WO2018066196A1

WO2018066196A1 - Method for producing packaging material

Info

Publication number: WO2018066196A1
Application number: PCT/JP2017/025289
Authority: WO
Inventors: ウェイホウ; 輝利熊木; 勉雁瀬; 宏琳王
Original assignee: 昭和電工パッケージング株式会社
Priority date: 2016-10-03
Filing date: 2017-07-11
Publication date: 2018-04-12
Also published as: CN109715392A; JP2018058230A; CN117885367A; CN116922805A

Abstract

Provided is a method for producing a packaging material, which is capable of greatly reducing the lead time, thereby improving the productivity, and which is also capable of ensuring excellent formability. This production method comprises: an inner layer formation step wherein a first laminate 48 is obtained by bonding a thermally fusible resin film 3 on one surface of a metal foil 4, with a molten resin film 47 extruded from an extruder 40 being interposed therebetween; and an outer layer formation step wherein a second laminate 49 is obtained by bonding a resin film 2 for substrate layers on the other surface of the metal foil 4 of the first laminate 48, with an electron beam curable resin composition 44 being interposed therebetween, and the second laminate 49 is subsequently irradiated with an electron beam 46 from the resin film for substrate layers side.

Description

Packaging material manufacturing method

The present invention is for batteries and capacitors used for mobile electric devices such as smartphones and tablets, hybrid vehicles, electric vehicles, wind power generation, solar power generation, and power storage devices such as batteries and capacitors used for power storage for night electricity. In addition to the outer packaging material (packaging material), the present invention relates to a method for producing a packaging material used as a food packaging material, a pharmaceutical packaging material, or the like.

Lithium ion secondary batteries are widely used as power sources for notebook computers, video cameras, mobile phones, electric vehicles, and the like. As this lithium ion secondary battery, one having a configuration in which the periphery of a battery main body (a main body including a positive electrode, a negative electrode, and an electrolyte) is surrounded by a case is used. As this case material (exterior material), a material having a structure in which an outer layer made of a heat-resistant resin film, an aluminum foil layer, and an inner layer made of a thermoplastic resin film are bonded and integrated in this order is known.

For example, a battery exterior material in which a base material layer (outer layer), a first adhesive layer, a metal foil layer, a second adhesive layer, and a sealant layer (inner layer) are laminated in this order, the first adhesive A battery exterior material having a structure in which both the layer and the second adhesive layer are formed by thermosetting (heat aging) is known (see Patent Document 1).

Japanese Patent Laid-Open No. 2015-144122

形成 In order to form the first and second adhesive layers by the thermosetting, it is necessary to perform a heat aging treatment at 40 ° C. for 5 days or 10 days after applying the adhesive (paragraph 0097 of Patent Document 1).

As described above, since the heat aging treatment must be performed for at least 5 days or more, there is a problem that the lead time (time required from material input to product completion) is considerably long, that is, the productivity is inferior.

The present invention has been made in view of such a technical background, and provides a method for manufacturing a packaging material that can significantly reduce the lead time and improve productivity, and can also ensure excellent moldability. With the goal.

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

[1] An inner layer forming step of bonding a heat-fusible resin film to one surface of a metal foil via an extruded molten resin film extruded from an extruder to obtain a first laminate,
After bonding the resin film for base material layers to the other surface of the metal foil of the first laminate through an electron beam curable resin composition to obtain a second laminate, the second laminate is applied to the second laminate And an outer layer forming step of irradiating an electron beam from the resin film side for the base material layer.

[2] A heat-bonding resin layer is formed on one surface of the metal foil by superimposing an extruded molten resin film extruded from an extruder on one surface of the metal foil to form a first laminate. An inner layer forming step to obtain;
After bonding the resin film for base material layers to the other surface of the metal foil of the first laminate through an electron beam curable resin composition to obtain a second laminate, the second laminate is applied to the second laminate And an outer layer forming step of irradiating an electron beam from the resin film side for the base material layer.

[3] A base layer resin film is adhered to one surface of a metal foil via an electron beam curable resin composition to obtain a first laminate, and then the base is applied to the first laminate. An outer layer forming step of irradiating an electron beam from the resin film side of the material layer;
An inner layer forming step of adhering a heat-fusible resin film to the other surface of the metal foil of the first laminate after the electron beam irradiation via an extruded molten resin film extruded from an extruder. A method for producing a packaging material characterized by the above.

[4] A base layer resin film is adhered to one surface of a metal foil via an electron beam curable resin composition to obtain a first laminate, and then the base is applied to the first laminate. An outer layer forming step of irradiating an electron beam from the resin film side of the material layer;
A heat-fusible resin layer is formed on the other surface of the metal foil layer by superimposing an extruded molten resin film extruded from an extruder on the other surface of the metal foil of the first laminate after the electron beam irradiation. A method for producing a packaging material, comprising: forming an inner layer.

[5] An inner layer forming step of obtaining a first laminate by adhering a heat-fusible resin film to one surface of a metal foil via an extruded molten resin film extruded from an extruder,
After applying an electron beam curable resin composition to the other surface of the metal foil of the first laminate to obtain a second laminate, the electron beam curable resin composition is applied to the second laminate. And an outer layer forming step of irradiating an electron beam from the side.

[6] By superposing an extruded molten resin film extruded from an extruder on one surface of the metal foil, a heat-fusible resin layer is formed on one surface of the metal foil to form a first laminate. An inner layer forming step to obtain;
After applying an electron beam curable resin composition to the other surface of the metal foil of the first laminate to obtain a second laminate, the electron beam curable resin composition is applied to the second laminate. And an outer layer forming step of irradiating an electron beam from the side.

[7] After applying the electron beam curable resin composition to one surface of the metal foil to obtain the first laminate, the electrons from the electron beam curable resin composition side to the first laminate are obtained. An outer layer forming step of irradiating a line;
An inner layer forming step of adhering a heat-fusible resin film to the other surface of the metal foil of the first laminate after the electron beam irradiation via an extruded molten resin film extruded from an extruder. A method for producing a packaging material characterized by the above.

[8] After applying an electron beam curable resin composition to one surface of the metal foil to obtain a first laminate, electrons from the electron beam curable resin composition side with respect to the first laminate are obtained. An outer layer forming step of irradiating a line;
A heat-fusible resin layer is formed on the other surface of the metal foil layer by superimposing an extruded molten resin film extruded from an extruder on the other surface of the metal foil of the first laminate after the electron beam irradiation. A method for producing a packaging material, comprising: forming an inner layer.

[9] The method for manufacturing a packaging material according to the above 1, 2, 5, or 6, wherein the inner layer forming step and the outer layer forming step are successively performed.

[10] The method for producing a packaging material according to any one of items 1 to 4, wherein a heat-resistant resin film having a hot water shrinkage of 1.5% to 12% is used as the base layer resin film.

[11] The method for producing a packaging material according to any one of items 1 to 10, wherein the extruded molten resin film is an extruded molten acid-modified polyolefin resin film.

In the inventions [1] to [8], a thermosetting resin is not used as an adhesive or the like (since a thermosetting resin that requires heat aging for several days is not used), that is, “electron beam Adhesion of curable resin composition using electron beam curing or formation of substrate layer by electron beam curing of electron beam curable resin composition "and" Adhesion using extruded molten resin film or using extruded molten resin film " “The formation of the heat-fusible resin layer” can be performed in a much shorter time compared to the curing of the thermosetting resin that requires heat aging for several days. Time) and cost can be reduced. Further, the electron beam curable resin composition and the extruded molten resin film do not need to contain a solvent, and can be made free of a solvent in this way, so that there is an advantage that an environmental load is small. In addition, since no thermosetting resin is used, a drying furnace is not required, so that the manufacturing equipment can be made compact. In addition, even if the molding material is deeply molded by cold (room temperature) molding such as deep drawing molding or overhang molding, pinholes and cracks do not occur, ensuring excellent moldability. it can.

