WO2018221037A1 - ポリオレフィン系接着剤組成物 - Google Patents

ポリオレフィン系接着剤組成物 Download PDF

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Publication number
WO2018221037A1
WO2018221037A1 PCT/JP2018/015431 JP2018015431W WO2018221037A1 WO 2018221037 A1 WO2018221037 A1 WO 2018221037A1 JP 2018015431 W JP2018015431 W JP 2018015431W WO 2018221037 A1 WO2018221037 A1 WO 2018221037A1
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Prior art keywords
acid
mass
parts
solvent
adhesive composition
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PCT/JP2018/015431
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English (en)
French (fr)
Japanese (ja)
Inventor
坂田　秀行
桃子 中島
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東洋紡株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=64455808&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2018221037(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to CN201880008954.3A priority Critical patent/CN110234721A/zh
Priority to JP2019522010A priority patent/JP7287276B2/ja
Priority to KR1020197021633A priority patent/KR102553615B1/ko
Publication of WO2018221037A1 publication Critical patent/WO2018221037A1/ja
Priority to JP2023014472A priority patent/JP2023041857A/ja
Priority to JP2024031140A priority patent/JP2024063150A/ja

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • 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
    • H01M50/193—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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an adhesive composition that exhibits good adhesion, chemical resistance, and moldability between a polyolefin resin substrate and a metal substrate. More specifically, the present invention relates to an adhesive composition containing an acid-modified polyolefin, a polyfunctional polyisocyanate curing agent, and an organic solvent. In particular, the present invention relates to an adhesive composition for a lithium ion battery (hereinafter abbreviated as LiB) and a packaging material that is a laminate including the same.
  • LiB lithium ion battery
  • LiB which can be made ultra-thin and miniaturized, has been actively developed as a battery for use in mobile terminal devices such as personal computers and mobile phones, video cameras, and satellites.
  • this LiB packaging material is lightweight and has the advantage of being able to freely select the shape of the battery. It has come to be used.
  • LiB is impregnated with a positive electrode material and a negative electrode material as battery contents, an electrolyte solution in which a lithium salt is dissolved in an aprotic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, or an electrolyte solution thereof. And an electrolyte layer made of polymer gel.
  • an aprotic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate
  • Lithium salts which are battery electrolytes, use substances such as LiPF6 and LiBF4, but these salts generate hydrofluoric acid by hydrolysis with moisture, and hydrofluoric acid corrodes the barrier layer. To reduce the laminate strength. Thus, the battery packaging material needs to have resistance to the electrolyte.
  • LiB is used in various environments, it is necessary to have more severe resistance.
  • liquid leakage resistance in a high temperature environment of 60 to 70 ° C. such as in a car is required.
  • water resistance is also required to prevent moisture from entering, assuming that it was used in a mobile phone and accidentally dropped into water.
  • the battery packaging material when the battery element is encapsulated, it is molded with a mold to form a space for accommodating the battery element. During this molding, the battery packaging material is stretched, There is a problem that cracks and pinholes are likely to occur in the barrier layer in the flange portion of the mold. In particular, with the recent demand for smaller and thinner batteries, thinner battery packaging materials are required, and such problems are more likely to occur.
  • the proposed lithium battery packaging material is still insufficient in terms of resistance to electrolytic solution and formability. Moreover, even if the electrolytic solution resistance and the moldability were greatly improved, problems were observed. Specifically, it is difficult to ensure the pot life of the adhesive after the curing agent is blended and the resistance to the electrolytic solution (Patent Document 1), and the laminating machine base is restricted because of adhesion by extrusion lamination.
  • the polyolefin base material is affected by thermal shrinkage due to bonding at a high temperature (Patent Document 2). Since the polyolefin base material is aqueous, the drying time is long and the production conditions are limited (Patent Document 3).
  • Patent Document 4 because only the unstretched polypropylene resin film is arranged on the inner layer side from the aluminum foil, or only the blend resin film of polypropylene and polyethylene is arranged on the inner layer side from the aluminum foil, When forming into a rectangular parallelepiped shape or the like, pinholes are generated in the aluminum foil, or broken portions (cracks) are easily generated in the aluminum foil, and sufficient formability cannot be obtained (Patent Document 5). It was something to be seen.
  • An object of the present invention is to provide an adhesive composition excellent in adhesiveness, chemical resistance (electrolytic solution resistance), and moldability without problems such as pot life and limitation of production conditions. Furthermore, it is providing the battery packaging material containing the adhesive bond layer which consists of the adhesive composition, and the battery using the said packaging material.
  • the present inventors have intensively studied and found that it is effective to arrange a layer capable of sufficiently following the elongation during molding not only on the outer layer side of the aluminum foil but also on the inner layer side.
  • the following inventions have been proposed.
