CN117922119A - Packaging material for molding processing, packaging case, and electricity storage device - Google Patents
Packaging material for molding processing, packaging case, and electricity storage device Download PDFInfo
- Publication number
- CN117922119A CN117922119A CN202311379629.7A CN202311379629A CN117922119A CN 117922119 A CN117922119 A CN 117922119A CN 202311379629 A CN202311379629 A CN 202311379629A CN 117922119 A CN117922119 A CN 117922119A
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- Prior art keywords
- layer
- adhesive
- packaging material
- reinforcing agent
- particles
- Prior art date
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- 238000003860 storage Methods 0.000 title claims abstract description 30
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- 230000005611 electricity Effects 0.000 title claims description 8
- 238000012545 processing Methods 0.000 title abstract description 16
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention relates to a packaging material for molding processing, a packaging case, and an electric storage device. A packaging material (1A) for molding comprises a metal foil layer (2), a heat-resistant resin layer (3) disposed on the outer surface side of the metal foil layer (2), and a heat-fusible resin layer (4) disposed on the inner surface side of the metal foil layer (2), wherein an outer adhesive layer (5) is provided between the metal foil layer (2) and the heat-resistant resin layer (3), and an inner adhesive layer (6R) is provided between the metal foil layer (2) and the heat-fusible resin layer (4). The inner adhesive layer (6R) contains an inner reinforcing agent. As the inner reinforcing agent, inner reinforcing particles satisfying the following requirements 1 and 2 are used. Element 1: the number average particle diameter of the inner reinforcing particles is in the range of 0.01 μm to 3. Mu.m. Element 2: the specific surface area of the inner reinforcing particles is 1m 2/g or more.
Description
Technical Field
The invention relates to a packaging material for molding processing, a packaging case, and an electric storage device. The packaging material can be used as a packaging material for non-stationary (notebook computer, mobile phone, vehicle-mounted device, etc.), stationary type power storage devices (lithium ion battery, etc.), and as a packaging material for foods and pharmaceuticals, for example.
In the present specification and claims, for convenience of description, the reinforcing agent and reinforcing particles contained in the inner adhesive layer are referred to as an inner reinforcing agent and an inner reinforcing particle, and the reinforcing agent and reinforcing particles contained in the outer adhesive layer are referred to as an outer reinforcing agent and an outer reinforcing particle.
In the present specification and claims, unless otherwise specifically indicated herein, various physical properties (specific surface area, tensile fracture strength, tensile elongation at break, etc.) are values at room temperature.
Background
Among various power storage devices, for example, lithium ion batteries used for mobile devices (for example, smart phones, tablet computers, and notebook computers), the battery main body is packaged with a packaging material. As the packaging material, for example, a packaging material formed of a metal-resin laminate in which resin films are laminated on the inner surface and the outer surface of a metal foil is used. In order to form a space for accommodating the battery body, the packaging material may be subjected to a predetermined molding process such as a drawing process (for example, a deep drawing molding process or a stretch molding process).
Such a battery is generally required to be thin and lightweight. If the metal foil and each resin film are thinned in the packaging material in order to cope with the demand, the probability of occurrence of pinholes becomes high at the time of molding processing of the packaging material, and if the molding processing depth becomes shallow in order to suppress occurrence of pinholes, it becomes difficult to cope with the increase in capacity of the battery. Further, when the resin film becomes thin, the puncture strength of the packaging material is reduced, and the battery is likely to be broken by an external impact.
The packaging material used for the non-stationary (mobile, portable, etc.) power storage device including the lithium ion battery for mobile equipment has a higher possibility of breakage due to external forces such as impact, vibration, external pressure, etc., than the packaging material used for the stationary power storage device. Therefore, a packaging material formed of a metal-resin laminate is also required to have excellent mechanical strength capable of withstanding external forces, in particular, puncture resistance.
In order to improve the puncture strength of the packaging material, patent document 1 discloses using a biaxially stretched polyester or biaxially stretched polyamide film as the outer layer of the packaging material. Patent document 2 discloses that a heat-fusible resin film in which a coating layer containing random copolymer polypropylene is laminated and integrated on each of the inner and outer surfaces of an intermediate layer containing block copolymer polypropylene is used as the inner layer of a packaging material. In addition, patent document 3, for example, discloses a method for improving the puncture strength of a packaging material.
Patent literature
Patent document 1: japanese patent application laid-open No. 2022-50325 (paragraph [0022 ]) and the like
Patent document 2: japanese patent application laid-open No. 2015-143107 (paragraph [0028 ]) and the like
Patent document 3: japanese patent laid-open No. 2020-161326
Disclosure of Invention
Problems to be solved by the invention
In recent years, with the increase in capacity of power storage devices such as lithium ion batteries, the safety of the power storage devices has been increasingly emphasized, and thus, higher puncture strength has been demanded for packaging materials.
The present invention has been made in view of the above-described technical background, and an object of the present invention is to provide a packaging material and a packaging case for molding processing having high puncture strength, and an electric storage device using the packaging material. Other objects and advantages of the present invention can be ascertained from the following preferred embodiments.
Means for solving the problems
The present invention provides the following means.
1) A packaging material for molding comprising a metal foil layer, a heat-resistant resin layer disposed on the outer surface side of the metal foil layer, and a heat-fusible resin layer disposed on the inner surface side of the metal foil layer, wherein an outer adhesive layer is provided between the metal foil layer and the heat-resistant resin layer, and an inner adhesive layer is provided between the metal foil layer and the heat-fusible resin layer,
The inner adhesive layer contains an inner reinforcing agent,
As the inner reinforcing agent, inner reinforcing particles satisfying the following requirements 1 and 2 are used.
Element 1: the number average particle diameter of the inner reinforcing particles is in the range of 0.01 μm to 3. Mu.m.
Element 2: the specific surface area of the inner reinforcing particles is 1m 2/g or more.
2) The packaging material for molding according to the above 1, wherein the inner adhesive layer is formed of a cured film of an inner adhesive composition containing an inner adhesive and the inner reinforcing agent,
The tensile elongation at break of the cured film of the inner adhesive composition was set to L1,
When the tensile elongation at break of the cured film of the inner adhesive composition containing the inner adhesive and not containing the inner reinforcing agent is L1 0,
The above-mentioned L1 satisfies the following relation 1.
15% Or less of { (L1-L1 0)/L10 } ×100% or less of 250% or less of … (formula 1).
3) The packaging material for forming according to the above 1 or 2, wherein the inner adhesive layer is provided between the metal foil layer and the heat-fusible resin layer in an application amount in the range of 2g/m 2～10g/m2,
The content of the inner reinforcing agent in the inner adhesive layer is in the range of 0.2g/m 2～1.0g/m2.
4) The molding packaging material according to any one of the above 1 to 3, wherein the outer adhesive layer contains an outer reinforcing agent,
As the outer reinforcing agent, outer reinforcing particles satisfying the following requirements 3 and 4 are used.
Element 3: the number average particle diameter of the outer reinforcing particles is in the range of 0.01 μm to 3. Mu.m.
Element 4: the specific surface area of the outer reinforcing particles is 1m 2/g or more.
5) The packaging material for molding according to the above item 4, wherein the outer adhesive layer is formed of a cured film of an outer adhesive composition containing an outer adhesive and the outer reinforcing agent,
The tensile elongation at break of the cured film of the outside adhesive composition was set to L2,
When the tensile elongation at break of the cured film of the outside adhesive composition containing the outside adhesive and not containing the outside reinforcing agent is L2 0,
The above-mentioned L2 satisfies the following relational expression 2.
15% Or less of { (L2-L2 0)/L20 } ×100% or less of 250% or less of … (formula 2).
6) A package case formed by subjecting the packaging material for forming according to any one of the preceding claims 1 to 5 to deep drawing forming or drawing forming.
7) An electricity storage device comprising an electricity storage device body and a package case for packaging the electricity storage device body,
The package case described in the above 6 is provided as the package case.
Effects of the invention
The present invention achieves the following effects.
In the former item 1, the inside reinforcing particles satisfy the above requirement 1, and thereby the fracture path in the inside adhesive layer becomes longer, and the fracture strength (tensile fracture strength, etc.) and the elongation at break (tensile elongation at break, etc.) of the inside adhesive layer are improved. In addition, the inner reinforcing particles satisfy the requirement 2, and thus the interaction between the inner reinforcing particles and the inner adhesive molecules becomes large, and the breaking strength of the inner adhesive layer is further improved. Thus, the puncture strength of the packaging material can be improved.
In the above item 2, the tensile elongation at break L1 of the cured film of the inner adhesive composition satisfies the above-described relational expression 1, and thus, in the packaging material, the inner adhesive layer has high followability to deformation of the metal foil layer. Therefore, the puncture strength of the packaging material can be reliably improved.
In the foregoing item 3, the inner adhesive layer is provided between the heat-resistant resin layer and the metal foil layer in an application amount in the range of 2g/m 2～10g/m2, and the content of the inner reinforcing agent in the inner adhesive layer is in the range of 0.2g/m 2～1.0g/m2, whereby the breaking strength and breaking elongation of the inner adhesive layer are reliably improved. Therefore, the puncture strength of the packaging material can be reliably improved.
In the former item 4, the outside reinforcing particles satisfy the above requirement 3, and thereby the breaking path in the outside adhesive layer becomes longer, and the breaking strength (tensile breaking strength, etc.) and the breaking elongation (tensile breaking elongation, etc.) of the outside adhesive layer are improved. In addition, the outside reinforcing particles satisfy the above requirement 4, and thereby the interaction between the outside reinforcing particles and the outside adhesive molecules becomes large, and the breaking strength of the outside adhesive layer is further improved. Thus, the puncture strength of the packaging material can be further improved.
In the above item 5, the tensile elongation at break L2 of the cured film of the outside adhesive composition satisfies the above-described relational expression 2, and thus, in the packaging material, the outside adhesive layer has high followability to deformation of the metal foil layer. Therefore, the puncture strength of the packaging material can be reliably improved.
In the foregoing item 6, a package case having high puncture strength can be provided.
In the foregoing item 7, the power storage device has high durability against external forces such as impact, vibration, external pressure, and the like, because the power storage device includes the package case described in the foregoing item 6.
Drawings
Fig. 1 is a schematic cross-sectional view of a molding packaging material according to embodiment 1 of the present invention.
Fig. 2 is a schematic cross-sectional view of a molding packaging material according to embodiment 2 of the present invention.
Fig. 3 is a schematic cross-sectional view of a molding packaging material according to embodiment 3 of the present invention.
Fig. 4 is a schematic cross-sectional view of a molding packaging material according to embodiment 4 of the present invention.
Fig. 5 is a schematic cross-sectional view of a molding packaging material according to embodiment 5 of the present invention.
Fig. 6 is a schematic cross-sectional view of an electric storage device according to an embodiment of the present invention.
Fig. 7 is a schematic perspective view showing the power storage device in an exploded manner.
Description of the reference numerals
1A to 1E: packaging material
2: Metal foil layer
3: Heat resistant resin layer
4: Thermally fusible resin layer
5. 5R: outer adhesive layer
6R: inner adhesive layer
7: Matte coating
8: Black coloring layer
30: Lithium ion battery (accumulator)
31: Lithium ion battery body (electric power storage device body)
Detailed Description
Some embodiments of the invention are described below with reference to the accompanying drawings.
As shown in fig. 1, a molding packaging material 1A according to embodiment 1 of the present invention has an inner surface 1A and an outer surface 1b.
The packaging material 1A is basically formed of a laminate including a metal foil layer 2, a heat-resistant resin layer 3 disposed on the outer surface side of the metal foil layer 2, and a heat-fusible resin layer 4 disposed on the inner surface side of the metal foil layer 2, wherein an outer adhesive layer 5 is provided between the metal foil layer 2 and the heat-resistant resin layer 3, and an inner adhesive layer 6R is provided between the metal foil layer 2 and the heat-fusible resin layer 4. The layers are joined (bonded) together in a laminated state.