[9] Since the inner layer forming step and the outer layer forming step are continuously performed, the production efficiency can be improved. In this way, when the inner layer forming step and the outer layer forming step are continuously performed, the inner layer forming step is performed before the outer layer forming step (the electron beam is formed after the inner layer is formed first). Since the outer layer forming step to be irradiated is performed), there is an advantage that the curling phenomenon hardly occurs in the packaging material.

In the invention of [10], since the heat-resistant resin film having a hot water shrinkage of 1.5% to 12% is used as the resin film for the base layer, even if molding is performed at a deep molding depth or at a high temperature Even when used under severe environments such as high humidity, delamination (peeling) between the outer layer (base material layer) and the metal foil layer can be sufficiently prevented.

In the invention of [11], since the extruded molten resin film is an extruded molten acid-modified polyolefin resin film, the adhesive strength between the metal foil layer and the heat-fusible resin layer can be improved.

It is a schematic side view which shows an example of the 1st manufacturing method which concerns on this invention. It is sectional drawing which shows one Embodiment of the packaging material obtained by the 1st or 2nd manufacturing method which concerns on this invention. It is sectional drawing which shows one Embodiment of the packaging material obtained by the 3rd or 4th manufacturing method which concerns on this invention. It is sectional drawing which shows one Embodiment of the packaging material obtained by the 5th or 6th manufacturing method which concerns on this invention. It is sectional drawing which shows one Embodiment of the packaging material obtained by the 7th or 8th manufacturing method 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 packaging material (planar thing) which comprises the electrical storage device of FIG. 6, the electrical storage device main-body part, and the shaping | molding case (molded object shape | molded in the solid shape).

The manufacturing method of the packaging material according to the present invention will be described. Examples of the production method of the present invention include the following first to eighth production methods.

(First manufacturing method)
An inner layer forming step of obtaining a first laminate 48 by bonding the heat-fusible resin film 3 to one surface of the metal foil 4 via an extruded molten resin film 47 extruded from an extruder 40; After the base layer resin film 2 is bonded to the other surface of the metal foil 4 of the one laminate 48 via the electron beam curable resin composition 44 to obtain the second laminate 49, the second laminate 49 is obtained. And an outer layer forming step of irradiating the electron beam 46 from the base layer resin film 2 side to the body 49 (see FIG. 1). By this first manufacturing method, the packaging material 1 having the configuration shown in FIG. 2 is obtained.

(Second manufacturing method)
A manufacturing method in which the execution order of the inner layer forming step and the outer layer forming step in the first manufacturing method is reversed is the second manufacturing method. That is, in the second production method, after the base layer resin film 2 is bonded to one surface of the metal foil 4 via the electron beam curable resin composition to obtain the first laminate, An outer layer forming step of irradiating an electron beam from the base layer resin film 2 side to one laminate, and the other surface of the metal foil 4 of the first laminate after the electron beam irradiation from an extruder An inner layer forming step of bonding the heat-fusible resin film 3 through the extruded extruded resin film. By this second manufacturing method, the packaging material 1 having the configuration shown in FIG. 2 is obtained.

The packaging material 1 shown in FIG. 2 has the above-mentioned base via an outer adhesive layer (first adhesive layer) 5 made of a cured film of an electron beam curable resin composition on one surface (upper surface) of the metal foil layer 4. A base material layer (outer layer) 2 made of a resin film for material layers is laminated and integrated, and an inner adhesive layer (second adhesive) made of an extruded resin film 47 on the other surface (lower surface) of the metal foil layer 4. The heat-fusible resin layer (inner layer) 3 is laminated and integrated through an agent layer 6.

(Third production method)
By superposing an extruded molten resin film extruded from an extruder on one surface of the metal foil 4, the heat-fusible resin layer 3 is formed on one surface of the metal foil 4 to form the first laminate. The inner layer forming step to be obtained and the base layer resin film 2 was adhered to the other surface of the metal foil 4 of the first laminate through an electron beam curable resin composition to obtain a second laminate. And an outer layer forming step of irradiating the second laminate with an electron beam from the base layer resin film 2 side. By this third manufacturing method, the packaging material 1 having the configuration shown in FIG. 3 is obtained.

In the third manufacturing method, the heat-fusible resin layer 3 is formed on one surface of the metal foil 4 by superimposing an extruded molten resin film extruded from an extruder on one surface of the metal foil 4. When forming, one layer of extruded molten resin film extruded from one extruder may be superposed on one surface of the metal foil 4 (single laminating method), or a plurality of extruders may be extruded. A plurality of layers of extruded molten resin films extruded from a machine may be superposed on one surface of the metal foil 4 (tandem laminating method).

(Fourth manufacturing method)
A manufacturing method in which the execution order of the inner layer forming step and the outer layer forming step in the third manufacturing method is reversed is the fourth manufacturing method. That is, in the fourth production method, after the base layer resin film 2 is adhered to one surface of the metal foil 4 via the electron beam curable resin composition to obtain the first laminate, An outer layer forming step of irradiating an electron beam from the base layer resin film 2 side to one laminate, and the other surface of the metal foil 4 of the first laminate after the electron beam irradiation from an extruder And an inner layer forming step of forming the heat-fusible resin layer 3 on the other surface of the metal foil 4 by overlapping the extruded molten resin films. By the fourth manufacturing method, the packaging material 1 having the configuration shown in FIG. 3 is obtained.

In the fourth manufacturing method, the other surface of the metal foil 4 is overlapped with the other surface of the metal foil 4 of the first laminate after irradiation with the electron beam by overlapping an extruded molten resin film extruded from an extruder. When the heat-fusible resin layer 3 is formed on the surface, one layer of the extruded molten resin film extruded from one extruder may be superposed on the other surface of the metal foil 4. (Single laminating method) A plurality of layers of extruded molten resin films extruded from a plurality of extruders may be superposed on the other surface of the metal foil 4 (tandem laminating method).

The packaging material 1 shown in FIG. 3 is a base material through the outer side adhesive layer (1st adhesive layer) 5 which consists of a cured film of an electron beam curable resin composition on one side (upper surface) of the metal foil layer 4. A base material layer (outer layer) 2 made of a resin film for layers is laminated and integrated, and a heat-fusible resin layer (inner layer) made of an extruded resin film 47 on the other surface (lower surface) of the metal foil layer 4. ) 3 is a laminated and integrated structure.

(Fifth manufacturing method)
An inner layer forming step for obtaining a first laminate by adhering the heat-fusible resin film 3 to one surface of the metal foil 4 via an extruded molten resin film extruded from an extruder, and the first laminate After applying an electron beam curable resin composition to the other surface of the metal foil 4 to obtain a second laminate, an electron beam is applied from the electron beam curable resin composition side to the second laminate. And an outer layer forming step of irradiating the substrate. By the fifth manufacturing method, the packaging material 1 having the configuration shown in FIG. 4 is obtained.

(Sixth manufacturing method)
A manufacturing method in which the execution order of the inner layer forming step and the outer layer forming step in the fifth manufacturing method is reversed is a sixth manufacturing method. That is, in the sixth production method, after the electron beam curable resin composition is applied to one surface of the metal foil 4 to obtain the first laminate, the electron beam curing is performed on the first laminate. An outer layer forming step of irradiating an electron beam from the conductive resin composition side, and an extruded molten resin film extruded from an extruder on the other surface of the metal foil 4 of the first laminate after the electron beam irradiation And an inner layer forming step for adhering the heat-fusible resin film 3. By the sixth manufacturing method, the packaging material 1 having the configuration shown in FIG. 4 is obtained.

