WO2017082418A1 - Adhesive tape - Google Patents

Adhesive tape Download PDF

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Publication number
WO2017082418A1
WO2017082418A1 PCT/JP2016/083594 JP2016083594W WO2017082418A1 WO 2017082418 A1 WO2017082418 A1 WO 2017082418A1 JP 2016083594 W JP2016083594 W JP 2016083594W WO 2017082418 A1 WO2017082418 A1 WO 2017082418A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
adhesive tape
base material
Prior art date
Application number
PCT/JP2016/083594
Other languages
French (fr)
Japanese (ja)
Inventor
茂樹 河邊
下川　大輔
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to EP16864379.9A priority Critical patent/EP3375834A4/en
Priority to CN201680065866.8A priority patent/CN108350327A/en
Priority to US15/772,174 priority patent/US20180316045A1/en
Priority claimed from JP2016220382A external-priority patent/JP6883973B2/en
Publication of WO2017082418A1 publication Critical patent/WO2017082418A1/en

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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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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.
  • a secondary battery includes an electrode member that includes a positive electrode, a negative electrode, and a porous separator disposed between the positive electrode and the negative electrode.
  • the electrode member it is necessary to fix the electrode (positive electrode, negative electrode) and the separator.
  • a method in which the end of the separator is fused to the electrode for example, Patent Document 1
  • the adhesive is directly coated on the separator.
  • a method of bonding the separator and the electrode for example, Patent Document 2 is known.
  • the method of fusing the end portions has a problem that the position of the electrode and the separator is likely to be shifted during battery manufacture, and a problem that the separator is easily contracted when the battery is used.
  • the adhesive may hinder the permeability of the electrolytic solution to the separator.
  • a drying process for a long time is needed, and there exists a problem that manufacturing efficiency worsens besides a separator being damaged by heating.
  • the present invention has been made in order to solve the above-described conventional problems, and the object of the present invention is to be used for fixing an electrode and a separator in the production of a secondary battery, and the permeability of the electrolyte solution to the separator It is providing the adhesive tape which can fix a separator and an electrode favorably, maintaining this.
  • the pressure-sensitive adhesive tape of the present invention comprises a first substrate and a pressure-sensitive adhesive layer formed on the first substrate so as to be peelable, and the pressure-sensitive adhesive layer is patterned. Is formed.
  • the pressure-sensitive adhesive tape of the present invention comprises a first substrate and a pressure-sensitive adhesive laminate formed on the first substrate so as to be peelable.
  • a pressure-sensitive adhesive layer is formed by patterning, including a base material and a pressure-sensitive adhesive layer formed on both sides of the second base material.
  • the above-mentioned adhesive layer contains a heat welding type adhesive.
  • the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive having a swelling degree with respect to the non-aqueous electrolyte solution of 5 to 200%.
  • the pressure-sensitive adhesive layer is formed in a dot shape. In one embodiment, the area ratio of the pressure-sensitive adhesive layer is 5% to 90% with respect to the area of the first base material. In one embodiment, the pressure-sensitive adhesive layer has a thickness of 1 ⁇ m to 30 ⁇ m. In one embodiment, the tack value in 25 degreeC of the said adhesive layer is 10 N or less. In one embodiment, the peeling force in 23 degreeC at the time of peeling a said 1st base material from the said adhesive layer is 2.00 N / 50mm or less. In one embodiment, the said adhesive tape is stuck and used for a separator at the time of non-aqueous secondary battery manufacture.
  • the pressure-sensitive adhesive tape of the present invention is configured such that a patterned pressure-sensitive adhesive layer can be transferred to an adherend.
  • the adhesive tape which can fix a separator and an electrode favorably can be obtained, maintaining the permeability of the electrolyte solution with respect to a separator.
  • a separator and an electrode can be fixed simply and easily, and the production efficiency in battery manufacture can be improved.
  • (A) is a schematic plan view of the adhesive tape by one Embodiment of this invention
  • (b) is a schematic sectional drawing of the adhesive tape by one embodiment of this invention. It is a schematic sectional drawing of the adhesive tape by one Embodiment of this invention. It is a schematic plan view which shows the example of the pattern shape of the adhesion layer in one embodiment of this invention.
  • FIG. 1 (b) is a schematic plan view of a pressure-sensitive adhesive tape according to one embodiment of the present invention
  • FIG. 1 (b) a schematic sectional view of a pressure-sensitive adhesive tape according to one embodiment of the present invention It is.
  • the pressure-sensitive adhesive tape 100 includes a first base material 10 and a pressure-sensitive adhesive layer 21.
  • the pressure-sensitive adhesive layer 21 is detachably formed on the first base material 10.
  • the pressure-sensitive adhesive layer 21 is formed by patterning on the first base material 10.
  • “Peelable” means that the pressure-sensitive adhesive layer 21 can be transferred to an adherend (eg, a polypropylene film).
  • the adhesive tape of the present invention may be provided with a release liner on the outside of the adhesive layer for the purpose of protecting the adhesive surface until it is used.
  • FIG. 2 is a schematic sectional view of an adhesive tape according to another embodiment of the present invention.
  • the pressure-sensitive adhesive tape 200 includes a first base material 10 and a pressure-sensitive adhesive laminate 20 that is detachably formed on the first base material.
  • the pressure-sensitive adhesive laminate 20 includes a second base material 22 and pressure-sensitive adhesive layers 21 and 21 ′ formed on both sides of the second base material 22. Also in this adhesive tape 200, the adhesive layer is formed in a pattern.
  • a release liner may be provided outside the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface until it is used.
  • the pressure-sensitive adhesive tape of the present invention can be used for bonding two adherends together. More specifically, after the pressure-sensitive adhesive tape is attached to one adherend (for example, a separator), the first base material is peeled off to transfer the pressure-sensitive adhesive layer to the adherend. The other adherend (for example, electrode) is laminated on the adhesive layer thus transferred, and the two adherends are bonded together.
  • the pressure-sensitive adhesive tape of the present invention is used by being attached to a separator (for example, a separator made of polypropylene, polyethylene, etc.) at the time of manufacturing a secondary battery (for example, a non-aqueous secondary battery).
  • this separator and an electrode (for example, the positive electrode for non-aqueous batteries, a negative electrode, etc.) can be bonded together.
  • the adherend can be bonded without depending on the pressure-sensitive adhesive coating, and the bonding process can be simplified.
  • the pressure-sensitive adhesive layer is patterned in the pressure-sensitive adhesive tape of the present invention.
  • the separator used in the battery is made porous so that ions can move.
  • the adhesive tape of the present invention in which the adhesive layer is patterned is used to separate the separator. This prevents the pores from being blocked and maintains the permeability of the electrolyte to the separator.
  • a separator and an electrode can be fixed favorably. Furthermore, the shrinkage of the separator during battery use can be effectively prevented.
  • the peeling force at 23 ° C. when peeling the first substrate from the pressure-sensitive adhesive layer is preferably 2.00 N / 50 mm or less, more preferably 0.01 to 1.00 N / 50 mm. is there. If it is such a range, the adhesive tape which can be favorably transferred with respect to a separator or an electrode can be obtained.
  • the “peeling force at 23 ° C. when peeling the first substrate from the adhesive layer” can be measured with an existing tensile tester such as Autograph AG-I manufactured by Shimadzu Corporation. It is measured under conditions of speed: 300 mm / min and peeling angle: 180 °.
  • the shear adhesive force at 25 ° C. when the electrode sheet of the nonaqueous battery and the porous film are bonded together by the adhesive layer (patterned adhesive layer) constituting the adhesive tape of the present invention is preferably 1 0.85 N / cm 2 or more, more preferably 2.00 N / cm 2 or more.
