WO2013133167A1 - Adhesive tape - Google Patents
Adhesive tape Download PDFInfo
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- WO2013133167A1 WO2013133167A1 PCT/JP2013/055685 JP2013055685W WO2013133167A1 WO 2013133167 A1 WO2013133167 A1 WO 2013133167A1 JP 2013055685 W JP2013055685 W JP 2013055685W WO 2013133167 A1 WO2013133167 A1 WO 2013133167A1
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- WIPO (PCT)
- Prior art keywords
- acrylic
- sensitive adhesive
- pressure
- weight
- adhesive tape
- Prior art date
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0431—Cells with wound or folded electrodes
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
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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
- 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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
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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
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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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
- C09J2471/00—Presence of polyether
- C09J2471/006—Presence of polyether in the substrate
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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
- C09J2475/00—Presence of polyurethane
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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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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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
- C09J2481/00—Presence of sulfur containing polymers
- C09J2481/006—Presence of sulfur containing polymers in the substrate
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- 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
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- 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 a pressure-sensitive adhesive tape that can maintain excellent adhesiveness in a non-aqueous battery internal environment.
- a battery in which an electrolyte such as a lithium ion battery is sealed has a purpose of improving the suitability of the electrode in the battery case, and between the electrodes caused by burrs or the like existing in the electrode plate penetrating the separator.
- An adhesive tape is used for the purpose of preventing a short circuit.
- an adhesive tape using an acrylic adhesive or a natural rubber-based adhesive is frequently used (Patent Document 1, etc.).
- the pressure-sensitive adhesive tape may be peeled off from the battery constituent member under the non-aqueous battery internal environment, and may not be able to maintain the effect of preventing a short circuit between the electrodes.
- an object of the present invention is to provide a pressure-sensitive adhesive tape that can be easily attached to a battery component at room temperature and can maintain excellent adhesiveness in a non-aqueous battery internal environment.
- the present inventors have at least 0.5 wt% of the acid group-containing monomer with respect to all monomer components including at least an acrylic urethane polymer and constituting the acrylic pressure-sensitive adhesive.
- the pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive has shape followability unique to acrylic urethane, and the acid group of the acid group-containing monomer has adhesion to inorganic materials such as glass and metal. Therefore, it is possible to exert an extremely excellent adhesive force to the battery constituent member at room temperature, and the above-mentioned excellent adhesive force can be lost even in a non-aqueous battery internal environment (that is, even in a high temperature and high humidity environment). It was found that there was no contact and adherence to the adherend. The present invention has been completed based on these findings.
- this invention provides the adhesive tape which has an adhesive layer containing the following acrylic adhesive on the at least one surface of a base material.
- Acrylic pressure-sensitive adhesive The ratio of the acid group-containing monomer with respect to all monomer components comprising at least an acrylic urethane polymer and constituting the acrylic pressure-sensitive adhesive is 0.5% by weight or more.
- the acrylic adhesive is (1) An acrylic urethane polymer (B1) obtained by mixing and reacting an acrylic polymer (A1) obtained by polymerizing a monomer component containing at least an acid group-containing monomer and a hydroxyl group-containing monomer. Or (2) A mixture of an acrylic polymer (A2) obtained by polymerizing a monomer component containing at least a hydroxyl group-containing monomer and an acrylic polymer (A3) obtained by polymerizing a monomer component containing at least an acid group-containing monomer, Contains acrylic urethane polymer (B2) obtained by mixing and reacting polyisocyanate, or (3) acrylic polymer (A2) obtained by polymerizing monomer component containing at least hydroxyl group-containing monomer and acid group It is preferable that an acrylic urethane polymer (B3) obtained by mixing and reacting a polyisocyanate with a mixture of the polymer (C1).
- the glass transition temperature (Tg) of the acrylic pressure-sensitive adhesive is preferably 25 ° C. or lower.
- the monomer component constituting the acrylic pressure-sensitive adhesive preferably further contains an alkyl group-containing monomer having 4 or more carbon atoms.
- the base material is preferably a plastic base material made of a material selected from polypropylene, polyethylene terephthalate, polyphenylene sulfide, polyimide, and polyetherimide.
- the present invention also provides a non-aqueous battery obtained by sticking the adhesive tape.
- the pressure-sensitive adhesive tape of the present invention Since the pressure-sensitive adhesive tape of the present invention has excellent adhesiveness at room temperature, it can be easily attached to battery components. And it can exhibit the outstanding adhesiveness and adhesiveness to a to-be-adhered body surface also in a non-aqueous battery internal environment, and can maintain it over a long period of time. Therefore, the pressure-sensitive adhesive tape of the present invention has the purpose of preventing the penetration of the separator due to foreign matter, burrs, etc., and the purpose of improving the suitability of the electrode into the battery case (for example, winding the end of the winding type battery) For the purpose and the purpose of preventing the peeling of the active material), it can be suitably used for an application in which it is stuck inside a non-aqueous battery.
- the pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer containing the following acrylic pressure-sensitive adhesive on at least one surface of a substrate.
- Acrylic pressure-sensitive adhesive The ratio of the acid group-containing monomer with respect to all monomer components comprising at least an acrylic urethane polymer and constituting the acrylic pressure-sensitive adhesive is 0.5% by weight or more.
- the pressure-sensitive adhesive layer of the present invention contains at least an acrylic pressure-sensitive adhesive containing at least an acrylic urethane polymer, and the ratio of the acid group-containing monomer to the total monomer component constituting the acrylic pressure-sensitive adhesive is 0.5% by weight or more. To do.
- the acrylic pressure-sensitive adhesive contains, for example, an acrylic urethane polymer (copolymerization type) obtained by mixing and reacting with an acrylic polymer containing both an acid group and a hydroxyl group, and / or an acid group.
- An acrylic urethane polymer (blend type) obtained by mixing and reacting a polyisocyanate with a mixture of an acrylic (or non-acrylic) polymer and an acrylic polymer containing a hydroxyl group.
- the acrylic pressure-sensitive adhesive of the present invention preferably contains at least one selected from the following acrylic urethane polymers (B1) to (B3).
- Acrylic urethane polymer (B1) obtained by mixing and reacting an acrylic polymer (A1) obtained by polymerizing a monomer component containing at least an acid group-containing monomer and a hydroxyl group-containing monomer.
- the polymerization method of the monomer component may be any of alternating copolymerization, random copolymerization, block copolymerization, and graft copolymerization.
- Examples of the acid group-containing monomer include carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, maleic anhydride, and itaconic anhydride. These can be used alone or in combination of two or more.
- (meth) acrylic acid is preferable because it is easy to copolymerize with an acrylic monomer.
- (meth) acryl means “acryl” and / or “methacryl”.
- the content of the acid group-containing monomer is 0.5% by weight or more, preferably 0.5 to 20%, based on the total amount of monomer components (100% by weight) constituting the acrylic pressure-sensitive adhesive. % By weight, particularly preferably 1 to 10% by weight, most preferably 3 to 8% by weight. In the case of a blend type, it is 0.5% by weight or more, preferably 0.5 to 10% by weight, most preferably 0.5% with respect to the total amount (100% by weight) of monomer components constituting the acrylic adhesive. % By weight or more and less than 3% by weight.
- the adhesiveness to an inorganic material such as glass or metal is lowered, and the adhesiveness to the battery constituent member tends to be lowered.