The heat-fusible resin layer 4 is disposed on the inner surface 1A of the packaging material 1A, and therefore the inner surface 1A of the packaging material 1A is formed by the inner surface of the heat-fusible resin layer 4. The heat-resistant resin layer 3 is also referred to as a base layer of the packaging material 1A, and is disposed on the outer surface 1b side of the metal foil layer 2 of the packaging material 1A.
A chemical conversion coating 2a for improving the corrosion resistance of the metal foil layer 2 is formed on at least one of the inner surface and the outer surface of the metal foil layer 2. In embodiment 1, chemical conversion coatings 2a and 2a are formed on the inner surface and the outer surface of the metal foil layer 2, respectively. Each of the chemical conversion coatings 2a is formed by subjecting the surface of the metal foil to chemical conversion treatment.
The packaging material 1A can be used for packaging of an electric storage device such as a battery device, as shown in fig. 6 and 7. Specifically, the power storage device is, for example, a lithium ion battery 30.
As shown in fig. 7, the lithium ion battery 30 as the power storage device includes a lithium ion battery main body 31 as the power storage device main body, and a package case 20 that houses the battery main body 31 in a state of surrounding the battery main body 31. The package case 20 includes a container-like package case body 21 that is open at the top, and a flat plate-like cover 22 that closes the opening of the package case body 21, as constituent members of the package case 20.
The package case body 21 is obtained by forming the package material 1A into a container shape by deep drawing or stretch forming such that the inner surface 1A thereof faces inward. That is, the package case body 21 is formed of a deep drawing molded product or a stretch molded product of the packaging material 1A.
A recess 21b for accommodating the battery body 31 is provided in the center of the inner surface 1a of the package case body 21. A flange portion 21a protruding outward is provided as a predetermined joint portion at an upper end of a side wall 21c disposed on an outer peripheral portion of the package case main body 21.
The lid 22 is a flat lid that is used without molding the packaging material 1A, and the outer peripheral portion 22a of the lid 22 is a predetermined joint portion of the lid 22.
In the battery 30, the lid 22 is disposed on the package case body 21 such that the inner surface 1a thereof faces the battery body 31 side (lower side) in a state in which the battery body 31 is accommodated in the recess 21b of the package case body 21, and the heat-fusible resin layer 4 of the flange portion 21a of the package case body 21 and the heat-fusible resin layer 4 of the outer peripheral portion 22a of the lid 22 are heat-sealed (bonded) in a sealed state by heat sealing, whereby the battery 30 in a state in which the battery body 31 is accommodated in the package case 20 is configured as shown in fig. 6.
In fig. 6, reference numeral "23" denotes a heat-sealed portion (heat-sealed portion) of the heat-sealable resin layer 4 of the flange portion 21a of the package case main body 21 and the heat-sealable resin layer 4 of the outer peripheral portion 22a of the lid body 22.
Tabs (not shown) connected to the battery body 31 are led out of the package case 20 through the heat seal portion 23 from the battery body 31.
Next, the structure of the packaging material 1A and the method of manufacturing the packaging material 1A according to embodiment 1 will be described in detail.
(Heat-resistant resin layer)
The heat-resistant resin layer 3 is formed of, for example, a heat-resistant resin film. The type of the heat-resistant resin layer (heat-resistant resin film) 3 is not limited, and a polyamide film, a polyester film, or the like may be used as the heat-resistant resin layer 3, and a stretched film thereof is preferably used. Among them, biaxially stretched polyamide film, biaxially stretched polybutylene terephthalate (PBT) film, biaxially stretched polyethylene terephthalate (PET) film, or biaxially stretched polyethylene naphthalate (PEN) film is preferably used as the heat-resistant resin layer 3 in view of its moldability and strength.
In addition, as the heat-resistant resin layer 3, a biaxially stretched polyamide film is particularly preferably used in view of excellent puncture strength and molding processability. The type of the polyamide film is not limited, and examples of the polyamide film include a nylon 6 film, a nylon 6,6 film, and a nylon MXD film.
The thickness of the heat-resistant resin layer 3 is not limited, but is preferably in the range of 9 μm to 50 μm. When a polyester film is used as the heat-resistant resin layer 3, the thickness thereof is preferably in the range of 9 μm to 50 μm, and when a polyamide film is used, the thickness thereof is preferably in the range of 10 μm to 50 μm. By setting the thickness to be equal to or greater than the lower limit of the preferable range, strength sufficient for the packaging material 1A can be reliably ensured, and by setting the thickness to be equal to or less than the upper limit of the preferable range, processing stress acting on the packaging material 1A during deep drawing forming processing and stretch forming processing can be reliably reduced, and the forming processability of the packaging material 1A can be reliably improved.
(Heat-fusible resin layer)
The heat-fusible resin layer 4 is a layer that plays the following roles: the packaging material 1A is provided with excellent chemical resistance to an electrolyte solution or the like having strong corrosiveness used in the power storage device 30 such as a lithium ion battery, and heat sealability is provided to the packaging material 1A.
The heat-fusible resin layer 4 is formed of, for example, a heat-fusible resin film. The type of the heat-fusible resin layer (heat-fusible resin film) 4 is not limited, and a heat-fusible resin unstretched film may be preferably used as the heat-fusible resin layer 4. As the heat-fusible resin unstretched film, an unstretched film formed of at least 1 heat-fusible resin selected from the group consisting of polyethylene, polypropylene, olefin-based copolymer, acid-modified products thereof and ionomer is preferably used in view of excellent chemical resistance and heat sealability. In particular, from the viewpoint of excellent puncture strength, a three-layer co-extruded polypropylene film obtained by laminating and integrating a coating layer containing a random copolymer polypropylene on both sides of an intermediate layer containing a block copolymer polypropylene is preferably used. The layer thickness ratio of the unstretched three-layer coextruded polypropylene film is not limited, but is preferably an ethylene-propylene random copolymer (rPP): ethylene-propylene block copolymer (bPP): ethylene-propylene random copolymer (rPP) =1 to 1.5: 7-8: 1 to 1.5.
The thickness of the heat-fusible resin layer 4 is not limited, but is preferably in the range of 20 μm to 80 μm. By setting the thickness to 20 μm or more, pinholes in the molded article can be reliably suppressed. By setting the thickness to 80 μm or less, the resin usage amount can be reliably reduced, and the manufacturing cost of the packaging material 1A can be reliably reduced. Among them, the thickness of the heat-fusible resin layer 4 is particularly preferably in the range of 30 μm to 50 μm.
(Metal foil layer)
The metal foil layer 2 is a layer that plays a role of imparting gas barrier properties to the packaging material 1A, which inhibits the intrusion of oxygen and moisture.
The metal foil layer 2 is formed of, for example, a metal foil. The type of the metal foil layer 2 is not limited, and as the metal foil layer 2, aluminum foil, copper foil, stainless steel foil, or the like can be used, and aluminum foil is generally used. The aluminum foil, in particular, an al—fe alloy foil containing 0.7 to 1.7 mass% of Fe has excellent strength and ductility, and good formability is obtained.
The thickness of the metal foil layer 2 is not limited, and may preferably be in the range of 20 μm to 100 μm. By setting the thickness to 20 μm or more, pinholes can be reliably suppressed during rolling in the production of the metal foil. By setting the thickness to 100 μm or less, the processing stress acting on the packaging material 1A during the deep drawing molding processing and the stretch molding processing can be reliably reduced, and the molding processability of the packaging material 1A can be reliably improved.
(Chemical conversion coating of Metal foil layer)
The chemical conversion coating 2a is a film (layer) for improving the corrosion resistance of the metal foil layer 2, and can be formed by, for example, subjecting the surface of the metal foil constituting the metal foil layer 2 to a chromate treatment or a non-chromium chemical conversion treatment using a zirconium compound or the like. For example, in the case of chromate treatment, an aqueous solution of any one of the following mixtures 1) to 3) is applied to the surface of a metal foil subjected to degreasing treatment, and then dried.
1) Mixtures of at least one of phosphoric acid, chromic acid, and metal salts of fluorides and nonmetallic salts of fluorides
2) Mixture of acrylic resin, chitosan derivative resin, phenol resin, at least one of chromic acid and chromium (III) salt, and phosphoric acid
3) A mixture of an acrylic resin, any one of a chitosan derivative resin and a phenol resin, at least one of chromic acid and a chromium (III) salt, at least one of a metal salt of a fluoride and a nonmetallic salt of a fluoride, and phosphoric acid.
The amount of chromium deposited on the chemical conversion coating 2a is not limited, but is preferably in the range of 0.1mg/m 2～50mg/m2, particularly preferably in the range of 2mg/m 2～20mg/m2, on one side of the metal foil. The thickness of the chemical conversion coating 2a is not limited, and may preferably be in the range of 0.001 μm to 0.1 μm. The chemical conversion coating 2a having such a chromium deposition amount or thickness can reliably improve the corrosion resistance of the metal foil layer 2.
In embodiment 1, the chemical conversion coating 2a is formed on each of the inner surface and the outer surface of the metal foil layer 2 as described above, but in the present invention, the chemical conversion coating 2a may be formed only on any one of the inner surface and the outer surface of the metal foil layer 2.
(Outer adhesive layer)
The outer adhesive layer 5 is a layer responsible for bonding between the metal foil layer 2 and a layer disposed on the outer surface side of the metal foil layer 2, and in embodiment 1, is a layer responsible for bonding between the metal foil layer 2 (specifically, the outer surface chemical conversion coating 2a of the metal foil layer 2) and the heat-resistant resin layer 3.
The outer adhesive layer 5 is formed of a cured film of the outer adhesive composition containing the outer adhesive. In embodiment 1, the outside adhesive composition does not contain an outside reinforcing agent.
Hereinafter, in order to distinguish the outside adhesive composition containing the outside adhesive and the outside reinforcing agent from the outside adhesive composition containing the outside adhesive and not containing the outside reinforcing agent, the former is also referred to as "outside adhesive composition containing the outside reinforcing agent", and the latter is referred to as "outside adhesive composition not containing the outside reinforcing agent". Therefore, in embodiment 1, the outer adhesive layer 5 is formed of a cured film of the outer adhesive composition containing no outer reinforcing agent.
The type of the outer adhesive is not limited, and as the outer adhesive, polyurethane adhesives, acrylic adhesives, polyacrylate adhesives, modified polypropylene adhesives, polyester adhesives, polyamide adhesives, epoxy adhesives, and the like can be used.
The outer adhesive is preferably an adhesive that can be used as an adhesive for dry lamination (for example, urethane adhesive and olefin adhesive). Specifically, as such an external adhesive, for example, an adhesive containing a two-part curable polyester urethane resin (polyester urethane resin) formed from a polyester resin as a main agent of the external adhesive and a polyfunctional isocyanate compound as a curing agent can be used.
The polyester resin is a copolymer prepared from dicarboxylic acid and diol, and preferable materials and compositions are as follows.
As the dicarboxylic acid, both aliphatic dicarboxylic acid and aromatic dicarboxylic acid are preferably used. In addition, the parity of the methylene number of the methylene chain of the aliphatic dicarboxylic acid is a factor affecting the crystallinity of the resin, and since dicarboxylic acids having an even number of methylene groups produce resins having high crystallinity and hardness, it is preferable to use aliphatic dicarboxylic acids having an even number of methylene groups as the dicarboxylic acid. Examples of the aliphatic dicarboxylic acid having an even number of methylene groups include succinic acid (having a methylene group of 2), adipic acid (having a methylene group of 4), suberic acid (having a methylene group of 6), and sebacic acid (having a methylene group of 8).
Examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, and phthalic anhydride.
The content of the aromatic dicarboxylic acid is preferably in the range of 40 to 80 mol% based on the total amount of the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, in other words, the content of the aliphatic dicarboxylic acid is preferably in the range of 20 to 60 mol%. In this case, a resin having high adhesive strength and good moldability is produced, and a packaging material having good moldability and capable of being molded into a packaging case having a high side wall and capable of reliably suppressing interlayer peeling between the metal foil layer 2 and the heat-resistant resin layer 3 can be produced. In addition, by setting the content of the aromatic dicarboxylic acid to 40 mol% or more, aggregation and peeling due to a decrease in film physical properties can be reliably suppressed, and further interlayer peeling can be reliably suppressed. By setting the content of the aromatic dicarboxylic acid to 80% or less, the decrease in adhesion performance due to the curing of the resin can be reliably suppressed. The content of the aromatic dicarboxylic acid is particularly preferably in the range of 50 to 70 mol%.
