WO2017131155A1 - 包装材料及び電池 - Google Patents

包装材料及び電池 Download PDF

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Publication number
WO2017131155A1
WO2017131155A1 PCT/JP2017/002921 JP2017002921W WO2017131155A1 WO 2017131155 A1 WO2017131155 A1 WO 2017131155A1 JP 2017002921 W JP2017002921 W JP 2017002921W WO 2017131155 A1 WO2017131155 A1 WO 2017131155A1
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WO
WIPO (PCT)
Prior art keywords
layer
laminate
packaging material
base material
acid
Prior art date
Application number
PCT/JP2017/002921
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English (en)
French (fr)
Japanese (ja)
Inventor
健太 平木
山下　力也
高萩　敦子
Original Assignee
大日本印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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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 JP2017563849A priority Critical patent/JP7244206B2/ja
Priority to CN201780008351.9A priority patent/CN108602596B/zh
Publication of WO2017131155A1 publication Critical patent/WO2017131155A1/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
    • H01M50/14—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
    • 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 packaging material and a battery.
  • packaging materials for packaging contents have been widely used in fields such as food and pharmaceuticals.
  • a packaging material a film-like laminate in which a base material / barrier layer / heat-sealable resin layer is sequentially laminated is known, and by heat-sealing the heat-sealable resin layers, The contents can be sealed.
  • Patent Document 1 A film-like laminate in which layers are sequentially laminated has been proposed (Patent Document 1).
  • the main object of the present invention is to provide a packaging material excellent in impact resistance in a packaging material comprising a laminate comprising at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order. .
  • the present inventors have intensively studied to solve the above problems.
  • a packaging material composed of a laminate comprising at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order
  • the breaking energy per 1 m unit width calculated from the “test force-displacement” curve is one direction perpendicular to the thickness direction of the laminate, and one direction perpendicular to the one direction and the thickness direction of the laminate. It was found that when the total in the other direction is 400 J or more, the packaging material has excellent impact resistance.
  • Test speed 50 mm / min
  • Specimen width 15mm
  • Test piece length 100 mm Distance between gauge points: 30mm
  • this invention provides the packaging material and battery of the aspect hung up below.
  • Item 1 It is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order, In the laminate, the breaking energy per unit width 1 m calculated from a test force-displacement curve measured when a tensile test is performed under the following test conditions is perpendicular to the thickness direction of the laminate.
  • a packaging material having a total of 400 J or more in one direction, the one direction and the thickness direction of the laminate in the other direction which is a vertical direction. (Test conditions) Test speed: 50 mm / min Specimen width: 15mm Test piece length: 100 mm Distance between gauge points: 30mm Item 2. Item 2.
  • the packaging material according to Item 1 wherein the one direction is MD of the laminate, and the other direction is TD of the laminate.
  • Item 3. Item 3.
  • Item 4. Any one of Items 1 to 3, wherein the laminate is based on JIS K7124-2: 1999, and the total penetration energy measured from the base material layer side is 1.4 J or more under the following measurement conditions.
  • Packaging material according to crab. (Measurement condition) Hammer weight: 6.4kg Drop height: 300mm Sample clamp diameter: 40mm ⁇ Hammer diameter: 12.7mm
  • Hammer shape hemispherical term 5.
  • Item 6. The packaging material according to any one of Items 1 to 5, wherein the barrier layer is composed of an aluminum foil.
  • Item 7. Item 7. A packaging material according to any one of Items 1 to 6, which is used for housing a battery element.
  • Item 8. A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the packaging material according to any one of Items 1 to 7.
  • a packaging material composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order
  • measurement is performed when a tensile test is performed under the test conditions of the laminate.
  • the rupture energy per unit width 1 m calculated from the “test force-displacement amount” curve is one direction perpendicular to the thickness direction of the laminate, the one direction and the thickness direction of the laminate. Is a total of 400 J or more in the other direction which is the vertical direction, it is possible to provide a packaging material excellent in impact resistance.
  • FIG. 3 is a test force-displacement curve (MD) obtained in a tensile test of the packaging material of Comparative Example 2.
  • MD test force-displacement curve
  • the packaging material of the present invention is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order, and the laminate is subjected to a tensile test under the following test conditions.
  • the fracture energy per 1 m unit width calculated from the test force-displacement curve measured in the following is one direction perpendicular to the thickness direction of the laminate, the one direction and the thickness direction of the laminate. Is a total of 400 J or more in the other direction, which is the vertical direction.
  • Test speed 50 mm / min
  • Specimen width 15mm
  • Test piece length 100 mm Distance between gauge points: 30mm
  • 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 packaging material of the present invention comprises, for example, a laminate in which at least a base material layer 1, a barrier layer 3, and a heat-fusible resin layer 4 are sequentially laminated as shown in FIG. Is done.
  • the base material layer 1 is the outermost layer side
  • the heat-fusible resin layer 4 is the innermost layer. That is, when the battery is assembled, the battery element is sealed by heat-sealing the heat-fusible resin layers 4 positioned at the periphery of the battery element to seal the battery element.
  • the packaging material of the present invention is provided with an adhesive layer 2 between the base material layer 1 and the barrier layer 3 for the purpose of enhancing the adhesion between them. Also good.