  • the shear adhesive force is less than 1.85 N / cm 2 , problems such as separation of the separator and electrode and separation of these members may occur during the non-aqueous battery manufacturing process.
  • the higher the shear adhesive force, the better, but the upper limit is, for example, 500 N / cm 2 .
  • the pressure-sensitive adhesive layer is formed without unevenness by patterning, the pressure-sensitive adhesive layer is excellent in shear adhesive strength.
  • the shear adhesive strength can be measured with an existing tensile tester such as Autograph AG-I manufactured by Shimadzu Corporation.
  • a porous film is used as a separator, and the porosity is generally 30 to 80%.
  • the porosity change of the porous sheet (porosity before transfer (%) ⁇ porosity after transfer (% )) Is preferably 50% or less, more preferably 0% to 30%.
  • the air permeability of the separator can be maintained by forming the patterned pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer is formed by patterning.
  • the pattern shape any appropriate shape can be taken as long as the pressure-sensitive adhesive layer is formed so as to cover only a part of the first substrate.
  • Examples of the pattern shape of the pressure-sensitive adhesive layer include dot shapes (FIGS. 3A to 3E), stripe shapes (FIG. 3F), lattice shapes (FIG. 3G), hairline shapes, and the like. A combination etc. are mentioned.
  • the pattern-shaped components (for example, dots forming a dot shape, lines forming a stripe shape or a lattice shape) are preferably distributed over the entire area of the first substrate.
  • the pressure-sensitive adhesive layer may be formed in a dot shape.
  • Such an adhesive layer pattern can be formed, for example, by spraying an adhesive.
  • the distance between the dots is, for example, 0.1 to 100 mm, and preferably 1 to 50 mm. If it is such a range, when the adhesive layer is transferred to the separator, the pores of the separator are more effectively prevented from being blocked, and the permeability of the electrolytic solution to the separator can be increased.
  • the separator since the pressure-sensitive adhesive layer is formed without unevenness by patterning the pressure-sensitive adhesive layer, the separator can be prevented from shrinking.
  • the area ratio of the pressure-sensitive adhesive layer is preferably 5% to 90%, more preferably 10% to 80%, still more preferably 20% to the area of the first substrate. 50%.
  • the pores of the separator are prevented from being blocked, and the permeability of the electrolytic solution to the separator is maintained.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m to 30 ⁇ m, more preferably 3 ⁇ m to 10 ⁇ m. If it is such a range, the adhesive layer which is excellent in the adhesive force with respect to an electrode and a separator can be formed.
  • the tack value at 25 ° C. of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape of the present invention is preferably 10 N or less, more preferably 8 N or less, and particularly preferably 5 N or less. When the tack value exceeds 10 N, the handling property in the nonaqueous battery manufacturing process may be deteriorated.
  • the tack value is preferably as small as possible, and the lower limit is, for example, 0N.
  • the tack value is measured by a probe tack method using a tacking tester manufactured by Resta Corporation.
  • the pressure-sensitive adhesive layer includes a heat-welding pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer containing the heat-welding type pressure-sensitive adhesive does not exhibit pressure-sensitive adhesive properties at room temperature, and develops pressure-sensitive adhesive properties when heated (for example, by heating at 40 ° C. to 150 ° C.).
  • a pressure-sensitive adhesive tape having excellent handling properties in the battery manufacturing process can be obtained.
  • the said adhesive layer may contain a pressure sensitive adhesive.
  • the above heat-welding type adhesive contains any appropriate base polymer as long as the effects of the present invention can be obtained.
  • Examples of the base polymer contained in the heat-welding pressure-sensitive adhesive include thermoplastic elastomers.
  • the thermoplastic elastomer content is preferably 80 to 100 parts by weight, more preferably 90 parts by weight, with respect to 100 parts by weight of the base polymer in the heat welding adhesive. -100 parts by weight, more preferably 95-100 parts by weight. If it is such a range, it is excellent in adhesiveness and can obtain the adhesive tape excellent in adherend retainability also in electrolyte solution.
  • the softening point of the thermoplastic elastomer is preferably 100 ° C. or less, more preferably 30 ° C. to 100 ° C., further preferably 50 ° C. to 95 ° C., and particularly preferably 60 ° C. to 95 ° C. If it is such a range, the damage to the to-be-adhered body by the heating at the time of sticking can be reduced, and the adhesive tape which is excellent in workability
  • the softening point can be measured by a ring and ball measurement method, a thermomechanical analysis method (TMA), or the like.
  • thermoplastic elastomer examples include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1
  • thermoplastic elastomer examples include, for example, a homopolymer of the monomer component; a random polymer or block polymer of two or more monomer components selected from the monomer components; a random of the monomer component and other monomer components, Block or graft polymer; and mixtures thereof.
  • the thermoplastic elastomer is a random polymer or block polymer composed of ⁇ -olefin and / or styrene.
  • thermoplastic elastomers include linear short-chain branched polyethylene (LLDPE), ethylene-propylene copolymer, propene-butene copolymer, ethylene-styrene copolymer, ethylene-butene-styrene copolymer. And an ethylene-propylene-styrene copolymer. If such a thermoplastic elastomer is used, an adhesive tape excellent in adhesiveness can be obtained.
  • thermoplastic elastomer Commercially available products may be used as the thermoplastic elastomer.
  • thermoplastic elastomers for example, trade names “Aron Melt PPET1600” manufactured by Toa Gosei Co., Ltd .; trade names “Clayton Polymer FG1924GT”, “Clayton Polymer FG1901X” manufactured by Kraton Polymer Japan; trade names manufactured by Asahi Kasei Chemicals “Tuff Tech M1913”, “Tuff Tech M1943”; trade names “Toyo Tack PMA-L” manufactured by Toyobo Co., Ltd.
  • an acid-modified thermoplastic elastomer a carbonyl-modified thermoplastic elastomer, a hydroxyl group-modified thermoplastic elastomer, an amine-modified thermoplastic elastomer, or the like is used as the thermoplastic elastomer.
  • acid-modified thermoplastic elastomers are preferably used.
  • the acid-modified thermoplastic elastomer can be obtained by graft polymerization of an unsaturated carboxylic acid and / or an acid anhydride thereof on the thermoplastic elastomer. More specifically, the acid-modified thermoplastic elastomer can be formed, for example, by bonding an unsaturated carboxylic acid as a side chain and / or an acid anhydride thereof to a thermoplastic elastomer as a main chain.
  • the graft ratio of the acid-modified thermoplastic elastomer can be appropriately adjusted by a known melt-kneading method.
  • the graft ratio of the acid-modified thermoplastic elastomer is, for example, 0.05% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight with respect to the thermoplastic elastomer to be grafted. If it is such a range, the adhesive layer which has moderate adhesive force can be formed as an adhesive layer which bonds a separator and an electrode together.
  • the above heat-welding type adhesive may further contain a tackifier.
  • tackifiers include rosin derivative resins, polyterpene resins, petroleum resins, and oil-soluble phenol resins.
  • petroleum resins aromatic petroleum resins, aliphatic petroleum resins, etc.
  • a hydrogenated petroleum resin saturated aliphatic hydrocarbon resin or aromatic hydrocarbon resin is preferable because it has low reactivity with the electrolyte component and hardly causes deterioration of the electrolyte solution.
  • the softening point of the tackifier is preferably 100 ° C to 150 ° C, more preferably 110 ° C to 140 ° C, and further preferably 115 ° C to 135 ° C.
  • the content of the tackifier is preferably 5 to 50 parts by weight, more preferably 10 parts by weight with respect to 100 parts by weight of the base polymer in the heat welding adhesive.
  • Part to 30 parts by weight more preferably 15 parts to 30 parts by weight.
  • the pressure-sensitive adhesive contains any appropriate adhesive base polymer as long as the effects of the present invention can be obtained.
