WO2020218363A1 - Ruban adhésif pour batteries non aqueuses - Google Patents

Ruban adhésif pour batteries non aqueuses Download PDF

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Publication number
WO2020218363A1
WO2020218363A1 PCT/JP2020/017372 JP2020017372W WO2020218363A1 WO 2020218363 A1 WO2020218363 A1 WO 2020218363A1 JP 2020017372 W JP2020017372 W JP 2020017372W WO 2020218363 A1 WO2020218363 A1 WO 2020218363A1
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WO
WIPO (PCT)
Prior art keywords
adhesive tape
weight
adhesive
parts
resin
Prior art date
Application number
PCT/JP2020/017372
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English (en)
Japanese (ja)
Inventor
茂樹 河邊
Original Assignee
日東電工株式会社
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Publication date
Priority claimed from JP2020074823A external-priority patent/JP2020184523A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2020218363A1 publication Critical patent/WO2020218363A1/fr

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    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an adhesive tape for non-aqueous batteries.
  • Adhesive tape is used for non-aqueous batteries, such as lithium-ion batteries, which are constructed by enclosing a non-aqueous electrolyte solution, for the purpose of improving the packing property of electrodes into the battery case and preventing short circuits between electrodes. Will be done.
  • Such an adhesive tape is required to have adhesive reliability in a non-aqueous electrolyte solution, and a highly hydrophobic adhesive (acrylic adhesive, rubber adhesive) is used, and the adhesive contains an acid component.
  • Means such as adding an additive such as a tackifier resin to the pressure-sensitive adhesive have been studied (for example, Patent Document 1).
  • the present invention has been made to solve the conventional problems, and an object of the present invention is a non-aqueous system having excellent adhesiveness in a non-aqueous electrolyte solution, less stickiness, and less adhesive squeeze out.
  • the purpose is to provide adhesive tape for batteries.
  • the adhesive tape for a non-aqueous battery of the present invention is an adhesive tape comprising a base material and an adhesive layer arranged on at least one side of the base material, and the adhesive layer exhibits adhesiveness by pressure bonding.
  • the pressure-sensitive adhesive contains an acrylic polymer having an acid functional group and a crystalline resin having a melting point of 25 ° C. or higher, and the haze value of the pressure-sensitive adhesive tape is 20% or less.
  • the non-aqueous battery adhesive tape exhibits adhesiveness when heated.
  • the acrylic polymer having an acid functional group has a structural unit a derived from a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 4 or more carbon atoms. ..
  • the content ratio of the structural unit a is 50 parts by weight or more with respect to 100 parts by weight of the acrylic polymer having an acid functional group.
  • the crystalline resin is a polyolefin resin.
  • the polyolefin-based resin is a maleic anhydride-modified polyolefin-based resin, a maleic acid-modified polyolefin-based resin, or an acrylic-modified polyolefin-based resin.
  • the pressure-sensitive adhesive comprises a C5-based petroleum resin and / or a C9-based petroleum resin.
  • the substrate is selected from polyacrylate, polyurethane, polyimide, aramid, polyamide, ethylene / vinyl alcohol copolymer, polyetherimide, polyvinylidene fluoride, polyester, polypropylene, polyethylene, polyphenylene sulfide. It is formed from at least one kind.
  • a release film is provided on the side of the pressure-sensitive adhesive layer opposite to the base material.
  • the pressure-sensitive adhesive layers are arranged on both sides of the base material.
  • an adhesive tape for non-aqueous batteries which has excellent adhesiveness in a non-aqueous electrolyte solution, has less stickiness, and does not easily protrude from the end face of the adhesive tape.
  • the adhesive tape for non-aqueous batteries of the present invention has a feature that the haze value is small and the haze value does not change much with time.
  • Such an adhesive tape for a non-aqueous battery has advantages such as excellent sensor sensitivity through the adhesive tape and easy positioning of the adhesive tape, and can be advantageously used in the manufacturing process of a non-aqueous battery.
  • FIG. 1 is a schematic cross-sectional view of an adhesive tape for non-aqueous batteries (hereinafter, also simply referred to as adhesive tape) according to one embodiment of the present invention.
  • the adhesive tape 100 includes a base material 10 and an adhesive layer 20 arranged on at least one side (both sides in the illustrated example) of the base material 10.
  • the adhesive tape is a release film on the outside of the adhesive layer (that is, the surface of the adhesive layer opposite to the substrate) for the purpose of protecting the adhesive surface until it is used. May be provided.
  • FIG. 2 is a schematic cross-sectional view of the adhesive tape for non-aqueous batteries according to another embodiment of the present invention.
  • the adhesive tape 200 includes a base material 10, a pressure-sensitive adhesive layer 20 arranged on one surface of the base material 10, and another pressure-sensitive adhesive layer 30 arranged on the other surface of the base material.
  • the pressure-sensitive adhesive layer 20 contains the pressure-sensitive adhesive described in item A above.
  • Another pressure-sensitive adhesive layer 30 contains any suitable pressure-sensitive adhesive (for example, acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive) other than the pressure-sensitive adhesive described in item A.