  • the packaging material of the present invention has an adhesive layer 5 between the barrier layer 3 and the heat-fusible resin layer 4 as necessary, for example, as shown in FIG. It may be provided.
  • the laminate constituting the packaging material of the present invention has a breaking energy per unit width of 1 m calculated from a “test force-displacement amount” curve, which is measured when a tensile test is performed under the above test conditions.
  • One direction perpendicular to the thickness direction of the laminated body that is, the lamination direction of the laminated body
  • the other direction that is perpendicular to the one direction and the thickness direction of the laminated body that is, the other direction
  • the vertical direction with respect to the thickness direction of the laminated body is 400 J or more in total.
  • the one direction is MD (Machine Direction) of the laminate
  • the other direction is TD (Transverse Direction) of the laminate.
  • MD Machine Direction
  • TD Transverse Direction
  • the tensile test means a test of tensile properties.
  • the lower limit of the breaking energy is preferably about 450 J or more, more preferably about 500 J or more.
  • the upper limit is about 1000 J or less, more preferably about 800 J or less.
  • the range of the breaking energy is preferably about 400 to 1000 J, about 400 to 800 J, about 450 to 1000 J, about 450 to 800 J, about 500 to 1000 J, and about 500 to 800 J.
  • MD and TD in the manufacturing process can usually be determined for a barrier layer described later.
  • the barrier layer is made of an aluminum foil
  • linear streaks called so-called rolling marks are formed on the surface of the aluminum foil in the rolling direction (RD: Rolling Direction) of the aluminum foil. Since the rolling trace extends along the rolling direction, the rolling direction of the aluminum foil can be grasped by observing the surface of the aluminum foil.
  • RD Rolling Direction
  • the rolling direction of the aluminum foil can be grasped by observing the surface of the aluminum foil.
  • MD of a laminated body and RD of aluminum foil correspond normally, the surface of the aluminum foil of a laminated body is observed and the rolling direction (RD) of aluminum foil is specified.
  • MD of a laminated body can be specified.
  • the TD of the laminate is perpendicular to the MD of the laminate, the TD of the laminate can also be specified.
  • the breaking energy per unit width of 1 m in the one direction and the other direction of the laminate constituting the packaging material is the tensile test under the test conditions for the one direction and the other direction of the laminate, respectively.
  • Data of the test force-displacement curve measured when the test is performed the data is saved in csv file format, and the laminate using spreadsheet software (Microsoft Excel (registered trademark))
  • the calculation is performed by integrating the data until the fracture occurs. At this time, calculation is performed by converting (dividing by 0.015) into breaking energy per 1 m width of each packaging material by the spreadsheet software. Then, the breaking energy per 1 m unit width in one direction and the breaking energy per 1 m unit width in the other direction are summed.
  • the time when the laminate is broken means when the test piece is broken.
  • five packaging materials to be measured are prepared, and the average of three values excluding the maximum value and the minimum value among the breaking energy values for five samples is used as the breaking energy of the laminate. . Even when five samples cannot be prepared, it is preferable to use an average measured by the number of measurable samples. In the tensile test, a commercially available tensile tester can be used.
  • the laminate constituting the packaging material of the present invention is formed on the base material layer 1 side by a method in accordance with the provisions of JIS Z1707: 1995.
  • the lower limit is preferably about 23 N or more, more preferably about 24 N or more, and still more preferably about 26 N or more.
  • the upper limit Is preferably about 50 N or less, more preferably about 40 N or less.
  • the range of the puncture strength is preferably about 23 to 50N, about 23 to 40N, about 24 to 50N, about 24 to 40N, about 26 to 50N, about 26 to 40N.
  • the laminate constituting the packaging material of the present invention includes a base material layer 1, a barrier layer 3, and a heat-fusible resin described later.
  • the total puncture strength measured in accordance with JIS Z1707: 1995 is preferably 23N or more, preferably 23 to 50N, and 23 to 40N. More preferably it is.
  • the laminated body which comprises the packaging material of this invention has only the heat-fusible resin layer 4 arrange
  • the puncture strength is a puncture strength measured only for the heat-fusible resin layer 4, but as shown in FIG.
  • the adhesive layer 5 and the heat-fusible property are placed inside the barrier layer 3.
  • the piercing strength is the piercing strength measured for the laminate of the adhesive layer 5 and the heat-fusible resin layer 4.
  • the laminate constituting the packaging material of the present invention conforms to the provisions of JIS K7124-2: 1999, and is subjected to the following measurement conditions.
  • the lower limit is preferably about 1.4 J or more, more preferably 1.5 J or more, and from the viewpoint of suitably molding the packaging material, the upper limit is Preferably it is 5.0J or less, More preferably, 4.5J or less is mentioned.
  • the total penetration energy range is preferably about 1.4 to 5.0 J, about 1.4 to 4.5 J, about 1.5 to 5.0 J, and about 1.5 to 4.5 J. .
  • the packaging material of the present invention breaks when a strong impact is applied from the outside.
  • the contents are evaluated by whether or not the contents are exposed to the outside.
  • a battery sealed with a metal can which has been widely used has been evaluated for impact resistance by a method based on the regulations of UL1642.
