WO2019112020A1 - 電池用包装材料、電池、これらの製造方法、及びポリエステルフィルム - Google Patents

電池用包装材料、電池、これらの製造方法、及びポリエステルフィルム Download PDF

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Publication number
WO2019112020A1
WO2019112020A1 PCT/JP2018/044989 JP2018044989W WO2019112020A1 WO 2019112020 A1 WO2019112020 A1 WO 2019112020A1 JP 2018044989 W JP2018044989 W JP 2018044989W WO 2019112020 A1 WO2019112020 A1 WO 2019112020A1
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Prior art keywords
layer
packaging material
polyester film
battery
acid
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PCT/JP2018/044989
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English (en)
French (fr)
Japanese (ja)
Inventor
かおる 津森
大佑 安田
山下　孝典
山下　力也
Original Assignee
大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to CN201880078138.XA priority Critical patent/CN111433933B/zh
Priority to CN202210697179.5A priority patent/CN115133185A/zh
Priority to KR1020207012944A priority patent/KR20200096494A/ko
Priority to JP2019521166A priority patent/JP6587039B1/ja
Publication of WO2019112020A1 publication Critical patent/WO2019112020A1/ja

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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
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—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 of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • 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
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
    • 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
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/197—Sealing members characterised by the material having a layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/133—Thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a battery packaging material, a battery, a method for producing them, and a polyester film.
  • a film-like laminate in which a base material / barrier layer / thermally fusible resin layer is sequentially laminated as a battery packaging material that can be easily processed into various shapes and can realize thinning and weight reduction has been proposed (see, for example, Patent Document 1).
  • a battery packaging material generally, 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. By heat-sealing the battery pack, a battery is obtained in which the battery element is housed inside the battery packaging material.
  • the ink is printed on the surface of the base material layer to form a bar code, a handle, characters and the like, and adhesion is performed on the printed base material layer
  • a method of printing on the packaging material (generally referred to as reverse printing) is widely adopted.
  • reverse printing a method of printing on the packaging material
  • the adhesion between the base material layer and the barrier layer is reduced, and delamination tends to occur between the layers.
  • the method of printing by such reverse printing is avoided in the battery packaging material. Therefore, conventionally, in the case of forming a print such as a bar code on the battery packaging material, generally, a method of sticking a seal on which the print is formed on the surface of the base material layer is employed.
  • the present inventors have proposed a method of printing directly by printing ink on the surface of the base material layer of the battery packaging material. investigated.
  • Pad printing is the following printing method. First, the ink is poured into the concave portion of the flat plate where the pattern to be printed is etched. Next, the silicon pad is pressed from above the recess to transfer the ink to the silicon pad. Next, the ink transferred to the surface of the silicon pad is transferred to a print target to form a print on the print target.
  • Such pad printing is easy to print on the surface of the formed battery packaging material because the ink is transferred to the printing object using an elastic silicon pad or the like, and the battery element is a battery packaging material. After sealing, it has the advantage of being able to print on the battery. Moreover, it has the same advantage also in inkjet printing.
  • the present inventors examined, in the battery packaging material provided with the polyester film layer on the outermost surface, when the ink is printed on the surface of the polyester film layer, the ink spreading is inadequate on the surface of the polyester film layer.
  • the dots of the printing portion formed by the ink tend to have irregular shapes and it is difficult to form a print of a desired size and shape.
  • the main object of the present invention is to provide a battery packaging material excellent in printability on the surface of the polyester film layer, in a battery packaging material having a polyester film layer on the outermost surface.
  • the present inventors diligently studied to solve the above-mentioned problems. As a result, it is comprised from the laminated body provided with the base material layer located at the outermost surface, the barrier layer, and the heat fusible resin layer in this order, and the outermost surface of the base material layer is comprised by the polyester film layer
  • the infrared absorption spectra in 18 directions are acquired at intervals of 10 ° from 0 ° to 170 ° on the surface of the polyester film layer using the total reflection method of Fourier transform infrared spectroscopy, the following equation
  • the ink spreading on the surface of the polyester film layer is inadequate and the dots in the printed portion are prevented from becoming irregularly shaped, and excellent printability is exhibited. Found out.
  • Y max / Y min ⁇ 1.4 Y max is the maximum value among the values obtained by dividing the absorption peak intensity Y 1340 at a wavenumber 1340 cm -1 of the infrared absorption spectrum in each of the 18 directions by the absorption peak intensity Y 1410 at a wave number 1410 cm -1 It is.
  • Y min is the minimum value of the value obtained by dividing the absorption peak intensity Y 1340 at a wavenumber of 1340 cm -1 in the infrared absorption spectrum in each direction of the 18 directions by the absorption peak intensity Y 1410 at a wavenumber of 1410 cm -1 It is.
  • Y 1340 / Y 1410 is obtained for each of the 18 directions, and the maximum value Y max and the minimum value Y min are respectively selected from these.
  • the present invention has been completed by further investigation based on these findings.
  • the laminate comprises at least a base layer located on the outermost surface, a barrier layer, and a heat-fusible resin layer in this order,
  • the outermost surface of the substrate layer is constituted of a polyester film layer,
  • infrared absorption spectra in 18 directions are acquired at intervals of 10 ° from 0 ° to 170 ° on the surface of the polyester film layer using the total reflection method of Fourier transform infrared spectroscopy, the following equation is satisfied , Packaging material for batteries.
  • Y max / Y min ⁇ 1.4 Y max is the maximum value among the values obtained by dividing the absorption peak intensity Y 1340 at a wavenumber 1340 cm -1 of the infrared absorption spectrum in each of the 18 directions by the absorption peak intensity Y 1410 at a wave number 1410 cm -1 It is.
  • Y min is the minimum value of the value obtained by dividing the absorption peak intensity Y 1340 at a wavenumber of 1340 cm -1 in the infrared absorption spectrum in each direction of the 18 directions by the absorption peak intensity Y 1410 at a wavenumber of 1410 cm -1 It is. Item 2. Item 2.
  • Item 3. The battery packaging material according to item 1 or 2, wherein the arithmetic average roughness Ra measured on the surface of the polyester film layer is 10 nm or more according to the method defined in JIS B 0601-2001.
  • 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 1 to 3, wherein the adhesive layer contains an acid-modified polyolefin.
  • the acid-modified polyolefin of the adhesive layer is maleic anhydride-modified polypropylene, 5.
  • the adhesive layer is a cured product of a resin composition containing at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group. Battery packaging material described in. Item 7.
  • the battery packaging material according to any one of Items 4 to 10 which is a coextruded laminate of the adhesive layer and the heat-fusible resin layer.
  • Item 12. 12 The battery packaging material according to any one of items 1 to 11, wherein the thickness of the polyester film layer is 10 ⁇ m to 50 ⁇ m.
  • Item 13 The battery packaging material according to any one of items 1 to 12, wherein the polyester film layer is composed of a stretched polyester film. Item 14. When infrared absorption spectra in 18 directions are acquired at intervals of 10 ° from 0 ° to 170 ° on the surface of the polyester film layer using the total reflection method of Fourier transform infrared spectroscopy, the following equation is satisfied The packaging material for a battery according to any one of Items 1 to 13. 1.1 ⁇ Y max / Y min ⁇ 1.4 Item 15.
  • An acid resistant coating is provided on at least one surface of the barrier layer,
  • the acid resistant coating is at least one selected from the group consisting of Ce 2 PO 4 + , CePO 4 ⁇ , CrPO 2 + , and CrPO 4 ⁇ when analyzed using time-of-flight secondary ion mass spectrometry.
  • the packaging material for a battery according to any one of Items 1 to 14, wherein a peak derived from a species is detected.
  • the acid-resistant film containing at least one selected from the group consisting of phosphorus compounds, chromium compounds, fluorides, and triazine thiol compounds on at least one surface of the barrier layer, any one of items 1 to 15.
  • the packaging material for batteries as described in. Item 17. 17. 17.
  • Item 18 The battery packaging material according to any one of Items 1 to 17, wherein a lubricant is present in at least one of the inside and the surface of the polyester film layer.
  • Item 19 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 1 to 18.
  • Item 20. The battery according to item 19, having a printed portion on the surface of the polyester film layer.
  • a method of manufacturing a battery comprising: Item 22.
  • a polyester film for use in a polyester film layer located on the outermost surface of a battery packaging material comprising: When infrared absorption spectra in 18 directions are acquired in 10 ° increments from 0 ° to 170 ° on the surface of the polyester film using total reflection method of Fourier transform infrared spectroscopy, the following equation is satisfied. Polyester film.
  • Y max / Y min ⁇ 1.4 Y max is the maximum value among the values obtained by dividing the absorption peak intensity Y 1340 at a wavenumber 1340 cm -1 of the infrared absorption spectrum in each of the 18 directions by the absorption peak intensity Y 1410 at a wave number 1410 cm -1 It is.
