CN211567189U - Molding packaging material and molded case - Google Patents

Molding packaging material and molded case Download PDF

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Publication number
CN211567189U
CN211567189U CN201920905212.2U CN201920905212U CN211567189U CN 211567189 U CN211567189 U CN 211567189U CN 201920905212 U CN201920905212 U CN 201920905212U CN 211567189 U CN211567189 U CN 211567189U
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China
Prior art keywords
layer
resin
molding
packaging material
easy
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CN201920905212.2U
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Chinese (zh)
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川北圭太郎
南堀勇二
唐津诚
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Lishennoco Packaging Co ltd
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Showa Denko Packaging Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The utility model relates to a packaging material and shaping casing are used in the shaping. The utility model relates to a packaging material (1) for shaping contains heat resistance resin stretch film layer (2) as the outside layer, thermoplastic resin layer (3) as the inside layer, and disposes metal foil layer (4) between above-mentioned two layers, and constitutes to have protective layer (20) through easy bonding layer (31) and range upon range of integration in the surface of outside layer (2). The easy adhesion layer (31) preferably has the following structure: containing 1 or 2 or more resins selected from the group consisting of epoxy resins, urethane resins, acrylate resins, methacrylate resins, and polyethyleneimine resins. The utility model discloses can provide and can prevent that the protective layer from peeling off from the tensile rete of heat resistance resin to organic solvent resistance is excellent packaging material for the shaping.

Description

Molding packaging material and molded case
Technical Field
The present invention relates to a molding packaging material and a molding case suitable for use as a case of a secondary battery (lithium ion secondary battery) of a notebook personal computer, a mobile phone, a vehicle, or a stationary type, and also suitable for use as a packaging material for food and a packaging material for pharmaceuticals.
Background
In recent years, with the reduction in thickness and weight of mobile electronic devices such as smartphones and tablet personal computer terminals, a laminate formed of a heat-resistant resin layer (base layer)/an outer adhesive layer/a metal foil layer/an inner adhesive layer/a heat-sealable resin layer (inner sealant layer) has been used as an outer material of an electric storage device such as a lithium ion secondary battery, a lithium polymer secondary battery, a lithium ion capacitor (lithium ion capacitor), and an electric double-layer capacitor (electric double-layer capacitor) mounted on the mobile electronic devices, instead of a conventional metal can (see patent document 1). Further, the laminated body (outer package) having the above-described structure is increasingly used for outer packaging of a power source for an electric vehicle or the like, a large-sized power source for electric storage, a capacitor, and the like. The outer covering material is formed into a three-dimensional shape such as a substantially rectangular parallelepiped shape by bulging or deep drawing. By forming the battery pack into such a three-dimensional shape, a storage space for storing the power storage device main body portion can be secured.
In order to protect the outer package and improve the formability, an outer package having a structure in which a matte coating layer is provided on the outer side of the base material layer is known (see patent document 2). The matte coating layer is formed by a resin composition which is formed by adding 0.1-1% by mass of inorganic particles with the average particle diameter of 1-10 μm into heat-resistant resin. By providing such a matte coating layer, good sliding properties can be imparted to the surface, and moldability can be improved.
Patent document 1: japanese laid-open patent publication No. 2003-288865
Patent document 2: japanese laid-open patent publication No. 2013-224014
SUMMERY OF THE UTILITY MODEL
Problem to be solved by utility model
In order to prevent appearance defects such as scratches from occurring on the surface of the matte coat layer (protective layer) that forms the outer surface of the outer package material, for example, in the battery production process, a protective tape is applied in advance to the surface of the outer package material (the surface of the matte coat layer). However, when the protective tape is peeled after the battery is manufactured, the matte coating layer is sometimes peeled.
In addition, a printed matter such as a manufacturer's name, model number, volume, lot number, barcode, CR code, or the like is printed on the surface of the matte coat layer as the outer surface of the outer covering material, and the printed matter is sometimes corrected, and at this time, the printed matter is wiped off with a cloth containing ethanol or MEK (methyl ethyl ketone). In this case, there is also a problem that the matte coating layer (protective layer) is easily peeled from the base material layer (outer layer).
The present invention has been made in view of the above-mentioned technical background, and an object of the present invention is to provide a packaging material for molding and a molding case, which can prevent an inner protective layer from being peeled off from a heat-resistant resin stretched film layer including when a protective tape is peeled off, and which are also excellent in organic solvent resistance.
Means for solving the problems
In order to achieve the above object, the present invention provides the following means.
[1] A packaging material for molding, which comprises a heat-resistant stretched resin film layer as an outer layer, a thermoplastic resin layer as an inner layer, and a metal foil layer disposed between the two layers,
a protective layer is laminated and integrated on the outer surface of the outer layer via an easy adhesive layer.
[2] The packaging material for molding according to the above-mentioned aspect [1], wherein the easy-adhesion layer contains 1 or 2 or more kinds of resins selected from the group consisting of epoxy resins, urethane resins, acrylate resins, methacrylate resins, and polyethyleneimine resins.
[3] The packaging material for molding according to the above-mentioned aspect [1], wherein the easy-adhesion layer is formed by containing a urethane resin and an epoxy resin.
[4] The packaging material for molding according to the above-mentioned aspect [3], wherein a content mass ratio of the urethane resin/the epoxy resin in the easy-adhesion layer is in a range of 98/2 to 40/60.
[5] The packaging material for molding according to the above-mentioned aspect [1], wherein the easy-adhesion layer contains 1 or 2 or more kinds of acrylic resins selected from the group consisting of acrylic ester resins and methacrylic ester resins, and an epoxy resin.
[6] The packaging material for molding according to the above-mentioned aspect [5], wherein the easy-adhesion layer contains the acrylic resin/the epoxy resin in a mass ratio of 98/2 to 40/60.
[7] The packaging material for molding as described in any one of the above aspects [1] to [6], wherein the easy-adhesion layer is an adhesive layer formed by applying a resin-water-based emulsion to the heat-resistant resin stretched film layer.
[8] The packaging material for molding as described in any one of the above aspects [1] to [7], wherein the protective layer is a layer formed by dispersing a resin composition containing inorganic fine particles and/or organic fine particles in a heat-resistant resin.
[9] A molded case comprising a deep-drawn molded body or a bulging molded body of the packaging material for molding according to any one of the above aspects [1] to [8 ].
Effect of the utility model
In the utility model according to [1], since the protective layer is laminated and integrated on the outer surface of the heat-resistant resin stretched film layer via the easy-adhesion layer, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is improved, peeling of the inner protective layer from the heat-resistant resin stretched film layer including peeling of the protective tape can be sufficiently prevented, and the organic solvent resistance can be improved.
In the utility model according to [2], since the easy-adhesion layer is constituted by containing 1 or 2 or more kinds of resins selected from the group consisting of epoxy resins, urethane resins, acrylate resins, methacrylate resins, and polyethyleneimine resins, the adhesion strength between the heat-resistant resin stretched film layer and the protective layer is improved, the inner protective layer can be sufficiently prevented from peeling off from the heat-resistant resin stretched film layer including the peeling off of the protective tape, and the organic solvent resistance can be improved.