  • Examples of the base polymer contained in the pressure-sensitive adhesive include acrylic resins, rubber resins, and silicone resins.
  • acrylic resin examples include an acrylic resin obtained by polymerizing a monomer component containing a (meth) acrylic acid alkyl ester.
  • examples of the (meth) acrylic acid alkyl ester include n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and (meth) acrylic.
  • Pentyl acid isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth) Nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, (meth) acrylic Acid tetradecyl, (meth) acrylic acid pentadecyl, (meth) acrylic Linear or branched alkyl groups having 4 to 20 carbon atoms such as hexadecyl, heptadecyl (meth) acryl
  • the content ratio of the alkyl (meth) acrylate is preferably 50 to 100 parts by weight, more preferably 70 to 100 parts by weight with respect to 100 parts by weight of the monomer component used for the polymerization of the acrylic resin. Part.
  • the acrylic resin contains structural units derived from other monomers copolymerizable with the alkyl (meth) acrylate as necessary for the purpose of modifying cohesive strength, heat resistance, crosslinkability and the like. May be.
  • examples of such other monomers include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and carboxyethyl acrylate; acid anhydrides such as maleic anhydride and itaconic anhydride Group-containing monomers; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide Amide monomers such as N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolprop
  • hydroxyl group- or carboxyl group-containing monomer is preferably used, and more preferably 2-hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate or acrylic acid (AA).
  • the content ratio of the hydroxyl group-containing monomer is preferably less than 10 parts by weight, more preferably 5 parts by weight or less, and further preferably 2 parts by weight with respect to 100 parts by weight of the monomer component used for the polymerization of the acrylic resin. Or less.
  • the content of the carboxyl group-containing monomer is preferably less than 20 parts by weight and more preferably 5 parts by weight or less with respect to 100 parts by weight of the monomer component used for the polymerization of the acrylic resin.
  • the acrylic resin preferably has a weight average molecular weight of 50,000 to 5,000,000, more preferably 100,000 to 2,000,000, and still more preferably 200,000 to 1,500,000.
  • the weight average molecular weight is less than 50,000, the pressure-sensitive adhesive component may be eluted in the non-aqueous electrolyte solution.
  • a weight average molecular weight exceeds 5 million, there exists a possibility that sufficient adhesiveness may not be expressed.
  • the weight average molecular weight is measured by GPC (gel permeation chromatography). The measurement conditions are as follows. The weight average molecular weight was calculated in terms of polystyrene.
  • Measuring device HLC-8120GPC (product name, manufactured by Tosoh Corporation) Column: TSKgel GMH-H (S) x 2 (product number, manufactured by Tosoh Corporation) Flow rate: 0.5ml / min Injection volume: 100 ⁇ l Column temperature: 40 ° C Eluent: THF Injection sample concentration: 0.1% by weight Detector: Differential refractometer
  • Natural rubber resins isoprene rubber, polyisobutylene rubber, butyl rubber, ethylene / propylene rubber, styrene / butadiene rubber, styrene / isoprene rubber, styrene / ethylene / propylene / styrene rubber, styrene / isoprene / styrene Block copolymer, styrene / butadiene / styrene block copolymer, styrene / ethylene / butylene / styrene block copolymer, styrene / ethylene / propylene / styrene block copolymer, styrene / ethylene / propylene block copolymer, recycled Examples thereof include rubber and synthetic rubber resins (including block copolymers and random copolymers) such as modified products thereof. These rubber resins may
  • silicone resin for example, silicone rubber or silicone resin mainly composed of organopolysiloxane, or a crosslinking agent such as a siloxane crosslinking agent or a peroxide crosslinking agent is added to the silicone rubber or the silicone resin. And the like.
  • an electrolytic solution for example, LiPF 6 and / or LiBF 4 as an electrolyte and cyclic carbonates such as ethylene carbonate and propylene carbonate as solvents, diethyl carbonate
  • An adhesive that can swell in an electrolytic solution containing a solvent obtained by mixing a chain carbonate such as ethyl methyl carbonate at any appropriate ratio is used. If an electrode member composed of a separator and an electrode is formed using a pressure-sensitive adhesive that can swell in the electrolyte solution, the electrode member will swell in the electrolyte solution when used in a battery. Excellent vibration control.
  • Such an effect is particularly useful in a form in which the patterned pressure-sensitive adhesive layer is transferred to the adherend, that is, in a form in which the pressure-sensitive adhesive layer is not formed on the entire surface of the adherend.
  • the adhesive that can swell in the electrolytic solution have a high affinity with non-aqueous electrolytic solutions such as acrylic adhesives, urethane adhesives, and silicone adhesives having an alkyl group having 4 or less carbon atoms in the side chain. An adhesive is mentioned.
  • the pressure-sensitive adhesive that can swell in the electrolytic solution has a degree of swelling with respect to the non-aqueous electrolytic solution of preferably 5 to 200%, more preferably 10 to 100%, and even more preferably 30 to 150%.
  • the pressure-sensitive adhesive layer may contain any appropriate additive as necessary.
  • the additive include a crosslinking agent, a tackifier, a plasticizer (for example, trimellitic acid ester plasticizer, pyromellitic acid ester plasticizer), pigment, dye, filler, anti-aging agent, conductive material. , Ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, solvents and the like.
  • the 1st base material may be comprised from arbitrary appropriate materials, as long as the said adhesive layer can be formed so that peeling is possible.
  • the first substrate include fiber-based substrates such as woven fabric and nonwoven fabric; paper-based substrates; plastic-based substrates such as resin films.
  • the base material may be a multilayer structure. When a base material has a form of a multilayer, each layer may be the same base material and may combine a different base material.
  • the thickness of the first base material is preferably 25 ⁇ m to 75 ⁇ m. If it is such a range, the adhesive tape excellent in workability
  • Second Base Material Any appropriate material can be used as the material constituting the second base material.
  • the second substrate include fiber-based substrates such as woven fabrics and nonwoven fabrics; paper-based substrates; plastic-based substrates such as resin films.
  • a plastic base material in that it is difficult to dissolve in the electrolytic solution and cause deterioration of the electrolytic solution, and in particular, a plastic type formed from polyimide, polyphenylene sulfide, or polyolefin (for example, polypropylene). It is preferable to use a substrate.
  • a plastic base material formed from polypropylene because it is inexpensive.
  • the second substrate may be a multilayer substrate. When a base material has a form of a multilayer, each layer may be the same base material and may combine a different base material.
  • the thickness of the second base material is, for example, 10 to 50 ⁇ m.
  • the said adhesive tape may be manufactured by arbitrary appropriate methods.
  • the pressure-sensitive adhesive tape can be obtained by applying a pressure-sensitive adhesive layer forming composition on the first substrate.
  • the adhesive tape is formed by coating the adhesive layer forming composition on both surfaces of the second substrate to form an adhesive layer, and bonding the one adhesive layer and the first substrate together. May be manufactured.
  • the composition for forming a pressure-sensitive adhesive layer contains the above pressure-sensitive adhesive and any appropriate additive.
  • the pressure-sensitive adhesive layer-forming composition is applied by a method such as screen printing, spray coating, gravure coating, flexographic coating, or die coater to form a patterned pressure-sensitive adhesive layer.
  • Example 1 4-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 inlet tube, and condenser, and 0.2 parts by weight of benzoyl peroxide as an initiator Then, 120 parts by weight of ethyl acetate was added, nitrogen gas was introduced while gently stirring, and the polymerization temperature was kept at around 60 ° C. for about 6 hours to carry out a polymerization reaction, and an acrylic copolymer having a weight average molecular weight of 1.3 million Combined (1) was obtained.
  • a 10% pressure-sensitive adhesive (1) was prepared. Dot the pressure-sensitive adhesive composition (1) on a first base material (made by Toray Film Processing Co., Ltd., trade name “Therapy MD”, thickness: 38 ⁇ m) composed of a polyester resin. It was applied to the shape.
