WO2024084775A1 - 冷間成形用二軸延伸ポリアミドフィルム - Google Patents

冷間成形用二軸延伸ポリアミドフィルム Download PDF

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Publication number
WO2024084775A1
WO2024084775A1 PCT/JP2023/027978 JP2023027978W WO2024084775A1 WO 2024084775 A1 WO2024084775 A1 WO 2024084775A1 JP 2023027978 W JP2023027978 W JP 2023027978W WO 2024084775 A1 WO2024084775 A1 WO 2024084775A1
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Prior art keywords
film
polyamide
biaxially oriented
stretching
mass
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PCT/JP2023/027978
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English (en)
French (fr)
Japanese (ja)
Inventor
昇 玉利
彩芽 永坂
考道 後藤
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to JP2024529215A priority Critical patent/JPWO2024084775A1/ja
Priority to EP23879428.3A priority patent/EP4606844A1/en
Priority to KR1020257014457A priority patent/KR20250095626A/ko
Publication of WO2024084775A1 publication Critical patent/WO2024084775A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • B32B2307/581—Resistant to cut
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/746—Slipping, anti-blocking, low friction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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

Definitions

  • the present invention relates to a polyamide film for cold forming used in the packaging fields of pharmaceuticals, industrial products, etc.
  • lithium batteries have come to be used in a wide variety of applications, including as small, high-capacity power sources for personal computers, portable terminal devices (mobile phones, PDAs, etc.), video cameras, electric vehicles, energy storage batteries, robots, satellites, etc.
  • the exterior bodies of lithium batteries are either metal cans made by pressing metal into cylindrical or rectangular containers, or bags made of multilayer film consisting of an outermost layer/aluminum/sealant layer.
  • bag-shaped exterior bodies made of multilayer film have become particularly popular in recent years from the standpoints of freedom of shape, miniaturization, and heat dissipation performance against heat generated by the battery.
  • Patent Document 1 discloses that a laminated film is preferably used as an exterior material for an electricity storage device, in which a base layer/thin metal layer/sealant layer are laminated in this order, the Young's modulus of the base layer being 2.5 GPa to 4.5 GPa, and the thickness of the base layer being 1.5 to 3.0 times the thickness of the thin metal layer.
  • a base layer a biaxially oriented polyethylene terephthalate film and a biaxially oriented nylon film are used, either alone or in a laminated state.
  • the properties required for a multilayer film exterior material for battery packaging include cold formability, low moisture absorption, and puncture resistance.
  • a laminate such as biaxially oriented polyester film/biaxially oriented polyamide 6 film/aluminum foil/unstretched polyolefin film is commonly used as a battery packaging exterior material, and cold formability and puncture resistance are exhibited by the biaxially oriented polyamide 6 film, while low moisture absorption is exhibited by the biaxially oriented polyester film.
  • a laminate such as biaxially oriented polyester film/biaxially oriented polyamide 6 film/aluminum foil/unstretched polyolefin film is commonly used as a battery packaging exterior material, and cold formability and puncture resistance are exhibited by the biaxially oriented polyamide 6 film, while low moisture absorption is exhibited by the biaxially oriented polyester film.
  • deep molding such as exterior materials for electric vehicle batteries, it may be unsuitable because it is laminated with biaxially oriented polyester film, which has
  • polyamide 6 film is highly hygroscopic, and when used in an environment where humidity is not controlled, the film may deform or break due to moisture absorption. Furthermore, since the outermost layer is made of two layers, the cost increases and becomes complicated due to the increase in the lamination process, and a single film is desired.
  • the present invention aims to provide a biaxially oriented polyamide film for cold forming that has good cold formability and low moisture absorption and can be used as the outermost layer of a battery exterior material even as a single film.
  • the inventors have found that a biaxially oriented polyamide film formed from a polyamide resin composition containing 80% to 100% by mass of polyamide 11 has excellent low moisture absorption. Furthermore, by focusing on the stress at 30% elongation (F30) as the upper yield stress, they have found that a biaxially oriented polyamide film having an F30/upper yield stress value, which is the value obtained by dividing the stress at 30% elongation (F30) by the upper yield stress, within a specified range has excellent cold forming properties, particularly deep drawability. The inventors have continued to conduct further studies and improvements, and have completed the inventions represented below.