The packaging material 1 shown in FIG. 4 has a base material layer (outer layer) 2 made of a cured film of an electron beam curable resin composition laminated and integrated on one surface (upper surface) of the metal foil layer 4. A heat-fusible resin layer (inner layer) made of a heat-fusible resin film via an inner adhesive layer (second adhesive layer) 6 made of an extruded resin film 47 on the other surface (lower surface) of the metal foil layer 4. ) 3 is a laminated and integrated structure.

(Seventh manufacturing method)
By superposing an extruded molten resin film extruded from an extruder on one surface of the metal foil 4, a heat-fusible resin layer 3 is formed on one surface of the metal foil to obtain a first laminate. After the inner layer forming step and applying the electron beam curable resin composition to the other surface of the metal foil 4 of the first laminated body to obtain a second laminated body, An outer layer forming step of irradiating an electron beam from the electron beam curable resin composition side. By the seventh manufacturing method, the packaging material 1 having the configuration shown in FIG. 5 is obtained.

In the seventh manufacturing method, the heat-fusible resin layer 3 is formed on one surface of the metal foil 4 by superimposing an extruded molten resin film extruded from an extruder on one surface of the metal foil 4. When forming, one layer of extruded molten resin film extruded from one extruder may be superposed on one surface of the metal foil 4 (single laminating method), or a plurality of extruders may be extruded. A plurality of layers of extruded molten resin films extruded from a machine may be superposed on one surface of the metal foil 4 (tandem laminating method).

(Eighth manufacturing method)
A manufacturing method in which the execution order of the inner layer forming step and the outer layer forming step in the seventh manufacturing method is reversed is an eighth manufacturing method. That is, in the eighth manufacturing method, after the electron beam curable resin composition is applied to one surface of the metal foil 4 to obtain the first laminate, the electron beam curing is performed on the first laminate. An outer layer forming step of irradiating an electron beam from the conductive resin composition side and an extruded molten resin film extruded from an extruder are superimposed on the other surface of the metal foil 4 of the first laminate after the electron beam irradiation. And an inner layer forming step of forming a heat-fusible resin layer on the other surface of the metal foil 4. By the eighth manufacturing method, the packaging material 1 having the configuration shown in FIG. 5 is obtained.

In the eighth manufacturing method, the other surface of the metal foil 4 is overlapped with the other surface of the metal foil 4 of the first laminate after irradiation with the electron beam by overlapping an extruded molten resin film extruded from an extruder. When the heat-fusible resin layer 3 is formed on the surface, one layer of the extruded molten resin film extruded from one extruder may be superposed on the other surface of the metal foil 4. (Single laminating method) A plurality of layers of extruded molten resin films extruded from a plurality of extruders may be superposed on the other surface of the metal foil 4 (tandem laminating method).

The packaging material 1 shown in FIG. 5 has a base material layer (outer layer) 2 made of a cured film of an electron beam curable resin composition laminated and integrated on one surface (upper surface) of the metal foil layer 4. The heat-fusing resin layer (inner layer) 3 made of the extruded resin film 47 is laminated and integrated on the other surface (lower surface) of the metal foil layer 4.

In the first, second, fifth, and sixth manufacturing methods, the heat-fusible resin film 3 is bonded to one surface of the metal foil 4 through the extruded molten resin film extruded from the extruder in the inner layer forming step. In this case, although not particularly limited, for example, a sandwich lamination method or the like is preferably used.

In the above third, fourth, seventh, and eighth manufacturing methods, in the inner layer forming step, the melted resin film extruded from the extruder is superposed on one surface of the metal foil 4 and heat-sealed by the extruded resin film. When forming the conductive resin layer 3, it is not particularly limited, but for example, a single laminating method or a tandem laminating method may be used.

The packaging material 1 obtained by the first to eighth manufacturing methods according to the present invention is suitably used as a battery exterior material such as a lithium ion secondary battery, but is particularly limited to such applications. is not. The packaging material 1 may be used as the packaging material 1 as it is without being molded (see FIG. 7), or used as a molding case 10 after being subjected to molding such as deep drawing molding or overhang molding. (See FIG. 7).

In the present invention, the base material layer (outer layer) 2 is a member mainly responsible for ensuring good formability as the packaging material 1, that is, the role of preventing breakage due to necking of the aluminum foil during molding. The main responsibility.

In the first to fourth manufacturing methods, the base layer resin film 2 is preferably formed of a heat resistant resin film. As the heat resistant resin constituting the heat resistant resin film 2, a heat resistant resin that does not melt at the heat sealing temperature when the packaging material 1 is heat sealed is used. As the heat-resistant resin, it is preferable to use a heat-resistant resin having a melting point higher by 10 ° C. or more than the melting point of the heat-fusible resin constituting the heat-fusible resin layer 3, and 20 higher than the melting point of the heat-fusible resin. It is particularly preferable to use a heat resistant resin having a melting point higher by at least ° C.

The heat-resistant resin film 2 is not particularly limited, and examples thereof include a stretched polyamide film such as a stretched nylon film and a stretched polyester film. Among them, the heat resistant resin film 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 preferable to use a phthalate (PEN) film. Moreover, as the heat resistant resin film 2, it is preferable to use a heat resistant resin biaxially stretched film stretched by a simultaneous biaxial stretching method. Although it does not specifically limit as said nylon, For example, 6 nylon, 6, 6 nylon, MXD nylon etc. are mentioned. The heat-resistant resin film 2 may be formed of a single layer (single stretched film) or a multilayer (stretched PET film / stretched nylon film) made of, for example, a stretched polyester film / stretched polyamide film. Etc.).

In the first to fourth manufacturing methods, the heat resistant resin film 2 is preferably composed of a heat resistant resin film having a hot water shrinkage of 1.5% to 12%. When the hot water shrinkage rate is 1.5% or more, it is possible to further prevent the occurrence of cracks and cracks during molding, and when the hot water shrinkage rate is 12% or less, between the outer layer 2 and the metal foil layer 4 The occurrence of delamination can be further prevented. Among them, it is more preferable to use a heat resistant resin film having a hot water shrinkage of 1.8 to 11% as the heat resistant resin film 2. Further, it is more preferable to use a heat resistant resin film having a hot water shrinkage of 1.8% to 6%. As the heat resistant resin film, a stretched heat resistant resin film is preferably used.

The “hot water shrinkage ratio” means the dimensional change in the stretching direction of the test piece before and after immersion when the test piece (10 cm × 10 cm) of the heat resistant resin stretched film is immersed in hot water at 95 ° C. for 30 minutes. It is a rate and is calculated | required by following Formula.

Hot water shrinkage (%) = {(XY) / X} × 100
X: Dimensions in the stretching direction before the immersion treatment Y: Dimensions in the stretching direction after the immersion treatment.

In addition, the hot water shrinkage | contraction rate in the case of employ | adopting a biaxially stretched film is an average value of the dimensional change rate in two extending directions.

The hot water shrinkage rate of the heat-resistant resin stretched film can be controlled, for example, by adjusting the heat setting temperature during stretching.

In the first to fourth production methods, the base layer resin film 2 is bonded to one surface of the metal foil 4 via the electron beam curable resin composition. The electron beam curable resin composition includes the following: Use a configuration. In the fifth to eighth manufacturing methods, the electron beam curable resin composition is applied to one side of the metal foil 4 by applying the electron beam curable resin composition to one side of the metal foil 4 and irradiating the electron beam. A substrate layer (outer layer) 2 made of a cured film is laminated, and the electron beam curable resin composition having the following configuration is used.

