Laminate, laminate selection method, molding, and molding manufacturing method

Abstract

One aspect according to the present disclosure is a laminate having a layered structure comprising a base material layer, a first adhesive layer, a barrier layer, and a sealant layer, in this order, the laminate being measured, using a nanoindenter, under the condition of the plastic deformation amount of the base material layer being 30 nm or more, and the plastic deformation amount of the base material layer being a maximum load of 100 μN.

Description

Laminate, method for selecting a laminate, molded body, and method for manufacturing a molded body. 【0001】 This disclosure relates to a laminate, a method for selecting a laminate, a molded article, and a method for manufacturing a molded article. 【0002】 As energy storage devices, secondary batteries such as lithium-ion batteries, nickel-metal hydride batteries, and lead-acid batteries, as well as electrochemical capacitors such as electric double-layer capacitors, are known. Due to the miniaturization of portable devices and limitations on installation space, there is a demand for further miniaturization of energy storage devices, and lithium-ion batteries, which have a high energy density, are attracting attention. Conventionally, metal cans were used as the outer casing material for lithium-ion batteries, but multilayer films (laminated structures) that are lightweight, have high heat dissipation properties, and can be manufactured at low cost are now being used. As such a laminate, for example, Patent Document 1 discloses a laminate comprising a specific substrate layer, an adhesive layer, a metal layer, and a heat-adhesive resin layer in that order. 【0003】 Lithium-ion batteries that use a laminate as an outer casing are called laminate-type lithium-ion batteries. A laminate-type lithium-ion battery comprises a storage element with a positive electrode, a liquid electrolyte, and a negative electrode, and an outer bag that houses the storage element, preventing moisture from entering the interior. The laminate used for the outer bag has a laminated structure comprising, for example, a base layer, an adhesive layer, a barrier layer, and a sealant layer in that order. The laminate covers the storage element with the sealant layer facing inward and the base layer facing outward. A laminate-type lithium-ion battery is manufactured, for example, by forming a recess in a part of the outer bag by cold molding, housing the storage element in the recess, folding back the remaining part of the outer bag, and sealing the edges with heat seal. In such a lithium-ion battery, the deeper the recess formed by cold molding, the more battery contents can be housed, thus increasing the energy density. 【0004】 International Publication No. 2016 / 158796 【0005】Incidentally, research and development is underway on energy storage devices, such as all-solid-state batteries, as a next-generation battery to lithium-ion batteries. An all-solid-state battery comprises, for example, an energy storage element and an outer bag that houses the energy storage element. Compared to conventional liquid lithium-ion batteries, all-solid-state batteries have a wider operating temperature range and can be charged quickly. For this reason, all-solid-state batteries are expected to be used in automotive applications. For this reason, the outer material requires sufficient deep-drawing moldability compared to conventional materials in order to package a higher capacity solid electrolyte. 【0006】 Figure 1(a) is a schematic perspective view showing an example of a molded body obtained by deep drawing of a laminate. Figure 1(b) is a schematic cross-sectional view along the line II-II in Figure 1(a). As shown in Figures 1(a) and 1(b), the molded body 30 comprises a recess 32 and a rectangular frame-shaped flange portion 34 surrounding the recess 32. The recess 32 consists of a bottom surface 32a and four side surfaces 32b. The corner portion 32c is a portion defined by the bottom surface 32a and a pair of adjacent side surfaces 32b. The corner portion 32c is formed in a curved shape that is convex outward from the recess 32. The ridge portion 32d is the boundary between the bottom surface 32a and the side surfaces 32b. The ridge portion 32e is the boundary between the side surfaces 32b and the flange portion 34. According to the inventors' studies, it has become clear that when the depth during molding is increased, a recess occurs in the corner portion 32c of the laminate disclosed in Patent Document 1. Furthermore, our investigations have revealed that, in the laminate disclosed in Patent Document 1, increasing the molding depth causes the ridges 32d and 32e to become rounded and indistinct. 【0007】 One aspect of this disclosure provides a laminate in which, when deep-drawn, corner indentations are suppressed and the edges are clearly defined. Another aspect of this disclosure provides a method for selecting a laminate in which, when deep-drawn, corner indentations are suppressed and the edges are clearly defined. Another aspect of this disclosure provides a molded body in which corner indentations are suppressed and the edges are clearly defined. Another aspect of this disclosure provides a method for manufacturing a molded body in which corner indentations are suppressed and the edges are clearly defined. 【0008】To solve the above problems, one aspect of this disclosure provides a laminate having a laminated structure comprising a base layer, a first adhesive layer, a barrier layer, and a sealant layer in this order, wherein the amount of plastic deformation of the base layer is 30 nm or more, and the amount of plastic deformation of the base layer is measured using a nanoindenter under the condition of a maximum load of 100 μN. 【0009】 According to the above laminate, when deep drawing is performed, a molded body is obtained in which the indentation at the corners is suppressed and the edges are clearly defined. The reason why the above laminate produces such an effect is not clear, but the inventors speculate as follows. That is, deep drawing is performed by pressing a punch die into the laminate, but the strength of the force applied from the punch die (the outward force in the recess 32) differs depending on the location in the laminate. In the parts that become corners and edges, the force applied from the punch die is stronger than in other parts. And this difference in the strength of the force applied from the punch die becomes larger as the molding depth increases. And when there is such a difference in the force applied from the punch die, the strength of the force that causes the laminate to return to its original shape after the punch die is pulled away (the inward force in the recess 32) also differs depending on the location. This difference in the strength of the force that causes the laminate to return to its original shape causes indentation at the corners and makes the edges unclear. The above laminate exhibits a plastic deformation of 30 nm or more in the base layer, as measured using a nanoindenter under a maximum load of 100 μN. This mitigates the difference in the strength of the forces that cause the laminate to return to its original shape. As a result, a molded body is obtained in which corner indentations are suppressed and the edges are clearly defined. 【0010】 In the above laminate, the base layer may contain at least one resin selected from the group consisting of polyester resin and polyamide resin. This tends to give the base layer excellent moldability. 【0011】 In the above laminate, the barrier layer may have aluminum foil, and the thickness of the aluminum foil may be 40 μm or more. This weakens the force that causes the laminate to return to its original shape after the punch die is separated. As a result, the indentation at the corners of the resulting molded body is further suppressed and the edges become more distinct. 【0012】 In the above-described laminate, the iron content in the aluminum foil may be 0.1% by mass or more and 9.0% by mass or less of 100% by mass of the aluminum foil. This tends to improve the flexibility of the laminate, as well as its pinhole resistance and ductility. 【0013】 In the above laminate, the base layer may contain polybutylene terephthalate. This further suppresses the indentation at the corners of the resulting molded body and makes the edges even more distinct. 【0014】 In the above laminate, the amount of plastic deformation of the base layer may be between 40 nm and 100 nm. This tends to further suppress the indentation at the corners of the resulting molded body and make the edges more distinct. 【0015】 In the above-described laminate, the thickness of the base material layer may be 10 μm or more and 30 μm or less. This makes the edges of the molded body more distinct while improving the insulating properties of the base material layer. 【0016】 The laminate may further include a heat-adhesive resin layer located between the barrier layer and the sealant layer. 【0017】 In the above-described laminate, the heat-bondable resin layer may contain an acid-modified polyolefin resin. This tends to further improve adhesion and moisture barrier properties. 【0018】 The laminate may further include a corrosion-preventive treatment layer located on the surface of the barrier layer facing the first adhesive layer. This suppresses corrosion of the barrier layer and tends to improve the adhesion between the barrier layer and the first adhesive layer. 【0019】 The laminate may further include a corrosion-preventive treatment layer located on the surface of the barrier layer that faces the heat-adhesive resin layer. This suppresses corrosion of the barrier layer and tends to improve the adhesion between the barrier layer and the heat-adhesive resin layer. 【0020】The above laminate has a laminated structure comprising a base layer, a first adhesive layer, a corrosion-preventive treatment layer, a barrier layer, a corrosion-preventive treatment layer, a heat-adhesive resin layer, and a sealant layer in this order, wherein the base layer contains polybutylene terephthalate, the thickness of the base layer is 10 μm or more and 30 μm or less, the amount of plastic deformation of the base layer is 42 nm or more and 90 nm or less, the barrier layer has aluminum foil, the thickness of the aluminum foil is 50 μm or more and 100 μm or less, the iron content in the aluminum foil is 0.1% by mass or more and 9.0% by mass or less per 100% by mass of the aluminum foil, and the heat-adhesive resin layer may contain an acid-modified polyolefin resin. With such a configuration, the molded body is particularly excellent in deep-draw formability, and when molded, the indentation of corners is extremely suppressed and the ridges are extremely clear. 【0021】 The above laminate has a laminated structure comprising a base layer, a first adhesive layer, a corrosion-preventive treatment layer, a barrier layer, a corrosion-preventive treatment layer, a heat-adhesive resin layer, and a sealant layer in this order, wherein the base layer contains polyethylene terephthalate, the thickness of the base layer is 10 μm or more and 30 μm or less, the amount of plastic deformation of the base layer is 42 nm or more and 90 nm or less, the barrier layer has aluminum foil, the thickness of the aluminum foil is 30 μm or more and 100 μm or less, the iron content in the aluminum foil is 0.1% by mass or more and 9.0% by mass or less per 100% by mass of the aluminum foil, and the heat-adhesive resin layer may contain an acid-modified polyolefin resin. Even with such a configuration, it is possible to obtain a molded body that has excellent deep-draw formability, suppresses corner indentation when molded, and has clear edges. 【0022】 The above laminate may be a packaging material subjected to deep drawing. With the above laminate, when deep drawing is performed, a molded body is obtained in which the indentation of the corners is suppressed and the edges are clearly defined. For this reason, the above laminate can be suitably used as a packaging material subjected to deep drawing. 【0023】The above laminate may be an outer casing material for an all-solid-state battery. With the above laminate, when deep drawing is performed, a molded body is obtained in which indentation at the corners is suppressed and the edges are clearly defined. Therefore, the above laminate can be suitably used as an outer casing material for an all-solid-state battery that requires sufficient deep drawing moldability compared to conventional materials. 