WO2020027089A1 - ポリアミド系積層フィルム及びその製造方法 - Google Patents

ポリアミド系積層フィルム及びその製造方法 Download PDF

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Publication number
WO2020027089A1
WO2020027089A1 PCT/JP2019/029742 JP2019029742W WO2020027089A1 WO 2020027089 A1 WO2020027089 A1 WO 2020027089A1 JP 2019029742 W JP2019029742 W JP 2019029742W WO 2020027089 A1 WO2020027089 A1 WO 2020027089A1
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Prior art keywords
polyamide
protective layer
film
laminated film
layer
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PCT/JP2019/029742
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English (en)
French (fr)
Japanese (ja)
Inventor
真実 松本
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Unitika Ltd
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Unitika Ltd
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Priority to JP2020534647A priority Critical patent/JP7336142B2/ja
Priority to CN201980050200.9A priority patent/CN112703111B/zh
Publication of WO2020027089A1 publication Critical patent/WO2020027089A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • 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
    • 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 particularly relates to a polyamide-based laminated film used for packaging or coating various products such as electronic components and electronic devices.
  • a laminated film including a polyamide film has been frequently used as an exterior material of a battery (such as a lithium ion secondary battery).
  • a battery such as a lithium ion secondary battery
  • a laminate in which a polyamide film / aluminum foil / sealant layer is sequentially laminated is known as an exterior material.
  • the laminate is formed in a container shape such that the polyamide film is disposed outside the battery and the sealant layer is disposed inside (inside the battery). It has been processed. Then, an electrolyte is injected into the container after electrodes and the like are wrapped.
  • a process of injecting the electrolyte into the battery and a process of heat sealing the exterior material after the injection are performed.
  • the electrolyte may spill and adhere to the polyamide film outside the exterior material.
  • the polyamide film has low resistance to the electrolyte (electrolyte resistance)
  • the surface of the film becomes white when the electrolyte adheres to the polyamide film, Alternatively, a decomposition reaction or the like occurs.
  • the appearance of the product may be poor and the strength of the film may be reduced.
  • the electrolytic solution enters from the deteriorated portion of the polyamide film and comes into contact with the aluminum foil, the aluminum foil may be corroded. In this case, there is a problem that the strength required for the exterior material is lost.
  • Patent Literature 1 discloses an exterior material using a polyethylene terephthalate film as a protective layer.
  • Patent Literature 2 discloses a packaging material using a film obtained by stretching a laminate of a polyester film and a polyamide film.
  • Patent Documents 3 to 5 propose an exterior material in which a coating layer made of a specific resin is laminated as an outermost layer as a protective layer.
  • Patent Documents 1 and 2 use a polyester film as a protective layer of a polyamide film.
  • a separate step of laminating the polyester-based film is required, which complicates the manufacturing process and hinders cost reduction.
  • the total weight increases by the amount of the adhesive, which is disadvantageous in terms of reducing the weight of the battery.
  • Patent Documents 3 to 5 contain resin components such as polyvinylidene chloride and polyurethane.
  • resin components such as polyvinylidene chloride and polyurethane.
  • the material cost of the protective layer itself is increased, and the energy cost required in the drying step is increased, which is economically disadvantageous.
  • the protective layer is formed by the post-coating method, the cost is increased due to an increase in the number of steps, and the amount of heat in the drying step may adversely affect the physical properties of the base film.
  • a main object of the present invention is to provide a polyamide-based laminated film that can exhibit excellent electrolytic solution resistance despite being a relatively thin protective layer.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above object can be achieved by providing a protective layer containing a specific copolymerized polyester resin on the surface of a polyamide film. Was completed.
  • a polyamide-based laminated film including a polyamide-based film substrate and a protective layer formed on at least one surface of the substrate, (1) The protective layer is formed so as to be in direct contact with the surface of the polyamide film substrate, (2) at least one of the protective layers is disposed as an outermost surface layer of the polyamide-based laminated film; (3) A protective layer comprising a copolyester resin containing a dicarboxylic acid component and a diol component as constituent components, and a dicarboxylic acid component having a naphthalene skeleton in 50 mol% or more in 100 mol% of structural units derived from dicarboxylic acid.
  • the thickness of the protective layer is 1.5 ⁇ m or less;
  • a polyamide-based laminated film characterized in that: 2.
  • the above-mentioned Hz0 is a haze value measured in accordance with Japanese Industrial Standards “JIS K 7136”
  • the above-mentioned HzX is a temperature of 23 ° C. and a humidity of 50% RH in a state where an electrolyte is attached to a protective layer after the measurement of the above-mentioned Hz0.
  • the polyamide-based film according to the above item wherein Hz is in a range of 10 or less.
  • Ra surface roughness
  • the polyamide-based laminated film according to item 1 wherein the copolymerized polyester resin has a glass transition temperature of 60 to 145 ° C. 5. Item 2.
  • Item 7. The polyamide-based laminated film according to any one of Items 1 to 6, which is used for packaging an article.
  • the battery, wherein the exterior material is the polyamide-based laminated film according to any one of the above items 1 to 5, and the protective layer is disposed as an outermost layer of the battery. 9.
  • a method for producing a polyamide-based laminated film comprising:
  • the protective layer of the polyamide-based laminated film of the present invention contains a copolyester resin having a dicarboxylic acid component having a naphthalene skeleton in an acid component of 50 mol% or more, the protective layer has a thickness of 1.5 ⁇ m or less. Even if it is relatively thin, excellent electrolytic solution resistance can be exhibited. For this reason, even when the electrolytic solution adheres, whitening and decomposition reaction of the polyamide film can be effectively suppressed. As a result, the strength of the polyamide-based laminated film can be maintained continuously.
  • the surface roughness of the protective layer is relatively small (there is little unevenness), even when the electrolytic solution adheres, the droplets are less likely to stay. Therefore, it is possible to prevent the protective layer from being deteriorated due to the long-term adhesion of the electrolytic solution.
  • the thickness of the protective layer is relatively thin, and thus the thickness of the polyamide-based laminated film can be reduced, excellent conformability to molding can be obtained even when coating is performed in a state in which the protective layer is in close contact with the package. Therefore, it can be suitably used for an exterior material of a lithium ion secondary battery or the like which requires adhesion and the like.
  • the thickness of the protective layer can be as thin as 1.5 ⁇ m or less, it can be easily formed under relatively mild heat treatment conditions, so that the influence on the physical properties of the polyamide-based film substrate can be minimized. This can also contribute to the realization of a polyamide-based laminated film having excellent electrolytic solution resistance, mechanical properties, blocking resistance, and the like.
  • an electrolytic solution used for a lithium ion secondary battery is an electrically conductive liquid prepared by dissolving an ionic substance in a polar solvent.
  • Those using lithium hexafluorophosphate (LiPF 6) as an ionic substance are common. LiPF 6 reacts with water to produce hydrofluoric acid (hydrogen fluoride), which is a strongly acidic medium. Therefore, when the electrolytic solution adheres in the air, the moisture in the air reacts with the LiPF 6 in the electrolytic solution to generate hydrofluoric acid.
  • the polyamide film used for the exterior material of the lithium ion secondary battery is dissolved by the hydrofluoric acid.
  • the polyamide-based laminated film of the present invention has the specific protective layer as described above, even if the electrolyte containing LiPF 6 or the like adheres, the polyamide film does not deteriorate and maintains its strength. can do.
  • the protective layer can be formed by applying a specific protective layer forming coating liquid by in-line coating, the above-described polyamide-based laminated film having excellent electrolytic solution resistance and the like can be industrially produced. It can be manufactured at a reasonable scale and at low cost.
  • the thickness of the protective layer can be as thin as 1.5 ⁇ m or less, it can be easily formed by in-line coating under relatively mild conditions, thereby minimizing the influence on the physical properties of the polyamide-based film substrate and the like. be able to. This point also contributes to the realization of a polyamide-based laminated film having excellent electrolytic solution resistance, mechanical properties, blocking resistance, and the like.
  • the surface of the protective layer can be made flatter. This can also contribute to improving the resistance to electrolyte.
  • the reason is not clear, but is presumed to be due to the following mechanism of action.
  • the coating film formed by the coating liquid for forming the protective layer is subjected to stretching and heat treatment together with the polyamide film. By performing the heat treatment simultaneously with the stretching, a high-density film mainly composed of a copolyester resin is formed. Can be formed, and the surface of the protective layer becomes smooth, so that a surface with less surface irregularities can be formed.
  • the surface of the protective layer has less unevenness, it does not easily stay even if the electrolytic solution adheres, and it is presumed that a protective layer having high protection performance against the electrolytic solution can be obtained.