That is, in the first to eighth production methods according to the present invention, the electron beam curable resin composition is a composition containing a polymerizable oligomer and an electron beam polymerization initiator, among which a polymerizable oligomer, a polymerizable A composition containing a monomer and an electron beam polymerization initiator is preferred. The electron beam curable resin composition may be a radical polymerization resin composition, a cationic polymerization resin composition, a radical polymerization and a cationic polymerization resin composition (radical). It may be a mixture of a polymerization system and a cationic polymerization system, and is not particularly limited. Among them, it is preferable to use an acrylic ultraviolet curable resin composition as the electron beam curable resin composition.

Although it does not specifically limit as said polymerizable oligomer, For example, radical polymerization type oligomers, such as a urethane acrylate oligomer, an epoxy acrylate oligomer, and a polyester acrylate oligomer, a vinyl ether oligomer, an alicyclic epoxy oligomer (resin), etc. Examples include cationic polymerization type oligomers.

The electron beam polymerization initiator is not particularly limited, and examples thereof include a photo radical polymerization initiator and a photo cationic polymerization initiator. The radical photopolymerization initiator is not particularly limited, and examples thereof include benzophenone, benzoin alkyl ether (benzoethyl ether, benzobutyl ether, etc.), benzyldimethyl ketal, acetophenone, thioxanthone, and the like.

The photocationic polymerization initiator is not particularly limited, and examples thereof include onium salts. The onium salt is not particularly limited, and examples thereof include a sulfonium salt, an iodonium salt, a bromonium salt, a diazonium salt, and a chloronium salt.

The sulfonium salt is not particularly limited. For example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [ Diphenylsulfonio] diphenylsulfide-bishexafluorophosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide-bishexafluoroantimonate, 4,4′-bis [di (β- Hydroxyethoxy) phenylsulfonio] diphenyl sulfide-bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide-hexafluorophosphate, 4- (p- ter-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4- (p-ter-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenylsulfide-tetrakis ( Pentafluorophenyl) borate, triphenylsulfonium bromide and the like.

The iodonium salt is not particularly limited. For example, diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluoro A phosphate etc. are mentioned.

The polymerizable monomer is not particularly limited, and examples thereof include an acrylate monomer and a vinyl ether monomer. The acrylate monomer is not particularly limited, and examples thereof include pentaerythritol triacrylate, neopentyl glycol diacrylate, and phosphoric acid-containing (meth) acrylate. The phosphoric acid-containing (meth) acrylate is not particularly limited, and examples thereof include monomers such as acryloyloxyethyl acid phosphate and bis (2- (meth) acryloyloxyethyl) acid phosphate.

The vinyl ether monomer is not particularly limited, and examples thereof include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 4-hydroxybutyl vinyl ether (HBVE) and the like.

The electron beam curable resin composition may contain a silane coupling agent, an acid anhydride, a sensitizer, various additives, and the like.

The silane coupling agent is not particularly limited. For example, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, etc. Is mentioned. Among them, as the silane coupling agent, a silane coupling agent having a carbon-carbon double bond such as vinyltriethoxysilane or allyltrimethoxysilane is preferably used. In this case, a radical polymerization reaction is particularly used. Bonding with the adhesive can be strengthened.

The acid anhydride is not particularly limited, and examples thereof include maleic anhydride, methyl maleic anhydride, itaconic anhydride, anhydrous hymic acid, and anhydrous methyl hymic acid. Among them, the acid anhydride is preferably an acid anhydride having a carbon-carbon double bond such as maleic anhydride, and the radical polymerization reaction is further promoted by the acid anhydride having such a double bond. be able to.

The sensitizer is not particularly limited, and examples thereof include a tertiary amine. The tertiary amine is not particularly limited, and examples thereof include N, N-dimethylethylamine, N, N-dimethylethanolamine, N, N, 3,5-tetramethylaniline and the like.

において The content of the polymerizable monomer in the electron beam curable resin composition is preferably 0.01% by mass to 5% by mass. The content of the polymerizable oligomer in the electron beam curable resin composition is preferably 85% by mass to 99% by mass. In addition, the content of the electron beam polymerization initiator in the electron beam curable resin composition is preferably 0.1% by mass to 10% by mass.

In the first to fourth production methods, the method for applying the electron beam curable resin composition to the metal foil 4 or the base layer resin film 2 is not particularly limited. For example, a gravure roll coating method , Screen coating, inkjet coating, die coating, and the like, and an optimal coating method may be selected according to the material to be coated (electron beam curable resin composition). At this time, the electron beam curable resin composition may be applied to the metal foil 4, the electron beam curable resin composition may be applied to the base layer resin film 2, or the metal foil 4 and You may apply | coat an electron beam curable resin composition to both the resin films 2 for base materials layers. Further, in the fifth to eighth production methods according to the present invention, the technique for applying the electron beam curable resin composition to the metal foil 4 is not particularly limited, but the same technique as exemplified above. Can be mentioned.

In the first to fourth manufacturing methods, the thickness (the thickness after drying) of the outer adhesive layer (first adhesive layer) 5 of the resulting packaging material 1 is preferably set to 1 μm to 6 μm.

In the present invention, the thickness of the base material layer 2 is preferably 10 μm to 50 μm. It is possible to secure sufficient strength as a packaging material by setting it to the above preferred lower limit value or more and to improve the formability by reducing the stress at the time of stretch molding or drawing by setting the preferred lower limit value or less. Can do.

In the present invention, the metal foil layer (metal foil) 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 4, For example, aluminum foil, copper foil, SUS foil (stainless steel foil), nickel foil, titanium foil etc. are mentioned, Aluminum foil is generally used. The thickness of the metal foil 4 is preferably 10 μm to 200 μm. When it is 10 μm or more, it is possible to prevent the occurrence of pinholes during rolling when manufacturing metal foil, and when it is 200 μm or less, it is possible to reduce the stress during forming such as stretch forming and draw forming, thereby improving formability. be able to. In particular, the thickness of the metal foil 4 is particularly preferably 20 μm to 100 μm.

The metal foil 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 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, and after drying an aqueous solution of any one of the above 1) to 3) Then, chemical conversion treatment is performed.

The chemical conversion film preferably has a chromium adhesion amount (per one surface) of 0.1 mg / m ² to 50 mg / m ² , particularly preferably 2 mg / m ² to 20 mg / m ² .

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

In the first, second, fifth, and sixth manufacturing methods, the heat-fusible resin film 3 is bonded to one surface of the metal foil 4 through the extruded molten resin film (inner adhesive 6) extruded from the extruder. As the resin constituting the heat-fusible resin film and the extruded molten resin film, the following are used. In the third, fourth, seventh, and eighth manufacturing methods, the extruded molten resin film extruded from the extruder is superposed on one side of the metal foil 4, so that the extruded resin film is formed on one side of the metal foil 4. The heat-fusible resin layer (inner layer) 3 is laminated, and the following resins are used as the resin constituting the extruded molten resin film.

That is, in the first, second, fifth, and sixth manufacturing methods, the resin constituting the heat-fusible resin film 3 is not particularly limited, and examples thereof include polyethylene, polypropylene, ionomer, and ethylene acrylic acid. Examples include ethyl (EEA), ethylene methyl acrylate (EAA), ethylene methyl methacrylate resin (EMMA), ethylene-vinyl acetate copolymer resin (EVA), maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, and polyester resin. It is done. The heat-fusible resin film 3 is preferably formed of a heat-fusible resin unstretched film.