  • the packaging material of the present invention passes the impact resistance evaluated by a method in accordance with the provisions of UL1642 (smoke, It is preferable that no ignition occurs.
  • the thickness of the laminate constituting the packaging material of the present invention is not particularly limited, but the upper limit is preferably about 160 ⁇ m or less, from the viewpoint of reducing the thickness as much as possible while ensuring excellent impact resistance. Preferably, it is about 155 ⁇ m or less, more preferably about 120 ⁇ m or less, and the lower limit is preferably about 35 ⁇ m or more, more preferably about 45 ⁇ m or more.
  • the thickness range of the laminate is preferably about 35 to 160 ⁇ m, about 35 to 155 ⁇ m, about 35 to 120 ⁇ m, about 45 to 160 ⁇ m, about 45 to 155 ⁇ m, and about 45 to 120 ⁇ m. Even when the thickness of the laminate constituting the packaging material of the present invention is as thin as about 160 ⁇ m or less, the present invention can exhibit excellent impact resistance. For this reason, the packaging material of this invention can contribute to the improvement of the energy density of a battery.
  • the base material layer 1 is a layer located on the outermost layer side.
  • the material for forming the base material layer 1 is not particularly limited as long as it has insulating properties. Examples of the material for forming the base material layer 1 include polyester, polyamide, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, and a mixture or copolymer thereof. Can be mentioned.
  • polyester examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, copolymerized polyester mainly composed of ethylene terephthalate, butylene terephthalate as a repeating unit.
  • examples thereof include a copolymer polyester mainly used.
  • the copolymer polyester mainly composed of ethylene terephthalate is a copolymer polyester that polymerizes with ethylene isophthalate mainly composed of ethylene terephthalate (hereinafter, polyethylene (terephthalate / isophthalate)).
  • polyethylene terephthalate / isophthalate
  • polyethylene terephthalate / adipate
  • polyethylene terephthalate / sodium sulfoisophthalate
  • polyethylene terephthalate / sodium isophthalate
  • polyethylene terephthalate / phenyl-dicarboxylate
  • polyethylene terephthalate / decanedicarboxylate
  • polyester mainly composed of butylene terephthalate as a repeating unit
  • a copolymer polyester that polymerizes with butylene isophthalate having butylene terephthalate as a repeating unit hereinafter referred to as polybutylene (terephthalate / isophthalate).
  • polybutylene (terephthalate / adipate) polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like.
  • These polyesters may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Polyester has the advantage of being excellent in electrolytic solution resistance and less likely to cause whitening due to the adhesion of the electrolytic solution, and is suitably used as a material for forming the base material layer 1.
  • polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid Nylon 6I, Nylon 6T, Nylon 6IT, Nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) and the like, and polymetaxylylene azide Polyamide containing aromatics such as Pamide (MXD6); Alicyclic polyamides such as Polyaminomethylcyclohexyl Adipamide (PACM6); and Lactam components and isocyanate components such as 4,4′-diphenylmethane-diisocyanate are copolymerized Polyamide, co-weight Polyester amide copolymer and polyether ester amide copolymer is a copolymer of polyamide and polyester and polyalkylene ether glycol; copolymers thereof, and the like.
  • MXD6 Polya
  • polyamides may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the stretched polyamide film is excellent in stretchability, can prevent whitening due to resin cracking of the base material layer 1 during molding, and is suitably used as a material for forming the base material layer 1.
  • the base material layer 1 may be formed of a uniaxial or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular, a biaxially stretched resin film has improved heat resistance by orientation crystallization, and thus is suitably used as the base material layer 1. Moreover, the base material layer 1 may be formed by coating the above-mentioned material on the barrier layer 3.
  • the resin film forming the base layer 1 is preferably nylon or polyester, more preferably biaxially stretched nylon, biaxially stretched polyester, and particularly preferably biaxially stretched nylon.
  • the base material layer 1 can be laminated (multi-layer structure) of at least one of resin films and coatings of different materials in order to improve pinhole resistance and insulation when used as a battery packaging. is there. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a plurality of nylon films are laminated, a multilayer structure in which a plurality of polyester films are laminated, and the like.
  • the base material layer 1 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate of a plurality of biaxially stretched nylon films, and a laminate of a plurality of biaxially stretched polyester films The body is preferred.
  • the base material layer 1 has a multilayer structure of a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film.
  • the base material layer 1 is preferably a laminate having biaxially stretched nylon and biaxially stretched polyester in this order from the barrier layer 3 side.
  • the thickness of each layer is preferably about 3 to 25 ⁇ m.
  • each resin film may be bonded via an adhesive or may be directly laminated without using an adhesive.
  • a method of bonding in a hot-melt state such as a co-extrusion method, a sandwich lamination method, or a thermal lamination method can be used.
  • the adhesive agent to be used may be a two-component curable adhesive, or a one-component curable adhesive.
  • the bonding 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 hot pressure type, an ultraviolet curable type, an electron beam curable type, and the like.
  • Specific examples of the adhesive include those similar to the adhesive exemplified in the adhesive layer 2. Further, the thickness of the adhesive can be the same as that of the adhesive layer 2.
  • a lubricant is attached to the surface of the base material layer 1.
  • an amide type lubricant is mentioned.