  • a biaxially oriented polyamide film for cold forming comprising 80% by mass or more and 100% by mass or less of polyamide 11, and having a value of F30/upper yield stress, which is a value obtained by dividing the stress at 30% elongation (F30) by the upper yield stress, of 2.0 or more and 3.0 or less in the machine direction and width direction of the film, in which the F30/upper yield stress value is larger.
  • F30/upper yield stress which is a value obtained by dividing the stress at 30% elongation (F30) by the upper yield stress, of 2.0 or more and 3.0 or less in the machine direction and width direction of the film, in which the F30/upper yield stress value is larger.
  • Item 2 Item 2. The biaxially oriented polyamide film for cold forming according to Item 1, wherein the moisture absorption elongation of the film in both the machine direction and the width direction is 0% or more and 0.5% or less.
  • Item 3 Item 3.
  • Item 4 The biaxially stretched polyamide film for cold forming according to any one of items 1 to 3, wherein the dynamic friction coefficient of the film is 0.1 or more and 1.0 or less.
  • Item 5 Item 5.
  • a laminate comprising a metal layer laminated on at least one surface of the biaxially oriented polyamide film for cold forming according to any one of items 1 to 4.
  • Item 6 Item 6.
  • the laminate according to item 5 wherein the metal layer is an aluminum layer having a thickness of 15 ⁇ m or more and 80 ⁇ m or less.
  • Item 7 The laminate according to item 6, wherein the biaxially oriented polyamide film, the metal layer, and the sealant layer are laminated in this order.
  • Item 8 Item 8. A battery packaging material using the laminate according to item 7.
  • the present invention provides a biaxial polyamide film that is suitable for cold forming, has excellent cold formability and low moisture absorption, and can be used as the outermost layer of a battery exterior material even as a single film.
  • FIG. 2 is a schematic diagram showing an example of a stress-strain curve.
  • FIG. 2 is a plan view of a mold used for evaluating the deep-drawing amount of a laminate. This is a cross-sectional view taken along the line A-A' of the mold used to evaluate the deep drawing amount of the laminate.
  • the preferred range of polyamide 11 in the polyamide resin components contained in the biaxially stretched polyamide film of the present invention is 80% by mass to 100% by mass, more preferably 83% by mass to 97% by mass, and most preferably 86% by mass to 94% by mass.
  • the hygroscopicity of the polyamide resin is mainly determined by the concentration of amide groups in the polymer chain. Polyamide 11 has 10 methylene groups in the repeating unit, and the concentration of amide groups is lower than that of polyamide 6, which has 5 methylene groups in the repeating unit. Therefore, the use of polyamide 11 exhibits low hygroscopicity.
  • the preferred range of polyamide resins other than polyamide 11 in the polyamide resin constituents is 0% by mass to 20% by mass, more preferably 3% by mass to 17% by mass, and most preferably 6% by mass to 14% by mass. It is not necessary to use polyamide resins other than polyamide 11, but adding them within the above range improves stretchability and film formation stability.
  • Polyamide 11 is a polyamide resin having a structure in which monomers with 11 carbon atoms are bonded via amide bonds.
  • Polyamide 11 is usually obtained using aminoundecanoic acid or undecane lactam as a monomer.
  • aminoundecanoic acid is a monomer obtained from castor oil, it is desirable to use polyamide 11 made from biomass materials from the perspective of carbon neutrality.
  • Polyamide resins other than polyamide 11 are not particularly limited, but examples include nylon 6, nylon 12, nylon 66, nylon 610, nylon 612, MXD nylon, or copolymer polyamides nylon 6-12, nylon 6-69, nylon 6-66, nylon 66-610, nylon 6-66-610, or aromatic polyamides nylon MXD6, nylon 6T-6I, etc.