【0024】 Another aspect of this disclosure is a method for selecting a laminate, comprising the steps of: preparing a laminate to be evaluated having a laminated structure comprising a base layer, a first adhesive layer, a barrier layer, and a sealant layer in that order; measuring the amount of plastic deformation of the base layer of the laminate to be evaluated using a nanoindenter under a maximum load of 100 μN; and determining that the laminate is a satisfactory product when the amount of plastic deformation is 30 nm or more. 【0025】 According to the above method for selecting laminates, it is possible to select a laminate that, when deep drawing is performed, will produce a molded body in which corner indentations are suppressed and the edges are clearly defined. 【0026】 Another aspect of this disclosure is to provide a molded body made of the above-mentioned laminate, comprising a recess and a rectangular frame-shaped flange portion surrounding the recess, wherein the depth of the recess is 5 mm or more. By performing deep drawing molding using the above-mentioned laminate, even when a deep recess of 5 mm or more is formed, a molded body can be obtained in which the indentation of the corners is suppressed and the edges are clearly defined. 【0027】 Another aspect of this disclosure is a method for manufacturing the above-mentioned molded article, comprising the steps of: preparing the laminate; and arranging the laminate on a die mold having an opening to form the recess and the flange portion. According to this manufacturing method, when deep drawing is performed, it is possible to manufacture a molded article in which the concavity of the corners is suppressed and the edges are clearly defined. 【0028】According to one aspect of this disclosure, a laminate is provided in which, when deep-drawn, a molded body is obtained in which corner recesses are suppressed and the edges are clearly defined. According to another aspect of this disclosure, a method for selecting a laminate is provided in which, when deep-drawn, a molded body is obtained in which corner recesses are suppressed and the edges are clearly defined. According to yet another aspect of this disclosure, a molded body is provided in which corner recesses are suppressed and the edges are clearly defined. According to yet another aspect of this disclosure, a method for manufacturing a molded body is provided in which corner recesses are suppressed and the edges are clearly defined. 【0029】 Figure 1(a) is a schematic perspective view showing an example of a molded body obtained by deep drawing of a laminate. Figure 1(b) is a schematic cross-sectional view along the line II-II in Figure 1(a). Figure 2 is a schematic cross-sectional view of an exterior material for an energy storage device according to one embodiment. Figure 3 is a perspective view showing an energy storage device according to one embodiment. Figure 4 is a schematic cross-sectional view of an exterior material for an energy storage device according to a modified example. Figure 5 is a diagram showing an example of a load-displacement curve with the load applied to the base layer on the vertical axis and the displacement of the base layer on the horizontal axis. 【0030】 Preferred embodiments of this disclosure will be described in detail below, with appropriate reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant descriptions are omitted. Furthermore, the dimensional ratios in the drawings are not limited to those shown. 【0031】[Laminated Body] Hereinafter, a laminated body according to an embodiment of the present disclosure will be described. FIG. 2 is a schematic cross-sectional view of the laminated body according to this embodiment. As shown in FIG. 2, the laminated body 10 is, for example, a multilayer film used as an exterior material (exterior material for a storage battery device) for a storage battery device such as a secondary battery such as a lithium-ion battery, a nickel-hydrogen battery, or a lead storage battery, or an electrochemical capacitor such as an electric double layer capacitor. The laminated body 10 has a laminated structure including a base material layer 11, an adhesive layer 12 (first adhesive layer), a barrier layer 13, a thermally adhesive resin layer 15, and a sealant layer 16 in this order. In the laminated body 10, the base material layer 11 is the outermost layer, and the sealant layer 16 is the innermost layer. The amount of plastic deformation of the base material layer 11 is 30 nm or more. The amount of plastic deformation of the base material layer 11 is measured using a nanoindenter under the condition of a maximum load of 100 μN. By performing deep drawing molding on the laminated body 10, the molded bodies 30 shown in FIGS. 1(a) and 1(b) are obtained. 【0032】 Hereinafter, each layer constituting the laminated body 10 will be specifically described. 【0033】 <Base Material Layer> The base material layer 11 is a sheet-like member that functions as the outermost layer of the storage battery device when the laminated body 10 is used as an exterior material. The base material layer 11 imparts heat resistance in the sealing process when manufacturing the storage battery device and plays a role in suppressing the occurrence of pinholes that may occur during molding, distribution, etc. Especially in the case of an exterior material for a large-scale storage battery device, scratch resistance, chemical resistance, insulation, etc. can also be imparted. 【0034】 The base material layer 11 may have a melting peak temperature higher than the melting peak temperature of the sealant layer 16. In this case, the appearance deformation of the laminated body 10 due to the melting of the base material layer 11 during heat sealing of the laminated body 10 can be suppressed. When the sealant layer 16 has a multilayer structure, the melting peak temperature of the sealant layer 16 means the melting peak temperature of the layer with the highest melting peak temperature. The melting peak temperature of the base material layer 11 is, for example, 290°C or higher and 350°C or lower. The melting peak temperature means a value obtained in accordance with the method described in JIS K7121-1987. The melting peak temperature T １１ of the base material layer 11 and the melting peak temperature T １６ of the sealant layer 16, the temperature difference (T１１ -T １６ )(For example, it is 20°C or higher. By having the temperature difference of 20°C or higher, the deterioration of the appearance of the laminate 10 due to heat sealing can be well suppressed.) 【0035】 The base material layer 11 is, for example, a layer formed of a resin having insulation properties. Examples of the resin include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, polyether ketone resin, polyphenylene sulfide resin, polyetherimide resin, polysulfone resin, fluororesin, phenol resin, melamine resin, urethane resin, allyl resin, silicone resin, epoxy resin, furan resin, and acetyl cellulose resin, etc.) 【0036】 Among these resins, as the resin of the base material layer 11, at least one of polyester resin and polyamide resin may be used from the viewpoint of moldability. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. The polyester resin is preferably polybutylene terephthalate because the generation of dents at the corners of the recesses formed by deep drawing molding is further suppressed. Examples of the polyamide resin include nylon 6, nylon 6,6, a copolymer of nylon 6 and nylon 6,6, nylon 9T, nylon 10, polymetaxylene adipamide (MXD6), nylon 11, and nylon 12. The resin of the base material layer 11 may contain additives and the like according to the required performance.) 【0037】 The content of the resin may be 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass based on the total amount of the base material layer 11.) 【0038】The amount of plastic deformation h1 of the base layer 11 is 30 nm or more. The amount of plastic deformation h1 is measured using a nanoindenter under a maximum load of 100 μN. The amount of plastic deformation h1 is preferably 40 nm or more, and more preferably 42 nm or more, because it further suppresses the indentation of the corners of the resulting molded body and makes the edges more distinct. From the viewpoint of wear resistance, the amount of plastic deformation h1 is preferably 100 nm or less, and more preferably 90 nm or less. The amount of plastic deformation may be 30 nm to 100 nm, 30 nm to 90 nm, 40 nm to 100 nm, 40 nm to 90 nm, 42 nm to 100 nm, or 42 nm to 90 nm. 【0039】 The amount of plastic deformation h1 can be obtained, for example, by the method described in the following examples. The object on which the amount of plastic deformation h1 is measured may be the surface (main surface) of the base layer 11, or it may be a cross-section. If there are two or more base layers 11, the amount of plastic deformation of each layer measured using a nanoindenter under a maximum load of 100 μN is all 30 nm or more. The amount of plastic deformation h1 can be adjusted, for example, by changing the film formation conditions such as the composition of the base layer 11 and the stretching ratio. 【0040】 The base layer 11 may be in the form of a stretched or unstretched film, or in the form of a coating film. The base layer 11 may be a single layer or a multilayer. If the base layer 11 is a multilayer, the layers contained in the base layer 11 may be formed from different resins or from the same resin. If the base layer 11 is in the form of a film, the base layer 11 may be formed by co-extrusion or laminated with an adhesive. If the base layer 11 is a coating film, the coating film may be obtained, for example, by coating multiple times with a coating film-forming composition. The base layer 11 may have a multilayer structure combining a film and a coating film. 【0041】When the above-mentioned resin is used in film form, the base layer 11 may be a biaxially oriented film. In this case, the moldability of the laminate 10 is improved. Examples of stretching methods for biaxially oriented films include sequential biaxial stretching, tubular biaxial stretching, and simultaneous biaxial stretching. From the viewpoint of obtaining better deep-draw moldability, the biaxially oriented film may be a film stretched by tubular biaxial stretching. 【0042】 The thickness of the base layer 11 is, for example, 10 μm or more and 60 μm or less. The thickness of the base layer 11 may be 15 μm or more, 20 μm or more, 25 μm or more, 50 μm or less, 40 μm or less, or 35 μm or less. By having the thickness of the base layer 11 within the above range, the thermal conductivity of the base layer 11 can be set within a good range. From the viewpoint of making the ridges even clearer and improving the insulation of the base layer, the thickness of the base layer 11 is preferably 10 to 30 μm. 【0043】 <Adhesive Layer> The adhesive layer 12 is a layer (first adhesive layer) that adheres the barrier layer 13, which is provided with the corrosion-preventive treatment layer 14a, to the base material layer 11. The adhesive layer 12 has the adhesive strength necessary to firmly bond the base material layer 11 and the barrier layer 13. The adhesive layer 12 also has conformability to prevent the barrier layer 13 from being broken by the base material layer 11. Conformability means that even if the member deforms due to expansion or contraction, the adhesive layer 12 remains on the member without peeling off. 【0044】 Examples of adhesive components for forming the adhesive layer 12 include urethane compounds, urea compounds, epoxy compounds, and silicone compounds. These compounds may be used individually or in combination of two or more. Urea compounds are obtained by reacting amine compounds and amine derivatives with polyfunctional isocyanate compounds. Urethane compounds are obtained by reacting polyol resins with polyfunctional isocyanate compounds. 【0045】Examples of polyol resins include polyester polyols, polyether polyols, polycarbonate diols, and polyacrylic polyols. Examples of polyester polyols include those obtained by reacting one or more dicarboxylic acids with a diol. Examples of polyether polyols include those produced by addition polymerization of ethylene oxide or propylene oxide to propylene glycol, glycerin, and pentaerythritol. Examples of polycarbonate polyols include those obtained by reacting a diester of carbonate, such as diphenyl carbonate, with a diol. Examples of polyacrylic polyols include copolymers obtained by copolymerizing at least a hydroxyl group-containing acrylic monomer with (meth)acrylic acid. In this case, structural units derived from (meth)acrylic acid may be included as the main component. Examples of hydroxyl group-containing acrylic monomers include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. 