  • the adhesive tape is outside the adhesive layer and / or another adhesive layer (ie, the adhesive layer and / or another) for the purpose of protecting the adhesive surface until it is used.
  • a release film may be provided on the surface of the pressure-sensitive adhesive layer opposite to the base material.
  • the adhesive layer constituting the adhesive tape exhibits adhesiveness by being pressure-bonded.
  • the adhesive tape (substantially the adhesive layer) may be an adhesive tape that exhibits adhesiveness at room temperature (25 ° C.), or may be an adhesive tape that exhibits adhesiveness by heating. An adhesive tape that develops adhesiveness by heating can exhibit adhesiveness in a state of being cooled to room temperature after heating.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer includes an acrylic polymer having an acid functional group and a crystalline resin having a melting point of 25 ° C. or higher.
  • an acrylic polymer having an acid functional group in combination with the above crystalline resin, stickiness is reduced (specifically, it has an appropriate probe tack value), and non-aqueous electrolysis is performed. It is possible to obtain a pressure-sensitive adhesive that exhibits excellent adhesiveness even in a liquid and whose adhesiveness does not easily decrease with time. By using such an adhesive, it is possible to obtain an adhesive tape having excellent internal short circuit prevention functionality and excellent handleability in the battery assembly process.
  • the adhesive tape can be suitably used for joining members (for example, separators, electrodes, exterior materials (metal cans, pouches, etc.)) used in a non-aqueous electrolytic solution.
  • the adhesive tape is a double-sided adhesive tape. It can be suitably used for joining a metal material to a metal material, a non-metal material to a non-metal material, and a metal material to a non-metal material.
  • the pressure-sensitive adhesive of the present invention Is sticky by adjusting the structure of the acrylic polymer having an acid functional group (for example, monomer component, molecular weight), the structure of the crystalline resin, the content ratio of the acrylic polymer having an acid functional group and the crystalline resin, and the like. The balance between the degree and the adhesive reliability can be easily controlled.
  • the adhesive tape for non-aqueous batteries obtained by using such an adhesive has advantages such as excellent sensor sensitivity through the adhesive tape and easy positioning of the adhesive tape, and is used in the manufacturing process of non-aqueous batteries. Can be used advantageously.
  • the adhesive strength at 25 ° C. when the adhesive layer of the adhesive tape of the present invention is attached to an aluminum foil is preferably 0.5 N / 10 mm or more, and more preferably 0.8 N / 10 mm to 20 N / 10 mm. , More preferably 1N / 10mm to 10N / 10mm. Within such a range, an adhesive tape suitable for non-aqueous batteries can be used.
  • the adhesive strength is the adhesive strength measured by a method according to JIS Z 0237: 2000, and the adhesive tape is attached to the aluminum foil by one reciprocation of a 2 kg roller and left at 25 ° C. for 30 minutes.
  • the adhesive tape is peeled off and measured under the conditions of a peeling angle of 180 ° and a peeling speed (tensile speed) of 300 mm / min.
  • the adhesive tape is an adhesive tape that develops adhesiveness by heating, it can be attached to the adhesive tape by an adhesive operation (for example, 130 ° C., 0.4 MPa, 5 seconds) at a temperature at which the adhesive tape exhibits adhesiveness.
  • the adhesive strength measured after adhering the aluminum foil and cooling to 25 ° C. corresponds to the above-mentioned adhesive strength.
  • the haze value of the adhesive tape is 20% or less, preferably 18% or less, more preferably 10% or less, further preferably 8% or less, and particularly preferably 5% or less.
  • the haze value of the adhesive tape is the base material type, the structure of the acrylic polymer having an acid functional group (for example, monomer component, molecular weight), the structure of the crystalline resin, and the content of the acrylic polymer having an acid functional group and the crystalline resin. It can be adjusted by adjusting the ratio and the like.
  • the rate of change in the haze value of the adhesive tape when the adhesive tape is stored at an environmental temperature of 5 ° C. for 72 hours is preferably 20. % Or less, more preferably 16% or less, still more preferably 10% or less, and particularly preferably 8% or less.
  • the thickness of the adhesive tape is preferably 5 ⁇ m to 200 ⁇ m, more preferably 15 ⁇ m to 150 ⁇ m, and further preferably 30 ⁇ m to 100 ⁇ m.
  • the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive containing an acrylic polymer having an acid functional group and a crystalline resin having a melting point of 25 ° C. or higher.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m to 100 ⁇ m, more preferably 3 ⁇ m to 80 ⁇ m, and further preferably 5 ⁇ m to 50 ⁇ m.
  • the haze value of the pressure-sensitive adhesive layer is preferably 20% or less, more preferably 18% or less, further preferably 10% or less, particularly preferably 8% or less, and most preferably 5% or less. Is.
  • Rate of change in haze value of the adhesive layer constituting the adhesive tape when the adhesive tape is stored at an environmental temperature of 5 ° C. for 72 hours Is preferably 20% or less, more preferably 16% or less, further preferably 10% or less, and particularly preferably 8% or less.