  • the relative viscosity of polyamide 11 is preferably 1.8 to 4.5, and more preferably 2.4 to 3.2. If the relative viscosity is 1.8 or more, not only will the film have sufficient puncture strength, but it will also be easier to orient during stretching, making it easier to adjust the F30/upper yield stress value to a specified range. If it is 4.5 or less, it will be possible to prevent extrusion problems such as an inability to extrude the molten resin due to a large load on the extruder.
  • the biaxially oriented polyamide film of the present invention may contain various additives such as lubricants, heat stabilizers, antioxidants, antistatic agents, antifogging agents, ultraviolet absorbers, dyes and pigments, if necessary.
  • the biaxially stretched polyamide film of the present invention may contain fine particles as a lubricant for the purpose of improving the slipperiness and cold formability.
  • the fine particles may be appropriately selected from inorganic fine particles such as silica, kaolin, and zeolite, and polymeric organic fine particles such as acrylic and polystyrene. From the viewpoint of transparency and slipperiness, it is preferable to use silica fine particles.
  • the average particle diameter of the fine particles is preferably 0.5 to 5.0 ⁇ m, and more preferably 1.0 to 3.0 ⁇ m. When the average particle diameter is 0.5 ⁇ m or more, good slipperiness can be obtained with a small amount of addition. On the other hand, when it is 5.0 ⁇ m or less, it is possible to prevent the surface roughness of the film from becoming too large and the appearance from being deteriorated.
  • the pore volume of the silica is preferably in the range of 0.5 to 2.0 ml/g, and more preferably 0.8 to 1.6 ml/g.
  • the pore volume is 0.5 ml/g or more, deterioration of film transparency due to the generation of voids can be prevented.
  • the pore volume is 2.0 ml/g or less, sufficient surface protrusions can be obtained.
  • the lower limit of the microparticle content is preferably 100 ppm by mass, more preferably 300 ppm by mass, and most preferably 500 ppm by mass. By making it 100 ppm by mass or more, the slipperiness of the film can be improved, and blocking can be suppressed when the film is rolled.
  • the upper limit of the microparticle content is preferably 10,000 ppm by mass, more preferably 6,000 ppm by mass, and most preferably 2,000 ppm by mass. By making it 10,000 ppm by mass or less, the transparency of the film can be improved.
  • the biaxially stretched polyamide film of the present invention may contain fatty acid amides and/or fatty acid bisamides in order to improve slipperiness.
  • fatty acid amides and/or fatty acid bisamides include erucic acid amide, stearic acid amide, ethylene bisstearic acid amide, ethylene bisbehenic acid amide, and ethylene bisoleic acid amide.
  • the preferred content is 0.01 to 0.40 mass%, and more preferably 0.05 to 0.30 mass%.
  • the fatty acid amide and/or fatty acid bisamide content is 0.01 mass% or more, sufficient slipperiness is obtained. On the other hand, when it is 0.40 mass% or less, deterioration of wettability can be prevented.
  • the biaxially stretched polyamide film of the present invention may contain an antioxidant.
  • the antioxidant is preferably a phenol-based antioxidant.
  • the phenol-based antioxidant is preferably a completely hindered phenol-based compound or a partially hindered phenol-based compound.
  • phenol-based antioxidant examples include tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, stearyl- ⁇ -(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[1,1-dimethyl-2-[ ⁇ -(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane.
  • a phenol-based antioxidant By containing a phenol-based antioxidant, the film-forming operability of the biaxially stretched polyamide film is improved.
  • the thickness of the biaxially oriented polyamide film of the present invention is not particularly limited, but is preferably 100 ⁇ m or less, and generally, a thickness of 5 to 50 ⁇ m is used, more preferably, a thickness of 8 to 30 ⁇ m is used.
  • the maximum value of F30/upper yield stress which is the value obtained by dividing the stress at 30% elongation by the upper yield stress, in either the MD direction or the TD direction is preferably 2.0 or more and 3.0 or less. More preferably, the maximum value is 2.1 or more and 2.9 or less, and even more preferably, the maximum value is 2.2 or more and 2.8 or less. By making it 2.0 or more, the cold formability is sufficient. By making it 3.0 or less, the stability during film formation is improved.