  • An adhesive composition comprising an acid-modified polyolefin (A), a polyfunctional polyisocyanate curing agent (B) and an organic solvent (C), wherein the acid value of the acid-modified polyolefin (A) is 2 to 50 mgKOH / g-resin
  • An adhesive composition having an acetone extraction component ratio of 0.01 to 2% by mass.
  • the adhesive composition is preferably used for adhesion between a polyolefin resin substrate and a metal substrate.
  • the adhesive composition according to the present invention contains an acid-modified polyolefin, a polyfunctional polyisocyanate curing agent, and an organic solvent, and maintains good pot life without thickening or gelling even when stored for a long period of time. can do. Furthermore, even if the polyolefin base material is laminated at a low temperature such as 120 ° C. or less where the thermal shrinkage effect is small and aging is performed at a low temperature such as 40 ° C. or less, good adhesion between the polyolefin resin base material and the metal base material, It is possible to achieve both chemical properties and moldability.
  • the present invention while maintaining good pot life, it can be sufficiently cured by the aging process after bonding, and can exhibit excellent adhesiveness and chemical resistance. Furthermore, it is possible to obtain an adhesive layer that satisfies the storage elastic modulus and elongation at break required to exhibit excellent moldability.
  • the acid-modified polyolefin (A) used in the present invention is an acid-modified polyolefin having an acid value of 2 to 50 mg KOH / g-resin and an acetone extraction component ratio of 0.01 to 2% by mass.
  • the acid-modified polyolefin (A) used in the present invention is not limited, but at least one of polyethylene, polypropylene, and propylene- ⁇ -olefin copolymer includes at least ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydride thereof. What is obtained by grafting 1 type is preferable.
  • the propylene- ⁇ -olefin copolymer is a copolymer in which ⁇ -olefin is copolymerized mainly with propylene.
  • ⁇ -olefin for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate or the like can be used. Of these ⁇ -olefins, ethylene and 1-butene are preferred.
  • the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
  • Examples of at least one of ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydrides thereof include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof.
  • acid anhydrides are preferable, and maleic anhydride is more preferable.
  • Specific examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, and the like.
  • These acid-modified polyolefins can be used alone or in combination of two or more.
  • the acid value of the acid-modified polyolefin (A) needs to be in the range of 2 to 50 mg KOH / g-resin from the viewpoints of adhesion between the polyolefin resin substrate and the metal substrate and resistance to electrolyte.
  • the range is preferably 3 to 45 mg KOH / g-resin, more preferably 5 to 40 mg KOH / g-resin, and particularly preferably 7 to 35 mg KOH / g-resin. If it is less than the above value, the compatibility with the curing agent may be poor. Therefore, the crosslinking density is low, and the adhesive strength and chemical resistance (electrolytic solution resistance) may be reduced. When the above value is exceeded, the molecular weight is low and the cohesive force is weakened, so the adhesive strength and chemical resistance (electrolytic solution resistance) may be lowered. Furthermore, it is not preferable because the production efficiency is also lowered.
  • the acid value of the acid-modified polyolefin (A) can be adjusted by the use amount of ⁇ , ⁇ -unsaturated carboxylic acid, acid anhydride of ⁇ , ⁇ -unsaturated carboxylic acid and radical generator.
  • the acetone-extracted component ratio of the acid-modified polyolefin (A) needs to be in the range of 0.01% by mass to 2% by mass from the viewpoints of adhesion between the polyolefin resin base material and the metal base material and resistance to the electrolytic solution. It is. Preferably, it is 0.03% by mass to 1.7% by mass, more preferably 0.05% by mass to 1.4% by mass, and still more preferably 0.07% by mass to 1.2% by mass. Particularly preferred is a range of 0.1% by mass to 1% by mass. If it is less than the above value, the production efficiency is lowered, which is not preferable. When the above value is exceeded, the cohesive force becomes weak and the adhesiveness, chemical resistance and moldability may be inferior.
  • the storage elastic modulus (E ′) at 25 ° C. of the acid-modified polyolefin (A) is in the range of 10 to 2000 MPa from the viewpoints of adhesion between the polyolefin resin substrate and the metal substrate and chemical resistance (electrolytic solution resistance).
  • the followability of the adhesive layer made of the adhesive composition is lowered, and the adhesiveness may be inferior. Further, if it is within the above range, the adhesiveness and the substrate followability are improved, and the moldability of the laminate is improved, so that it is more preferable as a packaging material for a lithium ion battery.
  • the tensile strength at break (Eb) of the acid-modified polyolefin (A) at 25 ° C. is preferably in the range of 50% to 1000%. More preferably, it is 80% to 900%, still more preferably 120% to 800%, particularly preferably 160% to 700%, and most preferably 200% to 600%. If it is less than the above value, the followability of the adhesive layer made of the adhesive composition is lowered, which may lead to pinholes at the time of molding, and the moldability may be inferior. In general, tensile elongation at break (Eb) and storage elastic modulus (E ′) are contradictory properties.