- the content of the acid group-containing monomer exceeds the above range, the viscosity tends to increase or gel, and the productivity tends to decrease.
- the corrosiveness of the metal adherend tends to increase, and the practical properties tend to deteriorate.
- the acid group-containing monomer has an action as a catalyst
- a metal compound such as dibutyltin dilaurate or an amine compound that is usually used as a reaction catalyst. Therefore, problems such as bleed out and contamination caused by outgas, odor, and coloring can be solved, and an adhesive layer having excellent transparency can be formed.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylic acid 6-hydroxyhexyl; vinyl alcohol, allyl alcohol and the like. These can be used alone or in combination of two or more. In the present invention, among them, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable because they are easily copolymerized with an acrylic monomer.
- the content of the hydroxyl group-containing monomer is, for example, about 0.01 to 5% by weight, preferably 0.02% with respect to the total amount of monomer components (100% by weight) constituting the acrylic pressure-sensitive adhesive. It is ⁇ 2% by weight, particularly preferably 0.05 to 1.5% by weight.
- a blend type for example, about 0.01 to 5% by weight, preferably 0.1 to 5% by weight, particularly preferably 2%, based on the total amount (100% by weight) of monomer components constituting the acrylic pressure-sensitive adhesive. ⁇ 5% by weight.
- the content of the hydroxyl group-containing monomer is less than the above range, it is difficult to perform urethane bonding sufficiently, and the shape followability tends to be lowered.
- the content of the hydroxyl group-containing monomer exceeds the above range, the hydrophilicity of the pressure-sensitive adhesive layer tends to be high, and the adhesive force tends to be lowered in the electrolytic solution.
- the monomer component constituting the acrylic pressure-sensitive adhesive of the present invention may contain other monomer components in addition to the acid group-containing monomer and hydroxyl group-containing monomer.
- the inclusion of an alkyl group-containing monomer can improve hydrophobicity and exhibits better adhesion in an electrolyte solution. It is preferable in that it can be performed.
- the alkyl group-containing monomer include n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and pentyl (meth) acrylate.
- Straight chain having 4 or more (for example, about 4 to 20 carbon atoms) of alkyl groups such as heptadecyl
- (meth) acrylic acid alkyl esters having a linear or branched alkyl group having 4 to 12 carbon atoms are preferable, and particularly preferable.
- the content of the alkyl group-containing monomer is, for example, about 50 to 97% by weight, preferably 70 to 97%, based on the total amount of monomer components (100% by weight) constituting the acrylic pressure-sensitive adhesive. % By weight, particularly preferably 85 to 97% by weight, most preferably 90 to 97% by weight.
- the blend type it is, for example, about 50 to 97% by weight, preferably 70 to 97% by weight, particularly preferably 85 to 97% with respect to the total amount (100% by weight) of monomer components constituting the acrylic pressure-sensitive adhesive. % By weight, most preferably 90-97% by weight.
- the monomer component constituting the acrylic pressure-sensitive adhesive of the present invention may further contain other monomer components in addition to the above monomer components.
- examples of other monomer components include vinyl group-containing monomers such as vinyl acetate, vinyl propionate, vinyl ether, styrene, and (meth) acrylonitrile; amide group-containing monomers such as (meth) acrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl ( N-substituted amide group-containing monomers such as (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-octylacrylamide, N-hydroxyethylacrylamide; aminoethyl (meth) acryl
- the content of the other monomer components is preferably, for example, less than 20% by weight, particularly preferably 10% by weight or less, most preferably 7% by weight with respect to the total amount of monomer components (100% by weight) constituting the acrylic pressure-sensitive adhesive. % Or less (for example, 1.0 to 6% by weight, preferably 3.0 to 5.5% by weight, particularly preferably 3.5 to 5.3% by weight).
- Examples of the acrylic polymer (A1) obtained by polymerizing a monomer component containing at least an acid group-containing monomer and a hydroxyl group-containing monomer include, for example, (meth) acryl having at least one alkyl group having 4 to 12 carbon atoms. Examples include an acid alkyl ester, at least one acid group-containing monomer, and a polymer obtained by polymerizing at least one hydroxyl group-containing monomer.
- an alkyl group having 4 to 12 carbon atoms preferably 4 to 10, particularly preferably 4 to 8 is particularly preferable because it is low in cost and easily polymerized.
- a (meth) acrylic acid alkyl ester / (meth) acrylic acid / (meth) acrylic acid 4-hydroxybutyl copolymer having an alkyl group is preferred.
- Examples of the acrylic polymer (A2) obtained by polymerizing a monomer component containing at least a hydroxyl group-containing monomer include (meth) acrylic acid alkyl ester having at least one alkyl group having 4 to 12 carbon atoms, Examples thereof include polymers obtained by polymerizing at least one of the hydroxyl group-containing monomers.
- an alkyl group having 4 to 12 carbon atoms preferably 4 to 10, particularly preferably 4 to 8) is particularly preferable because it is low in cost and easily polymerized.
- Examples of the acrylic polymer (A3) obtained by polymerizing a monomer component containing at least an acid group-containing monomer include, for example, (meth) acrylic acid alkyl ester having at least one alkyl group having 4 to 12 carbon atoms, Examples thereof include polymers obtained by polymerizing at least one of the acid group-containing monomers.
- the acrylic polymer (A3) in the present invention has 4 to 12 carbon atoms (preferably 4 to 10, particularly preferably 4 to 8) in terms of excellent compatibility with the acrylic polymer (A2).
- (Meth) acrylic acid alkyl ester / (meth) acrylic acid copolymer having the following alkyl group is preferred.
- (anhydrous) maleic acid-modified polyolefin for example, (anhydrous) maleic acid-modified polyolefin, (anhydrous) maleic acid-modified styrene-olefin copolymer (for example, SEBS, SEPS, SEEPS, SBS, etc.)
- An acrylic polymer etc. can be mentioned. These can be used alone or in combination of two or more.
- “(maleic anhydride)” means “maleic anhydride” and / or “maleic acid”.
- the acrylic polymers (A1) to (A3) and the acid group-containing polymer (C1) can be prepared by polymerizing monomer components by a known or conventional polymerization method.
- a known or conventional polymerization method for example, solution polymerization method, emulsion polymerization method, bulk Examples thereof include a polymerization method, a polymerization method by active energy ray irradiation (active energy ray polymerization method), and a pressure polymerization method in the presence of a catalyst.
- a solution polymerization method, an active energy ray polymerization method, or a pressure polymerization method is preferable.
- solvents include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methyl Examples thereof include alicyclic hydrocarbons such as cyclohexane; organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
- a solvent can be used individually or in combination of 2 or more types.
- a polymerization initiator can be used.
- the polymerization initiator is not particularly limited and can be appropriately selected from known or commonly used ones.
- the weight average molecular weight (Mw) of the acrylic polymers (A1) to (A3) is preferably, for example, about 10,000 to 3,000,000, and in particular, it is difficult to elute into the electrolyte and can suppress deterioration of the electrolyte. In this respect, about 100,000 to 3 million is preferable.
- the weight average molecular weight (Mw) of the acrylic polymers (A1) to (A3) is below the above range, the cohesive force is inferior, and the pressure-sensitive adhesive layer is deformed in an environment where high pressure is applied, such as when used inside the battery. Glue easily protrudes from the base material and is easily eluted into the electrolytic solution, which tends to cause deterioration of the electrolytic solution.
