JP2019055498A - Packaging material for molding, exterior case for power storage device, and power storage device - Google Patents

Abstract

To provide a packaging material for molding that can ensure excellent slipperiness when the packaging material for molding is molded, to ensure excellent moldability, and prevents white powder from appearing on the surface of the packaging material.SOLUTION: The packaging material for molding has a substrate layer 2 as an outside layer, a thermally fusible resin layer 3 as an inside layer, and a metal foil layer 4 disposed between both layers. The thermally fusible resin layer 3 is composed of a single layer or a plurality of layers. An innermost layer 7 of the thermally fusible resin layer 3 is composed of a resin composition containing a thermally fusible resin, a roughened material, a slip agent and a fluorine polymer lubricant. The roughened material contains a thermoplastic resin. On the inside surface 7a of the innermost layer 7, formed is a first lubricity layer 11 containing 50 mass% or more of the fluorine polymer lubricant.SELECTED DRAWING: Figure 1

Description

  The present invention is suitably used as a case for, for example, notebook computers, mobile phones, in-vehicle, stationary secondary batteries (lithium ion secondary batteries), and also suitable as food packaging materials and pharmaceutical packaging materials. The present invention relates to a packaging material for molding used in the field.

  In recent years, as mobile electrical devices such as smartphones and tablet terminals have become thinner and lighter, power storage devices such as lithium-ion secondary batteries, lithium-polymer secondary batteries, lithium-ion capacitors, and electric double-layer capacitors that are installed in these devices have been reduced. As the exterior material, a laminate composed of a heat resistant resin layer / adhesive layer / metal foil layer / adhesive layer / thermoplastic resin layer (inner sealant layer) is used instead of a conventional metal can. In addition, a power source for an electric vehicle, a large-scale power source for power storage, a capacitor, and the like are increasingly covered with a laminate (exterior material) having the above-described configuration. The laminated body is formed into a three-dimensional shape such as a substantially rectangular parallelepiped shape by performing overhang molding or deep drawing. By forming into such a three-dimensional shape, an accommodation space for accommodating the electricity storage device main body can be secured.

  In order to form such a three-dimensional shape in a good state without pinholes or breakage, it is required to improve the slipperiness of the surface of the inner sealant layer. A structure in which a fatty acid amide is contained in the inner sealant layer is known as a means for improving the slipperiness of the surface of the inner sealant layer to ensure good moldability (see Patent Document 1).

  Similarly, to improve the slipperiness and ensure good moldability, an acid resistance imparting layer is provided as the outermost layer on one surface of the base material layer, and the other surface of the base material layer is 1 an adhesive layer, an aluminum foil layer provided with a corrosion prevention treatment layer on at least one surface, a second adhesive layer, and a sealant layer, which are sequentially laminated, and a slip agent on the outer surface of the sealant layer (Fatty acid amide etc.) and antiblocking agent (silica particles etc.) are applied, or at least one of slip agent (fatty acid amide etc.) and antiblocking agent (silica particles etc.) is blended in the sealant layer. A packaging material for a lithium ion battery having the above-described configuration has been proposed (see Patent Document 2).

  In any of the above techniques, the slipperiness of the surface of the inner sealant layer can be improved and good moldability can be ensured.

JP 2013-101664 A JP2015-53289A

  However, in the above prior art, it is necessary to add a sufficient amount of fatty acid amide to ensure good moldability. In this case, the fatty acid amide is excessively precipitated on the surface, and at the time of molding the exterior material Fatty acid amide adheres and accumulates on the molding surface of the molding die, and white powder (white powder by fatty acid amide) is generated. When such white powder is deposited and deposited on the molding surface, it becomes difficult to perform good molding, and white powder may adhere to the molded product. Although it is necessary to remove the white powder, there is a problem in that the productivity of the exterior material is reduced by performing the cleaning removal of the white powder.

  In addition, even when various adjustments are made on the amount of fatty acid amide added, the aging temperature, and the aging time, the amount of bleed on the surface of the fatty acid amide tends to vary, and as a result, the formability and the degree of white powder adhesion vary. There was a problem that it was easy to occur and it was difficult to ensure stable quality.

  Of course, if the amount of fatty acid amide added is reduced, it becomes possible to suppress the adhesion and deposition of white powder, but in this case, the amount of fatty acid amide deposited on the surface is insufficient and the moldability becomes worse. . Thus, conventionally, it has been difficult to achieve both excellent moldability and suppression of white powder expression on the surface of the exterior material.

  The present invention has been made in view of such a technical background, and can ensure good slipperiness when molding a packaging material for molding, ensure good moldability, and white powder is displayed on the surface of the packaging material. It is an object of the present invention to provide a molding packaging material, an electricity storage device outer case, and an electricity storage device that are difficult to take out.

  In order to achieve the above object, the present invention provides the following means.

[1] A molding packaging material comprising a base material layer as an outer layer, a heat-fusible resin layer as an inner layer, and a metal foil layer disposed between these two layers,
The heat-fusible resin layer is composed of a single layer or a plurality of layers, and the innermost layer of the heat-fusible resin layer contains a heat-fusible resin, a roughening material, a slip agent, and a fluoropolymer lubricant. A resin composition,
The roughening material contains a thermoplastic resin,
A molding packaging material, wherein a first slipping layer containing a fluoropolymer lubricant at a content of more than 50% by mass is formed on the inner surface of the innermost layer.

  [2] The molding packaging material according to item 1, wherein a second slipping layer containing a slip agent at a content of greater than 50% by mass is formed on the inner surface of the first slipping layer.

  [3] The molding packaging material according to item 1 or 2, wherein the content of the fluoropolymer lubricant in the innermost layer is 5 ppm to 5000 ppm.

  [4] The molding packaging material according to any one of items 1 to 3, wherein the fluorine content in the fluoropolymer lubricant is 50% by mass or more.

  [5] The fluoropolymer lubricant is one or two fluoropolymers selected from the group consisting of a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer and a hexafluoropropylene-vinylidene fluoride copolymer. 5. The molding packaging material according to any one of items 1 to 4, which is a lubricant.

  [6] The molding packaging material according to any one of items 1 to 5, wherein the thermoplastic resin constituting the roughening material is a high-density polyethylene resin.

  [7] The molding packaging material according to any one of items 1 to 6, wherein the slip agent is a fatty acid amide.

  [8] The molding packaging material according to any one of items 1 to 7, wherein a third slipping layer containing a slip agent is formed on the outer surface of the base material layer.

  [9] The molding packaging material according to item 8, wherein the dynamic friction coefficient of the outer surface of the packaging material is 0.5 or less.

  [10] The molding packaging material according to any one of items 1 to 9, wherein a dynamic friction coefficient of the inner surface of the packaging material is 0.5 or less.

  [11] An exterior case for an electricity storage device comprising the molded body of the packaging material according to any one of items 1 to 10.

[12] An electricity storage device body,
An exterior member including at least the exterior case for an electricity storage device according to 11 above,
The electricity storage device, wherein the electricity storage device body is covered with the exterior member.

[13] A base material layer is laminated on one surface of the metal foil via an outer adhesive, and a heat-sealing property consisting of a single layer or a plurality of layers is formed on the other surface of the metal foil via an inner adhesive. A heat-fusible structure in which the innermost layer of the heat-fusible resin layer is made of a resin composition containing a heat-fusible resin, a roughening material, a slip agent, and a fluoropolymer lubricant. Preparing a laminate in which resin layers are laminated;
An aging step of obtaining a molding packaging material by heat-treating the laminate, and
The method for producing a molding packaging material, wherein the roughening material contains a thermoplastic resin.

  [14] The method for producing a packaging material for molding as described in 13 above, wherein the heating temperature of the heat treatment in the aging step is 30 ° C. to 50 ° C.

  [15] The method for producing a molding packaging material according to item 13 or 14, wherein the innermost layer is formed by melt extrusion film formation of the resin composition in the preparation step.

  [16] The method for producing a molding packaging material according to item 13 or 14, wherein the innermost layer is formed by applying and drying a coating solution containing the resin composition and a solvent in the preparation step.

  In the invention of [1], the innermost layer of the heat-fusible resin layer is composed of a resin composition containing a heat-fusible resin, a thermoplastic resin-containing roughening material, a slip agent, and a fluoropolymer lubricant. And the inner surface of the innermost layer is formed with a first slipping layer containing a fluoropolymer lubricant at a content of more than 50% by mass. The slipperiness with the mold surface is improved, the moldability at the time of molding such as deep drawing molding and stretch molding can be improved, and the white powder is difficult to be exposed on the surface of the packaging material. According to the present invention, even when the bleed amount of the slip agent is smaller than that of the conventional one, it is possible to ensure a stable slipping property at the time of molding.

  Furthermore, the surface of the innermost layer of the heat-fusible resin layer comes into contact with the surface of the base material layer when the packaging material for molding of the present invention is rolled up, but the surface of the innermost layer of the heat-fusible resin layer Since the surface is roughened, the area where the surface of the innermost layer and the surface of the base material layer come into contact with each other is small, and the amount of slip agent transferred to the surface of the base material layer (the innermost layer of the heat-fusible resin layer) The amount of slip agent transferred from the surface of the adhesive layer is reduced, and thus sufficient adhesive strength to the base material layer surface of the adhesive tape for fixing the electricity storage device (battery etc.) to the inside of the electronic device or the like can be obtained. In addition, there is an advantageous effect that the printed matter is hardly peeled off when printed items such as a product name and a lot number are printed on the surface of the packaging material (surface of the base material layer) packaging the power storage device (battery or the like).

