulfate, and titanium oxide are preferred from the viewpoint of dispersion stability and cost. Further, the additive may be subjected to various surface treatments such as insulation treatment and high dispersion treatment.

The method for forming the surface coating layer 6 is not particularly limited, and examples thereof include a method of applying a resin that forms the surface coating layer 6. When adding additives to the surface coating layer 6, a resin mixed with the additives may be applied.

The thickness of the surface coating layer 6 is not particularly limited as long as it exhibits the above-mentioned function as the surface coating layer 6, and may be, for example, about 0.5 to 10 μm, preferably about 1 to 5 μm.

3. Method for manufacturing an exterior material for an energy storage device The method for manufacturing an exterior material for an energy storage device is not particularly limited as long as a laminate in which each layer of the exterior material for an energy storage device of the present invention is laminated can be obtained. A method may include a step of laminating layer 1, barrier layer 3, and heat-fusible resin layer 4 in this order.

An example of the method for manufacturing the exterior material for a power storage device of the present invention is as follows. First, a laminate (hereinafter sometimes referred to as "laminate A") in which a base material layer 1, an adhesive layer 2, and a barrier layer 3 are laminated in this order is formed. Specifically, the formation of the laminate A is performed by applying the adhesive used for forming the adhesive layer 2 on the base layer 1 or on the barrier layer 3 whose surface has been subjected to a chemical conversion treatment as necessary, using a gravure coating method, It can be carried out by a dry lamination method in which the barrier layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after coating and drying by a coating method such as a roll coating method.

Next, a heat-fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A. When the heat-fusible resin layer 4 is directly laminated on the barrier layer 3, the heat-fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A by a method such as a thermal lamination method or an extrusion lamination method. do it. Further, when the adhesive layer 5 is provided between the barrier layer 3 and the heat-fusible resin layer 4, the adhesive layer 5 and the heat-fusible resin layer 4 can be formed by, for example, (1) extrusion lamination, (2) Lamination can be performed by a thermal lamination method, (3) a sandwich lamination method, (4) a dry lamination method, or the like. (1) As an extrusion lamination method, for example, a method of extruding and laminating the adhesive layer 5 and the heat-fusible resin layer 4 on the barrier layer 3 of the laminate A (co-extrusion lamination method, tandem lamination method) Examples include. (2) Thermal lamination method includes, for example, a method in which a laminate is formed in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated separately, and this is laminated on the barrier layer 3 of the laminate A; , a method of forming a laminate in which the adhesive layer 5 is laminated on the barrier layer 3 of the laminate A, and laminating this with the heat-fusible resin layer 4, and the like. (3) As a sandwich lamination method, for example, while pouring the molten adhesive layer 5 between the barrier layer 3 of the laminate A and the heat-fusible resin layer 4 formed into a sheet shape in advance, , a method of bonding the laminate A and the heat-fusible resin layer 4 via the adhesive layer 5, and the like. (4) As a dry lamination method, for example, the barrier layer 3 of the laminate A is coated with a solution of an adhesive to form the adhesive layer 5, and then laminated by a method of drying or a method of baking. For example, a method may be used in which a heat-fusible resin layer 4 previously formed in a sheet form is laminated on the adhesive layer 5.

When providing the surface coating layer 6, the surface coating layer 6 is laminated on the surface of the base material layer 1 on the side opposite to the barrier layer 3. The surface coating layer 6 can be formed, for example, by applying the above resin for forming the surface coating layer 6 onto the surface of the base material layer 1. Note that the order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer 6 on the surface of the base material layer 1 is not particularly limited. For example, after forming the surface coating layer 6 on the surface of the base material layer 1, the barrier layer 3 may be formed on the surface of the base material layer 1 on the opposite side to the surface coating layer 6.