Examples of the diols include ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, octanediol, 1, 4-cyclohexanediol, and 2-butyl-2-ethyl-1, 3-propanediol.
The molecular weight of the polyester resin is not limited, but it is preferable that the number average molecular weight (Mn) is in the range of 8,000 to 25,000, the weight average molecular weight (Mw) is in the range of 15,000 ～ 50,000, and the ratio (Mw/Mn) is preferably in the range of 1.3 to 2.5. By setting the number average molecular weight (Mn) to 8,000 or more and the weight average molecular weight (Mw) to 15,000 or more, appropriate coating film strength and heat resistance can be reliably obtained. By setting the number average molecular weight (Mn) to 25,000 or less and the weight average molecular weight (Mw) to 50,000 or less, the coating film can be reliably elongated without excessive hardening. Further, by setting the ratio (Mw/Mn) thereof to be in the range of 1.3 to 2.5, an appropriate molecular weight distribution is obtained, and the balance between the adhesive coating suitability (wide distribution) and the performance (narrow distribution) can be reliably ensured. In the polyester resin, a particularly preferable number average molecular weight (Mn) is in the range of 10,000 ～ 23,000, a particularly preferable weight average molecular weight (Mw) is in the range of 20,000 ～ 40,000, and a particularly preferable ratio (Mw/Mn) is in the range of 1.5 to 2.3.
The molecular weight of the polyester resin can be adjusted by chain extension using polyfunctional isocyanates. That is, when the polyester component in the main agent is linked by NCO, a polymer having hydroxyl groups at the end is produced, and the molecular weight of the polyester resin can be adjusted by adjusting the equivalent ratio of isocyanate groups to hydroxyl groups of the polyester. It is preferable to use a polyester resin obtained by connecting them so that the equivalent ratio (OH/NCO) thereof is in the range of 1.01 to 10. Further, as another molecular weight adjustment method, there is mentioned a change in the reaction conditions (adjustment of the molar ratio of the dicarboxylic acid to the diol) of the polycondensation reaction of the dicarboxylic acid and the diol. In addition, an epoxy resin or an acrylic resin may be added as an additive to the main agent of the adhesive.
The type of the polyfunctional isocyanate compound used as the curing agent is not limited, and various isocyanate compounds such as aromatic isocyanate compounds, aliphatic isocyanate compounds, and alicyclic isocyanate compounds can be used as the polyfunctional isocyanate compound. Specific examples thereof include polyfunctional isocyanate-modified products of 1 or 2 or more kinds of diisocyanates such as aliphatic Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), aromatic Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and the like. The modifying means is not limited, and examples of the modifying means include not only adducts with polyfunctional active hydrogen compounds such as water, glycerin and trimethylolpropane, but also polyfunctional isocyanate-modified products obtained by polymerization such as isocyanurate, carbodiimide and polymerization, and 1 or 2 or more of them may be mixed and used. In addition, in order to increase the adhesive strength after curing and to obtain the effect of suppressing peeling of the heat-resistant resin layer 3, it is preferable to contain 50 mol% or more of the aromatic isocyanate compound. The content of the aromatic isocyanate compound is particularly preferably 70 mol% or more.
In the two-part curable polyester urethane resin, the blending ratio of the main agent and the curing agent is not limited, and it is preferable to blend them in a ratio of 2 to 25 mol of isocyanate functional group (-NCO) relative to 1 mol of polyol hydroxyl group (-OH). By setting the molar ratio (-NCO)/(OH) to 2 or more, the curing reaction can be sufficiently performed with reliability, and appropriate coating film strength and heat resistance can be reliably obtained. By setting (-NCO)/(OH) to 25 or less, curing of the coating film due to excessive reaction with functional groups other than polyol can be reliably suppressed, and a suitable elongation can be reliably obtained. Particularly preferred polyol hydroxyl to isocyanate functional molar ratios (-NCO)/(OH) are in the range of 5 to 20.
(Inner adhesive layer)
The inner adhesive layer 6R is a layer responsible for bonding between the metal foil layer 2 and a layer disposed on the inner surface side of the metal foil layer 2, and in embodiment 1, is a layer responsible for bonding between the metal foil layer 2 (specifically, the inner surface chemical conversion coating 2a of the metal foil layer 2) and the heat-fusible resin layer 4.
The inner adhesive layer 6R is formed of a cured film of an inner adhesive composition containing an inner adhesive and an inner reinforcing agent.
Hereinafter, in order to distinguish the above-described inside adhesive composition containing the inside adhesive and the inside reinforcing agent from the inside adhesive composition containing the inside adhesive and not containing the inside reinforcing agent, the former is also referred to as "inside adhesive composition containing the inside reinforcing agent", and the latter is referred to as "inside adhesive composition not containing the inside reinforcing agent". Therefore, in embodiment 1, the inner adhesive layer 6R is formed of a cured film of the inner adhesive composition containing the inner reinforcing agent.
The type of the inner adhesive is not limited, and polyurethane adhesives, acrylic adhesives, epoxy adhesives, polyolefin adhesives (for example, acid-modified polypropylene adhesives), elastomer adhesives, fluorine adhesives, and the like can be used as the inner adhesive. 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 packaging material 1A can be improved.
As the inner reinforcing agent, inner reinforcing particles may be used. As the inner reinforcing particles, at least one of inorganic particles and organic particles may be used.
Examples of the inorganic particles include fillers and carbon black listed in "types and properties of fillers in Table 1" in the Japanese society for rubber and rubber, 1980, volume 53, phase 1, and pages 17 to 33, "reinforcing (one of them) inorganic reinforcing agents" in the Ministry of white wood "reinforcing agent (reinforcing agent of そ, 1)". Specifically, as the inorganic particles, particles of at least one selected from the group consisting of calcium carbonate (CaCO 3), magnesium carbonate, calcium magnesium carbonate, silicate, silica (SiO 2), aluminum hydrate, barium sulfate, calcium sulfite, and Carbon Black (CB) are preferably used.
As the organic particles, particles (beads) of at least one selected from the group consisting of acrylic resins, styrene resins, and fluororesin are preferably used.
Therefore, as the inner reinforcing particles, at least one selected from the group consisting of the above-mentioned inorganic particles and the above-mentioned organic particles is preferably used. In addition, inorganic particles and organic particles may be used in combination.
The inside reinforcing particles must satisfy the following requirements 1 and 2.
Element 1: the number average particle diameter of the inner reinforcing particles is in the range of 0.01 μm to 3. Mu.m.
Element 2: the specific surface area of the inner reinforcing particles is 1m 2/g or more.
By making the inside reinforcing particles satisfy the above requirement 1, the fracture path in the inside adhesive layer 6R becomes longer, and the fracture strength (tensile fracture strength, etc.) and the elongation at break (tensile elongation at break, etc.) of the inside adhesive layer 6R are improved. In addition, by making the inside reinforcing particles satisfy the above requirement 2, the interaction between the inside reinforcing particles and the inside adhesive molecules becomes large, and the breaking strength of the inside adhesive layer 6R is further improved. Therefore, the puncture strength of the packaging material 1A can be improved.
In addition, since the molding processability of the packaging material tends to be increased when the puncture strength of the packaging material is increased, the molding processability of the packaging material 1A can be improved by increasing the puncture strength of the packaging material 1A.
In the above-described element 1, the number average particle diameter of the inner reinforcing particles is 0.01 μm or more, whereby the inner adhesive layer 6R can be prevented from being hardened by the inclusion of the inner reinforcing particles. The number average particle diameter of the inner reinforcing particles is 3 μm or less, whereby the reinforcing effect of the inner adhesive layer 6R by the inclusion of the inner reinforcing particles can be reliably obtained. If the number average particle diameter of the inner reinforcing particles is smaller than 0.01 μm, the inner reinforcing particles tend to aggregate when the inner reinforcing particles are dispersed in the inner adhesive, and it is difficult to uniformly disperse the inner reinforcing particles in the inner adhesive. The preferred lower limit of the number average particle diameter of the inner reinforcing particles is 0.03. Mu.m, the preferred upper limit is 1.0. Mu.m, and the more preferred upper limit is 0.5. Mu.m.
In the above-mentioned element 2, the preferable lower limit of the specific surface area of the inner reinforcing particles is 10m 2/g, and the preferable upper limit is 500m 2/g. If the specific surface area is more than 500m 2/g, the interaction between the inside reinforcing particles and the inside adhesive molecules becomes saturated, and an increase in the fracture strength of the inside adhesive layer 6R is less likely to be observed, so that the specific surface area is preferably 500m 2/g or less. A more preferred upper limit is 450m 2/g.
The inner reinforcing particles are preferably insulating particles. In this case, the electrical insulation of the portion of the packaging material 1A closer to the inner surface 1A than the metal foil layer 3 can be improved. Therefore, even when the inner surface 1A of the packaging material 1A is damaged such as by cracking or scratching due to frequent or strong contact with the inner surface 1A of the packaging material 1A by the packaged object such as the power storage device main body 31 packaged by the packaging material 1A, for example, it is possible to suppress a decrease in electrical insulation of the packaging material 1A caused by the damage. In order to reliably achieve such an effect, the volume resistivity of the insulating inner reinforcing particles is preferably 1×10 12 Ω cm or more at room temperature.
As such an inner reinforcing particle having insulation properties, at least one selected from the group consisting of insulating inorganic particles and organic particles as described below is preferably used. The insulating inorganic particles and the organic particles may be used in combination.
Examples of the insulating inorganic particles include particles of calcium carbonate (CaCO 3), magnesium carbonate, calcium/magnesium carbonate, silicate, silica (SiO 2), aluminum hydrate, barium sulfate, calcium sulfate, and calcium sulfite.
Examples of the organic particles include particles (beads) of acrylic resin, styrene resin, and fluororesin. In general, the organic particles have insulating properties.
When the tensile elongation at break of the cured film of the inner adhesive composition containing the inner reinforcing agent is L1 and the tensile elongation at break of the cured film of the inner adhesive composition containing no inner reinforcing agent is L1 0, L1 preferably satisfies the following relational expression 1.
15% Or less of { (L1-L1 0)/L10 } ×100% or less of 250% or less of … (formula 1).
By satisfying the above-described relation 1 with L1, the inner adhesive layer 6R in the packaging material 1A has high followability to the deformation of the metal foil layer 2. Therefore, the puncture strength of the packaging material 1A can be reliably improved, and the molding processability of the packaging material 1A can be reliably improved.
In the above-mentioned relation 1, the { (L1-L1 0)/L10 } ×100% as the intermediate side thereof means an improvement rate Δl1 (i.e., Δl1= { (L1-L1 0)/L10 } ×100%) of the tensile elongation at break of the cured film of the inner adhesive composition (inner adhesive layer 6R) achieved by containing the inner reinforcing agent) }, and this improvement rate Δl1 is particularly preferably in the range of 20% to 230%, and further, Δl1 is very preferably in the range of 50% to 230%.
In the inner reinforcing agent (inner reinforcing particles), a functional group may be added to the inner reinforcing agent by subjecting the inner reinforcing agent to a silane-based or titanium-based coupling agent treatment or a surface treatment with a synthetic polymer or the like, and in this case, the surface activity of the inner reinforcing agent can be increased, thereby improving the interfacial adhesion between the inner reinforcing agent and the inner adhesive.
When dispersing the inner reinforcing agent in the inner adhesive so as to contain the inner reinforcing agent in the inner adhesive, it is preferable to use a dispersing machine for dispersing, and a dispersing agent such as a surfactant may be used in the dispersing.
The method of dispersing the inner reinforcing agent in the inner adhesive is not limited, and the following method is preferable.
That is, an ink containing the inner reinforcing agent at a high concentration (also referred to as "ink containing the inner reinforcing agent at a high concentration") is prepared in advance. Then, the ink is added to the inner adhesive (preferably, the main agent of the inner adhesive) and mixed so that the content of the inner reinforcing agent becomes a predetermined ratio, whereby the inner reinforcing agent is dispersed in the inner adhesive.