  In the invention of [2], since the second slipping layer containing the slip agent at a content of more than 50% by mass is formed on the inner surface of the first slipping layer, the slipping property can be further improved. It is possible to further improve the moldability during molding.

  In the invention of [3], the slipperiness can be further improved, and the moldability at the time of molding can be further improved.

  In the invention of [4], since the fluorine content in the fluoropolymer lubricant is 50% by mass or more, the slipperiness can be further improved, and the moldability during molding can be further improved.

  In the invention of [5], the fluoropolymer-based lubricant is one or two selected from the group consisting of a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer and a hexafluoropropylene-vinylidene fluoride copolymer. Therefore, the slipperiness can be further improved, and the moldability at the time of molding can be further improved.

  In the invention of [6], since the thermoplastic resin constituting the roughening material is a high-density polyethylene resin, the high-density polyethylene resin is effective because the compatibility with the heat-fusible resin is moderately low. The surface can be roughened and the slipperiness can be further improved.

  In the invention of [7], the slipperiness can be further improved, and the moldability during molding of the packaging material can be further improved.

  In invention of [8], the said slip property can be improved more and the moldability at the time of shaping | molding can further be improved.

  In invention of [9], the said slipperiness can be improved more and the moldability at the time of shaping | molding of a packaging material can further be improved.

  In the invention of [10], the slipperiness can be further improved, and the moldability at the time of molding can be further improved.

  In the invention of [11], it is possible to provide an exterior case for an electricity storage device that has been well molded.

  In the invention of [12], it is possible to provide an electricity storage device configured using an exterior case that is well-formed.

  The molding packaging material obtained by the invention (manufacturing method) of [13] consists of a resin composition containing a heat-fusible resin, a thermoplastic resin-containing roughening material, a slip agent and a fluoropolymer lubricant. A first lubricating layer containing a fluoropolymer lubricant at a content of more than 50% by mass is formed on the inner surface of the inner layer, and a slip agent is added at an inner surface of the first lubricant layer of more than 50% by mass. Since the second slipping layer contained in is formed, the slipperiness between the inner surface of the packaging material and the molding die surface during molding of the packaging material is improved, deep drawing molding, overhang molding, etc. The moldability at the time of molding can be improved, and white powder is difficult to be exposed on the surface of the packaging material.

  Furthermore, the surface of the innermost layer of the heat-fusible resin layer comes into contact with the surface of the base material layer when the molding packaging material obtained by the production method of the present invention is wound into a roll, but the heat-fusible resin layer Since the surface of the innermost layer is roughened, the area where the surface of the innermost layer and the surface of the base material layer are in contact with each other is small, and the amount of slip agent transferred to the surface of the base material layer (heat fusion property) The amount of slip agent transferred from the innermost surface of the resin layer) is reduced, and therefore the adhesive strength of the adhesive tape to the surface of the base material layer for fixing the electricity storage device (battery, etc.) inside the electronic device is reduced. It is advantageous in that it can be obtained sufficiently and is difficult to peel off when the product name, lot number, etc. are printed on the surface of the packaging material (surface of the base material layer) that packages the electricity storage device (battery, etc.) There is an effect.

  In the invention [14], since the aging heating temperature is 30 ° C. to 50 ° C., the second slipping layer can be reliably formed and the white powder expression on the surface of the packaging material can be sufficiently prevented. Especially, it is preferable to set the heating temperature of the said aging to 35 to 45 degreeC.

  In the invention of [15], since the innermost layer is formed by melt extrusion film formation of the resin composition, the first slipping layer can be reliably formed and white powder is exposed on the surface of the packaging material. Can be sufficiently prevented.

  In the invention of [16], since the innermost layer is formed by applying and drying a coating solution containing the resin composition and a solvent, the first slipping layer can be reliably formed and packaging White powder expression on the surface of the material can be sufficiently prevented.

  In addition, in the inventions of [15] and [16], it is possible to reliably form a uniform first lubricating layer having a higher content of the fluoropolymer lubricant, and to further improve the moldability. It is preferable to adopt the invention (manufacturing method) of [15].

It is sectional drawing which shows 1st Embodiment of the packaging material for shaping | molding which concerns on this invention. It is sectional drawing which shows 2nd Embodiment of the packaging material for shaping | molding which concerns on this invention. It is sectional drawing which shows 3rd Embodiment of the packaging material for shaping | molding which concerns on this invention. It is sectional drawing which shows one Embodiment of the electrical storage device which concerns on this invention. It is a perspective view shown in the separated state before heat-sealing the exterior material (planar thing) which comprises the electrical storage device of FIG. 4, an electrical storage device main-body part, and an exterior case (molded body shape | molded in the solid shape).

  The molding packaging material 1 according to the present invention includes a base material layer 2 as an outer layer, a heat-fusible resin layer 3 as an inner layer, and a metal foil layer 4 disposed between these two layers. The heat-fusible resin layer 3 is composed of a single layer or a plurality of layers, and the innermost layer 7 of the heat-fusible resin layer 3 is a heat-fusible resin, a roughening material, a slip agent, and a fluoropolymer lubricant. The roughening material has a structure containing a thermoplastic resin (see FIGS. 1 to 3).

  Three embodiments of the packaging material 1 for molding according to the present invention are shown in FIGS. These three embodiments are merely representative embodiments, and are not particularly limited to such a configuration.

  The molding packaging material 1 shown in FIGS. 1 to 3 is used for a lithium ion secondary battery case. The molding packaging material 1 is used, for example, as a case of a secondary battery by being subjected to molding such as deep drawing molding or stretch molding.

  In the embodiment shown in FIGS. 1 to 3, the molding packaging material 1 includes a heat-fusing resin layer (inner layer) 3 laminated and integrated on one surface of a metal foil layer 4 via an inner adhesive layer 6. In addition, the base layer (outer layer) 2 is laminated and integrated on the other surface of the metal foil layer 4 via the outer adhesive layer 5.

  In the first embodiment shown in FIG. 1, the heat-fusible resin layer (inner layer) 3 includes a first heat-fusible resin layer that forms the innermost layer 7 of the inner layer 3 and the first heat-fusible resin layer. This is a configuration (a two-layer configuration) including a second heat-fusible resin layer 8 laminated on the surface of the fusible resin layer 7 on the metal foil layer 4 side. On the inner surface 7a of the first heat-fusible resin layer (innermost layer) 7, a first slipping layer 11 containing a fluoropolymer lubricant in a content of more than 50% by mass is laminated, and the first slipping layer is further laminated. A second slipping layer 12 containing a slip agent at a content of greater than 50% by mass is laminated on the inner surface 11a of the conductive layer 11 (see FIG. 1). Moreover, the 3rd slipping layer 13 containing a slip agent is laminated | stacked on the outer surface 2a of the said base material layer (outer layer) 2 (refer FIG. 1).

  In the second embodiment shown in FIG. 2, the heat-fusible resin layer (inner layer) 3 includes the first heat-fusible resin layer constituting the innermost layer 7 of the inner layer 3 and the first heat-fusible resin layer. A second heat-fusible resin layer 8 laminated on the surface of the heat-fusible resin layer 7 on the metal foil layer 4 side, and a surface of the second heat-fusible resin layer 8 on the metal foil layer 4 side. And a third heat-fusible resin layer 9 laminated on each other. On the inner surface 7a of the first heat-fusible resin layer (innermost layer) 7, a first slipping layer 11 containing a fluoropolymer lubricant in a content of more than 50% by mass is laminated, and the first slipping layer is further laminated. A second slipping layer 12 containing a slip agent at a content of greater than 50% by mass is laminated on the inner surface 11a of the conductive layer 11 (see FIG. 2). Moreover, the 3rd slipping layer 13 containing a slip agent is laminated | stacked on the outer surface 2a of the said base material layer (outer layer) 2 (refer FIG. 2).

  In the third embodiment shown in FIG. 3, the heat-fusible resin layer (inner layer) 3 has a single-layer configuration including only the first heat-fusible resin layer (innermost layer) 7. Similarly to the above, on the inner surface 7a of the first heat-fusible resin layer (innermost layer) 7, a first slipping layer 11 containing a fluoropolymer lubricant at a content greater than 50% by mass is laminated, and On the inner surface 11a of the first slipping layer 11, a second slipping layer 12 containing a slip agent at a content of more than 50% by mass is laminated (see FIG. 3). Moreover, the 3rd slipping layer 13 containing a slip agent is laminated | stacked on the outer surface 2a of the said base material layer (outer layer) 2 (refer FIG. 3).

  In the present invention, the heat-fusible resin layer (inner layer; sealant layer) 3 has excellent chemical resistance against a highly corrosive electrolytic solution used in a lithium ion secondary battery or the like. It plays a role of imparting heat sealability to the packaging material.

  The resin constituting the heat-fusible resin layer 3 (including the first heat-fusible resin layer 7, the second heat-fusible resin layer 8, and the third heat-fusible resin layer 9) is particularly limited. However, it is preferable to use at least one heat-fusible resin selected from the group consisting of polyethylene, polypropylene, olefin copolymers and ionomers. In addition, it is not preferable from an economical viewpoint to use acid-modified polyolefin resin as resin which comprises the said heat-fusible resin layer 3. FIG. That is, it is preferable to use a non-acid-modified polyolefin resin as the resin constituting the heat-fusible resin layer 3.

  When the two-layer laminated structure is adopted as the heat-fusible resin layer (inner layer) 3 as in the first embodiment, the heat constituting the first heat-fusible resin layer (innermost layer) 7 As the fusible resin, a random copolymer containing “propylene” and “another copolymerization component excluding propylene” as a copolymer component is used, and the heat fusion constituting the second heat-fusible resin layer 8 is used. As the adhesive resin, it is preferable to use a block copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component.