The resin constituting the extruded molten resin film is not particularly limited. For example, maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, maleic anhydride-modified polyethylene, maleic acid-modified polyethylene, polypropylene resin, A polyethylene resin etc. are mentioned. In particular, in the third, fourth, seventh, and eighth manufacturing methods, examples of the resin constituting the extruded molten resin film include maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, maleic anhydride-modified polyethylene, and maleic acid-modified polyethylene. It is desirable to use a heat-fusible resin such as polypropylene resin or polyethylene resin.

In the first, second, fifth and sixth production methods, the thickness of the extruded molten resin film immediately before sandwiching between the metal foil 4 and the heat-fusible resin film 3 by the sandwich lamination method or the like (immediately before contact) is particularly Although not limited, it is preferably set to 5 μm to 40 μm. In the first, second, fifth, and sixth manufacturing methods, the thickness (the thickness after drying) of the inner adhesive layer (second adhesive layer) 6 of the resulting packaging material 1 is set to 5 μm to 40 μm. Preferably it is done.

In the present invention, the thickness of the heat-fusible resin layer (inner layer) 3 is preferably set to 20 μm to 100 μm. When the thickness is 20 μm or more, sufficient heat seal strength can be secured, and by setting the thickness to 100 μm or less, it contributes to a reduction in thickness and weight. The heat-fusible resin layer 3 may be a single layer or a multilayer. When the heat-fusible resin layer 3 is formed of a plurality of layers, the innermost layer of the heat-fusible resin layer 3 is an ethylene-propylene random copolymer or / and a propylene block copolymer (elastomer modified). Propylene resin) is preferable, and by adopting such a configuration, the sealing characteristics after heat sealing (after heat sealing) can be improved (high heat sealing strength and the like can be obtained).

In the production method of the present invention, examples of the electron beam include ultraviolet light, visible light, X-ray, and γ-ray. The ultraviolet light, when irradiated with visible light, the irradiation amount of light, but are not particularly limited, preferably set to one side per ^{50mJ / cm 2 ~ 1000mJ / cm} 2.

An outer case (such as an outer case for an electricity storage device) 10 can be obtained by molding (deep drawing molding, overhang molding, etc.) the packaging material 1 obtained by the manufacturing method of the present invention (see FIG. 7). In addition, the packaging material 1 obtained with the manufacturing method of this invention can also be used as it is, without using for shaping | molding (refer FIG. 7).

FIG. 6 shows an embodiment of an electricity storage device 30 configured using the packaging material 1 obtained by the manufacturing method of the present invention. The electricity storage device 30 is a lithium ion secondary battery. In this embodiment, as shown in FIGS. 6 and 7, a packaging member 15 is configured by a case 10 obtained by molding the packaging material 1 and a planar packaging material 1 that has not been used for molding. Yes. Thus, in the housing recess of the molding case 10 obtained by molding the packaging material 1 obtained by the manufacturing method of the present invention, a substantially rectangular parallelepiped power storage device body (electrochemical element or the like) 31 is housed. On the electricity storage device main body 31, the packaging material 1 obtained by the production method of the present invention is disposed without forming the inner layer 3 side inward (lower side), and the planar packaging material 1 and the inner layer 3 of the flange portion (sealing peripheral portion) 29 of the molded case 10 are sealed and sealed by heat sealing, whereby the electricity storage device of the present invention. 30 is configured (see FIGS. 6 and 7). The inner surface of the housing recess of the molded case 10 is an inner layer (heat-fusible resin layer) 3, and the outer surface of the housing recess is an outer layer (base material layer) 2 (FIG. 7).

In FIG. 6, reference numeral 39 denotes a heat seal part in which the peripheral part of the packaging material 1 and the flange part (sealing peripheral part) 29 of the molded case 10 are joined (fused). Note that, 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 packaging member 15, but the illustration is omitted.

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 portion 39 is preferably set to 0.5 mm or more. Sealing can be reliably performed by setting it as 0.5 mm or more. In particular, the width of the heat seal portion 39 is preferably set to 3 mm to 15 mm.

In the said embodiment, although the packaging member 15 was the structure which consists of the shaping | molding case 10 obtained by shape | molding the packaging material 1, and the planar packaging material 1 (refer FIG. 6, 7), especially this For example, the packaging member 15 may be composed of a pair of packaging materials 1 or may be composed of a pair of molded cases 10.

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

<Example 1>
Chemical conversion consisting of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water and alcohol on both sides of 40 μm thick aluminum foil (A8021H-O aluminum foil specified in JIS H4160) 4 After apply | coating a process liquid, it dried at 180 degreeC and formed the chemical conversion film. The amount of chromium deposited on this chemical film was 10 mg / m ² per side.

Next, as shown in FIG. 1, an extruded molten maleic acid-modified polyolefin resin film having a thickness of 15 μm extruded from an extruder 40 on one surface of the chemical conversion-treated aluminum foil 4 supplied from a supply roll 51. (Extruded molten resin film) 47 After bonding an unstretched polypropylene film (heat-fusible resin film) 3 having a thickness of 40 μm that has been supplied from the supply roll 52, between the pair of

rolls

41, 41 The first laminated body 48 was obtained by sandwiching (by sandwich lamination method) (inner layer forming step).

Next, as shown in FIG. 1, a urethane acrylate oligomer (polymerized) having two acryloyl groups on the other surface of the metal foil 4 of the first laminated body 48 continuously (in a continuous process) with the inner layer forming process. Curable oligomer) 94 parts by weight, 1 part by weight of pentaerythritol triacrylate (polymerizable monomer) and 5 parts by weight of benzophenone (photoradical polymerization initiator), photocurable resin composition A (electron beam curable resin composition) 44 was applied with an application roll 42 so that the mass after drying was 2.0 g / m ² , and then the hot water shrinkage supplied from the supply roll 53 to the application surface was 5.0%. After the biaxially stretched nylon film (resin film for base material layer) 2 having a thickness of 25 μm is bonded, the second laminate 49 is obtained by sandwiching between a pair of

rolls

45, 45. By irradiating the layer body 49 with 100 mJ / cm ² of ultraviolet light (UV light; wavelength 365 nm) 46 from the side of the base layer resin film 2 side (outer layer forming step), the electricity storage device having the configuration shown in FIG. The exterior packaging material 1 was obtained. In addition, in FIG. 1, 43 is an electron beam curable resin composition containing tank (container).

<Example 2>
In the same manner as in Example 1, a chemically treated aluminum foil was obtained. Next, after superposing an extruded molten maleic acid-modified polyolefin resin film (extruded molten resin film) having a thickness of 55 μm extruded from an extruder on one surface of the chemical conversion treated aluminum foil 4, a cooling roll and a room temperature By cooling and pinching between rolls (by a single laminating method), a first laminate in which a 55 μm thick heat-fusible resin layer 3 made of maleic acid-modified polyolefin resin is laminated on one surface of an aluminum foil Obtained (inner layer forming step).

Next, 94 parts by mass of a urethane acrylate oligomer (polymerizable oligomer) having two acryloyl groups on the other surface of the metal foil 4 of the first laminate continuously with the inner layer forming step (in the continuous step), The weight after drying a photocurable resin composition A (electron beam curable resin composition) containing 1 part by mass of pentaerythritol triacrylate (polymerizable monomer) and 5 parts by mass of benzophenone (photopolymerization initiator) is 2. After coating with a coating roll so as to be 0 g / m ² , a biaxially stretched nylon film (resin film for substrate layer) 2 having a hot water shrinkage of 5.0% and a thickness of 25 μm is applied to the coated surface. after bonding to, by nipping between a pair of rolls to obtain a second laminate, and thereafter, the second ultraviolet light from substrate layer for the resin film side of the laminate 100 mJ / cm ² ( UV light; By irradiating length 365 nm) (outer layer forming step), to give the outer package 1 for a power storage device having the structure shown in FIG. 3.