The ink can be prepared, for example, as follows.
That is, an inner reinforcing agent is added to a paint (a mixture of a resin and a solvent) and mixed to prepare a base of an ink, and an auxiliary agent (a surfactant, a viscosity modifier, an antistatic agent, an antioxidant, a dispersant, a leveling agent, an anti-settling agent, an antifoaming agent, etc.) is added thereto, and kneaded and dispersed by using a dispersing machine, whereby the inner reinforcing agent is uniformly dispersed in the paint, thereby preparing the ink containing the inner reinforcing agent at a high concentration.
As the resin for paint, 1 or a combination of 2 or more selected from the group consisting of a copolymer of vinyl chloride and vinyl acetate, chlorinated rubber, chlorinated polypropylene, acrylic resin, polyamide resin, polyurethane resin, polyester resin, and nitrocellulose can be used. In particular, as the resin, a resin of the same kind (more preferably, the same composition) as the main agent of the inner adhesive is preferably used, and thus the ink and the main agent of the inner adhesive become compatible (mixed) easily.
As the solvent for paint, 1 or a combination of 2 or more selected from the group consisting of toluene, methyl ethyl ketone, methylcyclohexane, ethyl acetate and isopropyl alcohol may be used. In particular, as the solvent, ethyl acetate, methyl ethyl ketone, methylcyclohexane, and the like, which are also used as a solvent for the inside adhesive, are preferably used. In addition, toluene, methyl ethyl ketone, or the like can be used as a cosolvent, if necessary.
The ink is preferably prepared using a paint resin, a paint solvent, an inner reinforcing agent and an auxiliary agent in the following blending ratio.
Resin: 15 to 25 mass percent
Solvent: 40 to 70 mass percent
Medial reinforcing agent: 5 to 50 mass percent
Auxiliary agent: 1 to 5 mass percent.
Further, it is preferable that the inner reinforcing agent is dispersed in the ink at a high concentration and uniformly. For the preparation of such ink, as the above-mentioned dispersing machine, a paint shaker, a ball mill, an attritor, a sand mill, a bead mill, dai Nuomo (Dynomill), a roll mill, an ultrasonic mill, a high-pressure impact dispersing machine, etc. may be used, and one or more dispersing treatments may be performed by using 1 dispersing machine, or a plurality of dispersing treatments may be performed by using 2 or more dispersing machines in combination.
As described above, by adding the ink containing the inner reinforcing agent in a high concentration to the inner adhesive (preferably, the main agent thereof) so that the content of the inner reinforcing agent becomes a predetermined ratio and uniformly mixing and dispersing the ink, the generation of 2-order aggregated particles of the inner reinforcing agent can be reliably suppressed from each other, and the inner reinforcing agent can be reliably uniformly dispersed in the inner adhesive (the main agent thereof). Thus, an inside adhesive (main agent) in which the inside reinforcing agent is well dispersed without causing sedimentation of the inside reinforcing agent even when left for several months after the inside reinforcing agent is added to the inside adhesive (main agent thereof) can be reliably obtained.
When the inner reinforcing agent is added to, for example, the main agent of the inner adhesive, the cured film (i.e., the inner adhesive layer 6R) of the inner adhesive composition having very few coating defects due to 2-time aggregated particles of the inner reinforcing agent can be reliably formed by reacting the main agent of the inner adhesive in which the inner reinforcing agent is well dispersed, obtained as described above, with the curing agent (e.g., isocyanate curing agent). As a result, the tensile elongation at break L1 of the cured film is reliably improved as compared with a cured film of an inner adhesive composition containing no inner reinforcing agent, and the cured film of the inner adhesive composition can reliably follow deformation and puncture deformation during molding processing. Therefore, the inner adhesive layer 6R can reliably maintain good adhesion.
For example, when a polyolefin adhesive is used as the inner adhesive, an acid-modified polypropylene resin (acid-modified PP resin) is preferably used as the main agent. In the case of using an acid-modified polypropylene resin as a main agent, it is preferable to use an acid-modified polypropylene resin as a resin for paint and methylcyclohexane, methyl ethyl ketone or a mixed solvent thereof as a solvent for paint.
The content of the inner reinforcing agent is preferably in the range of 2 to 10 mass% relative to the total amount of the inner reinforcing agent and the main agent (for example, acid-modified polypropylene resin) of the inner adhesive. In detail, the content refers to the solid content, that is, the content excluding the mass of the solvent. The following is the same.
The inner adhesive layer 6R is preferably provided between the metal foil layer 2 and the heat-fusible resin layer 4 in a coating amount in the range of 2g/m 2～10g/m2. Further, the content of the inner reinforcing agent in the inner adhesive layer 6R is preferably in the range of 0.2g/m 2～1.0g/m2. By setting the coating amount of the inner adhesive layer 6R within the above-described range and the content of the inner reinforcing agent within the above-described range, the breaking strength and breaking elongation of the inner adhesive layer 6R are reliably improved. Therefore, the puncture strength of the packaging material 1A can be reliably improved, and the molding processability of the packaging material 1A can be reliably improved. The application amount of the inner adhesive layer 6R is specifically the solid content application amount, and the content of the inner reinforcing agent is specifically the solid content. The following is the same.
The lower limit of the coating amount of the inner adhesive layer 6R is more preferably 4g/m 2, and the upper limit is more preferably 9g/m 2. The more preferable lower limit of the content of the above-mentioned inner reinforcing agent is 0.2g/m 2, and the more preferable upper limit is 0.7g/m 2.
The bonding method (bonding method) of the metal foil layer 2 and the heat-fusible resin layer 4 is not limited, and a dry lamination method is preferable.
(Method for producing packaging Material)
An example of a preferred manufacturing method of the packaging material 1A is as follows.
A metal foil layer 2 having a chemical conversion coating 2a formed on each of the inner and outer surfaces thereof is prepared. Next, the outer adhesive composition is applied in a layer form to the outer surface of the metal foil layer 2 by a predetermined application method, the solvent in the composition is dried and evaporated, and then the outer surface of the metal foil layer 2 is bonded to the inner surface of the heat-resistant resin layer 3, and the composition is cured by aging at a predetermined temperature in accordance with the curing conditions of the composition.
Next, the inner adhesive composition is applied in a layer form to the inner surface of the metal foil layer 2 by a predetermined application method, the solvent in the composition is dried and evaporated, and then the inner surface of the metal foil layer 2 is bonded to the outer surface of the heat-fusible resin layer 4, and the composition is cured by aging at a predetermined temperature in accordance with the curing conditions of the composition.
Thus, the heat-resistant resin layer 3 is bonded to the outer surface of the metal foil layer 2 via the outer adhesive layer 5, and the heat-fusible resin layer 4 is bonded to the inner surface of the metal foil layer 2 via the inner adhesive layer 6R, thereby obtaining the packaging material 1A.
The coating method is not limited, and specifically, a gravure coating method, a reverse roll coating method, a lip roll coating method, and the like are mentioned.
However, the packaging material according to the present invention is not limited to the packaging material manufactured by the above-described method for manufacturing the packaging material 1A, and may be a packaging material manufactured by another method.
The molding packaging material according to the present invention is not limited to the packaging material 1A of embodiment 1, but may be, for example, the packaging materials 1B to 1E of embodiments 2 to 5 shown in fig. 2 to 5, respectively. These packaging materials 1B to 1E are used for packaging of, for example, the power storage device 30 (see fig. 6 and 7) in the same manner as the packaging material 1A of embodiment 1.
In these drawings, elements that perform the same functions as those of the packaging material 1A of embodiment 1 are given the same reference numerals. The outer adhesive layer denoted by reference numeral "5" does not contain an outer reinforcing agent, similar to the outer adhesive layer of the packaging material 1A of embodiment 1, and the outer adhesive layer denoted by reference numeral "5R" contains an outer reinforcing agent. Hereinafter, embodiments 2 to 5 will be described mainly with respect to differences from embodiment 1.
In embodiment 2 shown in fig. 2, the outer adhesive layer 5R of the packaging material 1B contains an outer reinforcing agent, and specifically, is formed of a cured film of an outer adhesive composition containing an outer adhesive and an outer reinforcing agent, that is, a cured film of an outer adhesive composition containing an outer reinforcing agent.
As the outer reinforcing agent, outer reinforcing particles may be used. As the outer reinforcing particles, at least one of inorganic particles and organic particles can be used.
As the inorganic particles, particles of at least one selected from the group consisting of calcium carbonate (CaCO 3), magnesium carbonate, calcium magnesium carbonate, silicate, silica (silicic acid: siO 2), aluminum hydrate, barium sulfate, calcium sulfite, and Carbon Black (CB) are preferably used.
As the organic particles, particles of at least one selected from the group consisting of acrylic resins, styrene resins, and fluororesin are preferably used.
Therefore, as the outer reinforcing particles, at least one selected from the group consisting of the above inorganic particles and the above organic particles can be used. In addition, inorganic particles and organic particles may be used in combination.
The outer reinforcing particles preferably satisfy the following requirements 3 and 4.
Element 3: the number average particle diameter of the outer reinforcing particles is in the range of 0.01 μm to 3. Mu.m.
Element 4: the specific surface area of the outer reinforcing particles is 1m 2/g or more.
By making the outside reinforcing particles satisfy the above requirement 3, the breaking path in the outside adhesive layer 5R becomes longer, and the breaking strength (tensile breaking strength, etc.) and the breaking elongation (tensile breaking elongation, etc.) of the outside adhesive layer 5R are improved. In addition, by making the outer reinforcing particles satisfy the above requirement 4, the interaction between the outer reinforcing particles and the outer adhesive molecules becomes large, and the breaking strength of the outer adhesive layer 5R is further improved. Therefore, the puncture strength of the packaging material 1B can be further improved.
In addition, since the molding processability of the packaging material tends to be increased when the puncture strength of the packaging material is increased, the molding processability of the packaging material 1B can be further improved by further increasing the puncture strength of the packaging material 1B.
In the above-described element 3, the number average particle diameter of the outer reinforcing particles is 0.01 μm or more, whereby the hardening of the outer adhesive layer 5R due to the inclusion of the outer reinforcing particles can be reliably suppressed, and the elongation at break of the outer adhesive layer 5R can be reliably improved. The number average particle diameter of the outer reinforcing particles is 3 μm or less, whereby the reinforcing effect of the outer adhesive layer 5R by the inclusion of the outer reinforcing particles can be reliably obtained. The preferred lower limit of the number average particle diameter of the outer reinforcing particles is 0.03. Mu.m, and the preferred upper limit is 0.5. Mu.m.
In the above-mentioned element 4, the lower limit of the specific surface area of the outer reinforcing particles is more preferably 10m 2/g, and the upper limit is more preferably 500m 2/g. If the specific surface area is more than 500m 2/g, the interaction between the outside reinforcing particles and the outside adhesive molecules becomes saturated, and an increase in the breaking strength of the outside adhesive layer 5R is less likely to be observed, so that the specific surface area is preferably 500m 2/g or less. A more preferred upper limit is 450m 2/g.
When the tensile elongation at break of the cured film of the outer adhesive composition containing the outer reinforcing agent (i.e., the outer adhesive composition containing the outer adhesive and the outer reinforcing agent) is L2, and the tensile elongation at break of the cured film of the outer adhesive composition containing no outer reinforcing agent (i.e., the outer adhesive composition containing the outer adhesive and no outer reinforcing agent) is L2 0, L2 preferably satisfies the following relational expression 2.
15% Or less of { (L2-L2 0)/L20 } ×100% or less of 250% or less of … (formula 2).
By satisfying the above-described relation 2 with L2, the outer adhesive layer 5R has high followability to the deformation of the metal foil layer 2 in the packaging material 1B. Therefore, the puncture strength of the packaging material 1B can be more reliably improved, and the molding processability of the packaging material 1B can be more reliably improved.