  • the polyamide-based laminated film of the present invention having such characteristics can be suitably used for applications to which an electrolytic solution (or an acidic liquid) may adhere.
  • an electrolytic solution or an acidic liquid
  • it can be suitably used as an exterior material of various batteries (especially laminated batteries) such as a lithium ion secondary battery.
  • FIG. 1 is an external view of a battery using a polyamide-based laminated film of the present invention as an exterior material. It is a schematic diagram showing the composition of the battery using the polyamide system lamination film of the present invention as an exterior material. It is a schematic diagram showing the composition of the battery using the polyamide system lamination film of the present invention as an exterior material.
  • the polyamide-based laminated film (the film of the present invention) of the present invention is a polyamide-based laminated film including a polyamide-based film base material and a protective layer formed on at least one surface of the base material; )
  • the protective layer is formed so as to be in direct contact with the surface of the polyamide-based film substrate, (2) at least one of the protective layers is disposed as an outermost surface layer of the polyamide-based laminated film; (3)
  • a protective layer comprising a copolymer polyester resin containing a dicarboxylic acid component and a diol component as constituent components, and having a dicarboxylic acid component having a naphthalene skeleton in 50 mol% or more in 100 mol% of structural units derived from the dicarboxylic acid.
  • the thickness of the protective layer is 1.5 ⁇ m or less; It is characterized by the following.
  • the film of the present invention has a basic structure of a polyamide-based laminated film including a polyamide-based film substrate and a protective layer formed on at least one surface of the substrate. That is, the laminate has a basic structure in which a protective layer is formed so as to be adjacent to one or both surfaces of a polyamide-based film base material without using an adhesive layer.
  • FIG. 1 shows an example of the layer structure of the film of the present invention.
  • FIG. 1A shows a laminate (the film of the present invention) 10 in which a protective layer 12 is laminated on one surface of a polyamide-based film substrate 11.
  • FIG. 1B shows a laminate (the film of the present invention) 10 ′ in which protective layers 12, 12 are laminated on both surfaces of a polyamide-based film substrate 11.
  • the protective layer is disposed as the outermost layer (outermost layer).
  • the protective layer is directly formed on the polyamide-based film substrate as described above, and other layers are further laminated as long as at least one protective layer is arranged as the outermost surface layer. Is also good.
  • a barrier layer gas barrier layer, water vapor barrier layer, etc.
  • a printing layer a heat sealing layer (adhesive layer, sealant layer, heat seal layer), a primer layer (anchor coat layer), an antistatic layer, an evaporation layer, an ultraviolet ray An absorption layer, an ultraviolet blocking layer, and the like are included.
  • FIG. 2 shows a layer configuration example of a polyamide-based laminated film in which other optional layers are further laminated in addition to the polyamide-based film substrate and the protective layer.
  • FIG. 2A shows a laminate 20 in which a barrier layer 13 and a heat sealing layer 14 are further laminated on the laminate 10 of FIG. 1A in this order.
  • the barrier layer 13 and the heat-sealing layer 14 are laminated on the surface of the polyamide-based film substrate 11 where the protective layer 12 is not formed, so that the protective layer 12 is exposed as the outermost surface layer. Is maintained.
  • FIG. 2B shows a laminate 20 ′ in which a barrier layer 13 and a heat-sealing layer 14 are further laminated on the laminate 10 ′ of FIG. 1B in order.
  • the barrier layer 13 and the heat-sealing layer 14 are laminated on one of the protective layers 12 of the polyamide-based film substrate 11, but the other protective layer 12 is exposed as the outermost layer. State is maintained. Further, as shown in FIG. 2, when the film of the present invention has a heat-sealing layer, the heat-sealing layer is arranged as the outermost surface layer.
  • the polyamide-based film substrate serves as a substrate (core material) of the film of the present invention, and is usually provided in the form of a pre-formed film.
  • the polyamide-based film substrate may have a single-layer structure or a multilayer structure in which two or more polyamide-based films are laminated. In the case of a multi-layer structure, each layer may have the same composition or different compositions.
  • the polyamide-based film substrate is mainly composed of a polyamide-based resin, but may contain other components.
  • the content of the polyamide-based resin in the polyamide-based film substrate is not limited, but is usually 70 to 100% by mass, and particularly preferably 90 to 99.5% by mass.
  • any thermoplastic resin having an amide bond (—CONH—) in its molecule and capable of being melt-molded may be used, and a known or commercially available resin can be used.
  • polyamides obtained by polycondensation of lactams, ⁇ -amino acids or dibasic acids with diamines can be mentioned.
  • peractams examples include ⁇ -caprolactam, enantholactam, capryllactam, lauryl lactam and the like.
  • ⁇ -amino acids examples include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and the like.
  • dibasic acids examples include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecadionic acid, hexadecadionic acid, eicosandioic acid, eicosadienedioic acid, 2, Examples include 2,4-trimethyladipic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and xylylenedicarboxylic acid.
  • diamines examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, 2,2,4 (or 2,4,4) -Trimethylhexamethylenediamine, cyclohexanediamine, bis- (4,4'-aminocyclohexyl) methane, meta-xylylenediamine and the like.
  • nylon 6, 7, 11, 12, 6.6, 6.9, 6.11, 6.12, 6T, 9T, 10T, 6I, MXD6 (polymethaxylylene adipamide), 6 / 6.6, 6/12, 6 / 6T, 6 / 6I, 6 / MXD6 and the like can be used.
  • MXD6 polymethaxylylene adipamide
  • 6 / 6.6, 6/12, 6 / 6T, 6 / 6I, 6 / MXD6 and the like can be used.
  • the polyamide resin contains nylon 6 in that it has an excellent balance between heat resistance and mechanical properties.
  • the relative viscosity of the polyamide resin used for the polyamide film substrate is not limited, but is usually preferably about 1.5 to 5.0, and particularly preferably 2.0 to 4.0. More preferably, there is. If the relative viscosity of the polyamide is less than 1.5, the mechanical properties of the resulting film may be significantly reduced. On the other hand, if the relative viscosity exceeds 5.0, it tends to impair the film forming property of the film.
  • the relative viscosity is a value measured using a Ubbelohde viscometer on a sample solution (solution temperature: 25 ° C.) in which polyamide is dissolved in 96% sulfuric acid to a concentration of 1.0 g / dl.
  • the polyamide-based film base material may contain other components in addition to the polyamide-based resin within a range that does not impair the effects of the present invention.
  • Other components include known or commercially available additives. More specifically, examples include metals (metal ions), pigments, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, mold release agents, and reinforcing agents (fillers).
  • metals metal ions
  • examples include metals (metal ions), pigments, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, mold release agents, and reinforcing agents (fillers).
  • hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides and the like can be suitably used as the heat stabilizer or the antioxidant.
  • At least one of an inorganic lubricant and an organic lubricant may be preferably contained within a range where the surface roughness (Ra) satisfies 45 nm or less.
  • the lubricant include clay, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, magnesium aluminosilicate, glass balloon, carbon black, oxide
  • Inorganic lubricants such as zinc, antimony trioxide, zeolite, hydrotalside, and layered silicate, erucamide, oleamide, stearamide, ethylenebissteaamide, ethylenebisethylenebisoleamide, hexa
  • Organic lubricants such as methylenebisstearic acid amide and hexamethylenebisoleic acid amide methylenebisstearic acid amide are exemplified.
  • the thickness of the polyamide-based film substrate is not particularly limited, but is generally preferably 4 to 30 ⁇ m, and more preferably 5 to 25 ⁇ m. If the thickness is less than 4 ⁇ m, the mechanical strength tends to be insufficient, and the moldability decreases. On the other hand, when the thickness exceeds 30 ⁇ m, the weight increases, and it is difficult to use the thin film for applications in which weight reduction is desired. If the mechanical strength is sufficient, the thinner the thickness, the more the electrolytic solution can be sealed, which is preferable in terms of securing the content amount or the electric capacity.
  • the polyamide-based film substrate is preferably stretched from the viewpoint of mechanical strength. That is, it is preferable to adopt a structure having orientation. In this case, either uniaxial stretching or biaxial stretching may be used, but it is particularly preferable to have orientation by biaxial stretching.
  • the stretching ratio can be appropriately set within the range described below.
  • the polyamide-based film substrate has been subjected to a known surface treatment such as a corona treatment, a plasma treatment, and an ozone treatment on at least one surface in order to improve the adhesion between the layers constituting the laminate when the laminate is formed.
  • a known surface treatment such as a corona treatment, a plasma treatment, and an ozone treatment on at least one surface in order to improve the adhesion between the layers constituting the laminate when the laminate is formed.