  • a first base material made by Toray Film Processing Co., Ltd., trade name “Therapy MD”, thickness: 38 ⁇ m
  • Example 2 An adhesive tape (2) was obtained in the same manner as in Example 1, except that the thickness of the adhesive layer was 30 ⁇ m.
  • Example 3 Hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Chemicals Co., Ltd., trade name “Tuftec M1913” weight average molecular weight: 110,000) 100 parts by weight, alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Ltd.) , Trade name "Alcon P125”) and 30 parts by weight of toluene were added to obtain a heat-welded pressure-sensitive adhesive (1) having a solid content of 10%.
  • the said heat welding type adhesive (1) was apply
  • the coating layer is dried, and the first base material and a pressure-sensitive adhesive layer formed by patterning on the first base material in the form of dots (thickness: 1 ⁇ m, area ratio of the pressure-sensitive adhesive layer: 50%) , Dot spacing: 5 mm) was obtained.
  • Example 4 An adhesive tape (4) was obtained in the same manner as in Example 4 except that the thickness of the adhesive layer was 3 ⁇ m and the ratio of the total area of dots to the area of the first substrate was 30%.
  • Example 5 100 parts by weight of polyolefin pressure-sensitive adhesive (manufactured by Toyobo Co., Ltd., trade name “Toyotac PMA-L”, weight average molecular weight 80,000) and alicyclic saturated hydrocarbon resin (produced by Arakawa Chemical Industries, Ltd., trade name “Arcon”) P125 ”) and 30 parts by weight of toluene were added to obtain a heat-welded pressure-sensitive adhesive (2) having a solid content of 10%.
  • the said heat welding adhesive was apply
  • the coating layer is dried, and the first base material and a pressure-sensitive adhesive layer formed by patterning on the first base material in the form of dots (thickness: 1 ⁇ m, area ratio of the pressure-sensitive adhesive layer: 50%) , Dot spacing: 50 mm) was obtained.
  • Example 6 An adhesive tape (6) was obtained in the same manner as in Example 5 except that the thickness of the adhesive layer was 3 ⁇ m.
  • a polymerization reaction was carried out for 6 hours to obtain an acrylic copolymer (2) having a weight average molecular weight of 500,000.
  • 100 parts by weight of acrylic copolymer (2), 2 parts by weight of polyisocyanate compound (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.), tackifier resin Sumilite resin 12603N (manufactured by Sumitomo Bakelite Co., Ltd.) 20 Part by weight and toluene were added to obtain a heat-welding pressure-sensitive adhesive (3) having a solid content of 10%.
  • the said heat welding type adhesive (3) was apply
  • Example 8 100 parts by weight of rubber-based pressure-sensitive adhesive (BASF Japan Co., Ltd., trade name Opanol B80 weight average molecular weight 750,000) as a low molecular weight component (BASF Japan Co., Ltd. trade name Opanol B12SFN, weight average molecular weight 50,000) 30 parts by weight Toluene was added to obtain a pressure-sensitive adhesive (2) having a solid content of 10%.
  • the said adhesive (2) was apply
  • 1st base material Mitsubishi Resin Co., Ltd. make, brand name "Diafoil MRF", thickness: 38 micrometers
  • the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed in a stripe pattern on the first base material (thickness: 25 ⁇ m, area ratio of the pressure-sensitive adhesive layer: 70) %, Stripe interval: 100 mm).
  • Rubber pressure-sensitive adhesive (trade name Opanol B50 manufactured by BASF Japan Ltd., weight average molecular weight 340,000) and 100 parts by weight of an alicyclic saturated hydrocarbon resin (trade name “Alcon P125” manufactured by Arakawa Chemical Industries, Ltd.) 30 By weight, toluene was added to obtain an adhesive (3) having a solid content of 15%.
  • the said adhesive (3) was apply
  • the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed on the first base material in a stripe pattern (thickness: 10 ⁇ m, area ratio of the pressure-sensitive adhesive layer: 40%) , Stripe interval: 20 mm) was obtained.
  • an initiator 0.2 parts by weight of 2,2-azodiisobutyronitrile and 150 parts by weight of ethyl acetate were added, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was kept at around 60 ° C.
  • a polymerization reaction was performed for 6 hours to obtain an acrylic copolymer (3) having a weight average molecular weight of 1.1 million.
  • an acrylic copolymer (3) having a weight average molecular weight of 1.1 million.
  • a polyisocyanate compound trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.
  • ethyl acetate are added, and a pressure-sensitive adhesive (4 )
  • the said adhesive (4) was apply
  • the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed in a dot pattern on the first base material (thickness: 3 ⁇ m, area ratio of the pressure-sensitive adhesive layer: 10%) , Dot interval: 10 mm) was obtained.
  • a polyisocyanate compound (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) and ethyl acetate are added to form a pressure-sensitive adhesive (5 )
  • the said adhesive (4) was apply
  • the coating layer is dried, and the first base material and a pressure-sensitive adhesive layer formed by patterning on the first base material in the form of dots (thickness: 1 ⁇ m, area ratio of the pressure-sensitive adhesive layer: 50%) , Dot interval: 5 mm) was obtained.
  • Example 12 An adhesive tape (12) was obtained in the same manner as in Example 11 except that the thickness of the adhesive layer was 3 ⁇ m.
  • Ethyl acetate was added to 100 parts by weight of an acrylic pressure-sensitive adhesive (trade name Clarity LA2140, weight average molecular weight 80,000 manufactured by Kuraray Co., Ltd.) to obtain a heat-welded pressure-sensitive adhesive (4) having a solid content of 15%.
  • the heat welding type adhesive (4) was apply
  • the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed by patterning on the first base material in a stripe shape (thickness: 5 ⁇ m, area ratio of the pressure-sensitive adhesive layer: 30%) , Stripe interval: 5 mm) was obtained.
  • Example 14 An adhesive tape (14) was obtained in the same manner as in Example 1 except that the thickness of the adhesive layer was 50 ⁇ m.
  • Example 15 An adhesive tape (15) was obtained in the same manner as in Example 1 except that the dot area ratio was 2%.
  • Tack value The 1st base material was peeled from the said test body a, and the tack value was measured by the probe tack method about the exposed adhesive layer surface. The tack value was measured under the following conditions using a tacking tester (manufactured by Resuka Co., Ltd.). ⁇ Measurement conditions> Temperature: 25 ° C Probe material: SUS Probe shape: cylindrical (5mm ⁇ ) Pressurization (compression) speed: 30 mm / min Measurement (separation) speed: 30 mm / min Preload: 100gf Pressurization (compression) time: 1 second
  • Shear adhesive strength With respect to the specimen A, a precision universal testing machine (manufactured by Shimadzu Corporation, trade name “Autograph AG-I”) was used at a temperature of 25 ° C. and a tensile speed of 300 mm / min. Shear adhesive strength (positive electrode / separator) was measured. Further, for the test specimen B, the shear adhesive strength (negative electrode / separator) was measured by the same method as described above. In Table 1, the shear adhesive strength per unit adhesive area is shown (N / cm 2 ).
  • the adhesive tape of the present invention can be suitably used as an adhesive tape for fixing a separator and an electrode in an electrode member of a secondary battery.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided is an adhesive tape to be used for securing an electrode and a separator when producing a secondary cell, it being possible with the adhesive tape to secure the separator and electrode to an excellent degree while maintaining the ability of an electrolyte to permeate the separator. According to one embodiment, this adhesive tape is provided with a first base material and an adhesive layer detachably formed on the first base material, the adhesive layer being formed by patterning.

Description

粘着テープAdhesive tape
　本発明は、粘着テープに関する。 The present invention relates to an adhesive tape.