In the utility model described in [3], since the easy-adhesion layer is formed by containing the urethane resin and the epoxy resin, the adhesion strength between the heat-resistant resin stretched film layer and the protective layer is further improved, the protective layer can be more sufficiently prevented from peeling off from the heat-resistant resin stretched film layer, and the organic solvent resistance can be further improved.
In the utility model according to [4], since the content mass ratio of the urethane resin/epoxy resin is in the range of 98/2 to 40/60, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is further improved, the protective layer can be further sufficiently prevented from peeling off from the heat-resistant resin stretched film layer, and the organic solvent resistance can be further improved.
In the utility model according to [5], since the easy-adhesion layer is formed by containing the specific acrylic resin and the specific epoxy resin, the adhesion strength between the heat-resistant resin stretched film layer and the protective layer is further improved, the protective layer can be more sufficiently prevented from peeling off from the heat-resistant resin stretched film layer, and the organic solvent resistance can be further improved.
In the utility model according to [6], since the content mass ratio of the acrylic resin/the epoxy resin is in the range of 98/2 to 40/60, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is further improved, the protective layer can be further sufficiently prevented from peeling off from the heat-resistant resin stretched film layer, and the organic solvent resistance can be further improved.
In the utility model according to [7], since the easy-adhesion layer is formed by previously coating the resin-water based emulsion on the heat-resistant resin stretched film layer, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is improved, the protective layer can be sufficiently prevented from peeling off from the heat-resistant resin stretched film layer, and the organic solvent resistance can be improved.
In the utility model according to [8], since the protective layer is formed of the resin composition containing the inorganic fine particles and/or the organic fine particles dispersed in the heat-resistant resin, the surface hardness and the sliding property at the time of molding of the protective layer can be further improved.
The utility model according to [9], which can provide a molded case that is not peeled from the heat-resistant resin stretched film layer in the inner protective layer including the peeling of the protective tape, and has excellent organic solvent resistance.
Drawings
Fig. 1 is a cross-sectional view showing an embodiment of a packaging material for molding according to the present invention.
Fig. 2 is a cross-sectional view showing an embodiment of the power storage device according to the present invention.
Fig. 3 is a perspective view showing an outer covering (planar outer covering) constituting the power storage device of fig. 2, a power storage device main body, and a molded case (molded body molded in a three-dimensional shape) in a separated state before heat sealing.
Description of the reference numerals
1 … packaging material for molding
2 … Heat-resistant resin stretch film layer (outer layer)
3 … thermoplastic resin layer (inner layer)
4 … Metal foil layer
10 … moulded case
11 … easy adhesion layer 1
20 … protective layer
Detailed Description
Fig. 1 shows an embodiment of a molding packaging material 1 according to the present invention. The packaging material 1 for molding can be used as a packaging material for a lithium ion secondary battery case. That is, the molding packaging material 1 is used as a secondary battery case by being subjected to molding such as deep drawing.
The molding packaging material 1 includes the following components: a heat-resistant resin stretch film layer (outer layer) 2 is laminated and integrated on one surface of a metal foil layer 4 via a 1 st adhesive layer 5, and a thermoplastic resin layer (inner layer) 3 is laminated and integrated on the other surface of the metal foil layer 4 via a 2 nd adhesive layer 6. Further, a protective layer 20 (see fig. 1) is laminated and integrated on the outer surface (the surface opposite to the metal foil layer side) of the heat-resistant resin stretched film layer 2 via a 1 st easy adhesive layer 11.
In the present embodiment, the 1 st easy-adhesion layer 11 is laminated on the outer surface of the heat-resistant resin stretched film layer 2 by a gravure coating method.
In the present embodiment, a 2 nd easy-adhesive layer 12 is laminated on the lower surface (the surface on the metal foil layer side) of the heat-resistant resin stretched film layer 2, a colored ink layer 13 is laminated on the lower surface (the surface on the metal foil layer side) of the 2 nd easy-adhesive layer 12, and the colored ink layer 13 and the metal foil layer 4 are bonded and integrated via a 1 st adhesive layer 5 (see fig. 1). That is, a colored ink layer 13 is disposed between the metal foil layer 4 and the heat-resistant resin stretched film layer 2. In the present embodiment, the 2 nd easy-adhesion layer 12 is laminated on the lower surface of the heat-resistant resin stretched film layer 2 by a gravure coating method, and the colored ink layer 13 is laminated on the lower surface of the 2 nd easy-adhesion layer 12 by printing.
In the present invention, the protective layer (matte coating layer) 20 is a layer formed by dispersing a resin composition containing inorganic fine particles and/or organic fine particles in a heat-resistant resin. The heat-resistant resin is preferably a two-pack curable heat-resistant resin. The content of at least 1 kind of fine particles selected from the group consisting of the inorganic fine particles and the organic fine particles in the resin composition is preferably 0.1 to 60% by mass. The average particle diameter of the inorganic fine particles and the organic fine particles is preferably 0.5 to 10 μm. Examples of the heat-resistant resin constituting the protective layer 20 include acrylic resins, epoxy resins, urethane resins, polyolefin resins, fluorine resins, phenoxy resins, and the like, and among them, urethane resins are preferable. By providing such a protective layer 20, a molding packaging material 1 having excellent moldability can be obtained by imparting good slidability to the surface. The thickness of the protective layer 20 is preferably set to 0.1 μm to 10 μm.
The inorganic fine particles are not particularly limited, and examples thereof include silica, alumina, calcium oxide, calcium carbonate, calcium sulfate, calcium silicate, and the like, and among them, silica is preferably used. The organic fine particles are not particularly limited, and examples thereof include acrylic resin beads, styrene resin beads, urethane resin beads, and the like, and among them, acrylic resin beads and urethane resin beads are preferably used. Further, a lubricant may be added to the protective layer 20. The lubricant is not particularly limited, and examples thereof include fatty acid amides (erucamide, behenamide, stearic acid amide, oleic acid amide, ethylene bisstearic acid amide, and the like), waxes (polyethylene wax, Polytetrafluoroethylene (PTFE) wax, and the like), and the like.
The method for forming the protective layer 20 is not particularly limited, and examples thereof include a method in which the resin composition for forming the protective layer 20 is applied to the surface (outer surface) of the 1 st easy-adhesive layer 11 by a gravure coating method, a reverse roll coating method, a lip roll coating (lip roll coat) method, and the like.
The heat-resistant resin stretched film layer (outer layer) 2 is a member mainly responsible for ensuring good formability as an outer packaging material, that is, it is responsible for preventing the metal foil from being broken by necking (necking) at the time of forming. As the heat-resistant resin constituting the heat-resistant resin stretched film layer 2, a heat-resistant resin that does not melt at the heat-sealing temperature when the molding packaging material 1 is heat-sealed is used. As the heat-resistant resin, a heat-resistant resin having a melting point higher by 10 ℃ or more than the melting point of the resin constituting the thermoplastic resin layer 3 is preferably used, and particularly, a heat-resistant resin having a melting point higher by 20 ℃ or more than the melting point of the resin constituting the thermoplastic resin layer 3 is preferably used.