As described above, surface coating layer 6 provided as necessary/base material layer 1/adhesive layer 2 provided as necessary/barrier layer 3/adhesive layer 5 provided as necessary/thermal fusion A laminate including the adhesive resin layers 4 in this order is formed, but in order to strengthen the adhesiveness of the adhesive layer 2 and the adhesive layer 5 provided as necessary, it may be further subjected to heat treatment.

In the exterior material for a power storage device, each layer constituting the laminate may be subjected to surface activation treatment such as corona treatment, blasting treatment, oxidation treatment, or ozone treatment to improve processing suitability, if necessary. . For example, by subjecting the surface of the base layer 1 opposite to the barrier layer 3 to a corona treatment, the printability of the ink on the surface of the base layer 1 can be improved.

4. Application of exterior packaging material for power storage devices The exterior packaging material for power storage devices of the present disclosure is used for a package for sealing and accommodating power storage device elements such as a positive electrode, a negative electrode, and an electrolyte. That is, a power storage device element including at least a positive electrode, a negative electrode, and an electrolyte can be housed in a package formed of the exterior material for a power storage device according to the present disclosure to form a power storage device.

Specifically, an electricity storage device element including at least a positive electrode, a negative electrode, and an electrolyte is prepared using the exterior material for an electricity storage device of the present disclosure, with metal terminals connected to each of the positive electrode and the negative electrode protruding outward. , Covering the electricity storage device element so that a flange portion (an area where the heat-fusible resin layers contact each other) is formed around the periphery of the power storage device element, and sealing the heat-fusible resin layers of the flange portion by heat-sealing each other. provides an electricity storage device using an exterior material for an electricity storage device. Note that when a power storage device element is housed in a package formed of the power storage device exterior material of the present disclosure, the heat-fusible resin portion of the power storage device exterior material of the present disclosure is placed on the inside (the surface in contact with the power storage device element). ) to form a package. The heat-fusible resin layers of two exterior materials for power storage devices may be stacked facing each other, and the peripheral edges of the stacked exterior materials for power storage devices may be heat-sealed to form a package; As in the example shown in FIG. 8, a package may be formed by folding and overlapping one exterior material for a power storage device and heat-sealing the peripheral edge. In the case of folding and overlapping, as shown in the example shown in Fig. 8, the sides other than the folded sides may be heat-sealed and a three-sided seal may be used to form a package, or the package may be folded back so that a flange can be formed. It may be sealed on all sides, or the exterior material for the power storage device is wrapped around the power storage device element and the heat-sealable resin layers are sealed to form a heat-sealed part and the openings at both ends are closed. A lid body etc. may be arranged as shown in FIG. Further, a recessed portion for accommodating the power storage device element may be formed in the exterior material for the power storage device by deep drawing or stretch molding. As in the example shown in FIG. 8, one exterior material for an energy storage device may have a recess and the other exterior material for an energy storage device may not have a recess, or the other exterior material for an energy storage device may also have a recess. may be provided.

The exterior material for power storage devices of the present disclosure can be suitably used for power storage devices such as batteries (including capacitors, capacitors, etc.). Further, the exterior material for a power storage device of the present disclosure may be used for either a primary battery or a secondary battery, but is preferably used for a secondary battery. The types of secondary batteries to which the exterior material for power storage devices of the present disclosure is applied are not particularly limited, and include, for example, lithium-ion batteries, lithium-ion polymer batteries, all-solid-state batteries, semi-solid-state batteries, pseudo-solid-state batteries, and polymer batteries. , all-resin batteries, lead-acid batteries, nickel-hydrogen batteries, nickel-cadmium batteries, nickel-iron batteries, nickel-zinc batteries, silver-zinc oxide batteries, metal-air batteries, polyvalent cation batteries, capacitors, capacitors, etc. . Among these secondary batteries, lithium ion batteries, lithium ion polymer batteries, and all-solid-state batteries are suitable for application of the exterior material for power storage devices of the present disclosure, and it is particularly preferably used for all-solid-state batteries.

The present disclosure will be explained in detail by showing Examples and Comparative Examples below. However, the present disclosure is not limited to the examples.