  • the F30/upper yield stress value indicates the slope of the stress-strain curve (hereinafter sometimes abbreviated as SS curve), and the larger this value, the steeper the slope of the SS curve.
  • the steepness of the SS curve of the biaxially stretched polyamide film indicates that the film is uniformly stretched during cold forming.
  • the aluminum foil is the least likely to stretch during cold forming, and destruction occurs from the aluminum foil.
  • a film with a steep SS curve is used as in the present invention, it is formed uniformly, so localized stretching is unlikely to occur, and as a result, the aluminum foil is less likely to break, improving cold formability.
  • the moisture absorption elongation rate in the film flow direction and width direction of the biaxially stretched polyamide film of the present invention is preferably 0% or more and 0.50% or less, more preferably 0.05% or more and 0.45% or less, and particularly preferably 0.10% or more and 0.40% or less.
  • 0% or more it is possible to prevent the film from shrinking under high humidity conditions, and to suppress destruction of the battery packaging material due to moisture absorption and shrinkage.
  • By making it 0.50% or less it is possible to prevent the film from stretching under high humidity conditions, and to suppress deformation of the battery packaging material due to stretching.
  • the puncture strength of the biaxially oriented polyamide film of the present invention, converted to a thickness of 25 ⁇ m, is preferably 17.0 N/25 ⁇ m or more, more preferably 17.5 N/25 ⁇ m or more, and particularly preferably 18.0 N/25 ⁇ m or more. By making it 17.0 N/25 ⁇ m or more, it is possible to prevent breakage starting from a convex portion (e.g., the four corners of a rectangle) during cold forming.
  • There is no particular upper limit to the puncture strength but it is preferably 50 N/25 ⁇ m or less, more preferably 40 N/25 ⁇ m or less. If it is too high, film formation becomes unstable, and problems in the film formation process such as stretching breakage may occur.
  • the dynamic friction coefficient of the biaxially oriented polyamide film of the present invention is preferably 0.10 or more and 1.0 or less, more preferably 0.13 or more and 0.8 or less, and particularly preferably 0.16 or more and 0.6 or less.
  • the dynamic friction coefficient is high, slippage between the mold and the film during cold forming is difficult, and the stress of forming tends to concentrate in one area, which results in the film being more likely to break.
  • By making it 0.10 or more it is possible to suppress the decrease in transparency caused by using a large amount of lubricant.
  • the lower limit of the deep drawing amount of the laminate of the present invention is preferably 4.0 mm or more, more preferably 4.2 mm or more, and particularly preferably 4.4 mm or more. By making it 4.0 mm or more, it can be suitably used in deep drawing applications.
  • the laminate referred to here is a structure of biaxially oriented polyamide film (25 ⁇ m) / Al foil (40 ⁇ m) / unoriented polypropylene film (70 ⁇ m), which will be described later.
  • the raw resin is melt-extruded using an extruder, extruded from a T-die into a film, cast onto a cooling roll and cooled to obtain an unstretched film.
  • the resin melting temperature is preferably 220-350°C. If it is 220°C or higher, poor appearance due to defects such as unmelted material can be suppressed. If it is 350°C or lower, it is possible to prevent a decrease in strength due to a decrease in molecular weight caused by resin deterioration, and poor appearance due to carbonization.
  • the T-die temperature is preferably 250-350°C.
  • the cooling roll temperature is preferably -30 to 80°C, and more preferably 0 to 50°C.
  • a method using an air knife or an electrostatic adhesion method in which a static charge is applied can be preferably applied. The latter method is particularly preferably used.
  • the side of the cast unstretched film opposite the cooling roll It is also preferable to cool the side of the cast unstretched film opposite the cooling roll.
  • it is preferable to use a combination of methods such as contacting the side of the unstretched film opposite the cooling roll with a cooling liquid in a tank, applying a liquid that evaporates with a spray nozzle, or spraying a high-velocity fluid to cool the film.
  • the unstretched film thus obtained is stretched biaxially to obtain the biaxially stretched polyamide film of the present invention.
  • the stretching method may be either a simultaneous biaxial stretching method or a sequential biaxial stretching method.