  • the probe tack value of the pressure-sensitive adhesive layer at 25 ° C. is preferably 500 g or less, more preferably 400 g or less, further preferably 340 g or less, and particularly preferably 10 g to 300 g. The method for measuring the probe tack value will be described later.
  • acrylic polymer with acid functional group examples include an acrylic polymer containing a structural unit derived from one or more (meth) acrylic acid alkyl esters and a structural unit derived from a monomer having an acid functional group. Can be mentioned.
  • the content ratio of the acrylic polymer having an acid functional group in the pressure-sensitive adhesive is preferably 7 parts by weight to 95 parts by weight, more preferably 15 parts by weight or more, based on 100 parts by weight of the solid content in the pressure-sensitive adhesive. It is 90 parts by weight, more preferably 20 parts by weight to 85 parts by weight, and particularly preferably 40 parts by weight to 85 parts by weight.
  • the content of the acrylic polymer having an acid functional group can be an appropriate amount depending on the desired probe tack value, adhesiveness and the like.
  • the adhesive may contain an acrylic polymer having no acid functional group in addition to the acrylic polymer having an acid functional group, and may not contain an acrylic polymer having no acid functional group. You may.
  • the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester is preferably 50 parts by weight to 99 parts by weight, more preferably 70 parts by weight, based on 100 parts by weight of the acrylic polymer having an acid functional group. It is ⁇ 98 parts by weight, more preferably 80 parts by weight to 98 parts by weight.
  • the (meth) acrylic acid alkyl ester is linear or branched with 1 to 24 carbon atoms (more preferably 3 to 20, even more preferably 4 to 12, particularly preferably 4 to 8). It has an alkyl group.
  • Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylic acid, pentyl (meth) acrylic acid, and (meth). ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, eikosyl (meth) acrylate and the like.
  • the acrylic polymer having an acid functional group has a linear or branched alkyl group having 4 or more carbon atoms (preferably 4 to 12, more preferably 4 to 8). It has a structural unit a derived from (meth) acrylic acid alkyl ester, and the content ratio of the structural unit a is 50 parts by weight or more (preferably 50 parts by weight) with respect to 100 parts by weight of the acrylic polymer having an acid functional group. ⁇ 99 parts by weight, more preferably 70 parts by weight to 98 parts by weight, still more preferably 80 parts by weight to 98 parts by weight).
  • a (meth) acrylic acid alkyl ester having a branched alkyl group is used as the (meth) acrylic acid alkyl ester.
  • the effect of the present invention becomes particularly remarkable when a (meth) acrylic acid alkyl ester having a branched alkyl group is used.
  • the branched alkyl group preferably has 4 or more carbon atoms, more preferably 4 to 12 carbon atoms, and further preferably 4 to 8 carbon atoms.
  • a (meth) acrylic acid alkyl ester having a linear alkyl group and a (meth) acrylic acid alkyl ester having a branched alkyl group may be used in combination.
  • a (meth) acrylic acid alkyl ester having a branched alkyl group may be used alone.
  • the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester having a branched alkyl group is the constitution derived from the (meth) acrylic acid alkyl ester. It is preferable with respect to 100 parts by weight of the unit (that is, 100 parts by weight of the total amount of the (meth) acrylic acid alkyl ester having a linear alkyl group and the (meth) acrylic acid alkyl ester having a branched alkyl group). It is 50 parts by weight to 100 parts by weight, more preferably 70 parts by weight to 100 parts by weight, and further preferably 80 parts by weight to 100 parts by weight.
  • Examples of the (meth) acrylic acid alkyl ester having a branched alkyl group include isobutyl (meth) acrylic acid, sec-butyl (meth) acrylic acid, t-butyl (meth) acrylic acid, and 2-butyl (meth) acrylic acid.
  • Examples thereof include ethylhexyl, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, 2-methylbutyl (meth) acrylate and the like.
  • 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate or isodecyl (meth) acrylate are preferable, and 2-ethylhexyl (meth) acrylate is more preferable. ..
  • 2-ethylhexyl (meth) acrylate is used, a pressure-sensitive adhesive having particularly excellent adhesive reliability in a non-aqueous electrolyte solution can be obtained.
  • Examples of the acid functional group contained in the acrylic polymer having an acid functional group include a carboxyl group, an acid anhydride group, a phosphoric acid group, and a sulfonic acid group. Therefore, examples of the monomer having an acid functional group include a carboxyl group-containing monomer, an acid anhydride group-containing monomer, a phosphoric acid group-containing monomer, and a sulfonic acid group-containing monomer. Of these, a carboxyl group-containing monomer is preferable.
  • the adhesive force to the metal plate is easily developed, and in terms of design and production, it is easy to copolymerize with other acrylic monomers, and the polymer formed by the copolymerization is crosslinked. It has the characteristic of being easy.
  • carboxyl group-containing monomer examples include (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Of these, acrylic acid is preferable.
  • the content ratio of the structural unit derived from the monomer having an acid functional group is preferably 1.5 parts by weight to 20 parts by weight, more preferably 1. parts by weight, based on 100 parts by weight of the acrylic polymer having an acid functional group. It is 8 parts by weight to 15 parts by weight, more preferably 2 parts by weight to 10 parts by weight.