In the present invention, the heat-resistant resin stretched film layer 2 is preferably formed of a heat-resistant resin stretched film having a hot water shrinkage ratio of 2% to 20%. The hot water shrinkage rate of 2% or more can sufficiently prevent the protective layer from peeling off from the heat-resistant resin stretched film layer, and the hot water shrinkage rate of 20% or less can sufficiently prevent the protective layer from peeling off from the heat-resistant resin stretched film layer when molding such as deep drawing molding or bulging molding is performed. Among them, the heat-resistant stretched resin film preferably has a hot water shrinkage ratio of 2.5 to 10%. More preferably, a heat-resistant resin stretched film having a hot water shrinkage ratio of 3.0% to 6.0% is used, and even more preferably, a heat-resistant resin stretched film having a hot water shrinkage ratio of 3.5% to 5.0% is used.
The "hot water shrinkage ratio" is a dimensional change rate of a test piece (10cm × 10cm) of the heat-resistant resin stretched film 2 in the stretching direction before and after 30 minutes of immersion in hot water at 95 ℃.
Hot water shrinkage ratio (%) { (X-Y)/X } × 100
X: dimension in stretching direction before dipping treatment
Y: the dimension in the stretching direction after the dipping treatment.
In the case of using a biaxially stretched film, the hot water shrinkage ratio is an average value of dimensional change rates in 2 stretching directions.
The hot water shrinkage of the heat-resistant stretched resin film can be controlled by, for example, adjusting the heat setting temperature during stretching.
The heat-resistant resin stretched film layer (outer layer) 2 is not particularly limited, and examples thereof include a stretched polyamide film such as a stretched nylon film, a stretched polyester film, and the like. Among them, as the heat-resistant resin stretched film layer 2, 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 naphthalate (PEN) film is particularly preferably used. As the heat-resistant resin stretched film layer 2, a heat-resistant resin biaxially stretched film obtained by stretching by a simultaneous biaxial stretching method is preferably used. Further, it is preferable to use a heat-resistant resin biaxially stretched film having a ratio (MD/TD) of "hot water shrinkage in the M direction" to "hot water shrinkage in the T direction" in the range of 0.9 to 1.1. When the ratio (MD/TD) is in the range of 0.9-1.1, a packaging material for molding having particularly good moldability can be obtained. The "M direction" is a "machine traveling direction", and the "T direction" is a "direction perpendicular to the M direction". The nylon is not particularly limited, and examples thereof include nylon 6, and MXD nylon. The heat-resistant resin stretched film layer 2 may be formed of a single layer (a single stretched film), or may be formed of a plurality of layers including, for example, a stretched polyester film/a stretched polyamide film (a plurality of layers including a stretched PET film/a stretched nylon film, etc.).
Among them, as the heat-resistant resin stretched film layer 2, a biaxially stretched polyamide film having a shrinkage rate of 2 to 20%, a biaxially stretched polyethylene naphthalate (PEN) film having a shrinkage rate of 2 to 20%, or a biaxially stretched polyethylene terephthalate (PET) film having a shrinkage rate of 2 to 20% is preferably used. In this case, the effect of preventing the inner protective layer 20 from peeling off from the heat-resistant resin stretch film layer 2 including when the protective tape is peeled off from the protective layer 20 can be further improved.
The thickness of the heat-resistant resin stretched film layer 2 is preferably 6 to 50 μm. When a polyester film is used, the thickness is preferably 9 to 50 μm, and when a nylon film is used, the thickness is preferably 12 to 50 μm. By setting the above-described preferable lower limit or more, sufficient strength as a packaging material can be secured, and by setting the above-described preferable upper limit or less, stress at the time of bulging molding or at the time of drawing molding can be reduced, and moldability can be improved.
In the present invention, it is necessary to laminate the 1 st easy adhesion layer 11 on the outer surface (the surface opposite to the metal foil layer side) of the heat-resistant resin stretched film layer 2. That is, the protective layer 20 is laminated and integrated on the outer surface of the heat-resistant stretched resin film layer 2 via the 1 st easy-adhesive layer 11 (see fig. 1). By applying a polar resin having excellent adhesiveness and adhesiveness to the surface of the heat-resistant stretched resin film layer 2 which originally has poor adhesiveness, and laminating the 1 st easy-to-adhere layer 11, adhesiveness and adhesiveness to the protective layer 20 can be improved. Before the 1 st easy-adhesive layer 11 is laminated on the outer surface (surface on which the 1 st easy-adhesive layer 11 is laminated) of the heat-resistant resin stretch film layer 2, it is preferable to perform corona treatment or the like in advance to improve wettability.
In the present invention, it is preferable that the inner surface (the surface on the metal foil layer side) of the heat-resistant resin stretched film layer 2 is subjected to corona treatment, or an easy adhesion layer (2 nd easy adhesion layer) 12 is laminated on the inner surface (the surface on the metal foil layer side). When the easy-adhesion layer (2 nd easy-adhesion layer) 12 is laminated, the 2 nd easy-adhesion layer 12 is laminated by applying a polar resin having excellent adhesiveness and adhesiveness to the surface of the heat-resistant resin stretched film layer 2 which originally has poor adhesiveness, whereby adhesiveness and adhesiveness to the colored ink layer 13 can be improved. It is preferable to increase the wettability by performing a corona treatment or the like in advance before the 2 nd easy-adhesive layer 12 is laminated on the inner surface (the surface on which the 2 nd easy-adhesive layer 12 is laminated) of the heat-resistant resin stretched film layer 2.
The method for forming the 1 st easy-adhesive layer 11 and the 2 nd easy-adhesive layer 12 is not particularly limited, and for example, the easy- adhesive layers 11 and 12 can be formed by applying an aqueous emulsion (water-based emulsion) of 1 or 2 or more kinds of resins selected from the group consisting of epoxy resins, urethane resins, acrylate resins, methacrylate resins, and polyethyleneimine resins to the surface of the heat-resistant stretched resin film 2 and drying the applied aqueous emulsion. The coating method is not particularly limited, and examples thereof include a spray coating method, a gravure roll coating method, a reverse roll coating method, and a lip coating method.
Further, the 1 st easy-adhesive layer 11 and the 2 nd easy-adhesive layer 12 are preferably configured as follows: contains 1 or 2 or more resins selected from the group consisting of epoxy resins, urethane resins, acrylate resins, methacrylate resins, and polyethyleneimine resins. In the case where the preferred structure is adopted in the 1 st easy-adhesive layer 11, the protective layer 20 can be more sufficiently prevented from peeling off from the heat-resistant resin stretched film layer 2. In addition, in the case where the preferred configuration described above is adopted in the 2 nd easy-adhesion layer 12, the adhesion between the heat-resistant resin stretched film layer 2 and the colored ink layer 13 can be further improved.