　一般に、２次電池は、正極と、負極と、該正極と負極との間に配置された多孔質セパレーターとからなる電極部材を含む。該電極部材においては、電極（正極、負極）とセパレーターとを固定する必要があり、例えば、セパレーターの端部を電極に融着させる方法（例えば、特許文献１）、セパレーターに接着剤を直接コーティングした後、セパレーターと電極とを貼り合せる方法（例えば、特許文献２）等が知られている。しかしながら、端部を融着させる方法においては、電池製造時に電極とセパレーターとの位置ずれが生じやすいという問題、および、電池使用時にセパレーターの収縮が生じやすいという問題がある。これらの現象は、正極と負極とが接触して発生する内部短絡の原因となる。また、接着剤を直接コーティングする方法においては、接着剤が、セパレーターに対する電解液の浸透性を阻害するおそれがある。また、接着剤のコーティングにより上記部材を製造する場合、長時間の乾燥工程が必要となり、加熱によりセパレーターがダメージを受ける他、製造効率が悪くなるという問題がある。 Generally, a secondary battery includes an electrode member that includes a positive electrode, a negative electrode, and a porous separator disposed between the positive electrode and the negative electrode. In the electrode member, it is necessary to fix the electrode (positive electrode, negative electrode) and the separator. For example, a method in which the end of the separator is fused to the electrode (for example, Patent Document 1), and the adhesive is directly coated on the separator. Then, a method of bonding the separator and the electrode (for example, Patent Document 2) is known. However, the method of fusing the end portions has a problem that the position of the electrode and the separator is likely to be shifted during battery manufacture, and a problem that the separator is easily contracted when the battery is used. These phenomena cause an internal short circuit that occurs when the positive electrode and the negative electrode come into contact with each other. Further, in the method of directly coating the adhesive, the adhesive may hinder the permeability of the electrolytic solution to the separator. Moreover, when manufacturing the said member by coating of an adhesive agent, a drying process for a long time is needed, and there exists a problem that manufacturing efficiency worsens besides a separator being damaged by heating.
特開２０００－１７３６４２号公報JP 2000-173642 A 特開２００１－３５７８３９号公報JP 2001-357839 A
　本発明は上記従来の課題を解決するためになされたものであり、その目的とするところは、２次電池製造の際に電極とセパレーターとの固定に用いられ得、セパレーターに対する電解液の浸透性を維持させつつ、セパレーターと電極とを良好に固定し得る粘着テープを提供することにある。 The present invention has been made in order to solve the above-described conventional problems, and the object of the present invention is to be used for fixing an electrode and a separator in the production of a secondary battery, and the permeability of the electrolyte solution to the separator It is providing the adhesive tape which can fix a separator and an electrode favorably, maintaining this.
　１つの実施形態において、本発明の粘着テープは、第１の基材と、該第１の基材上に剥離可能に形成された粘着剤層とを備え、該粘着剤層が、パターン化して形成されている。
　別の実施形態において、本発明の粘着テープは、第１の基材と、該第１の基材上に剥離可能に形成された粘着積層体とを備え、該粘着積層体が、第２の基材と、該第２の基材の両側に形成された粘着剤層とを含み、粘着剤層が、パターン化して形成されている。
　１つの実施形態においては、上記粘着剤層が、熱溶着型粘着剤を含む。
　１つの実施形態においては、上記粘着剤層が、非水系電解液に対する膨潤度が、５～２００％である粘着剤を含む。
　１つの実施形態においては、上記粘着剤層が、ドット状に形成されている。
　１つの実施形態においては、上記粘着剤層の面積割合が、第１の基材の面積に対して、５％～９０％である。
　１つの実施形態においては、上記粘着剤層の厚みが、１μｍ～３０μｍである。
　１つの実施形態においては、上記粘着剤層の２５℃におけるタック値が、１０Ｎ以下である。
　１つの実施形態においては、上記粘着剤層から前記第１の基材を剥離する際の２３℃における剥離力が、２．００Ｎ／５０ｍｍ以下である。
　１つの実施形態においては、上記粘着テープは、非水系２次電池製造時に、セパレーターに貼着して用いられる。 In one embodiment, the pressure-sensitive adhesive tape of the present invention comprises a first substrate and a pressure-sensitive adhesive layer formed on the first substrate so as to be peelable, and the pressure-sensitive adhesive layer is patterned. Is formed.
In another embodiment, the pressure-sensitive adhesive tape of the present invention comprises a first substrate and a pressure-sensitive adhesive laminate formed on the first substrate so as to be peelable. A pressure-sensitive adhesive layer is formed by patterning, including a base material and a pressure-sensitive adhesive layer formed on both sides of the second base material.
In one embodiment, the above-mentioned adhesive layer contains a heat welding type adhesive.
In one embodiment, the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive having a swelling degree with respect to the non-aqueous electrolyte solution of 5 to 200%.
In one embodiment, the pressure-sensitive adhesive layer is formed in a dot shape.
In one embodiment, the area ratio of the pressure-sensitive adhesive layer is 5% to 90% with respect to the area of the first base material.
In one embodiment, the pressure-sensitive adhesive layer has a thickness of 1 μm to 30 μm.
In one embodiment, the tack value in 25 degreeC of the said adhesive layer is 10 N or less.
In one embodiment, the peeling force in 23 degreeC at the time of peeling a said 1st base material from the said adhesive layer is 2.00 N / 50mm or less.
In one embodiment, the said adhesive tape is stuck and used for a separator at the time of non-aqueous secondary battery manufacture.
　本発明の粘着テープは、パターン化された粘着剤層が、被着体に対して転写可能なように構成される。このような構成とすることにより、セパレーターに貼着した際、セパレーターに対する電解液の浸透性を維持させつつ、セパレーターと電極とを良好に固定し得る粘着テープを得ることができる。また、本発明の粘着テープを用いれば、セパレーターと電極とを簡便容易に固定することができ、電池製造における生産効率を向上させることができる。 The pressure-sensitive adhesive tape of the present invention is configured such that a patterned pressure-sensitive adhesive layer can be transferred to an adherend. By setting it as such a structure, when sticking to a separator, the adhesive tape which can fix a separator and an electrode favorably can be obtained, maintaining the permeability of the electrolyte solution with respect to a separator. Moreover, if the adhesive tape of this invention is used, a separator and an electrode can be fixed simply and easily, and the production efficiency in battery manufacture can be improved.
（ａ）は本発明の１つの実施形態による粘着テープの概略平面図であり、（ｂ）は本発明の１つの実施形態による粘着テープの概略断面図である。(A) is a schematic plan view of the adhesive tape by one Embodiment of this invention, (b) is a schematic sectional drawing of the adhesive tape by one embodiment of this invention. 本発明の１つの実施形態による粘着テープの概略断面図である。It is a schematic sectional drawing of the adhesive tape by one Embodiment of this invention. 本発明の１つの実施形態における粘着層のパターン形状の例を示す概略平面図である。It is a schematic plan view which shows the example of the pattern shape of the adhesion layer in one embodiment of this invention.