  • the acrylic polymer having an acid functional group may be combined with the (meth) acrylic acid alkyl ester and / or a monomer having an acid functional group, if necessary, for the purpose of modifying the cohesiveness, heat resistance, crosslinkability and the like. It may contain structural units derived from other copolymerizable monomers. Such other monomers include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, etc.
  • Hydroxyl group-containing monomers such as hydroxydecyl (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methylmethacrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (N-substituted) amide-based monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylate.
  • Aminoalkyl-based (meth) acrylates such as aminoethyl and t-butylaminoethyl (meth) acrylate; alkoxyalkyl-based (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
  • Maleimide-based monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide , N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide and other itaconimide-based monomers; N- (meth) acryloyloxymethylene succinimide, N- (meth) accurloyl-6-oxyhexamethylenesuccinimide, Succinimide-based monomers such as N- (meth) acryloyl-8-oxyoctamethylene succinimide; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrroli
  • Acrylate-based monomers having a heterocycle such as, halogen atom, silicon atom, etc .; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropanthry (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate Polyfunctional monomers such as; olefin-based monomers such as isoprene, butadiene, and isobutylene; vinyl ether-based monomers such as vinyl ether, and the like. These monomer components may be used alone or in
  • the content ratio of the structural unit derived from the other monomer is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 10 parts by weight, based on 100 parts by weight of the acrylic polymer having an acid functional group. It is 5 parts by weight or less.
  • the weight average molecular weight of the acrylic polymer having an acid functional group is preferably 300,000 to 2,000,000, more preferably 500,000 to 1,500,000.
  • the weight average molecular weight can be measured by GPC (solvent: THF).
  • the pressure-sensitive adhesive of the present invention contains a crystalline resin.
  • the crystalline resin refers to a resin having a clear endothermic peak (half width within 15 ° C.) in the differential calorimetry curve measured by a differential scanning calorimeter (DSC).
  • the content ratio of the crystalline resin in the pressure-sensitive adhesive is preferably 3 parts by weight to 90 parts by weight, more preferably 10 parts by weight to 85 parts by weight, based on 100 parts by weight of the solid content in the pressure-sensitive adhesive. More preferably, it is 15 to 80 parts by weight.
  • the melting point of the crystalline resin is 25 ° C. or higher, more preferably 40 ° C. or higher, further preferably 60 ° C. to 120 ° C., and particularly preferably 60 ° C. to 100 ° C. Within such a range, it is possible to obtain a pressure-sensitive adhesive which is excellent in heat resistance and chemical resistance and whose adhesive strength is suppressed from being lowered when it comes into contact with an oil component or an alcohol component.
  • the melting point can be measured by differential scanning calorimetry (DSC).
  • the weight average molecular weight of the crystalline resin is preferably 50,000 to 1,500,000, more preferably 70,000 to 1,000,000.
  • the crystallinity of the crystalline resin is preferably 10% or more, more preferably 20% or more. Crystallinity can typically be measured by differential scanning calorimetry (DSC).
  • the crystalline resin is a polyolefin resin.
  • the polyolefin resin include ethylene homopolymers, ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, and ethylene-.
  • 1-Heptene copolymer ethylene-1-octene copolymer, ethylene-1-nonene copolymer, ethylene-1-decene copolymer, ethylene-1-undecene copolymer, ethylene-1-dodecene Polymer, ethylene-1-tridecene copolymer, ethylene-1-tetradecene copolymer, ethylene-1-pentadecene copolymer, ethylene-1-hexadecene copolymer, ethylene-1-heptadecene copolymer, ethylene- Ethylene- ⁇ -olefin copolymers such as 1-octadecene copolymer, ethylene-1-nanodecene copolymer, ethylene-1-eicosene copolymer; ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer Ethylene-vinyl ester cop
  • a crystalline polypropylene-based resin is used as the crystalline resin.
  • the crystalline polypropylene-based resin may be a homopolymer, or may be a copolymer obtained from propylene and a monomer copolymerizable with propylene.
  • Examples of the monomer copolymerizable with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like. ⁇ -olefin and the like.
  • the content ratio of the constituent unit derived from propylene is preferably 60 mol% to 99 mol%, more preferably 65 mol% to 99 mol%, and further preferably 70 mol% to 99 mol%. It is mol%.
  • the content ratio of the constituent unit derived from ⁇ -olefin is preferably 1 mol% to 15 mol%, more preferably 1 mol% to 10 mol%.
  • a modified polyolefin resin is used as the crystalline resin.
  • the modified polyolefin resin is used, the phase separation between the crystalline resin and the acrylic polymer having an acid functional group is suppressed, and a pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer having less bleeding and excellent transparency is formed. be able to.
  • the modified polyolefin-based resin maleic anhydride-modified polyolefin-based resin, maleic acid-modified polyolefin-based resin, acrylic-modified polyolefin-based resin and the like can be preferably used. Specific examples thereof include resins obtained by modifying the above-mentioned polyolefin resin with maleic anhydride, maleic acid or acrylic.
  • a maleic anhydride polyolefin resin is preferable, and a maleic anhydride modified propylene resin is more preferable.