<Production of film>
(Examples 1 to 5 and Comparative Examples 1 to 2)
The resins used to form the films of the heat-fusible resin layers in Examples 1 and 2 each had two structural units of terephthalic acid and 1,4-butanediol forming the polybutylene terephthalate structure as the main components. Furthermore, a polyether structure is block polymerized as a subcomponent to a polybutylene terephthalate structure. The polyether structure is a structure in which polytetramethylene ether glycol is copolymerized with the above-mentioned terephthalic acid and introduced into the resin as the third type of structural unit. Therefore, the resin that forms the film has a polybutylene terephthalate structure (terephthalic acid and 1,4-butanediol as monomer units are two types of structural units) and a polyether structure (polytetramethylene ether as a monomer unit). glycol serves as one type of structural unit), and has a structure in which a total of three types of structural units are copolymerized. The resins forming the films of the heat-fusible resin layers of Examples 1 and 2 each contained a molar ratio of terephthalic acid, 1,4-butanediol, and polytetramethylene glycol (residual terephthalic acid) as monomer units. group: 1,4-butanediol residue: polytetramethylene glycol residue) in a ratio of 100:95:5. The difference between Example 1 and Example 2 is the difference in the ratio of polytetramethylene ether glycol, and Example 1 has a higher ratio.

In addition, in the resins used to form the films of the heat-fusible resin layers in Examples 3 and 4, polyester structure B was block polymerized into a polybutylene terephthalate structure instead of the polyether structure in Examples 1 and 2, respectively. It is what was done. Polyester structure B is a structure in which dodecanedioic acid (dodecanedioic acid) is introduced into the resin by copolymerizing with the above-mentioned 1,4-butanediol as the third type of structural unit. Therefore, the resin forming the film has a polybutylene terephthalate structure (terephthalic acid and 1,4-butanediol as monomer units are two types of structural units) and a polyester structure B (dodecanedioic acid as a monomer unit). , one type of structural unit), and has a structure in which a total of three types of structural units are copolymerized. The difference between Example 3 and Example 4 is that Example 4 uses a resin of one type of molecular weight, whereas Example 3 uses a mixture of resins of two types of molecular weight. In addition, the resin forming the film of the heat-fusible resin layer of Example 3 contained, as monomer units, a molar ratio of terephthalic acid, 1,4-butanediol, and dodecanedioic acid (terephthalic acid residue: 1 , 4-butanediol residue: dodecanedioic acid residue) in a ratio of 100:112:13. In the resin forming the film of the heat-fusible resin layer of Example 4, the molar ratio of terephthalic acid, 1,4-butanediol, and dodecanedioic acid (terephthalic acid residue: 1,4 -butanediol residue:dodecanedioic acid residue) in a ratio of 100:110:13.

Further, in the resin of Example 5, isophthalic acid was block polymerized into a polybutylene terephthalate structure as polyester structure B instead of dodecanedioic acid in Examples 3 and 4. Therefore, the resin of Example 5 has a polybutylene terephthalate structure (terephthalic acid and 1,4-butanediol as monomer units are two types of structural units) and a polyester structure B (isophthalic acid and 1,4-butanediol as monomer units are (constitutes one type of structural unit), and has a structure in which a total of three types of structural units are copolymerized. In the resin forming the film of the heat-fusible resin layer of Example 5, the molar ratio of terephthalic acid, 1,4-butanediol, and isophthalic acid (terephthalic acid residue: 1,4- butanediol residue: isophthalic acid residue) in a ratio of 100:110:11.

In Comparative Example 1, polybutylene terephthalate (consisting of two types of structural units: terephthalic acid and 1,4-butanediol) was prepared as a resin. Furthermore, in Comparative Example 2, polypropylene (constituent units are two types, propylene and ethylene) was prepared as the resin.

Next, each resin was subjected to extrusion molding to produce a film (50 μm thick for Examples 1 to 5 and Comparative Example 1, 80 μm thick for Comparative Example 2).