  • It preferably has a surface.
  • the surface roughness is preferably set to 10 nm or more.
  • the surface roughness of the protective layer is preferably equal to or higher than the surface roughness. That is, in the present invention, it is preferable that “surface roughness of protective layer surface ⁇ surface roughness of polyamide base film”.
  • the protective layer contains a dicarboxylic acid component and a diol component (glycol component) as constituent components, and the dicarboxylic acid component having a naphthalene skeleton is at least 50 mol% in 100 mol% of structural units derived from dicarboxylic acid.
  • a copolymerized polyester resin (hereinafter, this specific copolymerized polyester resin is also referred to as “copolymerized polyester resin A”).
  • a copolymerized polyester resin A for example, a copolymer obtained by performing a polycondensation reaction between the above dicarboxylic acid component and a diol component can be suitably used.
  • (A) Copolyester resin A Dicarboxylic acid component
  • the dicarboxylic acid component is not particularly limited.
  • Aromatic dicarboxylic acids such as carboxybiphenyl, phenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfondicarboxylic acid, oxalic acid, malonic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, undecane
  • Aliphatic dicarboxylic acids such as dicarboxylic acid, dodecane dicarboxylic acid, octadecane dicarboxylic acid, dimer acid
  • the dicarboxylic acid component having a naphthalene skeleton includes, for example, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid And the like.
  • 2,6-naphthalenedicarboxylic acid is particularly preferred from the viewpoint of low steric hindrance and high crystallinity.
  • the dicarboxylic acid component A is usually contained in an amount of at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, in the structural unit (100 mol%) derived from dicarboxylic acid. More preferably, the content is more preferably 80 mol% or more. Thereby, higher electrolytic solution resistance can be secured.
  • the upper limit of the content of the dicarboxylic acid component is not particularly limited, but can be usually about 95 mol%.
  • the content of the dicarboxylic acid component other than the dicarboxylic acid component A (hereinafter, referred to as “dicarboxylic acid component B”) is not particularly limited, but is usually 1 to 100 mol% in the structural unit derived from dicarboxylic acid (100 mol%). It is preferably about 50 mol%, particularly preferably 5 to 45 mol%.
  • terephthalic acid as the dicarboxylic acid component B from the viewpoint of low steric hindrance and high crystallinity.
  • the content of terephthalic acid in the structural unit (100 mol%) derived from dicarboxylic acid is not limited, but is usually about 3 to 50 mol%, and especially 5 to 45 mol%. Is more preferable, and among them, the content is most preferably 10 to 40 mol%. Therefore, in the present invention, a composition containing 2,6-naphthalenedicarboxylic acid and terephthalic acid as the dicarboxylic acid component can be suitably adopted.
  • the structural unit derived from dicarboxylic acid (100 mol%) contains at least 50 mol% of 2,6-naphthalenedicarboxylic acid in the structural unit derived from dicarboxylic acid (100 mol%), and terephthalic acid Is 5 mol% or more. Therefore, for example, 55 to 90 mol% of 2,6-naphthalenedicarboxylic acid is contained in the structural unit derived from dicarboxylic acid (100 mol%) in the structural unit derived from dicarboxylic acid (100 mol%), and terephthalic acid is contained in 5 Compositions containing up to 45 mole% can also be employed.
  • an aliphatic dicarboxylic acid such as adipic acid or sebacic acid may be contained as the dicarboxylic acid component B.
  • the content of the aliphatic dicarboxylic acid is preferably 20 mol% or less, more preferably 15 mol% or less, in the structural unit (100 mol%) derived from the dicarboxylic acid. Most preferably, it is 5 mol% or less.
  • the mixing ratio (molar ratio) of the dicarboxylic acid component A and the dicarboxylic acid component B is usually about 50:50 to 98: 2, particularly about 80:20 to 95: 5. It is desirable that
  • the diol component is not particularly limited, but for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Aliphatic dihydroxy compounds such as pentanediol, 1,6-hexanediol, and neopentyl glycol; polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; 1,4-cyclohexanedimethanol; spiro glycol And aromatic dihydroxy compounds such as bisphenol A. These can be used alone or in combination of two or more.
  • an aliphatic dihydroxy compound is preferable from the viewpoint of enhancing the resistance to an electrolytic solution, and among them, an aliphatic dihydroxy compound having 4 or less carbon atoms is more preferable. More specifically, at least one of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol and the like can be mentioned.
  • the aliphatic dihydroxy compound is usually preferably contained in an amount of at least 50 mol%, more preferably at least 60 mol%, and even more preferably at least 70 mol%, in the structural unit (100 mol%) derived from the diol component. Is more preferable, and among them, the content is most preferably 80 mol% or more. The upper limit of this content can be, for example, 100 mol%, but is not limited to this.
  • aliphatic diols having 5 or more carbon atoms such as 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol may be contained, but the content is large. If the content is too high, the resistance to the electrolytic solution tends to decrease. Therefore, the content of the aliphatic diol having 5 or more carbon atoms is preferably about 0 to 25 mol% in 100 mol% of the structural unit derived from the diol component.
  • the copolyester resin A When used as an aqueous coating solution for forming a protective layer, it may contain a dicarboxylic acid component having a sulfo group (—SO 3 H) as the dicarboxylic acid component B.
  • a dicarboxylic acid component having a sulfo group (—SO 3 H)
  • Preferred is an aromatic dicarboxylic acid having a sulfo group.
  • at least one of 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, sulfoterephthalic acid and 4-sulfonaphthalene-2,6-dicarboxylic acid is preferred, and 5-sulfoisophthalic acid is particularly preferred. It is preferable from the viewpoint.
  • a dicarboxylic acid component having no naphthalene skeleton and having a sulfo group can be suitably used as the dicarboxylic acid component B.
  • the content of the compound can be calculated as dicarboxylic acid B.
  • the content of the dicarboxylic acid component having a sulfo group is preferably 3.5 to 30 mol%, more preferably 4 to 20 mol%, in 100 mol% of the structural units derived from dicarboxylic acid. More preferably, the content is 4 to 10 mol%.
  • Copolyester resin A preferably has a glass transition temperature of 60 ° C. or higher, more preferably 80 ° C. or higher, and most preferably 100 ° C. or higher. .
  • the glass transition temperature is lower than 60 ° C., the binding force between the molecular chains constituting the copolymerized polyester resin is weakened, so that the electrolyte solution resistance may be poor.
  • the film of the present invention is preferably produced by applying a coating liquid for forming a protective layer to form a protective layer to an unstretched or uniaxially stretched polyamide film and then stretching the film.
  • the glass transition temperature of the polymerized polyester resin A increases, the stretchability with the polyamide film decreases, and the film is easily cut. Therefore, the glass transition temperature is preferably 145 ° C. or lower, and among them, 140 ° C. It is more preferred that:
  • the copolymerized polyester resin A may have a crosslinked structure.
  • a crosslinked structure can be formed by using a crosslinking agent that reacts with a carboxyl group or a hydroxyl group, which is a terminal group of the copolymerized polyester resin A.
  • the crosslinking agent is not limited as long as it can perform the above reaction, but preferably contains at least one of a melamine resin, an isocyanate compound, a carbodiimide compound, and an oxazoline compound. These may be known or commercially available ones.
  • the cross-linking agent is preferably contained in the protective layer in an amount of 0.1 to 15% by mass, particularly preferably 0.1 to 10% by mass, and more preferably 2.5 to 7.5% by mass. It is most preferred that By setting the content within such a range, more excellent electrolytic solution resistance and the like can be obtained.
  • the copolyester resin A can be synthesized basically according to a known method for producing a copolyester resin, except that the above-mentioned specific dicarboxylic acid component and diol component are used. it can. That is, the copolyester resin A is suitably produced by a production method including a step of performing a polycondensation reaction between a dicarboxylic acid component containing at least 50 mol% of a dicarboxylic acid component having a naphthalene skeleton in 100 mol% of the dicarboxylic acid component and a diol component. can do.
  • dicarboxylic acid component in addition to the dicarboxylic acids exemplified above, at least one kind of derivatives such as metal salts, anhydrides, and ester compounds thereof can be used. As these compounds themselves, those similar to those used in the synthesis of known copolyester resins can be employed.
  • diol component in addition to the diols (glycols) exemplified above, at least one kind of derivatives such as metal salts, anhydrides, and ester compounds thereof can be used. As these compounds themselves, the same compounds as those used in the synthesis of known copolyester resins can be employed.
  • the mixing ratio of the carboxylic acid component and the diol component can be appropriately set within a range in which a predetermined polycondensation reaction can be sufficiently performed.