  • the storage elastic modulus (E ′) decreases and adhesion and electrolyte resistance May be inferior. Moreover, if it is in the said range, since adhesiveness and base material followability will improve, since it becomes favorable to the moldability of a laminated body, it is more preferable as a packaging material for lithium ion batteries.
  • the weight average molecular weight (Mw) of the acid-modified polyolefin (A) is preferably in the range of 10,000 to 200,000. More preferably, it is in the range of 20,000 to 180,000, more preferably in the range of 30,000 to 160,000, particularly preferably in the range of 40,000 to 140,000, and most preferably 50 , 110,000 to 110,000. If it is less than the above value, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when the above value is exceeded, there may be a problem in operability when bonding due to low fluidity. If it is in the said range, since hardening reaction with a hardening
  • the crystallinity in the acid-modified polyolefin (A) means that the temperature is raised from ⁇ 100 ° C. to 250 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC), and a clear melting peak is observed in the temperature raising process. Refers to what is shown.
  • DSC differential scanning calorimeter
  • the melting point (Tm) of the acid-modified polyolefin (A) is preferably in the range of 50 ° C to 120 ° C. More preferably, it is in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C. If it is less than the above value, the cohesive force derived from crystals becomes weak, and the adhesiveness and chemical resistance may be inferior. On the other hand, when the above value is exceeded, the solution stability and fluidity are low, and there may be a problem in operability when bonding.
  • the heat of fusion ( ⁇ H) of the acid-modified polyolefin (A) is preferably in the range of 1 J / g to 60 J / g. More preferably, it is in the range of 3 J / g to 50 J / g, and most preferably in the range of 5 J / g to 40 J / g. If it is less than the above value, the cohesive force derived from crystals becomes weak, and the adhesiveness and chemical resistance may be inferior. On the other hand, when the above value is exceeded, the solution stability and fluidity are low, and there may be a problem in operability when bonding.
  • the method for producing the acid-modified polyolefin (A) is not particularly limited, and for example, radical graft reaction (that is, generating radical species for the polymer to be the main chain, and using the radical species as a polymerization initiation point, the unsaturated carboxylic acid and Reaction for graft polymerization of an acid anhydride).
  • radical graft reaction that is, generating radical species for the polymer to be the main chain, and using the radical species as a polymerization initiation point, the unsaturated carboxylic acid and Reaction for graft polymerization of an acid anhydride.
  • organic peroxide is not particularly limited, but di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples thereof include azonitriles.
  • the polyfunctional polyisocyanate curing agent (B) used in the present invention is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in one molecule, and well-known diisocyanates and compounds derived therefrom are preferably used. be able to.
  • diisocyanates such as added diphenylmethane diisocyanate.
  • a compound derived from the diisocyanate that is, isocyanurate body, adduct body, biuret type, uretdione body, allophanate body, prepolymer having an isocyanate residue (low polymer obtained from diisocyanate and polyol), or These composites etc. are mentioned. These may be used alone or in any combination of two or more.
  • a compound obtained by reacting a part of the isocyanate group of the isocyanate compound with a compound having reactivity with the isocyanate group may be used as a polyfunctional isocyanate curing agent.
  • Compounds having reactivity with isocyanate groups include compounds containing amino groups such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, aniline; methanol, ethanol, propanol, isopropanol , Butanol, hexanol, octanol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, phenol and other compounds containing hydroxyl groups; allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl gly
  • the polyfunctional polyisocyanate curing agent (B) used in the present invention is preferably a polyfunctional polyisocyanate curing agent (B) having an isocyanurate form of the diisocyanate because it has excellent resistance to electrolytic solution.
  • the blending amount of the polyfunctional polyisocyanate curing agent (B) used in the present invention is preferably in the range of 0.5 to 40 parts by mass, more preferably 1 to 1 part per 100 parts by mass of the acid-modified polyolefin (A).
  • the amount is 35 parts by mass, more preferably 2 to 30 parts by mass, and particularly preferably 3 to 25 parts by mass. If it is less than the above value, a sufficient curing effect may not be obtained and adhesion and chemical resistance may be low. If the above range is exceeded, pot life and adhesiveness may decrease, and pinholes may occur during molding due to a decrease in followability. Furthermore, it is not preferable from the viewpoint of cost.
  • Organic solvent (C) used in the present invention is not particularly limited as long as it dissolves the acid-modified polyolefin (A) and the polyfunctional polyisocyanate curing agent (B).
  • aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane
  • Halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol, acetone, methyl isobuty
  • the organic solvent (C) is preferably in the range of 80 to 2000 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin (A).