In the above-mentioned relational expression 2, the { (L2-L2 0)/L20 } ×100% as the intermediate side thereof means an improvement rate Δl2 (i.e., Δl2= { (L2-L2 0)/L20 } ×100%) in tensile elongation at break of the cured film of the outer adhesive composition (outer adhesive layer 5R) achieved by containing the outer reinforcing agent), and this improvement rate Δl2 is particularly preferably in the range of 20% to 230%, and further, Δl2 is very preferably in the range of 50% to 230%.
In the outer reinforcing agent (outer reinforcing particles), the functional group may be added to the outer adhesive by a silane-based or titanium-based coupling agent treatment or a surface treatment with a synthetic polymer or the like, and in this case, the surface activity of the outer reinforcing agent can be increased, thereby increasing the interfacial adhesion between the outer reinforcing agent and the outer adhesive.
When the outer reinforcing agent is dispersed in the outer adhesive in order to contain the outer reinforcing agent in the outer adhesive, it is preferable to disperse the outer reinforcing agent by using a dispersing machine, and a dispersing agent such as a surfactant may be used in the dispersing.
The method of dispersing the outer reinforcing agent in the outer adhesive is not limited, and may be preferably the same method as the above-described dispersing method of the inner reinforcing agent in the inner adhesive.
For example, when an outer adhesive based on a two-part curable polyester urethane resin is used as the outer adhesive, a paint containing the same types of polyester resin (paint resin) and ethyl acetate (paint solvent) as the main agent of the outer adhesive is prepared, an outer reinforcing agent and an auxiliary agent are added to the paint, and the mixture is kneaded and dispersed by a dispersing machine, whereby the outer reinforcing agent is uniformly dispersed in the paint, and an ink containing the outer reinforcing agent at a high concentration (also referred to as an "ink containing the outer reinforcing agent at a high concentration") is prepared.
Then, the ink is added to the main agent of the outer adhesive so that the content of the outer reinforcing agent becomes a predetermined ratio, and the outer reinforcing agent is uniformly mixed and dispersed, whereby the generation of 2-time aggregated particles of the outer reinforcing agent can be reliably suppressed from each other, and the outer reinforcing agent can be reliably uniformly dispersed in the main agent of the outer adhesive. Thus, a base agent of an external adhesive having excellent dispersibility of the external reinforcing agent can be obtained, in which sedimentation of the external reinforcing agent does not occur even after the external reinforcing agent is added to the base agent and left for several months.
In this ink, the preferable blending ratio of the resin for paint, the solvent for paint, the external reinforcing agent and the auxiliary agent is the same as in the case of the ink containing the high-concentration internal reinforcing agent.
The content of the external reinforcing agent is preferably in the range of 2 to 10 mass% relative to the total amount of the external reinforcing agent and the main agent of the external adhesive. In detail, the content refers to the solid content. The following is the same.
The outer adhesive layer 5R is preferably provided between the metal foil layer 2 and the heat-resistant resin layer 3 in a coating amount in the range of 2g/m 2～10g/m2. Further, the content of the outer reinforcing agent in the outer adhesive layer 5R is preferably in the range of 0.2g/m 2～1.0g/m2. By setting the coating amount of the outer adhesive layer 5R within the above-described range and the content of the outer reinforcing agent within the above-described range, the breaking strength and breaking elongation of the outer adhesive layer 5R are reliably improved. Therefore, the puncture strength of the packaging material 1B can be reliably improved, and the molding processability of the packaging material 1B can be reliably improved. The coating amount of the outer adhesive layer 5R is specifically the solid content coating amount, and the content of the outer reinforcing agent is specifically the solid content. The following is the same.
The lower limit of the coating amount of the outer adhesive layer 5R is more preferably 4g/m 2, and the upper limit is more preferably 9g/m 2. The more preferable lower limit of the content of the above-mentioned outer reinforcing agent is 0.2g/m 2, and the more preferable upper limit is 0.7g/m 2.
In embodiment 3 shown in fig. 3, the outer adhesive layer 5R of the packaging material 1C contains an outer reinforcing agent, and specifically, is formed of a cured film of an outer adhesive composition containing an outer adhesive and an outer reinforcing agent, that is, a cured film of an outer adhesive composition containing an outer reinforcing agent.
The packaging material 1C further includes a matte coating layer 7 formed in a laminated state on the outer surface of the heat-resistant resin layer 3.
(Matte coating)
The matte coating 7 is a layer for imparting good slidability to the outer surface 1b of the packaging material 1C and improving the molding processability of the packaging material 1C.
The kind of the matte coating 7 is not limited, and for example, the matte coating 7 is formed of a cured film of a resin composition containing inorganic particles and organic particles dispersed in a heat-resistant resin component. Among them, the matte coating 7 is preferably formed of a cured film of a resin composition containing 20 to 40 mass% of inorganic particles having a number average particle diameter of 1 to 10 μm and containing 5 to 15 mass% of organic particles having a number average particle diameter of 5 to 15 μm in a two-component curable heat resistant resin.
As the heat-resistant resin, for example, at least one selected from the group consisting of acrylic resins, epoxy resins, polyester resins, urethane resins, polyolefin resins, and fluorine resins can be used. In particular, as the heat-resistant resin, a fluorine-based resin based on tetrafluoroethylene or a vinyl fluoride-vinyl ether copolymer (Fluoroethylene-VINYL ETHER copolymer) is preferably used in view of excellent heat resistance and chemical resistance.
The kind of inorganic particles in the matte coating 7 is not limited, and as the inorganic particles, for example, particles of at least one kind selected from the group consisting of silica, alumina, calcium oxide, calcium carbonate, calcium sulfate, barium sulfate, and calcium silicate can be used, and among these, silica particles are preferably used.
The kind of the organic particles in the matte coating 7 is not limited, and at least one selected from the group consisting of polyethylene wax, polytetrafluoroethylene wax, acrylic resin particles, urethane resin particles, polyethylene resin particles, and polystyrene resin particles can be used as the organic particles (organic beads). Among them, polyethylene wax, polytetrafluoroethylene wax and polyethylene resin particles are preferably used.
The formation of the matte coating 7 can be performed, for example, by: the matte coating composition containing the inorganic particles and/or organic particles and the heat-resistant resin is applied in a layer form to the outer surface of the heat-resistant resin layer 3, and cured.
The thickness of the matte coating 7 after curing (drying) is preferably in the range of 0.5 μm to 5 μm. By setting the thickness to 0.5 μm or more, the slidability of the outer surface 1b of the packaging material 1C is reliably improved. By setting the thickness to 5 μm or less, the manufacturing cost of the packaging material 1C can be reliably reduced. Particularly preferred thicknesses are in the range of 1 μm to 3 μm.
The gloss value of the surface (outer surface) of the matte coating layer 7 is a measured value of 60 ° reflectance angle based on JIS (japanese industrial standard) Z8741, and is preferably set in the range of 1% to 15%. This gloss value can be measured at a reflection angle of 60 ° using, for example, a gloss meter "micro-TRI-gloss-s" manufactured by BYK corporation.
The time period of the step of forming the matte coating 7 is not limited, but the step of forming the matte coating is preferably performed after the step of bonding the heat-resistant resin layer 3 to the metal foil layer 2 via the outer adhesive layer 5R.
In embodiment 4 shown in fig. 4, the outer adhesive layer 5 of the packaging material 1D does not contain an outer reinforcing agent, and is formed of a cured film of an outer adhesive composition that does not contain an outer reinforcing agent.
The packaging material 1D further includes a matte coating layer 7 formed in a laminated state on the outer surface of the heat-resistant resin layer 3. The constitution of the matte coating 7 is, for example, the same as that of the matte coating 7 of embodiment 3 (fig. 3).
The packaging material 1D further includes a black colored layer 8 formed in a laminated state on the inner surface of the heat-resistant resin layer 3, and specifically, the black colored layer 8 is provided between the outer adhesive layer 5 and the heat-resistant resin layer 3.
(Black colored layer)
The black coloring layer 8 is a layer for masking the color and luster of the metal foil layer 2 on the outer surface 1b of the packaging material 1D.
The composition of the black colored layer 8 is not limited, but the black colored layer 8 preferably contains Carbon Black (CB), diamine, polyol, and a curing agent. However, the present invention is not limited to such a configuration of the black coloring layer 8.
The content of carbon black in the black colored layer 8 is not limited, and may preferably be in the range of 15 to 60 mass%. The total content of diamine, polyol and curing agent in the black coloring layer 8 is not limited, and may preferably be in the range of 40 to 85 mass%. Among them, the content of carbon black is preferably in the range of 20 to 50 mass%. In detail, the content of each of them means the solid content. The following is the same.
The thickness of the black colored layer 8 is not limited, and may be preferably in the range of 1 μm to 4 μm. By setting the thickness to 1 μm or more, the color and luster of the metal foil layer 2 can be reliably masked.
The method for forming the black colored layer 8 is not limited, and examples thereof include gravure printing, reverse roll coating, and lip roll coating.
The particle diameter of the carbon black is not limited, and carbon black having a number average particle diameter in the range of 0.01 μm to 3 μm is preferably used as the carbon black.
The type of diamine is not limited, and one or two or more selected from the group consisting of ethylenediamine, dimer diamine (DIMER DIAMINE), 2-hydroxyethyl ethylenediamine, 2-hydroxyethyl propylenediamine, dicyclohexylmethane diamine, and 2-hydroxyethyl propylenediamine may be used as the diamine.
The type of the polyol is not limited, and one or more selected from the group consisting of polyurethane polyols, polyester polyols and polyether polyols are preferably used as the polyol.
The type of the curing agent in the black colored layer 8 is not limited, and examples thereof include isocyanate compounds. As the isocyanate compound, for example, various isocyanate compounds of aromatic, aliphatic, and alicyclic systems can be used. Specific examples thereof include Toluene Diisocyanate (TDI), diphenylmethane diisocyanate, hexamethylene Diisocyanate (HDI) and isophorone diisocyanate.
In embodiment 5 shown in fig. 5, the outer adhesive layer 5R of the packaging material 1E contains an outer reinforcing agent, and specifically, is formed of a cured film of an outer adhesive composition containing an outer adhesive and an outer reinforcing agent, that is, a cured film of an outer adhesive composition containing an outer reinforcing agent.
The packaging material 1E further includes a matte coating layer 7 formed in a laminated state on the outer surface of the heat-resistant resin layer 3. The constitution of the matte coating 7 is, for example, the same as that of the matte coating 7 of embodiment 3 (fig. 3).
The packaging material 1E further includes a black colored layer 8 formed in a laminated state on the inner surface of the heat-resistant resin layer 3, and specifically, the black colored layer 8 is provided between the outer adhesive layer 5R and the heat-resistant resin layer 3. The configuration of the black colored layer 8 is, for example, the same as that of the black colored layer 8 of embodiment 4 (fig. 4).
While the embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and various modifications may be made without departing from the gist of the present invention.
Examples
Specific examples and comparative examples of the present invention are shown below. However, the present invention is not limited to the following examples.
In examples 1 to 10 and comparative examples 1 to 4 below, aluminum foils of the same material were used as the metal foil layer 2. The material is aluminum alloy A8079 defined in JIS H4160. The thickness of the whole aluminum foil was 35 μm. Further, chemical conversion coatings 2a obtained by the same chemical conversion treatment as in example 1 were formed on the inner and outer surfaces of all aluminum foils, respectively.
In examples 1 to 10 and comparative examples 1 to 4, the same single-layer biaxially stretched nylon (ONY) film was used as the heat-resistant resin layer 3. The thickness of the whole film was 15. Mu.m. In addition, corona treatment is performed in advance on the inner surfaces of all films (i.e., the surfaces of the films that are bonded to the metal foil layer 2) in order to improve wettability with the outside adhesive composition. In examples 7 to 10 and comparative examples 3 to 4, matte coatings 7 having the same composition were formed on the outer surfaces of the films, and in examples 8 to 10 and comparative examples 3 to 4, black colored layers 8 having the same composition were formed on the inner surfaces of the films.
In examples 1 to 10 and comparative examples 1 to 4 below, the same unstretched three-layer co-extruded polypropylene (CPP) film was used as the heat-fusible resin layer 4. The thickness of the whole film was 30. Mu.m, and the layer thickness ratio was rPP: bPP: rpp=1: 8:1. in addition, corona treatment is performed in advance on the outer surfaces of all films (i.e., the contact surfaces with the metal foil layer 2 in the films) in order to improve wettability with the inside adhesive composition.