- the weight average molecular weight of the acrylic polymers (A1) to (A3) can be controlled by adjusting the temperature, time, monomer concentration and the like during the polymerization.
- the weight average molecular weight (Mw) of the acid group-containing polymer (C1) is preferably, for example, about 10,000 to 500,000, and in particular, 10,000 to 250,000 in terms of compatibility with the acrylic polymer (A2). The degree is preferred.
- the weight average molecular weight (Mw) of the acid group-containing polymer (C1) is less than the above range, the resistance to electrolyte solution tends to decrease.
- the weight average molecular weight (Mw) of the acid group-containing polymer (C1) exceeds the above range, the compatibility with the acrylic polymer (A2) is lowered and the stability of physical properties tends to be lowered.
- the weight average molecular weight of the acid group-containing polymer (C1) can be controlled by adjusting the temperature, time, monomer concentration and the like during the polymerization.
- the weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) under the following conditions with reference to standard polystyrene.
- Measurement conditions Apparatus Product name “HLC-8120GPC” (manufactured by TOSHO) Column: TSKgel Super HZM-H / HZ4000 / HZ3000 / HZ2000 Column size: 6.0 mm I.D. D. ⁇ 150mm
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer in the present invention contains polyisocyanate together with a polymer selected from the acrylic polymers (A1) to (A3) and the acid group-containing polymer (C1).
- the hydroxyl group of the acrylic polymer (A1) and / or (A2) reacts with the isocyanate group of the polyisocyanate to form a urethane bond, resulting in excellent shape followability and adhesion to the adherend surface.
- An adhesive layer having adhesiveness can be formed.
- polyisocyanate examples include isocyanurate type polyisocyanate [eg, IPDI (isophorone diisocyanate) isocyanurate, HDI (hexamethylene diisocyanate) isocyanurate, etc.], adduct type polyisocyanate [eg, trimethylol of TDI (tolylene diisocyanate).
- IPDI isophorone diisocyanate
- HDI hexamethylene diisocyanate
- adduct type polyisocyanate eg, trimethylol of TDI (tolylene diisocyanate).
- Propane adduct trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of xylylene diisocyanate (XDI), trimethylolpropane adduct of IPDI (isophorone diisocyanate), etc.]
- biuret type polyisocyanate for example, HDI (Hexamethylene diisocyanate) etc.] and other polyisocyanates obtained from aliphatic and / or alicyclic diisocyanates Mention may be made of the over door or the like. These can be used alone or in combination of two or more.
- an adduct type polyisocyanate such as a trimethylolpropane adduct of TDI or XDI because it is excellent in reactivity with the functional group of the acrylic polymer.
- the amount of polyisocyanate used is, for example, about 0.5 to 20 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the acrylic polymer (A1). It is. Further, for example, about 1 to 20 parts by weight, preferably 2 to 10 parts by weight, and particularly preferably 2 to 5 parts by weight with respect to 100 parts by weight of the acrylic polymer (A2).
- polyisocyanate within the above range, it is possible to provide the pressure-sensitive adhesive layer with excellent shape followability and adhesion to the adherend surface while maintaining transparency.
- the glass transition temperature (Tg) of the acrylic pressure-sensitive adhesive of the present invention is preferably 25 ° C. or less, particularly preferably ⁇ 75 to 10 ° C. from the viewpoint that excellent adhesive force can be imparted to the pressure-sensitive adhesive tape. Most preferably, it is ⁇ 75 to 0 ° C.
- the glass transition temperature (Tg) of the acrylic pressure-sensitive adhesive can be controlled, for example, by adjusting the structure of the main chain of the acrylic polymer and the structure and length of the side chain alkyl chain.
- the glass transition temperature (Tg) of the acrylic pressure-sensitive adhesive in the present invention is determined by differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement.
- the temperature dependence of the loss elastic modulus G ′′ is measured using a dynamic viscoelasticity measuring device (trade name “ARES”, manufactured by Rheometrics) under the following conditions, and the obtained G “The temperature at which the curve becomes maximum was defined as the glass transition temperature (Tg) (° C.). Measurement: Shear mode Temperature range: -70 ° C to 150 ° C Temperature increase rate: 5 ° C / min Frequency: 1Hz
- the content of the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is about 60 to 100% by weight, preferably 80 to 100% by weight, based on the total solid content (100% by weight).
- the content of the acrylic pressure-sensitive adhesive is less than the above range, the adhesiveness and shape followability tend to be lowered.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer of the present invention may contain, for example, a tackifier, a softener, a plasticizer, a filler, an antioxidant and the like.
- tackifier examples include rosin resins and derivatives thereof, polyterpene resins, terpene phenol resins, coumarone-indene resins, petroleum resins, styrene resins, xylene resins, and the like.
- softening agent examples include liquid polyether, glycol ester, liquid polyterpene, liquid polyacrylate, phthalic acid ester, and trimetic acid ester.
- An acid group-containing polymer (C1) is mixed with polyisocyanate and additives used as necessary to prepare an adhesive, and this is applied onto a substrate or an appropriate separator (such as release paper), The method of drying after that can be mentioned.
- the viscosity may be adjusted using a solvent (for example, toluene, xylene, ethyl acetate, methyl ethyl ketone, etc.) as necessary.
- the thickness of the pressure-sensitive adhesive layer in the present invention is, for example, 1 to 45 ⁇ m (preferably 1 to 40 ⁇ m, particularly preferably 1 to 30 ⁇ m, more preferably 3 to 20 ⁇ m, most preferably 5 to 15 ⁇ m).
- the thickness of the pressure-sensitive adhesive layer is less than the above range, the adhesiveness may be insufficient, and it may be difficult to use it for the purpose of bonding to the inside of the battery and preventing a short circuit between the electrodes.
- the thickness of the pressure-sensitive adhesive layer exceeds the above range, deformation of the pressure-sensitive adhesive layer and protrusion of glue from the base material are likely to occur, workability is lowered, and electrolyte deterioration may be easily caused.
- the volume occupied in the battery becomes too large, and it tends to be difficult to increase the capacity of the battery.
- the substrate is not particularly limited, and various substrates can be used, for example, fiber-based substrates such as cloth, nonwoven fabric, felt, and net; paper-based substrates such as various papers; metal foils, Metal-based substrates such as metal plates; plastic-based substrates such as films and sheets made of various resins; rubber-based substrates such as rubber sheets; foams such as foam sheets; and appropriate thin leaves such as laminates thereof Can be used.
- fiber-based substrates such as cloth, nonwoven fabric, felt, and net
- paper-based substrates such as various papers
- metal foils Metal-based substrates such as metal plates
- plastic-based substrates such as films and sheets made of various resins
- rubber-based substrates such as rubber sheets
- foams such as foam sheets
- appropriate thin leaves such as laminates thereof Can be used.
- a plastic base material it is particularly preferable to use a plastic base material.
- plastic base material examples include raw materials such as polyester (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc.), polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.), and polyvinyl.
- Alcohol polyvinylidene chloride, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyamide, polyimide, cellulose, fluororesin, polyether, polyether amide, polyether imide, polyphenylene sulfide, polystyrene series Resins (polystyrene and the like), polycarbonate, polyethersulfone and the like can be mentioned.
