WO2019074016A1 - Film de poly(butylène téréphtalate), matériau d'emballage pour batteries, procédé de production de matériau d'emballage pour batteries et batterie - Google Patents

Film de poly(butylène téréphtalate), matériau d'emballage pour batteries, procédé de production de matériau d'emballage pour batteries et batterie Download PDF

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Publication number
WO2019074016A1
WO2019074016A1 PCT/JP2018/037799 JP2018037799W WO2019074016A1 WO 2019074016 A1 WO2019074016 A1 WO 2019074016A1 JP 2018037799 W JP2018037799 W JP 2018037799W WO 2019074016 A1 WO2019074016 A1 WO 2019074016A1
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Prior art keywords
heat
fusion
layer
temperature
packaging material
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English (en)
Japanese (ja)
Inventor
健太 平木
高萩　敦子
山下　力也
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority to CN201880062592.6A priority Critical patent/CN111164781B/zh
Priority to JP2019548225A priority patent/JP7143854B2/ja
Publication of WO2019074016A1 publication Critical patent/WO2019074016A1/fr
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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/62—Hybrid vehicles

Definitions

  • the present invention relates to a polybutylene terephthalate film, a packaging material for a battery, a method for producing a packaging material for a battery, and a battery.
  • a concave portion is formed by cold molding, and battery elements such as an electrode and an electrolytic solution are disposed in the space formed by the concave portions, and heat fusible resin layers are mutually attached.
  • battery elements such as an electrode and an electrolytic solution are disposed in the space formed by the concave portions, and heat fusible resin layers are mutually attached.
  • heat-sealing the battery pack a battery is obtained in which the battery element is housed inside the battery packaging material.
  • film-like packaging materials are thinner than metal packaging materials, and are prone to pinholes and cracks during molding. If pinholes or cracks occur in the battery packaging material, the electrolyte may penetrate into the aluminum alloy foil layer to form metal precipitates, which may result in a short circuit. It is essential for the battery packaging material of the present invention to have the characteristic that pinholes do not easily occur during molding, that is, excellent moldability.
  • a polyamide film and a polyester film are generally used as a base material layer.
  • polybutylene terephthalate film is excellent in chemical resistance and has high mechanical strength.
  • polybutylene terephthalate film has a problem that it is inferior in moldability as compared with a polyamide film. For this reason, there is a problem that it is difficult to use a polybutylene terephthalate film as a base material layer of a film-like battery packaging material.
  • Patent Document 1 is a biaxially oriented polyester film mainly containing polybutylene terephthalate resin, and 50 or more layers of a layer formed of polyester A and a layer formed of polyester B are laminated in the thickness direction. As a result, it is said that a laminate having excellent moldability, further excellent in warpage resistance and acid resistance, and without delamination at the time of molding can be obtained.
  • the main object of the present invention is to provide a polybutylene terephthalate film that exhibits excellent formability when used in a base material layer of a battery packaging material.
  • Another object of the present invention is to provide a battery packaging material using the polybutylene terephthalate film, a method for producing the battery packaging material, and a battery using the battery packaging material.
  • the present inventors diligently studied to solve the above-mentioned problems.
  • JIS K7122-2012 it is measured from the temperature of -50 ° C to the temperature of 250 ° C with a differential scanning calorimeter at a temperature rising rate of 10 ° C / min for the first measurement.
  • the temperature is lowered from 250 ° C. to a temperature of ⁇ 50 ° C. at a temperature decrease rate of 10 ° C./min, then the temperature rise rate is 10 ° C./min.
  • the polybutylene terephthalate film having an absolute value of the heat of fusion difference ⁇ H 1-2 which is the difference between the heat of fusion H 2 measured at a second time after heating to a temperature of 250 ° C., is 3.0 J / g or more
  • Item 1 It is a polybutylene terephthalate film used for the said base material layer of the packaging material for batteries provided with a base material layer, a barrier layer, and a heat fusible resin layer in this order, A polybutylene terephthalate film, wherein the absolute value of the heat of fusion difference ⁇ H 1-2 determined by the following method is 3.0 J / g or more.
  • the absolute value of the heat of fusion difference ⁇ H 1-2 which is the difference between the heat of fusion H 1 and the heat of fusion H 2 , is calculated.
  • Item 2. It is comprised from the laminated body provided with a base material layer, a barrier layer, and a heat bondable resin layer at least in this order, The packaging material for a battery, wherein the base material layer comprises a polybutylene terephthalate film in which the absolute value of the heat of fusion difference ⁇ H 1-2 determined by the following method is 3.0 J / g or more.
  • the absolute value of the heat of fusion difference ⁇ H 1-2 which is the difference between the heat of fusion H 1 and the heat of fusion H 2 , is calculated.
  • Item 3. The battery packaging material according to item 2, wherein the thickness of the polybutylene terephthalate film is 10 ⁇ m to 50 ⁇ m.
  • Item 4. The battery packaging material according to Item 2 or 3, wherein the barrier layer is made of an aluminum alloy foil.
  • An adhesive layer is provided between the barrier layer and the heat-fusible resin layer, The battery packaging material according to any one of Items 2 to 4, wherein the adhesive layer contains a polyolefin resin.
  • An adhesive layer is provided between the barrier layer and the heat-fusible resin layer,
  • Item 7 The battery packaging material according to any one of Items 2 to 6, wherein the thickness of the polybutylene terephthalate film is 30 ⁇ m or less.
  • the absolute value of the heat of fusion difference ⁇ H 1-2 which is the difference between the heat of fusion H 1 and the heat of fusion H 2 , is calculated.