Among them, the 1 st easy-adhesion layer 11 and the 2 nd easy-adhesion layer 12 are each particularly preferably configured as follows: contains urethane resin and epoxy resin; or a (meth) acrylate resin and an epoxy resin. In the case where the above-described particularly preferable configuration is adopted for the 1 st easy-adhesive layer 11, the protective layer 20 can be more sufficiently prevented from peeling off from the heat-resistant resin stretched film layer 2. In addition, when the above-described particularly preferable configuration is adopted in the 2 nd easy-adhesion layer 12, the adhesion between the heat-resistant resin stretched film layer 2 and the colored ink layer 13 can be further improved.
In the former structure, the urethane resin/epoxy resin content mass ratio in the 1 st and 2 nd easy- adhesion layers 11 and 12 is preferably in the range of 98/2 to 40/60. When such a content mass ratio (range) is used for the 1 st easy-adhesive layer 11, the protective layer 20 can be more sufficiently prevented from peeling off from the heat-resistant resin stretched film layer 2, and when such a content mass ratio (range) is used for the 2 nd easy-adhesive layer 12, the adhesion between the heat-resistant resin stretched film layer 2 and the colored ink layer 13 can be further improved. When the content ratio of the urethane resin is larger than the content mass ratio (98/2) of the urethane resin/epoxy resin, the crosslinking degree is not sufficient, and it is difficult to obtain sufficient solvent resistance and adhesive strength, which is not preferable. On the other hand, when the content ratio of the urethane resin is less than the content mass ratio (40/60) of the urethane resin/epoxy resin, it takes too much time until the completion of the crosslinking, which is not preferable. Among them, the content mass ratio of the urethane resin/epoxy resin in the 1 st and 2 nd easy- adhesion layers 11 and 12 is more preferably in the range of 90/10 to 50/50.
In the latter configuration, the content mass ratio of the (meth) acrylate resin/the epoxy resin in the 1 st and 2 nd easy- adhesion layers 11 and 12 is preferably in the range of 98/2 to 40/60. When such a content mass ratio (range) is used for the 1 st easy-adhesive layer 11, the protective layer 20 can be more sufficiently prevented from peeling off from the heat-resistant resin stretched film layer 2, and when such a content mass ratio (range) is used for the 2 nd easy-adhesive layer 12, the adhesion between the heat-resistant resin stretched film layer 2 and the colored ink layer 13 can be further improved. When the content ratio of the (meth) acrylate resin is larger than the content mass ratio of the (meth) acrylate resin/epoxy resin (98/2), the degree of crosslinking is insufficient, and it is difficult to obtain sufficient solvent resistance and adhesive strength, which is not preferable. On the other hand, when the content ratio of the (meth) acrylate resin is smaller than the content mass ratio of the (meth) acrylate resin/epoxy resin (40/60), it takes too much time until the completion of crosslinking, which is not preferable. Among them, the content mass ratio of the (meth) acrylate resin/the epoxy resin in the 1 st and 2 nd easy- adhesion layers 11 and 12 is more preferably in the range of 90/10 to 50/50.
In the case where a surfactant such as a glycol or an ethylene oxide adduct of a glycol is added to the aqueous resin emulsion (resin-water based emulsion) for forming the 1 st and 2 nd easy- adhesive layers 11 and 12, a sufficient defoaming effect can be obtained in the aqueous resin emulsion, and thus the 1 st and 2 nd easy- adhesive layers 11 and 12 having excellent surface smoothness can be formed. The surfactant is preferably contained in an amount of 0.01 to 2.0% by mass in the aqueous resin emulsion.
In addition, it is preferable that the resin aqueous emulsion (resin-water based emulsion) for forming the 1 st and 2 nd easy- adhesion layers 11 and 12 contains inorganic fine particles such as silica and colloidal silica, and in this case, an anti-blocking effect can be obtained. Preferably, the inorganic fine particles are added in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the resin component.
The amounts of the 1 st easy adhesion layer 11 and the 2 nd easy adhesion layer 12 (the amounts of solid components after drying) are preferably 0.01g/m2～0.5g/m2The range of (1). By making it 0.01g/m2As described above, the heat-resistant stretched resin film layer 2 and the protective layer 20 can be sufficiently bonded to the 1 st easy-adhesive layer 11, and the heat-resistant stretched resin film layer 2 and the colored ink layer 13 can be sufficiently bonded to the 2 nd easy-adhesive layer 12. Further, by adjusting the concentration to 0.5g/m2The cost can be reduced and the method is more economical.
The content of the resin in the 1 st easy-adhesive layer 11 and the 2 nd easy-adhesive layer 12 (content after drying) is preferably 88 to 99.9% by mass.
The thermoplastic resin layer (inner layer) 3 described above plays a role of: the packaging material is provided with excellent chemical resistance even for a highly corrosive electrolyte solution or the like used in a lithium ion secondary battery or the like, and heat sealability is imparted to the packaging material.
The thermoplastic resin layer 3 is not particularly limited, and is preferably a thermoplastic resin unstretched film layer. The thermoplastic resin unstretched film layer 3 is not particularly limited, and is preferably composed of an unstretched film containing at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, olefin copolymers, acid-modified products thereof, and ionomers. Among these, the laminated structure is more preferably a 3-layer laminated structure in which coating layers containing atactic polypropylene are laminated on both sides of an intermediate layer containing block polypropylene. The thermoplastic resin layer 3 may be a single layer or a plurality of layers.
The thickness of the thermoplastic resin layer 3 is preferably set to 20 to 80 μm. By setting the thickness to 20 μm or more, the occurrence of pinholes can be sufficiently prevented, and by setting the thickness to 80 μm or less, the amount of resin used can be reduced, thereby reducing the cost. Among them, the thickness of the thermoplastic resin layer 3 is particularly preferably set to 30 μm to 50 μm.
The metal foil layer 4 plays a role of imparting gas barrier properties to the molding packaging material 1 to prevent the intrusion of oxygen and moisture. The metal foil layer 4 is not particularly limited, and examples thereof include an aluminum foil, a copper foil, a nickel foil, and a stainless steel foil, and an aluminum foil is generally used. The aluminum foil is preferably a8079 or a8021 defined in JIS H4160. The thickness of the metal foil layer 4 is preferably 20 μm to 100 μm. By setting the thickness to 20 μm or more, pinholes can be prevented from being generated during rolling in the production of the metal foil, and by setting the thickness to 100 μm or less, stress during bulging or drawing can be reduced, and formability can be improved.
The metal foil layer 4 is preferably subjected to chemical conversion treatment at least on the inner surface 4a (inner layer 3 side surface). By performing such chemical conversion treatment, corrosion of the surface of the metal foil due to the contents (electrolyte of a battery, food, pharmaceutical, etc.) can be sufficiently prevented. For example, the metal foil is subjected to a chemical conversion treatment by performing the following treatment. That is, for example, the chemical conversion treatment is performed by applying any one of the following items 1) to 3) to the surface of the degreased metal foil and then drying the applied surface.