  • Specific examples of the maleic anhydride-modified propylene resin include a resin obtained by modifying the crystalline polypropylene resin with maleic anhydride.
  • the modification rate of the modified polyolefin resin is preferably 1% by weight to 5% by weight, more preferably 1.5% by weight to 2% by weight.
  • the pressure-sensitive adhesive may optionally contain any suitable additive.
  • the additive include a cross-linking agent, a tackifier, a plasticizer (for example, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plasticizer), a pigment, a dye, a filler, an antiaging agent, and a conductive material. , Ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, solvents and the like.
  • the pressure-sensitive adhesive may contain any suitable solvent.
  • tackifier any suitable tackifier is used.
  • a tackifier resin is used.
  • the tackifier resin include rosin-based tackifier resins (eg, unmodified rosin, modified rosin, rosinphenol-based resins, rosin ester-based resins, etc.) and terpene-based tackifier resins (eg, terpene-based resins, terpenphenols).
  • a pressure-sensitive adhesive As the pressure-sensitive adhesive, a C5-based petroleum resin and / or a C9-based petroleum resin is used as the tackifier. By using these pressure-sensitive adhesives, a pressure-sensitive adhesive having highly reliable adhesive strength in a non-aqueous electrolytic solution can be obtained.
  • the softening point of the tackifier is preferably 70 ° C. to 200 ° C., more preferably 80 ° C. to 190 ° C. Within such a range, a pressure-sensitive adhesive layer in which the storage elastic modulus and the loss elastic modulus are appropriately adjusted can be obtained.
  • the content ratio of the tackifier is preferably 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the total amount of the acrylic polymer having an acid functional group and the crystalline resin having a melting point of 25 ° C. or higher. , More preferably 10 to 40 parts by weight.
  • cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, and metals.
  • examples thereof include salt-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents. Of these, isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents are preferable.
  • isocyanate-based cross-linking agent examples include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; 2,4- Aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L”), tri Methylolpropane / hexamethylene diisocyanate trimeric adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL”), is
  • the content of the isocyanate-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength and elastic modulus, and the acrylic polymer having an acid functional group and the crystalline resin having a melting point of 25 ° C. or higher are used. It is typically 0.1 parts by weight to 20 parts by weight, more preferably 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of the total amount.
  • epoxy-based cross-linking agent examples include N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, and 1,3-bis (N, N-glycidyl aminomethyl) cyclohexane (Mitsubishi Gas).
  • the content of the epoxy-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength and elastic modulus, and the acrylic polymer having an acid functional group and the crystalline resin having a melting point of 25 ° C. or higher are used. It is typically 0.01 parts by weight to 10 parts by weight, more preferably 0.03 parts by weight to 5 parts by weight, based on 100 parts by weight of the total amount.
  • metal chelate-based cross-linking agent for example, a metal chelate compound in which the metal atom is aluminum, zirconium, titanium, zinc, iron, tin or the like can be used. Of these, an aluminum chelate compound or a titanium chelate compound portion is preferable.
  • Examples of the aluminum chelate compound include diisopropoxyaluminum monooleylacetate, monoisopropoxyaluminum bisoleylacetate, monoisopropoxyaluminum monooleate monoethylacetate, diisopropoxyaluminum monolaurylacetate, and diisopropoxy.
  • titanium chelate compound examples include titanium diisopropoxybis (acetylacetoneate), titaniumtetra-n-butyrate, titaniumtetra-2-ethylhexanonate, titaniumtetraacetylacetoneate, and titaniumdiisopropoxybis (ethylacetate). Acetate), titanium octylene glycolate and the like.
  • metal chelate compounds examples include zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetoneate.
  • the above-mentioned metal chelate-based cross-linking agent may be used alone or in combination of two or more.
  • the content of the metal chelate-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength and elasticity, and is crystalline with an acrylic polymer having an acid functional group and having a melting point of 25 ° C. or higher. It is typically 0.01 to 10 parts by weight, more preferably 0.03 to 7 parts by weight, still more preferably 0.05 parts by weight, based on 100 parts by weight of the total amount with the resin. Parts to 5 parts by weight.
  • a resin film is preferably used as the base material.
  • the resin constituting the resin film include polyacrylate, polyurethane, polyimide, aramid, polyamide, ethylene / vinyl alcohol copolymer, polyetherimide, polyvinylidene fluoride, polyester, polypropylene, polyethylene, polyphenylene sulfide and the like. .. These resins may be used alone or in combination of two or more.
  • the thickness of the base material is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, and further preferably 15 ⁇ m to 50 ⁇ m.
  • the haze value of the base material is preferably 20% or less, more preferably 18% or less, further preferably 10% or less, particularly preferably 8% or less, and most preferably 5% or less. is there.
  • Rate of change in haze value of the base material constituting the adhesive tape when the adhesive tape is stored at an environmental temperature of 5 ° C. for 72 hours ((haze value after storage for 72 hours-initial haze value) / initial haze value) Is preferably 20% or less, more preferably 16% or less, still more preferably 10% or less, and particularly preferably 8% or less.