【0046】 Polyfunctional isocyanate compounds contain multiple isocyanate groups and can function as crosslinking agents for the amine-based resin or polyol. Polyfunctional isocyanate compounds may be used individually or in combination of two or more. Examples of polyfunctional isocyanate compounds include aliphatic polyfunctional isocyanate compounds, alicyclic polyfunctional isocyanate compounds, and polyfunctional isocyanate compounds having aromatic rings. 【0047】Examples of aliphatic polyfunctional isocyanate compounds include hexamethylene diisocyanate (HDI) and xylylene diisocyanate (XDI). Examples of alicyclic polyfunctional isocyanate compounds include isophorone diisocyanate (IPDI). Examples of polyfunctional isocyanate compounds having an aromatic ring include tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). Polyfunctional isocyanate compounds can also be used in the form of polymers (e.g., trimers) of these compounds. Specifically, adducts, biuretes, isocyanurates, etc., can be used. 【0048】 From the viewpoint of improving pot life, the isocyanate group of the polyfunctional isocyanate compound may be bonded to the blocking agent. Examples of blocking agents include methyl ethyl ketoxime (MEKO). The temperature at which the blocking agent detaches from the isocyanate group of the polyfunctional isocyanate compound may be 50°C or higher. From the viewpoint of improving pot life, it may be 60°C or higher. The temperature at which the blocking agent detaches from the isocyanate group of the polyfunctional isocyanate compound may be 140°C or lower. From the viewpoint of the mold curl resistance of the laminate 10, the above temperature may be 120°C or lower. 【0049】 To lower the dissociation temperature of the blocking agent, a catalyst that lowers the dissociation temperature may be used. Examples of such catalysts that lower the dissociation temperature include tertiary amines such as triethylenediamine and N-methylmorpholine, and metal organic salts such as dibutyltin dilaurate. 【0050】 Amine compounds are compounds that have an amino group in their molecule. Here, an amino group is -NH ２ -NHR, -NR ２ This means that, where R represents an alkyl group and / or an aryl group. Amine derivatives are compounds derived from amine compounds that do not contain an amino group in their molecule. 【0051】Amine compounds and amine derivatives may be either active or latent curing agents. A latent curing agent is a curing agent that is activated by external stimuli to generate a reactive group that can react with isocyanate groups. When amine compounds and amine derivatives are latent curing agents, the pot life tends to improve. Examples of external stimuli include heat and humidity. Examples of latent curing agents include imidazole curing agents, imine curing agents, amineimide curing agents, dicyandiamide curing agents, aromatic polyamine curing agents, aliphatic polyamine curing agents, polyamidoamine curing agents, tertiary amine salt curing agents, and oxazolidine curing agents. Of these, examples of latent curing agents activated by heating include imidazole curing agents, dicyandiamide curing agents, polyamine curing agents, and amineimide curing agents. Examples of latent curing agents activated by humidity include imine curing agents and oxazolidine curing agents. From the perspective of improving pot life, the latent hardening agent may be one that is activated by moisture. 【0052】 From the viewpoint of suppressing corrosion of the barrier layer 13 by hydrogen sulfide, the first adhesive layer 12 may contain a hydrogen sulfide treated substance. The hydrogen sulfide treated substance is a substance that chemically reacts with hydrogen sulfide (hydrogen sulfide reactant), such as zinc oxide or potassium permanganate. In these cases, the hydrogen sulfide treated substance also functions as a thermally conductive filler. This improves the heat dissipation of the laminate 10. From the viewpoint of suppressing corrosion of the barrier layer 13 by hydrogen sulfide, the content of the hydrogen sulfide treated substance in the first adhesive layer 12 is, for example, 1% by mass or more and 50% by mass or less of the total amount of the first adhesive layer 12. 【0053】 The thickness of the adhesive layer 12 is not particularly limited, but from the viewpoint of obtaining desired adhesive strength, thermal conductivity, conformability, and processability, it is, for example, 1 μm to 10 μm, or 2 μm to 7 μm. 【0054】 The mass per unit area of ​​the adhesive layer 12 is set to 2.0 g / m², from the viewpoint of ensuring superior laminate strength in both room temperature and high-temperature environments, as well as obtaining superior deep-draw moldability. ２6.0 g / m or less ２ may be 2.5 g / m or more ２ 5.0 g / m or less ２ may be 3.0 g / m or more ２ 4.0 g / m or less ２ may also be 4.0 g / m or less 【0055】 <Barrier layer> The barrier layer 13 has a water vapor barrier property that prevents moisture from entering the interior of the power storage device. Further, the barrier layer 13 may have ductility for deep drawing molding. In one embodiment, the barrier layer 13 is a metal foil layer 13a provided with corrosion prevention treatment layers 14a and 14b. Here, the corrosion prevention treatment layer 14a is located on the surface 13b of the metal foil layer 13a that faces the adhesive layer 12, and the corrosion prevention treatment layer 14b is located on the surface 13c of the metal foil layer 13a that faces the heat adhesive resin layer 15. The thickness of the metal foil layer 13a is significantly larger than the thicknesses of the corrosion prevention treatment layers 14a and 14b. Therefore, the thickness of the barrier layer 13 corresponds to the thickness of the metal foil layer 13a. 【0056】 As the barrier layer 13, for example, various metal foils such as aluminum, stainless steel, and copper, or metal vapor deposition films, inorganic oxide vapor deposition films, carbon-containing inorganic oxide vapor deposition films, films provided with these vapor deposition films, etc. can be used. Examples of the film provided with a vapor deposition film include an aluminum vapor deposition film, an inorganic oxide vapor deposition film, etc. These can be used alone or in combination of two or more. The barrier layer 13 may include an aluminum foil in terms of barrier properties such as mass (specific gravity) and moisture resistance, workability, and cost. 【0057】If the barrier layer 13 contains aluminum foil, it may also contain annealed soft aluminum foil in order to provide the desired ductility during molding. To further improve pinhole resistance and ductility during molding, the barrier layer 13 may also contain iron-containing aluminum foil. The iron content in the aluminum foil may be 0.1% by mass or more and 9.0% by mass or 0.5% by mass or more and 2.0% by mass of 100% by mass of aluminum foil (for example, aluminum foil made of JIS standard 8021 or 8079 material). By having an iron content of 0.1% by mass or more, a laminate 10 with better pinhole resistance and ductility can be obtained. By having an iron content of 9.0% by mass or less, a laminate 10 with better flexibility can be obtained. Untreated aluminum foil may be used as the aluminum foil, but degreasing treatment may be used in order to provide corrosion resistance. When aluminum foil is degreased, the degreasing treatment may be applied to only one side of the aluminum foil, or to both sides. For example, a wet-type degreasing treatment or a dry-type degreasing treatment can be used, but a dry-type degreasing treatment may be performed from the viewpoint of simplifying the manufacturing process. 【0058】 One example of the dry-type degreasing treatment described above is a method in which degreasing is performed by extending the processing time during the annealing process of metal foil. Sufficient electrolyte resistance can be obtained even with a degreasing treatment performed simultaneously with the annealing process, which is carried out to soften the metal foil. 【0059】 Furthermore, as the dry-type degreasing treatment described above, treatments other than the annealing treatment, such as flame treatment and corona treatment, may also be used. In addition, as the dry-type degreasing treatment described above, for example, a degreasing treatment may be used in which contaminants are oxidized, decomposed, and removed by reactive oxygen species generated when a metal foil is irradiated with ultraviolet light of a specific wavelength. 【0060】As the wet-type degreasing treatment described above, for example, treatments such as acid degreasing and alkaline degreasing can be used. As the acid used in the acid degreasing treatment, for example, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid can be used. These acids may be used individually or in combination of two or more. As the alkali used in the alkaline degreasing treatment, for example, sodium hydroxide, which has a high etching effect, can be used. Alternatively, alkaline degreasing treatment may be performed using a material containing a weakly alkaline material and a surfactant. The wet-type degreasing treatment described above can be carried out by, for example, immersion or spraying. 【0061】 The thickness of the barrier layer 13 may be 9 μm or more, 15 μm or more, 40 μm or more, or 50 μm or more. A barrier layer thickness of 9 μm or more makes it less likely to break even when stress is applied during molding. The thickness of the barrier layer 13 may be 200 μm or less, or 100 μm or less. 【0062】 The barrier layer 13 preferably has a metal foil that is stretchable and has excellent moldability. The thickness of the metal foil may be 9 μm or more, or 15 μm or more. A metal foil thickness of 9 μm or more makes it less likely to break even when stress is applied during molding. The thickness of the metal foil is preferably 40 μm or more, and more preferably 50 μm or more, as this further suppresses the indentation of the corners of the resulting molded body and makes the edges more distinct. The thickness of the metal foil may be 200 μm or less, or 100 μm or less. A metal foil thickness of 200 μm or less reduces the mass increase of the laminate 10. 【0063】The metal foil is more preferably aluminum foil, which is stretchable and has excellent moldability. The thickness of the aluminum foil may be 9 μm or more, or 15 μm or more. A thickness of 9 μm or more in the aluminum foil makes it less likely to break even when stress is applied during molding. The thickness of the aluminum foil is preferably 40 μm or more, and more preferably 50 μm or more, because this further suppresses the indentation of the corners of the resulting molded body and makes the edges more distinct. The thickness of the aluminum foil may be 200 μm or less, or 100 μm or less. A thickness of 200 μm or less in the aluminum foil makes it possible to reduce the mass increase of the laminate 10. 【0064】 From the viewpoint of the thermal diffusivity of the laminate 10, the ratio of the thickness of the barrier layer 13 to the thickness of the laminate 10 may be 15% or more, 20% or more, 23% or more, 26% or more, or 30% or more. Also, from the viewpoint of the insulating properties of the laminate 10, the ratio of the thickness of the barrier layer 13 to the thickness of the laminate 10 may be 50% or less, 45% or less, 43% or less, or 40% or less. In one embodiment, the ratio of the thickness of the barrier layer 13 to the thickness of the laminate 10 may be 15% or more and 50% or less, 23% or more and 45% or less, or 26% or more and 45% or less. 【0065】 The base layer 11 may contain, for example, various additives (e.g., flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, tackifiers, etc.). 【0066】 <Corrosion Prevention Treatment Layers> The corrosion prevention treatment layers 14a and 14b are layers provided to prevent corrosion of the metal foil layer 13a contained in the barrier layer 13. The corrosion prevention treatment layer 14a plays a role in increasing the adhesion between the metal foil layer 13a and the adhesive layer 12. For this reason, the corrosion prevention treatment layer 14a is in contact with the adhesive layer 12. The corrosion prevention treatment layer 14b plays a role in increasing the adhesion between the metal foil layer 13a and the heat-adhesive resin layer 15. For this reason, the corrosion prevention treatment layer 14b is in contact with the heat-adhesive resin layer 15. The corrosion prevention treatment layers 14a and 14b may be layers with the same composition or layers with different compositions. 