Example 1 ]
Chemical conversion coatings 2a are formed on the inner and outer surfaces of the aluminum foil layer 2. The chemical conversion coating 2a is formed by applying a chemical conversion treatment liquid composed of polyacrylic acid, a trivalent chromium compound, water, and alcohol to the inner and outer surfaces of the aluminum foil, and then drying the aluminum foil at 150 ℃. The amount of chromium deposited on one surface of the aluminum foil was 10mg/m 2, and the thickness of each chemical conversion coating 2a was 0.01. Mu.m.
As the heat-resistant resin layer 3, the biaxially stretched nylon (ONY) film described above was prepared. The film had a TD hot water shrinkage of 2.7%, an MD hot water shrinkage of 2.0%, a difference in hot water shrinkage between TD and MD (TD-MD) of 0.7%, a TD elastic modulus of 1.7GPa, an MD elastic modulus of 2.7GPa, a TD breaking strength of 361MPa, an MD breaking strength of 280MPa, and a number average molecular weight of 25,000.
As the outer adhesive composition constituting the outer adhesive layer 5, an outer adhesive composition containing an outer adhesive and not containing an outer reinforcing agent, that is, an outer adhesive composition containing no outer reinforcing agent was prepared. In the outer adhesive composition, a two-part curable polyester urethane resin is used as the outer adhesive. The method for producing the outside adhesive composition is as follows.
First, a polyester resin (polyester polyol) as a main agent of a two-part curable polyester urethane resin was produced by the following method. Specifically, 30 parts by mole of neopentyl glycol, 30 parts by mole of ethylene glycol, and 40 parts by mole of 1, 6-hexanediol were melted at 80 ℃, and the melt was subjected to polycondensation reaction with 30 parts by mole of adipic acid (having a methylene number of 4) as an aliphatic dicarboxylic acid and 70 parts by mole of isophthalic acid as an aromatic dicarboxylic acid at 210 ℃ for 20 hours while stirring, to thereby obtain a polyester polyol as a main component. The polyester polyol had a number average molecular weight (Mn) of 12,000, a weight average molecular weight (Mw) of 20,500, and a ratio (Mw/Mn) of 1.7. Further, 60 parts by mass of ethyl acetate was added to 40 parts by mass of the polyester polyol, thereby preparing a fluidized polyester polyol resin solution. The hydroxyl value thereof was 2.2mgKOH/g (solution value).
Next, 7.1 parts by mass of an adduct of Toluene Diisocyanate (TDI) (aromatic system) and Trimethylolpropane (TMP) (NCO 13.0 mass%, solid content 75 mass%) as a curing agent was added to 100 parts by mass of the above-described polyester polyol resin solution as a main agent, and 34.1 parts by mass of ethyl acetate was further added thereto, followed by stirring and mixing, thereby producing an outer adhesive composition (i.e., a two-part curable polyester urethane resin) containing no outer reinforcing agent. In the outside adhesive composition, the molar ratio (-NCO)/(OH) of isocyanate functional groups (-NCO) to hydroxyl groups (-OH) of the polyester polyol was 10.
Next, a cured film of the outside adhesive composition was prepared by the following method to evaluate physical properties thereof.
Specifically, the outer adhesive composition was applied to a non-adhesive untreated polypropylene film in a layer-like manner so that the thickness of the composition after drying became 10 μm, the solvent in the composition was dried and evaporated, and then the composition was aged at 60 ℃ until the residual isocyanate was 5 mass% or less, whereby the composition was cured. Then, the cured product was peeled off from the untreated polypropylene film, thereby producing a cured film (thickness: 10 μm) of the outside adhesive composition.
The cured film was cut at a width of 15mm, whereby test pieces were collected. Then, the tensile test was conducted on the test piece, and the tensile breaking strength and the tensile breaking elongation of the test piece were measured, and as a result, the tensile breaking strength was 30MPa and the tensile breaking elongation was 18%.
The tensile test was conducted in accordance with JIS K7161-1:2014 under conditions of a punctuation distance of 50mm and a stretching speed of 100 mm/min. The following is the same.
Next, the outer adhesive composition was applied in a layer form to the outer surface of an aluminum foil at a coating amount of 5.0g/m 2 (more specifically, a solid content coating amount, the same applies hereinafter), the solvent in the composition was dried and evaporated, and then the outer surface of the aluminum foil was bonded to the inner surface of the biaxially stretched nylon (ONY) film as the heat-resistant resin layer 3, and aging was performed at 60 ℃.
Next, as the inner adhesive composition constituting the inner adhesive layer 6R, an inner adhesive composition containing silica particles (SiO 2 particles: number average particle diameter of 0.4 μm, specific surface area of 10m 2/g) as an inner reinforcing agent and an acid-modified polypropylene (PP) adhesive as an inner adhesive, that is, an inner adhesive composition containing silica particles, was prepared. The preparation method of the composition is as follows.
First, 20 parts by mass of acid-modified polypropylene (acid-modified PP) having the same composition as the main agent of the inside adhesive as a paint resin, methylcyclohexane as a paint solvent: methyl ethyl ketone=8 parts by mass: 2 parts by mass of a mixed organic solvent 40 parts by mass, the silica particles as an inner reinforcing agent 35 parts by mass, and an auxiliary agent (dispersant and anti-settling agent) 5 parts by mass were mixed, and the mixture was kneaded and dispersed by a dispersing machine to prepare an ink containing silica particles in high concentration (silica particles content: 35 mass%).
Then, 15 parts by mass of an acid-modified polypropylene resin solution and methylcyclohexane: methyl ethyl ketone=8 parts by mass: a prescribed amount of the ink was added to 85 parts by mass of the mixed organic solvent in 2 parts by mass, and the mixture was mixed and dispersed by a dispersing machine to prepare a main agent of the inside adhesive containing silica particles.
To 100 parts by mass of the main agent, 0.9 parts by mass of a polymer of Hexamethylene Diisocyanate (HDI) as a curing agent (polyfunctional isocyanate compound) was added so that the equivalent ratio (NCO/OH) became 1.8, and the mixture was stirred and mixed to prepare an inside adhesive composition containing silica particles (i.e., an acid-modified polypropylene adhesive containing silica particles). The content of silica particles in the inner adhesive composition (specifically, the solid content and the same shall apply hereinafter) was 4.5 mass%.
Next, a cured film of the inside adhesive composition was prepared by the following method to evaluate the physical properties thereof.
Specifically, the inner adhesive composition was applied to a non-adhesive untreated polypropylene film in a layer-like manner so that the thickness of the composition after drying became 10 μm, the solvent in the composition was dried and evaporated, and then the composition was aged at 40 ℃ until the residual isocyanate was 5 mass% or less, whereby the composition was cured. Then, the cured product was peeled off from the untreated polypropylene film, thereby producing a cured film (thickness: 10 μm) of the inner adhesive composition.
The cured film was cut at a width of 15mm, whereby test pieces were collected. Then, the tensile test was performed on the test piece, and the tensile breaking strength and the tensile breaking elongation L1 of the test piece were measured, and as a result, the tensile breaking strength was 25MPa and the tensile breaking elongation L1 was 172%.
In addition, an inner adhesive composition containing an inner adhesive and not containing silica particles, that is, an inner adhesive composition containing no silica particles was produced in the same manner as the inner adhesive composition described above, without using an ink containing a high concentration of silica particles. Next, a cured film of the inside adhesive composition containing silica particles was produced by the same method as the cured film of the inside adhesive composition.
The cured film was cut at a width of 15mm, whereby test pieces were collected. Then, the tensile test was performed on the test piece, the tensile breaking strength and the tensile breaking elongation L1 0 of the test piece were measured, and the increase in tensile breaking elongation Δl1 (= { (L1-L1 0)/L10 } ×100%) of the cured film of the inner adhesive composition obtained by containing silica particles was calculated, and as a result, Δl1 was 64%.
Next, the silica particle-containing inner adhesive composition was applied in layers to the inner surface of an aluminum foil at a coating amount of 5.5g/m 2 (specifically, solid content coating amount: the same applies hereinafter), the solvent in the composition was dried and evaporated, and then the inner surface of the aluminum foil was bonded to the outer surface of the unstretched three-layer co-extruded polypropylene (CPP) film as the heat-fusible resin layer 4, and aging was performed at 40 ℃. In this case, the content of silica particles in the inner adhesive layer 6R was 0.25g/m 2.
The packaging material was manufactured by the above method.
Example 2]
An outer adhesive composition containing a two-part curable polyester urethane resin used as an outer adhesive of example 1 and silica particles (SiO 2 particles: number average particle diameter: 0.4 μm and specific surface area: 10m 2/g) as an outer reinforcing agent, namely an outer adhesive composition containing silica particles, was prepared by the following method.
First, 20 parts by mass of the polyester polyol of example 1 as a paint resin, 40 parts by mass of ethyl acetate as a paint solvent, 35 parts by mass of the silica particles as an external reinforcing agent, and 5 parts by mass of an auxiliary agent (dispersant and anti-settling agent) were mixed and dispersed by a dispersing machine, whereby an ink containing silica particles at a high concentration (silica particle content: 35 mass%) was prepared.
Next, a predetermined amount of the ink was added to 100 parts by mass of the polyester polyol resin solution of example 1 and 64.4 parts by mass of ethyl acetate, and the mixture was mixed and dispersed by a dispersing machine, thereby producing a main agent of the outside adhesive containing silica particles.
7.1 Parts by mass of an adduct (NCO 13.0% by mass and 75% by mass in solid content) of Toluene Diisocyanate (TDI) (aromatic system) and Trimethylolpropane (TMP) as aromatic isocyanate compounds was added as a curing agent to 100 parts by mass of the main agent, and 34.1 parts by mass of ethyl acetate was further added, followed by stirring and mixing, to thereby prepare an outside adhesive composition containing silica particles. In the outside adhesive composition, the molar ratio (-NCO)/(OH) of isocyanate functional groups (-NCO) to hydroxyl groups (-OH) of the polyester polyol was 10. The silica particles contained in the outside adhesive composition were contained in an amount of 4.9 mass%.
Next, a cured film of the outside adhesive composition was prepared by the following method to evaluate physical properties thereof.
Specifically, the outer adhesive composition was applied to a non-adhesive untreated polypropylene film in a layer-like manner so that the thickness of the composition after drying became 10 μm, the solvent in the composition was dried and evaporated, and then the composition was aged at 60 ℃ until the residual isocyanate was 5 mass% or less, whereby the composition was cured. Then, the cured product was peeled off from the untreated polypropylene film, thereby producing a cured film (thickness: 10 μm) of the outside adhesive composition.
The cured film was cut at a width of 15mm, whereby test pieces were collected. Then, the tensile test was performed on the test piece, and the tensile breaking strength and the tensile breaking elongation L2 of the test piece were measured, and as a result, the tensile breaking strength was 35MPa and the tensile breaking elongation L2 was 42%.
In addition, an outside adhesive composition containing an outside adhesive and containing no silica particles, that is, an outside adhesive composition containing no silica particles was produced by the same method as the outside adhesive composition described above, without using an ink containing a high concentration of silica particles. Next, a cured film of the outside adhesive composition containing silica particles was produced by the same method as the cured film of the outside adhesive composition.
The cured film was cut at a width of 15mm, whereby test pieces were collected. Then, the tensile test was performed on the test piece, the tensile breaking strength and the tensile breaking elongation L2 0 of the test piece were measured, and the increase in tensile breaking elongation Δl2 (= { (L2-L2 0)/L20 } ×100%) of the cured film of the outer adhesive composition obtained by containing silica particles was calculated, and as a result, Δl2 was 133%.
Next, the above-mentioned outside adhesive composition containing silica particles was applied in a layer form to the outer surface of an aluminum foil in an application amount of 5.5g/m 2, the solvent in the composition was dried and evaporated, and then the outer surface of the aluminum foil was bonded to the inner surface of the biaxially stretched nylon (ONY) film as the heat-resistant resin layer 3, and aging was performed at 60 ℃. In this case, the content of silica particles in the outer adhesive layer 5R was 0.27g/m 2.