  • the range is more preferably 90 to 1600 parts by mass, still more preferably 100 to 1200 parts by mass, and particularly preferably 110 to 800 parts by mass. If it is less than the above range, the solution state and pot life may be reduced, and if it exceeds the above range, it may be disadvantageous in terms of productivity, manufacturing cost, and transportation cost of the laminate and the packaging material for LiB including the laminate. There is.
  • the organic solvent (C) is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons from the viewpoint of the solution state and pot life properties of the adhesive composition.
  • a mixed liquid of at least one solvent (C2) selected from the group consisting of at least one solvent (C1), an alcohol solvent, a ketone solvent, an ester solvent, and a glycol ether solvent is preferable.
  • the ratio is more preferably 60 to 90/40 to 10 (mass ratio), and particularly preferably 70 to 80/30 to 20 (mass ratio).
  • the solution state and pot life of the adhesive composition may be lowered.
  • the solvent (C1) is an aromatic hydrocarbon or an alicyclic hydrocarbon
  • the solvent (C2) is a ketone solvent.
  • the adhesive composition according to the present invention is a mixture of the acid-modified polyolefin (A), the polyfunctional polyisocyanate curing agent (B) and the organic solvent (C), and the acid-modified polyolefin (A) and the curing agent (B). May be dissolved in or dispersed in the organic solvent (C). It is preferably dissolved from the viewpoint of pot life.
  • the adhesive composition according to the present invention provides various tackifiers in addition to the acid-modified polyolefin (A), the polyfunctional polyisocyanate curing agent (B) and the organic solvent (C) as long as the performance of the present invention is not impaired.
  • An agent, a thermoplastic elastomer, and a plasticizer can be blended and used.
  • the tackifier is not particularly limited, and examples thereof include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, and hydrogenated petroleum resins.
  • Thermoplastic elastomers include styrene-ethylene-butylene-styrene copolymer resins, styrene elastomers such as styrene-ethylene-propylene-styrene, ethylene-propylene copolymer resins, ethylene-butene copolymer resins, ethylene-vinyl acetate. Examples thereof include olefin elastomers such as copolymer resins and ethylene-ethyl acrylate copolymer resins.
  • the plasticizer is preferably a liquid rubber such as polyisoprene or polybutene, or process oil. These tackifiers, thermoplastic elastomers, and plasticizers may be used alone or in combination of two or more.
  • the adhesive composition according to the present invention includes various curing agents in addition to the acid-modified polyolefin (A), the polyfunctional polyisocyanate curing agent (B), and the organic solvent (C) as long as the performance of the present invention is not impaired. Can be used in combination. Although it does not specifically limit as a hardening
  • Epoxy resins include glycidyl ester types such as glycidyl hexahydrophthalate and glycidyl dimer, triglycidyl isocyanurate, 3,4-epoxycyclohexylmethyl carboxylate, epoxidized polybutadiene, epoxidized soybean oil, and the like.
  • glycidyl ester types such as glycidyl hexahydrophthalate and glycidyl dimer
  • triglycidyl isocyanurate 3,4-epoxycyclohexylmethyl carboxylate
  • epoxidized polybutadiene epoxidized soybean oil
  • aliphatic epoxides, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and the like can be given.
  • carbodiimide compound examples include monocarbodiimide compounds such as dimethylcarbodiimide, diisopropylcarbodiimide, dicyclohexylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di- ⁇ -naphthylcarbodiimide, or aliphatic diisocyanate, aromatic diisocyanate, or alicyclic ring.
  • polycarbodiimide compounds that can be produced by subjecting an organic diisocyanate such as a group diisocyanate to a decarboxylation condensation reaction in the presence of a condensation catalyst in the absence of a solvent or in an inert solvent.
  • Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, and 2,4-diphenyl-2-oxazoline.
  • Oxazoline compounds 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,2-ethylene) -bis (2-oxazoline), 2,2 '-(1 , 4-butylene) -bis (2-oxazoline), or dioxazoline compounds such as 2,2 ′-(1,4-phenylene) -bis (2-oxazoline).
  • Examples of the coupling agent include silane coupling agents and titanate coupling agents.
  • the adhesive composition according to the present invention is a curing accelerator in addition to the acid-modified polyolefin (A), the polyfunctional polyisocyanate curing agent (B) and the organic solvent (C) as long as the performance of the present invention is not impaired.
  • the curing accelerator is not particularly limited, and examples thereof include carboxylic acid metal salts, tertiary amines, quaternary ammonium salts, organic peroxides, hydrazine compounds, metal chelate compounds, phosphorus-containing compounds, and basic vulcanizing agents.
  • Examples of the carboxylic acid metal salt include metal salts of carboxylic acids having 1 to 30 carbon atoms.
  • Examples of the carboxylic acid constituting the carboxylic acid metal salt include acetic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, octenoic acid, erucic acid, and elaidin.