  • Specific examples of the amide-based lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, and the like.
  • Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide and the like.
  • the unsaturated fatty acid amide include oleic acid amide and erucic acid amide.
  • substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like.
  • methylolamide include methylol stearamide.
  • saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide.
  • unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc.
  • fatty acid ester amide include stearoamidoethyl stearate.
  • aromatic bisamide include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-distearyl isophthalic acid amide and the like.
  • One type of lubricant may be used alone, or two or more types may be used in combination.
  • the content of the lubricant in the base material layer 1 is not particularly limited, and is preferably about 0.01 to 0.2% by mass, more preferably 0 from the viewpoint of improving the moldability and insulation of the electronic packaging material. About 0.05 to 0.15% by mass.
  • the thickness of the base material layer 1 is preferably about 10 ⁇ m or more, more preferably about 20 ⁇ m or more as the lower limit from the viewpoint of making the packaging material excellent in impact resistance while reducing the thickness of the packaging material.
  • the upper limit is preferably about 75 ⁇ m or less, more preferably about 50 ⁇ m or less.
  • the range of the thickness of the base material layer 1 is preferably about 10 to 75 ⁇ m, about 10 to 50 ⁇ m, about 20 to 75 ⁇ m, and about 20 to 50 ⁇ m. In the present invention, when the base material layer 1 has a multilayer structure bonded with an adhesive, the thickness of the base material layer 1 does not include the thickness of the adhesive.
  • the adhesive layer 2 is a layer provided between the base material layer 1 and the barrier layer 3 in order to firmly bond them.
  • the adhesive layer 2 is formed of an adhesive capable of bonding the base material layer 1 and the barrier layer 3 together.
  • the adhesive used for forming the adhesive layer 2 may be a two-component curable adhesive or a one-component curable adhesive.
  • the bonding mechanism of the adhesive used for forming 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 hot pressure type, and the like.
  • adhesive components that can be used to form the adhesive layer 2 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester; Polyether adhesives; Polyurethane adhesives; Epoxy resins; Phenol resins; Polyamide resins such as nylon 6, nylon 66, nylon 12, and copolymerized polyamides; Polyolefins such as polyolefins, carboxylic acid-modified polyolefins, and metal-modified polyolefins Resin, polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; amino resin such as urea resin and melamine resin; chloroprene rubber, nitrile rubber, styrene - rubbers such as butadiene rubber, silicone-based resins. These adhesive components may be used individually by 1 type, and may be used
  • the thickness of the adhesive layer 2 is not particularly limited as long as it exhibits a function as an adhesive layer, and may be, for example, about 1 to 10 ⁇ m, preferably about 2 to 5 ⁇ m.
  • the barrier layer 3 is a layer having a function of preventing the entry of water vapor, oxygen, light and the like into the battery in addition to improving the strength of the packaging material.
  • the metal constituting the barrier layer 3 include aluminum, stainless steel, and titanium, and preferably aluminum.
  • the barrier layer 3 can be formed by, for example, a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited films, etc. Is preferable, and it is more preferable to form with an aluminum alloy foil.
  • the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: 1994 A8079H-O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O) and the like are more preferable.
  • the thickness of the barrier layer 3 is not particularly limited as long as it functions as a barrier layer such as water vapor.
  • the thickness is preferably about 100 ⁇ m or less, more preferably about 10 to 100 ⁇ m, and still more preferably about 10 to 80 ⁇ m. .
  • the barrier layer 3 is preferably subjected to chemical conversion treatment on at least one side, preferably both sides, in order to stabilize adhesion, prevent dissolution and corrosion, and the like.
  • the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the barrier layer.
  • chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acid acetyl acetate, chromium chloride, potassium sulfate chromium; Phosphoric acid treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; an aminated phenol polymer having a repeating unit represented by the following general formulas (1) to (4) is used Chemical conversion treatment. In the aminated phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be contained singly or in any combination of two or more. Also good.
  • a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate
  • X represents a hydrogen atom, a hydroxyl 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 hydroxyl 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, an isobutyl group, Examples thereof include straight-chain or branched alkyl groups having 1 to 4 carbon atoms, such as a tert-butyl group.
  • Examples of the hydroxyalkyl group represented by X, R 1 and R 2 include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- A straight or branched chain having 1 to 4 carbon atoms substituted with one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group An alkyl group.
  • the alkyl group and hydroxyalkyl group represented by X, R 1 and R 2 may be the same or different.
  • X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group.
  • the number average molecular weight of the aminated phenol polymer having a repeating unit represented by the general formulas (1) to (4) is preferably about 500 to 1,000,000, for example, about 1,000 to 20,000. More preferred.
  • a phosphoric acid is coated with a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed therein.
  • a method of forming a corrosion-resistant treatment layer on the surface of the barrier layer 3 by performing a baking treatment at 150 ° C. or higher can be mentioned.
  • a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the corrosion-resistant treatment layer.
  • examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned.
  • these cationic polymers only one type may be used, or two or more types may be used in combination.
  • examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.
  • a phosphoric acid is coated with a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed therein.
  • a method of forming an acid-resistant film on the surface of the barrier layer 3 by performing a baking treatment at 150 ° C. or higher can be mentioned.