  • Item 9 A battery, wherein a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is contained in a package formed of the battery packaging material according to any one of Items 2 to 7.
  • Item 10 The base layer, the barrier layer, and the thermally fusible resin layer of a polybutylene terephthalate film, wherein the absolute value of the heat of fusion difference ⁇ H 1-2 determined by the following method is 3.0 J / g or more Use for the said base material layer of the battery packaging material provided in this order.
  • the present invention by being used for the base material layer of the battery packaging material provided with at least the base material layer, the barrier layer and the heat fusible resin layer in this order, the formability excellent for the battery packaging material
  • the polybutylene terephthalate film can be provided.
  • a packaging material for a battery using the polybutylene terephthalate film, a method of manufacturing the packaging material for the battery, and a battery using the packaging material for the battery can also be provided.
  • the polybutylene terephthalate film of the present invention is a polybutylene terephthalate film used for the base material layer of a battery packaging material comprising at least a base material layer, a barrier layer, and a heat fusible resin layer in this order,
  • the absolute value of the heat of fusion difference ⁇ H 1-2 determined by the following method is 3.0 J / g or more.
  • the polybutylene terephthalate film of the present invention When the polybutylene terephthalate film of the present invention has such properties, it can exhibit excellent formability when used in a base material layer of a battery packaging material.
  • the polybutylene terephthalate film of the present invention, a packaging material for a battery using the same, a method for producing the same, and a battery will be described in detail.
  • the numerical range indicated by “to” means “above” or “below”.
  • the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.
  • polybutylene terephthalate film 11 of the present invention (hereinafter, "polybutylene terephthalate” may be referred to as "PBT film”) is a PBT film for a battery packaging material. More specifically, as shown in FIG. 2 to FIG. 5, the polybutylene terephthalate film 11 of the present invention is provided for a battery in which a base material layer 1, a barrier layer 3 and a heat fusible resin layer 4 are provided in this order. It is used for the base material layer 1 of the packaging material 10.
  • the base layer 1 of the battery packaging material 10 only needs to include at least the PBT film 11 of the present invention, and for example, as shown in FIGS. 2, 4 and 5, the PBT of the present invention
  • the PBT of the present invention For example, as shown in FIG. 3, in order to enhance the adhesion between the polyamide film 13 and the polyamide film 13 and the PBT film 11 in addition to the PBT film 11 of the present invention.
  • other layers such as adhesive layer 12 may be provided. That is, the base material layer 1 may have a multilayer structure.
  • the base material layer 1 of the battery packaging material 10, to PBT film 11 may be stacked in the present invention, in addition to the PBT film 11 of the present invention, the heat of fusion difference [Delta] H 1-2
  • the PBT film whose absolute value is less than 3.0 J / g may be laminated.
  • base material layer 1 is multilayer structure
  • a configuration in which 11 is sequentially laminated; a configuration in which PBT film 11 / adhesive layer 12 / PET film is sequentially laminated; a configuration in which PET film / adhesive layer 12 / PBT film 11 is sequentially laminated, and the like.
  • the PBT film is excellent in resistance (chemical resistance) when the electrolytic solution is attached, in the battery packaging material 10, the PBT film is on the outermost layer side (opposite to the heat fusible resin layer). It is preferred to be located.
  • the battery packaging material when the absolute value of the heat of fusion difference ⁇ H 1-2 determined by the method described later is 3.0 J / g or more, the battery packaging material exhibits excellent formability.
  • the absolute value of the heat of fusion difference ⁇ H 1-2 is 3.0 J / g or more, the orientation of the crystals before the measurement of the heat of fusion H 1 is high, and the state of the battery packaging material It can be said that it has a hardness range suitable for forming in More specifically, in the film formation process of PBT film 11, the type of film formation method and conditions at the time of film formation (eg, film formation temperature, draw ratio, cooling temperature, cooling rate, heat setting temperature after drawing) By adjusting, the absolute value of the heat of fusion difference ⁇ H 1-2 of the PBT film 11 can be set to 3.0 J / g or more, whereby excellent formability can be exhibited.
  • the absolute value of the heat of fusion difference ⁇ H 1-2 of the PBT film 11 can also be adjusted by the molecular weight or molecular weight distribution of the polybutylene terephthalate constituting the PBT film.
  • polybutylene terephthalate although polybutylene terephthalate is a main component, it may contain an additive suitably as needed, and an additive also has an absolute value of the heat-of-melting difference difference ⁇ H 1-2 within the above range. It is good also as an element set to.
  • the lower limit of the absolute difference in heat of fusion ⁇ H 1-2 of PBT film 11 is preferably about 3.0 J / g or more, more preferably about 3.2 J / g or more, more preferably about 3.4 J / g or more, still more preferably about 4.0 J / g or more, further preferably 7.5 J / g or more, still more preferably 8.0 J / g or more
  • the upper limit is preferably about 12 J / g or less, more preferably about 11 J / g or less, still more preferably about 10 J / g or less.
  • the absolute value of the heat of fusion difference ⁇ H 1-2 about 3.0 to 12 J / g, about 3.0 to 10 J / g, about 3.2 to 12 J / g, or 3.2 to 10 J / G, about 3.4 to 12 J / g, about 3.4 to 10 J / g, about 4.0 to 12 J / g, about 4.0 to 10 J / g, about 7.5 to 12 J / g, 7 About 5 to 10 J / g, about 8.0 to 12 J / g, and about 8.0 to 10 J / g.
  • the thermal contraction rate as a packaging material for a battery can be made appropriate, and the packaging material for a battery It is easy to suppress curling that occurs when molding with a mold or the like.