  • the molar ratio of the carboxylic acid component: diol component 1: 0.5 to 1 .5, but is not limited to this.
  • a polymerization catalyst can be added to the raw materials as needed.
  • the polymerization catalyst is not limited, and a known catalyst can be used.
  • a titanium-based catalyst such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate can be suitably used.
  • the amount of the polymerization catalyst to be added is not particularly limited, but usually can be appropriately adjusted within the range of 5 ⁇ 10 ⁇ 5 to 5 ⁇ 10 ⁇ 4 mol per 1 mol of the carboxylic acid component.
  • the reaction system may be a liquid phase reaction. However, since the diol component is usually in a liquid state, the reaction can be performed particularly without a solvent. It is possible to use an organic solvent if necessary.
  • the reaction atmosphere may be at normal pressure, reduced pressure (including vacuum), or under pressure.
  • As the atmosphere gas an inert gas atmosphere such as a nitrogen gas or an argon gas may be usually used.
  • the reaction preferably proceeds in two stages including a transesterification reaction step as a first step and a polymerization reaction step as a second step.
  • the reaction temperature in the transesterification step is not particularly limited as long as all the components are melted, but can usually be set to about 200 to 260 ° C.
  • the reaction time depends on the reaction temperature and the like, but usually may be in the range of about 1 to 5 hours.
  • the reaction temperature in the polymerization reaction step is not particularly limited as long as the polymerization of the initial condensate (ester compound) can proceed, but can be usually set to about 200 to 260 ° C.
  • the reaction time depends on the reaction temperature and the like, but usually may be in the range of about 1 to 5 hours.
  • it is preferable to carry out the reaction under reduced pressure or under vacuum and more specifically, it is preferable to set the pressure to about 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 Pa. Therefore, for example, it can be set to about 1 ⁇ 10 ⁇ 4 to 1 ⁇ 5 Pa, or it may be set to about 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 1 Pa.
  • the obtained reaction product is usually in a liquid state at normal temperature and normal pressure, and thus can be used as it is as a raw material of a coating material for forming a protective layer. If necessary, the reaction product in liquid form may be subjected to solid-liquid separation, purification, etc., and then isolated. Thus, the copolymerized polyester resin A can be obtained.
  • a cross-linking agent can be further reacted with the copolyester resin A in order to provide the copolyester resin A with a crosslinked structure, if necessary.
  • a cross-linking agent included, the cross-linking density of the protective layer is increased by reacting with one or both of the carboxyl group and the hydroxyl group, which are terminal groups of the copolymerized polyester resin, so that the electrolytic solution of the protective layer Sex can be further enhanced.
  • the in-line coating method is adopted, at least one of a blocked isocyanate and an oxazoline is particularly effective in increasing the electrolytic solution resistance of the protective layer by such a crosslinking agent, and oxazoline is particularly preferable.
  • the amount of the crosslinking agent to be added may be such that it is contained in the protective layer at a specific ratio as described above. For example, the amount is appropriately adjusted within the range of about 1 to 15 parts by mass with respect to 100 parts by mass of the copolymerized polyester resin A. can do.
  • the cross-linking agent may be added to and mixed with the copolyester resin A and kept for a certain period of time.
  • the holding temperature in this case is not particularly limited, but usually may be about 5 to 30 ° C.
  • the holding time may be usually about 0 to 120 hours.
  • the protective layer contains the copolymerized polyester resin A.
  • the content of the copolymerized polyester resin A in the protective layer is 70 to 100% by mass. It is more preferably, and particularly preferably 80 to 95% by mass.
  • components other than the copolymerized polyester resin A may be contained in the protective layer as long as the effects of the present invention are not impaired.
  • various additives such as a lubricant, a heat stabilizer, an antioxidant, a reinforcing material (filler), a pigment, a deterioration inhibitor, a weathering agent, a flame retardant, a plasticizer, a release agent, and a crosslinking agent are exemplified. These may be the same as those applied to the above-mentioned polyamide-based film substrate.
  • the lubricant include organic lubricants such as ethylenebisstearic acid amide, organic particles such as acrylic particles, and inorganic particles such as silica. Since these also function as anti-blocking agents, it is preferable to add one or more of the above-mentioned lubricants.
  • heat stabilizer examples include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, halides of alkali metals, and mixtures thereof.
  • the reinforcing material examples include clay, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, zinc oxide, Examples include zeolite, hydrotalcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate whiskers, boron nitride, graphite, glass fibers, carbon fibers, and the like. One or more of these can be added.
  • an inorganic layered compound is an inorganic compound in which a unit crystal layer overlaps to form a layered structure, and specifically, zirconium phosphate (phosphate-based derivative type compound), chalcogenide, lithium aluminum composite hydroxide, graphite, clay Minerals and the like can be exemplified, and those which swell or cleave in a solvent are particularly preferable.
  • zirconium phosphate phosphate-based derivative type compound
  • chalcogenide lithium aluminum composite hydroxide
  • graphite graphite
  • clay Minerals and the like can be exemplified, and those which swell or cleave in a solvent are particularly preferable.
  • the thickness of the protective layer is required to be 1.5 ⁇ m or less, and particularly preferably 1 ⁇ m or less, from the viewpoint of improving productivity by reducing the drying time, improving blocking resistance, and the like.
  • the protective layer having a thickness of more than 1.5 ⁇ m is economical because unevenness occurs in the protective layer forming step or the drying step, productivity is reduced due to a long heat treatment time, and the cost of the coating liquid increases. In addition, there are few advantages, and the anti-blocking property may be poor.
  • the thickness of the protective layer is preferably 0.05 ⁇ m or more, particularly 0.1 ⁇ m or more, in order to sufficiently increase the resistance to an acidic liquid such as an electrolytic solution. It is more preferably 0.2 ⁇ m or more, and most preferably 0.4 ⁇ m or more.
  • the surface roughness Ra of the protective layer surface is not particularly limited, but is preferably 45 nm or less, more preferably 40 nm or less, and most preferably 35 nm or less, from the viewpoint of improving the electrolytic solution resistance. preferable. If the surface roughness of the protective layer surface exceeds 45 nm, the electrolytic solution tends to stay on the protective layer surface, and the resistance to the electrolytic solution may be impaired.
  • the lower limit of the surface roughness Ra may be, for example, 20 nm or 15 nm, but is not limited thereto.
  • the surface roughness can be controlled to 45 nm or less, for example, by forming a protective layer by an inline coating method using a predetermined protective layer forming coating liquid as described later.
  • various layers can be laminated as necessary in addition to the polyamide-based film substrate and the protective layer.
  • Each layer itself may be the same as that used in known packaging materials and the like.
  • a laminate composed of a protective layer / polyamide-based film substrate / barrier layer / heat-fused layer, protective layer / polyamide-based film substrate / protective layer / barrier layer / heat A laminate or the like made of a fusion layer is effective as a battery exterior material.
  • a preferred embodiment of the barrier layer and the heat sealing layer will be described.
  • the barrier layer is not particularly limited as long as it can exhibit gas barrier properties (oxygen barrier properties) and water vapor barrier properties.
  • a known or commercially available layer or film having a barrier property such as a metal foil or a vapor-deposited film may be used. it can.
  • metal foils are widely used and preferred.
  • the metal foil is preferably an aluminum foil, but is not limited to this.
  • various types of barrier layers used for exterior materials of lithium ion secondary batteries can be employed.
  • the thickness of the barrier layer is not particularly limited, but is usually preferably about 20 to 200 ⁇ m, and more preferably 30 to 150 ⁇ m.
  • one or both surfaces of the barrier layer have been subjected to a surface treatment suitable for a lithium ion secondary battery exterior material.
  • a surface treatment suitable for a lithium ion secondary battery exterior material examples include a chemical conversion treatment and a chromate treatment.
  • these surface treatments are preferably performed on the surface of the barrier layer that is in contact with the heat-sealing layer.
  • Heat-fused layer is not particularly limited as long as it can be heat-sealed.
  • a well-known material suitable for an exterior material of a lithium ion secondary battery can be used.
  • a polyvinyl chloride film, a polyolefin film or the like can be suitably used.
  • the polyolefin include polyethylene, polypropylene, a copolymer containing polypropylene as a main component, and acid-modified products thereof.
  • As the heat sealing layer either a stretched film or a non-stretched film can be used.
  • the method for forming the heat-sealing layer is not particularly limited, for example, a method of applying a coating liquid containing the heat-sealing component, and laminating a film in which a resin composition containing the heat-sealing component is previously formed into a film shape. Any of the methods and the like can be adopted.