  • Y min is the minimum value of the value obtained by dividing the absorption peak intensity Y 1340 at a wavenumber of 1340 cm -1 in the infrared absorption spectrum in each direction of the 18 directions by the absorption peak intensity Y 1410 at a wavenumber of 1410 cm -1 It is. Item 23.
  • a polyester film satisfying the following formula when infrared absorption spectra in 18 directions are acquired from 0 ° to 170 ° in 10 ° increments from 0 ° to 170 ° using the total reflection method of Fourier transform infrared spectroscopy Use as a polyester film layer located on the outermost surface of the battery packaging material.
  • Y max / Y min ⁇ 1.4 Y max is the maximum value among the values obtained by dividing the absorption peak intensity Y 1340 at a wavenumber 1340 cm -1 of the infrared absorption spectrum in each of the 18 directions by the absorption peak intensity Y 1410 at a wave number 1410 cm -1 It is.
  • Y min is the minimum value of the value obtained by dividing the absorption peak intensity Y 1340 at a wavenumber of 1340 cm -1 in the infrared absorption spectrum in each direction of the 18 directions by the absorption peak intensity Y 1410 at a wavenumber of 1410 cm -1 It is.
  • a battery packaging material provided with a polyester film layer on the outermost surface
  • a battery packaging material having excellent printability on the surface of the polyester film layer can be provided.
  • FIG. 1 It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is an image of the printing part formed in the biaxial stretching polyethylene terephthalate film surface observed with the laser microscope about Example 2. FIG. It is an image of the printing part formed in the biaxial stretching polyethylene terephthalate film surface observed with the laser microscope about comparative example 7. FIG.
  • the battery packaging material of the present invention is composed of a laminate having at least a base layer located on the outermost surface, a barrier layer, and a heat-fusible resin layer in this order, and the outermost surface of the base layer is It is composed of a polyester film layer, and infrared absorption spectra in 18 directions are acquired at intervals of 10 ° from 0 ° to 170 ° on the surface of the polyester film layer using total reflection method of Fourier transform infrared spectroscopy In this case, the following equation is satisfied.
  • the battery packaging material of the present invention will be described in detail.
  • Y max / Y min ⁇ 1.4
  • Y max the at 18 each direction direction, respectively, the infrared absorption spectrum at a wavenumber of 1340 cm -1 absorption peak intensity Y 1340 in the (CH 2 wagging vibrations), the absorption peak intensity at a wave number 1410 cm -1
  • C C stretching vibration
  • Y min is the minimum value of the value obtained by dividing the absorption peak intensity Y 1340 at a wavenumber of 1340 cm -1 in the infrared absorption spectrum in each direction of the 18 directions by the absorption peak intensity Y 1410 at a wavenumber of 1410 cm -1 It is.
  • Y 1340 / Y 1410 is obtained for each of the 18 directions, and the maximum value Y max and the minimum value Y min are respectively selected from these.
  • the battery packaging material of the present invention 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.
  • the battery packaging material of the present invention comprises a base material layer 1 located on the outermost surface, a barrier layer 3 and a heat fusible resin layer 4 in this order as shown in FIG. 1, for example. It consists of a laminated body. Moreover, the outermost surface of the base material layer 1 is comprised by the polyester film layer. In the battery packaging material of the present invention, the polyester film layer is the outermost layer side, and the heat-fusible resin layer 4 is the innermost layer. That is, when assembling the battery, the battery element is sealed by sealing the battery element by thermally fusing the heat-fusible resin layers 4 located on the peripheral edge of the battery element.
  • the substrate layer 1 may be provided with other layers in addition to the polyester film layer.
  • a polyester film layer and another layer may be adhere
  • the battery packaging material of the present invention has an adhesive layer 2 as needed between the base layer 1 and the barrier layer 3 for the purpose of enhancing the adhesiveness thereof. You may have.
  • an adhesive layer 5 may be provided between the barrier layer 3 and the heat-fusible resin layer 4 as needed in order to improve the adhesiveness.
  • the total thickness of the laminate constituting the battery packaging material of the present invention is not particularly limited, but it is preferably about 180 ⁇ m or less, from the viewpoint of improving formability while making the total thickness of the laminate as thin as possible. More preferably, it is about 35 to 160 ⁇ m, more preferably about 45 to 150 ⁇ m.
  • the battery packaging material of the present invention can be suitably used in applications where printing is performed on the surface of the polyester film layer located on the outermost surface.
  • printing by ink the above-mentioned pad printing, inkjet printing, etc. are suitable, for example, and in particular, inkjet printing is suitable.
  • Preferred examples of the solvent contained in the ink include methyl ethyl ketone, acetone, isopropyl alcohol and ethanol.
  • the solvents may be used alone or in combination of two or more.
  • the base material layer 1 is a layer located on the outermost surface.
  • the outermost surface of the base layer 1 is composed of a polyester film layer.
  • the polyester film layer to which the lubricant is attached constitutes the outermost surface of the battery packaging material.
  • the base material layer 1 is a layer located on the outermost surface of the battery packaging material also for the base material layer 1 in which the lubricant is present on the surface.
  • the polyester film layer constituting the outermost surface is 10 ° from 0 ° to 170 ° with respect to the surface of the polyester film layer using total reflection method of Fourier transform infrared spectroscopy.
  • Y max / Y min ⁇ 1.4 Y max is the maximum value among the values obtained by dividing the absorption peak intensity Y 1340 at a wavenumber 1340 cm -1 of the infrared absorption spectrum in each of the 18 directions by the absorption peak intensity Y 1410 at a wave number 1410 cm -1 It is.
  • Y min is a value obtained by dividing the absorption peak intensity Y 1340 at a wavenumber of 1340 cm ⁇ 1 in the infrared absorption spectrum in each direction of the 18 directions by the absorption peak intensity Y 1410 at a wave number of 1410 cm ⁇ 1 . It is the minimum value.
  • Y 1340 / Y 1410 is obtained for each of the 18 directions, and the maximum value Y max and the minimum value Y min are respectively selected from these.
  • the outermost surface of the substrate layer is constituted of a polyester film layer, and the polyester film layer has the above-mentioned specific surface orientation, so the outermost surface is Notwithstanding the polyester film, excellent printability is exhibited.
  • This mechanism can be considered, for example, as follows. That is, in the battery packaging material of the present invention, since the polyester film layer constituting the outermost surface has the above-mentioned specific surface orientation degree, it can be said that the orientation degree of polyester molecules in the polyester film layer is low. . For this reason, it is considered that the ink is easily spread in the uniform direction on the surface of the polyester film layer, and the excellent printability is exhibited.
  • a polyester film layer is used as the base material layer in the conventional battery packaging material
  • a polyester film having a high degree of orientation of polyester molecules is used, for example, by greatly stretching the polyester film from the viewpoint of enhancing the formability.
  • excellent printability is exhibited by having the surface orientation degree with respect to the polyester film layer constituting the outermost surface.
  • the measurement of the infrared absorption spectrum in the surface of a polyester film layer can be performed in the state laminated
  • the incident angle is the angle between the normal (normal) and the incident light.
  • the upper limit of the surface orientation (Y max / Y min ) is less than 1.4.
  • the upper limit is preferably about 1.3 or less, and the lower limit is preferably about 1.0 or more, more preferably about 1.1 or more, still more preferably about 1.2 or more, and the preferred range About 1.0 to less than 1.4, about 1.0 to 1.3, about 1.1 to less than 1.4, 1.1 to about 1.3, about 1.2 to less than 1.4 And about 1.2 to 1.3.
  • the surface orientation degree (Y max / Y min ) is about 1.1 or more, the formability can be suitably improved while improving the printability of the battery packaging material.
  • the polyester film having the above surface orientation degree: Y max / Y min can be adjusted, for example, by appropriately adjusting the stretching method, stretch ratio, stretching speed, cooling temperature, heat setting temperature, etc. when producing the polyester film. It can be manufactured.
  • the upper limit is preferably about 1000 nm or less, more preferably about 500 nm or less is mentioned, the lower limit is preferably about 10 nm or more, more preferably about 20 nm or more, and the preferable range is about 10 to 1000 nm, about 20 to 500 nm .
  • Arithmetic mean roughness Ra of the polyester film layer constituting the outermost surface is a value obtained according to the method defined in JIS B 0601-2001 for the surface of the polyester film layer. As a specific measurement method, the method described in the examples can be adopted. In addition, the measurement of the said arithmetic mean roughness Ra of a polyester film layer can be performed in the state laminated
  • Arithmetic mean roughness Ra of the surface of a polyester film layer can be adjusted with the height of the unevenness
  • the polyester film layer may contain, as particles, additives described later (flame retardant, anti blocking agent, antioxidant, light stabilizer, tackifier, antistatic agent, etc.), and the particles are not Arithmetic mean roughness Ra may be adjusted.