  • the heat of fusion H 1 of the PBT film 11 is, for example, about -70 to -30 J / g, preferably about -65 to -35 J / g. Further, as the heat of fusion H 2 , for example, about -60 to -30 J / g, about -55 to -35 J / g can be mentioned.
  • the PBT film 11 preferably has a heat of fusion H 1 smaller than the heat of fusion H 2 . That is, in the present invention, in the PBT film 11, it is preferable that the heat of fusion H 1 is larger in absolute value than the heat of fusion H 2 .
  • the method of determining the absolute value of the heat of fusion difference ⁇ H 1-2 of the PBT film is as follows.
  • the thick line A of FIG. 6 was obtained by cooling the sample from room temperature to -50.degree. C. at a rate of 10.degree. C./minute and holding it at -50.degree. 6 is a schematic graph (graph from -50.degree. C.
  • heat of fusion H 1 is in bold line A of FIG. 6, a portion endothermic peak is present, one of the two points (two points and the base line is in contact with, A1 is 200 ° C. the temperature 180 ° C. (A point at which line A leaves the baseline before transition, and A2 is between 230 ° C. and 240 ° C., a point at which line A returns to baseline after transition)
  • A1 is 200 ° C.
  • the temperature 180 ° C. A point at which line A leaves the baseline before transition
  • A2 is between 230 ° C. and 240 ° C., a point at which line A returns to baseline after transition
  • the heat of fusion H 2 is at two points where the endothermic peak is in contact with the baseline (B1 has a temperature of 180 ° C.
  • the polybutylene terephthalate film 11 of the present invention is a film composed of polybutylene terephthalate.
  • the proportion of polybutylene terephthalate contained in the polybutylene terephthalate film 11 is, for example, 81% by mass or more, preferably 90% by mass or more, more preferably 99% by mass or more, and particularly preferably 100% by mass.
  • the thickness of the polybutylene terephthalate film 11 of the present invention is not particularly limited, but from the viewpoint of enhancing the formability while thinning the thickness of the battery packaging material, the lower limit is preferably about 10 ⁇ m or more, more preferably Is about 12 ⁇ m or more, and the upper limit thereof is preferably about 50 ⁇ m or less, more preferably about 45 ⁇ m or less, still more preferably 30 ⁇ m or less, still more preferably 20 ⁇ m or less.
  • the preferable range of the thickness of the polybutylene terephthalate film 11 is about 10 to 50 ⁇ m, about 10 to 45 ⁇ m, about 10 to 30 ⁇ m, about 10 to 20 ⁇ m, about 12 to 50 ⁇ m, about 12 to 45 ⁇ m, about 12 to 30 ⁇ m There may be about -20 ⁇ m.
  • whether or not the polybutylene terephthalate film is provided with the absolute value, thickness and the like of the above-described difference in heat of fusion ⁇ H 1-2 may be determined by measuring the polybutylene terephthalate film alone. it can.
  • polybutylene terephthalate when polybutylene terephthalate is used as the said base material layer of the packaging material for batteries comprised from the laminated body provided with a base material layer, a barrier layer, and a heat-fusible resin layer in this order.
  • the absolute value of the difference ⁇ H 1-2 of the heat of fusion as described above by obtaining the polybutylene terephthalate from the laminate for example, peeling the PBT film from the laminate or dissolving a layer other than the PBT film
  • the thickness or the like is measured to determine whether it is the polybutylene terephthalate film of the present invention.
  • the PBT film 11 of the present invention can be suitably used for the base layer 1 of the packaging material for battery.
  • the laminated structure which consists of a laminated body which has the base material layer 1, the barrier layer 3, and the heat-fusible resin layer 4 in this order as the packaging material 10 for batteries is mentioned.
  • the cross-sectional structure of the battery packaging material 10 the aspect by which the base material layer 1, the barrier layer 3, and the heat-fusible resin layer 4 are laminated
  • the adhesive layer 2 may be provided between these layers as necessary. Further, as shown in FIG. 4 and FIG.
  • a surface coating layer 6 or the like may be provided on the outer side of the substrate layer 1 (the side opposite to the heat-fusible resin layer 4).
  • the base material layer 1 is on the outermost layer side, and the heat-fusible resin layer 4 is on the innermost layer.
  • the battery element is sealed by bringing the heat fusible resin layers 4 located at the peripheral edge of the battery element into contact with each other and heat-sealing them, thereby sealing the battery element.
  • the thickness of the laminate constituting the battery packaging material 10 is not particularly limited, but the thickness of the battery packaging material is reduced to increase the energy density of the battery, and the battery packaging material is excellent in formability and From the point of view, for example, about 180 ⁇ m or less, preferably about 150 ⁇ m or less, more preferably about 60 to 180 ⁇ m, further preferably about 60 to 150 ⁇ m.
  • the base material layer 1 should just contain the PBT film 11 of this invention at least, and may contain the other layer.
  • the base material layer 1 may be constituted only by the PBT film 11 of the present invention as shown in, for example, FIG. 2, FIG. 4 and FIG. 5, or as shown in FIG.
  • other layers such as a polyamide film 13 and an adhesive layer 12 for enhancing the adhesion between the polyamide film 13 and the PBT film 11 may be provided.
  • the base material layer 1 of the battery packaging material 10, to PBT film 11 may be stacked in the present invention, in addition to the PBT film 11 of the present invention, the heat of fusion difference [Delta] H 1-2
  • the PBT film whose absolute value is less than 3.0 J / g may be laminated.
  • the base material layer 1 is made of a polybutylene terephthalate film.
  • the base material layer 1 is comprised by the several layer, the base material layer 1 is comprised by the polybutylene-terephthalate film at least one layer, and also has another layer.