  When a three-layer laminated structure is adopted as the heat-fusible resin layer (inner layer) 3 as in the second embodiment, the first heat-fusible resin layer (innermost layer) 7 and the third layer As the heat-fusible resin constituting the heat-fusible resin layer 9, a random copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component is used, and the second heat As the heat-fusible resin constituting the fusible resin layer 8, it is preferable to use a block copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component. In the case of adopting a three-layer laminated structure as the heat-fusible resin layer 3, the third heat-fusible resin layer 9 may also contain a fluoropolymer lubricant, but there is a concern that the laminate strength is lowered. Therefore, it is preferable that the third heat-fusible resin layer 9 does not contain a fluoropolymer lubricant, or even if it is contained, the content of the fluoropolymer lubricant is preferably set to less than 1000 ppm.

  Further, when a single layer structure is adopted as the heat-fusible resin layer (inner layer) 3 as in the third embodiment, the heat-fusible resin constituting the first heat-fusible resin layer (innermost layer) 7 is used. As the adhesive resin, it is preferable to use a random copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component.

  With respect to the random copolymer, the “other copolymerization component excluding propylene” is not particularly limited. For example, ethylene, 1-butene, 1-hexene, 1-pentene, 4methyl-1 -In addition to olefin components such as pentene, butadiene and the like can be mentioned. Further, regarding the block copolymer, the “other copolymerization component excluding propylene” is not particularly limited, and examples thereof include ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl. In addition to olefin components such as -1-pentene, butadiene and the like can be mentioned.

  And in the packaging material 1 for shaping | molding which concerns on the said structure, the innermost layer 7 of the said heat-fusible resin layer 3 contains a heat-fusible resin, a thermoplastic resin containing roughening material, a slip agent, and a fluoropolymer lubricant. A first lubricating layer 11 containing a fluoropolymer lubricant at a content greater than 50% by mass is formed on the inner surface 7a of the first heat-fusible resin layer (innermost layer) 7. Since the second slipping layer 12 containing the slip agent is contained on the inner surface 11a of the first slipping layer 11 and having a content of greater than 50% by mass, the packaging material 1 is molded. The slipperiness between the inner surface of the packaging material 1 and the molding die surface at the time can be improved, and the moldability at the time of molding such as deep drawing molding and overhang molding can be improved. it can). Furthermore, since the 3rd slipping layer 13 containing a slip agent is laminated | stacked on the outer surface 2a of the said base material layer (outer layer) 2, the said moldability can further be improved.

  Although it does not specifically limit as said roughening material, For example, a thermoplastic resin containing pellet, a thermoplastic resin containing powder, etc. are used. Among these, the thermoplastic resin-containing powder is preferable in terms of dispersibility. The thermoplastic resin constituting the roughening material is not particularly limited. For example, polyethylene resin (high density polyethylene resin, low density polyethylene resin, etc.), polypropylene resin, ethylene-olefin (excluding ethylene). In addition to olefin resins such as (olefin) copolymer resins and ethylene-vinyl ester copolymer resins, polystyrene resins and the like can be mentioned. Among them, as the roughening material, it is preferable to use a roughening material containing a high-density polyethylene resin. In this case, the innermost layer of the heat-fusible resin layer without impairing the heat sealability. 7 can be effectively roughened, and the slipperiness can be further improved.

  The roughening material is applied to the surface 7a of the innermost layer 7 in a state in which the roughening material having low compatibility with the matrix is dispersed in the matrix of the heat-fusible resin constituting the innermost layer 7. Is partially exposed (protruded), whereby irregularities are formed on the surface 7a (the surface is roughened). For example, after mixing thermoplastic resin pellets or thermoplastic resin powder as a surface roughening material into the heat-fusible resin pellets or powder, the mixture is melt-kneaded with an extruder or the like and finely dispersed. By cooling and solidifying, the surface 7a of the innermost layer 7 having irregularities (the surface is roughened) is obtained.

  The average diameter (average value of the major axis) of the roughened material in a dispersed state is preferably in the range of 0.05 μm to 10 μm. In this case, the slipperiness can be further improved.

The density of high-density polyethylene resin forming the roughening material (HDPE) is preferably in the range of ^{0.935g / cm 3 ~0.965g / cm 3} . In the case of such a density range, the slip property can be further improved and the moldability can be further improved. Among them, the density of the high density polyethylene resin (HDPE) constituting the roughening material, and more preferably in the range of ^{0.945g / cm 3 ~0.960g / cm 3} .

  The density of the high-density polyethylene resin can be adjusted by changing the content of the comonomer (copolymerization component). Examples of such comonomers include unsaturated olefins other than ethylene such as 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, but are not particularly limited thereto. . As the comonomer, it is preferable to use at least one comonomer selected from the group consisting of 1-butene and 1-hexene.

  The melt flow rate (MFR) at 190 ° C. of the high-density polyethylene resin constituting the roughening material is preferably in the range of 0.01 g / 10 min to 2 g / 10 min. When the MFR is “0.01 g / 10 min” or more, the surface roughening material can be finely and uniformly dispersed in the heat-fusible resin, and the MFR is “2 g / 10 min” or less. The roughness of the surface can be increased and the slipperiness can be further improved. Especially, it is especially preferable that the melt flow rate (MFR) at 190 degreeC of the high density polyethylene resin (HDPE) which comprises the said roughening material is the range of 0.1g / 10min-1g / 10min.

  The melt flow rate (MFR) of the high-density polyethylene resin can be adjusted, for example, as follows. In the case of producing the high-density polyethylene resin using a Philips catalyst, the MFR of the high-density polyethylene resin can be adjusted by changing the reactor temperature during polymerization, or the reactor temperature can be adjusted after adding a small amount of hydrogen. By changing, the MFR of the high density polyethylene resin can be adjusted. In the case of producing the high-density polyethylene resin using a Ziegler catalyst, the MFR of the high-density polyethylene resin can be adjusted by changing the amount of hydrogen supplied to the reactor during polymerization. In the case of using the Phillips catalyst, the high-density polyethylene resin can be produced by slurry polymerization using isobutane as a solvent, but the method is not particularly limited thereto.

  The melting point of the high-density polyethylene resin constituting the roughening material is preferably in the range of 130 ° C to 145 ° C. Moreover, it is preferable that a high density polyethylene resin has a branch which is a long chain (10 or more carbon atoms). When high-density polyethylene resin having long-chain branches is used, when the roughening material is melt-kneaded with the heat-fusible resin, the molten roughening material (thermoplastic resin) is finely dispersed. Therefore, the innermost surface 7a of the heat-fusible resin layer 3 can be roughened more effectively, and the slipperiness can be further improved.

  The swell of the high density polyethylene resin constituting the roughening material is preferably in the range of 25% to 55%, and in this case, the melt viscoelasticity of the resin constituting the roughening material is relatively high. It is easy to form high-density polyethylene resin particles, the innermost surface 7a can be more effectively roughened, and the slipperiness can be further improved. Especially, it is more preferable that the swell of the high density polyethylene resin which comprises the said roughening material is 35 to 45% of range.

The “swell” means a room temperature die swell percentage (%) by the capillary rheometer A method defined by JIS K7119-2001, and a standard die (hole diameter) defined by JIS K7210-1-2014. : 2.095 mm, length: 8 mm) at a temperature of 190 ° C. and a load of 2.16 kg, when the strand of resin extruded from the capillary die (string-like resin) has a length of 2 cm, the strand is tweezers. After being collected by natural cooling and solidified by cooling, the diameter of the 1 cm portion of the strand from the tip was measured with a micrometer, and when this measured value was D ₁ (mm),
Swell (%) = {(D ₁ −D ₀ ) / D ₀ )} × 100
D ₁ : Extruded resin diameter
D ₀ : Standard die hole diameter (2.095 mm)
This is the value (%) obtained by the above formula.

  The high load swell (swell when the load is 21.6 kg) of the high density polyethylene resin constituting the surface roughening material is preferably in the range of 55% to 90%. In this case, the surface roughening material Since the melt viscoelasticity of the resin constituting the resin is relatively high, it is easy to form particles of a high-density polyethylene resin, and the surface 7a of the innermost layer can be more effectively roughened to further improve the slipperiness.

In addition, the said high load swell uses a standard die (hole diameter: 2.095 mm, length: 8 mm) defined by JIS K7210-1-2014, in accordance with JIS K7119-2001, at a temperature of 190 ° C., When the strand of the resin extruded from the capillary die (strand-shaped resin) reaches a length of 2 cm under a load of 21.6 kg, the strand is collected with tweezers, and naturally cooled and solidified. When measured with a micrometer and the measured value is D ₂ (mm),
High load swell (%) = {(D ₂ −D ₀ ) / D ₀ )} × 100
D ₂ : Diameter of extruded resin
D ₀ : Standard die hole diameter (2.095 mm)
It is a value obtained by the above formula.

  It is preferable that “high load MFR (MFR at a load of 21.6 kg) / MFR (MFR at a load of 2.16 kg)” of the high density polyethylene resin constituting the roughened material is in a range of 25 to 40. In this case, the compatibility between the random copolymer and the roughening material can be secured to some extent, and the whitening of the sealant layer 3 during molding can be further suppressed.

The difference in melt density of roughening material and density of the roughening material is preferably in the range of ^{0.15g / cm 3 ~0.25g / cm 3} , in this case mixed resin melt Since the volume shrinkage of the roughening material increases in the process of cooling and solidifying from the state, the surface 7a of the innermost layer 7 can be efficiently roughened, and the center line average roughness Ra of the surface 7a of the innermost layer 7 can be obtained. Can be easily adjusted to 0.05 μm to 1 μm.