  • the stretching method in the MD direction may be a multi-stage stretching method such as one-stage stretching or two-stage stretching.
  • Multi-stage stretching in the MD direction such as two-stage stretching is preferred in terms of physical properties and uniformity of physical properties in the MD direction and TD direction (isotropy) rather than one-stage stretching.
  • Roll stretching is preferred for stretching in the MD direction in the sequential biaxial stretching method.
  • the lower limit of the MD stretching temperature is preferably 50°C, more preferably 55°C, and particularly preferably 60°C. Stretching is possible at a temperature of 50°C or higher.
  • the upper limit of the MD stretching temperature is preferably 110°C, more preferably 105°C, and particularly preferably 100°C. Stable stretching is possible at a temperature of 110°C or lower.
  • the lower limit of the stretch ratio in the MD direction (when stretching in multiple stages, the total stretch ratio multiplied by each stretch ratio) is preferably 2.2 times, more preferably 2.5 times, and particularly preferably 2.8 times. By making it 2.2 times or more, not only will the thickness accuracy in the MD direction be sufficient, but the puncture strength will also be sufficient, and the F30/upper yield stress value will also be easily adjusted to within the range of the claims.
  • the upper limit of the stretch ratio in the MD direction is preferably 4.0 times, more preferably 3.9 times, and particularly preferably 3.8 times. By making it 4.0 times or less, stretching in the subsequent TD process is possible.
  • the above-mentioned stretching is possible for each stretching, but it is preferable to adjust the stretching ratio so that the product of all stretching ratios in the MD direction is 4.0 or less.
  • the film stretched in the MD direction is stretched in the TD direction in a tenter, heat-set, and relaxed (also called relaxation treatment).
  • the lower limit of the stretching temperature in the TD direction is preferably 50°C, more preferably 55°C, and particularly preferably 60°C. Stretching is possible at 50°C or higher.
  • the upper limit of the stretching temperature in the TD direction is preferably 160°C, more preferably 155°C, and particularly preferably 150°C. Stable stretching can be achieved by keeping the temperature at 160°C or lower.
  • the lower limit of the stretch ratio in the TD direction (when stretching in multiple stages, the total stretch ratio multiplied by each stretch ratio) is preferably 2.8, more preferably 3.2, and particularly preferably 3.5. By making it 2.8 or more, not only is the thickness accuracy in the TD direction sufficient, but the puncture strength is also sufficient, and the F30/upper yield stress value can be easily adjusted to within the range of the claims.
  • the upper limit of the stretch ratio in the TD direction is preferably 5.0, more preferably 4.7, and particularly preferably 4.3. By making it 5.0 or less, breakage during TD stretching can be suppressed.
  • the lower limit of the areal stretch ratio (MD stretch ratio x TD stretch ratio) is preferably 10.0 times, more preferably 10.5 times, and particularly preferably 11.0 times. By making it 10.0 times or more, not only will the thickness precision be sufficient, but the puncture strength will also be sufficient, and the F30/upper yield stress value will also be easily adjusted to within the range of the claims.
  • the upper limit of the areal stretch ratio is preferably 16.5 times, more preferably 16.0 times, and particularly preferably 15.5 times. By making it 16.5 times or less, breakage during stretching can be suppressed.
  • the lower limit of the heat setting temperature is preferably 150°C, and more preferably 160°C. By setting the temperature at 150°C or higher, the thermal shrinkage rate can be kept low, and the processability in the subsequent lamination process and the like can be improved.
  • the upper limit of the heat setting temperature is preferably 210°C, and more preferably 200°C. By setting the temperature at 210°C or lower, it is possible to suppress poor appearance due to whitening of the film, a decrease in puncture strength, and a decrease in the F30/upper yield stress value.
  • the heat setting time is preferably 0.5 to 20 seconds, and more preferably 1 to 15 seconds.
  • the heat setting time can be adjusted appropriately based on the heat setting temperature and the wind speed in the heat setting zone.