  • a non-water battery including the above-mentioned adhesive tape for non-water battery is provided.
  • the non-aqueous battery adhesive tape can be used, for example, for the purpose of improving the packing property of the electrodes into the battery case, preventing a short circuit between the electrodes, and the like.
  • Adhesive Strength A test piece was obtained by adhering the adhesive tapes obtained in Examples and Comparative Examples to the surface of an aluminum foil under the following conditions. Since the adhesive tapes of Example 10, Example 11, Example 13, Example 14, Comparative Example 6 and Comparative Example 7 are thermocompression adhesive tapes, they are pressure-bonded only by heating (130 ° C.). Adhesive tapes other than the above were pressure-bonded at room temperature (25 ° C.) and heating (130 ° C.), respectively. For the obtained test piece, the force (N / 10 mm) required to peel the adhesive tape from the aluminum foil surface using a precision universal testing machine (trade name "Autograph AG-I", manufactured by Shimadzu Corporation) is as follows. It was measured under the conditions and used as the adhesive strength of the adhesive tape.
  • the test piece prepared in (1) above contains ethylene carbonate and diethyl carbonate in a volume ratio (ethylene) containing 1.0 mol / L lithium hexafluorophosphate as an electrolyte.
  • the adhesive solution was immersed in an electrolytic solution obtained by mixing (carbonate: diethyl carbonate) at a ratio of 1: 2 at 80 ° C. for 72 hours, and the adhesive tape was visually observed for floating or peeling. After that, the test piece from which the adhesive tape did not peel off was withdrawn from the electrolytic solution, washed with ethanol, and then the force (N / 10 mm) required to peel off the adhesive tape from the aluminum foil surface by the same method as in (1) above. was measured and used as the adhesive strength in the non-aqueous electrolyte solution.
  • Probe tack value The probe tack value was measured on the surface of the pressure-sensitive adhesive layer by the probe tack method. The probe tack value was measured under the following conditions using a tacking tester (manufactured by Reska). (Measurement condition) Temperature: 25 ° C Probe material: SUS Probe shape: Cylindrical (5 mm ⁇ ) Pressurization (compression) speed: 30 mm / min Measurement (disengagement) speed: 30 mm / min Preload: 100gf Pressurization (compression) time: 1 second
  • the haze value of the adhesive tape was measured by using a haze meter (model number: HM-150, manufactured by Murakami Color Research Institute) by injecting incident light from the adhesive layer surface side. Further, the adhesive tape was stored in an environment of 5 ° C. for 72 hours, and the rate of change in the haze value ((haze value after storage for 72 hours-initial haze value) / initial haze value) was determined.
  • Adhesive squeeze test The adhesive tape cut into 10 mm squares was pressure-bonded onto a SUS plate under the same conditions as in (1) above. Then, the tape was pressed under the following conditions, and the amount of adhesive squeezed out from the end face of the tape was evaluated. Pressurizing condition: 0.4 MPa x 6 hours with the surface temperature of the hot press device set to 130 ° C.
  • Example 1 2-Ethylhexyl acrylate / acrylic acid (95 parts by weight / 5 parts by weight) in a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas introduction tube, and cooler, 0.2 part by weight of benzoyl peroxide as an initiator , 120 parts by weight of ethyl acetate was charged, nitrogen gas was introduced while gently stirring, and the polymerization reaction was carried out for about 6 hours while keeping the liquid temperature in the flask at around 60 ° C., and the acrylic acid-based common weight having a weight average molecular weight of 1.3 million was carried out. The coalescence (1) was obtained.
  • Acrylic copolymer (1) With respect to 75 parts by weight, as a modified olefin resin, a maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyo Boseki Co., Ltd., trade name "Toyo Tuck PMA-L", weight average molecular weight 7. Add 25 parts by weight of an isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate L”) and dilute with toluene to prepare a pressure-sensitive adhesive (1) having a solid content of 15%. did.
  • a maleic anhydride-modified propylene-butene copolymer resin manufactured by Toyo Boseki Co., Ltd., trade name "Toyo Tuck PMA-L”
  • weight average molecular weight 7 weight average molecular weight 7.
  • Add 25 parts by weight of an isocyanate-based cross-linking agent manufactured by Toso Co., Ltd
  • Adhesive tape (1) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 2 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Acrylic copolymer (1) 75 parts by weight, as a modified olefin resin, maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyo Boseki Co., Ltd., trade name "Toyo Tuck PMA-L", weight average molecular weight 7.5 (Million, melting point 70 ° C) 25 parts by weight, hydrogenated derivative of C9 petroleum resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "Arcon P-125", hydrogenation rate: 95%, softening point: 125 ° C) 30 parts by weight , 2 parts by weight of an isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate L”) was added and diluted with toluene to prepare a pressure-sensitive adhesive (2) having a solid content of 15%.
  • Adhesive tape (2) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 3 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyo Boseki Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight: 7) as a modified olefin resin with respect to 75 parts by weight of the acrylic copolymer (1). .50,000, melting point: 90 ° C.) 25 parts by weight, 2 parts by weight of isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate L”), diluted with toluene, adhesive with a solid content of 15% (3) Was prepared.