The composition of the resin forming the film of the heat-fusible resin layer was confirmed as follows. Regarding GCMS, a derivatization method was applied as a pretreatment, and then GCMS measurement was performed. In the 450° C. simultaneous derivatization method, approximately 0.1 mg of the sample was placed in a sample cup, 1 μl of TMAH was added dropwise, and measurements were performed under the following conditions to qualitatively characterize the structure contained in the resin. As the apparatus, 7890A/5975C (Agilent Technologies) and pyrolysis furnace AS-1020E (Frontier Lab) were used. InertCap 5MS/Sil was used as a column. The temperature raising conditions were: held at 50°C for 5 minutes, heated at 10°C/min, and held at 320°C for 3 minutes. The split ratio was 1:50. Next, for NMR, as a pretreatment, the sample was dissolved in HFIP to a concentration of about 4 wt %, and diluted 2 times with CDCl ₃ . NMR measurement was carried out using an apparatus: AVANCE III HD (BRUKER) under the following conditions, and the structure was identified. The nuclide was 1H, the solvent was CDCl ₃ +HFIP (1:1), room temperature, and the number of integrations was 64.

<Manufacture of exterior materials>
As the base material layer, a polyethylene terephthalate film (thickness 25 μm in Examples 1 to 5 and Comparative Example 1) was prepared by corona treatment on the bonding surface side. In addition, in Comparative Example 2, a film in which a polyethylene terephthalate film (thickness: 12 μm) and a nylon film (thickness: 15 μm) were laminated using a two-component curable urethane adhesive was prepared as a base material layer (polyethylene terephthalate film). (I used it so that the side was on the outside). Further, an aluminum alloy foil (JIS H4160:1994 A8021H-O, thickness 40 μm) was prepared as a barrier layer. In addition, each of the above-mentioned films was used as the heat-fusible resin layer. Next, the base material layer and barrier layer are bonded together by dry lamination using a two-component curable urethane adhesive (polyester polyol and alicyclic isocyanate compound), and the base material layer/adhesive layer/barrier layer is bonded together. A laminate was produced in which the layers were stacked in order.

Next, the barrier layer side of the obtained laminate is adhered to the film by a dry lamination method using a two-component curable urethane adhesive (polyester polyol and alicyclic isocyanate compound), and the film is placed on top of the barrier layer. Adhesive layer (4 μm)/thermal adhesive resin layer (Examples 1 to 5 and Comparative Example 1 had a thickness of 50 μm, Comparative Example 2 had a thickness of 80 μm) were laminated. Next, the obtained laminate is aged and heated to form a laminate in which the base material layer/adhesive layer/barrier layer/adhesive layer/thermal adhesive resin layer (film) are laminated in this order. An exterior material for a power storage device was obtained.

<Measurement of glass transition temperature (Tg)>
The glass transition temperature of the resin forming the film was measured by DMA (dynamic mechanical analysis). The measurement was performed using Rheogel-E4000 manufactured by UBM. The distance between the chucks was 10 mm, and a film cut out to a width of 5 mm and a length of 20 mm was installed.The measurement conditions were: heating from -30 to 250 °C at a heating rate of 5 °C/min, frequency: 10 Hz, static load of 70 g, The peak temperature of the loss sine (tan δ) obtained by dividing the loss modulus by the storage modulus when the strain was set to 5 μm was defined as the glass transition temperature.