In the innermost layer 7 of the heat-fusible resin layer 3, the density of the random copolymer (random copolymer containing propylene and other copolymer components excluding propylene as a copolymer component) and the roughening the difference between the density of the wood is, 0.04 g / cm ³ is preferably in the range of ~0.07g / cm ^3, the random copolymer in the process of mixing the resin is cooled and solidified in the melt in this case Since the difference in volume shrinkage between the surface roughening material and the surface roughening material becomes large, the unevenness of the surface 7a of the innermost layer 7 becomes larger, and the surface 7a of the innermost layer can be roughened more effectively to further improve the slipperiness. be able to.

The difference between the melt density of the random copolymer (random copolymer containing propylene and other copolymer components excluding propylene as a copolymer component) and the melt density of the roughening material is 0.3 g. / Cm ³ or less is preferable.

  The content of the roughening material in the innermost layer 7 of the heat-fusible resin layer 3 is preferably set to 1% by mass to 30% by mass. In this case, the content of the lubricant in the innermost layer 7 is Even if it is 1000 ppm or less, excellent moldability can be secured. In addition, when the content of the lubricant in the innermost layer 7 is more than 0 ppm and not more than 1000 ppm, the white powder is more difficult to be exposed on the surface 7a of the innermost layer 7 of the heat-fusible resin layer of the exterior material. Become. Especially, it is especially preferable that the content of the roughening material in the innermost layer 7 is set to 1% by mass to 20% by mass.

  Although it does not specifically limit as said slipping agent, Fatty acid amide is used suitably. The fatty acid amide is not particularly limited, and examples thereof include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, and aromatic bisamides. Is mentioned.

  The saturated fatty acid amide is not particularly limited, and examples thereof include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. The unsaturated fatty acid amide is not particularly limited, and examples thereof include oleic acid amide and erucic acid amide.

  The substituted amide is not particularly limited, and examples thereof include N-oleyl palmitate, N-stearyl stearate, N-stearyl oleate, N-oleyl stearate, N-stearyl erucic acid. Examples include amides. The methylolamide is not particularly limited, and examples thereof include methylol stearamide.

  The saturated fatty acid bisamide is not particularly limited. For example, methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene Bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, etc. It is done.

  The unsaturated fatty acid bisamide is not particularly limited, and examples thereof include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl sebacic acid amide and the like. Can be mentioned.

  The fatty acid ester amide is not particularly limited, and examples thereof include stearamide ethyl stearate. The aromatic bisamide is not particularly limited, and examples thereof include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-cysteallyl isophthalic acid amide, and the like. Can be mentioned.

  As the slip agent, a plurality of the fatty acid amides may be used in combination. Among them, it is preferable to use ethylenebisstearic acid amide in combination with at least one fatty acid amide selected from the group consisting of erucic acid amide and behenic acid amide.

  The concentration (content) of the slip agent in the innermost layer 7 is preferably set to 100 ppm to 3000 ppm, and particularly preferably 500 ppm to 1500 ppm.

  In addition, when employ | adopting the two-layer laminated structure (refer FIG. 1) mentioned above as the said heat-fusible resin layer 3, it is preferable to also contain a slip agent in the said 2nd heat-fusible resin layer 8. FIG. In this case, it is preferable to contain the slip agent in the second heat-fusible resin layer 8 at a content of 100 ppm to 5000 ppm, and it is particularly preferable to contain the slip agent at a content of 500 ppm to 3000 ppm.

  Further, when the above-described three-layer laminated structure (see FIG. 2) is adopted as the heat-fusible resin layer 3, the third heat-fusible resin layer 9 may contain a slip agent, Since there is a concern that the laminate strength is lowered, the third heat-fusible resin layer 9 is preferably configured not to contain a slip agent, or even if it is contained, the slip agent content is preferably set to less than 2000 ppm. .

  The fluoropolymer lubricant is a fluorine-containing polymer (a polymer having one or more fluorine atoms in a molecule) that can impart slipperiness, and examples thereof include a fluorine elastomer, a fluorine resin (excluding an elastomer), and the like. It is done. By including such a fluoropolymer lubricant in the innermost layer 7, the fluoropolymer lubricant has little interaction with the slip agent, and can form a slipping layer on the surface 7 a of the innermost layer 7, resulting in dynamic friction. Since the coefficient can be reduced, the moldability during molding such as deep drawing can be greatly improved (a good molded product can be obtained even by performing deeper molding). Further, by incorporating the fluoropolymer lubricant in the innermost layer 7, surface roughness of the surface 7a of the innermost layer 7 can be suppressed.

  The fluorine elastomer is not particularly limited, and examples thereof include a copolymer of fluorine-containing monomers. The copolymer of the fluorine-containing monomer is not particularly limited. For example, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-vinylidene fluoride- Examples include hexafluoropropylene copolymers. The copolymer exemplified above is a polymer having a Tg in the range of -35 ° C to -5 ° C and does not exhibit a melting point. Among these, it is preferable to use a vinylidene fluoride-hexafluoropropylene copolymer. In this case, polyethylene glycol may be blended with the vinylidene fluoride-hexafluoropropylene copolymer. At this time, the blending amount of polyethylene glycol is 1 mass per 100 mass parts of the vinylidene fluoride-hexafluoropropylene copolymer. Part to 70 parts by mass, preferably 5 parts to 65 parts by mass. You may mix | blend an inorganic type anti-blocking agent etc. with the said fluorine elastomer, for example. The inorganic anti-tacking agent is not particularly limited, and examples thereof include talc, amorphous silica, kaolin (aluminum silicate), calcium carbonate and the like. Examples of the fluorine elastomer include Dynamer (trademark) “FX5920A” and Dynamer (trademark) “FX9613” manufactured by 3M Co., which contains a vinylidene fluoride-hexafluoropropylene copolymer.

  As the fluororesin (not including an elastomer), it is preferable to use a fluororesin having a melting point (crystalline having a melting point). The fluororesin having a melting point is not particularly limited. For example, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer Polymer (FEP), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPA), tetrafluoroethylene-ethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-propylene copolymer (TFE / P), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV), and the like. The fluororesin having the melting point is superior in heat resistance as compared with the fluoroelastomer, and has an advantage of less interaction (reaction) with the slip agent (fatty acid amide or the like).

  As the fluororesin (not including an elastomer), it is preferable to use a resin having a melting point in the range of 100 ° C to 300 ° C. When the melting point is 100 ° C. or higher, the dispersibility of the fluororesin (fluoropolymer lubricant) in the resin composition can be improved. When the melting point is 300 ° C. or lower (no need to increase the molding temperature), the workability can be improved. Among these, it is particularly preferable to use a fluororesin (not including an elastomer) having a melting point in the range of 110 ° C to 230 ° C. Among the fluororesins exemplified above, those having a melting point of 100 ° C. to 300 ° C. are FEP, PCTFE, ETFE, PVDF, TFE / P, THV and the like. Those having a melting point of 110 ° C. to 230 ° C. are PVDF, TFE / P, THV, and the like. Among these, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) is most suitable.

  The tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer includes both those corresponding to "fluorine elastomer" and those corresponding to "fluorine resin having a melting point". It is particularly preferable to use a material corresponding to the latter (that is, a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer having a melting point). Examples of the tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer having the melting point include Dynamer (trademark) “FX5911” manufactured by 3M.

  As the fluoropolymer lubricant, the fluoroelastomer lubricant and the fluororesin lubricant (not containing an elastomer) may be used in combination (may be used in combination).

  The fluorine (F atom) content in the fluoropolymer lubricant is preferably 50% by mass or more. When the content is 50% by mass or more, the heat resistance can be further improved, and the surface 7a of the innermost layer can be more easily bleeded. Among these, the fluorine (F atom) content in the fluoropolymer lubricant is more preferably 60% by mass to 80% by mass, and particularly preferably 66% by mass to 76% by mass.

  The concentration (content) of the fluoropolymer lubricant in the innermost layer 7 is preferably set to 5 ppm to 5000 ppm. When it is 5 ppm or more, moldability can be sufficiently improved, and when it is 5000 ppm or less, uniform extrusion molding (film molding) of the innermost layer 7 becomes possible. Among them, the concentration (content) of the fluoropolymer lubricant in the innermost layer 7 is more preferably set to 50 ppm to 3000 ppm, particularly preferably set to 100 ppm to 1500 ppm, and set to 200 ppm to 1200 ppm. Is most preferred. When the fluoropolymer lubricant is blended to obtain the resin composition of the innermost layer 7, the master polymer batch is prepared by mixing the fluoropolymer lubricant with a resin such as a polyolefin resin. A batch may be blended to obtain the resin composition of the innermost layer 7.

  An antiblocking agent (particles) may be further added to the resin composition constituting the innermost layer 7. The anti-blocking agent is not particularly limited, and examples thereof include inorganic particles and resin particles. The inorganic particles are not particularly limited, and examples thereof include silica particles and aluminum silicate particles. The resin particles are not particularly limited, and examples thereof include acrylic resin particles, polyolefin resin particles (polyethylene resin particles, polypropylene resin particles), polystyrene resin particles, and the like. By further adding an antiblocking agent, fine projections (corresponding to the particle size of the antiblocking agent) are formed on the uneven surface formed by the roughening material on the surface 7a of the innermost layer 7 of the heat-fusible resin layer 3. (Fine unevenness) can be formed, so that a higher roughening effect can be obtained.

  The particle size of the antiblocking agent is preferably in the range of 0.1 μm to 10 μm in terms of average particle size, and more preferably in the range of 1 μm to 5 μm in terms of average particle size.