  • Acids adipic acid, malonic acid, succinic acid, glutaric acid, citric acid, tartaric acid, malic acid, diglycolic acid and other aliphatic carboxylic acids; benzoic acid, chlorobenzoic acid, anisic acid, aminobenzoic acid, phthalic acid, terephthalic acid Aromatic carboxylic acids such as acid, naphthoic acid, naphthalenedicarboxylic acid and benzenetricarboxylic acid; naphthenic acid; acetone acid and the like.
  • a metal which comprises the said carboxylic acid metal salt Li, Na, K, Mg, Ca, Zn, Al, Cu, Pb, Co, Fe, Mn, Sn, Ti etc.
  • carboxylic acid metal salt examples include lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium octoate, calcium octoate, potassium decanoate, magnesium decanoate, and decane.
  • Zinc oxide lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, Calcium stearate, zinc stearate, sodium oleate, sodium behenate, sodium benzoate, zinc benzoate, sodium phthalate, phthalic acid Minium, magnesium terephthalate, calcium naphthalenedicarboxylate, dibutyltin laurate, tributyltin laurate, dioctyltin laurate, tributyltin acetate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin 2-ethylhexoate, tetrabutyl titanate, tetraisobutyl Examples thereof include titanate, tetra-2-ethylhexyl titanate, co
  • lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate examples include potassium stearate, calcium stearate, zinc stearate, and sodium oleate.
  • a polymer having a metal salt structure of carboxylic acid can also be used. Such polymers include ethylene and radically polymerizable carboxylic acid group IA, IIA, IIB, and IIIB metal (eg, Li, Na, K, Mg, Ca, Zn, Al, etc.) salts.
  • Examples thereof include those having a polymerized structure; those having a structure in which ethylene, a metal salt of a radically polymerizable carboxylic acid and other radically polymerizable carboxylic acid and / or a derivative thereof are copolymerized in a multi-component system.
  • Examples of the tertiary amines include dimethylaniline, triethanolamine, dimethyl-p-toluidine, and the like.
  • the hydrazine compound include 1-acetyl-2-phenylhydrazine.
  • the metal chelate compound vanadium acetylacetonate etc. are mentioned, for example.
  • Examples of the phosphorus-containing compound include dimethylphosphine and triphenylphosphine.
  • Examples of the basic vulcanizing agent include hexamethylenetetraamine, n-butyraldehyde-aniline condensate, and the like.
  • the adhesive composition according to the present invention contains various additives in addition to the acid-modified polyolefin (A), the polyfunctional polyisocyanate curing agent (B) and the organic solvent (C) as long as the performance of the present invention is not impaired. It can be used in combination. Although it does not specifically limit as an additive, It is preferable to use a flame retardant, a pigment, an antiblocking agent, etc.
  • the laminate of the present invention is obtained by laminating a polyolefin resin substrate and a metal substrate with the adhesive composition according to the present invention.
  • the adhesive composition is applied to the surface of the metal substrate using an appropriate application means such as a roll coater or a bar coater, and dried. After drying, while the layer of the adhesive composition (adhesive layer) formed on the surface of the metal substrate is in a molten state, the polyolefin resin substrate is laminated and bonded (laminar bonding) to the coated surface. Obtainable.
  • the thickness of the adhesive layer formed by the adhesive composition is not particularly limited, but is preferably 0.5 to 10 ⁇ m, more preferably 0.8 to 9.5 ⁇ m, and 1 to 9 ⁇ m. More preferably.
  • ⁇ Polyolefin resin substrate> What is necessary is just to select suitably from a conventionally well-known polyolefin resin as a polyolefin resin base material.
  • a conventionally well-known polyolefin resin for example, although not particularly limited, polyethylene, polypropylene, ethylene-propylene copolymer, and the like can be used. Among these, the use of an unstretched polypropylene film (hereinafter also referred to as CPP) is preferable.
  • the thickness is not particularly limited, but is preferably 20 to 100 ⁇ m, more preferably 25 to 95 ⁇ m, and even more preferably 30 to 90 ⁇ m.
  • a pigment and various additives may be mix
  • Metal base material Although it does not specifically limit as a metal base material, various metals, such as aluminum, copper, steel, chromium, zinc, duralumin, die-casting, and their alloys can be used. Moreover, as the shape, arbitrary shapes, such as metal foil, a rolled steel plate, a panel, a pipe, a can, and a cap, can be taken. In general, aluminum foil is preferable from the viewpoint of workability and the like. Although it varies depending on the purpose of use, it is generally used in the form of a sheet having a thickness of 0.01 to 10 mm, preferably 0.02 to 5 mm. Moreover, the surface of these metal base materials may be surface-treated in advance, or may be left untreated. In either case, the same effect can be exhibited.
  • various metals such as aluminum, copper, steel, chromium, zinc, duralumin, die-casting, and their alloys can be used.