【0067】The corrosion-preventive treatment layers 14a and 14b can be formed, for example, by performing a corrosion-preventive treatment on the base material layer of the corrosion-preventive treatment layers 14a and 14b, such as a degreasing treatment, a hot water modification treatment, an anodizing treatment, a chemical conversion treatment, a coating type treatment in which a coating agent having corrosion-preventive properties is applied, or a combination of these treatments. 【0068】 Of the treatments described above, degreasing, hydrothermal modification, and anodizing, particularly hydrothermal modification and anodizing, are treatments that dissolve the surface of the metal foil (aluminum foil) with a treatment agent to form a metal compound (aluminum compound (boehmite, anodized aluminum)) with excellent corrosion resistance. For this reason, such treatments are sometimes included in the definition of chemical conversion treatment in order to obtain a structure in which a co-continuous structure is formed from the metal foil layer 13a to the corrosion prevention treatment layers 14a and 14b. 【0069】 Degreasing treatments include acid degreasing and alkaline degreasing. Acid degreasing can be achieved by using an acid degreasing agent obtained by using an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid, either individually or in combination thereof. Furthermore, by using an acid degreasing agent obtained by dissolving a fluorine-containing compound such as ammonium monohydrogendifluoride in the above inorganic acid, it is possible not only to degrease the metal foil layer 13a but also to form a fluoride of the passive metal, which is effective in terms of hydrofluoric acid resistance. Alkaline degreasing can be achieved by using a method such as sodium hydroxide. 【0070】 As the above-mentioned hydrothermal modification treatment, for example, a boehmite treatment obtained by immersing the metal foil layer 13a in boiling water to which triethanolamine has been added can be used. As the above-mentioned anodic oxidation treatment, for example, an anodizing treatment can be used. As the above-mentioned chemical conversion treatment, for example, chromate treatment, zirconium treatment, titanium treatment, vanadium treatment, molybdenum treatment, calcium phosphate treatment, strontium hydroxide treatment, cerium treatment, ruthenium treatment, or a combination of two or more of these can be used. The above-mentioned degreasing treatment may be performed before these hydrothermal modification treatments, anodic oxidation treatments, and chemical conversion treatments. 【0071】Furthermore, the above chemical conversion treatment is not limited to the wet method; for example, a method in which the treatment agent used in these treatments is mixed with the resin component and applied may also be used. From the viewpoint of wastewater treatment, a coating-type chromate treatment can be mentioned as the above corrosion prevention treatment. 【0072】 Coating agents used in coating-type corrosion prevention treatments include those containing at least one selected from the group consisting of rare earth element oxide sols, anionic polymers, and cationic polymers. In this case, a coating agent containing a rare earth element oxide sol may be used. 【0073】 The mass per unit area of ​​the corrosion-preventive treatment layers 14a and 14b is 0.005 g / m². ２ 0.200g / m or more ２ The following is also acceptable, or 0.010 g / m ２ 0.100g / m or more ２ The following is also acceptable: The mass per unit area is 0.005 g / m². ２ If the above is achieved, the barrier layer 13 can be effectively provided with corrosion prevention functionality. The above mass per unit area is 0.200 g / m². ２ The corrosion prevention function will saturate even beyond this limit. Note that the above description uses mass per unit area, but if the specific gravity is known, it is also possible to convert the thickness from that value. 【0074】 The thickness of the corrosion-preventive treatment layers 14a and 14b may be, for example, 10 nm to 5 μm, or 20 nm to 500 nm, from the viewpoint of corrosion prevention function and anchor function. 【0075】 From the viewpoint of adhesion between the sealant layer 16 and the barrier layer 13, the corrosion-preventive treatment layers 14a and 14b may, for example, contain cerium oxide, 1 to 100 parts by mass of phosphoric acid or phosphate per 100 parts by mass of cerium oxide, and a cationic polymer. 【0076】<Heat-Adhesive Resin Layer> The heat-adhesive resin layer 15 is a layer (second adhesive layer) that adheres the sealant layer 16 and the barrier layer 13, and contains an adhesive resin. The adhesive resin of the heat-adhesive resin layer 15 is not particularly limited as long as it contains a resin that adheres the sealant layer 16 and the barrier layer 13. From the viewpoint of adhesion and moisture barrier properties, the adhesive resin may be an acid-modified polyolefin resin. 【0077】 The acid-modified polyolefin resin may be a polyolefin resin modified with maleic anhydride, carboxylic acid, sulfonic acid, or their derivatives. Examples of acid-modified polyolefin resins include graft copolymers, block copolymers, and random copolymers. From the viewpoint of adhesion to the barrier layer 13, the acid-modified polyolefin resin may also be a polyolefin resin graft-modified with maleic anhydride. Alternatively, the acid-modified polyolefin resin may include a reaction product (hereinafter also referred to as "reaction product A") of the acid-modified polyolefin and a polyfunctional isocyanate compound that acts as a curing agent. The components for obtaining reaction product A may consist only of the acid-modified polyolefin and the polyfunctional isocyanate compound, or they may include other components in addition to the acid-modified polyolefin and the polyfunctional isocyanate compound. The acid-modified polyolefin may contain polar groups such as hydroxyl groups and carbone groups. From the viewpoint of reactivity, the hydroxyl value of acid-modified polyolefin may be 5 KOH mg / g or more and 120 KOH mg / g or less, 10 KOH mg / g or more and 80 KOH mg / g or less, or 20 KOH mg / g or more and 60 KOH mg / g or less. 【0078】Acid-modified polyolefins may also be polyolefins graft-modified with unsaturated carboxylic acid derivatives derived from unsaturated carboxylic acids, unsaturated sulfonic acids, acid anhydrides of unsaturated carboxylic acids, and esters of unsaturated carboxylic acids. In this case, the degree of acid modification in the acid-modified polyolefin may be 2% by mass or less, 1.5% by mass or less, or 1% by mass or less. Examples of acid-modified polyolefins include maleic anhydride-modified polyolefins obtained by reacting maleic anhydride with a polyolefin. Examples of maleic anhydride-modified polyolefins include maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene. 【0079】 Examples of polyfunctional isocyanate compounds include diisocyanates such as tolylene diisocyanate, xylylene diisocyanate or its hydrogenated derivatives, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate or its hydrogenated derivatives, and isophorone diisocyanate; or polyisocyanates such as adducts obtained by reacting these isocyanates with polyhydric alcohols such as trimethylolpropane, biuret compounds obtained by reacting them with water, or trimer isocyanurates (isocyanurate-type polyfunctional isocyanate compounds); or blocked polyisocyanates obtained by blocking these polyisocyanates with alcohols, lactams, oximes, etc. The polyfunctional isocyanate compound may also include isocyanurates (isocyanurate-type polyfunctional isocyanate compounds). In this case, the heat-adhesive resin layer 15 can have excellent adhesion and heat resistance. 【0080】 The heat-adhesive resin layer 15 may optionally contain various additives such as various compatible and incompatible elastomers, flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, crystal nucleating agents, and tackifiers. The resin in the heat-adhesive resin layer 15 can be analyzed using known analytical methods such as IR, NMR, various mass (mass) analysis methods, X-ray analysis, Raman spectroscopy, GPC, DSC, and DMA. 【0081】<Sealant Layer> The sealant layer 16 is a layer that provides heat sealing properties to the laminate 10, and is placed on the inside and heat-sealed (heat-fused) during the assembly of the energy storage device. Examples of resins included in the sealant layer 16 include polypropylene resin and polyethylene resin. When the sealant layer 16 contains both polypropylene resin and polyethylene resin, the ratio of polypropylene resin to the total of polypropylene resin and polyethylene resin is, for example, 85% by mass or more and less than 100% by mass, based on the total amount of the sealant layer 16. That is, in the sealant layer 16, the ratio of polyethylene resin to the total of polypropylene resin and polyethylene resin is, for example, greater than 0% by mass and 20% by mass or less. From the viewpoint of the deformation rate of the sealant layer 16 in a high-temperature environment, the ratio of polypropylene resin to the total of polypropylene resin and polyethylene resin may be 85% by mass or more, 87.5% by mass or more, or 92.5% by mass or more. Furthermore, the above percentage is not particularly limited as long as it is less than 100% by mass, but for example, it may be 98% by mass or less, or 95% by mass or less. 【0082】 The polypropylene resin contained in the sealant layer 16 is, in one example, the base resin of the sealant layer 16. The polypropylene resin is a resin obtained from a polymer monomer containing propylene. Examples of polypropylene resins include homopolypropylene, block polypropylene, and random polypropylene. These may be used individually or in combination of two or more types. From the viewpoint of the hardness of the laminate 10, the polypropylene resin may contain at least one of homopolypropylene and block polypropylene. In this case, the scratch resistance of the laminate 10 is improved compared to the case in which the polypropylene is composed only of random polypropylene. 【0083】The crystallization temperature of the polypropylene resin is not particularly limited, but for example, it is between 100°C and 120°C. From the viewpoint of scratch resistance of the laminate 10, the crystallization temperature of the polypropylene resin may be 102°C or higher, or 105°C or higher. The melting temperature (melting point) of the polypropylene resin is, for example, between 160°C and 168°C. From the viewpoint of sealing performance in high-temperature environments, the melting point may be 162°C or higher. The difference between the melting temperature and the crystallization temperature is not particularly limited, but for example, it is between 30°C and 70°C. From the viewpoint of balancing hardness and softness in the sealant layer 16, the difference may be between 40°C and 65°C, or between 50°C and 60°C. 【0084】 Polyethylene resins are resins obtained from polymerized monomers containing ethylene, and they play a role in imparting softness (stress relaxation). Examples of polyethylene resins include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and polyethylene elastomers. These may be used individually or in combination of two or more types. From the viewpoint of imparting softness to the sealant layer 16, the polyethylene resin may also contain a polyethylene elastomer. 【0085】 As polyethylene-based elastomers, elastomers using α-olefins as comonomers can be used. Specifically, such polyethylene-based elastomers include compounds (copolymers) obtained by copolymerizing ethylene with an α-olefin composed of at least one selected from 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Examples of such copolymers include polyethylene-butene copolymers, polyethylene-pentene copolymers, and polyethylene-hexene copolymers. 