- the material or material of the plastic base material can be appropriately selected and used according to the characteristics required for the adhesive tape of the present invention.
- polyolefin particularly polypropylene
- polyester particularly polyethylene terephthalate
- polyphenylene sulfide, polyimide, or polyetherimide is preferable.
- the base material may have a single layer form or may have a multiple layer form.
- a conventional surface treatment for example, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc.
- a conventional surface treatment for example, chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc.
- an oxidation treatment by a chemical or physical method.
- the thickness of the substrate is not particularly limited, but is, for example, about 8 to 100 ⁇ m, preferably 10 to 50 ⁇ m, and particularly preferably 10 to 30 ⁇ m.
- the thickness of the substrate is less than the above range, the strength of the pressure-sensitive adhesive tape becomes too low, which may impair practicality.
- the thickness of the substrate exceeds the above range, the volume occupied in the battery becomes too large, and it is difficult to increase the capacity of the battery.
- the pressure-sensitive adhesive tape of the present invention is obtained by laminating a pressure-sensitive adhesive layer on at least one surface of a substrate.
- 1 and 2 are schematic cross-sectional views showing an example of the pressure-sensitive adhesive tape of the present invention.
- the pressure-sensitive adhesive tape 31 is provided with the pressure-sensitive adhesive layer 2 on one side of the base material 1
- the pressure-sensitive adhesive tape 32 is provided with the pressure-sensitive adhesive layer 21 on one side of the base material 1 and the pressure-sensitive adhesive on the other side.
- a layer 22 is provided.
- a method for forming the pressure-sensitive adhesive tape of the present invention for example, a method for directly forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, or a method for forming the pressure-sensitive adhesive layer on a suitable separator (release paper, etc.)
- Examples include a method in which an adhesive is applied to form an adhesive layer, which is transferred (transferred) to a substrate and laminated.
- a void may remain at the interface with the substrate.
- a heating and pressurizing process can be performed by an autoclave process or the like, and the voids can be diffused and eliminated.
- a conventional coater for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, a direct coater, etc.
- a gravure roll coater for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, a direct coater, etc.
- the pressure-sensitive adhesive tape of the present invention can also be formed by a method in which the base material and the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer are integrated by melt extrusion. Any known technique such as an inflation method or a T-die method can be used for melt extrusion. Further, after the melt extrusion molding, a longitudinal or lateral stretching (uniaxial stretching) treatment, a longitudinal or lateral sequential or simultaneous stretching (biaxial stretching) treatment, or the like may be performed.
- the pressure-sensitive adhesive tape of the present invention may be provided with a separator (release liner) on the surface of the pressure-sensitive adhesive layer from the viewpoint of protecting the surface of the pressure-sensitive adhesive layer and preventing blocking.
- the separator is peeled off when the pressure-sensitive adhesive tape of the present invention is attached to an adherend, and is not necessarily provided.
- the separator to be used is not particularly limited, and a known and commonly used release paper or the like can be used.
- a substrate having a release layer for example, a plastic film or paper surface-treated with a release agent such as silicone, long chain alkyl, fluorine, or molybdenum sulfide
- a release layer for example, a plastic film or paper surface-treated with a release agent such as silicone, long chain alkyl, fluorine, or molybdenum sulfide
- polytetrafluoroethylene polychlorotrifluoro Low adhesion substrate made of fluorine polymer such as ethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer
- nonpolar polymer for example, A low-adhesive base material made of an olefin resin such as polyethylene or polypropylene can be used.
- the separator may be provided on the surface of both pressure-sensitive adhesive layers of the pressure-sensitive adhesive tape of the present invention, or a separator having a back release layer is provided on one pressure-sensitive adhesive surface. By winding the sheet, the back surface release layer of the separator may be in contact with the surface of the pressure-sensitive adhesive layer on the opposite side.
- the pressure-sensitive adhesive tape of the present invention has an excellent adhesive strength at room temperature, and the 180 ° peel-off adhesive strength to an aluminum foil at 25 ° C. is, for example, 0.1 N / 10 mm or more, preferably 0.5 to 5 N / 10 mm, particularly The thickness is preferably 1.2 to 5 N / 10 mm, and most preferably 1.2 to 3 N / 10 mm.
- the adhesive force can be measured by a method based on JIS Z0237 (2000 version).
- the pressure-sensitive adhesive tape of the present invention can maintain excellent adhesiveness even in a non-aqueous battery internal environment.
- the adhesive tape of the present invention is preferably used for the production of a battery in which a non-aqueous electrolyte such as a lithium ion battery is enclosed.
- the non-aqueous battery of the present invention is a battery in which a non-aqueous electrolyte solution such as a lithium ion battery is enclosed, and has the purpose of preventing penetration of the separator due to foreign matter, burrs, etc., and the suitability of filling the electrode into the battery case. It is a battery obtained by adhering the adhesive tape to a battery constituent member for the purpose of improving (for example, the purpose of preventing the end of the winding type battery from being wound or the purpose of preventing the active material from peeling off).
- a non-aqueous battery such as a lithium ion battery has a positive electrode plate coated with a positive electrode active material on a positive electrode core and a negative electrode plate coated with a negative electrode active material on a negative electrode core, which are opposed to each other through a separator. It has a structure in which a wound electrode group obtained by winding in a spiral shape, an electrode terminal drawn from a positive electrode plate and a negative electrode plate, and an electrolyte solution are enclosed in an outer can, for example, the wound electrode group It can be manufactured by being housed in an outer can, further filled with an electrolytic solution, and sealing the injection hole.
- the electrolytic solution is not particularly limited, and examples thereof include cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
- cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
- An electrolyte solution in which a lithium salt such as LiPF 6 is dissolved as an electrolyte can be used in a mixed solvent such as a chain carbonate.
- the adhesion site of the pressure-sensitive adhesive tape of the present invention is not particularly limited as long as the above object can be achieved.
- an electrode plate, an electrode terminal, an electrode plate end of a lithium ion battery, and an electrode plate end of a separator The part which contacts, the edge part of an active material, an end part, etc. can be mentioned (refer FIG. 3).
- the non-aqueous battery of the present invention uses the above adhesive tape having excellent adhesive force even in a high temperature and high humidity environment for the purpose of preventing the penetration of the separator due to foreign matters, burrs, etc. during battery production, and for the electrode in the battery case.
- the battery is bonded to a part that is immersed in or in contact with the electrolytic solution, so that excellent battery characteristics can be exhibited over a long period of time.
- Example 1 n-Butyl acrylate (BA) / acrylic acid (AA) / 2-hydroxyethyl acrylate (HEA) copolymer (100 parts by weight / 5 parts by weight / 0.07 parts by weight, Mw: 2,200,000) and polyisocyanate (product) 2 parts by weight of the name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (1).
- the obtained pressure-sensitive adhesive (1) was applied on the substrate (1) (polypropylene film, trade name “Trephan”, manufactured by Toray Industries, Inc., thickness: 20 ⁇ m) so that the thickness after drying was 10 ⁇ m. It dried and produced the adhesive tape (1).
- Example 2 2-ethylhexyl acrylate / acrylic acid copolymer (100 parts by weight / 5) was added to 75 parts by weight of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, Mw: 550,000). 25 parts by weight, Mw: 1.3 million) was added (blend), and further 2 parts by weight of polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (2).