  • shape arbitrary shapes, such as metal foil, a rolled steel plate, a
  • reaction solution was cooled to 100 ° C., poured into a container containing 717 parts by mass of toluene and 950 parts by mass of methyl ethyl ketone, which had been preliminarily heated to 40 ° C., cooled to 40 ° C., and further stirred for 30 minutes. Then, the resin was precipitated by further cooling to 25 ° C. (Here, the operation of pouring the reaction liquid into a solvent such as methyl ethyl ketone while stirring and cooling to precipitate the resin was called “reprecipitation”).
  • the slurry containing the resin was centrifuged to separate the acid-modified propylene-ethylene copolymer grafted with maleic anhydride from (poly) maleic anhydride and a low molecular weight product. Further, the acid-modified propylene-ethylene copolymer taken out by centrifugation was charged into a container containing new 2000 parts by mass of methyl ethyl ketone previously kept at 25 ° C. while stirring, and stirring was continued for 1 hour. Thereafter, the slurry was centrifuged to further separate the acid-modified propylene-ethylene copolymer, (poly) maleic anhydride and low molecular weight product.
  • the procedure was purified by repeating the procedure twice (in this case, the acid-modified propylene-ethylene copolymer taken out by centrifugation was added to methyl ethyl ketone with stirring and centrifuged again to enhance the purification. To “reslurry”). After purification, it is dried at 70 ° C. under reduced pressure for 5 hours to give an acid-modified polyolefin, maleic anhydride-modified propylene-ethylene copolymer (PO-1, acid value 2 mg KOH / g-resin, acetone extraction component ratio 0.1). Mass%, storage elastic modulus at 25 ° C. of 300 MPa, tensile elongation at break of 600% at 25 ° C., weight average molecular weight 190,000, Tm 88 ° C., ⁇ H37 J / g).
  • Production Example 3 150 parts by mass of toluene, 40 parts by mass of maleic anhydride, 8 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 700 mass of methyl ethyl ketone as a solvent used for reprecipitation Part, the number of reslurries was changed to 5 times, and the same procedure as in Production Example 1 was carried out, whereby an acid-modified polyolefin maleic anhydride-modified propylene-ethylene copolymer (PO-3, acid value 48 mgKOH / g-resin, Acetone-extracted component ratio 0.1 mass%, storage elastic modulus 180 MPa at 25 ° C., tensile elongation at break 350% at 25 ° C., weight average molecular weight 31,000, Tm 85 ° C., ⁇ H 31 J / g).
  • PO-3 acid-modified polyolefin maleic anhydride-modified propylene-ethylene copolymer
  • Production Example 4 150 parts by mass of toluene, 40 parts by mass of maleic anhydride, 8 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 700 mass of methyl ethyl ketone as a solvent used for reprecipitation Parts, the maleic anhydride-modified propylene-ethylene copolymer (PO—), which is an acid-modified polyolefin, in the same manner as in Production Example 1 except that the solvent used for reslurry was changed to 1000 parts by mass of methyl ethyl ketone and the number of reslurries was changed to 3. 4.
  • PO— propylene-ethylene copolymer
  • Production Example 5 150 parts by mass of toluene, 20 parts by mass of maleic anhydride, 6 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 700 masses of methyl ethyl ketone as a solvent used for reprecipitation Parts, the maleic anhydride-modified propylene-ethylene copolymer (PO—), which is an acid-modified polyolefin, in the same manner as in Production Example 1 except that the solvent used for reslurry was changed to 1000 parts by mass of methyl ethyl ketone and the number of reslurries was changed to 2. 5.
  • PO— propylene-ethylene copolymer
  • Acid value 25 mg KOH / g-resin, acetone extraction component ratio 0.9 mass%, storage elastic modulus 400 MPa at 25 ° C., tensile elongation at break 500% at 25 ° C., weight average molecular weight 60,000, Tm 87 ° C., ⁇ H35J / G).
  • Production Example 6 100 parts by mass of propylene-ethylene copolymer (storage modulus at 25 ° C., 52 MPa, tensile elongation at break of 1050% at 25 ° C.), 150 parts by mass of toluene, 30 parts by mass of maleic anhydride, The amount of di-tert-butyl peroxide charged was changed to 6 parts by mass, the reaction time was 3 hours, the solvent used for reprecipitation was 700 parts by mass of methyl ethyl ketone, the solvent used for reslurry was 1000 parts by mass, and the number of reslurries was changed to 2 times.
  • maleic anhydride modified propylene-ethylene copolymer (PO-6, acid value 25 mgKOH / g-resin, acetone extraction component ratio 1.0% by mass, Storage elastic modulus at 25 ° C. 12 MPa, tensile elongation at break 900% at 25 ° C., weight average molecular weight 0,000, Tm58 °C, ⁇ H7J / g) was obtained.