  • a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the acid resistant film.
  • examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned.
  • these cationic polymers only one type may be used, or two or more types may be used in combination.
  • examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. As 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 alloy foil is firstly immersed in an alkali soaking method, electrolytic cleaning method, acid cleaning method, electrolytic acid cleaning method.
  • Treatment liquid (aqueous solution) mainly composed of a mixture of metal salts, or treatment liquid (aqueous solution) principally composed of a non-metallic phosphate and a mixture of these non-metallic salts, or acrylic resin Coating a treatment liquid (aqueous solution) consisting of a mixture with a water-based synthetic resin such as phenolic resin or urethane resin by a well-known coating method such as roll coating, gravure printing, or dipping.
  • the acid-resistant coating For example, when treated with a chromium phosphate salt treatment solution, it becomes an acid-resistant film made of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc., and treated with a zinc phosphate salt treatment solution. In this case, an acid-resistant film made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride or the like is obtained.
  • an acid-resistant film for example, at least the surface on the inner layer side of the aluminum alloy foil is first subjected to an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid-resistant film can be formed by performing a degreasing process by a known processing method such as an activation method and then performing a known anodizing process on the degreasing surface.
  • acid-resistant films include phosphate-based and chromic acid-based films.
  • phosphate-based and chromic acid-based films examples include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate.
  • chromic acid system examples include chromium chromate.
  • an acid-resistant film by forming an acid-resistant film such as phosphate, chromate, fluoride, triazine thiol compound, between the aluminum and the base material layer at the time of embossing molding
  • an acid-resistant film such as phosphate, chromate, fluoride, triazine thiol compound
  • hydrogen fluoride generated by the reaction between electrolyte and moisture prevents dissolution and corrosion of the aluminum surface, especially the dissolution and corrosion of aluminum oxide present on the aluminum surface, and adhesion of the aluminum surface This improves the wettability and prevents delamination between the base material layer and aluminum at the time of heat sealing.
  • embossed type it shows the effect of preventing delamination between the base material layer and aluminum at the time of press molding.
  • an aqueous solution composed of three components of a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is applied to the aluminum surface, and the dry baking treatment is good.
  • the acid-resistant film includes a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent that crosslinks the anionic polymer, and the phosphoric acid or phosphate is About 1 to 100 parts by mass may be blended with 100 parts by mass of cerium oxide. It is preferable that the acid-resistant film has a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.
  • the anionic polymer is poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component.
  • the said crosslinking agent is at least 1 sort (s) chosen from the group which has a functional group in any one of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.
  • the phosphoric acid or phosphate is preferably condensed phosphoric acid or condensed phosphate.
  • the chemical conversion treatment only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion processing may be performed in combination. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds.
  • a chromate treatment a chemical conversion treatment combining a chromium compound, a phosphate compound, and an aminated phenol polymer are preferable.
  • chromium compounds chromic acid compounds are preferred.
  • the acid resistant film examples include those containing at least one of phosphate, chromate, fluoride, and triazine thiol.
  • An acid resistant film containing a cerium compound is also preferable.
  • cerium compound cerium oxide is preferable.
  • the acid resistant film examples include a phosphate film, a chromate film, a fluoride film, and a triazine thiol compound film.
  • a phosphate film As an acid-resistant film, one of these may be used, or a plurality of combinations may be used.
  • a treatment solution comprising a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a non-metal phosphate and an aqueous synthetic resin It may be formed of a treatment liquid consisting of
  • the composition of the acid resistant film can be analyzed using, for example, time-of-flight secondary ion mass spectrometry.
  • time-of-flight secondary ion mass spectrometry for example, a peak derived from at least one of Ce + and Cr + is detected.
  • the surface of the aluminum alloy foil is provided with an acid resistant film containing at least one element selected from the group consisting of phosphorus, chromium and cerium.
  • the acid-resistant film on the surface of the aluminum alloy foil of the battery packaging material contains at least one element selected from the group consisting of phosphorus, chromium and cerium using X-ray photoelectron spectroscopy. can do. Specifically, first, in the battery packaging material, the heat-fusible resin layer, the adhesive layer, and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is put in an electric furnace, and organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Then, it confirms that these elements are contained using the X-ray photoelectron spectroscopy of the surface of aluminum alloy foil.
  • the amount of the acid-resistant film to be formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited.
  • the chromium compound is chromium per 1 m 2 of the surface of the barrier layer 3.
  • About 0.5 to 50 mg in terms of conversion preferably about 1.0 to 40 mg, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and about 1.0 to 40 mg of aminated phenol polymer. It is desirable that it is contained in a proportion of about 200 mg, preferably about 5.0 to 150 mg.
  • the thickness of the acid-resistant film is not particularly limited, but is preferably about 1 nm to 10 ⁇ m, more preferably about 1 to 100 nm, from the viewpoint of the cohesive strength of the film and the adhesive strength with the aluminum alloy foil or the heat-sealing resin layer. More preferably, about 1 to 50 nm is mentioned.
  • the thickness of the acid-resistant film can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron energy loss spectroscopy.
  • a solution containing a compound used for forming an acid-resistant film is applied to the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, etc., and then the temperature of the barrier layer is 70. It is performed by heating to about 200 ° C.