【0086】The polyethylene resin may contain a copolymer that functions as a compatibilizer. This copolymer efficiently imparts softness by finely dispersing the polyethylene resin in the polypropylene resin, which is the base resin. The copolymer has, for example, a part that is compatible with the polypropylene resin (hereinafter also referred to as the "PP compatible part") and a part that is compatible with the polyethylene resin (hereinafter also referred to as the "PE compatible part"). Specific examples of the copolymer include a graft copolymer in which the PP compatible part is the main chain and the PE compatible part is the side chain, a graft copolymer in which the PE compatible part is the main chain and the PP compatible part is the side chain, and a block copolymer in which the PP compatible part and the PE compatible part each exist as blocks. From the viewpoint of improving the dispersibility of the polyethylene resin, the copolymer may also be a block copolymer in which at least the PP compatible part exists as a block, or a block copolymer in which the PP compatible part and the PE compatible part each exist as blocks. Examples of such block copolymers include block copolymers of polypropylene and polyethylene (PP-PE block copolymer) and block copolymers of polyethylene and polyethylene-butylene (PE-PE-butylene block copolymer). In PE-PE-butylene block copolymer, the butylene portion corresponds to the PP compatible portion. 【0087】The crystallization temperature of the polyethylene resin is not particularly limited, but for example, it is between 50°C and 90°C. The melting temperature (melting point) of the polyethylene resin is, for example, greater than 70°C and 120°C or less. When both the crystallization temperature and melting temperature of the polyethylene resin are within the above ranges, a good balance between the hardness and softness of the sealant layer 16 can be achieved. In this case, the stress applied to the sealant layer 16 during the manufacturing of the laminate 10 is more easily relieved. For example, when the laminate 10 is transported by a roll and stress is applied to the sealant layer 16 from the roll, the rebound of stress from the roll towards the barrier layer 13 is suppressed. Therefore, the surface of the sealant layer 16 becomes less susceptible to damage. From the viewpoint of scratch resistance of the laminate 10, the crystallization temperature of the polyethylene resin may be between 55°C and 85°C, or between 60°C and 80°C. From the viewpoint of scratch resistance of the laminate 10, the melting temperature of the polyethylene resin may be 80°C or higher, or 90°C or higher. The difference between the melting temperature and the crystallization temperature is not particularly limited, and is, for example, 10°C or more and 45°C or less. From the viewpoint of balancing hardness and softness in the sealant layer 16, this difference may be 15°C or more and 40°C or 20°C or more and 35°C or less. 【0088】 The sealant layer 16 may contain other additive components as needed, such as slip agents, antiblocking agents, antioxidants, light stabilizers, nucleating agents, and flame retardants. The content of these additive components is, for example, 5% by mass or less when the total mass of the sealant layer 16 is considered as 100% by mass. 【0089】 When the laminate 10 includes a heat-adhesive resin layer 15 and a sealant layer 16, the heat-adhesive resin layer 15 and the sealant layer 16 may be formed simultaneously by methods such as the T-die method or the inflation method, or they may be formed at different timings. In the latter case, the heat-adhesive resin layer 15 and the sealant layer 16 may be bonded together with an adhesive. In this case, the adhesive may include acid-modified polypropylene and a curing agent (e.g., isocyanate) from the viewpoint of interfacial adhesion. 【0090】The laminate 10 may be a packaging material subjected to deep drawing. With the laminate 10, deep drawing suppresses corner indentation and results in a molded body with clearly defined edges. Therefore, the laminate 10 can be suitably used as a packaging material subjected to deep drawing. The laminate 10 may be an outer casing material for all-solid-state batteries. With the laminate 10, deep drawing suppresses corner indentation and results in a molded body with clearly defined edges. Therefore, the laminate 10 can be suitably used as an outer casing material for all-solid-state batteries where sufficient deep drawing moldability is required compared to conventional materials. 【0091】 [Energy Storage Device] An energy storage device according to one embodiment will be described below. Figure 3 is a perspective view showing the energy storage device according to this embodiment. As shown in Figure 3, the all-solid-state battery 50 as an energy storage device has an energy storage element 52, two metal terminals 53 for extracting current from the energy storage element 52 to the outside, and an outer bag 54 for housing the energy storage element 52 in an airtight state. 【0092】 The outer bag 54 is a component used as a container for housing the energy storage element 52, and has a bag body 54a and a sealing portion 54b provided on the bag body 54a. The outer bag 54 is a bag-shaped molded body of the laminate 10. In the outer bag 54, the base material layer 11 is the outermost layer, and the sealant layer 16 is the innermost layer. Therefore, the outer bag 54 can house the energy storage element 52 inside by folding one laminate 10 in half and heat-sealing the peripheral portion, or by stacking two laminates 10 and heat-sealing the peripheral portion, so that the base material layer 11 is on the outside of the all-solid-state battery 50 and the sealant layer 16 is on the inside of the all-solid-state battery 50. For this reason, the heat-sealed portion in the outer bag 54 is the part where a part of the sealant layer 16 is heat-sealed to another part. 【0093】 The metal terminal 53 is held in place by an outer bag 54 with a sealant layer 16 on the inside. The metal terminal 53 may also be held in place by the outer bag 54 via a tab sealant. The metal terminal 53 is a part of the current collector that is exposed to the outside of the laminate 10, and is made of metal foil such as copper foil or aluminum foil. 【0094】The energy storage element 52 has a pair of electrodes and a solid electrolyte sandwiched between the pair of electrodes. One of the electrodes is the positive electrode and the other is the negative electrode. Examples of solid electrolytes include sulfide-based solid electrolytes and oxide-based solid electrolytes. 【0095】 [Method for Manufacturing the Laminate] A method for manufacturing the laminate 10 according to one embodiment of this disclosure will be described below. However, the method for manufacturing the laminate 10 is not limited to the following method. 【0096】 As a method for manufacturing the laminate 10, for example, a method is to carry out the following steps S11 to S13 in this order. The method for manufacturing the laminate 10 may, if necessary, include an aging treatment step in addition to steps S11 to S13. Step S11: A step of forming a corrosion-preventive treatment layer 14a on the surface 13b of the metal foil layer 13a and a corrosion-preventive treatment layer 14b on the surface 13c of the metal foil layer 13a. Step S12: A step of bonding the corrosion-preventive treatment layer 14a and the base layer 11 via an adhesive layer 12. Step S13: A step of laminating a heat-adhesive resin layer 15 and a sealant layer 16 on the corrosion-preventive treatment layer 14b. 【0097】<Step S11> In step S11, a corrosion-preventive treatment layer 14a is formed on the surface 13b of the metal foil layer 13a, and a corrosion-preventive treatment layer 14b is formed on the surface 13c of the metal foil layer 13a. The corrosion-preventive treatment layers 14a and 14b may be formed separately or simultaneously. In one example, after applying a corrosion-preventive treatment agent (base material for the corrosion-preventive treatment layer) to the surfaces 13b and 13c of the metal foil layer 13a, the corrosion-preventive treatment layers 14a and 14b are formed simultaneously by sequentially drying, hardening, and baking. Alternatively, a corrosion-preventive treatment agent may be applied to the surface 13b of the metal foil layer 13a, and then sequentially drying, hardening, and baking to form the corrosion-preventive treatment layer 14a. The corrosion-preventive treatment layer 14b may then be formed on the surface 13c of the metal foil layer 13a in the same manner. The order in which the corrosion-preventive treatment layers 14a and 14b are formed is not particularly limited. Furthermore, the corrosion inhibitor used to form the corrosion-preventive treatment layer 14a may be different from or the same as the corrosion inhibitor used to form the corrosion-preventive treatment layer 14b. The method of applying the corrosion inhibitor is not particularly limited, but for example, methods such as gravure coating, gravure reverse coating, roll coating, reverse roll coating, die coating, bar coating, kiss coating, comma coating, and small-diameter gravure coating can be used. 【0098】 <Step S12> In step S12, the corrosion-preventive treatment layer 14a and the base layer 11 are bonded together using an adhesive that forms the adhesive layer 12, by methods such as dry lamination, non-solvent lamination, or wet lamination. In step S12, heat treatment may be performed to promote the adhesion of the adhesive layer 12. From the viewpoint of the mold curl resistance of the base layer 11, the temperature during heat treatment may be 140°C or lower, or 120°C or lower. The dry application amount of the adhesive layer 12 is, for example, 1 g / m². ２ 10g / m or more ２ The following is also acceptable, or 2 g / m ２ 7g / m or more ２ The following is also acceptable. 【0099】<Step S13> After step S12, a laminate is formed in which the base layer 11, adhesive layer 12, corrosion prevention treatment layer 14a, barrier layer 13, and corrosion prevention treatment layer 14b are laminated in this order. In step S13, a heat-adhesive resin layer 15 and a sealant layer 16 are formed on the corrosion prevention treatment layer 14b of the laminate. For the formation of the heat-adhesive resin layer 15 and the sealant layer 16, for example, a method of sand lamination of the heat-adhesive resin layer 15 together with the sealant layer 16 using an extrusion laminating machine is carried out. Alternatively, a tandem lamination method or co-extrusion method in which the heat-adhesive resin layer 15 and the sealant layer 16 are extruded may be carried out. 【0100】 After step S13, a laminate 10 is obtained, as shown in Figure 2, in which the following layers are stacked in the order of base material layer 11 / adhesive layer 12 / corrosion prevention treatment layer 14a / metal foil layer 13a / corrosion prevention treatment layer 14b / heat-bondable resin layer 15 / sealant layer 16. 【0101】 <Aging Process> The aging process is a process of aging (curing) the laminate 10. By aging the laminate 10, adhesion between the base material layer 11 / adhesive layer 12 / corrosion prevention treatment layer 14a / metal foil layer 13a, and adhesion between the metal foil layer 13a / corrosion prevention treatment layer 14b / heat-bondable resin layer 15 / sealant layer 16 can be promoted. The aging temperature may be 80°C or higher, 100°C or higher, or 120°C or higher, and may be 140°C or lower, 150°C or lower, or 160°C or lower. The aging time may be 1 hour or more, 2 hours or more, or 3 hours or more, and may be 24 hours or less, 48 ​​hours or less, or 72 hours or less. 【0102】 Below, a modified example of the above embodiment (exterior material) will be described with reference to Figure 4. In the modified example, explanations that overlap with the above embodiment will be omitted. Figure 4 is a schematic cross-sectional view of an exterior material for an energy storage device according to a modified example. As shown in Figure 4, the laminate 20 is an exterior material used for an energy storage device and includes, in order, a base layer 11, a barrier layer 13, an adhesive layer 15A (second adhesive layer), and a sealant layer 16. 【0103】The laminate 20 differs from the laminate 10 in that it includes an adhesive layer 15A instead of the heat-bonding resin layer 15. Since the thickness of the adhesive layer 15A in the laminate 20 is significantly thinner than the thickness of the sealant layer 16, it does not substantially affect the physical properties of the sealant layer 16. 【0104】 <Adhesive Layer 15A> The adhesive layer 15A will now be described. The adhesive layer 15A is a layer that adheres the barrier layer 13 and the sealant layer 16. A general adhesive for adhering the barrier layer 13 and the sealant layer 16 can be used for the adhesive layer 15A. 