1) Aqueous solution comprising a mixture of metal salts of phosphoric acid, chromic acid and fluoride
2) Aqueous solution comprising a mixture of phosphoric acid, chromic acid, metal fluoride salts and non-metal salts
3) An aqueous solution comprising a mixture of an acrylic resin or/and a phenolic resin, phosphoric acid, chromic acid, and a metal fluoride salt.
In the present invention, a coloring ink layer 13 (see fig. 1) may be further provided between the heat-resistant resin stretch film layer (outer side layer) 2 and the metal foil layer 4. By providing such a coloring ink layer 13, a color (including an achromatic color) can be imparted to the outer surface side (protective layer 20 side) of the molding packaging material 1.
The coloring ink layer 13 is not particularly limited, and examples thereof include a black ink layer, a white ink layer, a gray ink layer, a red ink layer, a blue ink layer, a green ink layer, and a yellow ink layer.
The black ink layer 13 will be described. The black ink layer 10 is generally formed of a composition containing carbon black.
The black ink layer 13 preferably contains carbon black, diamine, polyol, and a curing agent, but is not particularly limited to this configuration.
The content of carbon black in the black ink layer (dried ink layer) 13 is 15 to 60% by mass, and the total content of the diamine, the polyol, and the curing agent is preferably 40 to 85% by mass. Among them, the content of carbon black is particularly preferably 20 to 50% by mass.
When the content of carbon black is less than 15% by mass, the metallic luster feeling due to the metal foil layer 4 remains, giving a feeling of thickness, and local color unevenness occurs during molding, which is not preferable. On the other hand, if the content of carbon black is more than 60 mass%, the black ink layer 13 becomes hard and brittle, and the adhesion to the metal foil layer 4 decreases, and peeling between the metal foil layer 4 and the black ink layer 13 is likely to occur during molding, which is not preferable.
The black ink layer 13 is preferably configured to contain the curing agent in an amount of 2 to 20 parts by mass per 100 parts by mass of the total amount of the carbon black, the diamine, and the polyol. When the curing agent is less than 2 parts by mass, peeling is likely to occur between the metal foil layer 4 and the black ink layer 13 during molding, and when the curing agent is more than 20 parts by mass, the following disadvantages are generated, which are not preferable: when the molding packaging material 1 in a wound state is unwound (unwound), blocking occurs, and transfer, adhesion, and the like occur on the outer surfaces of the protective layer 20 and the thermoplastic resin layer 3.
As the carbon black, carbon black having an average particle diameter of 0.2 to 5 μm is preferably used.
The diamine is not particularly limited, and examples thereof include those selected from the group consisting of ethylenediamine, dimer diamine (dimeramine), 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, dicyclohexylmethanediamine, and 2-hydroxyethylpropylenediamine. Among them, as the diamine, 1 or 2 or more kinds of diamines selected from the group consisting of ethylenediamine, dimer diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine and dicyclohexylmethanediamine are preferably used.
The diamine has a higher reaction rate with a curing agent (isocyanate or the like) than the polyol, and can be cured in a short time. That is, the diamine reacts with the curing agent together with the polyol to promote crosslinking and curing of the ink composition.
The polyol is not particularly limited, and 1 or 2 or more kinds of polyols selected from the group consisting of polyurethane polyols, polyester polyols, and polyether polyols are preferably used.
The number average molecular weight of the polyol is preferably in the range of 1000 to 8000. By setting the amount to 1000 or more, the bonding strength after curing can be increased, and by setting the amount to 8000 or less, the reaction rate with the curing agent can be increased.
The curing agent is not particularly limited, and examples thereof include isocyanate compounds and the like. As the isocyanate compound, various aromatic, aliphatic, and alicyclic isocyanate compounds can be used, for example. Specific examples thereof include Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate, Hexamethylene Diisocyanate (HDI), isophorone diisocyanate, xylylene diisocyanate, and the polymers of the above-exemplified isocyanates (adducts with polyols, isocyanurate compounds, biuret compounds, etc.).
The colored ink layer (excluding the black ink layer) will be described. The coloring ink layer (excluding the black ink layer) 13 is preferably a cured film containing a coloring ink composition containing: a two-pack curable polyester urethane resin binder based on a polyester resin as a main agent and a polyfunctional isocyanate compound as a curing agent; and a colored pigment comprising an inorganic pigment.
As the coloring pigment, a composition containing at least an inorganic pigment can be used. Examples of the colored pigment include azo pigments, phthalocyanine pigments, and condensed polycyclic pigments in addition to the inorganic pigments. The inorganic pigment is not particularly limited, and examples thereof include carbon black, calcium carbonate, titanium oxide, zinc oxide, iron oxide, and aluminum powder. As the inorganic pigment, inorganic pigments having an average particle diameter of 0.1 to 5 μm, particularly 0.5 to 2.5 μm, are preferably used. When the above-mentioned coloring pigment is dispersed, it is preferable to disperse the coloring pigment using a pigment dispersing machine. When the above-mentioned coloring pigment is dispersed, a pigment dispersant such as a surfactant can be used.
Preferably, 50% by mass or more of the colored pigment is composed of the inorganic pigment. In this case, it is possible to form the colored ink layer 13 having a specific color tone which can obtain a masking force for masking the metal foil layer 4 more sufficiently and can impart a heavy feeling and a high-grade feeling sufficiently. Among these, it is more preferable that 60% by mass or more of the colored pigment is composed of the inorganic pigment.
The thickness (after drying) of the colored ink layer 13 is preferably 1 μm to 4 μm. By making the thickness of the colored ink layer 10 to be 1 μm or more, the color and gloss of the metal foil layer 4 can be sufficiently masked without leaving a transparent feeling in the color tone. Further, by setting the thickness to 4 μm or less, local cracking of the colored ink layer 10 during molding can be sufficiently prevented.
The colored ink layer 13 is not particularly limited, and can be formed by printing (coating) the following composition on the surface of the 2 nd easy-adhesion layer 12 on the lower surface of the heat-resistant resin stretched film layer 2 by, for example, gravure printing or the like:
1) ink composition containing carbon black, diamine, polyol, curing agent and organic solvent
Or
2) A colored ink composition comprising a two-liquid curable polyester urethane resin binder based on a polyester resin as a main agent and a polyfunctional isocyanate compound as a curing agent, and a colored pigment comprising an inorganic pigment.
The organic solvent is not particularly limited, and examples thereof include toluene, methyl ethyl ketone, ethyl acetate, and n-propyl acetate.
The method for forming the colored ink layer 13 is not particularly limited, and examples thereof include a gravure printing method, a reverse roll coating method, and a lip roll coating method.
The 1 st adhesive layer 5 is not particularly limited, and examples thereof include an adhesive layer formed by a two-liquid reaction type adhesive. Examples of the two-component reactive adhesive include a two-component reactive adhesive composed of a 1 st liquid and a 2 nd liquid (curing agent) containing isocyanate, and the 1 st liquid contains one or two or more kinds of polyols selected from the group consisting of polyurethane polyols, polyester polyols, and polyether polyols. The 1 st adhesive layer 5 can be formed, for example, by the following method: the adhesive such as the two-component reactive adhesive is applied to the "upper surface of the metal foil layer 4" or/and the "lower surface of the colored ink layer 13 laminated on the lower surface of the heat-resistant resin layer 2 via the 2 nd easy-adhesive layer 12" by a method such as gravure coating.