  • Production Example 7 100 parts by mass of propylene homopolymer (storage modulus 2100 MPa at 25 ° C., tensile elongation at break 900% at 25 ° C.), 150 parts by mass of toluene, 30 parts by mass of maleic anhydride, di- Except for changing the charge amount of tert-butyl peroxide to 6 parts by mass, the reaction time to 3 hours, the solvent used for reprecipitation to 700 parts by mass of methyl ethyl ketone, the solvent used for reslurry to 1000 parts by mass of methyl ethyl ketone, and the number of reslurries to 2
  • maleic anhydride-modified propylene homopolymer PO-7, acid value 25 mgKOH / g-resin, acetone extraction component ratio 0.9% by mass, storage at 25 ° C., which is an acid-modified polyolefin.
  • Production Example 8 100 parts by mass of a propylene-ethylene copolymer (storage modulus 2720 MPa at 25 ° C., tensile elongation at break 400% at 25 ° C.), 186 parts by mass of toluene, 20 parts by mass of maleic anhydride, The amount of di-tert-butyl peroxide charged was changed to 6 parts by mass, the reaction time was 3 hours, the solvent used for reprecipitation was 700 parts by mass of methyl ethyl ketone, the solvent used for reslurry was 1000 parts by mass, and the number of reslurries was changed to 2 times.
  • a propylene-ethylene copolymer storage modulus 2720 MPa at 25 ° C., tensile elongation at break 400% at 25 ° C.
  • the amount of di-tert-butyl peroxide charged was changed to 6 parts by mass
  • the reaction time was 3 hours
  • the solvent used for reprecipitation was 700 parts by mass
  • Production Example 9 186 parts by weight of toluene, 20 parts by weight of maleic anhydride, 6 parts by weight of di-tert-butyl peroxide, 3 hours of reaction time, and 1200 parts of methyl ethyl ketone as the solvent used for reprecipitation
  • the solvent used for reslurry was changed to 1200 parts by mass of methyl ethyl ketone and the number of reslurries was changed to 2
  • Acid value 25 mg KOH / g-resin, acetone extraction component ratio 1.2% by mass, storage elastic modulus 7 MPa at 25 ° C., tensile elongation at break 1200% at 25 ° C., weight average molecular weight 60,000, no Tm peak, ⁇ H0J / g) was obtained.
  • Production Example 10 100 parts by mass of propylene-ethylene copolymer (storage elastic modulus 500 MPa at 25 ° C., tensile elongation at break 680% at 25 ° C.), 150 parts by mass of toluene, and 0.5 parts by mass of maleic anhydride Parts, di-tert-butyl peroxide charge amount 0.2 parts by mass, reaction time 1 hour, re-precipitation solvent 1000 parts by weight methyl ethyl ketone 1000 parts by weight methyl ethyl ketone 1000 parts by weight, reslurry number of times 2
  • PO-10 acid value of 1 mg KOH / g-resin
  • Production Example 11 150 parts by mass of toluene, 50 parts by mass of maleic anhydride, 10 parts by mass of di-tert-butyl peroxide, 3 hours of reaction time, 700 masses of methyl ethyl ketone as a solvent used for reprecipitation Parts, the maleic anhydride-modified propylene-ethylene copolymer (PO—), which is an acid-modified polyolefin, in the same manner as in Production Example 1 except that the solvent used for reslurry was changed to 1000 parts by mass of methyl ethyl ketone and the number of reslurries was changed to 3. 11.
  • PO— propylene-ethylene copolymer
  • Acid value 55 mg KOH / g-resin, acetone extraction component ratio 1.0 mass%, storage elastic modulus 150 MPa at 25 ° C., tensile elongation at break 320% at 25 ° C., weight average molecular weight 30,000, Tm 83 ° C., ⁇ H25J / G).
  • Production Example 12 Except for changing the amount of toluene charged to 150 parts by mass, the amount of maleic anhydride charged to 40 parts by mass, the amount of di-tert-butyl peroxide charged to 8 parts by mass, the reaction time for 3 hours and the number of reslurries to 3 times.
  • maleic anhydride-modified propylene-ethylene copolymer (PO-12, acid value 46 mg KOH / g-resin, acetone extraction component ratio 4.5% by mass, 25 ° C.) is an acid-modified polyolefin.
  • Example 1 500 parts by mass of the main agent 1 and 1 part by mass of Sumijoule (registered trade table) N-3300 as a polyfunctional polyisocyanate curing agent (B) were blended to obtain an adhesive composition.
  • Table 2 shows the evaluation results of pot life, adhesiveness, chemical resistance and moldability.
  • Examples 2 to 21, Comparative Examples 1 to 3 The main agents 1 to 19 and the curing agents were changed as shown in Tables 2 and 3, and Examples 2 to 21 and Comparative Examples 1 to 3 were performed in the same manner as in Example 1.