  • the temperature during the relaxation process is preferably in the range from the heat setting process temperature to the glass transition temperature (Tg) of the resin, and more preferably from "heat setting process temperature -10°C" to "Tg +10°C.” If the relaxation process temperature is too high, the shrinkage speed will be too fast, which is undesirable and can cause distortion. Conversely, if the relaxation temperature is too low, the relaxation process will not occur and the material will simply slacken, the thermal shrinkage rate will not decrease, and workability may deteriorate.
  • Tg glass transition temperature
  • the lower limit of the relaxation rate in the relaxation process is preferably 0.5%, and more preferably 1%. By making it 0.5% or more, the thermal shrinkage rate can be sufficiently suppressed, and processability can be improved.
  • the upper limit of the relaxation rate is preferably 20%, more preferably 15%, and particularly preferably 10%. By making it 20% or less, sagging within the TD can be suppressed, and wrinkles and deterioration of productivity can be prevented.
  • a printing layer may be laminated on the biaxially stretched polyamide film of the present invention.
  • the printing ink for forming the printing layer water-based and solvent-based resin-containing printing inks can be preferably used.
  • the resins used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof.
  • the printing ink may contain known additives such as antistatic agents, light blocking agents, ultraviolet absorbing agents, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, defoamers, crosslinking agents, anti-blocking agents, and antioxidants.
  • the printing method for providing the printing layer is not particularly limited, and known printing methods such as offset printing, gravure printing, and screen printing can be used.
  • known drying methods such as hot air drying, heated roll drying, and infrared drying can be used.
  • the lamination method is not particularly limited, and may include laminating the biaxially oriented polyamide film after production, laminating during film production, etc.
  • the present invention further provides a laminate in which a metal layer is laminated on at least one surface of the biaxially oriented polyamide film of the present invention.
  • the metal layer may be laminated so as to be in direct contact with the biaxially oriented polyamide film of the present invention, or may be laminated via another layer such as an adhesive layer.
  • the metal of the metal layer may be any of a variety of metal elements (aluminum, iron, copper, nickel, etc.), with an aluminum layer being particularly preferred. From the viewpoint of deep-draw formability, the thickness of the metal layer is preferably 15 ⁇ m to 80 ⁇ m, and particularly preferably 20 ⁇ m to 60 ⁇ m.
  • the present invention provides a laminate in which a sealant layer is laminated on a surface of the metal layer different from the surface on which the biaxially oriented polyamide film is laminated.
  • the sealant layer may be laminated so as to be in direct contact with the metal layer, or may be laminated via another layer such as an adhesive layer.
  • the sealant layer is preferably a non-oriented polyolefin film.
  • the non-oriented polyolefin film is preferably a film containing a polyethylene-based resin composition and/or a polypropylene-based resin composition.
  • the sealant layer is mainly formed from a polyethylene-based resin composition
  • examples of the polyethylene-based resin composition include linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE).
  • LLDPE linear low-density polyethylene
  • LDPE low-density polyethylene
  • the sealant layer may be a single layer or a multilayer structure of two or more layers, and includes at least one layer formed from a polyethylene-based resin composition, and may also include layers made of any other resin.
  • the lower limit of the thickness of the sealant layer is preferably 15 ⁇ m, more preferably 20 ⁇ m, and particularly preferably 25 ⁇ m. If it is 15 ⁇ m or more, it is easy to obtain heat seal strength.
  • the upper limit of the thickness of the sealant layer is preferably 80 ⁇ m, more preferably 70 ⁇ m, and particularly preferably 60 ⁇ m. If it is 80 ⁇ m or less, the film does not feel too stiff, and the laminate is easy to process.
  • the laminate of the present invention is suitable for cold forming, and in one preferred embodiment, it can be used as a packaging material for the exterior of batteries such as lithium batteries.
  • the physical property evaluation method for the present invention is shown below.
  • the film was cut into 100 mm long sheets in the MD direction and conditioned for 2 hours or more in an environment of 23° C. and 65% relative humidity. The thickness was then measured using a thickness measuring device manufactured by Tester Sangyo Co., Ltd. at 10 equal positions in the TD direction of the film (for narrow films, the positions were divided so that the width was sufficient to measure the thickness). The average value was divided by the number of films stacked to obtain the film thickness.