  • the polybutylene terephthalate film is made of, for example, polybutylene terephthalate or a copolymerized polyester containing butylene terephthalate as a main component of the repeating unit.
  • a copolyester having butylene terephthalate as the main component of the repeating unit specifically, a copolymer polyester having butylene terephthalate as the main component of the repeating unit and polymerizing with butylene isophthalate (hereinafter referred to as polybutylene (terephthalate / isophthalate) And polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decane dicarboxylate) and the like.
  • the polybutylene terephthalate film may contain polyethylene terephthalate, a polyester elastomer, and the like.
  • the other layer may be made of the polybutylene terephthalate film described above, or may be made of another material.
  • the other material is not particularly limited as long as it has insulation properties, and, for example, polyester (but excluding polybutylene terephthalate), polyamide, epoxy resin, acrylic resin, fluorine resin, polyurethane And silicone resins, phenol resins, polycarbonate resins, polyetherimides, polyimides, and mixtures and copolymers thereof.
  • polyester examples include polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester having ethylene terephthalate as a main component of the repeating unit.
  • a copolymerized polyester having ethylene terephthalate as the main component of the repeating unit specifically, a copolymer polyester in which ethylene terephthalate is polymerized as the main component of the repeating unit with ethylene isophthalate (hereinafter, polyethylene (terephthalate / isophthalate) Polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) And polyethylene (terephthalate / decanedicarboxylate).
  • polyethylene (terephthalate / isophthalate) Polyethylene (terephthalate / isophthalate)
  • Polyethylene (terephthalate / isophthalate) Polyethylene (terephthalate / isophthalate)
  • polyesters are mentioned as another copolymerized polyester which made the butylene terephthalate the main body of a repeating unit. These polyesters may be used alone or in combination of two or more. Polyester has an advantage that it is excellent in electrolytic solution resistance and is less likely to be whitened due to adhesion of the electrolytic solution, and is suitably used as a forming material of the base material layer 1.
  • polyamides specifically, aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid Hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamide such as nylon 6 I, nylon 6 T, nylon 6 IT, nylon 6 I 6 T (I is isophthalic acid, T represents terephthalic acid) containing constitutional units derived from An aromatic polyamide such as pamide (MXD6); an alicyclic polyamide such as polyaminomethylcyclohexyl adipamide (PACM 6); and a copolymer of a lactam component and an isocyanate component such as 4,4'-diphenylmethane diisocyanate.
  • MXD6 pamide
  • POM 6 polyaminomethylcyclohexyl adipamide
  • POM 6 polyaminomethylcyclohex
  • the stretched polyamide film is excellent in stretchability, can prevent the occurrence of whitening due to resin cracking of the base material layer 1 at the time of molding, and is suitably used as a forming material of the base material layer 1.
  • the base material layer 1 is formed of a plurality of layers
  • a multilayer structure in which a polybutylene terephthalate film and a polybutylene terephthalate film are laminated a multilayer structure in which a polybutylene terephthalate film and a nylon film are laminated
  • the multilayer structure etc. which laminated the polybutylene terephthalate film and the polyester film (except a polybutylene terephthalate film) etc. are mentioned.
  • the base material layer 1 is formed of two resin films, a structure in which a polybutylene terephthalate film and a polybutylene terephthalate film are laminated, a structure in which a polybutylene terephthalate film and a nylon film are laminated, a polybutylene terephthalate film A configuration in which a polyethylene terephthalate film is laminated is preferable.
  • the polybutylene terephthalate film is difficult to discolor, for example, when the electrolytic solution adheres to the surface, when the substrate layer 1 has a multilayer structure including a nylon film, the substrate layer 1 is on the barrier layer 3 side. It is preferable that it is a laminated body which has a nylon film and a polybutylene terephthalate film in this order.
  • each resin film may be bonded via an adhesive, or may be directly laminated without using an adhesive.
  • a method of bonding in a hot-melted state such as coextrusion method, sandwich lamination method, thermal lamination method and the like can be mentioned.
  • the adhesive agent to be used may be a 2 liquid curing adhesive, and may be a 1 liquid curing adhesive.
  • the adhesion mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type, an electron beam curing type, an ultraviolet ray curing type, and the like.
  • Specific examples of the adhesive include those similar to the adhesive exemplified in the adhesive layer 2 described later.
  • the thickness of the adhesive can be the same as that of the adhesive layer 2.
  • the multilayer structure of the base material layer 1 a structure in which PBT film 11 / adhesive layer 12 / polyamide film 13 is sequentially laminated; a structure in which PBT film 11 / adhesive layer 12 / PBT film 11 is sequentially laminated PBT film 11 / polyamide film 13 laminated in sequence; PBT film 11 / PBT film 11 laminated in order; PBT film 11 / PET film laminated in sequence; PBT film 11 / adhesive layer 12 / PET film laminated in order; PET film / adhesive layer 12 / PBT film laminated in order.
  • the PBT film is excellent in resistance (chemical resistance) when the electrolytic solution is attached, in the battery packaging material 10, the PBT film is on the outermost layer side (opposite to the heat fusible resin layer). It is preferred to be located.
  • a lubricant is preferably attached to the surface of the base layer 1.
  • the lubricant is not particularly limited, but preferably includes amide lubricants.
  • Specific examples of the amide lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide and the like.
  • Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and the like.
  • the unsaturated fatty acid amide include oleic acid amide and erucic acid amide.
  • substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like.
  • methylolamide include methylol stearic acid amide and the like.
  • saturated fatty acid bisamide examples include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, hexamethylene bisstearin Acid amide, hexamethylene bisbehenamide, hexamethylene hydroxystearic amide, N, N'-distearyl adipamide, N, N'-distearyl sebacate amide and the like can be mentioned.