- An adhesive tape (2) was produced in the same manner as in Example 1 except that the adhesive (2) was used in place of the adhesive (1).
- Example 3 2-ethylhexyl acrylate / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, Mw: 550,000) 85 parts by weight and 2-ethylhexyl acrylate / acrylic acid copolymer (100 parts by weight / 5 parts by weight, Mw: 1.3 million) 15 parts by weight was added (blend), and further 2 parts by weight of polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (3).
- An adhesive tape (3) was produced in the same manner as in Example 1 except that the adhesive (3) was used in place of the adhesive (1).
- Example 4 2-Ethylhexyl acrylate / acrylic acid / 4-hydroxybutyl acrylate (4HBA) copolymer (95 parts by weight / 5 parts by weight / 0.1 part by weight, Mw: 500,000) and polyisocyanate (trade name “Coronate L” ( 2 parts by weight of Nippon Polyurethane Co., Ltd. was added to prepare an adhesive (4).
- An adhesive tape (4) was produced in the same manner as in Example 1 except that the adhesive (4) was used in place of the adhesive (1).
- Example 5 n-Butyl acrylate / acrylic acid / 4-hydroxybutyl acrylate copolymer (95 parts by weight / 5 parts by weight / 1 part by weight, Mw: 850,000) and polyisocyanate (trade name “Coronate L” (Nippon Polyurethane Co., Ltd.) 2 parts by weight were added to prepare an adhesive (5).
- An adhesive tape (5) was produced in the same manner as in Example 1 except that the adhesive (5) was used in place of the adhesive (1).
- Example 6 2-Ethylhexyl acrylate / n-butyl acrylate / acrylic acid / 4-hydroxybutyl acrylate copolymer (45 parts by weight / 45 parts by weight / 5 parts by weight / 0.1 part by weight, Mw: 320,000) and polyisocyanate (product) 2 parts by weight of the name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (6).
- An adhesive tape (6) was produced in the same manner as in Example 1 except that the adhesive (6) was used in place of the adhesive (1).
- Example 7 2-ethylhexyl acrylate / acrylic acid copolymer (100 parts by weight / 5 parts by weight) was added to 75 parts by weight of 2-ethylhexyl acrylate / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, Mw: 550,000). Mw: 1.3 million) 25 parts by weight was added (blend), and further 3 parts by weight of polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (7).
- An adhesive tape (7) was produced in the same manner as in Example 1 except that the adhesive (7) was used in place of the adhesive (1).
- Example 8 n-Butyl acrylate / acrylic acid / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 5 parts by weight / 0.07 parts by weight, Mw: 2.2 million) and polyisocyanate (trade name “Coronate L” (Nippon Polyurethane ( 1 part by weight) was added to prepare an adhesive (8).
- An adhesive tape (8) was produced in the same manner as in Example 1 except that the adhesive (8) was used in place of the adhesive (1).
- Example 9 In the same manner as in Example 4 except that the base material (2) (polyimide film, trade name “Kapton 100H”, manufactured by Toray DuPont Co., Ltd., thickness: 25 ⁇ m) was used instead of the base material (1). An adhesive tape (9) was produced.
- the base material (2) polyimide film, trade name “Kapton 100H”, manufactured by Toray DuPont Co., Ltd., thickness: 25 ⁇ m
- Example 10 Adhesive tape in the same manner as in Example 1 except that the base material (3) (polyester film, trade name “Lumirror”, manufactured by Toray Industries, Inc., thickness: 12 ⁇ m) was used instead of the base material (1). (10) was produced.
- the base material (3) polyester film, trade name “Lumirror”, manufactured by Toray Industries, Inc., thickness: 12 ⁇ m
- Comparative Example 1 Polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) is added to 100 parts by weight of 2-ethylhexyl acrylate / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, Mw: 550,000).
- An adhesive (9) was prepared by adding parts by weight.
- An adhesive tape (11) was produced in the same manner as in Example 1 except that the adhesive (9) was used in place of the adhesive (1).
- An adhesive tape (13) was produced in the same manner as in Example 1 except that the adhesive (11) was used in place of the adhesive (1).
- the adhesive tapes obtained in the examples and comparative examples were subjected to the following tests to evaluate the adhesive strength and the electrolytic solution resistance.
- the pressure-sensitive adhesive tape of the present invention Since the pressure-sensitive adhesive tape of the present invention has excellent adhesiveness at room temperature, it can be easily attached to battery components. And it can exhibit the outstanding adhesiveness and adhesiveness to a to-be-adhered body surface also in a non-aqueous battery internal environment, and can maintain it over a long period of time. Therefore, the pressure-sensitive adhesive tape of the present invention is applied to a non-aqueous battery and used for the purpose of preventing the penetration of the separator due to foreign matter, burrs, etc., and for improving the suitability of the electrode in the battery case. It can be preferably used.
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Abstract
Description
アクリル系粘着剤:アクリルウレタンポリマーを少なくとも含み、且つアクリル系粘着剤を構成する全モノマー成分に対する酸基含有モノマーの割合が0.5重量%以上である That is, this invention provides the adhesive tape which has an adhesive layer containing the following acrylic adhesive on the at least one surface of a base material.
Acrylic pressure-sensitive adhesive: The ratio of the acid group-containing monomer with respect to all monomer components comprising at least an acrylic urethane polymer and constituting the acrylic pressure-sensitive adhesive is 0.5% by weight or more.
(1) 酸基含有モノマーとヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A1)に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B1)を含むか、
(2) ヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A2)と酸基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A3)の混合物に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B2)を含むか、又は
(3) ヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A2)と酸基含有ポリマー(C1)の混合物に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B3)を含むことが好ましい。 The acrylic adhesive is
(1) An acrylic urethane polymer (B1) obtained by mixing and reacting an acrylic polymer (A1) obtained by polymerizing a monomer component containing at least an acid group-containing monomer and a hydroxyl group-containing monomer. Or
(2) A mixture of an acrylic polymer (A2) obtained by polymerizing a monomer component containing at least a hydroxyl group-containing monomer and an acrylic polymer (A3) obtained by polymerizing a monomer component containing at least an acid group-containing monomer, Contains acrylic urethane polymer (B2) obtained by mixing and reacting polyisocyanate, or (3) acrylic polymer (A2) obtained by polymerizing monomer component containing at least hydroxyl group-containing monomer and acid group It is preferable that an acrylic urethane polymer (B3) obtained by mixing and reacting a polyisocyanate with a mixture of the polymer (C1).
アクリル系粘着剤:アクリルウレタンポリマーを少なくとも含み、且つアクリル系粘着剤を構成する全モノマー成分に対する酸基含有モノマーの割合が0.5重量%以上である The pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer containing the following acrylic pressure-sensitive adhesive on at least one surface of a substrate.
Acrylic pressure-sensitive adhesive: The ratio of the acid group-containing monomer with respect to all monomer components comprising at least an acrylic urethane polymer and constituting the acrylic pressure-sensitive adhesive is 0.5% by weight or more.
本発明の粘着剤層には、アクリルウレタンポリマーを少なくとも含み、且つアクリル系粘着剤を構成する全モノマー成分に対する酸基含有モノマーの割合が0.5重量%以上であるアクリル系粘着剤を少なくとも含有する。 [Adhesive layer]
The pressure-sensitive adhesive layer of the present invention contains at least an acrylic pressure-sensitive adhesive containing at least an acrylic urethane polymer, and the ratio of the acid group-containing monomer to the total monomer component constituting the acrylic pressure-sensitive adhesive is 0.5% by weight or more. To do.