  • [F30/Upper yield stress value] A sample with a width of 15 mm and a length of 180 mm was cut out in the MD and TD directions of the film. The cut out sample was aged for 12 hours in an environment of 23°C and 65% relative humidity, and then measured at 23°C and 65% relative humidity using an Autograph AG-1 manufactured by Shimadzu Corporation, with a chuck distance of 100 mm and a tensile speed of 360 mm/min. The measurement was repeated five times, and the average value of the stress (F30) when the film was stretched by 30% was divided by the average value of the upper yield stress to obtain the F30/upper yield stress value.
  • the coefficient of dynamic friction between the same surfaces of the film was evaluated under the following conditions in accordance with JIS-C2151 (the surface can be specified arbitrarily).
  • the test piece had a width of 130 mm and a length of 250 mm, and the test speed was 150 mm/min.
  • a urethane-based two-component curing adhesive (Mitsui Chemicals'"Takelac (registered trademark) A525S” and “Takenate (registered trademark) A50” were mixed in a ratio of 13.5:1.0 (mass ratio) on any surface of the biaxially stretched polyamide film, and a 40 ⁇ m-thick "Aluminum Haku CE 8079" manufactured by Toyo Aluminum was bonded by dry lamination.
  • the urethane-based two-component curing adhesive was similarly bonded to a 70 ⁇ m-thick unstretched polypropylene film (Toyobo's "P1147”) by dry lamination on the aluminum layer side of the above laminate.
  • This laminate was aged at 40° C. for 4 days to obtain a laminate.
  • the lamination directions of the films and aluminum layers used were all aligned in the longitudinal direction and the width direction.
  • the thickness of the adhesive layer formed with the urethane-based two-component curing adhesive after drying was 4 ⁇ m in all cases.
  • Example 1 A polyamide 11 resin composition [99.85% by mass] and porous silica particles [0.15% by mass] were charged into an extruder. The resin was melted at 260°C in the extruder, cast from a T-die at 260°C, and adhered to a cooling roll at 20°C by electrostatic adhesion to obtain an unstretched sheet. The unstretched sheet was then stretched 1.79 times in the MD direction at a temperature of 70° C., and then further stretched 1.79 times at 60° C. Then, the sheet was passed through a tenter and stretched 3.8 times in the TD direction at 130° C. After the TD stretching, the sheet was immediately subjected to a heat setting treatment at 180° C. for 3 seconds and a relaxation treatment of 7% for 1 second to obtain a biaxially stretched polyamide film having a thickness of 25 ⁇ m.
  • Example 2 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the mixing ratio of the raw materials fed into the extruder was changed to polyamide 11 resin composition [89.87% by mass], polyamide 6 resin composition [9.98% by mass], and porous silica particles [0.15% by mass].
  • Example 3 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the mixing ratio of the raw materials fed into the extruder was changed to polyamide 11 resin composition [79.88 mass%], polyamide 6 resin composition [19.97 mass%], and porous silica particles [0.15 mass%].
  • Example 4 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the MD stretching process was changed to stretching 1.73 times in the MD direction at a temperature of 70°C, and then further stretching 1.73 times at 60°C.
  • Example 5 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the MD stretching process was changed to stretching 1.92 times in the MD direction at a temperature of 70°C, followed by further stretching 1.92 times at 60°C, and the TD stretching process was changed to stretching 3.9 times in the TD direction at 130°C.
  • Example 6 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the MD stretching process was changed to stretching 1.92 times in the MD direction at a temperature of 70°C, followed by further stretching 1.92 times at 60°C, and the TD stretching process was changed to stretching 4.3 times in the TD direction at 130°C.
  • Example 1 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the mixing ratio of the raw materials fed into the extruder was changed to polyamide 11 resin composition [29.96% by mass], polyamide 6 resin composition [69.89% by mass], and porous silica particles [0.15% by mass]. Many breaks occurred during film formation, and film formation stability was poor. In addition, it was impossible to collect samples sufficient for measuring various physical properties.
  • Example 2 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the mixing ratio of the raw materials fed into the extruder was changed to 19.97% by mass of the polyamide 11 resin composition, 79.88% by mass of the polyamide 6 resin composition, and 0.15% by mass of the porous silica particles.