<Measurement of melting peak temperature>
The melting peak temperature of the resin forming the film was measured in accordance with the provisions of JIS K7121:2012 (Method for Measuring the Transition Temperature of Plastics (Addendum 1 to JIS K7121:1987)). The measurement was performed using a differential scanning calorimeter (DSC, differential scanning calorimeter Q200 manufactured by TA Instruments). After holding the measurement sample at -50 ° C. for 15 minutes, raising the temperature from -50 ° C. to 300 ° C. at a heating rate of 10 ° C./min, and measuring the first melting peak temperature P (° C.), It was held at 300°C for 2 minutes. Next, the temperature was lowered from 300°C to -50°C at a rate of 10°C/min and held for 15 minutes. Furthermore, the temperature was raised from -50°C to 300°C at a heating rate of 10°C/min, and the second melting peak temperature Q (°C) was measured. Note that the flow rate of nitrogen gas was 50 ml/min. By the above procedure, the melting peak temperature P (°C) measured at the first time and the melting peak temperature Q (°C) measured at the second time are determined, and the melting peak temperature measured at the first time is defined as the melting peak temperature. did.

<Measurement of tensile elongation at break of film (-30°C, 23°C, 120°C or 150°C)>
The tensile elongation at break was measured for each film. The measurement was carried out using a tensile tester (manufactured by Shimadzu Corporation, AG-Xplus (trade name)) in accordance with the regulations of JIS K7127. The test sample width was JIS-K 6251-7 dumbbell type, the distance between gauge lines was 15 mm, the tensile speed was 50 mm/min, and the test environments were -30°C, 23°C, 120°C, and 150°C, respectively. The measurement was performed three times each, and the average value of the three measurements was taken as the tensile elongation at break. The results are shown in Table 1.

[Measurement of indentation modulus]
The laminate was cut out, and the indentation modulus was measured from the heat-sealing resin layer side. The indentation modulus was measured in accordance with ISO 14577:2015, using a Vickers indenter (square pyramidal diamond indenter with a facing angle of 136°) attached to the surface of the sample in an environment of approximately 23°C and approximately 60% RH. A method of measuring the indentation modulus using a micro-load hardness tester was used. The measurement was performed at a pushing speed of 0.1 μm/sec, a pushing depth of 2 μm, a holding time of 5 seconds, and a pulling speed of 0.1 μm/sec. The ultra-microload hardness tester was Picodenter HM500 (manufactured by Fisher Instruments). At least five samples were measured, and the average of the measured values was taken as the value of the indentation modulus under that condition. A suction table was used to fix the sample. The results are shown in Table 1.

<Seal strength evaluation (-30°C, 23°C, 120°C, or 150°C environment)>
In accordance with the provisions of JIS K7127:1999, the seal strength of the exterior material at each measurement temperature of -30°C, 23°C, 120°C, or 150°C was measured as follows. A test sample is prepared by cutting the exterior material into a strip having a width of 15 mm in the TD direction. Specifically, as shown in FIG. 9, each exterior material was first cut into 60 mm (TD direction) x 200 mm (MD direction) (FIG. 9a). Next, the exterior material was folded in half in the MD direction at the crease P (midway in the MD direction) so that the heat-fusible resin layers faced each other (FIG. 9b). About 10 mm inward from the crease P in the MD direction, heat is applied under conditions such as a seal width of 7 mm, a temperature of 240°C, a surface pressure and a sealing time such that the thickness of the heat-sealing resin layer is 80 ± 5% of the thickness before sealing. The fusible resin layers were heat sealed (FIG. 9c). In FIG. 9c, the shaded portion S is the heat-sealed portion. Next, the test piece 13 was obtained by cutting in the MD direction (cutting at the position of the two-dot chain line in FIG. 9d) so that the width in the TD direction was 15 mm (FIG. 9e). Next, the test piece 13 was left for 2 minutes at each measurement temperature, and the heat-fusible resin layer at the heat-sealed part was tested using a tensile tester (AG-Xplus (trade name) manufactured by Shimadzu Corporation) in each measurement temperature environment. was peeled off at a speed of 300 mm/min (FIG. 10). The maximum strength at the time of peeling was defined as the seal strength (N/15 mm). The distance between chucks was 50 mm. The evaluation criteria for seal strength are as follows, and evaluations A and B are acceptable. The results are shown in Table 1.
(Seal strength evaluation criteria)
A: When the measurement temperature is -30°C and 23°C, the seal strength is 80N/15mm or more. When the measurement temperature is 120° C. and 150° C., the seal strength is 50 N/15 mm or more.
B: When the measurement temperature is -30°C and 23°C, the seal strength is 40N/15mm or more and less than 80N/15mm. When the measurement temperature is 120° C. and 150° C., the seal strength is 30 N/15 mm or more and less than 50 N/15 mm.
C: The seal strength is less than 40N/15mm when the measurement temperature is -30°C and 23°C. When the measurement temperature is 120°C and 150°C, the seal strength is less than 30N/15mm.