  • unsaturated fatty acid bisamides include ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide Etc.
  • fatty acid ester amides include stearoamidoethyl stearate and the like.
  • specific examples of the aromatic bisamides include m-xylylene bis-stearic acid amide, m-xylylene bis-hydroxystearic acid amide, N, N'-distearyl isophthalic acid amide and the like.
  • the lubricant may be used alone or in combination of two or more.
  • the amount thereof is not particularly limited, but it is preferably about 3 mg / m 2 or more, more preferably 4 to 15 mg / in an environment of 24 ° C. and 60% relative humidity. About m 2 , more preferably about 5 to 14 mg / m 2 .
  • the base material layer 1 may contain a lubricant.
  • the lubricant present on the surface of the substrate layer 1 may be one in which the lubricant contained in the resin constituting the substrate layer 1 is exuded, or the lubricant coated on the surface of the substrate layer 1 It may be
  • the thickness (total thickness) of the base layer 1 is preferably about 10 ⁇ m or more, more preferably from the viewpoint of enhancing the formability while thinning the battery packaging material using the base layer containing the polybutylene terephthalate film Is about 10 to 50 ⁇ m.
  • the polybutylene terephthalate of the present invention is used as the base material layer 1 in the packaging material for a battery depends on the absolute value of the difference ⁇ H 1-2 of the heat of fusion ⁇ for the polybutylene terephthalate alone peeled from the laminate. It can carry out by measuring a value, thickness, etc.
  • the adhesive layer 2 is a layer provided between the substrate layer 1 and the barrier layer 3 as needed in order to firmly bond the substrate layer 1 and the barrier layer 3.
  • the adhesive layer 2 is formed of an adhesive capable of adhering the base layer 1 and the barrier layer 3.
  • the adhesive used to form the adhesive layer 2 may be a two-part curable adhesive, or may be a one-part curable adhesive.
  • the adhesive used to form the adhesive layer 2 is not particularly limited, and any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type, etc. may be used.
  • the adhesive layer 2 may also contain a colorant such as a pigment.
  • the thickness of the adhesive layer 2 is not particularly limited as long as it exhibits a function as an adhesive layer, and for example, about 0.1 to 10 ⁇ m, preferably about 0.5 to 5 ⁇ m.
  • the barrier layer 3 is a layer having a function to prevent water vapor, oxygen, light and the like from invading the inside of the battery, in addition to the strength improvement of the battery packaging material.
  • the barrier layer 3 is preferably a metal layer, that is, a layer formed of a metal. Specifically as a metal which comprises the barrier layer 3, aluminum, stainless steel, titanium steel etc. are mentioned, Preferably aluminum is mentioned.
  • the barrier layer 3 can be formed of, for example, a metal foil, a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, a film provided with these vapor deposition films, or the like. It is more preferable to form by aluminum alloy foil. From the viewpoint of preventing the occurrence of wrinkles and pinholes in the barrier layer 3 during the production of the battery packaging material, the barrier layer is more preferably formed of an aluminum alloy foil or a stainless steel foil.
  • the aluminum alloy foil for example, softened aluminum alloy foil (JIS H4160: 1994 A8021 H-O, JIS H 4 160: 1994 A8079 H-O, JIS H 4000: 2014 A8021 P-O, JIS H 4000: 2014 A 8079 P-O) which has been subjected to annealing treatment. It is more preferable to form by aluminum alloy foil.
  • the stainless steel foil is preferably made of austenitic stainless steel.
  • austenitic stainless steels that constitute stainless steel foil include SUS304, SUS301, SUS316L, etc.
  • SUS304 is particularly preferable.
  • the barrier layer 3 it is preferable that at least one surface, preferably both surfaces, of the barrier layer 3 be subjected to chemical conversion treatment in order to stabilize adhesion, to prevent dissolution or corrosion, and the like.
  • the chemical conversion treatment means a treatment for forming an acid resistant film on the surface of the barrier layer.
  • the barrier layer 3 contains the acid resistant film.
  • chromate chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium borate, chromium biphosphate, chromium acetate acetyl acetate, chromium chloride, potassium chromium sulfate and the like
  • a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium borate, chromium biphosphate, chromium acetate acetyl acetate, chromium chloride, potassium chromium sulfate and the like
  • Phosphoric acid treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid and the like
  • the thickness of the barrier layer 3 is not particularly limited as long as it exhibits a function as a barrier layer such as water vapor, but can be, for example, about 10 to 50 ⁇ m, preferably about 10 to 40 ⁇ m.
  • the thermally fusible resin layer 4 corresponds to the innermost layer, and is a layer that thermally fuses the thermally fusible resin layers at the time of assembly of the battery to seal the battery element.
  • the resin component used for the heat fusible resin layer 4 is not particularly limited as long as heat fusible is possible, and examples thereof include polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin. That is, the resin constituting the heat-fusible resin layer 4 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton.
  • the resin constituting the heat-fusible resin layer 4 can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, etc., as long as it contains a polyolefin skeleton, and the analysis method is not particularly limited.
  • a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.
  • polystyrene resin examples include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; homopolypropylene, block copolymers of polypropylene (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers of (for example, random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like.
  • polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene
  • homopolypropylene block copolymers of polypropylene (for example, block copolymers of propylene and ethylene)
  • polypropylene Polypropylenes such as random copolymers of (for example, random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like.
  • polyethylene and polypropylene are mentioned.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, isoprene and the like. .
  • a cyclic monomer which is a constituent monomer of the cyclic polyolefin for example, cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like can be mentioned.