  • the barrier layer may be previously subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing the degreasing process in this manner, it is possible to more efficiently perform the chemical conversion process on the surface of the barrier layer.
  • the heat-fusible resin layer 4 corresponds to the innermost layer and is a layer that heat-fuses the heat-fusible resin layers and seals the battery element when the battery is assembled.
  • the resin component used in the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-sealed, and examples thereof include polyolefins, cyclic polyolefins, carboxylic acid-modified polyolefins, and carboxylic acid-modified cyclic polyolefins. It is done. That is, the heat-fusible resin layer 4 may include a polyolefin skeleton, and preferably includes a polyolefin skeleton. The fact that the heat-fusible resin layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited.
  • maleic anhydride-modified polyolefin when measured by infrared spectroscopy, maleic anhydride-derived peaks are detected in the vicinity of wave numbers 1760 cm-1 and 1780 cm-1. However, if the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • polystyrene resin examples include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymer (for example, block copolymer of propylene and ethylene), polypropylene And a random copolymer (eg, a random copolymer of propylene and ethylene); an ethylene-butene-propylene terpolymer; and the like.
  • polyethylene and polypropylene are preferable.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer
  • examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, and isoprene. It is done.
  • examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Styrene is also exemplified as a constituent monomer.
  • cyclic alkene is preferable, and norbornene is more preferable.
  • the carboxylic acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of the polyolefin with carboxylic acid.
  • Examples of the 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 a part of the monomer constituting the cyclic polyolefin in place of the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or by ⁇ , ⁇ with respect to the cyclic polyolefin.
  • the cyclic polyolefin to be modified with carboxylic acid is the same as described above.
  • the carboxylic acid used for modification is the same as that used for modification of the carboxylic acid-modified polyolefin.
  • carboxylic acid-modified polyolefin is preferable; carboxylic acid-modified polypropylene is more preferable.
  • the heat-fusible resin layer 4 may be formed of one kind of resin component alone or may be formed of a blend polymer in which two or more kinds 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 using the same or different resin components.
  • the thickness of the heat-fusible resin layer 4 can be selected as appropriate, and is about 10 to 100 ⁇ m, preferably about 15 to 50 ⁇ m.
  • the heat-fusible resin layer 4 may contain a lubricant or the like as necessary.
  • the lubricant is not particularly limited, and a known lubricant can be used, and examples thereof include those exemplified in the base material layer 1 described above.
  • One type of lubricant may be used alone, or two or more types may be used in combination.
  • the content of the lubricant in the heat-fusible resin layer 4 is not particularly limited, and is preferably about 0.01 to 0.20% by mass from the viewpoint of improving the moldability and insulation of the electronic packaging material. Preferably, it is about 0.05 to 0.15% by mass.
  • the adhesive layer 5 is a layer provided between the barrier layer 3 and the heat-fusible resin layer 4 as necessary in order to firmly bond them.
  • the adhesive layer 5 is formed of a resin capable of bonding the barrier layer 3 and the heat-fusible resin layer 4.
  • the resin used for forming the adhesive layer 5 the adhesive mechanism, the kind of the adhesive component, and the like can be the same as the adhesive exemplified in the adhesive layer 2.
  • polyolefin resins such as polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, carboxylic acid-modified cyclic polyolefin exemplified in the above-mentioned heat-fusible resin layer 4 can also be used. .
  • the polyolefin is preferably a carboxylic acid-modified polyolefin, and particularly preferably a carboxylic acid-modified polypropylene. That is, the adhesive layer 5 may include a polyolefin skeleton, and preferably includes a polyolefin skeleton. The fact that the adhesive layer 5 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited.
  • maleic anhydride-modified polyolefin when measured by infrared spectroscopy, maleic anhydride-derived peaks are detected in the vicinity of wave numbers 1760 cm-1 and 1780 cm-1. However, if the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • the adhesive layer 5 is also preferably a cured product of a resin composition containing an acid-modified polyolefin and a curing agent.
  • Preferred examples of the acid-modified polyolefin include the same carboxylic acid-modified polyolefin and carboxylic acid-modified cyclic polyolefin exemplified in the heat-fusible resin layer 4.
  • the curing agent is not particularly limited as long as it can cure the acid-modified polyolefin.
  • the curing agent include an epoxy curing agent, a polyfunctional isocyanate curing agent, a carbodiimide curing agent, and an oxazoline curing agent.
  • the epoxy curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
  • examples of the epoxy curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
  • the polyfunctional isocyanate curing agent is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or nurating these, Examples thereof include mixtures and copolymers with other polymers.
  • the carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (—N ⁇ C ⁇ N—).
  • a polycarbodiimide compound having at least two carbodiimide groups is preferable.
  • the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the oxazoline-based curing agent include Epocros series manufactured by Nippon Shokubai Co., Ltd.
  • the curing agent may be composed of two or more kinds 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, more preferably in the range of about 0.1 to 30% by mass, More preferably, it is in the range of about 0.1 to 10% by mass.