  • the average particle diameter of the particles is, for example, about 0.1 to 5 ⁇ m, and the content of the particles is, for example, about 0.01 to 0.1 mass%.
  • polyester constituting the polyester film layer examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymer polyester having ethylene terephthalate as a main component of the repeating unit, The copolyester etc. which made the butylene terephthalate the main body of a repeating unit are mentioned.
  • 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) , Polyethylene (terephthalate / decane dicarboxylate) and the like.
  • polyethylene (terephthalate / isophthalate) Polyethylene (terephthalate / isophthalate) Polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / isophthalate), polyethylene (terephthalate
  • polyesters having butylene terephthalate as the main component of the repeating unit specifically, a copolymer polyester in which butylene terephthalate is polymerized with butylene isophthalate as the main component of the repeating unit (hereinafter, polybutylene (terephthalate / isophthalate) And polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like.
  • polyesters may be used alone or in combination of two or more. Polyester is excellent in heat resistance and electrolytic solution resistance, and has the advantage of being less likely to cause whitening or the like due to adhesion of the electrolytic solution, and is suitably used as a forming material of the base material layer 1.
  • the polyester film layer may be either an oriented polyester film or an unoriented polyester film, but from the viewpoint of suitably improving the formability of the battery packaging material, preferably an oriented polyester film, more preferably a biaxially oriented polyester It can be composed of a film, more preferably a biaxially stretched polyethylene terephthalate film.
  • a sequential biaxial stretching method, an inflation method, the simultaneous biaxial stretching method etc. are mentioned, for example.
  • the thickness of the polyester film layer is not particularly limited, but the upper limit is, for example, about 50 ⁇ m or less, preferably about 30 ⁇ m or less, and more preferably, from the viewpoint of improving formability while thinning the battery packaging material.
  • the lower limit is preferably about 1 ⁇ m or more, more preferably about 5 ⁇ m or more, and further about 10 ⁇ m or more, and the preferable range is about 1 to 50 ⁇ m, about 1 to 30 ⁇ m, 1 to There are about 25 ⁇ m, about 5 to 50 ⁇ m, about 5 to 30 ⁇ m, about 5 to 25 ⁇ m, about 10 to 50 ⁇ m, about 10 to 30 ⁇ m, and about 10 to 25 ⁇ m.
  • the polyester film layer may be a single layer or a multilayer (multilayer structure).
  • the polyester film layer is a multilayer, at least the polyester film located on the outermost layer side (the side opposite to the barrier layer 3) may satisfy the above-mentioned degree of surface orientation;
  • the polyester film may have a surface orientation degree: Y max / Y min of 1.4 or more.
  • the base material layer 1 is added to the polyester film layer for the purpose of improving the moldability of the packaging material for batteries, etc.,
  • resin film used for the base material layer for example, polyamide, polyolefin, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicone resin, phenol resin, polyether imide, polyimide, and a mixture or copolymer thereof
  • the resin film comprised with things etc. is mentioned.
  • stacked are mentioned.
  • polyamide film constituting the polyamide film layer examples include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 6, 6; Hexamethylenediamine-isophthalic acid-terephthalic acid copolymer such as nylon 6I, nylon 6T, nylon 6IT, nylon 6 I 6T (I represents isophthalic acid and T represents terephthalic acid) containing a structural unit derived from an acid and / or isophthalic acid Polyamide, polyamide MXD6 (polyamide containing an aromatic such as polymetaxylylene adipamide; alicyclic polyamide such as polyaminomethylcyclohexyl adipamide (PACM 6); further, a lactam component, 4,4'-diphenylmethane diisocyanate, etc.
  • aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 6, 6
  • polyamide resin polyesteramide copolymer and polyetheresteramide copolymer which are copolymers of copolymerized polyamide and polyester or polyalkylene ether glycol; polyamide films such as these copolymers
  • polyamide films may be used alone or in combination of two or more.
  • the polyamide film is excellent in stretchability and whitening due to resin cracking during molding It can prevent the occurrence of and is suitably used as a resin film used for the base layer 1 together with the polyester film.
  • the base material layer 1 has a multilayer structure of a polyester film
  • a laminate of a polyester film and a nylon film, and a laminate of a plurality of polyester films are preferable.
  • a laminate of a stretched polyester film and a stretched nylon film, and a laminate in which a plurality of stretched polyester films are laminated are more preferable.
  • the base material layer 1 has a two-layer structure
  • a configuration in which a polyester film and a polyamide film are laminated or a configuration in which a polyester film and a polyester film are laminated is preferable, and a configuration in which polyethylene terephthalate and nylon are laminated, or More preferably, polyethylene terephthalate and polyethylene terephthalate are laminated.
  • the polyester film is difficult to discolor, for example, when the electrolytic solution adheres to the surface, and in the battery packaging material of the present invention, the polyester film layer constitutes the outermost surface, so that it is excellent in electrolytic solution resistance. Can be configured.
  • the thickness of the polyester film not positioned in the outermost layer or the resin film other than the polyester film is preferably about 3 ⁇ m or more, more preferably about 5 ⁇ m or more for the lower limit.
  • the upper limit is preferably about 30 ⁇ m or less, preferably about 25 ⁇ m or less, and the preferable range is about 3 to 30 ⁇ m, about 3 to 25 ⁇ m, about 5 to 30 ⁇ m, or about 5 to 25 ⁇ m.
  • the polyester film and each resin film may be bonded via an adhesive, or may be directly laminated without using an adhesive.
  • bonding without using an adhesive for example, a method of bonding in a hot-melted state such as co-extrusion 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 adhesives exemplified for the adhesive layer 2.
  • the thickness of the adhesive can be the same as that of the adhesive layer 2.
  • the base material layer 1 when making the base material layer 1 into a multilayer structure, is a resin composition containing the modified thermoplastic resin graft-modified by the unsaturated carboxylic acid derivative component as an adhesive which adhere
  • the said modified thermoplastic resin Preferably, resin which modified
  • the said resin may be used individually by 1 type, and may be used combining 2 or more types.
  • unsaturated carboxylic acid derivative component unsaturated carboxylic acid, an acid anhydride of unsaturated carboxylic acid, ester of unsaturated carboxylic acid, etc. are mentioned.
  • unsaturated carboxylic acid derivative component one type may be used alone, or two or more types may be used in combination.
  • polyolefins in the modified thermoplastic resin low density polyethylene, medium density polyethylene, high density polyethylene; ethylene- ⁇ -olefin copolymer; homo, block or random polypropylene; propylene- ⁇ -olefin copolymer; And copolymers obtained by copolymerizing polar molecules such as methacrylic acid; polymers such as cross-linked polyolefins;
  • the polyolefin may be one kind alone or a combination of two or more kinds.
  • styrene-based elastomer in the modified thermoplastic resin examples include copolymers of styrene (hard segment) and butadiene or isoprene or a hydrogenated product thereof (soft segment).
  • the polyolefin resins may be used alone or in combination of two or more.
  • polyester elastomers in the modified thermoplastic resin include copolymers of crystalline polyester (hard segment) and polyalkylene ether glycol (soft segment).
  • the polyolefin may be one kind alone or a combination of two or more kinds.
  • unsaturated carboxylic acids in the modified thermoplastic resin include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo [2,2,1] hept-2-ene- 5,6-dicarboxylic acid and the like.
  • unsaturated carboxylic acids for example, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6- Dicarboxylic acid anhydride etc. are mentioned.
  • esters of unsaturated carboxylic acids for example, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, tetrahydro
  • esters of unsaturated carboxylic acids such as dimethyl phthalic anhydride and dimethyl bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylate.
  • the modified thermoplastic resin is reacted by heating about 0.2 to 100 parts by mass of the unsaturated carboxylic acid derivative component in the presence of a radical initiator with respect to 100 parts by mass of the base thermoplastic resin. It is obtained by
  • the reaction temperature is preferably about 50 to 250 ° C., and more preferably about 60 to 200 ° C.
  • the reaction time depends on the production method, but in the case of a melt grafting reaction by a twin-screw extruder, it is preferably about 2 to 30 minutes within the residence time of the extruder, and more preferably about 5 to 10 minutes.
  • the modification reaction can be carried out under either normal pressure or increased pressure.
  • radical initiator used in the modification reaction examples include organic peroxides.
  • organic peroxide various materials can be selected depending on the temperature conditions and reaction time, and, for example, alkyl peroxide, aryl peroxide, acyl peroxide, ketone peroxide, peroxy ketal, peroxy carbonate, peroxy carbonate Oxyester, hydroperoxide and the like can be mentioned.