  • the thickness of the heat-sealing layer is not particularly limited as long as the desired heat-sealing property is obtained, but is generally preferably about 20 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
  • the thickness (total thickness) of the film of the present invention can be appropriately set depending on the application, the method of use, and the like.
  • the thickness is preferably about 10 to 25 ⁇ m, and more preferably 15 to 25 ⁇ m.
  • the film of the present invention has high thickness accuracy (thickness uniformity). That is, the standard deviation value with respect to the average thickness is usually preferably 0.200 or less, more preferably 0.180 or less, and most preferably 0.160 or less.
  • the method of evaluating the thickness accuracy is performed as follows. After humidifying the film of the present invention at 23 ° C. ⁇ 50% RH for 2 hours, as shown in FIG. 3, a reference direction (0 ° direction) is specified around an arbitrary point A on the film, and then the center point is determined. From A, a reference direction (a), a 45-degree direction (b), a 90-degree direction (c), a 135-degree direction (d), a 180-degree direction (e), and a 225-degree direction (f) clockwise with respect to the reference direction. A total of eight 100 mm straight lines L1 to L8 are drawn in eight directions of the 270 degree direction (g) and the 315 degree direction (h).
  • FIG. 3 shows, as an example, a state where measurement points (10 points) are taken when measuring L2 in the 45-degree direction. Then, an average value of the measured values of a total of 80 data obtained by measuring all the straight lines is calculated, and the average value is used as the average thickness to calculate a standard deviation value with respect to the average thickness.
  • the reference direction is not particularly limited, and may be, for example, the MD in the stretching step during film production.
  • the average thickness and the standard deviation may be based on any one point (point A) of the polyamide-based film.
  • point A any one point of the polyamide-based film.
  • the average thickness and the standard deviation within the above ranges are more preferable.
  • the three points are a) a position near the center of the winding width and half the winding amount, b) a position near the right end of the winding width and half the winding amount, and c) a winding width. Is near the left end and near the end of the winding.
  • the film of the present invention has excellent performance in electrolytic solution resistance, and it is preferable that the film satisfy the value of the following formula (1) as an index.
  • Hz0 Haze value measured according to Japanese Industrial Standard "JIS K 7136". The measurement of the haze value can be performed using a commercially available measuring device (for example, a haze meter “NDH 4000” manufactured by Nippon Denshoku Co., Ltd.).
  • HzX Haze value measured in the same manner as Hz0 after 12 hours at a temperature of 23 ° C. and a humidity of 50% RH with the electrolyte solution shown below adhered to the protective layer after measuring Hz0.
  • the value of the above formula (1) is usually less than 3, as described above, but is particularly preferably 2 or less, more preferably 1.8 or less, and particularly preferably 1 or less. Most preferred. If the value of the above formula (1) is large, it means that corrosion has occurred due to the electrolytic solution and whitening has occurred, indicating that the electrolytic resistance is poor.
  • the lower limit of this value is not particularly limited, and may be, for example, 0.1.
  • the haze value (Hz0) of the film of the present invention before the electrolytic droplets are dropped is not particularly limited. However, when the film is used for an application requiring transparency, it is usually preferably 10 or less, Among them, the number is preferably 5 or less.
  • the lower limit of the haze value (Hz0) is not particularly limited, and may be, for example, about 0.1.
  • the film of the present invention also satisfies the following formula (2) as an index excellent in electrolytic solution resistance.
  • Expression (2) Hz0: Haze value measured in accordance with Japanese Industrial Standard "JIS K 7136". The measurement of the haze value can be performed using a commercially available measuring device (for example, a haze meter “NDH 4000” manufactured by Nippon Denshoku Co., Ltd.).
  • HzY Haze value measured in the same manner as Hz0 after 24 hours at a temperature of 23 ° C. and a humidity of 50% RH after the measurement of Hz0 and the following electrolytic solution adhered to the protective layer.
  • the value of the above formula (2) is usually less than 3, particularly preferably 2.6 or less, more preferably 2 or less, and even more preferably 1.8 or less. It is more preferable, and among them, it is most preferably 1 or less.
  • the lower limit of this value is not particularly limited, and may be, for example, about 0.1.
  • the film of the present invention that satisfies the above formula (1) or the above formulas (1) and (2) can more reliably exhibit excellent electrolytic solution resistance. That is, the haze hardly changes after being left for 12 hours after the electrolytic solution is attached, and the haze hardly changes even after being left for 24 hours. It is expected that, even if the electrolyte solution is left for a long time in the state where it is attached, not only the change in haze before and after the attachment but also the change in the appearance or the decrease in elongation is effectively suppressed.
  • the film of the present invention contains, for example, (1) a dicarboxylic acid component and a diol component as constituent components, and a dicarboxylic acid component having a naphthalene skeleton in 100 mol% of structural units derived from dicarboxylic acid.
  • a step of applying a coating liquid for forming a protective layer containing a copolymerized polyester resin of not less than mol% to an unstretched polyamide-based film or a uniaxially stretched polyamide-based film (coating step); (2) a step of stretching a polyamide-based film having a coating film by the application to obtain a polyamide-based laminated film having a protective layer formed on one or both sides of a biaxially stretched film stretched in the MD and TD directions. (Stretching process) Can be suitably produced by a method for producing a polyamide-based laminated film containing.
  • the method for forming the protective layer is not limited, and any method such as an in-line coating method and a post-coating method can be adopted.
  • an in-line coating method it is preferable to employ a method of stretching an unstretched film or a uniaxially stretched film on which a coating film is formed with the coating liquid for forming a protective layer together with the coating film. Therefore, a manufacturing method including the above-described coating method and stretching method can be suitably adopted.
  • the protective layer can be made smoother than the post-coating method, so that the protective layer can be formed thinly and uniformly. Further, as described above, the electrolytic solution resistance of the protective layer containing the copolymerized polyester resin is also improved.
  • the procedure is not particularly limited as long as it has the coating step and the stretching step as described above.
  • any method such as stretching in a direction (MD direction or TD direction) orthogonal to the uniaxial direction can be adopted.
  • MD direction or TD direction a direction orthogonal to the uniaxial direction
  • a copolymerized polyester resin containing a dicarboxylic acid component and a diol component as constituent components, and a dicarboxylic acid component having a naphthalene skeleton in 50 mol% of structural units derived from dicarboxylic acid is 50 mol% or more.
  • a coating liquid for forming a protective layer (the coating liquid of the present invention) containing (copolymerized polyester resin A) is applied to one or both surfaces of an unstretched polyamide film or a uniaxially stretched polyamide film.
  • the unstretched polyamide-based film or uniaxially stretched polyamide-based film can be a polyamide-based film substrate of the film of the present invention, and a known film itself can be used according to a known method. Prepared films can also be used.
  • an unstretched polyamide film can be obtained by molding a melt-kneaded product containing a polyamide resin into a film.
  • the preparation of the melt-kneaded product itself may be performed according to a known method.
  • it can be produced by molding a melt-kneaded product obtained by melting a resin composition containing a polyamide resin into a film. This can be done by using known or commercially available equipment.
  • a melt extruder having a T-die can be used.
  • a starting material for example, a pellet-shaped raw material
  • a melt extruder plasticized and melted by a melt extruder
  • the melt-kneaded material is extruded into a sheet shape from a T-die attached to the tip of the extruder and cooled by a cast roll Solidify.
  • the unkneaded film can be obtained by pressing the melt-kneaded product against the cast roll with air.
  • additives can be added to the above resin composition as required.
  • examples of the additive include additives that are added to the polyamide-based film substrate.
  • the uniaxially stretched polyamide-based film for example, a film obtained by uniaxially stretching the above-mentioned unstretched polyamide-based film can be used.
  • the coating liquid of the present invention contains a copolyester resin containing a dicarboxylic acid component and a diol component as constituent components and a dicarboxylic acid component having a naphthalene skeleton in 100 mol% of the dicarboxylic acid component of 50 mol% or more.
  • a copolymerized polyester resin those described above can be used.
  • the coating liquid of the present invention can be prepared by dissolving or dispersing the copolymerized polyester resin A in a solvent. That is, the coating liquid of the present invention can be prepared in the form of a solution or a dispersion.
  • the solvent is not particularly limited.
  • alcohols such as methanol, ethanol, and isopropanol
  • cellosolves such as butyl cellosolve, toluene, methyl ethyl ketone (MEK), cyclohexanone, solvesso, isophorone, xylene, and methyl isobutyl ketone (MIBK)
  • organic solvents such as ethyl acetate, propyl acetate, butyl acetate and isobutyl acetate.