  The concentration (content ratio) of the antiblocking agent in the innermost layer 7 is preferably set to 100 ppm to 50000 ppm, and particularly preferably 500 ppm to 15000 ppm.

  In the present invention, the base material layer (outer layer) 2 is preferably formed of a heat resistant resin layer. As the heat-resistant resin constituting the heat-resistant resin layer 2, a heat-resistant resin that does not melt at the heat sealing temperature when heat-sealing the packaging material is used. The heat-resistant resin has a heat resistance having a melting point higher by 10 ° C. or more than the melting point of the heat-fusible resin layer 3 (the melting point of the layer having the highest melting point when the heat-fusible resin layer is composed of a plurality of layers). It is preferable to use a resin, and the heat resistance is 20 ° C. higher than the melting point of the heat-fusible resin layer 3 (the melting point of the layer having the highest melting point when the heat-fusible resin layer is composed of a plurality of layers). It is particularly preferable to use a resin.

  The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include polyamide films such as nylon films, polyester films, and the like, and these stretched films are preferably used. Among them, the heat-resistant resin layer 2 includes a biaxially stretched polyamide film such as a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film, or a biaxially stretched polyethylene film. It is particularly preferable to use a phthalate (PEN) film. The nylon film is not particularly limited, and examples thereof include 6 nylon film, 6,6 nylon film, MXD nylon film, and the like. The heat-resistant resin layer 2 may be formed as a single layer, or may be formed as a multilayer composed of a polyester film / polyamide film (such as a multilayer composed of PET film / nylon film). Also good.

  The heat-resistant resin layer (outer layer) 2 preferably has a thickness of 2 μm to 50 μm. When using a polyester film, the thickness is preferably 2 μm to 50 μm, and when using a nylon film, the thickness is preferably 7 μm to 50 μm. By setting it above the preferred lower limit value, it is possible to ensure sufficient strength as a packaging material, and by setting it below the preferred upper limit value, it is possible to reduce the stress at the time of molding such as stretch molding and draw molding, and improve moldability. Can be made.

  The metal foil layer 4 plays a role of providing the packaging material 1 with a gas barrier property that prevents oxygen and moisture from entering. Although it does not specifically limit as said metal foil layer 4, For example, aluminum foil, SUS foil (stainless steel foil), copper foil etc. are mentioned, Among these, aluminum foil and SUS foil (stainless steel foil) are used. Is preferred. The thickness of the metal foil layer 4 is preferably 5 μm to 120 μm. When it is 5 μm or more, it can prevent the occurrence of pinholes during rolling when producing a metal foil, and when it is 120 μm or less, it can reduce the stress during forming such as stretch forming and draw forming, thereby improving formability. be able to. Among these, the thickness of the metal foil layer 4 is more preferably 10 μm to 80 μm.

The metal foil layer 4 is preferably subjected to chemical conversion treatment on at least the inner surface (the surface on the inner layer 3 side). By performing such a chemical conversion treatment, corrosion of the metal foil surface by the contents (battery electrolyte or the like) can be sufficiently prevented. For example, the metal foil is subjected to chemical conversion treatment by the following treatment. That is, for example, on the surface of the metal foil that has been degreased,
1) phosphoric acid;
Chromic acid,
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of a metal salt of fluoride and a nonmetal salt of fluoride; 2) phosphoric acid;
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins;
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of chromic acid and a chromium (III) salt, 3) phosphoric acid,
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins;
At least one compound selected from the group consisting of chromic acid and a chromium (III) salt;
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of a fluoride metal salt and a fluoride non-metal salt. After applying an aqueous solution of any one of the above 1) to 3), drying is performed. Then, chemical conversion treatment is performed.

The conversion coating, chromium coating weight preferably is 0.1mg / m ² ~50mg / m ² as a (per one surface), in particular 2mg / m ² ~20mg / m 2 preferred.

  The outer adhesive 5 is not particularly limited, and examples thereof include a thermosetting adhesive. Although it does not specifically limit as said thermosetting adhesive, For example, an olefin type adhesive agent, an epoxy-type adhesive agent, an acrylic adhesive agent etc. are mentioned. The thickness of the outer adhesive layer 5 is preferably set to 1 μm to 5 μm. Especially, it is especially preferable that the thickness of the said outer side adhesive layer 5 is set to 1 micrometer-3 micrometers from a viewpoint of thickness reduction of the packaging material 1, and weight reduction.

  The inner adhesive 6 is not particularly limited, and examples thereof include the thermosetting adhesive. The thickness of the inner adhesive layer 6 is preferably set to 1 μm to 5 μm. Especially, it is especially preferable that the thickness of the said inner side adhesive layer 6 is set to 1 micrometer-3 micrometers from a viewpoint of thickness reduction of the packaging material 1, and weight reduction.

  The following additives are added to the base material layer 2 and the heat-fusible resin layer 3 (including the innermost layer 7) constituting the molding packaging material 1 as long as the effects of the present invention are not impaired. May be. The additive is not particularly limited. For example, an antioxidant, a plasticizer, an ultraviolet absorber, an antifungal agent, a colorant (pigment, dye, etc.), an antistatic agent, an antirust agent, and a hygroscopic agent. Agents, oxygen absorbers and the like. The plasticizer is not particularly limited. Examples include fatty acid esters, propylene glycol fatty acid esters, special fatty acid esters, and higher alcohol fatty acid esters.

  The thickness of the first slipping layer 11 is preferably 0.01 μm to 5 μm. Moreover, it is preferable that the thickness of the second slipping layer 12 is 0.01 μm to 5 μm. The thickness of the third slipping layer 13 is preferably 0.01 μm to 5 μm.

The formation of the first lubricating layer 11 is preferably in the range of ^{0.05μg / cm 2 ~1.0μg / cm 2} . Forming amount of the second lubricating layer 12 is preferably in the range of ^{0.05μg / cm 2 ~1.0μg / cm 2} . With such a formation amount, the dynamic friction coefficient of the inner surface of the molding packaging material 1 becomes 0.5 or less. Among them, the dynamic friction coefficient of the inner surface of the molding packaging material 1 is preferably 0.25 or less, more preferably 0.20 or less, and particularly preferably 0.18 or less.

  By forming the innermost layer 7 by melt extrusion film-forming the resin composition forming the innermost layer 7, the first slipping layer 11 can be reliably formed, and the first slipperiness The content of the fluoropolymer lubricant in the layer 11 can be increased.

  In addition, the first slipping layer 11 can be reliably formed by forming the innermost layer 7 by applying and drying a coating solution containing a resin composition that forms the innermost layer 7 and a solvent. In addition, the content of the fluoropolymer lubricant in the first slipping layer 11 can be increased.

  Moreover, by setting the heat treatment temperature during aging to 30 ° C. to 50 ° C., the second slipping layer 12 can be reliably formed and the content of the slip agent in the second slipping layer 12 is increased. Can do. The second slipping layer 12 can be sufficiently formed when the heating temperature during aging is 30 ° C. or higher, and the white powder can be sufficiently prevented from appearing on the surface of the molding packaging material when it is 50 ° C. or lower. . Especially, it is preferable to set the heating temperature at the time of the said aging to 35 to 45 degreeC.

The formation of the third lubricating layer 13 is preferably in the range of ^{0.05μg / cm 2 ~1.0μg / cm 2} . With such a formation amount, the dynamic friction coefficient of the outer surface of the molding packaging material 1 becomes 0.5 or less. Especially, it is preferable that the dynamic friction coefficient of the outer surface of the said packaging material 1 is 0.25 or less, It is more preferable that it is 0.20 or less, It is especially preferable that it is 0.18 or less.

  When the packaging material obtained by laminating is stored in a wound state, the third slipping layer 13 is transferred from the inner surface by contact between the inner surface and the outer surface of the packaging material in the wound state. It is a layer formed. After the molding packaging material 1 is molded by deep drawing or the like, the third slipping layer 13 may be removed or left as it is, or it may disappear naturally. You may do it.

  An outer case (battery case or the like) 10 can be obtained by molding the packaging material 1 of the present invention (deep drawing molding, stretch molding or the like) (see FIGS. 4 and 5).

  One embodiment of the electrical storage device 30 comprised using the packaging material 1 of this invention is shown in FIG. The electricity storage device 30 is a lithium ion secondary battery. In this embodiment, as shown in FIGS. 4 and 5, an exterior member 15 is configured by an exterior case 10 obtained by molding the packaging material 1 and the planar packaging material 1 without being used for molding. ing. Accordingly, a power storage device main body 31 (electrochemical element or the like) 31 having a substantially rectangular parallelepiped shape is stored in the storage recess of the outer case 10 obtained by molding the packaging material 1 of the present invention. The flat packaging material 1 is arranged with the inner layer 3 side inward (lower side), the peripheral edge of the inner layer 3 (innermost layer 7) of the planar outer packaging material 1, The inner layer 3 (innermost layer 7) of the flange portion (sealing peripheral portion) 29 of the outer case 10 is sealed and sealed by heat sealing, whereby the power storage device 30 of the present invention is configured. (See FIGS. 4 and 5). The inner surface of the housing recess of the outer case 10 is an inner layer 3 (innermost layer 7), and the outer surface of the housing recess is a base material layer (outer layer) 2 (see FIG. 5). .

  In FIG. 4, reference numeral 39 denotes a heat seal portion in which the peripheral portion of the packaging material 1 and the flange portion (sealing peripheral portion) 29 of the exterior case 10 are joined (welded). In the electricity storage device 30, the tip end portion of the tab lead connected to the electricity storage device main body 31 is led out of the exterior member 15, but is not shown.