Ａ．粘着テープの全体構成
　図１（ａ）は、本発明の１つの実施形態による粘着テープの概略平面図であり、図１（ｂ）は、本発明の１つの実施形態による粘着テープの概略断面図である。粘着テープ１００は、第１の基材１０と、粘着剤層２１とを備える。粘着剤層２１は、第１の基材１０上に剥離可能に形成されている。また、粘着剤層２１は、第１の基材１０上でパターン化して形成されている。なお、「剥離可能」とは、粘着剤層２１が、被着体（例えば、ポリプロピレンフィルム）に転写され得ることを意味する。図示していないが、本発明の粘着テープは、使用に供するまでの間、粘着面を保護する目的で、粘着剤層の外側に剥離ライナーが設けられていてもよい。 A. Overall adhesive tape diagram 1 (a) is a schematic plan view of a pressure-sensitive adhesive tape according to one embodiment of the present invention, FIG. 1 (b), a schematic sectional view of a pressure-sensitive adhesive tape according to one embodiment of the present invention It is. The pressure-sensitive adhesive tape 100 includes a first base material 10 and a pressure-sensitive adhesive layer 21. The pressure-sensitive adhesive layer 21 is detachably formed on the first base material 10. The pressure-sensitive adhesive layer 21 is formed by patterning on the first base material 10. “Peelable” means that the pressure-sensitive adhesive layer 21 can be transferred to an adherend (eg, a polypropylene film). Although not shown, the adhesive tape of the present invention may be provided with a release liner on the outside of the adhesive layer for the purpose of protecting the adhesive surface until it is used.
　図２は、本発明の別の実施形態による粘着テープの概略断面図である。粘着テープ２００は、第１の基材１０と、第１の基材上に剥離可能に形成された粘着積層体２０とを備える。粘着積層体２０は、第２の基材２２と、第２の基材２２の両側に形成された粘着剤層２１、２１’を含む。この粘着テープ２００においても、粘着剤層は、パターン化して形成されている。また、図示していないが、使用に供するまでの間、粘着面を保護する目的で、粘着剤層の外側に剥離ライナーが設けられていてもよい。 FIG. 2 is a schematic sectional view of an adhesive tape according to another embodiment of the present invention. The pressure-sensitive adhesive tape 200 includes a first base material 10 and a pressure-sensitive adhesive laminate 20 that is detachably formed on the first base material. The pressure-sensitive adhesive laminate 20 includes a second base material 22 and pressure-sensitive adhesive layers 21 and 21 ′ formed on both sides of the second base material 22. Also in this adhesive tape 200, the adhesive layer is formed in a pattern. Although not shown, a release liner may be provided outside the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface until it is used.
　本発明の粘着テープは、２つの被着体を貼り合せるために用いられ得る。より具体的には、上記粘着テープを一方の被着体（例えば、セパレーター）に貼着した後、第１の基材を剥離することにより、粘着剤層を該被着体に転写する。このようにして転写された粘着剤層に他方の被着体（例えば、電極）を積層して、２つの被着体を貼り合せる。１つの実施形態においては、本発明の粘着テープは、２次電池（例えば、非水系２次電池）製造時に、セパレーター（例えば、ポリプロピレン、ポリエチレン等から構成されるセパレーター）に貼着して用いられ、これにより、該セパレーターと電極（例えば、非水系電池用正極、負極等）とを貼り合せることができる。本発明の粘着テープによれば、粘着剤のコーティングによらずに被着体を貼り合せることができ、貼り合せ工程の簡略化が可能となる。 The pressure-sensitive adhesive tape of the present invention can be used for bonding two adherends together. More specifically, after the pressure-sensitive adhesive tape is attached to one adherend (for example, a separator), the first base material is peeled off to transfer the pressure-sensitive adhesive layer to the adherend. The other adherend (for example, electrode) is laminated on the adhesive layer thus transferred, and the two adherends are bonded together. In one embodiment, the pressure-sensitive adhesive tape of the present invention is used by being attached to a separator (for example, a separator made of polypropylene, polyethylene, etc.) at the time of manufacturing a secondary battery (for example, a non-aqueous secondary battery). Thereby, this separator and an electrode (for example, the positive electrode for non-aqueous batteries, a negative electrode, etc.) can be bonded together. According to the pressure-sensitive adhesive tape of the present invention, the adherend can be bonded without depending on the pressure-sensitive adhesive coating, and the bonding process can be simplified.
　上記のとおり、本発明の粘着テープにおいては、粘着剤層がパターン化されている。電池に用いられるセパレーターは、イオンの移動が可能なように多孔質化されているが、セパレーターと電極とを貼り合せる際、粘着剤層がパターン化された本願発明の粘着テープを用いれば、セパレーターの孔の閉塞が防止されて、セパレーターに対する電解液の浸透性が維持される。また、粘着剤層の形成位置が所定の箇所（例えば、端部）に偏ることもないため、セパレーターと電極とを良好に固定することができる。さらに、電池使用時のセパレーターの収縮も有効に防止し得る。 As described above, the pressure-sensitive adhesive layer is patterned in the pressure-sensitive adhesive tape of the present invention. The separator used in the battery is made porous so that ions can move. However, when the separator and the electrode are bonded together, the adhesive tape of the present invention in which the adhesive layer is patterned is used to separate the separator. This prevents the pores from being blocked and maintains the permeability of the electrolyte to the separator. Moreover, since the formation position of an adhesive layer does not deviate to a predetermined location (for example, edge part), a separator and an electrode can be fixed favorably. Furthermore, the shrinkage of the separator during battery use can be effectively prevented.
　上記粘着テープにおいて、粘着剤層から第１の基材を剥離する際の２３℃における剥離力は、好ましくは２．００Ｎ／５０ｍｍ以下であり、より好ましくは０．０１～１．００Ｎ／５０ｍｍである。このような範囲であれば、セパレーターまたは電極に対して、良好に転写し得る粘着テープを得ることができる。「粘着剤層から第１の基材を剥離する際の２３℃における剥離力」は、（株）島津製作所製のオートグラフＡＧ－Ｉなどの既存の引張試験機により測定することができ、引張速度：３００ｍｍ／ｍｉｎ、剥離角度：１８０°の条件で測定される。 In the pressure-sensitive adhesive tape, the peeling force at 23 ° C. when peeling the first substrate from the pressure-sensitive adhesive layer is preferably 2.00 N / 50 mm or less, more preferably 0.01 to 1.00 N / 50 mm. is there. If it is such a range, the adhesive tape which can be favorably transferred with respect to a separator or an electrode can be obtained. The “peeling force at 23 ° C. when peeling the first substrate from the adhesive layer” can be measured with an existing tensile tester such as Autograph AG-I manufactured by Shimadzu Corporation. It is measured under conditions of speed: 300 mm / min and peeling angle: 180 °.
　本発明の粘着テープを構成する粘着剤層（パターン化された粘着剤層）により、非水系電池の電極シートと多孔質フィルムとを貼り合せた際の２５℃におけるせん断粘着力は、好ましくは１．８５Ｎ／ｃｍ２以上であり、より好ましくは２．００Ｎ／ｃｍ２以上である。当該せん断粘着力が、１．８５Ｎ／ｃｍ２未満の場合、非水系電池製造工程中で、セパレーターと電極とがズレる、これらの部材が剥離する等の問題が生じるおそれがある。当該せん断粘着力は、高いほど好ましいが、その上限値は、例えば、５００Ｎ／ｃｍ２である。本発明においては、パターン化することにより粘着剤層が偏りなく形成されているため、該粘着剤層はせん断粘着力に優れる。せん断粘着力は、（株）島津製作所製のオートグラフＡＧ－Ｉなどの既存の引張試験機により測定することができる。 The shear adhesive force at 25 ° C. when the electrode sheet of the nonaqueous battery and the porous film are bonded together by the adhesive layer (patterned adhesive layer) constituting the adhesive tape of the present invention is preferably 1 0.85 N / cm 2 or more, more preferably 2.00 N / cm 2 or more. When the shear adhesive force is less than 1.85 N / cm 2 , problems such as separation of the separator and electrode and separation of these members may occur during the non-aqueous battery manufacturing process. The higher the shear adhesive force, the better, but the upper limit is, for example, 500 N / cm 2 . In the present invention, since the pressure-sensitive adhesive layer is formed without unevenness by patterning, the pressure-sensitive adhesive layer is excellent in shear adhesive strength. The shear adhesive strength can be measured with an existing tensile tester such as Autograph AG-I manufactured by Shimadzu Corporation.