In Table 1, ">1000" indicates that no breakage occurred even at 1000% of the measurement limit. Furthermore, the tensile elongation at break at 150° C. in Comparative Example 2 was measured at a temperature exceeding the melting point of polypropylene and could not be measured. The tensile elongation at break at -30°C and 23°C of Comparative Examples 1 and 2 and the indentation modulus of Comparative Example 2 have not been measured.

As described above, the present disclosure provides inventions of the following aspects.
Item 1. It is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
The heat-fusible resin layer includes a film,
The film has a glass transition temperature of 67°C or less,
The resin forming the film has at least a polyester structure A, and is an exterior material for a power storage device.
Item 2. Item 2. The exterior material for a power storage device according to Item 1, wherein the polyester structure A is a polybutylene terephthalate structure.
Item 3. Item 3. The exterior material for an electricity storage device according to Item 1 or 2, wherein the resin forming the film further has at least one selected from the group consisting of a polyether structure and a polyester structure B.
Item 4. Item 3, wherein the polyester structure B is a polyester structure formed by polycondensation of a polyol forming the polyester structure A and at least one dicarboxylic acid selected from the group consisting of isophthalic acid, sebacic acid, and dodecanedioic acid. The exterior material for an electricity storage device described in .
Item 5. Item 5. The exterior packaging material for an electricity storage device according to item 3 or 4, wherein the polyether structure is a polyether structure derived from at least one selected from the group consisting of polytetramethylene ether glycol and neopentyl glycol.
Item 6. Item 5. The exterior material for a power storage device according to any one of Items 1 to 5, wherein the laminate has an indentation modulus of elasticity from the heat-fusible resin layer side of 0.3 GPa or more.
Section 7. Item 7. The exterior packaging material for a power storage device according to any one of Items 1 to 6, wherein the film has a melting peak temperature of 170° C. or higher.
Section 8. Item 8. The exterior packaging material for an electricity storage device according to any one of Items 1 to 7, which is for an all-solid battery, a semi-solid battery, a pseudo-solid battery, a polymer battery, or an all-resin battery. Item 9. A film with a glass transition temperature of 67°C or less,
The resin forming the film has at least a polyester structure A.
Item 10. 10. The film according to Item 9, wherein the polyester structure A is a polybutylene terephthalate structure.
Item 11. Item 11. The film according to Item 9 or 10, wherein the resin forming the film further has at least one selected from the group consisting of polyether structure and polyester structure B.
Item 12. Item 11, wherein the polyester structure B is a polyester structure formed by polycondensation of a polyol forming the polyester structure A and at least one dicarboxylic acid selected from the group consisting of isophthalic acid, sebacic acid, and dodecanedioic acid. The film described in.
Item 13. Item 13. The film according to Item 11 or 12, wherein the polyether structure is a polyether structure derived from at least one selected from the group consisting of polytetramethylene ether glycol and neopentyl glycol.
Section 14. Item 14. The film according to any one of Items 9 to 13, wherein the film has an indentation modulus of 0.3 GPa or more.
Item 15. Item 15. The film according to any one of Items 9 to 14, wherein the film has a melting peak temperature of 170° C. or higher.
Section 16. Item 16. The film according to any one of Items 9 to 15, which is used for a heat-fusible resin layer of an exterior material for a power storage device.
Section 17. At least a step of obtaining a laminate in which a base material layer, a barrier layer, and a heat-fusible resin layer are laminated in this order,
The heat-fusible resin layer includes a film,
The film has a glass transition temperature of 67°C or less,
The method for manufacturing an exterior material for a power storage device, wherein the resin forming the film has at least a polyester structure A.
Section 18. Item 18. The method for producing an exterior packaging material for an electricity storage device according to item 17, wherein the exterior packaging material for an electricity storage device is for an all-solid battery, a semi-solid battery, a pseudo-solid battery, a polymer battery, or an all-resin battery.
Section 19. An electricity storage device, wherein an electricity storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the exterior material for an electricity storage device according to any one of Items 1 to 8.