  • the thickness of the adhesive layer 5 is not particularly limited as long as it functions as an adhesive layer. However, when the adhesive exemplified in the adhesive layer 2 is used, it is preferably about 2 to 10 ⁇ m, more preferably 2 to For example, about 5 ⁇ m. Further, when the resin exemplified in the heat-fusible resin layer 4 is used, it is preferably about 2 to 50 ⁇ m, more preferably about 10 to 40 ⁇ m. In the case of 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. When the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing it by heating or the like.
  • a surface coating layer is a layer located in the outermost layer when a battery is assembled.
  • the surface coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. Of these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix
  • Examples of the additive include fine particles having a particle size of about 0.5 nm to 5 ⁇ m.
  • the material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the additive is not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an indeterminate shape, and a balloon shape.
  • Specific additives include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high Melting
  • money, aluminum, copper, nickel etc. are mentioned.
  • additives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • silica, barium sulfate, and titanium oxide are preferably used from the viewpoints of dispersion stability and cost.
  • the surface of the additive may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment.
  • the content of the additive in the surface coating layer is not particularly limited, but is preferably about 0.05 to 1.0% by mass, more preferably about 0.1 to 0.5% by mass.
  • the method for forming the surface coating layer is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the surface coating layer on one surface of the base material layer 1.
  • the additive may be added to the two-component curable resin, mixed, and then applied.
  • the thickness of the surface coating layer is not particularly limited as long as it exhibits the above function as the surface coating layer, and for example, it is about 0.5 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the production method of the packaging material of the present invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained.
  • An example of the method for producing the packaging material of the present invention is as follows. First, a laminate in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are laminated in this order (hereinafter also referred to as “laminate A”) is formed. Specifically, the layered product A is formed by applying an adhesive used for forming the adhesive layer 2 to the barrier layer 3 whose surface is subjected to chemical conversion treatment on the base material layer 1 or, if necessary, a gravure coating method. After applying and drying by a coating method such as a roll coating method, the barrier layer 3 or the base material layer 1 can be laminated and the adhesive layer 2 can be cured by a dry laminating method.
  • the heat-fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A.
  • the resin component constituting the heat-fusible resin layer 4 is applied to the barrier layer 3 of the laminate A by a gravure coating method or a roll coating method. It may be applied by such a method.
  • the adhesive layer 5 is provided between the barrier layer 3 and the heat-fusible resin layer 4, for example, (1) the adhesive layer 5 and the heat-fusible resin layer on the barrier layer 3 of the laminate A 4 by coextrusion (coextrusion lamination method), (2) Separately, a laminate in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated is formed, and this is formed as a barrier layer of the laminate A 3 by a thermal laminating method, and (3) an extrusion method for forming an adhesive layer 5 on the barrier layer 3 of the laminate A, or a method of drying and baking at a high temperature after solution coating.
  • the surface coating layer is laminated on the surface of the base material layer 1 opposite to the barrier layer 3.
  • the surface coating layer can be formed, for example, by applying the above-described resin for forming the surface coating layer to the surface of the base material layer 1.
  • the order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer on the surface of the base material layer 1 are not particularly limited.
  • the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer.
  • a laminate composed of the adhesive layer 5 / the heat-fusible resin layer 4 to be provided is formed.
  • a hot roll contact type You may use for heat processing, such as a hot-air type, a near or far-infrared type. Examples of such heat treatment conditions include a temperature of about 150 to 250 ° C. and a time of about 1 to 5 minutes.
  • each layer constituting the laminate is improved or stabilized as necessary, for example, film forming property, lamination processing, final product secondary processing (pouching, embossing) suitability, etc.
  • Surface activation treatment such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed.
  • packaging material of the present invention is used in a wide range of fields as a package for accommodating foods, drugs, battery elements and the like (molded so that the packaging material can accommodate the contents).
  • contents such as foods, medicines, and battery elements are stored using the package of the present invention
  • the package is used such that the sealant portion of the package is on the inner side (the surface in contact with the contents).
  • a battery element including at least a positive electrode, a negative electrode, and an electrolyte is connected to each of the positive electrode and the negative electrode with a package formed of the packaging material of the present invention.
  • a flange portion region where the heat-fusible resin layers are in contact with each other
  • a battery in which the battery element is accommodated in the package is provided.
  • 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 is not particularly limited.
  • a lithium ion battery, a lithium ion polymer battery, a lead battery, a nickel / hydrogen battery, a nickel / cadmium battery, a nickel / iron battery, a nickel / zinc battery Examples include batteries, silver oxide / zinc livestock batteries, metal-air batteries, multivalent cation batteries, capacitors, capacitors, and the like.
  • lithium ion batteries and lithium ion polymer batteries are suitable applications for battery packaging materials.
  • Example 1-5 and Comparative Example 1-4 ⁇ Manufacture of packaging materials>
  • a barrier layer made of an aluminum foil JIS H4160: 1994 A8021H-O
  • chemical conversion treatment on both sides was laminated on the base material layer by a dry laminating method.
  • a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the barrier layer to form an adhesive layer (thickness 3 ⁇ m) on the barrier layer.
  • an aging treatment was performed to prepare a base material layer / adhesive layer / barrier layer laminate.
  • the chemical conversion treatment of the aluminum foil used as the barrier layer is performed by roll coating a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry mass). It was performed by applying and baking on both sides of the aluminum foil by the method.