  • the coating liquid for forming the protective layer is preferably a water-soluble or water-dispersed aqueous coating agent containing water as a main component from the viewpoints of workability, environmental aspects, and the like. From the viewpoint, an aqueous dispersion is more preferable. In this case, it is preferable that the crosslinking agent is also aqueous.
  • an organic solvent such as alcohol may be contained in a small amount.
  • the concentration of the copolyester resin A in the coating liquid of the present invention can be appropriately set according to the type of the copolyester resin to be used and the like, but is usually about 3 to 40% by mass, particularly 5 to 20% by mass. It is desirable.
  • the coating liquid of the present invention may contain other components as long as the effects of the present invention are not impaired.
  • various additives exemplified above can be blended.
  • the solid content concentration of the coating liquid for forming a protective layer containing the copolymerized polyester resin used in the present invention is appropriately adjusted depending on the specifications of a coating apparatus and a drying / heat treatment apparatus.
  • a coating solution that is too dilute makes it difficult to form a protective layer having a sufficient thickness to exhibit resistance to an acidic liquid such as an electrolytic solution, and also requires a long time in a subsequent drying step. Tends to occur.
  • a coating solution having a too high concentration is difficult to be uniform, and tends to cause problems in coatability.
  • the solid content concentration of the coating liquid for forming a protective layer is preferably about 5 to 70% by mass, but is not limited thereto.
  • the preparation of the coating liquid for forming the protective layer containing the copolymerized polyester resin used in the present invention may be performed by a known method using a dissolving pot equipped with a stirrer or the like.
  • the method of applying using the coating solution of the present invention is not particularly limited, and a known method can be appropriately employed.
  • a known method can be appropriately employed.
  • gravure roll coating, reverse roll coating, wire bar coating, air knife coating, curtain coating, doctor knife, die coating, dip coating, bar coating, etc. can be adopted.
  • the solvent can be removed by drying as necessary, but the liquid film before drying or a semi-dried film may be subjected to the stretching step.
  • the drying step after the application is not particularly limited, for example, using a known method such as a drying treatment in a drying atmosphere such as an oven, a drying treatment by contact with a hot roll, a drying treatment in a stretching machine, and the like.
  • a drying treatment in a drying atmosphere such as an oven
  • a drying treatment by contact with a hot roll a drying treatment in a stretching machine
  • the drying temperature is not limited, but can usually be set within a range of about 30 to 160 ° C.
  • the drying time can be appropriately set depending on the drying temperature and the like, but is generally in the range of 0.5 to 10 minutes.
  • a protective layer was formed on one or both surfaces of a biaxially stretched film stretched in the MD and TD directions by stretching a polyamide film having a coating film formed by the coating. Obtain a polyamide-based laminated film.
  • the preheating temperature is not limited, it is usually from 180 to 250 ° C., particularly preferably from 200 to 245 ° C., and most preferably from 210 to 240 ° C.
  • the preheating time depends on the preheating temperature and the like, but is usually preferably about 0.5 to 5 seconds.
  • the method of preheating is not particularly limited.
  • the method of setting the stretching temperature to the above-mentioned temperature is not limited, but it is preferable to set the temperature of the hot air blown to the film running in the stretching zone of the stretching machine within the above-mentioned temperature range.
  • the time for the polyamide film to travel in the stretching zone is usually preferably about 0.5 to 5 seconds.
  • the biaxially stretched film of the present invention is finally obtained, so that the simultaneous biaxial stretching method or the sequential biaxial stretching method can be employed.
  • the classification by the stretching device include a tubular method and a tenter method, and any of them can be applied.
  • a stretching method by a tenter method is particularly preferable in view of quality stability and dimensional stability. Accordingly, a tenter-type simultaneous biaxial stretching method or a tenter-type sequential biaxial stretching method can be suitably employed.
  • a coating liquid for forming a protective layer is applied to a film that has been uniaxially stretched in the MD or TD direction in advance, and then the direction perpendicular to the uniaxial direction (TD (Or MD direction) to obtain a film of the present invention in which a protective layer is formed on a predetermined biaxially stretched film.
  • the stretching ratio is not particularly limited, but it is usually sufficient to stretch in the MD direction and the TD direction to about 2.0 to 4.5 times each. In this case, the stretching ratios in the MD and TD directions may be the same or different. In this way, a stretched film having good physical properties such as tensile strength and tensile elongation can be obtained.
  • the stretching temperature is not limited, and can be appropriately set within a range of 220 ° C or less according to, for example, the stretching method, the application of the film of the present invention, the use form, and the like.
  • an unstretched film is uniaxially stretched at a stretching temperature of 40 to 80 ° C. (preferably 50 to 65 ° C.), and then a coating liquid for forming a protective layer is applied.
  • the uniaxially stretched film coated with the coating liquid for forming a protective layer can be dried at 50 to 220 ° C. in the same manner as in the simultaneous biaxial stretching method described above.
  • the uniaxially stretched film coated with the coating liquid for forming a protective layer is stretched in the direction perpendicular to the film at a stretching temperature of 200 ° C. or lower (preferably 90 to 190 ° C.) to obtain a biaxially stretched film. .
  • a roll stretching method and a tenter type stretching method in combination. That is, after being stretched in a uniaxial direction (MD or TD direction) by a roll (usually a device that stretches while passing through two or more rolls), it is stretched in a direction substantially perpendicular to the uniaxial direction (TD or MD direction) by a tenter. By stretching, biaxial stretching can be performed.
  • a coating liquid for forming a protective layer is applied at a stretching temperature of 215 ° C. or lower (preferably 190 to 210 ° C.).
  • the unstretched film is simultaneously biaxially stretched.
  • the simultaneous biaxial stretching of the unstretched film is preferably performed by a tenter method, a LISIM biaxial stretching method, or the like.
  • the heat treatment temperature is not particularly limited, but is usually preferably about 190 to 220 ° C., and more preferably 195 to 215 ° C.
  • the heat treatment temperature is lower than 190 ° C., the formation of a coating film of the copolymerized polyester resin becomes insufficient, and a protective layer having insufficient resistance to an electrolytic solution may be formed.
  • a curing agent is added, the crosslinking reaction does not proceed sufficiently, and the effect of adding the crosslinking agent may not be obtained.
  • the heat treatment temperature exceeds 220 ° C., the strength of the polyamide film may decrease.
  • an aging treatment may be performed after the completion of the stretching.
  • the heat treatment time can be appropriately set according to the heat treatment temperature and the like, but is usually preferably about 1 to 15 seconds.
  • the heat treatment method is not particularly limited, and for example, a method of blowing hot air, a method of irradiating infrared rays, a method of irradiating microwaves, and the like can be employed.
  • the method of blowing hot air is preferable from the viewpoint that heating can be performed uniformly and accurately.
  • the heat setting process can be performed by blowing hot air set in the above temperature range onto a film running in the heat setting zone of the stretching machine.
  • the method of laminating each layer is not particularly limited, and includes, for example, a) a method of forming a coating film using a coating liquid, b) a method of laminating a pre-formed film, c) a PVD method, a CVD method, and the like. Any of the methods for forming a vapor-deposited film can be adopted. In the case of b), any of a method of laminating via an adhesive, a method of laminating by co-extrusion molding, and the like can be adopted. In particular, when the film of the present invention is used as an exterior material of a battery such as a lithium ion secondary battery, a known method for producing an exterior material can be employed. In this case, it is also possible to laminate using a known adhesive.
  • a laminate including a protective layer / a polyamide-based film substrate or a laminate including a protective layer / a polyamide-based film substrate / a protective layer, and a metal foil for forming a barrier layer are included. It is possible to employ a method such as dry lamination or heat lamination via a two-part urethane-based adhesive or the like.
  • a known method dry lamination, heat lamination, extrusion lamination, sandwich lamination, or the like.
  • the barrier layer On the surface of the polyamide film on which the layer of the adhesive is formed, the barrier layer, and the surface of the heat-sealing layer, other layers such as an anchor coat layer and a primer layer may be added as necessary, as long as the effects of the present invention are not impaired. May be provided.
  • the film of the present invention can be used for various applications, but can be particularly suitably used as a packaging material. That is, it can be used as a packaging material for packaging the contents.
  • the contents are not limited. For example, contents such as electronic components, chemical products, cosmetics, medical products (medical devices), food and drink, and the like can be packaged.
  • the film of the present invention can be suitably used as an exterior material of a lithium ion battery.
  • the film of the present invention when used as an exterior material, the film of the present invention (particularly, a polyamide-based substrate layer) can be protected from the electrolytic solution by the protective layer. As a result, it is possible to effectively suppress or prevent problems caused by corrosion of the exterior material and the like.