  • Tables 2 and 3 show the results of blending amount, pot life property, adhesiveness, chemical resistance and moldability.
  • the curing agents used in Tables 2 and 3 are as follows.
  • ⁇ Multifunctional polyisocyanate curing agent (B)> Isocyanurate of hexamethylene diisocyanate: Sumidur (registered trademark) N-3300 (manufactured by Bayer) Hexamethylene diisocyanate biuret: Duranate (registered trademark) 24A-100 (manufactured by Asahi Kasei Chemicals)
  • the acid value (mgKOH / g-resin) in the present invention is the amount of KOH required to neutralize 1 g of the acid-modified polyolefin (A), and is a test method of JIS K0070 (1992). Measured according to Specifically, 1 g of acid-modified polyolefin was dissolved in 100 g of xylene adjusted to a temperature of 100 ° C., and then a 0.1 mol / L potassium hydroxide ethanol solution [trade name “0” was used at the same temperature with phenolphthalein as an indicator.
  • the storage elastic modulus (E ′) in the present invention was measured in accordance with the test method of JIS K7244-4 (1999). Specifically, it is a value measured by using a dynamic viscoelasticity measuring device DVA-200 manufactured by IT Measurement & Control Co., Ltd. while increasing the temperature at a rate of ⁇ 50 ° C. to 5 ° C./min at a frequency of 10 Hz. .
  • the tensile elongation at break (Eb) in the present invention was measured according to the test method of JIS K7161 (2014). Specifically, it is a value obtained by measuring the elongation (%) at the time of breaking in tension at a speed of 50 mm / min in a 25 ° C. environment using Tensilon RTM-100 manufactured by Orientec Corporation.
  • the melting point and heat of fusion in the present invention are increased at a rate of 20 ° C./minute using a differential scanning calorimeter (hereinafter DSC, manufactured by TA Instruments Japan, Q-2000). It is a value measured from the top temperature and area of the melting peak when heated and melted into a cooled resin and then heated and melted again.
  • DSC differential scanning calorimeter
  • Pot life property refers to the stability of the solution immediately after the compounding or after a certain time has elapsed after the compounding with the acid-modified polyolefin. If the pot life is good, it means that the viscosity of the solution is small and can be stored for a long time. If the pot life is poor, the viscosity of the solution increases (thickens). It means that gelation occurs, application to a substrate becomes difficult, and long-term storage is impossible.
  • the pot life properties of the adhesive compositions obtained in Examples 1 to 21 and Comparative Examples 1 to 3 were stored at 25 ° C. and 40 ° C. for 24 hours, and then the solution viscosity at 25 ° C. using a B-type viscometer. It was evaluated by measuring.
  • the laminate obtained as described above was evaluated by the following method.
  • the laminate was cut into a size of 100 mm x 15 mm, and the adhesiveness was evaluated according to the following criteria by a T-type peel test. The evaluation results are shown in Tables 2-3.
  • ⁇ T-type peel test> Based on the test method of ASTM-D1876-61, the peel strength at a tensile speed of 50 mm / min was measured in a 25 ° C environment using Tensilon RTM-100 manufactured by Orientec Corporation. The peel strength (N / cm) between the metal substrate / polyolefin resin substrate was the average of five test values.
  • breakage means that the metal substrate or CPP is destroyed without peeling at the metal substrate / CPP interface.
  • the limit forming depth of the sample For the samples after cold forming, the deepest forming depth at which pinholes and cracks did not occur in all 10 samples of the wrinkles and aluminum foil was defined as the limit forming depth of the sample. From this limit molding depth, the moldability of the battery packaging material was evaluated according to the following criteria. The evaluation results are shown in Tables 3-4. ⁇ Criteria> ⁇ (Particularly excellent in practical use): Limit forming depth 6.0 mm or more ⁇ (Practical use excellent): Limit forming depth 4.0 mm or more and less than 6.0 mm ⁇ (Practical use): Limit forming depth 2.0 mm or more 4 Less than 0 mm x: Limit molding depth less than 2.0 mm
  • the adhesive composition according to the present invention contains an acid-modified polyolefin, a polyfunctional polyisocyanate curing agent and an organic solvent, and maintains good pot life without causing thickening or gelation even when stored for a long period of time.
  • good adhesion between the metal substrate and the polyolefin resin substrate, electrolytic solution resistance, and moldability can be achieved. Therefore, the laminate of the polyolefin resin base material and the metal base material formed from the adhesive composition of the present invention is not only used in the fields of home appliance outer panels, furniture materials, building interior members, etc., but also personal computers and mobile phones. It can also be widely used as a packaging material (pouch form) for lithium batteries used in video cameras and the like.

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  • Electrochemistry (AREA)
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