　非水系電池には、セパレーターとして多孔質フィルムが用いられ、一般にその気孔率は３０～８０％である。上記粘着テープの第１の基材から、当該多孔質フィルムに、粘着剤層を転写した際、該多孔質シートの気孔率変化（転写前の気孔率（％）－転写後の気孔率（％））は、好ましくは５０％以下であり、より好ましくは０％～３０％である。本発明においては、パターン化された粘着剤層が形成されていることにより、セパレーター（多孔質フィルム）の通気性を維持することができる。 For non-aqueous batteries, a porous film is used as a separator, and the porosity is generally 30 to 80%. When the pressure-sensitive adhesive layer was transferred from the first substrate of the pressure-sensitive adhesive tape to the porous film, the porosity change of the porous sheet (porosity before transfer (%) − porosity after transfer (% )) Is preferably 50% or less, more preferably 0% to 30%. In the present invention, the air permeability of the separator (porous film) can be maintained by forming the patterned pressure-sensitive adhesive layer.
Ｂ．粘着剤層
　上記のとおり、粘着剤層は、パターン化されて形成される。パターン形状としては、第１の基材の一部のみが覆われるようにして粘着剤層が形成される限り、任意の適切な形状をとり得る。粘着剤層のパターン形状としては、例えば、ドット状（図３（ａ）～（ｅ））、ストライプ状（図３（ｆ））、格子状（図３（ｇ））、ヘアライン状、これらの組み合わせ等が挙げられる。パターン形状の構成要素（例えば、ドット形状を形成するドット、ストライプ形状または格子形状を形成するライン）は、第１の基材上の全域に分布していることが好ましい。１つの実施形態において、粘着剤層は、ドット状に形成され得る。このような粘着剤層パターンは、例えば、粘着剤をスプレー塗布して形成することができる。ドット状にパターンを形成した場合、ドットとドットとの間隔は、例えば、０．１～１００ｍｍであり、好ましくは１～５０ｍｍである。このような範囲であれば、セパレーターに粘着剤層を転写した際に、セパレーターの孔の閉塞がより有効に防止されて、セパレーターに対する電解液の浸透性を高くすることができる。本発明においては、粘着剤層をパターン化することにより粘着剤層が偏りなく形成されているため、セパレーターの収縮を防止することができる。 B. As described above, the pressure-sensitive adhesive layer is formed by patterning. As the pattern shape, any appropriate shape can be taken as long as the pressure-sensitive adhesive layer is formed so as to cover only a part of the first substrate. Examples of the pattern shape of the pressure-sensitive adhesive layer include dot shapes (FIGS. 3A to 3E), stripe shapes (FIG. 3F), lattice shapes (FIG. 3G), hairline shapes, and the like. A combination etc. are mentioned. The pattern-shaped components (for example, dots forming a dot shape, lines forming a stripe shape or a lattice shape) are preferably distributed over the entire area of the first substrate. In one embodiment, the pressure-sensitive adhesive layer may be formed in a dot shape. Such an adhesive layer pattern can be formed, for example, by spraying an adhesive. When the pattern is formed in a dot shape, the distance between the dots is, for example, 0.1 to 100 mm, and preferably 1 to 50 mm. If it is such a range, when the adhesive layer is transferred to the separator, the pores of the separator are more effectively prevented from being blocked, and the permeability of the electrolytic solution to the separator can be increased. In the present invention, since the pressure-sensitive adhesive layer is formed without unevenness by patterning the pressure-sensitive adhesive layer, the separator can be prevented from shrinking.
　平面視において、粘着剤層の面積割合は、第１の基材の面積に対して、好ましくは５％～９０％であり、より好ましくは１０％～８０％であり、さらに好ましくは２０％～５０％である。このような範囲であれば、セパレーターに粘着剤層を転写した際に、セパレーターの孔の閉塞が防止されて、セパレーターに対する電解液の浸透性が維持される。 In plan view, the area ratio of the pressure-sensitive adhesive layer is preferably 5% to 90%, more preferably 10% to 80%, still more preferably 20% to the area of the first substrate. 50%. Within such a range, when the pressure-sensitive adhesive layer is transferred to the separator, the pores of the separator are prevented from being blocked, and the permeability of the electrolytic solution to the separator is maintained.
　粘着剤層の厚みは、好ましくは１μｍ～３０μｍであり、より好ましくは３μｍ～１０μｍである。このような範囲であれば、電極およびセパレーターに対する粘着力に優れる粘着剤層を形成することができる。 The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 30 μm, more preferably 3 μm to 10 μm. If it is such a range, the adhesive layer which is excellent in the adhesive force with respect to an electrode and a separator can be formed.
　本発明の粘着テープを構成する上記粘着剤層の２５℃におけるタック値は、好ましくは１０Ｎ以下であり、より好ましくは８Ｎ以下であり、特に好ましくは５Ｎ以下である。当該タック値が、１０Ｎを超えると、非水系電池製造工程中でのハンドリング性が悪くなるおそれがある。当該タック値は小さいほど好ましく、その下限値は、例えば、０Ｎである。なお、上記タック値は、プローブタック法により、（株）レスタ社製のタッキング試験機を使用して、測定される。 The tack value at 25 ° C. of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape of the present invention is preferably 10 N or less, more preferably 8 N or less, and particularly preferably 5 N or less. When the tack value exceeds 10 N, the handling property in the nonaqueous battery manufacturing process may be deteriorated. The tack value is preferably as small as possible, and the lower limit is, for example, 0N. The tack value is measured by a probe tack method using a tacking tester manufactured by Resta Corporation.
　１つの実施形態においては、上記粘着剤層は、熱溶着型粘着剤を含む。熱溶着型粘着剤を含む粘着剤層は、常温では粘着性を示さず、加熱することにより（例えば、４０℃～１５０℃での加熱により）粘着性を発現する。このような粘着剤層を用いれば、電池製造工程上でのハンドリング性に優れる粘着テープを得ることができる。また、別の実施形態においては、上記粘着剤層は、感圧型粘着剤を含み得る。 In one embodiment, the pressure-sensitive adhesive layer includes a heat-welding pressure-sensitive adhesive. The pressure-sensitive adhesive layer containing the heat-welding type pressure-sensitive adhesive does not exhibit pressure-sensitive adhesive properties at room temperature, and develops pressure-sensitive adhesive properties when heated (for example, by heating at 40 ° C. to 150 ° C.). By using such a pressure-sensitive adhesive layer, a pressure-sensitive adhesive tape having excellent handling properties in the battery manufacturing process can be obtained. Moreover, in another embodiment, the said adhesive layer may contain a pressure sensitive adhesive.
　上記熱溶着型粘着剤は、本発明の効果が得られる限りにおいて、任意の適切なベースポリマーを含む。熱溶着型粘着剤に含まれるベースポリマーとしては、例えば、熱可塑性エラストマーが挙げられる。 The above heat-welding type adhesive contains any appropriate base polymer as long as the effects of the present invention can be obtained. Examples of the base polymer contained in the heat-welding pressure-sensitive adhesive include thermoplastic elastomers.
　上記熱溶着型粘着剤において、熱可塑性エラストマーの含有割合は、熱溶着型粘着剤中のベースポリマー１００重量部に対して、好ましくは８０重量部～１００重量部であり、より好ましくは９０重量部～１００重量部であり、さらに好ましくは９５重量部～１００重量部である。このような範囲であれば、粘着性に優れ、電解液中においても被着体保持性に優れる粘着テープを得ることができる。 In the above heat welding adhesive, the thermoplastic elastomer content is preferably 80 to 100 parts by weight, more preferably 90 parts by weight, with respect to 100 parts by weight of the base polymer in the heat welding adhesive. -100 parts by weight, more preferably 95-100 parts by weight. If it is such a range, it is excellent in adhesiveness and can obtain the adhesive tape excellent in adherend retainability also in electrolyte solution.