  • an electrolytic solution used for a lithium ion secondary battery is an electrically conductive liquid prepared by dissolving an ionic substance (particularly, a lithium salt) in a polar solvent such as carbonate.
  • the lithium salt include a lithium salt that generates hydrofluoric acid (hydrogen fluoride) by reacting with water. More specifically, fluorine-containing lithium salts such as lithium hexafluorophosphate (LiPF 6 ) and lithium tetrafluoroborate (LiBF 4 ) are exemplified. Therefore, when the electrolytic solution adheres in the air, the moisture in the air reacts with the fluorine-containing lithium salt in the electrolytic solution to generate hydrofluoric acid.
  • the hydrofluoric acid may dissolve the polyamide film used for the exterior material of the lithium ion secondary battery.
  • the film of the present invention since the polyamide-based substrate layer is covered with the specific protective layer, even if the electrolytic solution comes into contact with the exterior material (especially, the protective layer), the film has a high electrolytic solution resistance. As a result of effectively protecting the exterior material, a highly reliable lithium ion secondary battery can be provided. Therefore, the film of the present invention can be suitably used, for example, as an exterior material of a lithium ion secondary battery, and is also applicable to embossed type or deep drawing lithium ion secondary batteries. Then, even when the electrolytic solution adheres to the exterior material at the time of manufacturing the lithium ion secondary battery, the performance as the exterior material of the lithium ion secondary battery can be favorably maintained.
  • the form is not particularly limited, and for example, it can be used as a packaging bag or packaging container.
  • the packaging bag for example, various types of bags such as a pillow bag, a gusset bag, and a stand bag can be used.
  • the bag may be formed according to a known method.
  • the present invention further includes a product (packaged product) in which the contents are packaged by the above-described packaging material or packaging bag.
  • a product packaged product
  • Examples of the packaging state in this case include a state in which the contents are sealed from the outside by a packaging material or a packaging bag.
  • Battery The present invention is a battery including a power generation element including a negative electrode, a positive electrode, a separator and an electrolyte, and a packaging material for packaging the power generation element, wherein the packaging material is the film of the present invention, and the protective layer is
  • the battery includes a battery which is disposed as an outermost layer of the battery.
  • the film of the present invention can be suitably used for a laminate type (pouch type) battery. Therefore, for example, in addition to the method of forming the film of the present invention in advance into a concave shape (container shape) and then loading and sealing the power generating element, the film of the present invention may be placed on the film of the present invention and then wrapped around it. And a method of sealing the power generation element by molding the same.
  • the power generation element is not particularly limited, and a known or commercially available power generation element can be used. Further, any of a primary battery and a secondary battery may be used. For example, a lithium ion battery, a nickel hydride battery, a nickel cadmium battery and the like can be mentioned.
  • Fig. 4 shows a schematic diagram of the battery.
  • the battery 40 has a configuration in which the power generation element 41 is covered with an exterior material made of the film 10 of the present invention. More specifically, the power generation element 21 is covered with the film 10 of the present invention such that the protective layer 10a surface of the film 10 of the present invention is on the outside.
  • the power generating element 41 in FIG. 4 includes a positive electrode made of a positive electrode active material and a current collector, a separator, a negative electrode made of a negative electrode active material and a current collector, an electrolyte, and the like (all are not shown).
  • Each of the positive electrode and the negative electrode has a lead wire (tab) 43 extending to an end.
  • Examples of the positive electrode active material include lithium metal such as lithium manganate, and lithium metal.
  • Examples of the current collector of the positive electrode include an aluminum foil.
  • Examples of the separator include a microporous membrane such as polyethylene and polypropylene.
  • Examples of the negative electrode active material include graphite, lithium salts such as lithium manganate, metallic lithium, and the like, and examples of the current collector of the positive electrode include aluminum foil.
  • lithium salts such as lithium tetrafluoroborate (LiBF 4 ) and lithium hexafluorophosphate (LiPF 6 ) are dissolved in ethyl carbonate (EC), ethyl methyl carbonate (EMC), propylene carbonate and the like. Solution.
  • FIG. 5 shows a cross-sectional view of an example of an embodiment of a battery using the film body of the present invention as an exterior material.
  • the battery 50 has a configuration in which the film 10 of the present invention as an exterior material is folded in two such that the protective layer surface 10a is on the outside, and the power generation element 41 is loaded therein.
  • the surface on the opposite side of the protective layer of the film 10 of the present invention is the heat-sealing layer surface 10b, and the bonded portion S1 is formed by heat sealing with the ends thereof facing each other.
  • a lead wire 43 is sandwiched between the heat-sealed layers in the bonding portion S1. Although only one lead wire 43 is shown in FIG. 4 for simplification, in practice, a positive lead wire and a negative lead wire are provided.
  • the power generating element 41 is covered with the film 10 of the present invention so that the lead wire is exposed to the outside.
  • the power generation element 21 is coated by bonding the heat-fused layer surfaces 10b of the film 10 of the present invention to each other. In this case, a part is not joined, but is secured as an inlet for the electrolytic solution.
  • the injection port is also closed by heat sealing. In this way, the power generation element 21 is sealed by the film 10 of the present invention as an exterior material.
  • FIG. 6 is a schematic view showing a cross section of a battery according to another embodiment.
  • the periphery of a power generation element (power generation element) 41 having a lead wire 43 for connection to the outside is covered with two films 10 and 10 of the present invention. Both ends of the films 10, 10 of the present invention are sealed by bonding portions S1, S2 by heat sealing or the like.
  • the lead wire 43 extends so as to be exposed from the electrode in the battery 60 to the outside, and the current from the power generation element 41 can be taken out.
  • a positive lead wire and a negative lead wire are provided.
  • the power generating element 41 is covered with the films 10 of the present invention so that the lead wire is exposed to the outside.
  • the power generation element 21 is coated by joining the two heat-sealing layer surfaces 10b of the films 10 of the present invention by heat sealing. In this case, a part is not joined, but is secured as an inlet for the electrolytic solution.
  • the injection port is also closed by heat sealing.
  • the power generation element 41 is sealed by the two films 10 and 10 of the present invention.
  • Example 1 (1) Synthesis of copolymerized polyester resin A
  • a dicarboxylic acid component (709.4 parts of 2,6-naphthalenedicarboxylic acid, 26.6 parts of terephthalic acid, 56.2 parts of sodium 5-sulfoisophthalate) and a diol component (ethylene (176.7 parts of glycol, 126.2 parts of diethylene glycol, 336.8 parts of 1,6-hexanediol) and 0.26 part of tetrabutyl titanate as a polymerization catalyst were charged into a reactor, and the system was replaced with nitrogen. did. Then, the reactor was heated to 200 ° C. while stirring these raw materials at 1000 rpm. Next, the temperature was gradually raised to 260 ° C.
  • the unstretched film is passed through a water absorption treatment device at a water temperature of 50 ° C., and the coating liquid for forming a protective layer is coated on one surface of the unstretched film by a fountain method so that the thickness after drying becomes 0.70 ⁇ m.
  • the coating liquid for forming a protective layer is coated on one surface of the unstretched film by a fountain method so that the thickness after drying becomes 0.70 ⁇ m.
  • the simultaneous biaxial stretching machine the applied unstretched film was simultaneously biaxially stretched 3.0 times in the MD direction and 3.3 times in the TD direction at a preheating temperature of 200 ° C. and a stretching temperature of 190 ° C. .
  • a heat treatment was performed at a heat treatment temperature of 210 ° C.
  • the above adhesive is applied to the aluminum foil surface under the same conditions and dried, and a non-stretched polypropylene film (manufactured by Mitsui Chemicals Tosello Co., GHC, thickness of 50 ⁇ m) is bonded as a heat-sealing layer, and the atmosphere is heated at 40 ° C. For 72 hours. In this way, a polyamide laminated film laminated in the order of “protective layer / polyamide film / aluminum foil / heat fusion layer” was obtained.
  • Examples 2 to 19 and Comparative Examples 1 to 6 A polyamide-based laminated film was produced in the same manner as in Example 1 except that the conditions shown in Table 1 and below were used. In addition, * 1 in Table 1 shows the example by a post-coat method.
  • the coating liquid for forming a protective layer was applied to one surface of the stretched film using a gravure coater so that the thickness after drying was 0.70 ⁇ m, and then the preheating temperature was 60 ° C. and the stretching temperature was 90 ° C. Under the conditions, the film was stretched in the TD direction at a stretch ratio of 3.2 times. Further, heat treatment was performed under the conditions of a heat treatment temperature of 215 ° C. and a heat treatment time of 3 seconds. Further, the surface of the polyamide film having no protective layer was subjected to corona treatment. Thus, a stretched film having a film thickness of 15 ⁇ m and a protective layer having a thickness of 0.70 ⁇ m was obtained.