Next, as the inner adhesive composition constituting the inner adhesive layer 6R, an inner adhesive composition containing silica particles (SiO 2 particles: number average particle diameter of 0.4 μm, specific surface area of 10m 2/g) as an inner reinforcing agent and an acid-modified polypropylene (PP) adhesive as an inner adhesive, that is, an inner adhesive composition containing silica particles, was prepared. The preparation method of the composition is as follows.
First, 20 parts by mass of acid-modified polypropylene having the same composition as the main agent of the inside adhesive as a paint resin and methylcyclohexane as a paint solvent were mixed: methyl ethyl ketone=8 parts by mass: 2 parts by mass of a mixed organic solvent 40 parts by mass, the silica particles as an inner reinforcing agent 35 parts by mass, and an auxiliary agent (dispersant and anti-settling agent) 5 parts by mass were mixed, and the mixture was kneaded and dispersed by a dispersing machine to prepare an ink containing silica particles in high concentration (silica particles content: 35 mass%).
Then, 15 parts by mass of an acid-modified polypropylene resin solution and methylcyclohexane: methyl ethyl ketone=8 parts by mass: a prescribed amount of the ink was added to 85 parts by mass of the mixed organic solvent in 2 parts by mass, and the mixture was mixed and dispersed by a dispersing machine to prepare a main agent of the inside adhesive containing silica particles.
To 100 parts by mass of the main agent, 0.9 parts by mass of a polymer of Hexamethylene Diisocyanate (HDI) as a curing agent (polyfunctional isocyanate compound) was added so that the equivalent ratio (NCO/OH) became 1.8, and the mixture was mixed and stirred to prepare an inside adhesive composition containing silica particles (i.e., an acid-modified polypropylene adhesive containing silica particles). The content of silica particles in the inner adhesive composition was 3.5 mass%.
Next, a cured film of the inside adhesive composition containing silica particles was prepared by the following method to evaluate the physical properties thereof.
Specifically, the inner adhesive composition was applied to a non-adhesive untreated polypropylene film in a layer-like manner so that the thickness of the composition after drying became 10 μm, the solvent in the composition was dried and evaporated, and then the composition was aged at 40 ℃ until the residual isocyanate was 5 mass% or less, whereby the composition was cured. Then, the cured product was peeled off from the untreated polypropylene film, thereby producing a cured film (thickness: 10 μm) of the inner adhesive composition.
The cured film was cut at a width of 15mm, whereby test pieces were collected. Then, the tensile test was performed on the test piece, and the tensile breaking strength and the tensile breaking elongation L1 of the test piece were measured, and as a result, the tensile breaking strength was 23MPa and the tensile breaking elongation L1 was 165%.
In addition, an inner adhesive composition containing an inner adhesive and not containing silica particles, that is, an inner adhesive composition containing no silica particles was produced in the same manner as the inner adhesive composition described above, without using an ink containing a high concentration of silica particles. Next, a cured film of the inside adhesive composition containing silica particles was produced by the same method as the cured film of the inside adhesive composition.
The cured film was cut at a width of 15mm, whereby test pieces were collected. Then, the tensile test was performed on the test piece, the tensile breaking strength and the tensile breaking elongation L1 0 of the test piece were measured, and the increase in tensile breaking elongation Δl1 of the cured film of the inner adhesive composition obtained by containing silica particles was calculated, and as a result, Δl1 was 57%.
Next, the above-mentioned silica particle-containing inner adhesive composition was applied in a layer form to the inner surface of an aluminum foil in an application amount of 6.5g/m 2, the solvent in the composition was dried and evaporated, and then the inner surface of the aluminum foil was bonded to the outer surface of the above-mentioned unstretched three-layer co-extruded polypropylene (CPP) film as the heat-fusible resin layer 4, and aging was performed at 40 ℃. In this case, the content of silica particles in the inner adhesive layer 6R was 0.23g/m 2.
The packaging material was manufactured by the above method.
Example 3 ]
In example 1, a tensile test of a cured film of each adhesive composition was performed in the same manner as in example 1 except that the content of silica particles as the inner reinforcing agent was 9.0 mass% and the coating amount of the inner adhesive composition was 12.5g/m 2, and a packaging material was produced. In this case, the content of silica particles in the inner adhesive layer 6R was 1.13g/m 2.
The values of the tensile elongation at break and the increase rate Δl2 thereof measured and calculated by the tensile test of the cured film of the outer adhesive composition are shown in the column of the "cured film" of the "outer adhesive layer" in table 1, and the values of the tensile elongation at break and the increase rate Δl1 thereof measured and calculated by the tensile test of the cured film of the inner adhesive composition are shown in the column of the "cured film" of the "inner adhesive layer" in table 1. The same applies to examples 4 to 10 and comparative examples 1 to 4.
Example 4 ]
In example 2, a tensile test of a cured film of each adhesive composition was performed in the same manner as in example 2 except that the outside reinforcing agent was calcium carbonate particles (CaCO 3 particles: number average particle diameter: 0.03 μm, specific surface area: 130m 2/g) and the content of calcium carbonate particles in the outside adhesive composition was 4.5 mass%, the coating amount of the outside adhesive composition was 5.5g/m 2, and the inside reinforcing agent was calcium carbonate particles (CaCo 3 particles: number average particle diameter: 130m 2/g) and the content of calcium carbonate particles in the inside adhesive composition was 5.0 mass%, and the coating amount of the inside adhesive composition was 5.0g/m 2, and a packaging material was produced. In this case, the content of calcium carbonate particles in the outer adhesive layer 5R was 0.25g/m 2, and the content of calcium carbonate particles in the inner adhesive layer 6R was 0.25g/m 2.
Example 5]
In example 1, a tensile test of a cured film of an inner adhesive composition was performed and a packaging material was produced in the same manner as in example 1, except that the inner reinforcing agent was calcium carbonate particles (CaCO 3 particles: number average particle diameter: 1.0 μm, specific surface area: 3.0m 2/g), the content of calcium carbonate particles in the inner adhesive composition was 2.5 mass%, and the coating amount of the inner adhesive composition was 8.5g/m 2. In this case, the content of calcium carbonate particles in the inner adhesive layer 6R was 0.21g/m 2.
Example 6]
In example 1, a tensile test of a cured film of an inner adhesive composition was performed and a packaging material was produced in the same manner as in example 1, except that the inner reinforcing agent was acrylic resin particles (number average particle diameter: 2.0 μm, specific surface area: 2.5m 2/g), the content of acrylic resin particles in the inner adhesive composition was 4.0 mass%, and the coating amount of the inner adhesive composition was 5.5g/m 2. In this case, the content of acrylic resin particles in the inner adhesive layer 6R was 0.22g/m 2.
Example 7 ]
In example 1, a tensile test of a cured film of the outside adhesive composition was performed in the same manner as in example 1 except that the outside reinforcing agent was carbon black (CB: number average particle diameter: 0.05 μm, specific surface area: 45m 2/g), the content of carbon black in the outside adhesive composition was 4.8 mass%, and the coating amount of the outside adhesive composition was 6.5g/m 2, and the outside surface of the aluminum foil was bonded to the inner surface of the biaxially stretched nylon film (heat-resistant resin layer 3), and the composition was cured by aging at 60 ℃. In this case, the content of carbon black in the outer adhesive layer 5R was 0.31g/m 2.
Next, an inner adhesive composition containing silica particles was produced in which the inner adhesive (main agent) was an acrylic polyol (which was one of the acrylic adhesives (main agent)), the inner reinforcing agent was silica particles (SiO 2 particles: number average particle diameter: 0.2 μm, specific surface area: 25m 2/g), and the content of silica particles in the inner adhesive composition was 7.5 mass%. Then, the inner adhesive composition was applied to the inner surface of an aluminum foil in an application amount of 5.5g/m 2, the solvent in the composition was dried and evaporated, and then the inner surface of the aluminum foil was bonded to the outer surface of an unstretched three-layer co-extruded polypropylene film (heat-fusible resin layer 4), and aging was performed at 40 ℃. In this case, the content of silica particles in the inner adhesive layer 6R was 0.41g/m 2. In addition, a tensile test of a cured film of the inside adhesive composition was performed in the same manner as in example 1.
Next, a matte coating 7 was formed on the outer surface of the biaxially stretched nylon film (heat-resistant resin layer 3) by the following method.
Specifically, 70 parts by mass of a vinyl fluoride-acrylic acid ester copolymer (Fluoroethyle ne-ACRYLIC ACID ESTER copolymer) as a heat-resistant resin, 10 parts by mass of barium sulfate particles (number average particle diameter: 2.0 μm) and silica particles (number average particle diameter: 1.0 μm) as inorganic particles, 5 parts by mass of polytetrafluoroethylene wax (number average particle diameter: 10.0 μm) as a wax, and 5 parts by mass of polyethylene resin particles (number average particle diameter: 5.0 μm) as organic particles (organic beads) were mixed to prepare a matte coating composition. Then, the matte coating composition was applied to the outer surface of the biaxially stretched nylon film in a layer-like manner so that the thickness after drying became 2 μm, and left to stand at 40℃for 5 days for aging, whereby a matte coating 7 (thickness: 2 μm) was formed on the outer surface of the biaxially stretched nylon film.
The packaging material was manufactured by the above method.
Example 8 ]
The black colored layer 8 was formed on the inner surface of the biaxially stretched nylon film (heat-resistant resin layer 3) by the following method.
That is, to a resin composition having a total content of ethylenediamine, polyester polyol, and toluene diisocyanate curing agent of 75 mass%, carbon Black (CB) having a number average particle diameter of 0.4 μm was added so that the content of carbon black became 25 mass%, and uniformly mixed and dispersed, thereby preparing a black ink. Then, the black ink was applied in layers to the inner surface of the biaxially stretched nylon film by a gravure roll, and dried. Further, the mixture was left at 40℃for 1 day, whereby the crosslinking reaction was carried out while drying. Thus, a black colored layer 8 (thickness: 3 μm) was formed on the inner surface of the biaxially stretched nylon film.
Next, the same outer adhesive composition as in example 1 was applied in a layer form to the outer surface of an aluminum foil in an application amount of 5.0g/m 2, the solvent in the composition was dried and evaporated, and then the outer surface of the aluminum foil was bonded to the inner surface of a biaxially stretched nylon film (i.e., black colored layer 8), and aging was performed at 60 ℃.
Next, an acrylic resin adhesive composition (i.e., an inner adhesive composition containing carbon black) containing the same acrylic adhesive as in example 7 and carbon black (CB: number average particle diameter of 0.01 μm, specific surface area of 420m 2/g) as an inner reinforcing agent at a carbon black content of 8.0 mass% was applied in a layer-wise manner to the inner surface of an aluminum foil in a coating amount of 6.0g/m 2, and the solvent in the composition was dried and evaporated, and then the inner surface of the aluminum foil was bonded to the outer surface of an unstretched three-layer co-extruded polypropylene film (heat-fusible resin layer 4), and aged at 40 ℃. In this case, the content of carbon black in the inner adhesive layer 6R was 0.48g/m 2. In addition, a tensile test of a cured film of the inside adhesive composition was performed in the same manner as in example 1.
Next, a matte coating layer 7 was formed on the outer surface of the biaxially stretched nylon film by the same method as in example 7, thereby producing a packaging material.
Example 9]
A black colored layer 8 (thickness of 3 mm) was formed on the inner surface of the biaxially stretched nylon film (heat-resistant resin layer 3) by the same method as in example 8 using the same black ink as in example 8.
Next, a polyester urethane resin adhesive composition (i.e., an outer adhesive composition containing silica particles) containing the same two-component curable polyester urethane resin as in example 1 as an outer adhesive and silica particles (SiO 2 particles: number average particle diameter 0.4 μm, specific surface area 10m 2/g) as an outer reinforcing agent in such a manner that the content of silica particles became 4.3 mass%, was applied to the outer surface of an aluminum foil in a layer-like manner in a coating amount of 6.5g/m 2, the solvent in the composition was dried and evaporated, and then the outer surface of the aluminum foil was bonded to the inner surface of a biaxially stretched nylon film (i.e., black colored layer 8), and the composition was aged at 60 ℃. In this case, the content of silica particles in the outer adhesive layer 5R was 0.28g/m 2. In addition, a tensile test of a cured film of the outside adhesive composition was performed in the same manner as in example 1.