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

  The width of the heat seal part 39 is preferably set to 0.5 mm or more. Sealing can be reliably performed by setting it as 0.5 mm or more. Especially, it is preferable to set the width | variety of the said heat seal part 39 to 3 mm-15 mm.

  In the above embodiment, the exterior member 15 has a configuration including the exterior case 10 obtained by molding the packaging material 1 and the planar packaging material 1 (see FIGS. 4 and 5). The configuration is not particularly limited to such a combination, and for example, a configuration including a pair of exterior cases 10 may be used.

  Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

<Materials used>
[Fluoropolymer lubricant A (fluorine resin, not elastomer)]
Dynamer (trademark) “FX5911” manufactured by 3M Co., Ltd .: tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (the melting point of the copolymer is 118 ° C., and the fluorine content in the copolymer is 69% by mass) )
[Fluoropolymer lubricant B (fluorine elastomer)]
Dynamer (trademark) “FX5920A” manufactured by 3M Co., Ltd. A mixture of 35% by mass of hexafluoropropylene-vinylidene fluoride copolymer (fluorine content in the copolymer is 66% by mass) and 65% by mass of ethylene glycol.
[Fluoropolymer lubricant C (fluorine elastomer)]
Dynamer (trademark) “FX9613” manufactured by 3M Co., Ltd. Hexafluoropropylene-vinylidene fluoride copolymer (fluorine content in the copolymer is 66% by mass) 90% by mass, inorganic particles (talc 6.5% by mass) , Amorphous silica 2.5 mass%, calcium carbonate 1 mass%) 10 mass% mixture.

<Example 1>
After applying a chemical conversion treatment solution composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol on both surfaces of the aluminum foil 4 having a thickness of 30 μm, drying is performed at 180 ° C. Then, a chemical conversion film was formed. The amount of chromium deposited on this chemical film was 10 mg / m ² per side.

  Next, a biaxially stretched 6 nylon film 2 having a thickness of 15 μm was dry-laminated (laminated) on one surface of the chemical conversion-treated aluminum foil 4 via a two-component curable urethane adhesive 5.

  Next, ethylene-propylene random copolymer, 1000 ppm erucic acid amide (slip agent), 5.0 mass% high density polyethylene resin powder A (average particle diameter 650 μm; roughening material), 50 ppm fluoropolymer system A first heat-fusible resin unstretched film 7 having a thickness of 3 μm, which contains lubricant A (“FX5911” manufactured by 3M) and 2500 ppm of silica particles (average particle diameter: 2 μm; antiblocking agent), ethylene-propylene block 14 μm thick second heat-fusible resin unstretched film 8 containing copolymer and 2000 ppm erucamide, thickness comprising ethylene-propylene random copolymer and 1000 ppm erucamide The 3 μm third heat-fusible resin unstretched film 9 is laminated in this order in three layers. By co-extrusion using a die, a sealant film having a thickness of 20 μm formed by laminating these three layers (first heat-fusible resin unstretched film layer 7 / second heat-fusible resin unstretched film layer 8) / After obtaining the third heat-fusible resin unstretched film layer 9) 3, the surface of the third heat-fusible resin unstretched film layer 9 of the sealant film 3 is bonded to a two-component curable maleic acid-modified polypropylene. The laminate 6 is placed on the other surface of the aluminum foil 4 after the dry laminating via the agent 6 and sandwiched between a rubber nip roll and a laminating roll heated to 100 ° C. and subjected to a dry laminating process. Winding around the shaft, and then aging (heating) at 40 ° C. for 10 days in the state wound on the roll shaft, and then withdrawing from the roll shaft, the storage of the configuration shown in FIG. Outer casing material for a device (for molding packaging material) was obtained 1.

As the two-component curable maleic acid-modified polypropylene adhesive, 100 parts by mass of maleic acid-modified polypropylene (melting point: 80 ° C., acid value: 10 mgKOH / g) as a main agent, isocyanurate of hexamethylene diisocyanate as a curing agent (NCO content: 20% by mass) 8 parts by mass, and using an adhesive solution in which a solvent is further mixed, the aluminum foil 4 has a solid content applied amount of 2 g / m ² . After applying to the other surface and heating and drying, the sealant film 3 was superposed on the surface of the third unstretched film layer 9.

The high density polyethylene resin A (roughening material) has an MFR at 190 ° C. of 0.2 g / 10 min, a density of 0.963 g / cm ³ , and a swell of 40%. , Manufactured by a slurry loop method using a Philips catalyst.

<Example 2>
The structure shown in FIG. 2 is the same as that of Example 1, except that the content of the fluoropolymer lubricant A (“FX5911” manufactured by 3M) in the first heat-fusible resin unstretched film 7 is changed to 500 ppm. The outer packaging material (molding packaging material) 1 for an electricity storage device was obtained.

<Comparative Example 1>
A power storage device exterior material (molding packaging material) was obtained in the same manner as in Example 1 except that the first heat-fusible resin unstretched film 7 did not contain a fluoropolymer lubricant.

<Example 3>
The thickness of the aluminum foil 4 was changed to 35 μm, and only the thickness was changed as a sealant film (the composition was not changed). A 30 μm-thick sealant film (the first heat-fusible resin having a thickness of 3 μm was not stretched) Example 1 except that film layer 7/24 μm thick second heat fusible resin unstretched film layer 8/3 μm thick third heat fusible resin unstretched film layer 9) was used. As a result, an exterior packaging material (molding packaging material) 1 for an electricity storage device having the configuration shown in FIG.

<Example 4>
The thickness of the aluminum foil 4 was changed to 35 μm, and only the thickness was changed as a sealant film (the composition was not changed). A sealant film with a thickness of 30 μm (a first heat-fusible resin with a thickness of 4.5 μm) Except for using unstretched film layer 7 / second heat-fusible resin unstretched film layer 8 having a thickness of 21 μm / third heat-fusible resin unstretched film layer 9 having a thickness of 4.5 μm. In the same manner as in Example 2, an electricity storage device exterior material (molding packaging material) 1 having the configuration shown in FIG. 2 was obtained.

<Comparative example 2>
A power storage device exterior material (molding packaging material) was obtained in the same manner as in Example 3 except that the first heat-fusible resin unstretched film 7 did not contain a fluoropolymer lubricant.

<Example 5>
The structure shown in FIG. 2 is the same as that of Example 3, except that the content of the fluoropolymer lubricant A (“FX5911” manufactured by 3M) in the first heat-fusible resin unstretched film 7 is changed to 1000 ppm. The outer packaging material (molding packaging material) 1 for an electricity storage device was obtained.

<Example 6>
As a fluoropolymer lubricant to be contained in the first heat-fusible resin unstretched film 7, instead of 50 ppm fluororesin lubricant (“FX5911” manufactured by 3M), 50 ppm fluororesin lubricant (“FX5911” manufactured by 3M) ) And a 50 ppm fluoroelastomer lubricant (“FX5920A” manufactured by 3M) were used in the same manner as in Example 3 to obtain a power storage device exterior material (molding packaging material) 1 having the configuration shown in FIG. .

<Example 7>
As a fluoropolymer lubricant to be incorporated in the first heat-fusible resin unstretched film 7, instead of 50 ppm of a fluororesin lubricant (“FX5911” manufactured by 3M), a 250 ppm fluororesin lubricant (“FX5911” manufactured by 3M) ) And 250 ppm fluorine elastomer lubricant (“FX5920A” manufactured by 3M) was used in the same manner as in Example 3 to obtain an electricity storage device exterior material (molding packaging material) 1 having the configuration shown in FIG. .

<Example 8>
As a fluoropolymer lubricant contained in the first heat-fusible resin unstretched film 7, instead of 50 ppm fluororesin lubricant (“FX5911” manufactured by 3M), 500 ppm fluororesin lubricant (“FX5911” manufactured by 3M) ) And 500 ppm of fluoroelastomer lubricant (“FX5920A” manufactured by 3M) were used in the same manner as in Example 3 to obtain a power storage device exterior material (molding packaging material) 1 having the configuration shown in FIG. .

<Example 9>
The thickness of the biaxially stretched nylon film 2 is changed to 25 μm, the thickness of the aluminum foil 4 is changed to 40 μm, and the fluoropolymer lubricant contained in the first heat-fusible resin unstretched film 7 is fluorine. Change to elastomer lubricant (“FX5920A” manufactured by 3M) and sealant film with a thickness of 40 μm (first heat-fusible resin unstretched film layer 4 with thickness 4 μm / second heat-sealing with thickness 32 μm) Non-stretchable film layer 8 / third heat-sealable resin non-stretched film layer 9 having a thickness of 4 μm), except that a non-stretched film layer 9) was used in the same manner as in Example 1, and an exterior material for an electricity storage device having the configuration shown in FIG. (Molding packaging material) 1 was obtained.

<Example 10>
The thickness of the biaxially stretched 6 nylon film 2 is changed to 25 μm, the thickness of the aluminum foil 4 is changed to 40 μm, and the fluoropolymer lubricant contained in the first heat-fusible resin unstretched film 7 is 500 ppm. As a sealant film, a sealant film having a thickness of 40 μm (first heat-fusible resin unstretched film layer 7 having a thickness of 6 μm / second heat having a thickness of 28 μm) is used. 2 for the electricity storage device having the configuration shown in FIG. 2 except that the fusible resin unstretched film layer 8 / the third heat fusible resin unstretched film layer 9) having a thickness of 6 μm was used. An exterior material (molding packaging material) 1 was obtained.