【0105】 If a corrosion-preventive treatment layer 14b is provided on the metal foil layer 13a, and the corrosion-preventive treatment layer 14b has a layer containing at least one polymer selected from the group consisting of cationic polymers and anionic polymers described above, the adhesive layer 15A may also contain a compound that is reactive with the polymer contained in the corrosion-preventive treatment layer 14b (hereinafter also referred to as a "reactive compound"). 【0106】 For example, if the corrosion-preventive treatment layer 14b contains a cationic polymer, the adhesive layer 15A may contain a compound that is reactive with the cationic polymer. If the corrosion-preventive treatment layer 14b contains an anionic polymer, the adhesive layer 15A may contain a compound that is reactive with the anionic polymer. If the corrosion-preventive treatment layer 14b contains both a cationic polymer and an anionic polymer, the adhesive layer 15A may contain at least one of a compound that is reactive with the cationic polymer and a compound that is reactive with the anionic polymer. Here, "reactive" means forming a covalent bond with the cationic polymer or the anionic polymer. The adhesive layer 15A may further contain an acid-modified polyolefin resin. 【0107】Compounds that react with cationic polymers include at least one compound selected from the group consisting of polyfunctional isocyanate compounds, glycidyl compounds, compounds having a carboxyl group, and compounds having an oxazoline group. Polyfunctional isocyanate compounds, for example, can function as crosslinking agents for forming a crosslinked structure of cationic polymers. From the viewpoint of reactivity with cationic polymers and the ability to form crosslinked structures, polyfunctional isocyanate compounds may be used. Compounds that react with anionic polymers include at least one compound selected from the group consisting of glycidyl compounds and compounds having an oxazoline group. From the viewpoint of reactivity with anionic polymers, glycidyl compounds may be used. 【0108】 If the adhesive layer 15A contains an acid-modified polyolefin resin, the reactive compound may also be reactive with the acidic groups in the acid-modified polyolefin resin (i.e., form covalent bonds with the acidic groups). This further enhances the adhesion between the adhesive layer 15A and the corrosion-preventive treatment layer 14b. In addition, the acid-modified polyolefin resin becomes a cross-linked structure, further improving the solvent resistance of the laminate 20. 【0109】 The content of the reactive compound is, for example, equal to or 10 times the amount of the acidic groups in the acid-modified polyolefin resin. If the amount is equal to or greater than the amount of the acidic groups in the acid-modified polyolefin resin, the reactive compound will react sufficiently with the acidic groups in the acid-modified polyolefin resin. On the other hand, if the amount exceeds 10 times the amount, the crosslinking reaction with the acid-modified polyolefin resin will be sufficiently saturated, and unreacted material will remain, raising concerns about a decrease in various performance characteristics. Therefore, for example, the content of the reactive compound is, in terms of solid content ratio, 5 parts by mass or more and 20 parts by mass or less per 100 parts by mass of acid-modified polyolefin resin. 【0110】 Acid-modified polyolefin resin is a polyolefin resin into which acidic groups have been introduced. Examples of acidic groups include carboxyl groups, sulfonic acid groups, and acid anhydride groups. For example, maleic anhydride groups and (meth)acrylic acid groups may also be used. As the acid-modified polyolefin resin, for example, the same type as the modified polyolefin resin used in the sealant layer 16 can be used. 【0111】 The adhesive layer 15A may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers, and tackifiers. 【0112】 The adhesive layer 15A may contain, for example, an acid-modified polyolefin and at least one curing agent selected from the group consisting of a polyfunctional isocyanate compound, a glycidyl compound, a compound having a carboxyl group, a compound having an oxazoline group, and a carbodiimide compound, from the viewpoint of suppressing a decrease in heat seal strength and a decrease in insulating properties caused by corrosive gases such as hydrogen sulfide and electrolytes. Examples of carbodiimide compounds include N,N'-di-o-toluylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, N,N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N,N'-di-2,2-di-t-butylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-di-cyclohexylcarbodiimide, and N,N'-di-p-toluylcarbodiimide. 【0113】 As the adhesive for forming the adhesive layer 15A, for example, a polyurethane-based adhesive containing a polyester polyol composed of hydrogenated dimer fatty acids and diols, and a polyisocyanate can be used. From the viewpoint of heat resistance, examples of adhesives that may be used include polyurethane resins obtained by reacting a bifunctional or more isocyanate compound with a main component such as polyester polyol, polyether polyol, acrylic polyol, or carbonate polyol, and epoxy resins obtained by reacting an amine compound with a main component having epoxy groups. 【0114】 The thickness of the adhesive layer 15A is not particularly limited, but from the viewpoint of obtaining the desired adhesive strength and processability, it may be 1 μm to 10 μm or 2 μm to 7 μm. 【0115】 Next, an example of a method for manufacturing the laminate 20 shown in Figure 4 will be described. Note that the method for manufacturing the laminate 20 is not limited to the method described below. 【0116】 A modified method for manufacturing the laminate 20 includes, for example, a method in which steps S11 and S12 above are performed in order, and step S14 below is performed instead of step S13 above. The method for manufacturing the laminate 20 may also include the aging treatment step as needed. Step S14: A step of bonding the corrosion prevention treatment layer 14b and the sealant layer 16 via the adhesive layer 15A. 【0117】 <Process S14> (Lamination process of the second adhesive layer and sealant layer) In process S14, the corrosion-preventive treatment layer 14b and the sealant layer 16 are bonded together via the adhesive layer 15A, for example, by a wet process or dry lamination. This produces the laminate 20. 【0118】 In the wet process, first, a solution or dispersion of the adhesive constituting the adhesive layer 15A is applied onto the corrosion-preventive treatment layer 14b. Subsequently, the solvent is evaporated at a predetermined temperature to form a dry film. At this time, if necessary, a baking treatment may be performed on the dry film. After that, a sealant layer 16 is laminated to produce a laminate 20. Examples of coating methods include the various coating methods exemplified above. The dry application amount of the adhesive layer 15A is, for example, the same as that of the adhesive layer 12. 【0119】 In this case, the sealant layer 16 can be manufactured by a melt extrusion molding machine using, for example, a resin composition for forming a sealant layer containing the base resin, additive resin, and compatibilizer described above. From the viewpoint of productivity, the processing speed of the melt extrusion molding machine can be set to 80 m / min or more. 【0120】[Method for Selecting a Laminate] A method for selecting a laminate according to one embodiment of the present disclosure will be described below. The method for selecting a laminate according to the present embodiment includes the steps of: preparing a laminate to be evaluated having a laminated structure comprising a base layer, a first adhesive layer, a barrier layer, and a sealant layer in this order; measuring the amount of plastic deformation of the base layer of the laminate to be evaluated using a nanoindenter under a maximum load of 100 μN; and determining that the laminate is a satisfactory product when the amount of plastic deformation is 30 nm or more. 【0121】 By setting the maximum load to 100 μN, the influence from layers adjacent to the base material layer is weakened, and the amount of plastic deformation of the base material layer tends to be measured more accurately. 【0122】 The layer structure of the laminate, the materials that make up the layers, and the thickness of each layer may be the same as those of the laminate according to the above embodiment. 【0123】 [Molded Body] A molded body according to one embodiment of the present disclosure will be described below. The molded body according to this embodiment is composed of a laminate according to the above embodiment. The configuration of the molded body according to this embodiment may be the same as that of the molded body shown in Figures 1(a) and 1(b). That is, the molded body 30 according to this embodiment includes a recess 32 and a rectangular frame-shaped flange portion 34 surrounding the recess 32. The recess 32 consists of a bottom surface 32a and four side surfaces 32b. A corner portion 32c is a portion defined by the bottom surface 32a and a pair of adjacent side surfaces 32b. The corner portion 32c is formed in a curved shape that is convex to the outside of the recess 32. A ridge portion 32d is the boundary between the bottom surface 32a and the side surface 32b. A ridge portion 32e is the boundary between the side surface 32b and the flange portion 34. 【0124】 The depth of the recess may be, for example, 5 mm or more, 10 mm or more, or 13 mm or more. The depth of the recess refers to the distance in the normal direction from the inner surface of the flange portion 34 (the surface continuous with the opening of the recess) to the surface of the bottom surface 32a of the recess that faces the internal space. 【0125】When the height from the end 32d1 on the bottom surface 32a side of the ridge portion 32d to the flange portion 34 is defined as H1, and the height from the end 32d2 on the side surface 32b side of the ridge portion 32d to the flange portion 34 is defined as H2, the value obtained by subtracting H2 from H1 (H1-H2) is preferably less than 5.5 mm, more preferably less than 4.5 mm, and even more preferably less than 3.5 mm. 【0126】 [Method for Manufacturing a Molded Article] A method for manufacturing a molded article according to one embodiment of the present disclosure will be described below. According to the method for manufacturing a molded article according to the present embodiment, a molded article according to the above embodiment can be obtained. The method for manufacturing a molded article according to the present embodiment may include the following steps 1 and 2. Step 1: A step of preparing the laminate according to the above embodiment. Step 2: A step of placing the laminate on a die mold having an opening and pressing a punch die into the opening of the die mold to form a recess 32 and a flange portion 34. 【0127】 In step 2, the depth to which the punch mold is pressed into the opening of the die mold may be, for example, 5 mm or more, 10 mm or more, or 13 mm or more. 【0128】[Summary of the Disclosure] The summary of the disclosure is as follows: [1] A laminate having a laminated structure comprising a base layer, a first adhesive layer, a barrier layer, and a sealant layer in this order, wherein the amount of plastic deformation of the base layer is 30 nm or more, and the amount of plastic deformation of the base layer is measured using a nanoindenter under the condition of a maximum load of 100 μN. [2] The laminate according to [1], wherein the base layer comprises at least one resin selected from the group consisting of polyester resin and polyamide resin. [3] The laminate according to [1] or [2], wherein the barrier layer comprises aluminum foil, and the thickness of the aluminum foil is 40 μm or more. [4] The laminate according to [3], wherein the iron content in the aluminum foil is 0.1% by mass or more and 9.0% by mass or less of 100% by mass of the aluminum foil. [5] The laminate according to any one of [1] to [4], wherein the base layer comprises polybutylene terephthalate. [6] The laminate according to any one of [1] to [5], wherein the amount of plastic deformation of the base layer is 40 nm or more and 100 nm or less. [7] The laminate according to any one of [1] to [6], wherein the thickness of the base layer is 10 to 30 μm. [8] The laminate according to any one of [1] to [7], further comprising a heat-adhesive resin layer located between the barrier layer and the sealant layer. [9] The laminate according to [8], wherein the heat-adhesive resin layer comprises an acid-modified polyolefin resin.