The 2 nd adhesive layer 6 is not particularly limited, and examples thereof include adhesive layers formed of a urethane adhesive, an acrylic adhesive, an epoxy adhesive, a polyolefin adhesive, an elastomer adhesive, a fluorine adhesive, and the like. Among them, an acrylic adhesive and a polyolefin adhesive are preferably used, and in this case, the electrolyte resistance and the water vapor barrier property of the molding packaging material 1 can be improved.
By molding (deep drawing molding, bulging molding, etc.) the molding packaging material 1 of the present invention, a molded case (battery case, etc.) 10 can be obtained (see fig. 3). The outer package material 1 of the present invention can be used without molding (see fig. 3).
Fig. 2 shows an embodiment of an electricity storage device 30 formed using the molding package material 1 of the present invention. The power storage device 30 is a lithium ion secondary battery. As shown in fig. 2 and 3, in the present embodiment, the outer jacket material 15 is constituted by the molded case 10 (which is obtained by molding the molding jacket material 1) and the planar jacket material 1. Further, an electric storage device main body portion (electrochemical element or the like) 31 having a substantially rectangular parallelepiped shape is housed in a housing concave portion of a molded case 10 obtained by molding the packaging material for molding 1 of the present invention, and the heat-fusible resin layer 3 side is disposed on the inside (lower side) of the electric storage device main body portion 31 without molding the packaging material 1 of the present invention, and the peripheral edge portion of the heat-fusible resin layer 3 of the planar packaging material 1 and the heat-fusible resin layer 3 of the flange portion (sealing peripheral edge portion) 29 of the molded case 10 are sealed by heat sealing, thereby constituting an electric storage device 30 of the present invention (see fig. 2 and 3). The surface of the molded case 10 on the inner side of the housing recess is the heat-fusible resin layer 3, and the outer surface of the housing recess is the protective layer 20 (see fig. 3).
In fig. 2, reference numeral 39 denotes a heat-sealed portion obtained by joining (welding) the peripheral edge portion of the packaging material 1 and the flange portion (sealing peripheral edge portion) 29 of the molded case 10. In the power storage device 30, the tip portions of the tabs (tabs) connected to the power storage device body 31 are led out of the outer jacket 15, and the illustration thereof is omitted.
The power storage device body 31 is not particularly limited, and examples thereof include a battery body, a capacitor body, and a capacitor body.
In the above embodiment, the outer jacket material 15 is configured to include the molded case 10 obtained by molding the molding material 1 and the planar packaging material 1 (see fig. 2 and 3), but the configuration is not particularly limited to such a combination, and for example, the outer jacket material 15 may be configured to include a pair of molded cases 10.
Examples
Specific examples of the present invention will be described below, but the present invention is not particularly limited to these examples.
< adhesives for Forming easily adhesive layers 1 and 2>
(adhesive composition W)
An adhesive composition W having a nonvolatile content of 2% by mass was obtained by mixing 70 parts by mass of "Takelac W-6010" made by Mitsui chemical Co., Ltd., an aqueous urethane resin, "30 parts by mass of" Denacol EX-521 "made by Nagase Chemtex Co., Ltd., an aqueous epoxy resin," 5 parts by mass of colloidal silica "Snowtex ST-C" (average particle diameter of 10nm to 20nm) made by Nissan chemical Co., Ltd., an antiblocking agent (anti-blocking agent), and diluting the mixture with ion-exchanged water.
(adhesive composition V)
An adhesive composition V having a nonvolatile content of 2% by mass was obtained by mixing 70 parts by mass of "Rikabond SA-513" manufactured by Central chemical industry Co., Ltd., an aqueous acrylate resin, "Denacol EX-521" manufactured by Nagase Chemtex Co., Ltd., 30 parts by mass of a colloidal silica "Snowtex ST-C" (average particle diameter of 10nm to 20nm) manufactured by Nissan chemical industry Co., Ltd., an antiblocking agent, and diluting the mixture with ion-exchanged water.
(adhesive composition Z)
100 parts by mass of "Denacol EX-521" manufactured by Nagase Chemtex corporation as an aqueous epoxy resin, and 5 parts by mass of "Snowtex ST-C" (average particle diameter 10nm to 20nm) as an anti-blocking agent, and further diluted with ion-exchanged water, an adhesive composition Z having a nonvolatile content of 2% by mass was obtained.
< example 1>
A main component was prepared by mixing 50 parts by mass of carbon black having an average particle diameter of 0.8 μm, 5 parts by mass of ethylenediamine, and 45 parts by mass of a polyester polyol (number average molecular weight: 2500). An ink composition was obtained by mixing 3 parts by mass of Toluene Diisocyanate (TDI) as a curing agent and further 50 parts by mass of toluene with 100 parts by mass of the main agent and sufficiently stirring the mixture.
One surface of a biaxially stretched nylon (nylon 6) film (heat-resistant resin stretched film layer, MD/TD ═ 0.95)2 having a thickness of 15 μm and a hot water shrinkage of 4.0%, which was obtained by stretching by a simultaneous biaxial stretching methodThe adhesive composition W was applied to (inner surface of) the substrate by gravure roll coating, dried, and then left to stand at 40 ℃ for 1 day to undergo curing reaction, thereby forming a 2 nd easy-adhesion layer 12, wherein the amount of the 2 nd easy-adhesion layer 12 was 0.1g/m2。
Next, the ink composition was printed (applied) on the surface of the 2 nd easy-adhesion layer 12 of the biaxially stretched nylon film 2 by a gravure printing method, and then left to stand at 40 ℃ for 1 day, thereby drying and simultaneously performing a crosslinking reaction to form a black ink layer (colored ink layer) 13 having a thickness of 3 μm.
On the other hand, a chemical conversion treatment solution containing polyacrylic acid, a trivalent chromium compound, water and alcohol was applied to both sides of an aluminum foil 4 having a thickness of 35 μm, and the aluminum foil was dried at 180 ℃ so that the amount of chromium adhered was 10mg/m2。
Next, the biaxially stretched nylon film 2 was bonded to one surface of the chemically converted aluminum foil 4 via the polyester urethane adhesive 5 on the black ink layer (colored ink layer) 13 side, and then the unstretched polypropylene film (thermoplastic resin layer) 3 having a thickness of 30 μm was bonded to the other surface of the aluminum foil 4 via the polyacrylic adhesive 6, and then left to stand at 40 ℃ for 5 days, thereby obtaining a laminate.