  • these polyolefins preferred are cyclic alkenes, more preferably norbornene.
  • the acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with an acid component such as a carboxylic acid.
  • an acid component such as a carboxylic acid.
  • carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or anhydrides thereof.
  • the acid-modified cyclic polyolefin is prepared by copolymerizing part of the monomers constituting the cyclic polyolefin with an ⁇ , ⁇ -unsaturated carboxylic acid or an anhydride thereof, or ⁇ , ⁇ - to the cyclic polyolefin. It is a polymer obtained by block polymerization or graft polymerization of unsaturated carboxylic acid or its anhydride.
  • the cyclic polyolefin to be carboxylic acid modified is the same as described above. Moreover, as a carboxylic acid used for modification
  • polyolefins such as polypropylene, carboxylic acid-modified polyolefins, and more preferably polypropylene and acid-modified polypropylenes.
  • the heat fusible resin layer 4 may be formed of one type of resin component alone, or may be formed of a blend polymer in which two or more types of resin components are combined. Furthermore, the heat-fusible resin layer 4 may be formed of only one layer, but may be formed of two or more layers of the same or different resin components.
  • the thickness of the heat fusible resin layer 4 is not particularly limited as long as it exhibits the function as a heat fusible resin layer, but preferably about 60 ⁇ m or less, more preferably about 10 to 40 ⁇ m.
  • the adhesive layer 5 is a layer optionally provided between the barrier layer 3 and the heat-fusible resin layer 4 in order to firmly bond the layer.
  • the adhesive layer 5 is formed of a resin capable of adhering the barrier layer 3 and the heat fusible resin layer 4.
  • resin used for formation of adhesion layer 5 the thing of the adhesion mechanism, the kind of adhesive agent component, etc. can use the thing similar to the adhesive illustrated by adhesive agent layer 2.
  • resin used for formation of the contact bonding layer 5 polyolefin resin, such as polyolefin mentioned above-mentioned heat-fusion resin layer 4, cyclic polyolefin, carboxylic acid modified polyolefin, carboxylic acid modified cyclic polyolefin, can also be used. .
  • the polyolefin a carboxylic acid-modified polyolefin is preferable, and a carboxylic acid-modified polypropylene is particularly preferable, from the viewpoint of excellent adhesion between the barrier layer 3 and the heat-fusible resin layer 4. That is, the resin constituting the adhesive layer 5 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. It is possible to analyze that the resin constituting the adhesive layer 5 contains a polyolefin skeleton, for example, by infrared spectroscopy, gas chromatography mass spectrometry, etc., and there is no particular limitation on the analysis method.
  • a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.
  • the adhesive layer 5 is a resin composition containing an acid-modified polyolefin and a curing agent. It may be a cured product.
  • the acid-modified polyolefin preferably, the same ones as the carboxylic acid-modified polyolefin and the carboxylic acid-modified cyclic polyolefin exemplified in the heat fusible resin layer 4 can be exemplified.
  • the curing agent is not particularly limited as long as it cures acid-modified polyolefin.
  • examples of the curing agent include epoxy-based curing agents, polyfunctional isocyanate-based curing agents, carbodiimide-based curing agents, oxazoline-based curing agents, and the like.
  • the epoxy curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
  • the epoxy curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolak glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether and the like.
  • the polyfunctional isocyanate-based curing agent is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or denating these, or the like Mixtures and copolymers with other polymers may be mentioned.
  • curing agent the polycarbodiimide compound which has a carbodiimide group 2 or more at least is preferable.
  • the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the oxazoline curing agent include Epocross series manufactured by Nippon Shokubai Co., Ltd.
  • the curing agent may be composed of two or more types of compounds.
  • the content of the curing agent in the resin composition forming the adhesive layer 5 is preferably in the range of about 0.1 to 50% by mass, and more preferably in the range of about 0.1 to 30% by mass, More preferably, it is in the range of about 0.1 to 10% by mass.
  • the thickness of the adhesive layer 5 is not particularly limited as long as it exhibits a function as an adhesive layer, but for example, the upper limit is 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 10 ⁇ m or less, 5 ⁇ m or less, and the lower limit is 0 1 ⁇ m or more, 0.5 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more. Further, although not restrictive, for example, in the case of using the adhesive exemplified in the adhesive layer 2, it is preferably about 1 to 10 ⁇ m, more preferably about 1 to 5 ⁇ m.
  • the resin exemplified in the heat fusible resin layer 4 it is preferably about 2 to 50 ⁇ m, more preferably about 10 to 40 ⁇ m.
  • a cured product of an acid-modified polyolefin and a curing agent it is preferably about 30 ⁇ m or less, more preferably about 0.1 to 20 ⁇ m, and still more preferably about 0.5 to 5 ⁇ m.
  • the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing it by heating or the like.
  • a surface covering layer 6 In the battery packaging material of the present invention, on the base material layer 1 (the barrier layer of the base material layer 1), as needed, for the purpose of improving designability, electrolytic solution resistance, abrasion resistance, moldability, etc. If necessary, a surface covering layer 6 may be provided on the side opposite to 3). The surface covering layer 6 is a layer located in the outermost layer when the battery is assembled.
  • the surface coating layer 6 can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin or the like. Among these, the surface coating layer 6 is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface covering layer 6 include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Further, an additive may be blended in the surface coating layer 6.
  • Examples of the additive include fine particles having a particle diameter of about 0.5 nm to 5 ⁇ m.
  • the material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the additive is not particularly limited, and examples thereof include spheres, fibers, plates, indeterminate shapes, and balloons.