(1) 酸基含有モノマーとヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A1)に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B1)
(2) ヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A2)と酸基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A3)の混合物に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B2)
(3) ヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A2)と酸基含有ポリマー(C1)の混合物に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B3) The acrylic pressure-sensitive adhesive of the present invention preferably contains at least one selected from the following acrylic urethane polymers (B1) to (B3).
(1) Acrylic urethane polymer (B1) obtained by mixing and reacting an acrylic polymer (A1) obtained by polymerizing a monomer component containing at least an acid group-containing monomer and a hydroxyl group-containing monomer.
(2) A mixture of an acrylic polymer (A2) obtained by polymerizing a monomer component containing at least a hydroxyl group-containing monomer and an acrylic polymer (A3) obtained by polymerizing a monomer component containing at least an acid group-containing monomer, Acrylic urethane polymer (B2) obtained by mixing and reacting polyisocyanate
(3) Acrylic urethane polymer obtained by mixing and reacting a mixture of an acrylic polymer (A2) obtained by polymerizing a monomer component containing at least a hydroxyl group-containing monomer and an acid group-containing polymer (C1). (B3)
測定条件
装置:商品名「HLC-8120GPC」((株)TOSHO製)
カラム:TSKgel Super HZM-H/HZ4000/HZ3000/HZ2000
カラムサイズ:6.0mmI.D.×150mm
溶離液:テトラヒドロフラン
検出器:RI The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) under the following conditions with reference to standard polystyrene.
Measurement conditions Apparatus: Product name “HLC-8120GPC” (manufactured by TOSHO)
Column: TSKgel Super HZM-H / HZ4000 / HZ3000 / HZ2000
Column size: 6.0 mm I.D. D. × 150mm
Eluent: Tetrahydrofuran Detector: RI
測定:せん断モード
温度範囲:-70℃~150℃
昇温速度:5℃/min
周波数:1Hz In the present invention, the temperature dependence of the loss elastic modulus G ″ is measured using a dynamic viscoelasticity measuring device (trade name “ARES”, manufactured by Rheometrics) under the following conditions, and the obtained G “The temperature at which the curve becomes maximum was defined as the glass transition temperature (Tg) (° C.).
Measurement: Shear mode Temperature range: -70 ° C to 150 ° C
Temperature increase rate: 5 ° C / min
Frequency: 1Hz
基材としては、特に限定されず、各種基材を用いることが可能であり、例えば、布、不織布、フェルト、ネット等の繊維系基材;各種の紙等の紙系基材;金属箔、金属板等の金属系基材;各種樹脂によるフィルムやシート等のプラスチック系基材;ゴムシート等のゴム系基材;発泡シート等の発泡体や、これらの積層体等の適宜な薄葉体を用いることができる。本発明においては、なかでも、プラスチック系基材を使用することが好ましい。 [Base material]
The substrate is not particularly limited, and various substrates can be used, for example, fiber-based substrates such as cloth, nonwoven fabric, felt, and net; paper-based substrates such as various papers; metal foils, Metal-based substrates such as metal plates; plastic-based substrates such as films and sheets made of various resins; rubber-based substrates such as rubber sheets; foams such as foam sheets; and appropriate thin leaves such as laminates thereof Can be used. In the present invention, it is particularly preferable to use a plastic base material.
本発明の粘着テープは、基材の少なくとも一方の面に粘着剤層を積層して得られる。図1、2は本発明の粘着テープの一例を示す概略断面図である。粘着テープ31は、基材1の一方の面に粘着剤層2が設けられており、粘着テープ32は、基材1の一方の面に粘着剤層21が設けられ、他の面に粘着剤層22が設けられている。 [Adhesive tape]
The pressure-sensitive adhesive tape of the present invention is obtained by laminating a pressure-sensitive adhesive layer on at least one surface of a substrate. 1 and 2 are schematic cross-sectional views showing an example of the pressure-sensitive adhesive tape of the present invention. The pressure-
本発明の非水系電池は、リチウムイオン電池等の非水系電解液が封入された電池であって、異物やバリ等によるセパレータの貫通を防止する目的や、電池ケース内への電極の詰め込み適性を改善する目的(例えば、巻回型電池の巻末部を巻き止めする目的、活物質の剥がれを防止する目的)で、上記粘着テープを電池構成部材に貼着して得られる電池である。 [Non-aqueous battery]
The non-aqueous battery of the present invention is a battery in which a non-aqueous electrolyte solution such as a lithium ion battery is enclosed, and has the purpose of preventing penetration of the separator due to foreign matter, burrs, etc., and the suitability of filling the electrode into the battery case. It is a battery obtained by adhering the adhesive tape to a battery constituent member for the purpose of improving (for example, the purpose of preventing the end of the winding type battery from being wound or the purpose of preventing the active material from peeling off).
n-ブチルアクリレート(BA)/アクリル酸(AA)/2-ヒドロキシエチルアクリレート(HEA)共重合体(100重量部/5重量部/0.07重量部、Mw:220万)にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え、粘着剤(1)を調製した。
得られた粘着剤(1)を基材(1)(ポリプロピレンフィルム、商品名「トレファン」、東レ(株)製、厚さ:20μm)上に乾燥後の厚みが10μmになる様に塗布、乾燥し、粘着テープ(1)を作製した。 Example 1
n-Butyl acrylate (BA) / acrylic acid (AA) / 2-hydroxyethyl acrylate (HEA) copolymer (100 parts by weight / 5 parts by weight / 0.07 parts by weight, Mw: 2,200,000) and polyisocyanate (product) 2 parts by weight of the name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (1).
The obtained pressure-sensitive adhesive (1) was applied on the substrate (1) (polypropylene film, trade name “Trephan”, manufactured by Toray Industries, Inc., thickness: 20 μm) so that the thickness after drying was 10 μm. It dried and produced the adhesive tape (1).
2-エチルヘキシルアクリレート(2EHA)/2-ヒドロキシエチルアクリレート共重合体(100重量部/4重量部、Mw:55万)75重量部に2-エチルヘキシルアクリレート/アクリル酸共重合体(100重量部/5重量部、Mw:130万)25重量部を加え(ブレンド)、更にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え、粘着剤(2)を調製した。
粘着剤(1)に代えて粘着剤(2)を使用した以外は実施例1と同様にして、粘着テープ(2)を作製した。 Example 2
2-ethylhexyl acrylate / acrylic acid copolymer (100 parts by weight / 5) was added to 75 parts by weight of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, Mw: 550,000). 25 parts by weight, Mw: 1.3 million) was added (blend), and further 2 parts by weight of polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (2).
An adhesive tape (2) was produced in the same manner as in Example 1 except that the adhesive (2) was used in place of the adhesive (1).