Next, an acrylic resin adhesive composition (i.e., an inner adhesive composition containing carbon black) containing the same acrylic adhesive as in example 7 and carbon black (CB: number average particle diameter of 0.01 μm, specific surface area of 420m 2/g) as an inner reinforcing agent at a carbon black content of 3.0 mass% was applied to the inner surface of an aluminum foil in a layer-wise manner in a coating amount of 6.5g/m 2, and the solvent in the composition was dried and evaporated, and then the inner surface of the aluminum foil was bonded to the outer surface of an unstretched three-layer co-extruded polypropylene film (heat-fusible resin layer 4), and aged at 40 ℃. In this case, the content of carbon black in the inner adhesive layer 6R was 0.20g/m 2. In addition, a tensile test of a cured film of the inner adhesive composition was performed in the same manner as in example 1.
Next, a matte coating layer 7 was formed on the outer surface of the biaxially stretched nylon film by the same method as in example 7, thereby producing a packaging material.
Example 10 ]
A black colored layer 8 (thickness of 3 mm) was formed on the inner surface of the biaxially stretched nylon film (heat-resistant resin layer 3) by the same method as in example 8 using the same black ink as in example 8.
Next, the same outer adhesive composition as in example 1 was applied in a layer form to the outer surface of an aluminum foil in an application amount of 5.0g/m 2, the solvent in the composition was dried and evaporated, and then the outer surface of the aluminum foil was bonded to the inner surface of a biaxially stretched nylon film (i.e., black colored layer 8), and aging was performed at 60 ℃.
Next, an acrylic resin adhesive composition (i.e., an inner adhesive composition containing calcium carbonate particles) containing the same acrylic adhesive as in example 7 and calcium carbonate particles (Ca CO 3 particles: number average particle diameter 0.02 μm and specific surface area 210m 2/g) as an inner reinforcing agent at a calcium carbonate particle content of 9.0 mass% was applied to the inner surface of an aluminum foil in a coating amount of 7.5g/m 2 and in a layer form, the solvent in the composition was dried and evaporated, and then the inner surface of the aluminum foil was bonded to the outer surface of an unstretched three-layer coextruded polypropylene film (heat-fusible resin layer 4) and aged at 40 ℃. In this case, the content of calcium carbonate particles in the inner adhesive layer 6R was 0.68g/m 2. In addition, a tensile test of a cured film of the inner adhesive composition was performed in the same manner as in example 1.
Next, a matte coating layer 7 was formed on the outer surface of the biaxially stretched nylon film by the same method as in example 7, thereby producing a packaging material.
Comparative example 1 ]
In example 1, a tensile test of a cured film of each adhesive composition was performed and a packaging material was produced in the same manner as in example 1, except that the inside reinforcing agent was not contained in the inside adhesive layer.
Comparative example 2 ]
In example 1, a tensile test of a cured film of the inside adhesive composition was performed and a packaging material was produced in the same manner as in example 1, except that the inside reinforcing agent was silica particles (SiO 2 particles: number average particle diameter: 4.0 μm, specific surface area: 1.0m 2/g), the content of silica particles in the inside adhesive composition containing silica particles was 3.5 mass%, and the coating amount of the inside adhesive composition was 6.5g/m 2. In this case, the content of silica particles in the inner adhesive layer 6R was 0.23g/m 2.
Comparative example 3 ]
In example 8, a tensile test of a cured film of the inner adhesive composition was performed and a packaging material was produced in the same manner as in example 8, except that the inner reinforcing agent was not contained in the inner adhesive layer and the coating amount of the inner adhesive layer was set to 6.5g/m 2.
Comparative example 4 ]
In example 8, a tensile test of a cured film of the inner adhesive composition was performed and a packaging material was produced in the same manner as in example 8, except that the inner reinforcing agent was calcium carbonate particles (CaCO 3 particles: number average particle diameter: 3.0 μm, specific surface area: 0.8m 2/g), the content of calcium carbonate particles in the inner adhesive composition containing calcium carbonate particles was 4.5% by mass, and the coating amount of the inner adhesive composition was 4.5g/m 2. In this case, the content of calcium carbonate particles in the inner adhesive layer 6R was 0.20g/m 2.
(Method for measuring specific surface area)
Here, in examples 1 to 10 and comparative examples 1 to 4, the specific surface areas of the inner reinforcing agent (inner reinforcing particles) and the outer reinforcing agent (outer reinforcing particles) were set in accordance with JI S Z8330:2013 by the following method.
Specifically, the reinforcing agent was weighed, and the specific surface area of the reinforcing agent was measured by the BET multipoint method after the weighed reinforcing agent was subjected to pretreatment by a gas adsorption type pore distribution measuring instrument (NOVA 4200e: SEISHIN ENTERPRISE Co., ltd.) using an N 2 gas purging method (gas flow rate: 20cm 3/min, gas pressure: 20kPa, heating temperature: 200 ℃ C., treatment time: 2 hours).
(Determination of number average particle diameter)
The number average particle diameter of the inner reinforcing particles and the outer reinforcing particles was determined by the following method.
A suspension of inner reinforcing particles was prepared, and the particle size distribution of the inner reinforcing particles was measured using a laser diffraction/scattering particle size distribution measuring apparatus (PARTICA LA-960V2: horiba, inc.) for the suspension, and the number average particle size of the inner reinforcing particles was obtained. The number average particle diameter of the outer reinforcing particles was also obtained in the same manner as the above.
(Evaluation of packaging Material)
The puncture strength and the molding processability were measured for each of the packaging materials of examples 1 to 10 and comparative examples 1 to 4. The results are shown in tables 1 and 2 below.
TABLE 1
TABLE 2
< Puncture Strength >
The puncture strength of the packaging material is according to JIS Z1707: 2019. The puncture strength test at this time was performed in accordance with the following steps 1 to 2.
Step 1: a test piece collected from a packaging material was fixed with a jig, a semicircular needle having a diameter of 1.0mm and a tip shape radius of 0.5mm was punched from the heat-resistant resin layer side at a test speed of 50.+ -.5 mm/min, and the maximum force (N) until penetration of the needle was measured.
Step 2: the number of test pieces collected from the packaging material was set to 5 or more, and the test pieces were collected so as to be averaged over the total width of the packaging material.
In the "puncture strength" column in tables 1 and 2, the meaning of the symbols is as follows. The excellent and o were regarded as acceptable in the puncture strength test.
And (3) the following materials: puncture strength of greater than 19N
O: the puncture strength is more than 16N and less than 19N
X: the puncture strength is 16N or less.
< Test of molding processability >
The punch shape is prepared: 33mm×54mm, corner R of punch: 2mm, punch shoulder R:1.3mm, die shoulder R in die shape: a press machine was manufactured by AMAD A Co., ltd. Of a 1mm mold.
Then, a rectangular test piece having a longitudinal dimension of 100mm×a transverse dimension of 125mm was collected from the packaging material, and the test piece was subjected to deep drawing forming processing using the press machine, thereby forming a formed processed product.
The presence or absence of pinholes and cracks at the corners of the molded article was confirmed by a transmitted light method in a darkroom, and the "maximum molding depth (mm)" at which pinholes and cracks were not generated was examined, and the molding processability of the packaging material was evaluated. The evaluation criteria are as follows. The excellent and the o were regarded as acceptable in the molding processability test.
And (3) the following materials: no crack or pinhole when the maximum molding depth is 7mm or more
O: no crack or pinhole when the maximum molding depth is 6mm or more and less than 7mm
X: cracks and/or pinholes are present at a maximum forming depth of less than 6 mm.
From tables 1 and 2, it was confirmed that the packaging materials of examples 1 to 10 using the inner reinforcing particles satisfying the above requirements 1 and 2 had high puncture strength.
Further, it was confirmed that, as in examples 1, 2, and 4 to 10, when the coating amount of the inner adhesive layer 6R was in the range of 2g/m 2～10g/m2 and the content of the inner reinforcing agent in the inner adhesive layer 6R was in the range of 0.2g/m 2～1.0g/m2, the improvement rate Δl1 of the tensile elongation at break was large, and therefore the molding processability of the packaging material was high.
The present application claims the priority of Japanese patent application No. 2022-169759 filed on 10/24/2022 and Japanese patent application No. 2023-145339 filed on 9/2023, the disclosures of which are directly made part of the present application.
The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such equivalents of the features shown and described herein, it being recognized that various modifications are possible within the scope of the invention claimed.
Industrial applicability
The invention can be used in packaging materials for molding processing, packaging cases and power storage devices.
Claims (7)
1. A packaging material for molding comprising a metal foil layer, a heat-resistant resin layer disposed on the outer surface side of the metal foil layer, and a heat-fusible resin layer disposed on the inner surface side of the metal foil layer, wherein an outer adhesive layer is provided between the metal foil layer and the heat-resistant resin layer, and an inner adhesive layer is provided between the metal foil layer and the heat-fusible resin layer,
The inner adhesive layer contains an inner reinforcing agent,
As the inner reinforcing agent, inner reinforcing particles satisfying the following requirements 1 and 2 are used,
Element 1: the number average particle diameter of the inner reinforcing particles is in the range of 0.01 to 3 [ mu ] m;
Element 2: the specific surface area of the inside reinforcing particles is 1m 2/g or more.
2. The molding packaging material according to claim 1, wherein the inner adhesive layer is formed of a cured film of an inner adhesive composition containing an inner adhesive and the inner reinforcing agent,
The tensile elongation at break of the cured film of the inside adhesive composition was set to L1,
When the tensile elongation at break of the cured film of the inner adhesive composition containing the inner adhesive and not containing the inner reinforcing agent is L1 0,
The L1 satisfies the following relation 1,
15% Or less of { (L1-L1 0)/L10 } ×100% or less of 250% or less of … (formula 1).
3. The molding packaging material according to claim 1 or 2, wherein the inner adhesive layer is provided between the metal foil layer and the heat-fusible resin layer in a coating amount in a range of 2g/m 2～10g/m2,
The content of the inner reinforcing agent in the inner adhesive layer is in the range of 0.2g/m 2～1.0g/m2.
4. The molding packaging material according to claim 1 or2, wherein the outer adhesive layer contains an outer reinforcing agent,
As the outer reinforcing agent, outer reinforcing particles satisfying the following requirements 3 and 4 are used,
Element 3: the number average particle diameter of the outer reinforcing particles is in the range of 0.01 to 3 [ mu ] m;
Element 4: the specific surface area of the outer reinforcing particles is more than 1m 2/g.
5. The molding packaging material according to claim 4, wherein the outer adhesive layer is formed of a cured film of an outer adhesive composition containing an outer adhesive and the outer reinforcing agent,
The tensile elongation at break of the cured film of the outside adhesive composition was set to L2,
When the tensile elongation at break of the cured film of the outside adhesive composition containing the outside adhesive and not containing the outside reinforcing agent is L2 0,
The L2 satisfies the following relation 2,
15% Or less of { (L2-L2 0)/L20 } ×100% or less of 250% or less of … (formula 2).
6. A package case formed by subjecting the packaging material for forming according to any one of claims 1 to 5 to deep drawing forming or drawing forming.
7. An electricity storage device comprising an electricity storage device body and a package case for packaging the electricity storage device body,
The package case according to claim 6 is provided as the package case.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-169759 | 2022-10-24 | ||
| JP2023145339A JP2024062383A (en) | 2022-10-24 | 2023-09-07 | Packaging materials for molding, packaging cases and power storage devices |
| JP2023-145339 | 2023-09-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117922119A true CN117922119A (en) | 2024-04-26 |
Family
ID=90752433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311379629.7A Pending CN117922119A (en) | 2022-10-24 | 2023-10-23 | Packaging material for molding processing, packaging case, and electricity storage device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117922119A (en) |
-
2023
- 2023-10-23 CN CN202311379629.7A patent/CN117922119A/en active Pending
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