  • Examples 3 and 4 and Comparative Examples 3 and 4 a solution obtained by mixing carboxylic acid-modified polypropylene and an epoxy curing agent was applied on the barrier layer of the laminate and dried. Further, an unstretched polypropylene film (innermost layer) was laminated thereon. In addition, content of the hardening
  • Example 1 Nylon (25 ⁇ m) / Adhesive layer (3 ⁇ m) / Aluminum foil (40 ⁇ m) / Carboxylic acid modified polypropylene (23 ⁇ m) / Polypropylene (23 ⁇ m)
  • Example 2 Nylon (25 ⁇ m) / adhesive layer (3 ⁇ m) / aluminum foil (25 ⁇ m) / carboxylic acid-modified polypropylene (14 ⁇ m) / polypropylene (10 ⁇ m)
  • Example 3 Nylon (25 ⁇ m) / adhesive layer (3 ⁇ m) / aluminum foil (25 ⁇ m) / cured product of carboxylic acid-modified polypropylene and curing agent (2 ⁇ m) / unstretched polypropylene (25 ⁇ m)
  • Example 4 Nylon (25 ⁇ m) / adhesive layer (3 ⁇ m) / aluminum foil (35 ⁇ m) / cured product of carboxylic acid
  • Comparative Example 1 PET (12 ⁇ m) / Adhesive layer (3 ⁇ m) / Aluminum foil (25 ⁇ m) / Carboxylic acid modified polypropylene (14 ⁇ m) / Polypropylene (10 ⁇ m) Comparative Example 2: Nylon (15 ⁇ m) / adhesive layer (3 ⁇ m) / aluminum foil (35 ⁇ m) / carboxylic acid-modified polypropylene (20 ⁇ m) / polypropylene (15 ⁇ m) Comparative Example 3: PET (12 ⁇ m) / adhesive layer (3 ⁇ m) / aluminum foil (25 ⁇ m) / cured product of carboxylic acid-modified polypropylene and curing agent (2 ⁇ m) / unstretched polypropylene (25 ⁇ m) Comparative Example 4: Nylon (15 ⁇ m) / adhesive layer (3 ⁇ m) / aluminum foil (35 ⁇ m) / cured product of carboxylic acid-modified polypropylene and curing agent (2 ⁇ m) / unst
  • a curve of test force-displacement obtained in a tensile test (MD) of the packaging material of Comparative Example 2 is shown in FIG.
  • the part where the data of the test force-displacement curve data was integrated is an integrated value from the start of the tensile test (displacement amount 0) to the breaking point P of the laminate as shown in the schematic diagram of FIG. This corresponds to the area of the hatched portion in FIG.
  • Total penetration energy of the laminate With respect to each of the packaging materials obtained above, the total penetration energy was measured from the base material layer side by a method in accordance with the provisions of JIS K7124-2: 1999.
  • a falling weight graphic impact tester manufactured by Toyo Seiki
  • the measurement conditions were a hammer weight of 6.4 kg, a drop height of 300 mm, a sample clamp diameter of 40 mm ⁇ , a hammer diameter of 12.7 mm ⁇ , and a hammer shape of a hemisphere. The results are shown in Table 1.
  • Each packaging material obtained above is cut into 90 mm ⁇ 150 mm, and then molded at 0.9 MPa with a molding die (female die) having a diameter of 32 mm ⁇ 55 mm and a corresponding molding die (male die). Cold forming to a depth of 0.0 mm and forming a recess at the center. In this recess, a PET resin having a width of 30 mm, a length of 52 mm, and a thickness of 3 mm was artificially installed as a battery element. Next, the non-molded part of the molded product was bent so that the sealant surface was opposed, and the peripheral part was heat-sealed to prepare a pseudo battery.
  • the heat sealing conditions were 190 ° C., surface pressure 1.0 MPa, and 3 seconds.
  • the molded product was placed on a rigid and flat surface, and a round bar having a diameter of 16 mm was placed at the center of the molded product so as to cross the molded product.
  • a weight of 9.1 kg was dropped onto the round bar.
  • the molded product without cutting was evaluated as being excellent in impact resistance (A), and the cut product was evaluated as being inferior in impact resistance (C). The results are shown in Table 1.
  • the breaking energy per 1 m unit width calculated from the test force-displacement curve measured when the tensile test was performed under the above test conditions is The packaging material of Examples 1 to 5 in which the total of the one direction (MD) in the vertical direction with respect to the thickness direction and the other direction (TD) in which the one direction and the thickness direction of the laminate are perpendicular to each other is 400 J or more It can be seen that is excellent in impact resistance. On the other hand, it can be seen that the packaging materials of Comparative Examples 1 to 4 in which the total breaking energy is less than 400 J are inferior in impact resistance as compared with Examples 1 to 5.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
PCT/JP2017/002921 2016-01-29 2017-01-27 包装材料及び電池 WO2017131155A1 (ja)

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WO2019124281A1 (ja) * 2017-12-18 2019-06-27 大日本印刷株式会社 電池用包装材料、その製造方法、及び電池
WO2020071254A1 (ja) * 2018-10-01 2020-04-09 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
CN110998893A (zh) * 2017-08-23 2020-04-10 大日本印刷株式会社 电池用包装材料和电池
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