<Example 3>
In the same manner as in Example 1, a chemically treated aluminum foil was obtained. Next, the mass after drying the same photocurable resin composition A (electron beam curable resin composition) as in Example 1 on one surface of the chemical conversion treated aluminum foil 4 is 2.0 g / m ^2. Then, a biaxially stretched nylon film (resin film for substrate layer) 2 having a hot water shrinkage of 5.0% and a thickness of 25 μm is bonded to the coated surface. of by nipping between rolls, to obtain a first laminate, thereafter, the first ultraviolet light from substrate layer for the resin film side of the laminate 100 mJ / cm ^2; (wavelength 365nm electron beam) Irradiation (outer layer forming step).

Next, continuously with the outer layer forming step (in the continuous step), the other surface of the aluminum foil 4 of the first laminate after the electron beam irradiation is extruded and melted with a thickness of 15 μm extruded from an extruder. An unstretched polypropylene film (heat-fusible resin film) 3 having a thickness of 40 μm is bonded through a maleic acid-modified polyolefin resin film (extruded molten resin film), and then sandwiched between a pair of rolls (sandwich) (By the laminating method) (inner layer forming step), an exterior material 1 for an electricity storage device having the configuration shown in FIG. 2 was obtained.

<Example 4>
In the same manner as in Example 1, a chemically treated aluminum foil was obtained. Then, the chemical conversion treated on one surface of the aluminum foil 4, Example 1 and the same light-curable resin composition A mass after drying (electron beam-curable resin composition) is 2.0 g / m ² Then, a biaxially stretched nylon film (resin film for substrate layer) 2 having a hot water shrinkage of 5.0% and a thickness of 25 μm is bonded to the coated surface. By sandwiching between the rolls, a first laminate is obtained, and then 100 mJ / cm ² of ultraviolet light (wavelength 365 nm; electron beam) is applied to the first laminate from the resin film side of the base layer. Irradiation (outer layer forming step).

Next, in succession to the outer layer forming step (in a continuous step), the other surface of the aluminum foil 4 of the first laminate after the electron beam irradiation is extruded from an extruder with a thickness of 55 μm. After the maleic acid-modified polyolefin resin film (extruded molten resin film) is overlaid, the maleic acid-modified polyolefin is formed on the other surface of the aluminum foil 4 by cooling and clamping between a cooling roll and a room temperature roll (by a single laminating method). A heat-fusible resin layer 3 made of resin and having a thickness of 55 μm was laminated (inner layer forming step) to obtain an electricity storage device exterior material 1 having the configuration shown in FIG.

<Example 5>
In the same manner as in Example 1, a chemically treated aluminum foil was obtained. Next, non-stretched with a thickness of 40 μm on one surface of the chemically treated aluminum foil 4 through an extruded molten maleic acid-modified polyolefin resin film (extruded molten resin film) having a thickness of 15 μm extruded from an extruder. After bonding the polypropylene film (heat-fusible resin film) 3 together, the first laminate was obtained by sandwiching between a pair of rolls (by sandwich lamination method) (inner layer forming step).

Continuously with the inner layer forming step (in a continuous step), the same photocurable resin composition A (electron beam curable resin composition as in Example 1) is formed on the other surface of the metal foil 4 of the first laminate. ) Is applied so that the mass after drying is 10 g / m ² , to obtain a second laminate, and then 100 mJ / cm from the electron beam curable resin composition side to the second laminate. By irradiating ² ultraviolet light (wavelength 365 nm; electron beam) (outer layer forming step), an exterior material 1 for an electricity storage device having the configuration shown in FIG. 4 was obtained.

<Example 6>
In the same manner as in Example 1, a chemically treated aluminum foil was obtained. Next, after superposing an extruded molten maleic acid-modified polyolefin resin film (extruded molten resin film) having a thickness of 55 μm extruded from an extruder on one surface of the chemical conversion treated aluminum foil 4, a cooling roll and a room temperature A first laminate in which a 55 μm-thick heat-fusible resin layer 3 made of maleic acid-modified polyolefin resin is laminated on one surface of the aluminum foil 4 by cooling and clamping between rolls (by a single laminating method). (Inner layer forming step).

Continuously with the inner layer forming step (in a continuous step), the same photocurable resin composition A (electron beam curable resin composition as in Example 1) is formed on the other surface of the metal foil 4 of the first laminate. Product) is applied so that the mass after drying is 10 g / m ² , to obtain a second laminate, and then 100 mJ / from the electron beam curable resin composition side to the second laminate. By irradiating with cm ² ultraviolet light (wavelength 365 nm; electron beam) (outer layer forming step), the electricity storage device exterior material 1 having the configuration shown in FIG. 5 was obtained.

<Example 7>
In the same manner as in Example 1, a chemically treated aluminum foil was obtained. Next, the weight after drying the same photocurable resin composition A (electron beam curable resin composition) as in Example 1 on one surface of the chemical conversion treated aluminum foil 4 becomes 10 g / m ² . After the first laminated body is obtained by coating in this manner, the first laminated body is irradiated with 100 mJ / cm ² of ultraviolet light (wavelength 365 nm; electron beam) from the electron beam curable resin composition side. (Outer layer forming step).

Continuously with the outer layer forming step (in the continuous step), the other surface of the metal foil 4 of the first laminate after irradiation with the electron beam was extruded from an extruder with a 15 μm thick extruded melt maleic acid modified. After pasting together an unstretched polypropylene film (heat-fusible resin film) 3 having a thickness of 40 μm through a polyolefin resin film (extruded molten resin film), it is sandwiched between a pair of rolls (by sandwich lamination method) ) (Inner layer forming step), an exterior material 1 for an electricity storage device having the configuration shown in FIG. 4 was obtained.

<Example 8>
In the same manner as in Example 1, a chemically treated aluminum foil was obtained. Next, the weight after drying the same photocurable resin composition A (electron beam curable resin composition) as in Example 1 on one surface of the chemical conversion treated aluminum foil 4 becomes 10 g / m ² . by applying such, after obtaining the first laminated body, wherein with respect to the first laminate electron beam-curable resin composition side from 100 mJ / cm ² of ultraviolet light; illumination (wavelength 365nm electron beam) (Outer layer forming step).

Continuously with the outer layer forming step (in a continuous step), the other surface of the metal foil 4 of the first laminate after the electron beam irradiation was extruded from an extruder with a thickness of 55 μm by extrusion melt maleic acid modification. After superposing the polyolefin resin film (extruded molten resin film), it is made of maleic acid-modified polyolefin resin on the other surface of the aluminum foil 4 by cooling and pressing between the cooling roll and the room temperature roll (by a single laminating method). A heat-fusible resin layer 3 having a thickness of 55 μm was laminated (inner layer forming step) to obtain a power storage device exterior material 1 having the configuration shown in FIG.

<Example 9>
As the photocurable resin composition (electron beam curable resin composition) 44, instead of the photocurable resin composition A, 96.0 parts by mass of a vinyl ether oligomer (polymerizable oligomer) having two vinyl groups, 2- Except for using a photocurable resin composition B containing 3.0 parts by mass of hydroxyethyl vinyl ether (polymerizable monomer) and 1.0 part by mass of triphenylsulfonium hexafluorophosphate (sulfonium salt; photocationic polymerization initiator) In the same manner as in Example 1, an exterior material 1 for an electricity storage device having the configuration shown in FIG. 2 was obtained.