  • talc silica, graphite, kaolin, montmorrroid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high Melting point nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like can be mentioned.
  • additives may be used alone or in combination of two or more.
  • silica, barium sulfate and titanium oxide are preferably mentioned from the viewpoint of dispersion stability and cost.
  • the surface may be subjected to various surface treatments such as insulation treatment, high dispersion treatment, and the like.
  • coating 2-component curable resin which forms the surface coating layer 6 on one surface of the base material layer 1 is mentioned.
  • the additive may be added to and mixed with the two-component curable resin and then applied.
  • the thickness of the surface coating layer 6 is not particularly limited as long as the above-described function as the surface coating layer 6 is exhibited, and for example, about 0.5 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the method for producing the battery packaging material is not particularly limited as long as a laminate obtained by laminating each layer of a predetermined composition can be obtained. That is, the battery packaging material comprises at least a step of laminating the base material layer, the barrier layer, and the heat fusible resin layer in this order, and the above-described difference in heat of fusion ⁇ H 1 is applied to the base material layer. It can manufacture using the polybutylene-terephthalate film whose absolute value of -2 is 3.0 J / g or more.
  • a laminate in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are sequentially laminated is formed.
  • the laminate A is formed by gravure coating an adhesive used for forming the adhesive layer 2 on the base layer 1 or on the barrier layer 3 whose surface has been subjected to a chemical conversion treatment if necessary. It can carry out by the dry lamination method which makes the barrier layer 3 or the substrate layer 1 concerned laminate, and hardens the adhesive layer 2 after applying and drying with application methods, such as a roll coat method.
  • the heat fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A.
  • the resin component constituting the heat fusible resin layer 4 is gravure-coated or roll-coated on the barrier layer 3 of the laminate A It may be applied by a method such as When the adhesive layer 5 is provided between the barrier layer 3 and the heat fusible resin layer 4, for example, (1) the adhesive layer 5 and the heat fusible resin layer on the barrier layer 3 of the laminate A Method of laminating 4 by coextrusion (co-extrusion laminating method), (2) Separately, a laminated body in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated is formed, (3) A method of laminating by thermal laminating method, (3) A method of extruding or solution coating an adhesive for forming the adhesive layer 5 on the barrier layer 3 of the laminated body A, drying at a high temperature, and baking Method of laminating the thermally fusible resin layer
  • the surface covering layer is laminated on the surface of the base layer 1 opposite to the barrier layer 3.
  • the surface coating layer can be formed, for example, by applying the above-mentioned resin forming the surface coating layer to the surface of the base material layer 1.
  • the order of the step of laminating the barrier layer 3 on the surface of the base layer 1 and the step of laminating the surface coating layer on the surface of the base layer 1 is not particularly limited.
  • the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer.
  • a laminate of the adhesive layer 5 / thermal adhesive resin layer 4 to be provided is formed, but in order to strengthen the adhesion of the adhesive layer 2 and the adhesive layer 5 to be provided if necessary, heat is further applied. It may be subjected to heat treatment such as roll contact type, hot air type, near infrared type or far infrared type. The conditions for such heat treatment include, for example, at 150 to 250 ° C. for 1 to 5 minutes.
  • each layer constituting the laminate is, if necessary, to improve or stabilize the film forming property, lamination processing, final product secondary processing (pouching, embossing) suitability, etc. It may be subjected to surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment and the like.
  • surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment and the like.
  • film forming property, lamination processing, final product secondary processing suitability and the like can be improved or stabilized.
  • the printability of the ink on the surface of the base layer 1 can be improved.
  • the battery packaging material is used for a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, the battery element provided with at least the positive electrode, the negative electrode, and the electrolyte can be accommodated in a package formed of the battery packaging material to make a battery.
  • a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is a battery packaging material of the present invention, in which the metal terminal connected to each of the positive electrode and the negative electrode protrudes outward.
  • the battery is covered by forming flanges (areas in which the heat fusible resin layers are in contact with each other) on the periphery of the element, and heat sealing the heat fusible resin layers of the flanges to seal them.
  • a battery using a packaging material is provided.
  • the packaging material for batteries may be used for any of a primary battery and a secondary battery, it is preferably a secondary battery.
  • the type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited.
  • lithium ion battery, lithium ion polymer battery, lead storage battery, nickel hydrogen storage battery, nickel cadmium storage battery, nickel Iron storage batteries, nickel-zinc storage batteries, silver oxide-zinc storage batteries, metal air batteries, multivalent cation batteries, capacitors, capacitors and the like can be mentioned.
  • lithium ion batteries and lithium ion polymer batteries are mentioned as a suitable application object of the packaging material for batteries of the present invention.
  • Examples 1 to 3 and Comparative Example 1 The barrier layer was laminated on the substrate layer by dry lamination.
  • the heat of fusion H 1 , the heat of fusion H 2 , and the heat of fusion described in Table 1 were each measured by the method of ⁇ determination of absolute value of difference of heat of fusion ⁇ H 1-2 > described later.
  • a biaxially stretched polybutylene terephthalate film (PBT film, thickness 15 ⁇ m) with an absolute value of the difference ⁇ H 1-2 was used.
  • an aluminum alloy foil JIS H4160: 1994 A8021 H-O, thickness 35 ⁇ m
  • a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of an aluminum alloy foil to form an adhesive layer (3 ⁇ m in thickness) on the barrier layer.
  • an aging treatment was performed to produce a laminate of base layer / adhesive layer / barrier layer.
  • the chemical conversion treatment of the aluminum foil used as the barrier layer is performed by roll coating a treatment liquid comprising a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry mass). It applied by baking on both sides of the aluminum foil by the method.