Further, the adhesive composition W was applied to the outer surface (non-laminated surface; corona-treated surface) of the biaxially stretched nylon film 2 of the laminate by a gravure roll coating method, dried, and then allowed to stand at 40 ℃ for 1 day to undergo a curing reaction, thereby forming a 1 st easy-adhesion layer 11, wherein the amount of the 1 st easy-adhesion layer 11 was 0.1g/m2。
Next, a resin composition containing 20 parts by mass of a urethane resin, 3 parts by mass of powdery silica having an average particle size of 2 μm, 5 parts by mass of acrylic resin beads having an average particle size of 3 μm, 5 parts by mass of powdery barium sulfate having an average particle size of 1 μm, 1 part by mass of Polytetrafluoroethylene (PTFE) wax having an average particle size of 3 μm, and 66 parts by mass of toluene was applied to the surface (outer surface) of the 1 st easy-adhesion layer 11 by a gravure coating method, thereby forming a protective layer 20 having a thickness of 2 μm, and obtaining a packaging material for molding 1 shown in fig. 1.
< example 2>
A molding packaging material 1 shown in fig. 1 was obtained in the same manner as in example 1, except that a biaxially stretched nylon 6 film (MD/TD ═ 0.9) having a thickness of 15 μm and a hot water shrinkage rate of 2.5%, which was obtained by stretching by the simultaneous biaxial stretching method, was used instead of the biaxially stretched nylon 6 film (MD/TD ═ 0.95) having a thickness of 15 μm and a hot water shrinkage rate of 4.0%.
< example 3>
Using a biaxially stretched nylon 6 film (MD/TD ═ 1.0) having a thickness of 15 μm and a hot water shrinkage of 3.5% obtained by stretching by a simultaneous biaxial stretching method, instead of the biaxially stretched nylon 6 film (MD/TD ═ 0.95) having a thickness of 15 μm and a hot water shrinkage of 4.0%, as a resin composition for forming the protective layer 20, a resin composition comprising 20 parts by mass of a polyester resin, 3 parts by mass of a powdery silica having an average particle diameter of 2 μm, 5 parts by mass of an acrylic resin bead having an average particle diameter of 3 μm, 5 parts by mass of a powdery barium sulfate having an average particle diameter of 1 μm, 1 part by mass of a Polytetrafluoroethylene (PTFE) wax having an average particle diameter of 3 μm, and 66 parts by mass of toluene was used, and the 2 nd easy-adhesion layer 12 was not provided (that is, namely, the black ink layer (coloring ink layer) 13 was directly laminated on the inner surface (corona-treated) of the biaxially stretched, except for this, a packaging material for molding 1 shown in fig. 1 was obtained in the same manner as in example 1.
< example 4>
A packaging material 1 for molding shown in fig. 1 was obtained in the same manner as in example 1 except that a biaxially stretched nylon 6 film (MD/TD ═ 1.1) having a thickness of 15 μm and a hot water shrinkage of 5.0% obtained by simultaneous biaxial stretching was used in place of the biaxially stretched nylon 6 film (MD/TD ═ 0.95) having a thickness of 15 μm and a hot water shrinkage of 4.0%, as the resin composition forming the protective layer 20, a resin composition was used which contained 20 parts by mass of a urethane resin, 3 parts by mass of powdery alumina having an average particle diameter of 1 μm, 5 parts by mass of acrylic resin beads having an average particle diameter of 3 μm, 5 parts by mass of powdery barium sulfate having an average particle diameter of 1 μm, 1 part by mass of Polytetrafluoroethylene (PTFE) wax having an average particle diameter of 3 μm, and 66 parts by mass of toluene.
< example 5>
A packaging material 1 for molding was obtained in the same manner as in example 1 except that a biaxially stretched polyethylene terephthalate (PET) film (MD/TD ═ 1.1) having a thickness of 15 μm and a hot water shrinkage of 2.0%, obtained by stretching by a simultaneous biaxial stretching method, was used in place of the biaxially stretched nylon 6 film (MD/TD ═ 0.95) having a thickness of 15 μm and a hot water shrinkage of 4.0%, as a resin composition for forming the protective layer 20, a resin composition was used which contained 20 parts by mass of a urethane resin, 3 parts by mass of powdery calcium carbonate having an average particle size of 2 μm, 5 parts by mass of acrylic resin beads having an average particle size of 3 μm, 5 parts by mass of powdery barium sulfate having an average particle size of 1 μm, 1 part by mass of Polytetrafluoroethylene (PTFE) wax having an average particle size of 3 μm, and 66 parts by mass of toluene.
< example 6>
A packaging material 1 for molding shown in fig. 1 was obtained in the same manner as in example 1, except that the adhesive composition V was used instead of the adhesive composition W to form the 1 st easy-adhesion layer 11 and the 2 nd easy-adhesion layer 12.
< example 7>
A packaging material 1 for molding shown in fig. 1 was obtained in the same manner as in example 1, except that the adhesive composition Z was used instead of the adhesive composition W to form the 1 st easy-adhesion layer 11 and the 2 nd easy-adhesion layer 12.
< example 8>
A biaxially stretched polyethylene terephthalate (PET) film (MD/TD ═ 1.1) having a thickness of 15 μm and a hot water shrinkage of 5.0% obtained by stretching by a simultaneous biaxial stretching method was used in place of the biaxially stretched nylon 6 film (MD/TD ═ 0.95) having a thickness of 15 μm and a hot water shrinkage of 4.0%, a packaging material 1 for molding having a thickness of 3 μm was obtained in the same manner as in example 7 except that a resin composition containing 20 parts by mass of an epoxy resin, 3 parts by mass of powdery silica having an average particle diameter of 2 μm, 5 parts by mass of acrylic resin beads having an average particle diameter of 3 μm, 5 parts by mass of powdery barium sulfate having an average particle diameter of 1 μm, 1 part by mass of Polytetrafluoroethylene (PTFE) wax having an average particle diameter of 3 μm, and 66 parts by mass of toluene was used as the resin composition for forming the protective layer 20 to form the protective layer 20 having a thickness of 3 μm.
< example 9>
A biaxially stretched nylon 6 film (MD/TD 1.0) having a thickness of 15 μm and a hot water shrinkage of 4.0% was used instead of the biaxially stretched nylon 6 film (MD/TD 1.0) having a thickness of 15 μm and a hot water shrinkage of 3.5%, a packaging material 1 for molding having a thickness of 4 μm was obtained in the same manner as in example 3, except that the protective layer 20 having a thickness of 4 μm was formed using a resin composition containing 20 parts by mass of a polyester resin, 3 parts by mass of powdery alumina having an average particle size of 1 μm, 5 parts by mass of acrylic resin beads having an average particle size of 3 μm, 5 parts by mass of powdery barium sulfate having an average particle size of 1 μm, 1 part by mass of Polytetrafluoroethylene (PTFE) wax having an average particle size of 3 μm, and 66 parts by mass of toluene as a resin composition for forming the protective layer 20 without subjecting the outer surface of the biaxially stretched nylon 6 film to corona treatment.
< comparative example 1>
A packaging material for molding was obtained in the same manner as in example 2, except that the first easy-adhesive layer 11 was not provided (i.e., the protective layer 20 was directly laminated on the outer surface of the biaxially stretched nylon film 2 (after completion of corona treatment)).