<Example 10>
Example 2 except that instead of the photocurable resin composition A, the photocurable resin composition B used in Example 9 was used as the photocurable resin composition (electron beam curable resin composition). In the same manner as described above, an electricity storage device exterior material 1 having the configuration shown in FIG. 3 was obtained.

<Example 11>
Example 5 except that instead of the photocurable resin composition A, the photocurable resin composition B used in Example 9 was used as the photocurable resin composition (electron beam curable resin composition). In the same manner as above, an exterior device 1 for an electricity storage device having the configuration shown in FIG. 4 was obtained.

<Example 12>
Example 6 except that the photocurable resin composition B used in Example 9 was used in place of the photocurable resin composition A as the photocurable resin composition (electron beam curable resin composition). In the same manner as above, an exterior device 1 for an electricity storage device having the configuration shown in FIG. 5 was obtained.

<Example 13>
As the irradiation light (electron beam), in place of the ultraviolet light 100 mJ / cm ^2, except for using the ultraviolet light of 250 mJ / cm ^2, in the same manner as in Example 1, exterior storage device having the structure shown in FIG. 2 Material 1 was obtained.

<Example 14>
The exterior for an electricity storage device having the configuration shown in FIG. 2 is the same as that of Example 1, except that 500 mJ / cm ² ultraviolet light is used instead of 100 mJ / cm ² ultraviolet light as irradiation light (electron beam). Material 1 was obtained.

<Example 15>
In the inner layer forming step of Example 2, an extruded molten maleic acid-modified polyolefin resin film (extruded molten resin film) having a thickness of 10 μm extruded from the first extruder is overlaid on one surface of the chemically treated aluminum foil 4. Then, after cooling and clamping between a cooling roll and a room temperature roll, an extruded molten polypropylene resin film (extruded molten resin film) having a thickness of 45 μm extruded from the second extruder is further applied on the resin film. After the superposition, the first heat-resisting resin layer 3 having a total thickness of 55 μm is laminated on one surface of the aluminum foil by cooling and pressing between the cooling roll and the room temperature roll (by tandem laminating method). Except having obtained the laminated body, it carried out similarly to Example 2, and obtained the exterior material 1 for electrical storage devices of the structure shown in FIG.

<Reference example>
In the same manner as in Example 1, a chemically treated aluminum foil was obtained. Next, after applying the urethane adhesive (outer adhesive) 5 on one surface of the chemical conversion treated aluminum foil 4 so that the thickness after drying becomes 2 μm, on the outer adhesive application surface, A biaxially stretched nylon film 2 having a hot water shrinkage of 5.0% and a thickness of 25 μm was superposed and bonded to obtain a first laminate. The first laminate was left to stand in a 60 ° C. environment for 7 days and subjected to a heat aging treatment, whereby the outer adhesive was cured to form an outer adhesive layer.

Next, the inner adhesive 6 made of a thermosetting acid-modified polypropylene adhesive was applied to the other surface of the aluminum foil 4 of the first laminate so that the mass after drying was 2.0 g / m ² . Then, the 2nd laminated body was obtained by bonding the 40 micrometer-thick unstretched polypropylene film 3 to this inner side adhesive application surface.

The second laminate is left to stand in a 40 ° C. environment for 7 days and subjected to a heat aging treatment, whereby the inner adhesive is cured to form the inner adhesive layer 6, thereby storing the structure shown in FIG. A device exterior material was obtained.

In Examples 1 to 4, 9, 10, 13, 14, 15 and the reference examples, the biaxially stretched nylon film having a hot water shrinkage of 5.0% is obtained when the nylon film is biaxially stretched. It was obtained by setting the heat setting temperature to 191 ° C.

In Tables 1 and 2, in the column of the type of photocurable resin composition, “A” represents a photoradical polymerization resin composition, and “B” represents a photocationic polymerization resin composition.

Examples 1, 9, 13, and 14 are examples corresponding to the first manufacturing method, and Examples 2, 10, and 15 are examples corresponding to the third manufacturing method. Example 3 is an example corresponding to the second manufacturing method, Example 4 is an example corresponding to the fourth manufacturing method, and Examples 5 and 11 are examples corresponding to the fifth manufacturing method. Examples 6 and 12 correspond to the seventh manufacturing method, Example 7 corresponds to the sixth manufacturing method, and Example 8 corresponds to the above-described seventh manufacturing method. It is an Example corresponding to the 8th manufacturing method.

Evaluation was performed based on the following measurement method and evaluation method for each of the electricity storage device packaging materials (packaging materials) obtained as described above.

<Method for measuring laminate strength at high temperature>
A test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained exterior material and peeled between the aluminum foil and the base material layer in a region extending from one end in the length direction of the test piece to a position 10 mm inward. It was.

In accordance with JIS K6854-3 (1999), a laminated body containing an aluminum foil is sandwiched and fixed with one chuck using a strut (AGS-5kNX) manufactured by Shimadzu Corporation, and the above-mentioned peeling is performed with the other chuck. The substrate layer is sandwiched and fixed, held for 1 minute in a temperature environment of 120 ° C., and then measured for peel strength when peeled at a tensile rate of 100 mm / min. The value at which the value was stabilized was defined as “lamination strength at high temperature (N / 15 mm width)”. A laminate having a laminate strength of “2.0 N / 15 mm width” or more was regarded as acceptable.

<Formability (maximum forming depth) evaluation method>
Using a deep drawing tool manufactured by Amada Co., Ltd., deep-drawing into an exterior material of approximately 55 mm length × 35 mm width × approximately cuboid shape (approximately cuboid shape with one surface open; see Fig. 7). In other words, deep molding is performed by changing the molding depth in increments of 0.5 mm, and the presence or absence of pinholes and cracks at the corners in the obtained molded body is examined, and such pinholes and cracks do not occur. The maximum forming depth (mm) was examined. The presence or absence of pinholes or cracks was examined by a light transmission method in a dark room. Those having a maximum molding depth of 5.0 mm or more were regarded as acceptable.

<Sealability evaluation method> (Evaluation of the presence or absence of delamination when forming with a deep forming depth)
As a molding with a deep molding depth, a substantially rectangular parallelepiped shape having a length of 55 mm × width of 35 mm × 5.0 mm with respect to the exterior material using the above-described deep drawing tool (a substantially rectangular parallelepiped shape with one surface opened; see FIG. 7) Deep drawing was performed. At this time, it shape | molded so that the base material layer 2 might become the outer side of a molded object. Two molded bodies are produced for each example and each comparative example, and the flange portions (sealing peripheral portion; see FIG. 7) 29 of the two molded bodies (molded cases) 10 are brought into contact with each other and stacked. In addition, after heat sealing at 170 ° C. for 6 seconds, the presence or absence of delamination (peeling) in the heat seal portion 39 and the presence or absence of floating of the appearance were examined by visual observation and evaluated based on the following criteria.
(Criteria)
“○”: No delamination was observed, and no appearance was observed (pass)
“△”: Slight delamination (peeling) may occur rarely, but virtually no delamination (exfoliation) and appearance did not float (pass)
“X”: Delamination occurred, and the appearance was also lifted (failed).

<Heat-resistant water evaluation method> (Evaluation of the occurrence of delamination when used in harsh environments such as high temperature and high humidity)
By performing deep drawing on the exterior material using the above-mentioned deep drawing tool, it is formed into a substantially rectangular parallelepiped shape (length 55 mm × width 35 mm × 5 mm) (refer to FIG. 7). did. At this time, it shape | molded so that the outer side layer (base material layer) 2 might become the outer side of a molded object. Two molded bodies were produced for each example and each comparative example, and the flange portions (sealing peripheral portions; see FIG. 7) 29 of the two molded bodies 10 were brought into contact with each other and overlapped to 170 ° C. X Heat seal is performed for 6 seconds, and then the heat-sealed product is immersed in hot water at 85 ° C. for 240 hours, then taken out and visually observed, the presence or absence of delamination (peeling) in the heat-sealed portion 39 and the appearance floating The presence or absence of was examined and evaluated based on the following criteria.
(Criteria)
“○”: No delamination was observed, and no appearance was observed (pass)
“△”: Slight delamination (peeling) may occur rarely, but virtually no delamination (exfoliation) and appearance did not float (pass)
“X”: Delamination occurred, and the appearance was also lifted (failed).