[10] The laminate according to any one of [1] to [8], further comprising a corrosion-preventive treatment layer located on the surface of the barrier layer facing the first adhesive layer.

[11] The laminate according to [8] or [9], further comprising a corrosion-preventive treatment layer located on the surface of the barrier layer facing the heat-adhesive resin layer.

[12] The laminate according to [2], wherein the barrier layer has aluminum foil, and the thickness of the aluminum foil is 40 μm or more.

[13] The laminate according to

[12] , wherein the base material layer comprises polybutylene terephthalate.

[14] The laminate according to [1], having a laminated structure comprising the above-mentioned base material layer, the above-mentioned first adhesive layer, a corrosion-preventive treatment layer, the above-mentioned barrier layer, a corrosion-preventive treatment layer, a heat-adhesive resin layer, and the above-mentioned sealant layer in this order, wherein the base material layer contains polybutylene terephthalate, the thickness of the base material layer is 10 to 30 μm, the amount of plastic deformation of the base material layer is 42 nm to 90 nm, the barrier layer has aluminum foil, the thickness of the aluminum foil is 50 μm to 100 μm, the iron content in the aluminum foil is 0.1% to 9.0% by mass per 100% by mass of the aluminum foil, and the heat-adhesive resin layer contains an acid-modified polyolefin resin.

[15] The laminate according to [1], comprising the above-mentioned base layer, the above-mentioned first adhesive layer, a corrosion-preventive treatment layer, the above-mentioned barrier layer, a corrosion-preventive treatment layer, a heat-adhesive resin layer, and the above-mentioned sealant layer in this order, wherein the base layer contains polyethylene terephthalate, the thickness of the base layer is 10 to 30 μm, the amount of plastic deformation of the base layer is 42 nm to 90 nm, the barrier layer has aluminum foil, the thickness of the aluminum foil is 30 μm to 100 μm, the iron content in the aluminum foil is 0.1% to 9.0% by mass of 100% by mass of the aluminum foil, and the heat-adhesive resin layer contains an acid-modified polyolefin resin.

[16] The laminate according to any one of [1] to

[15] , which is a packaging material subjected to deep drawing.

[17] The laminate according to any one of [1] to

[16] , which is an exterior material for all-solid-state batteries.

[18] A method for selecting a laminate, comprising: preparing a laminate to be evaluated having a laminated structure comprising a base layer, a first adhesive layer, a barrier layer, and a sealant layer in this order; measuring the amount of plastic deformation of the base layer of the laminate to be evaluated using a nanoindenter under the condition of a maximum load of 100 μN; and determining that the laminate is a good product when the amount of plastic deformation is 30 nm or more.

[19] A molded body comprising a laminate as described in any of [1] to

[17] , wherein the molded body comprises a recess and a rectangular frame-shaped flange portion surrounding the recess, and the depth of the recess is 5 mm or more.