<Example 11>
Instead of the biaxially stretched 6 nylon film, a polyethylene terephthalate film having a thickness of 12 μm is used, the thickness of the aluminum foil 4 is changed to 35 μm, and the fluorine to be included in the first heat-fusible resin unstretched film 7 The polymer lubricant was changed to a 50 ppm fluoroelastomer lubricant (“FX9613” manufactured by 3M), and a sealant film having a thickness of 80 μm (a first heat-fusible resin unstretched film layer having a thickness of 8 μm 7 / thickness) FIG. 2 shows the same as in Example 1 except that the second heat-fusible resin unstretched film layer 8 of 64 μm / the third heat-fusible resin unstretched film layer 9) having a thickness of 8 μm was used. An exterior material for an electricity storage device (molding packaging material) 1 having a configuration was obtained.

<Example 12>
Instead of the biaxially stretched 6 nylon film, a polyethylene terephthalate film having a thickness of 12 μm is used, the thickness of the aluminum foil 4 is changed to 35 μm, and the fluorine to be included in the first heat-fusible resin unstretched film 7 The polymer lubricant was changed to a 500 ppm fluoroelastomer lubricant (“FX9613” manufactured by 3M), and a sealant film having a thickness of 80 μm (first heat-fusible resin unstretched film layer 7 having a thickness of 12 μm / thickness as a sealant film) FIG. 2 shows the same as in Example 1 except that a 56 μm second heat fusible resin unstretched film layer 8 / a 12 μm thick third heat fusible resin unstretched film layer 9) was used. An exterior material for an electricity storage device (molding packaging material) 1 having a configuration was obtained.

<Comparative Example 3>
An exterior material for a power storage device (molding packaging material) was obtained in the same manner as in Example 11 except that the first heat-fusible resin unstretched film 7 did not contain a fluoropolymer lubricant.

<Example 13>
A 27 μm thick laminated film (12 μm thick polyethylene terephthalate film / 15 μm thick biaxially stretched 6 nylon film) was used as the outer layer 2 and the thickness of the aluminum foil 4 was changed to 40 μm and the first heat fusion was performed. The fluoropolymer lubricant contained in the adhesive resin unstretched film 7 is changed to a 500 ppm fluorine elastomer lubricant (“FX9613” manufactured by 3M), and a sealant film having a thickness of 80 μm (first heat having a thickness of 8 μm) is used as the sealant film. Except for using fusible resin unstretched film layer 7 / second heat fusible resin unstretched film layer 8 having a thickness of 64 μm / third heat fusible resin unstretched film layer 9 having a thickness of 8 μm, In the same manner as in Example 1, an electricity storage device exterior material (molding packaging material) 1 having the configuration shown in FIG. 2 was obtained.

<Comparative example 4>
An exterior material for a power storage device (molding packaging material) was obtained in the same manner as in Example 13, except that the first heat-fusible resin unstretched film 7 did not contain a fluoropolymer lubricant.

<Example 14>
As a fluoropolymer lubricant to be incorporated in the first heat-fusible resin unstretched film 7, instead of 50 ppm fluororesin lubricant (“FX5911” manufactured by 3M), 250 ppm fluoroelastomer lubricant (“FX9613” manufactured by 3M) ) And 250 ppm fluorine elastomer lubricant (“FX5920A” manufactured by 3M) was used in the same manner as in Example 3 to obtain an electricity storage device exterior material (molding packaging material) 1 having the configuration shown in FIG. .

<Example 15>
As the roughening material, 10.0% by mass of high density polyethylene resin powder B (average particle size 1.1 mm) was used instead of 5.0% by mass of high density polyethylene resin powder A (average particle size of 650 μm). The fluoropolymer lubricant contained in the first heat-fusible resin unstretched film 7 is replaced with a 750 ppm fluororesin lubricant (“FX5911” manufactured by 3M) instead of the 50 ppm fluororesin lubricant (“FX5911” manufactured by 3M). )) And a 250 ppm fluoroelastomer lubricant (“FX5920A” manufactured by 3M Co.) were used in the same manner as in Example 3 to obtain an electricity storage device exterior material (molding packaging material) 1 having the configuration shown in FIG. It was.

The high density polyethylene resin B (roughening material) has an MFR at 190 ° C. of 0.2 g / 10 min, a density of 0.945 g / cm ³ , and a swell of 35%. , Manufactured by a slurry loop method using a Philips catalyst.

<Example 16>
As a roughening material, 15.0% by mass of low density polyethylene resin powder C (average particle size 1.0 mm) was used instead of 5.0% by mass of high density polyethylene resin powder A (average particle size of 650 μm). As a fluoropolymer lubricant contained in the first heat-fusible resin unstretched film 7, instead of 50 ppm fluororesin lubricant (“FX5911” manufactured by 3M), 1000 ppm fluororesin lubricant (“FX5911 manufactured by 3M”). )) And a 500 ppm fluoroelastomer lubricant (“FX5920A” manufactured by 3M Co.) were used in the same manner as in Example 3 to obtain an electricity storage device exterior material (molding packaging material) 1 having the structure shown in FIG. It was.

The low density polyethylene resin C (roughening material) has an MFR at 190 ° C. of 2 g / 10 min, a density of 0.921 g / cm ³ and a swell of 20%. The low density polyethylene resin C is a Ziegler It is a linear low density polyethylene resin produced in a gas phase fluidized bed using a catalyst.

<Example 17>
As a slip agent to be contained in the first heat-fusible resin unstretched film 7 and the third heat-fusible resin unstretched film 9, 1000 ppm stearamide was used instead of 1000 ppm erucamide, and the second heat As a slip agent to be contained in the non-stretchable film 8 of the fusible resin, 2000 ppm stearamide is used in place of 2000 ppm of erucic amide, and the fluoropolymer system to be contained in the non-stretched film 7 of the first heat-fusible resin. As a lubricant, instead of a 50 ppm fluororesin lubricant (“FX5911” manufactured by 3M), a 500 ppm fluororesin lubricant (“FX5911” manufactured by 3M) and a 250 ppm fluoroelastomer lubricant (“FX5920A” manufactured by 3M) were used. Except for the above, the same as in Example 3 is shown in FIG. Formation of an energy storage device for exterior materials was obtained (molding packaging) 1.

<Example 18>
As a slip agent to be contained in the first heat-fusible resin unstretched film 7 and the third heat-fusible resin unstretched film 9, 1000 ppm behenamide is used instead of 1000 ppm erucamide, and the second heat Fluoropolymer system containing 2000 ppm behenamide instead of 2000 ppm erucamide as a slip agent to be included in the non-stretchable resin film 8 in the first heat-fusible resin 7 As a lubricant, a 750 ppm fluororesin lubricant (“FX5911” manufactured by 3M) and a 750 ppm fluoroelastomer lubricant (“FX5920A” manufactured by 3M) were used in place of the 50 ppm fluororesin lubricant (“FX5911” manufactured by 3M). Except for the above, the configuration shown in FIG. Exterior material device (molding packaging) to give a 1.

<Example 19>
As a slip agent to be contained in the first heat-fusible resin unstretched film 7 and the third heat-fusible resin unstretched film 9, 1000 ppm of erucic acid amide and 500 ppm of ethylenebisstearic acid amide were used. As a slip agent to be included in the adhesive resin unstretched film 8, in place of 1000 ppm erucamide, 2000 ppm erucamide and 500 ppm ethylene bis stearamide were used in the same manner as in Example 17, An exterior material for an electricity storage device (molding packaging material) 1 having the configuration shown in FIG. 2 was obtained.

<Example 20>
A 27 μm thick laminated film (12 μm thick polyethylene terephthalate film / 15 μm thick biaxially stretched 6 nylon film) is used as the outer layer 2 and the thickness of the aluminum foil 4 is changed to 40 μm. In addition, the fluoropolymer lubricant contained in the first heat-fusible resin unstretched film 7 is changed to a 500 ppm fluoroelastomer lubricant (“FX9613” manufactured by 3M) and the first heat-fusible resin is not stretched. The film 7 does not contain silica particles (anti-blocking agent), and the sealant film (heat-fusible resin layer 3) is a 80 μm-thick sealant film (8 μm-thick first heat-fusible resin unstretched film). Layer 7/64 μm thick second heat fusible resin unstretched film layer 8/8 μm thick third heat fusible resin unstretched film Except having used the film layer 9), it carried out similarly to Example 1, and obtained the electrical storage device exterior material (molding packaging material) 1 of the structure shown in FIG.

<Comparative Example 5>
The content (concentration) of erucamide included in the first heat-fusible resin unstretched film 7 is changed to 2500 ppm, and the content of erucamide included in the second heat-fusible resin unstretched film 8 ( Concentration) was changed to 2500 ppm, and in the same manner as in Example 3 except that the first heat-fusible resin unstretched film 7 did not contain a fluoropolymer-based lubricant, a packaging material for an electricity storage device (for molding) Packaging material).

  Each power storage device exterior material (molding packaging material) obtained as described above was evaluated based on the following evaluation method. The results are shown in Table 2. In addition, the dynamic friction coefficient of the surface of the innermost layer described in Tables 3 and 4 is a dynamic friction coefficient measured for the surface 7a of the innermost layer of each exterior material in accordance with JIS K7125-1995. Moreover, the dynamic friction coefficient of the surface 2a of the base material layer described in Tables 3 and 4 is a dynamic friction coefficient measured with respect to the surface 2a of the base material layer of each exterior material in accordance with JIS K7125-1995.