<Heat seal strength measurement method>
After cutting out two test bodies having a width of 15 mm and a length of 200 mm from the obtained exterior material, the two test bodies were overlapped so as to be in contact with each other of the inner sealant layers. Using a heat seal device (TP-701-A), heat seal temperature is 200 ° C, seal pressure is 0.2 MPa (gauge display pressure), and seal time is 2 seconds. went.

Next, for the pair of exterior materials in which the inner sealant layers are heat-sealed as described above, in accordance with JIS K7127-1998, a strograph (tensile test device) (AGS-5kNX) manufactured by Shimadzu Access Co., Ltd. is used. The peel strength when the exterior material (test body) was peeled 180 degrees between the sealant inner sealant layers at a tensile speed of 100 mm / min was measured, and this was determined as the heat seal strength (N / 15 mm width). did. Those having a heat seal strength of 50 N / 15 mm width or more are considered acceptable.

As is apparent from the table, in Examples 1 to 15 to which the production method of the present invention was applied, a thermosetting resin requiring heat aging for several days was not used, but “electron beam curable resin composition of "Adhesion using electron beam curing or formation of substrate layer by electron beam curing of electron beam curable resin composition" and "Heat bonding resin layer using adhesion or extrusion molten resin film using extrusion molten resin film" In addition to being able to significantly reduce the lead time and improve productivity, the packaging materials (exterior materials for power storage devices) of Examples 1 to 15 obtained by the production method of the present invention are: Pinholes and cracks do not occur even when molding is performed at a deep molding depth, and excellent moldability is provided, and delamination can be suppressed even when molding is performed at a deep molding depth.

Further, as is clear from the comparison between Examples 1 to 15 to which the production method of the present invention is applied and the reference examples, the packaging materials (exterior for power storage devices) of Examples 1 to 15 obtained by the production method of the present invention are also shown. The material) has a performance equivalent to that of the packaging material of the reference example using a conventional thermosetting resin as an adhesive.

A specific example of the packaging material according to the present invention is, for example,
-It is used suitably as exterior materials (exterior material for electrical storage devices) of various electrical storage devices, such as electrical storage devices, such as a lithium secondary battery (lithium ion battery, lithium polymer battery, etc.), a lithium ion capacitor, and an electric double layer capacitor. Moreover, the packaging material which concerns on this invention can be used as a packaging material for foodstuffs, a packaging material for pharmaceuticals, etc.

This application is accompanied by the priority claim of Japanese Patent Application No. 2016-195469 filed on Oct. 3, 2016, the disclosure of which constitutes part of the present application as it is. .

The terms and explanations used here are used to describe the embodiments according to the present invention, and the present invention is not limited thereto. The present invention allows any design changes within the scope of the claims without departing from the spirit thereof.

DESCRIPTION OF SYMBOLS 1 ... Packaging material 2 ... Base material layer (outer layer) (resin film for base material layers, etc.)
3. Heat-sealable resin layer (inner layer) (heat-sealable resin film, etc.)
4 ... Metal foil layer (metal foil)
5 ... Outer adhesive layer (first adhesive layer)
6 ... Inner adhesive layer (second adhesive layer)
40 ... Extruder 44 ... Electron beam curable resin composition 46 ... Electron beam (ultraviolet light, etc.)
47 ... extruded molten resin film 48 ... first laminate 49 ... second laminate

Claims

An inner layer forming step of obtaining a first laminate by adhering a heat-fusible resin film to one surface of the metal foil via an extruded molten resin film extruded from an extruder;
After bonding the resin film for base material layers to the other surface of the metal foil of the first laminate through an electron beam curable resin composition to obtain a second laminate, the second laminate is applied to the second laminate And an outer layer forming step of irradiating an electron beam from the resin film side for the base material layer.
An inner layer to obtain a first laminate by forming a heat-fusible resin layer on one surface of the metal foil by superimposing an extruded molten resin film extruded from an extruder on one surface of the metal foil Forming process;
After bonding the resin film for base material layers to the other surface of the metal foil of the first laminate through an electron beam curable resin composition to obtain a second laminate, the second laminate is applied to the second laminate And an outer layer forming step of irradiating an electron beam from the resin film side for the base material layer.
A base layer resin film is adhered to one surface of a metal foil via an electron beam curable resin composition to obtain a first laminate, and then the base layer is used for the first laminate. An outer layer forming step of irradiating an electron beam from the resin film side;
An inner layer forming step of adhering a heat-fusible resin film to the other surface of the metal foil of the first laminate after the electron beam irradiation via an extruded molten resin film extruded from an extruder. A method for producing a packaging material characterized by the above.
A base layer resin film is adhered to one surface of a metal foil via an electron beam curable resin composition to obtain a first laminate, and then the base layer is used for the first laminate. An outer layer forming step of irradiating an electron beam from the resin film side;
A heat-fusible resin layer is formed on the other surface of the metal foil layer by superimposing an extruded molten resin film extruded from an extruder on the other surface of the metal foil of the first laminate after the electron beam irradiation. A method for producing a packaging material, comprising: forming an inner layer.
An inner layer forming step of obtaining a first laminate by adhering a heat-fusible resin film to one surface of the metal foil via an extruded molten resin film extruded from an extruder;
After applying an electron beam curable resin composition to the other surface of the metal foil of the first laminate to obtain a second laminate, the electron beam curable resin composition is applied to the second laminate. And an outer layer forming step of irradiating an electron beam from the side.
An inner layer to obtain a first laminate by forming a heat-fusible resin layer on one surface of the metal foil by superimposing an extruded molten resin film extruded from an extruder on one surface of the metal foil Forming process;
After applying an electron beam curable resin composition to the other surface of the metal foil of the first laminate to obtain a second laminate, the electron beam curable resin composition is applied to the second laminate. And an outer layer forming step of irradiating an electron beam from the side.
After applying the electron beam curable resin composition to one surface of the metal foil to obtain the first laminate, the electron beam is irradiated from the electron beam curable resin composition side to the first laminate. An outer layer forming step,
An inner layer forming step of adhering a heat-fusible resin film to the other surface of the metal foil of the first laminate after the electron beam irradiation via an extruded molten resin film extruded from an extruder. A method for producing a packaging material characterized by the above.
After applying the electron beam curable resin composition to one surface of the metal foil to obtain the first laminate, the electron beam is irradiated from the electron beam curable resin composition side to the first laminate. An outer layer forming step,
A heat-fusible resin layer is formed on the other surface of the metal foil layer by superimposing an extruded molten resin film extruded from an extruder on the other surface of the metal foil of the first laminate after the electron beam irradiation. A method for producing a packaging material, comprising: forming an inner layer.
The manufacturing method of the packaging material of Claim 1, 2, 5, 6 which performs the said inner side layer formation process and the said outer side layer formation process continuously.
The method for producing a packaging material according to any one of claims 1 to 4, wherein a heat-resistant resin film having a hot water shrinkage of 1.5% to 12% is used as the resin film for the base material layer.
The method for producing a packaging material according to any one of claims 1 to 10, wherein the extruded molten resin film is an extruded molten acid-modified polyolefin resin film.