  • the obtained biaxially stretched polyamide film had a large elongation due to moisture absorption and was poor.
  • Example 3 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the mixing ratio of the raw materials fed into the extruder was changed to polyamide 11 resin composition [9.98% by mass], polyamide 6 resin composition [89.97% by mass], and porous silica particles [0.15% by mass].
  • the obtained biaxially stretched polyamide film had a large elongation due to moisture absorption and was poor.
  • Example 4 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the MD stretching step was changed to stretching 1.73 times in the MD direction at a temperature of 70° C., followed by further stretching 1.73 times at 60° C., and the TD stretching step was changed to stretching 3.3 times in the TD direction at 130° C.
  • the obtained biaxially stretched polyamide film had low puncture strength and a low F30/upper yield stress value, and therefore had poor deep drawability.
  • Example 5 A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the MD stretching step was changed to stretching 1.92 times in the MD direction at a temperature of 70° C., followed by further stretching 1.92 times at 60° C., and the TD stretching step was changed to stretching 4.5 times in the TD direction at 130° C. Many breaks occurred during film formation, and film formation stability was poor.

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PCT/JP2023/027978 2022-10-21 2023-07-31 冷間成形用二軸延伸ポリアミドフィルム Ceased WO2024084775A1 (ja)

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WO2012173105A1 (ja) * 2011-06-14 2012-12-20 東洋紡株式会社 共重合ポリアミドフィルム
JP2015026438A (ja) * 2013-07-24 2015-02-05 興人フィルム＆ケミカルズ株式会社 冷間成形用電池ケース包材
JP2016003305A (ja) * 2014-06-18 2016-01-12 興人フィルム＆ケミカルズ株式会社 冷間成形用二軸延伸ポリアミドフィルム及びそれを用いた包材
JP2018095863A (ja) * 2016-12-14 2018-06-21 東洋紡株式会社 二軸延伸ポリアミド樹脂フィルム及びそれを用いた積層体。
JP2018147860A (ja) 2017-03-09 2018-09-20 昭和電工パッケージング株式会社 蓄電デバイス用外装材及び蓄電デバイス
WO2020064858A1 (en) * 2018-09-28 2020-04-02 Dsm Ip Assets B.V. Backsheet for photovoltaic modules comprising an aliphatic polyamide
WO2020203836A1 (ja) * 2019-03-29 2020-10-08 ユニチカ株式会社 ポリアミド系積層フィルム及びその製造方法
JP2022025168A (ja) * 2020-07-29 2022-02-10 ユニチカ株式会社 二軸延伸ポリアミド系樹脂フィルム

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012117884A1 (ja) * 2011-03-01 2012-09-07 東洋紡績株式会社 延伸ポリアミドフィルム
WO2012173105A1 (ja) * 2011-06-14 2012-12-20 東洋紡株式会社 共重合ポリアミドフィルム
JP2015026438A (ja) * 2013-07-24 2015-02-05 興人フィルム＆ケミカルズ株式会社 冷間成形用電池ケース包材
JP2016003305A (ja) * 2014-06-18 2016-01-12 興人フィルム＆ケミカルズ株式会社 冷間成形用二軸延伸ポリアミドフィルム及びそれを用いた包材
JP2018095863A (ja) * 2016-12-14 2018-06-21 東洋紡株式会社 二軸延伸ポリアミド樹脂フィルム及びそれを用いた積層体。
JP2018147860A (ja) 2017-03-09 2018-09-20 昭和電工パッケージング株式会社 蓄電デバイス用外装材及び蓄電デバイス
WO2020064858A1 (en) * 2018-09-28 2020-04-02 Dsm Ip Assets B.V. Backsheet for photovoltaic modules comprising an aliphatic polyamide
WO2020203836A1 (ja) * 2019-03-29 2020-10-08 ユニチカ株式会社 ポリアミド系積層フィルム及びその製造方法
JP2022025168A (ja) * 2020-07-29 2022-02-10 ユニチカ株式会社 二軸延伸ポリアミド系樹脂フィルム

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