2-エチルヘキシルアクリレート/2-ヒドロキシエチルアクリレート共重合体(100重量部/4重量部、Mw:55万)85重量部に2-エチルヘキシルアクリレート/アクリル酸共重合体(100重量部/5重量部、Mw:130万)15重量部を加え(ブレンド)、更にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え、粘着剤(3)を調製した。
粘着剤(1)に代えて粘着剤(3)を使用した以外は実施例1と同様にして、粘着テープ(3)を作製した。 Example 3
2-ethylhexyl acrylate / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, Mw: 550,000) 85 parts by weight and 2-ethylhexyl acrylate / acrylic acid copolymer (100 parts by weight / 5 parts by weight, Mw: 1.3 million) 15 parts by weight was added (blend), and further 2 parts by weight of polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (3).
An adhesive tape (3) was produced in the same manner as in Example 1 except that the adhesive (3) was used in place of the adhesive (1).
2-エチルヘキシルアクリレート/アクリル酸/4-ヒドロキシブチルアクリレート(4HBA)共重合体(95重量部/5重量部/0.1重量部、Mw:50万)にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え、粘着剤(4)を調製した。
粘着剤(1)に代えて粘着剤(4)を使用した以外は実施例1と同様にして、粘着テープ(4)を作製した。 Example 4
2-Ethylhexyl acrylate / acrylic acid / 4-hydroxybutyl acrylate (4HBA) copolymer (95 parts by weight / 5 parts by weight / 0.1 part by weight, Mw: 500,000) and polyisocyanate (trade name “Coronate L” ( 2 parts by weight of Nippon Polyurethane Co., Ltd. was added to prepare an adhesive (4).
An adhesive tape (4) was produced in the same manner as in Example 1 except that the adhesive (4) was used in place of the adhesive (1).
n-ブチルアクリレート/アクリル酸/4-ヒドロキシブチルアクリレート共重合体(95重量部/5重量部/1重量部、Mw:85万)にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え、粘着剤(5)を調製した。
粘着剤(1)に代えて粘着剤(5)を使用した以外は実施例1と同様にして、粘着テープ(5)を作製した。 Example 5
n-Butyl acrylate / acrylic acid / 4-hydroxybutyl acrylate copolymer (95 parts by weight / 5 parts by weight / 1 part by weight, Mw: 850,000) and polyisocyanate (trade name “Coronate L” (Nippon Polyurethane Co., Ltd.) 2 parts by weight were added to prepare an adhesive (5).
An adhesive tape (5) was produced in the same manner as in Example 1 except that the adhesive (5) was used in place of the adhesive (1).
2-エチルヘキシルアクリレート/n-ブチルアクリレート/アクリル酸/4-ヒドロキシブチルアクリレート共重合体(45重量部/45重量部/5重量部/0.1重量部、Mw:32万)にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え、粘着剤(6)を調製した。
粘着剤(1)に代えて粘着剤(6)を使用した以外は実施例1と同様にして、粘着テープ(6)を作製した。 Example 6
2-Ethylhexyl acrylate / n-butyl acrylate / acrylic acid / 4-hydroxybutyl acrylate copolymer (45 parts by weight / 45 parts by weight / 5 parts by weight / 0.1 part by weight, Mw: 320,000) and polyisocyanate (product) 2 parts by weight of the name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (6).
An adhesive tape (6) was produced in the same manner as in Example 1 except that the adhesive (6) was used in place of the adhesive (1).
2-エチルヘキシルアクリレート/2-ヒドロキシエチルアクリレート共重合体(100重量部/4重量部、Mw:55万)75重量部に2-エチルヘキシルアクリレート/アクリル酸共重合体(100重量部/5重量部、Mw:130万)25重量部を加え(ブレンド)、更にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を3重量部加え、粘着剤(7)を調製した。
粘着剤(1)に代えて粘着剤(7)を使用した以外は実施例1と同様にして、粘着テープ(7)を作製した。 Example 7
2-ethylhexyl acrylate / acrylic acid copolymer (100 parts by weight / 5 parts by weight) was added to 75 parts by weight of 2-ethylhexyl acrylate / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, Mw: 550,000). Mw: 1.3 million) 25 parts by weight was added (blend), and further 3 parts by weight of polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (7).
An adhesive tape (7) was produced in the same manner as in Example 1 except that the adhesive (7) was used in place of the adhesive (1).
n-ブチルアクリレート/アクリル酸/2-ヒドロキシエチルアクリレート共重合体(100重量部/5重量部/0.07重量部、Mw:220万)にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を1重量部加え、粘着剤(8)を調製した。
粘着剤(1)に代えて粘着剤(8)を使用した以外は実施例1と同様にして、粘着テープ(8)を作製した。 Example 8
n-Butyl acrylate / acrylic acid / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 5 parts by weight / 0.07 parts by weight, Mw: 2.2 million) and polyisocyanate (trade name “Coronate L” (Nippon Polyurethane ( 1 part by weight) was added to prepare an adhesive (8).
An adhesive tape (8) was produced in the same manner as in Example 1 except that the adhesive (8) was used in place of the adhesive (1).
基材(1)に代えて基材(2)(ポリイミドフィルム、商品名「カプトン100H」、東レ・デュポン(株)製、厚さ:25μm)を使用した以外は実施例4と同様にして、粘着テープ(9)を作製した。 Example 9
In the same manner as in Example 4 except that the base material (2) (polyimide film, trade name “Kapton 100H”, manufactured by Toray DuPont Co., Ltd., thickness: 25 μm) was used instead of the base material (1). An adhesive tape (9) was produced.
基材(1)に代えて基材(3)(ポリエステルフィルム、商品名「ルミラー」、東レ・(株)製、厚さ:12μm)を使用した以外は実施例1と同様にして、粘着テープ(10)を作製した。 Example 10
Adhesive tape in the same manner as in Example 1 except that the base material (3) (polyester film, trade name “Lumirror”, manufactured by Toray Industries, Inc., thickness: 12 μm) was used instead of the base material (1). (10) was produced.
2-エチルヘキシルアクリレート/2-ヒドロキシエチルアクリレート共重合体(100重量部/4重量部、Mw:55万)100量部にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え粘着剤(9)を調製した。
粘着剤(1)に代えて粘着剤(9)を使用した以外は実施例1と同様にして、粘着テープ(11)を作製した。 Comparative Example 1
Polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) is added to 100 parts by weight of 2-ethylhexyl acrylate / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, Mw: 550,000). An adhesive (9) was prepared by adding parts by weight.
An adhesive tape (11) was produced in the same manner as in Example 1 except that the adhesive (9) was used in place of the adhesive (1).
2-エチルヘキシルアクリレート/2-ヒドロキシエチルアクリレート共重合体(100重量部/4重量部、Mw:55万)95重量部に2-エチルヘキシルアクリレート/アクリル酸共重合体(100重量部/5重量部、Mw:130万)5重量部を加え(ブレンド)、更にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え、粘着剤(10)を調製した。
粘着剤(1)に代えて粘着剤(10)を使用した以外は実施例1と同様にして、粘着テープ(12)を作製した。 Comparative Example 2
2-ethylhexyl acrylate / acrylic acid copolymer (100 parts by weight / 5 parts by weight) was added to 95 parts by weight of 2-ethylhexyl acrylate / 2-hydroxyethyl acrylate copolymer (100 parts by weight / 4 parts by weight, 550,000). Mw: 1.3 million) 5 parts by weight was added (blend), and further 2 parts by weight of polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to prepare an adhesive (10).
An adhesive tape (12) was produced in the same manner as in Example 1 except that the adhesive (10) was used instead of the adhesive (1).