  • alkyl peroxide, peroxy ketal, peroxy ester is preferable, and di-t-butyl peroxide, 2,5-dimethyl-2,5-di-t- More preferably, butylperoxy-hexyne-3, dicumyl peroxide is used.
  • the thickness of the adhesive layer located between the polyester film and each resin film is preferably about 0.1 to 5 ⁇ m, more preferably about 0.5 to 3 ⁇ m.
  • the adhesive layer may contain the same colorant as that of the adhesive layer 2 described later.
  • a lubricant be present in at least one of the inside and the surface of the polyester film layer. That is, a lubricant may be contained in the polyester film layer, or a lubricant may be present on the surface of the battery packaging material.
  • the lubricant present on the surface of the polyester film layer may be one in which the lubricant contained in the polyester film layer is exuded, or one on which the lubricant is applied to the surface of the polyester film layer.
  • the lubricant is not particularly limited, but preferably includes amide-based lubricants and silicone-based lubricants.
  • Specific examples of the lubricant include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides 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.
  • Specific examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide.
  • substituted amide examples 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 examples 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 bisamide include m-xylylene bis-stearic acid amide, m-xylylene bis-hydroxystearic acid amide, N, N'-distearyl isophthalic acid amide and the like.
  • non-reactive modified silicone oils such as alkyl-modified silicone oils, higher fatty acid ester-modified silicone oils, and polyether-modified silicone oils are preferable.
  • the lubricant may be used alone or in combination of two or more.
  • the amount thereof is not particularly limited, but from the viewpoint of exhibiting excellent printability, it is preferably about 3 mg / m 2 or more, more preferably 3 to 15 mg / m. About m 2 , more preferably about 4 to 14 mg / m 2 . Even when a lubricant is present on the surface of the polyester film layer, the infrared absorption spectrum can be measured on the surface of the polyester film layer on which the lubricant is present.
  • additives such as a flame retardant, an antiblocking agent, an antioxidant, a light stabilizer, a tackifier, and an antistatic agent may be present in at least one of the inside and the surface of the base layer 1. Only one type of additive may be used, or two or more types may be mixed and used.
  • the thickness (total thickness) of the base material layer 1 is not particularly limited, but from the viewpoint of improving formability while thinning the battery packaging material, the upper limit is, for example, about 50 ⁇ m or less, preferably about 40 ⁇ m or less
  • the lower limit is preferably about 3 ⁇ m or more, more preferably about 5 ⁇ m or more, and further preferably about 10 ⁇ m or more.
  • the preferred range of the thickness of the substrate layer 1 is about 3 to 50 ⁇ m, 3 to There are about 40 ⁇ m, about 5 to 50 ⁇ m, about 5 to 40 ⁇ m, about 10 to 50 ⁇ m, and about 10 to 40 ⁇ m.
  • 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 adhesion mechanism of the adhesive used to form the adhesive layer 2 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, and the like.
  • Polyolefin carboxylic acid modified polyolefin, polyolefin such as metal modified polyolefin, polyvinyl acetate; Cellulose adhesive (Meth) acrylic resin; polyimide; polycarbonate; amino resin such as urea resin, melamine resin; rubber such as chloroprene rubber, nitrile rubber, styrene-butadiene rubber; silicone Resins.
  • These adhesive components may be used alone or in combination of two or more.
  • a polyurethane adhesive is preferably mentioned.
  • the polyurethane adhesive is a polyurethane adhesive containing a main component containing a polyol component (A) and a curing agent containing a polyisocyanate component (B), wherein the polyol component (A) is a polyester polyol (A1) And the polyester polyol (A1) is a polyester polyol having a number average molecular weight of 5,000 to 50,000 composed of a polybasic acid component and a polyhydric alcohol component, wherein the aromatic polybase is 100% by mole of the polybasic acid component Examples thereof include those containing 45 to 95% by mole of an acid component, and the tensile stress at 100% elongation of the adhesive layer is 100 kg / cm 2 or more and 500 kg / cm 2 or less.
  • the adhesive layer 2 may also contain a colorant.
  • the adhesive layer 2 contains a coloring agent
  • the battery packaging material can be colored.
  • the colorant known ones such as pigments and dyes can be used. Moreover, only one type of colorant may be used, or two or more types may be mixed and used.
  • the inorganic pigment preferably, carbon black, titanium oxide and the like can be mentioned.
  • the pigment of an organic type Preferably an azo pigment, a phthalocyanine pigment, a condensation polycyclic pigment etc. are mentioned.
  • azo pigments include soluble pigments such as watching red and carmine 6C; insoluble azo pigments such as monoazo yellow, disazo yellow, pyrazolone orange, pyrazolone red and permanent red, and examples of phthalocyanine pigments include copper phthalocyanine pigments, no Blue-based pigments and green-based pigments as metal phthalocyanine pigments may be mentioned, and as condensed polycyclic pigments, dioxazine violet, quinacridone violet etc. may be mentioned. In addition, as pigments, pearl pigments, fluorescent pigments and the like can be used.
  • carbon black is preferable, for example, in order to make the appearance of the battery packaging material black.
  • the average particle size of the pigment is not particularly limited, and, for example, about 0.05 to 5 ⁇ m, preferably about 0.08 to 2 ⁇ m.
  • the average particle diameter of a pigment be the median diameter measured by laser diffraction / scattering type particle diameter distribution measuring apparatus.
  • the content of the pigment in the adhesive layer 2 is not particularly limited as long as the battery packaging material is colored, and may be, for example, about 5 to 60% by mass.
  • 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 1 to 10 ⁇ m, preferably about 2 to 5 ⁇ m.
  • the colored layer is a layer provided as needed between the base material layer 1 and the adhesive layer 2 (not shown). By providing the colored layer, the battery packaging material can be colored.
  • the colored layer can be formed, for example, by applying an ink containing a colorant to the surface of the base layer 1 or the surface of the barrier layer 3.
  • a colorant known ones such as pigments and dyes can be used.
  • only one type of colorant may be used, or two or more types may be mixed and used.
  • 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 can be formed of a metal foil, a metal deposition film, an inorganic oxide deposition film, a carbon-containing inorganic oxide deposition film, a film provided with these deposition layers, or the like, and is a layer formed of metal Is preferred. Specifically as a metal which comprises the barrier layer 3, aluminum, stainless steel, titanium steel etc. are mentioned, Preferably aluminum or stainless steel is mentioned.
  • the barrier layer 3 is preferably formed of a metal foil, more preferably an aluminum alloy foil or a stainless steel foil.
  • the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021 H-O, JIS H4160: More preferably, it is formed of a soft aluminum foil such as 1994 A8079 H-O, JIS H4000: 2014 A8021 P-O, JIS H 4000: 2014 A8079 P-O).
  • 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 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 from the viewpoint of reducing the thickness of the battery packaging material, the upper limit is preferably about 85 ⁇ m or less, more preferably The thickness is about 50 ⁇ m or less, more preferably 45 ⁇ m or less, and the lower limit is preferably about 10 ⁇ m or more.
  • the thickness range is, for example, about 10 to 85 ⁇ m, preferably about 10 to 50 ⁇ m, more preferably It can be about 10 to 45 ⁇ m.
  • the thickness of the stainless steel foil is preferably about 85 ⁇ m or less, more preferably about 50 ⁇ m or less, still more preferably about 40 ⁇ m or less, still more preferably about 30 ⁇ m or less Particularly preferably, the thickness is about 25 ⁇ m or less, the lower limit is about 10 ⁇ m or more, and the preferable thickness range is about 10 to 85 ⁇ m, about 10 to 50 ⁇ m, more preferably about 10 to 40 ⁇ m, more preferably The thickness is about 10 to 30 ⁇ m, more preferably about 15 to 25 ⁇ m.
  • 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 using a chromate compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromate acetyl acetate, chromium chloride, potassium chromium sulfate, etc.
  • a chromate compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromate acetyl acetate, chromium chloride, potassium chromium sulfate, etc.
  • Phosphoric acid chromate treatment using phosphoric acid compounds such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid, etc .
  • X represents a hydrogen atom, a hydroxy group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group.
  • R 1 and R 2 are the same or different and each represents a hydroxy group, an alkyl group or a hydroxyalkyl group.
  • examples of the alkyl group represented by X, R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group,
  • a linear or branched alkyl group having 1 to 4 carbon atoms such as a tert-butyl group can be mentioned.
  • examples of the hydroxyalkyl group represented by X, R 1 and R 2 include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3- C 1-4 linear or branched C 1 -C 4 substituted with one hydroxy group, such as hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like
  • An alkyl group is mentioned.
  • the alkyl group and the hydroxyalkyl group represented by X, R 1 and R 2 may be identical to or different from each other.
  • X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group.