<Evaluation method of amount of slip agent present on inner surface of exterior material>
After cutting out two rectangular test pieces of 110 mm in length and 110 mm in width from the outer packaging material for each power storage device, these two test pieces are overlapped to form the innermost layer of each heat-fusible resin layer (inner layer). The peripheral parts of each were heat sealed at a heat seal temperature of 200 ° C. and a seal width of 5 mm to produce a bag. 1 mL of acetone was injected into the inner space of the bag body using a syringe and left for 3 minutes in a state where the inner surface of the bag body and acetone were in contact with each other, and then the acetone in the bag body was extracted. By measuring and analyzing the amount of components contained in the extracted liquid using a gas chromatograph, the amount of slip agent (μg / cm ² ) of the ^second slipping layer 12 of the exterior material was determined. That was determined formation of the second lubricating layer 12 per 1 cm ² of (μg / cm ^2).

<Evaluation method of the amount of fluoropolymer-based lubricant present on the inner surface of the exterior material>
After cutting out a rectangular test piece having a length of 101 mm × width of 100.5 mm from each power storage device exterior material, the test pieces were folded in half and overlapped to form a heat-fusible resin layer (inner layer). The peripheral portions of the innermost layers were heat sealed at a heat seal temperature of 200 ° C. with a seal width of 5 mm to prepare a bag. 100 mL of acetone was injected into the interior space of the bag using a syringe, and the bag was left at room temperature for 3 minutes in a state where the inner surface of the bag and the acetone were in contact with each other, and then the acetone in the bag was extracted. The slip agent (second slipping layer 12) was removed by repeating this operation twice. Next, 100 mL of acetone is further injected into the inner space of the bag body using a syringe, and the bag is left in an oven at 50 ° C. for 30 minutes in a state where the inner surface of the bag body and the acetone are in contact with each other. Extracted. The extracted liquid was concentrated with a rotary evaporator, and then vacuum-dried at 140 ° C. for 6 hours, and then the amount of the fluoropolymer-based lubricant (μg of the first lubricating layer 11 of the exterior material was measured by measuring the mass of the residue. / Cm ² ). That was determined amount of the formed first lubricating layer 11 per 1 cm ² of (μg / cm ^2).

<Evaluation method of amount of slip agent present on surface of base material layer of exterior material>
After cutting out two rectangular test pieces of 110 mm in length and 110 mm in width from the outer packaging material for each power storage device, the two test pieces were overlapped, and the peripheral portions of the outer surfaces of each were heat-sealed at 250 ° C. A bag was produced by heat sealing with a seal width of 5 mm. 1 mL of acetone was injected into the interior space of the bag using a syringe, and the bag was allowed to stand for 3 minutes with the inner surface of the bag in contact with the acetone, and then the acetone in the bag was removed. By measuring and analyzing the amount of components contained in the extracted liquid using a gas chromatograph, the amount of slip agent (μg / cm ² ) of the third slipping layer 13 outside the exterior material was determined. That was determined formation of the third lubricating layer 13 per 1 cm ² of (μg / cm ^2).

<Formability evaluation method>
Using a straight mold free of the molding depth, the drawing material is deep-drawn in one step under the following molding conditions, and each molding depth (9.0 mm, 8.5 mm, 8.0 mm, 7.5 mm, 7. (0mm, 6.5mm, 6.0mm, 5.5mm, 5.0mm, 4.5mm, 4.0mm, 3.5mm, 3.0mm, 2.5mm, 2.0mm) The maximum forming depth (mm) at which good forming with no pinholes at the corners could be performed was investigated. Table 2 shows the maximum molding depth (mm). The presence / absence of a pinhole was examined by visually observing the presence / absence of transmitted light passing through the pinhole.
(Molding condition)
Mold: Punch: 33.3 mm x 53.9 mm, Die: 80 mm x 120 mm, Corner R: 2 mm, Punch R: 1.3 mm, Die R: 1 mm
Wrinkle holding pressure: Gauge pressure: 0.475 MPa, actual pressure (calculated value): 0.7 MPa
Material: SC (carbon steel) material, punch R only is chrome plated.

<Evaluation method for white powder>
After cutting out a rectangular test piece of length 600 mm × width 100 mm from each energy storage device exterior material, the obtained test piece is placed on the test stand with the inner layer 3 side (that is, the innermost layer surface 7 a) facing upward. In a state where a SUS weight (mass 1.3 kg, the size of the grounding surface is 55 mm × 50 mm) in which a black cloth is wound and the surface is black is placed on the upper surface of the test piece, The weight was pulled and moved over a length of 400 mm in contact with the upper surface of the test piece by pulling the weight in a horizontal direction parallel to the upper surface of the test piece at a pulling speed of 4 cm / second. The waste (black) on the contact surface of the weight after the tensile movement was visually observed, and white powder on the surface of the waste (black) was marked “x”, and only a small amount of white powder was produced. The thing was set as "(triangle | delta)", and the thing which hardly had white powder or the white powder was not recognized was set as "(circle)". In addition, as the black waste, “Static removal sheet SSD2525 3100” manufactured by TRUSCO was used.

  As is clear from the table, the power storage device exterior materials (molding packaging materials) of Examples 1 to 20 of the present invention have a maximum molding depth of 4.5 mm or more, and are good even when deeper molding is performed. While being able to obtain a molded product, it was difficult for the white powder to appear on the surface of the exterior material.

  In contrast, in Comparative Examples 1 to 4, in which a slip agent and a roughening material are added in the innermost layer of the heat-fusible resin layer, but no fluoropolymer lubricant is added, deep drawing is performed. The maximum molding depth at the time of performing became a result lower than Examples 1-20. Further, in Comparative Example 5, white powder was remarkably exposed on the surface of the exterior material.

  The molding packaging material according to the present invention is suitably used as a battery case for notebook computers, mobile phones, in-vehicle, stationary lithium ion polymer secondary batteries and the like. Although suitable as a packaging material for pharmaceuticals, it is not particularly limited to these uses. Among these, it is particularly suitable for battery cases.

DESCRIPTION OF SYMBOLS 1 ... Molding packaging material 2 ... Base material layer (outer layer)
2a ... outer surface 3 of base material layer ... heat-fusible resin layer (inner layer)
4 ... metal foil layer 7 ... innermost layer (innermost layer of heat-fusible resin layer; first heat-fusible resin layer)
7a ... inner surface 8 of innermost layer of heat-fusible resin layer ... second heat-fusible resin layer 9 ... third heat-fusible resin layer 10 ... outer case 11 for power storage device ... first slipping layer 11a ... Inner surface 12 of the first slipping layer ... Second slipping layer 13 ... Third slipping layer 15 ... Exterior member 30 ... Power storage device 31 ... Power storage device main body

Claims (16)

A packaging material for molding comprising a base material layer as an outer layer, a heat-fusible resin layer as an inner layer, and a metal foil layer disposed between these two layers,
The heat-fusible resin layer is composed of a single layer or a plurality of layers, and the innermost layer of the heat-fusible resin layer contains a heat-fusible resin, a roughening material, a slip agent, and a fluoropolymer lubricant. A resin composition,
The roughening material contains a thermoplastic resin,
A molding packaging material, wherein a first slipping layer containing a fluoropolymer lubricant at a content of more than 50% by mass is formed on the inner surface of the innermost layer.   2. The molding packaging material according to claim 1, wherein a second slipping layer containing a slip agent at a content of greater than 50 mass% is formed on the inner surface of the first slipping layer.   The packaging material for molding according to claim 1 or 2, wherein the content of the fluoropolymer lubricant in the innermost layer is 5 ppm to 5000 ppm.   The molding packaging material according to any one of claims 1 to 3, wherein the fluorine content in the fluoropolymer lubricant is 50 mass% or more.   The fluoropolymer lubricant is one or two fluoropolymer lubricants selected from the group consisting of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer and hexafluoropropylene-vinylidene fluoride copolymer. The molding packaging material according to any one of claims 1 to 4.   The molding packaging material according to any one of claims 1 to 5, wherein the thermoplastic resin constituting the roughening material is a high-density polyethylene resin.   The molding packaging material according to any one of claims 1 to 6, wherein the slip agent is a fatty acid amide.   The molding packaging material according to any one of claims 1 to 7, wherein a third slipping layer containing a slip agent is formed on an outer surface of the base material layer.   The molding packaging material according to claim 8, wherein a dynamic friction coefficient of an outer surface of the packaging material is 0.5 or less.   The packaging material for molding according to any one of claims 1 to 9, wherein a dynamic friction coefficient of an inner surface of the packaging material is 0.5 or less.   The exterior case for electrical storage devices which consists of a molded object of the packaging material for shaping | molding of any one of Claims 1-10. An electricity storage device body,
An exterior member including at least the exterior case for an electricity storage device according to claim 11,
The electricity storage device, wherein the electricity storage device body is covered with the exterior member. A base material layer is laminated on one surface of the metal foil via an outer adhesive and a heat-fusible resin layer composed of a single layer or a plurality of layers via an inner adhesive on the other surface of the metal foil. And the innermost layer of the heat-fusible resin layer is a heat-fusible resin layer having a structure comprising a resin composition containing a heat-fusible resin, a roughening material, a slip agent, and a fluoropolymer lubricant. A step of preparing a laminated body formed by lamination;
An aging step of obtaining a molding packaging material by heat-treating the laminate, and
The method for producing a molding packaging material, wherein the roughening material contains a thermoplastic resin.   The method for producing a molding packaging material according to claim 13, wherein the heating temperature of the heat treatment in the aging step is 30C to 50C.   The method for producing a packaging material for molding according to claim 13 or 14, wherein the innermost layer is formed by melt extrusion film formation of the resin composition in the preparation step.   The method for producing a molding packaging material according to claim 13 or 14, wherein in the preparation step, the innermost layer is formed by applying and drying a coating solution containing the resin composition and a solvent.

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