エチルアクリレート(EA)/2-エチルヘキシルアクリレート/メチルメタクリレート(MMA)/アクリル酸/2-ヒドロキシエチルアクリレート共重合体(70重量部/30重量部/5重量部/0.2重量部/0.8重量部、Mw:42万)にポリイソシアネート(商品名「コロネートL」(日本ポリウレタン(株)製)を2重量部加え、粘着剤(11)を調製した。
粘着剤(1)に代えて粘着剤(11)を使用した以外は実施例1と同様にして、粘着テープ(13)を作製した。 Comparative Example 3
Ethyl acrylate (EA) / 2-ethylhexyl acrylate / methyl methacrylate (MMA) / acrylic acid / 2-hydroxyethyl acrylate copolymer (70 parts by weight / 30 parts by weight / 5 parts by weight / 0.2 parts by weight / 0.8 2 parts by weight of polyisocyanate (trade name “Coronate L” (manufactured by Nippon Polyurethane Co., Ltd.) was added to parts by weight and Mw: 420,000 to prepare an adhesive (11).
An adhesive tape (13) was produced in the same manner as in Example 1 except that the adhesive (11) was used in place of the adhesive (1).
精密万能試験機オートグラフ((株)島津製作所製)を使用し、下記条件下で剥離力を測定した。尚、被着体はアルミ箔を使用し、2kgローラーで1往復して貼り合せ、室温で20分静置後に接着力を測定した。
測定条件
剥離速度:300mm/min
剥離角度:180°
剥離温度:常温(25℃) <Adhesion test>
Using a precision universal testing machine Autograph (manufactured by Shimadzu Corporation), the peel force was measured under the following conditions. In addition, the adherend used aluminum foil, it adhered by reciprocating once with a 2 kg roller, and the adhesive force was measured after leaving still at room temperature for 20 minutes.
Measurement conditions Peeling speed: 300mm / min
Peel angle: 180 °
Peeling temperature: normal temperature (25 ° C)
実施例及び比較例で得られた粘着テープをアルミ箔に2kgローラーで1往復して貼り合わせ、室温で20分静置した後、電解液(エチレンカーボネート/ジエチルカーボネート=1/1[v/v])中に浸漬させ、60℃で24時間静置後の粘着テープの剥がれ部分の有無及び、剥がれ部分がある場合はその剥がれ量を測定することにより評価した。尚、剥がれ量は、剥がれ部分の最大長さ(mm)で示す(図4参照)。 <Electrolytic resistance test>
The pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples were bonded to aluminum foil by one reciprocation with a 2 kg roller, and allowed to stand at room temperature for 20 minutes, and then electrolyte solution (ethylene carbonate / diethyl carbonate = 1/1 [v / v ]), And the presence or absence of a peeling portion of the pressure-sensitive adhesive tape after standing at 60 ° C. for 24 hours and the peeling amount were evaluated by measuring the peeling amount. In addition, the amount of peeling is shown by the maximum length (mm) of a peeling part (refer FIG. 4).
2、21、22 粘着剤層
3、31、32 粘着テープ
4 電極端子
5 正極板
6 負極板
7 セパレータ
8 活物質
9 アルミ箔
10A 粘着テープ剥がれ部分
10B 粘着テープ密着部分
11 剥がれ部分の最大長さ DESCRIPTION OF
Claims (6)
- 基材の少なくとも一方の面に、下記アクリル系粘着剤を含む粘着剤層を有する粘着テープ。
アクリル系粘着剤:アクリルウレタンポリマーを少なくとも含み、且つアクリル系粘着剤を構成する全モノマー成分に対する酸基含有モノマーの割合が0.5重量%以上である An adhesive tape having an adhesive layer containing the following acrylic adhesive on at least one surface of a substrate.
Acrylic pressure-sensitive adhesive: The ratio of the acid group-containing monomer with respect to all monomer components comprising at least an acrylic urethane polymer and constituting the acrylic pressure-sensitive adhesive is 0.5% by weight or more. - 前記アクリル系粘着剤が、
(1) 酸基含有モノマーとヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A1)に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B1)を含むか、
(2) ヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A2)と酸基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A3)の混合物に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B2)を含むか、又は
(3) ヒドロキシル基含有モノマーを少なくとも含むモノマー成分を重合して得られるアクリル系ポリマー(A2)と酸基含有ポリマー(C1)の混合物に、ポリイソシアネートを混合し反応させることにより得られるアクリルウレタンポリマー(B3)を含む請求項1に記載の粘着テープ。 The acrylic adhesive is
(1) An acrylic urethane polymer (B1) obtained by mixing and reacting an acrylic polymer (A1) obtained by polymerizing a monomer component containing at least an acid group-containing monomer and a hydroxyl group-containing monomer. Or
(2) A mixture of an acrylic polymer (A2) obtained by polymerizing a monomer component containing at least a hydroxyl group-containing monomer and an acrylic polymer (A3) obtained by polymerizing a monomer component containing at least an acid group-containing monomer, Contains acrylic urethane polymer (B2) obtained by mixing and reacting polyisocyanate, or (3) acrylic polymer (A2) obtained by polymerizing monomer component containing at least hydroxyl group-containing monomer and acid group The pressure-sensitive adhesive tape according to claim 1, comprising an acrylic urethane polymer (B3) obtained by mixing and reacting a polyisocyanate with a mixture of the polymer (C1). - アクリル系粘着剤のガラス転移温度(Tg)が25℃以下である請求項1に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1, wherein the acrylic pressure-sensitive adhesive has a glass transition temperature (Tg) of 25 ° C or lower.
- アクリル系粘着剤を構成するモノマー成分として、更に炭素数4以上のアルキル基含有モノマーを含む請求項1又は2に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1 or 2, further comprising an alkyl group-containing monomer having 4 or more carbon atoms as a monomer component constituting the acrylic pressure-sensitive adhesive.
- 基材が、ポリプロピレン、ポリエチレンテレフタレート、ポリフェニレンサルファイド、ポリイミド、及びポリエーテルイミドから選択される素材で構成されるプラスチック系基材である請求項1~4の何れか1項に記載の粘着テープ。 The pressure-sensitive adhesive tape according to any one of claims 1 to 4, wherein the base material is a plastic base material made of a material selected from polypropylene, polyethylene terephthalate, polyphenylene sulfide, polyimide, and polyetherimide.
- 請求項1~5の何れか1項に記載の粘着テープを貼着して得られる非水系電池。 A nonaqueous battery obtained by sticking the adhesive tape according to any one of claims 1 to 5.
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KR1020147022484A KR101544685B1 (en) | 2012-03-09 | 2013-03-01 | Pressure-sensitive adhesive tape |
CN201380012584.8A CN104159987B (en) | 2012-03-09 | 2013-03-01 | Self adhesive tape |
JP2014503814A JP5639733B2 (en) | 2012-03-09 | 2013-03-01 | Adhesive tape |
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Also Published As
Publication number | Publication date |
---|---|
TWI488938B (en) | 2015-06-21 |
KR20140138127A (en) | 2014-12-03 |
JP5639733B2 (en) | 2014-12-10 |
JPWO2013133167A1 (en) | 2015-07-30 |
KR101544685B1 (en) | 2015-08-13 |
CN104159987B (en) | 2015-12-09 |
CN104159987A (en) | 2014-11-19 |
TW201343865A (en) | 2013-11-01 |
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