  • the number average molecular weight of the aminated phenol polymer having repeating units represented by the general formulas (1) to (4) is, for example, preferably 500 to 1,000,000, and more preferably 1,000 to 20,000. .
  • a coating in which fine particles of aluminum oxide, titanium oxide, cerium oxide, metal oxide such as tin oxide, or barium sulfate are dispersed in phosphoric acid is coated;
  • a method of forming an acid resistant film on the surface of the barrier layer 3 can be mentioned by carrying out the baking treatment at 150 ° C. or higher.
  • a resin layer may be further formed by crosslinking the cationic polymer with a crosslinking agent.
  • the cationic polymer for example, polyethylene imine, an ionic polymer complex composed of polyethylene imine and a polymer having a carboxylic acid, primary amine graft acrylic resin obtained by graft polymerizing a primary amine on an acrylic main skeleton, polyallylamine Or derivatives thereof, aminophenol and the like.
  • these cationic polymers only 1 type may be used and you may use combining 2 or more types.
  • a crosslinking agent the compound which has an at least 1 sort (s) of functional group chosen from the group which consists of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, a silane coupling agent etc. are mentioned, for example.
  • these crosslinking agents only one type may be used, or two or more types may be used in combination.
  • At least the surface on the inner layer side of the aluminum foil (barrier layer) is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolysis method.
  • the degreasing treatment is performed by a known treatment method such as an acid cleaning method or an acid activation method, and then the surface to be degreased is treated with Cr (chromium) phosphate, Ti (titanium) phosphate, Zr (zirconium) phosphate, phosphorus Acid solution (aqueous solution) mainly composed of phosphoric acid metal salts such as zinc (zinc) salts and mixtures of these metal salts, or phosphoric acid nonmetal salts and mixtures of these nonmetallic salts Roll coating method, gravure printing method, immersion method using a treatment liquid (aqueous solution), or a mixture of these and an aqueous synthetic resin such as acrylic resin, phenol resin or polyurethane, etc.
  • a known treatment method such as an acid cleaning method or an acid activation method
  • the acid-resistant coating By coating with a known coating method, it is possible to form the acid-resistant coating.
  • CrPO 4 chromium phosphate
  • AlPO 4 aluminum phosphate
  • Al 2 O 3 aluminum oxide
  • Al (OH) x water It becomes an acid-resistant film consisting of aluminum oxide), AlF x (aluminum fluoride), etc.
  • a phosphoric acid Zn (zinc) salt-based treatment solution Zn 2 PO 4 ⁇ 4H 2 O (zinc phosphate hydrate) ), AlPO 4 (aluminum phosphate), Al 2 O 3 (aluminum oxide), Al (OH) x (aluminum hydroxide), AlF x (aluminum fluoride) and the like.
  • an acid resistant coating for example, at least the surface on the inner layer side of an aluminum foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid activity
  • An acid resistant film can be formed by degreasing treatment by a known treatment method such as chemical conversion method and then applying known anodizing treatment to the degreasing treatment surface.
  • the film of a phosphorus compound (for example, phosphate type) and a chromium compound (chromic acid type) is mentioned as another example of an acid resistant film.
  • phosphates include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate and chromium phosphate.
  • chromic acid include chromium chromate.
  • the acid resistant coating by forming an acid resistant coating such as phosphate, chromate, fluoride, triazine thiol compound, etc., between the aluminum at the time of embossing and the substrate layer Anti-delamination, hydrogen fluoride generated by the reaction between electrolyte and water prevents dissolution and corrosion of the aluminum surface, especially dissolution and corrosion of aluminum oxide present on the aluminum surface, and adhesion of the aluminum surface
  • the properties (wettability) are improved, and the effect of preventing the delamination of the base layer and aluminum during heat sealing and the prevention of the delamination of the base layer and aluminum during press molding are shown in the embossed type.
  • an aqueous solution composed of three components of a phenol resin, a chromium fluoride (3) compound and a phosphoric acid is applied to the aluminum surface, and the dry baking treatment is good.
  • the acid resistant film further comprises a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent for crosslinking the anionic polymer, wherein the phosphoric acid or phosphate is any of the above. It may be blended in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of cerium oxide. It is preferable that the acid resistant coating be a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.
  • the said anionic polymer is a copolymer which has poly (meth) acrylic acid or its salt, or (meth) acrylic acid or its salt as a main component.
  • the said crosslinking agent is at least 1 sort (s) chosen from the group which consists of a compound which has a functional group in any one of an isocyanate group, glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.
  • the said phosphoric acid or phosphate is condensed phosphoric acid or condensed phosphate.
  • chemical conversion treatment only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion treatments may be performed in combination. Furthermore, these chemical conversion treatments may be performed using one type of compound alone, or may be performed using two or more types of compounds in combination.
  • chemical conversion treatments chromate chromate treatment, chromate treatment in which a chromic acid compound, a phosphoric acid compound, and an aminated phenol polymer are combined are preferable.
  • the acid resistant coating include those containing at least one of a phosphorus compound (such as phosphate), a chromium compound (chromate), a fluoride, and a triazine thiol compound.
  • a phosphorus compound such as phosphate
  • chromate chromium compound
  • fluoride a fluoride
  • a triazine thiol compound an acid resistant film containing a cerium compound is also preferable.
  • a cerium compound cerium oxide is preferable.
  • an acid resistant film a phosphate type film, a chromate type film, a fluoride type film, a triazine thiol compound film, etc. are mentioned.
  • the acid resistant coating may be one of these or a combination of two or more.
  • a treatment liquid comprising a mixture of a metal salt of phosphoric acid and an aqueous synthetic resin, or a mixture of a nonmetallic metal salt of phosphoric acid and an aqueous synthetic resin It may be formed by the treatment liquid.
  • the analysis of the composition of the acid-resistant film can be performed using, for example, time-of-flight secondary ion mass spectrometry.
  • Analysis of the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry for example, secondary ions consisting of Ce, P and O (for example, at least one of Ce 2 PO 4 + , CePO 4 ⁇ , etc.
  • peaks derived from secondary ions for example, at least one of CrPO 2 + , CrPO 4 ⁇ and the like) consisting of Cr, P and O, for example.
  • the amount of the acid resistant coating formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, but, for example, in the case of performing the above-mentioned chromate treatment, a chromic acid compound is contained per 1 m 2 of the surface of the barrier layer 3 About 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of chromium, about 0.5 to 50 mg, preferably about 1.0 to 40 mg, of the phosphorus compound in terms of phosphorus, and The content is desirably about 0 to 200 mg, preferably about 5.0 to 150 mg.
  • the thickness of the acid-resistant coating is not particularly limited, but is preferably about 1 nm to 20 ⁇ m, more preferably about 1 to 100 nm, from the viewpoint of the cohesion of the film and the adhesion to the barrier layer and the heat fusible resin layer. More preferably, it is about 1 to 50 nm.
  • the thickness of the acid-resistant film can be measured by a transmission electron microscope or a combination of an observation by a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy.
  • the temperature of the barrier layer is 70 after the solution containing the compound used for forming the acid resistant coating is applied to the surface of the barrier layer by the bar coating method, roll coating method, gravure coating method, immersion method or the like. It is carried out by heating to a temperature of ⁇ 200 ° C.
  • the barrier layer may be subjected in advance to a degreasing treatment by an alkaline immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like. By performing the degreasing treatment in this manner, the chemical conversion treatment on the surface of the barrier layer can be performed more efficiently.
  • the thermally fusible resin layer 4 corresponds to the innermost layer, and is a layer that thermally fuses the thermally fusible resin layers when the battery is assembled to seal the battery element.
  • the resin component used for the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-fused, but examples include polyolefins, cyclic polyolefins, carboxylic acid-modified polyolefins, and carboxylic acid-modified cyclic polyolefins.
  • 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.
  • infrared spectroscopy when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, 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. However, if the acid denaturation degree is low, 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 And polypropylenes such as random copolymers of propylene and ethylene (eg, 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 And polypropylenes such as random copolymers of propylene and ethylene (eg, random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like.
  • 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, etc. may be mentioned.
  • these polyolefins preferred are cyclic alkenes, more preferably norbornene.
  • styrene can be used as a constituent monomer.
  • the carboxylic acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of the polyolefin with a carboxylic acid.
  • carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.
  • the carboxylic acid-modified cyclic polyolefin is obtained by copolymerizing part of the monomers constituting the cyclic polyolefin with an ⁇ , ⁇ -unsaturated carboxylic acid or an anhydride thereof, or ⁇ , ⁇ to the cyclic polyolefin A polymer obtained by block polymerization or graft polymerization of an unsaturated carboxylic acid or its anhydride.
  • the cyclic polyolefin to be carboxylic acid modified is the same as described above.