  • an adhesive layer (thickness 20 ⁇ m, disposed on the barrier layer side) made of a maleic anhydride-modified polypropylene resin and a heat fusible resin layer (thickness 15 ⁇ m) made of a random polypropylene resin
  • a laminated film in which a base material layer, an adhesive layer, a barrier layer, an adhesive layer, and a thermally fusible resin layer were laminated in this order was obtained.
  • the laminated film was subjected to an aging step to obtain battery packaging materials of Examples 1 to 3 and Comparative Example 1, respectively.
  • Comparative example 2 As a base material layer, instead of a biaxially stretched polybutylene terephthalate film (PBT film, thickness 15 ⁇ m), the absolute values of heat of fusion H 1 , heat of fusion H 2 , and heat of fusion difference ⁇ H 1-2 described in Table 1 A battery packaging material of Comparative Example 2 was obtained in the same manner as in Example 1 except that a biaxially stretched polyethylene terephthalate film (PET film, 15 ⁇ m in thickness) was used.
  • PET film biaxially stretched polyethylene terephthalate film
  • Comparative example 3 As a base material layer, instead of a biaxially stretched polybutylene terephthalate film (PBT film, thickness 15 ⁇ m), the absolute values of heat of fusion H 1 , heat of fusion H 2 , and heat of fusion difference ⁇ H 1-2 described in Table 1 A battery packaging material of Comparative Example 3 was obtained in the same manner as Example 1, except that a biaxially stretched nylon film (thickness 15 ⁇ m) was used.
  • PBT film polybutylene terephthalate film
  • the absolute values of the heat of fusion H 1 , the heat of fusion H 2 and the heat of fusion difference ⁇ H 1-2 of each film are respectively the film forming process of these films.
  • the conditions were set by adjusting the type of film formation method and conditions at the time of film formation (for example, film formation temperature, draw ratio, cooling temperature, cooling rate, heat setting temperature after drawing).
  • the absolute value of the heat of fusion difference ⁇ H 1-2 which is the difference from the heat of fusion H 2 was calculated.
  • the specific way of obtaining is as follows.
  • "DSC 204F1 Phoenix" made by NETZSCH, and Proteus made by NETZSCH as analysis software were used.
  • an aluminum pan was used as a sample pan.
  • the sample is cooled from room temperature to ⁇ 50 ° C. at a rate of 10 ° C./min in a nitrogen atmosphere and held at ⁇ 50 ° C. for 15 minutes, then 10 ° C./min It was heated to 250 ° C.
  • each heat of fusion is a region surrounded by a point where the endothermic peak is in contact with the baseline. , And was determined as described using the schematic diagram of FIG. 6 described above.
  • the battery packaging material was cut into a rectangle of 90 mm (MD) x 150 mm (TD) to prepare a sample.
  • a molding die having a diameter of 32 mm (MD) x 54 mm (TD) of this sample female surface is specified in Table 2 of surface roughness standard piece for comparison in JIS B 0 656-1: 2002 Annex 1 (reference)
  • the maximum height roughness (nominal value of Rz) is 3.2 ⁇ m) and the corresponding molding die (male mold surface, JIS B 0 659-1: 2002 Annex 1 (reference) for comparison Using the maximum height roughness (nominal value of Rz) specified in Table 2 of the surface roughness standard piece, which is 1.6 ⁇ m, it is possible to obtain 0.
  • the rolling direction of aluminum foil becomes MD
  • the same plane perpendicular direction becomes MD
  • the rolling direction of the aluminum foil can be confirmed by the rolling marks of the aluminum foil, and the MD and TD of the battery packaging material can be confirmed from the rolling direction.
  • the absolute value of the heat of fusion difference ⁇ H 1-2 of the polybutylene terephthalate film used for the base layer is 3.0 J / g or more, and the formability is excellent. It is also excellent in chemical resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne un film de poly(butylène téréphtalate) qui peut être utilisé en tant que couche de base dans un matériau d'emballage pour batteries et qui comprend au moins, dans l'ordre, la couche de matériau de base, une couche barrière et une couche de résine pouvant être fusionnée thermiquement, la valeur absolue d'une différence de chaleur de fusion ΔH1-2 qui est déterminée par le procédé suivant est de 3,0 J/g ou plus. (Procédé permettant de déterminer la valeur absolue d'une différence de chaleur de fusion ΔH1-2) Une chaleur de fusion H1 lors de la première étape est mesurée conformément à la spécification du JIS K7122-2012 à l'aide d'un calorimètre à balayage différentiel par chauffage d'une température de -50 °C à une température de 250 °C à condition que le taux d'augmentation de température soit de 10 °C/min. Ensuite, après la mesure de la chaleur de fusion H1, le refroidissement est effectué d'une température de 250 °C à une température de -50 °C à un taux d'abaissement de température de 10 °C/min, puis une chaleur de fusion H2 lors d'une seconde étape est mesurée par chauffage d'une température de -50 °C à une température de 250 °C à condition qu'un taux d'augmentation de température soit de 10 °C/min. Une valeur absolue d'une différence de chaleur de fusion ΔH1-2, qui est une différence entre la chaleur de fusion H1 et la chaleur de fusion H2, est calculée.
PCT/JP2018/037799 2017-10-11 2018-10-10 Film de poly(butylène téréphtalate), matériau d'emballage pour batteries, procédé de production de matériau d'emballage pour batteries et batterie Ceased WO2019074016A1 (fr)

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JP2019548225A JP7143854B2 (ja) 2017-10-11 2018-10-10 ポリブチレンテレフタレートフィルム、電池用包装材料、電池用包装材料の製造方法、及び電池

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