  • isocyanate-based cross-linking agent manufactured by Toso Co., Ltd., trade name "Coronate L
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 12 ⁇ m) so that the thickness of the adhesive layer after drying is 15 ⁇ m.
  • Adhesive tape (3) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 4 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Maleic anhydride-modified propylene-butene copolymer resin manufactured by Toyo Boseki Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight: 7) as a modified olefin resin with respect to 85 parts by weight of the acrylic copolymer (1).
  • Example 5 As a base material, a polyester film having a thickness of 6 ⁇ m (DuPont Hongji Films Foshan Co. Ltd., trade name “KLBD”) was used, and the thickness of the adhesive layer was set to 3 ⁇ m in the same manner as in Example 4. , An adhesive tape (5) was prepared. The obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 6 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyo Boseki Co., Ltd., trade name "Toyotac PMA-Lz", weight average molecular weight: 10) as a modified olefin resin with respect to 75 parts by weight of the acrylic copolymer (1).
  • Add 25 parts by weight of an isocyanate-based cross-linking agent manufactured by Toso Co., Ltd., trade name "Coronate L"
  • dilute with toluene to prepare a pressure-sensitive adhesive (5) having a solid content of 15%. did.
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 30 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • An adhesive tape (6) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 7 2-Ethylhexyl acrylate / acrylic acid (90 parts by weight / 10 parts by weight) in a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas introduction tube, and cooler, 0.2 part by weight of benzoyl peroxide as an initiator , 120 parts by weight of ethyl acetate was charged, nitrogen gas was introduced while gently stirring, and the polymerization reaction was carried out for about 6 hours while keeping the liquid temperature in the flask at around 60 ° C., and the acrylic acid-based common weight having a weight average molecular weight of 1.2 million was carried out. The coalescence (2) was obtained.
  • Maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyo Boseki Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight: 7) as a modified olefin resin with respect to 85 parts by weight of the acrylic copolymer (2). .50,000, melting point: 70 ° C.) 15 parts by weight, 2 parts by weight of isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate L”), diluted with toluene, adhesive with a solid content of 15% (6) Was prepared.
  • the obtained adhesive is applied onto a base material (polyimide film, manufactured by Toray Industries, Inc., trade name "Kapton 100H", thickness: 25 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • An adhesive tape (7) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 8 2-Ethylhexyl acrylate / acrylic acid (100 parts by weight / 2 parts by weight) in a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas introduction tube, and cooler, 0.2 part by weight of benzoyl peroxide as an initiator , 230 parts by weight of ethyl acetate was charged, nitrogen gas was introduced while gently stirring, and the polymerization reaction was carried out for about 6 hours while keeping the liquid temperature in the flask at around 60 ° C., and the weight average molecular weight of acrylic acid was 650,000.
  • the coalescence (3) was obtained.
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 30 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • An adhesive tape (8) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 9 N-butyl / acrylic acid (95 parts by weight / 5 parts by weight) acrylate in a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas introduction tube, and cooler, 2,2'-azobisiso as an initiator 0.2 parts by weight of butyronitrile and 233 parts by weight of ethyl acetate were charged, nitrogen gas was introduced while gently stirring, the liquid temperature in the flask was maintained at around 60 ° C., and the polymerization reaction was carried out for about 6 hours, and the weight average was obtained. An acrylic copolymer (4) having a molecular weight of 700,000 was obtained.
  • Maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyo Boseki Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight: 7) as a modified olefin resin with respect to 85 parts by weight of the acrylic copolymer (4). .50,000, melting point: 70 ° C.) 15 parts by weight, 2 parts by weight of isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate L”), diluted with toluene, adhesive with a solid content of 15% (8) Was prepared.
  • isocyanate-based cross-linking agent manufactured by Toso Co., Ltd., trade name "Coronate L
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 30 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • An adhesive tape (9) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 10 An acrylic copolymer (2) was obtained in the same manner as in Example 7.
  • Maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyo Boseki Co., Ltd., trade name "Toyotack PMA-L", weight average molecular weight: 7) as a modified olefin resin with respect to 25 parts by weight of the acrylic copolymer (2).
  • Add 75 parts by weight of an isocyanate-based cross-linking agent manufactured by Toso Co., Ltd., trade name "Coronate L"
  • dilute with toluene and add a pressure-sensitive adhesive (9) having a solid content of 15%.
  • the obtained adhesive is applied onto a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 12 ⁇ m) so that the thickness of the adhesive layer after drying is 3 ⁇ m.
  • Adhesive tape (10) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 11 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Maleic anhydride-modified propylene-butene copolymer resin manufactured by Toyo Boseki Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight: 7) as a modified olefin resin with respect to 15 parts by weight of the acrylic copolymer (1).
  • Example 12 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Maleic anhydride-modified propylene-butene copolymer resin manufactured by Toyo Boseki Co., Ltd., trade name "Toyotack PMA-L", weight average molecular weight 7) as a modified olefin resin with respect to 85 parts by weight of the acrylic copolymer (1).