  • denaturation it is the same as that of what is used for modification
  • carboxylic acid-modified polyolefins preferred are carboxylic 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 heat fusible resin layer 4 may contain a lubricant.
  • the lubricant present on the surface of the heat-fusible resin layer 4 may be one in which the lubricant contained in the resin constituting the heat-fusible resin layer 4 is exuded, or the heat-fusible resin layer The surface of 4 may be coated with a lubricant.
  • the heat fusible resin layer 4 contains a lubricant, the formability of the battery packaging material can be enhanced.
  • the lubricant is not particularly limited, and known lubricants can be used, and examples thereof include those exemplified for the above-mentioned base layer 1 and the like.
  • the lubricant may be used alone or in combination of two or more.
  • the amount of the lubricant present on the surface of the heat-fusible resin layer 4 is not particularly limited, but is preferably about 10 to 50 mg / m 2 , more preferably 15 to 50, from the viewpoint of enhancing the moldability of the electronic packaging material. About 40 mg / m 2 can be mentioned.
  • 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 for example, about 100 ⁇ m or less, preferably about 85 ⁇ m or less, more preferably about 15 to 85 ⁇ m. Can be mentioned.
  • the thickness of the adhesive layer 5 described later is 10 ⁇ m or more
  • the thickness of the heat-fusible resin layer 4 is preferably about 85 ⁇ m or less, more preferably about 15 to 65 ⁇ m, for example
  • the thickness of the heat-fusible resin layer 4 is preferably about 20 ⁇ m or more, more preferably 35 to 85 ⁇ m. The degree is mentioned.
  • 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 barrier layer 3 and the heat-fusible resin layer 4.
  • 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 be used for the adhesive agent illustrated by adhesive agent layer 2, and the like.
  • resin used for formation of the contact bonding layer 5 polyolefin, such as polyolefin mentioned by the above-mentioned heat-fusible 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 preferably contains an acid-modified polyolefin from the viewpoint of improving the adhesion between the barrier layer 3 (or the acid resistant coating) and the heat-fusible resin layer 4.
  • the acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of a polyolefin with an acid component such as a carboxylic acid.
  • the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or anhydrides thereof.
  • polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, etc .
  • homopolypropylene, block copolymer of polypropylene for example, block copolymer of propylene and ethylene
  • polypropylene Polypropylenes such as random copolymers (eg, random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like.
  • polyethylene and polypropylene are mentioned.
  • maleic anhydride-modified polyolefin and more preferably maleic anhydride-modified polypropylene are preferable.
  • the adhesive layer 5 cures the resin composition containing the acid-modified polyolefin and the curing agent. It is more preferable that it is a thing.
  • the acid-modified polyolefin preferably, those described above can be exemplified.
  • the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin, and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group. Particularly preferred is a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group.
  • the adhesive layer 5 preferably contains at least one selected from the group consisting of a urethane resin, an ester resin, and an epoxy resin, and more preferably contains a urethane resin and an epoxy resin.
  • ester resin an amide ester resin is preferable, for example.
  • Amide ester resins are generally formed by the reaction of carboxyl groups with oxazoline groups.
  • the adhesive layer 5 is more preferably a cured product of a resin composition containing at least one of these resins and the acid-modified polyolefin.
  • the presence of the non-reacted substance is, for example, infrared spectroscopy, It can be confirmed by a method selected from Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS) and the like.
  • the adhesive layer 5 is an oxygen atom, a heterocyclic ring, CNN bond, It is preferable that it is a cured product of a resin composition containing a curing agent having at least one selected from the group consisting of C—O—C bonds.
  • a curing agent which has a heterocyclic ring the curing agent which has an oxazoline group, the curing agent which has an epoxy group, etc. are mentioned, for example.
  • a curing agent having a C—O—C bond a curing agent having an oxazoline group, a curing agent having an epoxy group, a urethane resin and the like can be mentioned.
  • That the adhesive layer 5 is a cured product of a resin composition containing these curing agents is, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF) -SIMS), X-ray photoelectron spectroscopy (XPS), etc. can confirm.
  • GCMS gas chromatography mass spectrometry
  • IR infrared spectroscopy
  • TOF time-of-flight secondary ion mass spectrometry
  • XPS X-ray photoelectron spectroscopy
  • the compound having an isocyanate group is not particularly limited, but from the viewpoint of effectively enhancing the adhesion between the acid-resistant film and the adhesive layer 5, a polyfunctional isocyanate compound is preferably mentioned.
  • the polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • Specific examples of the polyfunctional isocyanate curing agent include pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and these. And copolymers of these with other polymers and the like.
  • the content of the compound having an isocyanate group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably 0.5 to 40% by mass, in the resin composition constituting the adhesive layer 5. It is more preferable to be in the range.
  • the compound having an oxazoline group is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the compound having an oxazoline group include those having a polystyrene main chain, and those having an acryl main chain.
  • Epocross series manufactured by Nippon Shokubai Co., Ltd. and the like can be mentioned.
  • the proportion of the compound having an oxazoline group in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 40% by mass, in the resin composition constituting the adhesive layer 5. It is more preferable that Thereby, the adhesion between the barrier layer 3 (or the acid resistant film) and the adhesive layer 5 can be effectively enhanced.
  • the epoxy resin is not particularly limited as long as it is a resin capable of forming a cross-linked structure by an epoxy group present in the molecule, and a known epoxy resin can be used.
  • the weight average molecular weight of the epoxy resin is preferably about 50 to about 2000, more preferably about 100 to about 1000, and still more preferably about 200 to about 800.
  • the weight average molecular weight of the epoxy resin is a value measured by gel permeation chromatography (GPC), which is measured under the condition of using polystyrene as a standard sample.
  • the epoxy resin examples include glycidyl ether derivative of trimethylolpropane, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether and the like.
  • the epoxy resin may be used alone or in combination of two or more.
  • the proportion of the epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 0.5 to 40% by mass, in the resin composition constituting the adhesive layer 5. Is more preferred. Thereby, the adhesion between the barrier layer 3 (or the acid resistant film) and the adhesive layer 5 can be effectively enhanced.
  • an acid-modified polyolefin functions as a main agent, and a compound having an isocyanate group, a compound having an oxazoline group, and an epoxy resin each function as a curing agent.
  • a polycarbodiimide compound having at least two carbodiimide groups is preferable.
  • 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 adhesive layer 5 can also be suitably formed using, for example, an adhesive.
  • an adhesive for example, a non-crystalline polyolefin resin (A) having a carboxyl group, a polyfunctional isocyanate compound (B), and a tertiary amine having no functional group reactive with the polyfunctional isocyanate compound (B)
  • the polyfunctional isocyanate compound (B) is contained in a range of 0.3 to 10 moles of the isocyanate group per 1 mole of total carboxyl groups, containing C), based on 1 mole of total carboxyl groups.
  • those formed from an adhesive composition containing a tertiary amine (C) in the range of 1 to 10 moles are examples of 1 to 10 moles.
  • the adhesive contains a styrene-based thermoplastic elastomer (A), a tackifier (B) and a polyisocyanate (C), and the styrene-based thermoplastic elastomer (A) and a tackifier (B)
  • the styrene-based thermoplastic elastomer (A) comprises 20 to 90% by weight of the styrene-based thermoplastic elastomer (A) and 10 to 80% by weight of the tackifier (B) in a total of 100% by weight of Or 0.0003 to 0.04 mmol / g of the above-mentioned tackifier (B) per 1 mol of the above-mentioned active hydrogen derived from a styrene thermoplastic elastomer (A) having an active hydrogen derived from an amino group or a hydroxyl group 0 to 15 moles of active hydrogen derived from the functional group of the above, and the polyisocyanate (C
  • 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, about 50 ⁇ m or less, about 40 ⁇ m or less, preferably about 30 ⁇ m or less, more preferably about 20 ⁇ m or less, more preferably about 5 ⁇ m or less
  • the lower limit is about 0.1 ⁇ m or more, about 0.5 ⁇ m or more, about 10 ⁇ m or more, and the thickness range is preferably about 0.1 to 50 ⁇ m, or about 0.1 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 thickness after drying and curing may be about 1 to 30 g / m 2 .
  • a barrier layer is used as a method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 in this order on the barrier layer 3
  • stacking by co-extruding the adhesive layer 5 and the heat-fusion-bonding resin layer 4 on 3 can be employ
  • the method for producing the battery packaging material of the present invention is not particularly limited as long as a laminate obtained by laminating each layer of a predetermined composition is obtained.
  • the method for producing a battery packaging material includes, for example, at least a step of laminating a base material layer located on the outermost surface, a barrier layer, and a heat-fusible resin layer in this order to obtain a laminate.