[20] A method for manufacturing the molded body as described in

[19] , comprising the following steps 1 and 2: Step 1: A step of preparing the laminate. Step 2: A step of placing the laminate on a die mold having an opening and pressing a punch die into the opening to form the recess and the flange portion. 【0129】 The following describes embodiments of this disclosure. This disclosure is not limited to the following embodiments. 【0130】 [Fabrication of Laminates] <Example 1> The materials used as the base layer, first adhesive layer, metal foil layer, material for forming the first corrosion-preventive treatment layer, material for forming the second corrosion-preventive treatment layer, heat-bonding resin layer, and sealant layer are as follows. 【0131】 (Base layer) Polyamide film: Sequentially biaxially oriented film made from nylon 6, thickness 25 μm, referred to as "Ny1" in Table 1 【0132】 (First adhesive layer (mass per unit area: 4.0 g / m²) ２ (First adhesive for forming the first adhesive layer) As the material for the first adhesive layer, a urethane resin (manufactured by Mitsui Chemicals, trade name "Main component: Takelac A-515 (solid content concentration 50% by mass), curing agent: Takenate D-140 (solid content concentration 74% by mass)") was prepared. These materials were mixed in a ratio of 30 parts by mass of curing agent to 100 parts by mass of main component, and diluted with ethyl acetate to a solid content concentration of 30% by mass to form the first adhesive. 【0133】 (Metal foil layer) Annealed and degreased soft aluminum foil: Toyo Aluminum Co., Ltd., "8079 material", thickness 60 μm 【0134】(Materials for forming the first corrosion-preventive treatment layer and materials for forming the second corrosion-preventive treatment layer) The materials for forming the first corrosion-preventive treatment layer and the materials for forming the second corrosion-preventive treatment layer are as follows: (CL-1) and (CL-2). (CL-1): Sodium polyphosphate stabilized cerium oxide sol adjusted to a solid content concentration of 10% by mass using distilled water as the solvent. (CL-2): A composition adjusted to a solid content concentration of 5% by mass using distilled water as the solvent. 【0135】 The above sodium polyphosphate-stabilized cerium oxide sol was obtained by blending 10 parts by mass of sodium phosphoric acid with 100 parts by mass of cerium oxide. In addition, in the above composition, the mass ratio of "polyallylamine (manufactured by Nitto Boseki Co., Ltd.)" and "polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX Corporation)" was 90:10. 【0136】 (Resin composition for forming a heat-adhesive resin layer) A random polypropylene-based acid-modified polypropylene resin composition was used as the resin composition for forming a heat-adhesive resin layer. 【0137】 (Sealant layer) Polypropylene resin: Polypropylene-polyethylene random copolymer (manufactured by Prime Polymer, trade name: F744NP) 【0138】 First, a barrier layer was formed by applying first and second corrosion-preventive treatment layers to the metal foil layer. Specifically, (CL-1) was applied to both surfaces of the metal foil layer at a dry coating rate of 70 mg / m². ２ The material was coated using microgravure coating and then baked in a drying unit at 200°C. Next, (CL-2) was applied to the resulting layer at a dry coating rate of 20 mg / m². ２ By applying a microgravure coating in this manner, a composite layer consisting of (CL-1) and (CL-2) was formed as the first and second corrosion-preventive treatment layers. This composite layer exhibits corrosion-preventive performance by combining the two types, (CL-1) and (CL-2). 【0139】Next, the first corrosion-preventive treatment layer of the barrier layer was bonded to the substrate layer using a first adhesive to form the first adhesive layer by a dry lamination method. Specifically, the first adhesive was applied to the first corrosion-preventive treatment layer so that its thickness after drying was 4 μm. Subsequently, the first adhesive was dried at 80°C for 1 minute, and then the substrate layer and the barrier layer were bonded together. After that, aging was performed at 80°C for 120 hours. As a result, the first laminate (substrate layer / first adhesive layer / first corrosion-preventive treatment layer / metal foil layer / second corrosion-preventive treatment layer) was obtained. 【0140】 The first laminate was set in the unwinding section of an extrusion laminating machine. A heat-adhesive resin layer and a sealant layer were laminated in this order on the second corrosion-preventive treatment layer of the first laminate by co-extrusion from a T-die under processing conditions of 270°C and 80 m / min. This resulted in a laminate (base layer / first adhesive layer / first corrosion-preventive treatment layer / metal foil layer / second corrosion-preventive treatment layer / heat-adhesive resin layer / sealant layer). At this time, the thicknesses of the heat-adhesive resin layer and the sealant layer were 25 μm and 55 μm, respectively. 【0141】 <Example 2> A laminate was prepared in the same manner as in Example 1, except that a polybutylene terephthalate film (manufactured by Kojin Co., Ltd., trade name "Boblet CF", thickness 25 μm, referred to as "PBT1" in Table 1) was used as the base layer. 【0142】 <Example 3> A laminate was prepared in the same manner as in Example 1, except that a polyethylene terephthalate film (25 μm thick, referred to as "PET1" in Table 1) was used as the base layer. The polyethylene terephthalate film was obtained from a polyester resin composition based on polyethylene terephthalate with an elastic modulus of 2.9 GPa. 【0143】 <Example 4> A laminate was prepared in the same manner as in Example 2, except that the thickness of the base layer was 15 μm. 【0144】 <Example 5> A laminate was prepared in the same manner as in Example 2, except that the thickness of the soft aluminum foil was 40 μm. 【0145】<Comparative Example 1> A laminate was prepared in the same manner as in Example 1, except that a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumirror T60", thickness 25 μm, modulus of elasticity: 4.7 GPa, referred to as "PET2" in Table 1) was used as the base layer. 【0146】 <Comparative Example 2> A laminate was prepared in the same manner as in Example 1, except that polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "E5100", thickness 16 μm, modulus of elasticity: 3.9 GPa, referred to as "PET3" in Table 1) was used as the base layer, and the thickness of the soft aluminum foil was set to 30 μm. 【0147】 <Comparative Example 3> A laminate was prepared in the same manner as in Example 1, except that a co-extruded film of polyethylene terephthalate and nylon (manufactured by Gunze Corporation, product name "Heptax HBF", polyethylene terephthalate layer thickness: 5 μm, nylon layer thickness: 20 μm, total thickness 25 μm) was used as the base layer, and the thickness of the soft aluminum foil was set to 30 μm. 【0148】 [Amount of plastic deformation of the base layer] <Examples 1-5, Comparative Examples 1-3> In each example, the amount of plastic deformation of the surface of the film used as the base layer of the laminate (surface of the base layer) was measured by nanoindentation. 【0149】(Preparation of the measurement sample) The front and back surfaces of the film were each treated with corona at 0.20 kW (equipment: Kasuga Electric Co., Ltd. corona treatment machine CT-0212). Next, the film was cut into a wedge shape with a base of 1.0 mm and a height of 5.0 mm using a razor blade. The cut film was embedded in a photocurable resin and cured with a halogen lamp KTX-100R. D-800 manufactured by Toagosei Co., Ltd. was used as the photocurable resin. After photocuring, the film-embedded resin was fixed with an AFM sample holder insert (manufactured by Leica Microsystems Co., Ltd.), and the cross-section of the film was cut with a glass knife at room temperature (25°C). Subsequently, the cross-section was further cut with a diamond knife at room temperature (cutting speed: 10 mm / sec, cutting film thickness: 1000 nm), and the cross-section cutting was stopped when the cross-section became mirror-like. This obtained the sample to be measured. An ultramicrotome (EM UC7, Leica Microsystems) and a cryosystem (EM FC7, Leica Microsystems) were used as cross-sectional cutting devices. The cutting direction of the knife was parallel to the layer interface. 【0150】(Measurement) The amount of plastic deformation was measured on the obtained sample. The measuring device used was the Hystron TI-Premier (product name) manufactured by Bruker Japan Co., Ltd. The indenter used was a Berkovich-type diamond indenter manufactured by Bruker Japan Co., Ltd. For the nanoindentation method measurement, in load control mode, the load was applied up to 100 μN at an indentation (loading) speed of 100 μN / sec, held at the maximum load for 1 second, and then withdrawn (unloaded) at a speed of 100 μN / sec. For the measurement points, the shape image of the sample cross-section was obtained using the shape measurement function of the measuring device, which scans the sample surface with the indenter, and 30 points were specified on the substrate layer at intervals of 2 μm or more from the shape image, and measurements were performed using the nanoindentation method. Prior to the measurement, fused silica, which would serve as a standard sample, was tested to calibrate the relationship between the contact depth and contact projected area between the indenter and the sample. A load-displacement curve was obtained through these operations. Figure 5 shows an example of a load-displacement curve, with the load applied to the base layer on the vertical axis and the displacement of the base layer on the horizontal axis. As shown in Figure 5, the plastic deformation amount h1 is the displacement when the load changes from a positive value to a negative value in the unloading curve. The plastic deformation amounts h1 are shown in Table 1. In Table 1, for the plastic deformation amount of Comparative Example 3, 28 nm is the value for the polyethylene terephthalate layer and 55.8 nm is the value for the nylon layer. 【0151】 [Deep Drawing Molding] <Examples 1-5, Comparative Examples 1-3> The laminates obtained in each example were placed in a molding apparatus with the sealant layer facing upwards as test pieces, and deep drawing molding was performed under the conditions shown below to obtain the molded bodies shown in Figures 1(a) and 1(b). Deep drawing molding was performed under the conditions shown below. 【0152】 (Conditions) Specimen size: 200 mm x 150 mm Punch die cross-section size: 150 mm x 100 mm Corner radius of punch die side: 1.8 mm Punch radius of punch die bottom: 1.0 mm Die radius of die opening top: 1.0 mm Pressing pressure: 0.8 MPa Molding speed: 3.3 mm / sec Pre-conditioning: Dry room (-40°C dp) for 12 hours or more Drawing depth: 5.5 mm Molding temperature: 25°C 【0153】[Evaluation of corner indentations] <Examples 1-5, Comparative Examples 1-3> For each example of the molded body, the indentations at the four corners 32c were visually inspected and evaluated according to the following criteria. The results are shown in Table 1. A score of "3" or higher was considered acceptable. 【0154】 (Criteria) 5: No indentations are observed in any of the four corners 32c. 4: An indentation less than 1 mm deep is observed in one of the four corners 32c, and no indentations are observed in the other three corners 32c. 3: An indentation of 1 mm or more deep is observed in two or three of the four corners 32c, and no indentations of 1 mm or more deep are observed in the remaining corners 32c. 2: An indentation of 1 mm or more deep is observed in all four corners 32c, but no indentations of 2 mm or more deep are observed in any of the four corners 32c. 1: An indentation of 2 mm or more deep is observed in all four corners 32c. 【0155】 [Evaluation of the clarity of the ridge lines] Each molded body 30 was placed on a horizontal stand with the bottom surface 32a of the molded body and recess 32 facing upwards and the flange portion 34 facing downwards. The height H1 from the bottom surface 32a side end 32d1 of the ridge line 32d to the flange portion 34 and the height H2 from the side surface 32b side end 32d2 of the ridge line 32d to the flange portion 34 were measured. The measurements were taken visually using a ruler from a distance of 15 cm from the measurement point. The value obtained by subtracting H2 from H1 (H1-H2) was calculated. This process was repeated five times, and the average value of the five measurements was calculated. The average value was evaluated according to the following criteria. The results are shown in Table 1. A value of "3" or higher was judged to be acceptable. 【0156】 (Criteria) 5: The above value (H1-H2) is less than 3.5 mm 4: The above value (H1-H2) is 3.5 mm or more and less than 4.5 mm 3: The above value (H1-H2) is 4.5 mm or more and less than 5.5 mm 2: The above value (H1-H2) is 5.5 mm or more and less than 6.5 mm 1: The above value (H1-H2) is 6.5 mm or more 【0157】 【0158】 10, 20... Laminate, 11... Base material layer, 12... Adhesive layer (first adhesive layer), 13... Barrier layer, 16... Sealant layer.

Claims

1. A laminate having a laminated structure comprising a base layer, a first adhesive layer, a barrier layer, and a sealant layer in this order, wherein the amount of plastic deformation of the base layer is 30 nm or more, and the amount of plastic deformation of the base layer is measured using a nanoindenter under a maximum load of 100 μN.

2. The laminate according to claim 1, wherein the base layer comprises at least one resin selected from the group consisting of polyester resins and polyamide resins.

3. The laminate according to claim 1 or 2, wherein the barrier layer has an aluminum foil, and the thickness of the aluminum foil is 40 μm or more.

4. The laminate according to claim 3, wherein the iron content in the aluminum foil is 0.1% by mass or more and 9.0% by mass or less of 100% by mass of the aluminum foil.

5. The laminate according to claim 1 or 2, wherein the base layer comprises polybutylene terephthalate.

6. The laminate according to claim 1 or 2, wherein the amount of plastic deformation of the base layer is 40 nm or more and 100 nm or less.

7. The laminate according to claim 1 or 2, wherein the thickness of the base material layer is 10 μm or more and 30 μm or less.

8. The laminate according to claim 1 or 2, further comprising a heat-adhesive resin layer located between the barrier layer and the sealant layer.

9. The laminate according to claim 8, wherein the heat-bondable resin layer comprises an acid-modified polyolefin resin.

10. The laminate according to claim 1 or 2, further comprising a corrosion-preventive treatment layer located on the surface of the barrier layer that faces the first adhesive layer.

11. The laminate according to claim 8, further comprising a corrosion-preventive treatment layer located on the surface of the barrier layer that faces the heat-adhesive resin layer.

12. The laminate according to claim 2, wherein the barrier layer has an aluminum foil, and the thickness of the aluminum foil is 40 μm or more.

13. The laminate according to claim 11, wherein the base layer contains polybutylene terephthalate.

14. The laminate according to claim 1, having a laminated structure comprising, in this order: the base layer, the first adhesive layer, the corrosion prevention treatment layer, the barrier layer, the corrosion prevention treatment layer, the heat-adhesive resin layer, and the sealant layer, wherein the base layer contains polybutylene terephthalate, the thickness of the base layer is 10 μm or more and 30 μm or less, the amount of plastic deformation of the base layer is 42 nm or more and 90 nm or less, the barrier layer has aluminum foil, the thickness of the aluminum foil is 50 μm or more and 100 μm or less, the iron content in the aluminum foil is 0.1% by mass or more and 9.0% by mass or less per 100% by mass of the aluminum foil, and the heat-adhesive resin layer contains an acid-modified polyolefin resin.

15. The laminate according to claim 1, having a laminated structure comprising, in this order: the base layer, the first adhesive layer, the corrosion prevention treatment layer, the barrier layer, the corrosion prevention treatment layer, the heat-adhesive resin layer, and the sealant layer, wherein the base layer contains polyethylene terephthalate, the thickness of the base layer is 10 μm or more and 30 μm or less, the amount of plastic deformation of the base layer is 42 nm or more and 90 nm or less, the barrier layer has aluminum foil, the thickness of the aluminum foil is 30 μm or more and 100 μm or less, the iron content in the aluminum foil is 0.1% by mass or more and 9.0% by mass or less per 100% by mass of the aluminum foil, and the heat-adhesive resin layer contains an acid-modified polyolefin resin.

16. The laminate according to claim 1 or 2, which is a packaging material that is subjected to deep drawing.

17. The laminate according to claim 1 or 2, which is an outer casing material for an all-solid-state battery.

18. A method for selecting a laminate, comprising the steps of: preparing a laminate to be evaluated having a laminated structure comprising a base layer, a first adhesive layer, a barrier layer, and a sealant layer in that order; measuring the amount of plastic deformation of the base layer of the laminate to be evaluated using a nanoindenter under the condition of a maximum load of 100 μN; and determining that the laminate is a satisfactory product when the amount of plastic deformation is 30 nm or more.

19. A molded body comprising a laminate according to claim 1 or 2, the molded body comprising a recess and a rectangular frame-shaped flange portion surrounding the recess, wherein the depth of the recess is 5 mm or more.

20. A method for manufacturing a molded article according to claim 19, comprising the following steps 1 and 2. Step 1: A step of preparing the laminate. Step 2: A step of placing the laminate on a die mold having an opening and pressing a punch mold into the opening to form the recess and the flange portion.

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