1 Base material layer 2 Adhesive layer 3 Barrier layer 4 Heat-fusible resin layer 5 Adhesive layer 6 Surface coating layer 10 Exterior material for power storage device 13 Test piece 41 First layer 42 Second layer 43 Third layer

Claims (19)

It is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
The heat-fusible resin layer includes a film,
The film has a glass transition temperature of 67°C or less,
The resin forming the film has at least a polyester structure A, and is an exterior material for a power storage device. The exterior material for a power storage device according to claim 1, wherein the polyester structure A is a polybutylene terephthalate structure. The exterior material for a power storage device according to claim 1 or 2, wherein the resin forming the film further has at least one selected from the group consisting of a polyether structure and a polyester structure B. The polyester structure B is a polyester structure formed by polycondensation of a polyol forming the polyester structure A and at least one dicarboxylic acid selected from the group consisting of isophthalic acid, sebacic acid, and dodecanedioic acid. 3. Exterior material for power storage device according to 3. The exterior material for a power storage device according to claim 3, wherein the polyether structure is a polyether structure derived from at least one selected from the group consisting of polytetramethylene ether glycol and neopentyl glycol. The exterior material for an electricity storage device according to claim 1 or 2, wherein the laminate has an indentation modulus of elasticity from the heat-fusible resin layer side of 0.3 GPa or more. The exterior material for an electricity storage device according to claim 1 or 2, wherein the film has a melting peak temperature of 170°C or higher. The exterior packaging material for an electricity storage device according to claim 1 or 2, which is for an all-solid battery, a semi-solid battery, a pseudo-solid battery, a polymer battery, or an all-resin battery. A film with a glass transition temperature of 67°C or less,
The resin forming the film has at least a polyester structure A. 10. The film of claim 9, wherein the polyester structure A is a polybutylene terephthalate structure. The film according to claim 9 or 10, wherein the resin forming the film further has at least one selected from the group consisting of a polyether structure and a polyester structure B. The polyester structure B is a polyester structure formed by polycondensation of a polyol forming the polyester structure A and at least one dicarboxylic acid selected from the group consisting of isophthalic acid, sebacic acid, and dodecanedioic acid. 12. The film according to 11. The polyether structure is a polyether structure derived from at least one selected from the group consisting of polytetramethylene ether glycol and neopentyl glycol.
The film according to claim 11 or 12. The film according to claim 9 or 10, wherein the film has an indentation modulus of 0.3 GPa or more. The film according to claim 9 or 10, wherein the film has a melting peak temperature of 170°C or higher. The film according to claim 9 or 10, which is used for a heat-fusible resin layer of an exterior material for a power storage device. At least a step of obtaining a laminate in which a base material layer, a barrier layer, and a heat-fusible resin layer are laminated in this order,
The heat-fusible resin layer includes a film,
The film has a glass transition temperature of 67°C or less,
The method for manufacturing an exterior material for a power storage device, wherein the resin forming the film has at least a polyester structure A. The method for manufacturing an exterior material for an electricity storage device according to claim 17, wherein the exterior material for an energy storage device is for an all-solid battery, a semi-solid battery, a pseudo-solid battery, a polymer battery, or an all-resin battery. An electricity storage device, wherein an electricity storage device element comprising at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the exterior material for an electricity storage device according to claim 1 or 10.