  • the outermost surface of the substrate layer is constituted by a polyester film layer, and as the polyester film, the total reflection method of Fourier transform infrared spectroscopy is used, and from 0 ° to 180 ° on the surface of the polyester film If you get the 18 direction of the infrared absorption spectrum at 10 ° increments, the ratio of the absorption peak intensity Y 1340 in 1340 cm -1 of the infrared absorption spectrum, the absorption peak intensity Y 1410 in 1410cm -1 (Y 1340 / There is a method using a method in which the ratio of the maximum value Y max to the minimum value Y min (surface orientation degree: Y max / Y min ) of Y 1410 ) is less than 1.4.
  • 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 said barrier layer 3 or the base material layer 1 laminate, and hardens the adhesive layer 2 after applying and drying by application methods, such as a roll coating method.
  • the adhesive layer 5 and the heat-fusible resin layer 4 are laminated in this order on the barrier layer 3 of the laminate A.
  • a method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 by coextrusion on the barrier layer 3 of the laminate A co-extrusion laminating method
  • An adhesive for forming the layer 5 is extruded or solution coated, laminated by drying or baking at a high temperature, etc., and the heat fusible resin layer 4 previously formed into a sheet on the adhesive layer 5 is formed.
  • a laminate comprising base material layer 1 / adhesive layer 2 / optionally provided / barrier layer 3 / adhesive layer 5 / thermally fusible resin layer 4 whose surface is chemically treated as needed
  • the body in order to strengthen the adhesion of the adhesive layer 2 or the adhesive layer 5, it may be subjected to heat treatment such as hot roll contact, hot air, near infrared, far infrared or the like.
  • heat treatment such as hot roll contact, hot air, near infrared, far infrared or the like.
  • the conditions for such heat treatment include, for example, about 150 to 250 ° C. and about 1 to 5 minutes.
  • each layer constituting the laminate improves or stabilizes film forming ability, lamination processing, final product secondary processing (pouching, embossing) suitability, etc., as necessary.
  • surface activation treatment such as corona treatment, blast treatment, oxidation treatment, or ozone treatment may be performed.
  • the battery packaging material of the present invention 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 a positive electrode, a negative electrode, and an electrolyte can be accommodated in a package formed of the battery packaging material of the present invention to make a battery.
  • the battery packaging material of the present invention is suitably used for applications where printing is performed on the surface of the polyester film layer located on the outermost surface.
  • 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 measurement of the said infrared absorption spectrum and the said arithmetic mean roughness Ra in the surface of a polyester film layer acquire the packaging material for batteries from a battery, and measure about the polyester film layer of the obtained packaging material for batteries.
  • the measurement of the infrared absorption spectrum and the arithmetic mean roughness Ra of the packaging material for a battery obtained from the battery can be performed by using the peripheral flanges of the battery (a portion where the heat-fusible resin layers are heat-fused) ) Or the packaging material of the part different from the side part (preferably, the top or bottom of the cell) is measured.
  • the battery of the present invention can be a battery having a printing portion on the surface.
  • the printing portion is a portion on the surface of the battery on which a barcode, a pattern, characters, symbols, etc. are printed.
  • the radius of the dots forming the printed portion is preferably 130 ⁇ m or more, 135 ⁇ m or more, 140 ⁇ m or more when the printability of the surface of the polyethylene terephthalate film is evaluated under the following conditions.
  • the preferred range is 151 ⁇ m or less and 149 ⁇ m or less, and the preferable range of the radius is about 130 to 151 ⁇ m, about 130 to 149 ⁇ m, about 135 to 151 ⁇ m, about 135 to 149 ⁇ m, about 140 to 151 ⁇ m, or 140 to 149 ⁇ m.
  • the degree is mentioned. When the radius of the dot satisfies such a value, it can be evaluated that the printability is excellent.
  • the printing of the bar code, pattern, characters, symbols, etc. is formed by an aggregation of ink dots, and the dot radius is too small if the radius of the dots forming the printing portion satisfies the above value.
  • the desired print can be appropriately performed without being too large.
  • the circularity of the dots forming the print portion is 0.725 or more preferable. It can be evaluated that the printability is excellent as the degree of circularity of the printed portion is closer to 1. Specifically, when printing the bar code, pattern, characters, symbols, etc., if the circularity of the dots forming the printing portion satisfies the above value, the shape of the dots will not be distorted, and the desired printing will be appropriately performed. be able to.
  • the setting conditions for printing are ink viscosity: 3.4 cps, temperature: 34 ° C., pressure: 270 bar, nozzle size: diameter 50 ⁇ m, resolution (dot density): 115 dpi.
  • the method of measuring the radius and the degree of circularity of the dots of the printing unit is as described later.
  • the said evaluation is performed in the state of the packaging material for batteries.
  • the radius of the dots and the degree of circularity of the printing portion are set to an average value of 3 in N number. In the evaluation, no operation such as wiping the surface of the polyethylene terephthalate film is performed.
  • the distance between the print head of the inkjet printer and the surface of the polyethylene terephthalate film is 20 mm, and the ink uses 5157E standard ink.
  • a laser microscope for example, a laser microscope VK-9710 manufactured by KEYENCE
  • a laser microscope VK-9710 manufactured by KEYENCE is used to observe the radius and circularity of the dots of the printed portion formed on the surface of the polyethylene terephthalate film, and the magnification is 10 times.
  • the battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but 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.
  • polyester film of the present invention is a polyester film used for the polyester film layer located on the outermost surface of the battery packaging material.
  • the polyester film of the present invention acquires infrared absorption spectra in 18 directions at intervals of 10 ° from 0 ° to 170 ° on the surface of the polyester film by using total reflection method of Fourier transform infrared spectroscopy, It is characterized by satisfying Y max / Y min ⁇ 1.4.
  • the specific configuration (composition, thickness, etc.) of the polyester film of the present invention is the same as the polyester film of the polyester film layer constituting the outermost surface in the above-mentioned "2. each layer forming the packaging material for battery”. .
  • the measurement of the infrared absorption spectrum in the surface of a polyester film can be performed in the state of only a polyester film about the surface used as the outermost surface side of the packaging material for batteries.
  • the measurement of the arithmetic average roughness Ra of the polyester film can also be performed on the surface on the outermost surface side of the battery packaging material in the state of only the polyester film.
  • Example 1 Aluminum on which an acid resistant film is formed on both sides of a biaxially stretched polyethylene terephthalate film (having a thickness of 25 ⁇ m, having a surface orientation degree of Table 1: Y max / Y min and an arithmetic mean roughness Ra) as a substrate layer
  • a barrier layer consisting of a foil JIS H4160: 1994 A8021 H-O, thickness 40 ⁇ m
  • an adhesive layer thickness 3 ⁇ m
  • the adhesive layer on the aluminum foil and the biaxially stretched polyethylene terephthalate film were laminated, and then an aging treatment was carried out to produce a laminate of base material layer / adhesive layer / barrier layer.
  • the chemical conversion treatment which forms the acid-resistant film of the aluminum foil used as a barrier layer adds the coating amount of chromium to 10 mg / m ⁇ 2 > (dry mass) with the processing liquid which consists of a phenol resin, a chromium fluoride compound, and phosphoric acid. As it becomes, it carried out by apply
  • the aluminum foil used as the barrier layer is provided with an acid resistant film containing chromium oxide and phosphate.
  • the obtained laminate coextrusion of maleic anhydride modified polypropylene (25 ⁇ m in thickness) as an adhesive layer and random polypropylene (55 ⁇ m in thickness) as a heat fusible resin layer
  • the adhesive layer / heat sealable resin layer was laminated on the barrier layer.
  • the obtained laminate is aged and heated to laminate a base layer / adhesive layer / barrier layer / adhesive layer / thermal adhesive resin layer provided with an acid resistant film on both sides in this order.
  • the obtained battery packaging material was obtained.
  • the analysis of the acid resistant film was performed as follows. First, the space between the barrier layer and the adhesive layer was peeled off. Under the present circumstances, it was made to exfoliate physically, without using the water, the organic solvent, and the aqueous solution of an acid, an alkali, etc. After peeling between the barrier layer and the adhesive layer, since the adhesive layer remained on the surface of the barrier layer, the remaining adhesive layer was removed by etching with Ar-GCIB. With respect to the surface of the barrier layer thus obtained, analysis of the acid resistant film was conducted using time-of-flight secondary ion mass spectrometry. As a result, the acid-resistant coating, Ce 2 PO 4 +, CePO 4 - secondary ions consisting of Ce and P and O, such as have been detected. The details of the measurement device and measurement conditions of time-of-flight secondary ion mass spectrometry are as follows.
  • Measuring device ION-TOF time-of-flight secondary ion mass spectrometer TOF.