  • Examples 3 to 4, 9, 16 to 18, and Comparative Example 2> A polyamide-based laminated film was obtained in the same manner as in Example 2, except that the composition of the coating liquid for forming the protective layer and the heat treatment temperature during the formation of the protective layer were set to the conditions shown in Table 1.
  • Example 6 to 8, 10 to 15> A polyamide-based laminated film was obtained in the same manner as in Example 5, except that the composition of the coating liquid for forming the protective layer and the heat treatment temperature during the formation of the protective layer were set to the conditions shown in Table 1.
  • ⁇ About Example 19> (3) Production of stretched film (simultaneous biaxial stretching) Using an extruder equipped with a T-die, a polyamide resin (nylon 6, A1030BRF, relative viscosity 2.7) was extruded from a T-die orifice into a sheet under the condition of 260 ° C. Subsequently, this was brought into close contact with a casting roll adjusted to a surface temperature of 18 ° C. and quenched, and the supply amount of the polyamide resin was adjusted so that the thickness of the polyamide film obtained after stretching was 15 ⁇ m.
  • a polyamide resin nylon 6, A1030BRF, relative viscosity 2.7
  • the unstretched film is passed through a water-absorbing treatment device at a water temperature of 50 ° C., and then guided to a simultaneous biaxial stretching machine. It was simultaneously biaxially stretched 3.3 times in the direction.
  • heat treatment was performed at a heat treatment temperature of 210 ° C. and a heat treatment time of 3 seconds.
  • one side was subjected to corona treatment.
  • a stretched film having a thickness of 15 ⁇ m was obtained.
  • the obtained stretched film is guided to a gravure coater, and the coating liquid for forming a protective layer obtained in Example 2 is coated so that the final coating thickness becomes 0.7 ⁇ m.
  • the film is dried by passing through [Zone 1 (80 ° C.) ⁇ Zone 2 (100 ° C.) ⁇ Zone 3 (120 ° C.) ⁇ Zone 4 (110) ° C. ⁇ Zone 5 (80 ° C.)] for 3 seconds.
  • Zone 1 80 ° C.
  • Zone 2 100 ° C.
  • Zone 3 120 ° C.
  • Zone 4 (110) ° C.
  • Zone 5 80 ° C.
  • Example 1 A polyamide-based laminated film was obtained in the same manner as in Example 19, except that the composition of the coating liquid for forming a protective layer was as shown in Table 1, and the thickness of the protective layer was 2.00 ⁇ m.
  • Example 4 A polyamide-based laminated film was obtained in the same manner as in Example 1, except that the coating liquid for forming the protective layer was changed to the same PVDC coating liquid as in Comparative Example 3, and the heat treatment temperature during the formation of the protective layer was changed.
  • Example 6 A polyamide-based laminated film was obtained in the same manner as in Example 1, except that the coating liquid for forming the protective layer was changed to the same saturated polyester resin emulsion as in Comparative Example 5, and the heat treatment temperature at the time of forming the protective layer was changed.
  • Test example 1 The following properties were measured for the polyamide-based laminated films obtained in each of the examples and comparative examples. Table 2 shows the results. “Unmeasurable” in Table 2 indicates that measurement was not possible because wrinkles and the like occurred after the electrolytic solution was attached and the surface of the polyamide-based laminated film was deformed.
  • Thickness unevenness (thickness accuracy) of the laminated film
  • the reference direction (0 ° direction) was set around an arbitrary point A on the film.
  • a total of eight 100 mm straight lines are drawn.
  • the thickness was measured at 10 mm intervals from the center point A using a length gauge “HEIDENHAIN-METRO MT1287” (manufactured by HEIDENHAIN) (measured at 10 points), and measured on all straight lines. The average value of the measured values at a total of 80 data points was calculated, and the average value was used as the average thickness.
  • the reference direction is not particularly limited, and may be, for example, the MD in the stretching step during film production.
  • Electrolytic solution resistance Using the obtained polyamide-based laminated film, electrolytic solution resistance was evaluated for three types of standing times shown below: 6 hours, 12 hours, and 24 hours.
  • the haze value of the obtained polyamide-based laminated film is measured using a haze meter (NDH 4000) manufactured by Nippon Denshoku Co., Ltd. in accordance with Japanese Industrial Standards “JIS K 7136”. This is defined as the haze (Hz0) before the electrolytic liquid drops.
  • NDH 4000 haze meter manufactured by Nippon Denshoku Co., Ltd. in accordance with Japanese Industrial Standards “JIS K 7136”. This is defined as the haze (Hz0) before the electrolytic liquid drops.
  • three samples are prepared in which the opening of the glass Petri dish (200 mm in diameter) is covered with a polyamide-based laminated film such that the protective layer is on the surface.
  • a solution in which LiPF 6 was blended with a mixed solution composed of an electrolytic solution (ethylene carbonate / diethyl carbonate / methyl ethyl carbonate 1/1/1 (volume ratio), concentration: 1 mol / L) 10 ml), and an electrolytic solution is attached to the protective layer.
  • the electrolytic solution on the protective layer is wiped off with a gauze, and measured in the same manner as above using a haze meter (NDH 4000) manufactured by Nippon Denshoku Co., Ltd. in accordance with JIS K 7136.
  • the haze value measured after standing at 23 ° C. and a humidity of 50% RH for 6 hours after application of the electrolyte was HzW
  • the haze value measured after standing for 12 hours was HzX
  • the haze value measured after standing for 24 hours was HzY.
  • Wetting Wetting was measured based on Japanese Industrial Standard "JIS K6768". A case where the measured value is 42 dyn or more can be evaluated as good.
  • the protective layer contains a copolymerized polyester resin having the composition specified in the present invention and has a thickness of 1.5 ⁇ m or less. Even when adhered, the appearance of the polyamide film did not change for at least 12 hours or more, showing good electrolytic solution resistance and good blocking resistance.
  • the dicarboxylic acid component of the copolymerized polyester resin contains at least 80 mol% of a dicarnrubonic acid component having a naphthalene skeleton, has a glass transition temperature of at least 80 ° C., and has excellent electrolytic solution resistance of a protective layer containing a crosslinking agent.
  • the protective layer composition was not specified in the present invention. Therefore, when the protective layer thickness was as thin as 1.50 ⁇ m or less, sufficient electrolytic solution resistance was not obtained. When the electrolytic solution adhered, the polyamide-based laminated film was whitened, and the appearance was greatly impaired. In Comparative Example 5, even when the thickness of the protective layer was large, the polyamide-based laminated film was whitened and the appearance was significantly impaired.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/JP2019/029742 2018-07-31 2019-07-30 ポリアミド系積層フィルム及びその製造方法 Ceased WO2020027089A1 (ja)

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CN113955281A (zh) * 2021-09-06 2022-01-21 浙江野马电池股份有限公司 一种提高干电池耐高温高湿腐蚀的包装方法
JP2023533525A (ja) * 2020-07-08 2023-08-03 ボスティック，インコーポレイテッド 工業用コーティングのための非晶質コポリエステル樹脂、それらを含むコーティング組成物、及びそのようなコーティング組成物を使用する金属表面をコーティングするための方法
WO2025058332A1 (ko) * 2023-09-11 2025-03-20 주식회사 릴엠 내화학성이 우수한 이차전지용 셀 파우치
EP4435938A4 (en) * 2021-12-23 2025-05-07 LG Energy Solution, Ltd. METHOD FOR MANUFACTURING POCKET CASE FOR SECONDARY BATTERY
KR102963317B1 (ko) 2021-12-30 2026-05-08 동우 화인켐 주식회사 전지용 포장재 및 이를 포함하는 이차 전지

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CN113955281A (zh) * 2021-09-06 2022-01-21 浙江野马电池股份有限公司 一种提高干电池耐高温高湿腐蚀的包装方法
EP4435938A4 (en) * 2021-12-23 2025-05-07 LG Energy Solution, Ltd. METHOD FOR MANUFACTURING POCKET CASE FOR SECONDARY BATTERY
KR102963317B1 (ko) 2021-12-30 2026-05-08 동우 화인켐 주식회사 전지용 포장재 및 이를 포함하는 이차 전지
WO2025058332A1 (ko) * 2023-09-11 2025-03-20 주식회사 릴엠 내화학성이 우수한 이차전지용 셀 파우치

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TW202015916A (zh) 2020-05-01
CN112703111A (zh) 2021-04-23

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