  • Add 15 parts by weight of an aluminum chelate-based cross-linking agent (trade name "Aluminum Chelate A", manufactured by Kawaken Fine Chemicals Co., Ltd.), dilute with toluene, and have a solid content of 15 parts.
  • %% Adhesive (11) was prepared.
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 12 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • An adhesive tape (12) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 13 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Maleic anhydride-modified propylene-butene copolymer resin manufactured by Toyo Boseki Co., Ltd., trade name "Toyotack PMA-L", weight average molecular weight 7) as a modified olefin resin with respect to 15 parts by weight of the acrylic copolymer (1).
  • Add 85 parts by weight of an aluminum chelate-based cross-linking agent (trade name "Aluminum Chelate A", manufactured by Kawaken Fine Chemicals Co., Ltd.), dilute with toluene, and have a solid content of 15 parts.
  • %% Adhesive (12) was prepared.
  • the obtained adhesive is applied onto a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 12 ⁇ m) so that the thickness of the adhesive layer after drying is 5 ⁇ m.
  • An adhesive tape (13) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 14 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyo Boseki Co., Ltd., trade name "Toyotack PMA-T", weight average molecular weight 7) as a modified olefin resin with respect to 25 parts by weight of the acrylic copolymer (1). .50,000, 75 parts by weight of melting point 90 ° C., 0.1 part by weight of epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemicals, trade name "Tetrad C"", diluted with toluene, adhesive with a solid content of 15% ( 13) was prepared.
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 12 ⁇ m) so that the thickness of the adhesive layer after drying is 5 ⁇ m.
  • An adhesive tape (14) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 1 An acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Acrylic copolymer (1) 18 parts by weight of modified rosin resin (manufactured by Harima Kasei Co., Ltd., trade name "Hariester KT-3"), isocyanate-based cross-linking agent (manufactured by Tosoh Co., Ltd., trade name " Coronate L ”) 2 parts by weight was added and diluted with toluene to prepare a pressure-sensitive adhesive (11) having a solid content of 15%.
  • modified rosin resin manufactured by Harima Kasei Co., Ltd., trade name "Hariester KT-3
  • isocyanate-based cross-linking agent manufactured by Tosoh Co., Ltd., trade name " Coronate L ”
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 30 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • An adhesive tape (12) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Example 2 An acrylic copolymer (1) was obtained in the same manner as in Example 1. To 100 parts by weight of the acrylic copolymer (1), 2 parts by weight of an isocyanate-based cross-linking agent (manufactured by Tosoh Corporation, trade name “Coronate L”) is added, diluted with toluene, and a pressure-sensitive adhesive having a solid content of 15% ( 12) was prepared. The obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name “Trefan", thickness: 30 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m. , Adhesive tape (13) was obtained. The obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • an isocyanate-based cross-linking agent manufactured by Tosoh Corporation, trade name "Coronate L
  • a pressure-sensitive adhesive having a solid content of 15% ( 12) was prepared.
  • the obtained adhesive is coated
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 30 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • An adhesive tape (15) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • the obtained adhesive is applied onto a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness 30 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • Adhesive tape (16) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Acrylic copolymer (1) was obtained in the same manner as in Example 1.
  • Acrylic copolymer (1) 25 parts by weight of polyisobutylene resin (manufactured by BASF, trade name "OPPANOL 12SFN", weight average molecular weight: 51,000), isocyanate-based crosslinked as an olefin resin with respect to 75 parts by weight of the acrylic copolymer (1).
  • Two parts by weight of an agent manufactured by Toso Co., Ltd., trade name "Coronate L" was added and diluted with toluene to prepare an adhesive (18) having a solid content of 15%.
  • the obtained adhesive is coated on a base material (polypropylene film, manufactured by Toray Industries, Inc., trade name "Trefan", thickness: 30 ⁇ m) so that the thickness of the adhesive layer after drying is 10 ⁇ m.
  • An adhesive tape (19) was obtained.
  • the obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.
  • Adhesive layer 100 Adhesive tape for non-aqueous batteries

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Abstract

La présente invention concerne un ruban adhésif pour batteries non aqueuses, qui présente une excellente adhésivité dans une solution électrolytique non aqueuse, tout en étant moins collant, et qui est supprimé dans la saillie d'un adhésif.　Un ruban adhésif pour batteries non aqueuses selon la présente invention comporte un matériau de base et une couche adhésive qui est disposée sur au moins un côté du matériau de base ; la couche adhésive contient un adhésif qui présente une adhésivité par compression ; l'adhésif contient un polymère acrylique qui a un groupe fonctionnel acide et une résine cristalline qui a un point de fusion supérieur ou égal à 25 °C ; et la valeur de trouble du ruban adhésif est inférieure ou égale à 20 %.
PCT/JP2020/017372 2019-04-26 2020-04-22 Ruban adhésif pour batteries non aqueuses WO2020218363A1 (fr)

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WO2013133167A1 (fr) * 2012-03-09 2013-09-12 日東電工株式会社 Ruban adhésif
JP2014156505A (ja) * 2013-02-14 2014-08-28 Dic Corp 易接着剤組成物、積層ポリエステル樹脂フィルム及び太陽電池バックシート

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