< comparative example 2>
A packaging material for molding was obtained in the same manner as in example 3, except that the first easy-adhesive layer 11 was not provided (i.e., the protective layer 20 was directly laminated on the outer surface of the biaxially stretched nylon film 2 (after completion of corona treatment)).
Each of the molding packaging materials obtained above was evaluated based on the following evaluation method. The results are shown in Table 1.
Figure DEST_PATH_GDA0002508267170000221
< method for evaluating solvent resistance A (alcohol resistance) >
Using a chemical vibration type rubbing fastness TESTER (an aluminum jig with a load of 200 g) manufactured by TESTER SANGYO co., ltd., absorbent cotton was wound around the aluminum jig, and the resultant evaluation jig was immersed in ethanol, and the surface of the molding packaging material (the surface of the protective layer 20) was reciprocated and contacted with the jig for evaluation 20 times, and then the presence or absence of peeling of the protective layer and the degree of peeling were examined, and ethanol resistance was evaluated based on the following criteria.
(criteria for determination)
". O" … was found to have no peeling of the protective layer at all
". DELTA" … confirmed some peeling of the protective layer, but was not substantially apparent
Peeling of the protective layer was clearly confirmed by "×" ….
< method for evaluating solvent resistance B (MEK resistance) >
After absorbent cotton was wound around the aluminum jig and MEK (methyl ethyl ketone) was impregnated into the absorbent cotton, the resultant jig for evaluation was reciprocated and contacted 20 times on the surface of the packaging material for molding (the surface of the protective layer 20) using a chemical vibration type rubbing fastness TESTER (aluminum jig with a load of 200 g) manufactured by TESTER SANGYO co.
(criteria for determination)
". O" … was found to have no peeling of the protective layer at all
". DELTA" … confirmed some peeling of the protective layer, but was not substantially apparent
Peeling of the protective layer was clearly confirmed by "×" ….
< evaluation method of tape peeling resistance (resistance to tape peeling) >
The molding packaging material was cut into a size of 10cm in length by 10cm in width to obtain a test piece, and the test piece was attached and fixed to a substrate with a double-sided adhesive tape having high adhesive force. "Scotch Tape # 600" (protective Tape) manufactured by 3M corporation was bonded to the surface of a test piece (surface of the protective layer 20) fixed to the substrate with a load of a 2kg roller, and then the protective Tape was immediately peeled off with force to observe the state of the protective layer, and the "Tape peeling test" was repeated 15 times to evaluate the Tape peeling resistance based on the following criteria.
(criteria for determination)
". Otom" …, no protective layer was peeled off at all even if the tape peeling test was repeated 15 times
". DELTA" … showed no peeling of the protective layer at all even when the tape peeling test was repeated 10 times, but in the tape peeling test of 11 th, 12 th, 13 th or 14 th time, peeling of the protective layer was confirmed
"×" … the protective layer was peeled off until the tape peeling test was repeated 10 times.
< method for evaluating moldability >
The molding was carried out by deep drawing a molding packaging material under the following molding conditions by 1-stage molding using a Straight die (Straight mold) with an adjustable molding depth, and moldability was evaluated for each of the molding depths (6.0mm, 5.5mm, 5.0mm, 4.5mm, 4.0mm, 3.5mm, 3.0mm, 2.5mm, and 2.0mm), and the maximum molding depth (mm) at which good molding was possible without generating any pin hole at the corner was investigated, and moldability was evaluated based on the following criteria. The presence or absence of pinholes was examined as follows: the presence or absence of transmitted light through the pinhole was visually observed.
(Molding conditions)
Forming die … punch: 33.3mm × 53.9mm, die: 80mm × 120mm, corner (corner) R: 2mm, punch R: 1.3mm, die R: 1mm
Crease resist device pressure … gauge: 0.475MPa, actual pressure (calculated): 0.7MPa
The material … SC (carbon steel) was chrome plated only with the punch R.
(criteria for determination)
"very good" … the maximum molding depth of no pinhole or crack was 5.5mm or more (acceptable)
The maximum molding depth of "O" … was 4.5mm or more and less than 5.5mm (acceptable)
"Delta" … the maximum molding depth at which pinholes and cracks were not generated was 3.0mm or more and less than 4.5mm (acceptable)
The maximum molding depth of "×" … with no pinhole or crack generation was less than 3.0 mm.
As is clear from table 1, the molding packaging materials of examples 1 to 9 of the present invention are excellent in moldability, can sufficiently prevent the protective layer from peeling off from the heat-resistant resin stretched film layer, and are also excellent in organic solvent resistance.
On the other hand, in comparative examples 1 and 2 in which the 1 st easy adhesive layer was not provided, the tape peeling resistance was poor, and the solvent resistance was also poor in comparative example 2.
Industrial applicability
The molding packaging material according to the present invention is suitably used as a case for a battery such as a notebook-size personal computer, a mobile phone, a vehicle-mounted or a stationary lithium ion polymer secondary battery, and is also suitably used as a packaging material for food or a packaging material for pharmaceuticals, but is not particularly limited to these applications. Among them, it is particularly preferably used as a battery case.
The present application claims priority from japanese patent application No. 2018-118461, filed on 22.6.2018, the disclosure of which directly forms part of the present application.
The terms and descriptions used herein are used for describing the embodiments of the present invention, and the present invention is not limited thereto. The present invention can be modified in any design without departing from the spirit of the present invention as long as the present invention is defined in the claims.

Claims (8)

1. A packaging material for molding, characterized by comprising a heat-resistant stretched resin film layer as an outer layer, a thermoplastic resin layer as an inner layer, and a metal foil layer disposed between the two layers,
a protective layer is laminated and integrated on the outer surface of the outer layer via an easy adhesive layer.
2. The molding packaging material according to claim 1, wherein the easy adhesion layer contains 1 resin selected from the group consisting of an epoxy resin, a urethane resin, an acrylate resin, a methacrylate resin, and a polyethyleneimine resin.
3. The molding packaging material according to claim 1 or 2, wherein the easy adhesion layer is an adhesion layer formed by applying a resin-water based emulsion to the heat-resistant stretched resin film layer.
4. A packaging material for molding as claimed in claim 1 or 2, wherein said easy-adhesion layer contains an antiblocking agent.
5. The wrapping material for molding according to claim 1 or 2, wherein the easy adhesion layer is a 1 st easy adhesion layer, and a 2 nd easy adhesion layer is laminated on an inner surface of the outer layer.
6. A packaging material for molding according to claim 5, wherein a colored ink layer is formed on an inner surface of the 2 nd easy-adhesive layer, and the colored ink layer and the metal foil layer are integrally bonded to each other with a 1 st adhesive layer interposed therebetween.
7. The molding packaging material according to claim 1 or 2, wherein the protective layer is a layer formed by dispersing a resin composition containing inorganic fine particles or organic fine particles in a heat-resistant resin.
8. A molded case comprising the deep-drawn molded body or the bulging molded body of the packaging material for molding according to any one of claims 1 to 7.
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