  • SIMS5 Measurement conditions Primary ion: Double charge ion of bismuth cluster (Bi 3 ++ ) Primary ion acceleration voltage: 30 kV Mass range (m / z): 0 to 1500 Measurement range: 100 ⁇ m ⁇ 100 ⁇ m Number of scans: 16 scan / cycle Number of pixels (one side): 256 pixels Etching ion: Ar gas cluster ion beam (Ar-GCIB) Etching ion acceleration voltage: 5.0 kV
  • Example 2 A lubricant (erucic acid amide (coating amount is 6 mg / m 2 ) on the surface of a biaxially stretched polyethylene terephthalate film (thickness 25 ⁇ m, having a surface orientation degree of Table 1: Y max / Y min and arithmetic average roughness Ra) And a packaging material for a battery was obtained in the same manner as in Example 1 except that a polyether-modified silicone oil (coating amount: 1 mg / m 2 ) was applied (coating amount: 7 mg / m 2 in total).
  • Example 3 As a base material layer, a biaxially stretched polyethylene terephthalate film (having a thickness of 12 ⁇ m, having a surface orientation degree of Table 1: Y max / Y min and an arithmetic average roughness Ra) and a biaxially stretched nylon film (having a thickness of 15 ⁇ m) are dry laminated A laminated film laminated by the method was prepared. In the laminated film, the biaxially stretched polyethylene terephthalate film and the biaxially stretched nylon film are adhered by a urethane adhesive (a thickness of 3 ⁇ m after curing) using a polyol and an isocyanate curing agent.
  • a urethane adhesive a thickness of 3 ⁇ m after curing
  • a barrier layer composed of an aluminum foil JIS H4160: 1994 A8021 H-O, thickness 40 ⁇ m
  • an acid resistant film by subjecting both surfaces to a chemical conversion treatment on the biaxially stretched nylon film side by dry lamination method It was made to stack.
  • a two-component polyurethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum foil provided with an acid resistant film, and an adhesive layer (3 ⁇ m in thickness) is formed on the aluminum foil. It formed.
  • a base material layer (biaxially stretched polyethylene terephthalate film / adhesive / biaxially A laminate of a stretched nylon film) / adhesive layer / barrier layer provided with an acid resistant film on both sides was produced.
  • the aluminum foil used as a barrier layer is equipped with the acid-resistant film which contains a chromium oxide and a phosphate on both surfaces.
  • the analysis of the acid-resistant film on the barrier layer was performed using time-of-flight secondary ion mass spectrometry as in Example 1. As a result, the acid-resistant coating, CrPO 2 +, CrPO 4 - secondary ions of Cr and P and O, such as have been detected.
  • the obtained laminate coextrusion of maleic anhydride modified polypropylene (40 ⁇ m in thickness) as an adhesive layer and random polypropylene (40 ⁇ m in thickness) as a heat fusible resin layer
  • the adhesive layer / heat sealable resin layer was laminated on the barrier layer.
  • the obtained laminate was aged and heated to obtain a packaging material for a battery in which the base material layer / adhesive layer / barrier layer / adhesive layer / thermally fusible resin layer was laminated in this order. .
  • Example 1 The biaxially oriented polyethylene terephthalate film of the base material layer is the same as in Example 3 except that the one having the surface orientation degree: Y max / Y min and the arithmetic average roughness Ra described in Table 1 is used.
  • the packaging material for batteries was obtained.
  • Comparative example 2 A polyethylene terephthalate film and a nylon film were laminated by coextrusion to prepare a biaxially stretched laminated film.
  • Biaxially stretched polyethylene terephthalate film (having a thickness of 5 ⁇ m, with a surface orientation degree of Table 1: Y max / Y min and arithmetic average roughness Ra) and a biaxially stretched nylon film (thickness: 5 ⁇ m)
  • An adhesive layer (thickness 1 ⁇ m) composed of polyester (polyester elastomer) is present between 20 ⁇ m and 20 ⁇ m).
  • biaxially stretched polyethylene terephthalate film / adhesive / biaxially stretched nylon film is sequentially laminated.
  • a chemical conversion treatment is applied to both surfaces of the surface on the biaxially stretched nylon film side to dry laminate a barrier layer composed of an aluminum foil (JIS H4160: 1994 A8021 H-O, thickness 40 ⁇ m) provided with an acid resistant film. It was laminated by the method. Specifically, a two-component polyurethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of an aluminum foil provided with an acid resistant film to form an adhesive layer (thickness 3 ⁇ m).
  • the substrate layer (biaxially stretched polyethylene terephthalate film is carried out by carrying out an aging treatment) / Adhesive / biaxially stretched nylon film) / Adhesive layer / A laminate of a barrier layer provided with an acid resistant film on both sides was produced.
  • a non-crystalline polyolefin resin having a carboxyl group and an adhesive composed of a polyfunctional isocyanate compound are applied and dried at 100 ° C., and the barrier layer side of the obtained laminate and An adhesive layer / heat sealable resin layer was laminated on the barrier layer by passing a non-stretched polypropylene film (CPP, thickness 80 ⁇ m) between two rolls set at 60 ° C. and bonding.
  • CPP non-stretched polypropylene film
  • the substrate layer biaxially stretched polyethylene terephthalate film / adhesive / biaxially stretched nylon film
  • adhesive layer / barrier layer / adhesive layer / non-oriented polypropylene film is laminated in this order by carrying out an aging treatment.
  • the obtained battery packaging material was obtained.
  • Example 3 The biaxially oriented polyethylene terephthalate film of the base material layer is the same as in Example 3 except that the one having the surface orientation degree: Y max / Y min and the arithmetic average roughness Ra described in Table 1 is used.
  • the packaging material for batteries was obtained.
  • Example 4 The biaxially oriented polyethylene terephthalate film of the base material layer is the same as in Example 3 except that the one having the surface orientation degree: Y max / Y min and the arithmetic average roughness Ra described in Table 1 is used.
  • the packaging material for batteries was obtained.
  • Example 5 The biaxially oriented polyethylene terephthalate film of the base material layer is the same as in Example 3 except that the one having the surface orientation degree: Y max / Y min and the arithmetic average roughness Ra described in Table 1 is used.
  • the packaging material for batteries was obtained.
  • Example 2 the lubricant on the surface of the biaxially stretched polyethylene terephthalate film was wiped off with 2-butanone, and the degree of surface orientation of the surface of the biaxially stretched polyethylene terephthalate film was measured.
  • the incident angle is the angle between the normal (normal) and the incident light.
  • the setting conditions for printing were ink viscosity: 3.4 cps, temperature: 34 ° C., pressure: 270 bar, nozzle size: diameter 50 ⁇ m, resolution (dot density): 115 dpi.
  • the method of measuring the radius and the degree of circularity of the dots of the printing unit is as described later.
  • the said evaluation was performed in the state of the packaging material for batteries.
  • the radius of the dots and the degree of circularity of the printed portion were set to an average value of 3 in N number. In the evaluation, no operation such as wiping the surface of the polyethylene terephthalate film was performed. The results are shown in Table 1.
  • the distance between the print head of the inkjet printer and the surface of the biaxially oriented polyethylene terephthalate film was 20 mm, and the ink used was 5157E standard ink.
  • Example 2 a laser microscope (laser microscope VK-9710 manufactured by KEYENCE) was used to observe the radius and circularity of dots of the printed portion formed on the surface of the biaxially stretched polyethylene terephthalate film, and the magnification was 10 times.
  • a laser microscope laser microscope VK-9710 manufactured by KEYENCE
  • FIG. 4 images of the printed portion formed on the surface of the biaxially stretched polyethylene terephthalate film observed with a laser microscope are shown in FIG. 4 (Example 2) and FIG. 5 (Comparative Example), respectively. 7).
  • the polyester film layer constituting the outermost surface satisfies the relationship of the formula: Y max / Y min ⁇ 1.4, and the dot radius of the printed portion is small. And, evaluation of the roundness of the dot of a printing part was also excellent, and was excellent in print aptitude.
  • the results of Examples 1 to 3 show that excellent printability is exhibited regardless of the presence or absence of a lubricant on the surface of the polyester layer.
  • Comparative Example 7 has a small circularity of 0.723 although the dot radius of the printed portion is small, and the dots of the printed portion have irregular circles on the surface of the polyethylene terephthalate film layer, and the printing suitability (See Figure 5).
  • Comparative Example 6 a lubricant is present on the surface of the polyester layer, and the dot radius of the printed portion is comparable to that of Comparative Example 2, but the dot radius of the printed portion is larger than in Examples 1 to 3. The print aptitude was poor. Further, in Comparative Example 7 in which the amount of lubricant was increased more than Comparative Example 6, as described above, although the radius of the dots in the printed portion was small, the dots in the printed portion had irregular circles and were inferior in printability. .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/JP2018/044989 2017-12-06 2018-12-06 電池用包装材料、電池、これらの製造方法、及びポリエステルフィルム WO2019112020A1 (ja)

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