　熱可塑性エラストマーの軟化点は、好ましくは１００℃以下であり、より好ましくは３０℃～１００℃であり、さらに好ましくは５０℃～９５℃であり、特に好ましくは６０℃～９５℃である。このような範囲であれば、貼着時の加熱による被着体へのダメージを低減し得、かつ、作業性に優れる粘着テープを得ることができる。軟化点は、環球式測定法や熱機械分析法（ＴＭＡ）などにより測定することができる。 The softening point of the thermoplastic elastomer is preferably 100 ° C. or less, more preferably 30 ° C. to 100 ° C., further preferably 50 ° C. to 95 ° C., and particularly preferably 60 ° C. to 95 ° C. If it is such a range, the damage to the to-be-adhered body by the heating at the time of sticking can be reduced, and the adhesive tape which is excellent in workability | operativity can be obtained. The softening point can be measured by a ring and ball measurement method, a thermomechanical analysis method (TMA), or the like.
　熱可塑性エラストマーを形成するモノマー成分としては、例えば、エチレン、プロピレン、１－ブテン、１－ヘキセン、３－メチル－１－ブテン、４－メチル－１－ペンテン、１－ヘプテン、１－オクテン、１－デセン等の炭素数２～１０の程度（好ましくは、炭素数２～４）のα－オレフィン；スチレン等を挙げることができる。熱可塑性エラストマーとしては、例えば、上記モノマー成分の単独重合体；上記モノマー成分から選択される２種類以上のモノマー成分のランダム重合体またはブロック重合体；上記モノマー成分とその他のモノマー成分とのランダム、ブロック、又はグラフト重合体；これらの混合物等が挙げられる。 Examples of the monomer component forming the thermoplastic elastomer include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1 An α-olefin having about 2 to 10 carbon atoms (preferably 2 to 4 carbon atoms) such as decene; styrene and the like. Examples of the thermoplastic elastomer include, for example, a homopolymer of the monomer component; a random polymer or block polymer of two or more monomer components selected from the monomer components; a random of the monomer component and other monomer components, Block or graft polymer; and mixtures thereof.
　１つの実施形態においては、上記熱可塑性エラストマーは、α－オレフィンおよび／またはスチレンから構成されるランダム重合体またはブロック重合体である。このような熱可塑性エラストマーとしては、例えば、直鎖状短鎖分岐ポリエチレン（ＬＬＤＰＥ）、エチレン－プロピレン共重合体、プロペン－ブテン共重合体、エチレン－スチレン共重合体、エチレン－ブテン－スチレン共重合体、エチレン－プロピレン－スチレン共重合体等が挙げられる。このような熱可塑性エラストマーを用いれば、粘着性に優れる粘着テープを得ることができる。 In one embodiment, the thermoplastic elastomer is a random polymer or block polymer composed of α-olefin and / or styrene. Examples of such thermoplastic elastomers include linear short-chain branched polyethylene (LLDPE), ethylene-propylene copolymer, propene-butene copolymer, ethylene-styrene copolymer, ethylene-butene-styrene copolymer. And an ethylene-propylene-styrene copolymer. If such a thermoplastic elastomer is used, an adhesive tape excellent in adhesiveness can be obtained.
　上記熱可塑性エラストマーとして、市販品を用いてもよい。熱可塑性エラストマーの市販品としては、例えば、東亜合成社製の商品名「アロンメルト　ＰＰＥＴ１６００」；クレイトンポリマージャパン社製の商品名「クレイトンポリマーＦＧ１９２４ＧＴ」、「クレイトンポリマーＦＧ１９０１Ｘ」；旭化成ケミカルズ社製の商品名「タフテックＭ１９１３」、「タフテックＭ１９４３」；東洋紡績社製の商品名「トーヨータック　ＰＭＡ-Ｌ」等が挙げられる。 Commercially available products may be used as the thermoplastic elastomer. As commercial products of thermoplastic elastomers, for example, trade names “Aron Melt PPET1600” manufactured by Toa Gosei Co., Ltd .; trade names “Clayton Polymer FG1924GT”, “Clayton Polymer FG1901X” manufactured by Kraton Polymer Japan; trade names manufactured by Asahi Kasei Chemicals “Tuff Tech M1913”, “Tuff Tech M1943”; trade names “Toyo Tack PMA-L” manufactured by Toyobo Co., Ltd.
　１つの実施形態においては、熱可塑性エラストマーとして、酸変性熱可塑性エラストマー、カルボニル変性熱可塑性エラストマー、水酸基変性熱可塑性エラストマー、アミン変性熱可塑性エラストマー等が用いられる。なかでも、酸変性熱可塑性エラストマーが好ましく用いられる。 In one embodiment, an acid-modified thermoplastic elastomer, a carbonyl-modified thermoplastic elastomer, a hydroxyl group-modified thermoplastic elastomer, an amine-modified thermoplastic elastomer, or the like is used as the thermoplastic elastomer. Of these, acid-modified thermoplastic elastomers are preferably used.
　上記酸変性熱可塑性エラストマーは、熱可塑性エラストマーに不飽和カルボン酸および／またはその酸無水物をグラフト重合して得られ得る。より詳細には、酸変性熱可塑性エラストマーは、例えば、主鎖となる熱可塑性エラストマーに、側鎖としての不飽和カルボン酸および／またはその酸無水物が結合して形成され得る。 The acid-modified thermoplastic elastomer can be obtained by graft polymerization of an unsaturated carboxylic acid and / or an acid anhydride thereof on the thermoplastic elastomer. More specifically, the acid-modified thermoplastic elastomer can be formed, for example, by bonding an unsaturated carboxylic acid as a side chain and / or an acid anhydride thereof to a thermoplastic elastomer as a main chain.
　上記酸変性熱可塑性エラストマーのグラフト率は、公知の溶融混練方法により適宜調整することができる。酸変性熱可塑性エラストマーのグラフト率は、例えば、グラフトされる熱可塑性エラストマーに対して０．０５重量％～１０重量％であり、好ましくは０．１重量％～５重量％である。このような範囲であれば、セパレーターと電極とを貼り合せる粘着剤層として適度な粘着力を有する粘着剤層を形成することができる。 The graft ratio of the acid-modified thermoplastic elastomer can be appropriately adjusted by a known melt-kneading method. The graft ratio of the acid-modified thermoplastic elastomer is, for example, 0.05% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight with respect to the thermoplastic elastomer to be grafted. If it is such a range, the adhesive layer which has moderate adhesive force can be formed as an adhesive layer which bonds a separator and an electrode together.
　上記熱溶着型粘着剤は、粘着付与剤をさらに含んでいてもよい。粘着付与剤としては、例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂等を挙げることができる。なかでも好ましくは、石油樹脂（芳香族系石油樹脂、脂肪族系石油樹脂等）である。特に、電解液成分との反応性が低く、電解液の劣化を引き起こしにくい点で、水素添加石油樹脂（飽和脂肪族炭化水素樹脂または芳香族炭化水素樹脂）が好ましい。 The above heat-welding type adhesive may further contain a tackifier. Examples of tackifiers include rosin derivative resins, polyterpene resins, petroleum resins, and oil-soluble phenol resins. Among these, petroleum resins (aromatic petroleum resins, aliphatic petroleum resins, etc.) are preferable. In particular, a hydrogenated petroleum resin (saturated aliphatic hydrocarbon resin or aromatic hydrocarbon resin) is preferable because it has low reactivity with the electrolyte component and hardly causes deterioration of the electrolyte solution.
　上記粘着付与剤の軟化点は、好ましくは１００℃～１５０℃であり、より好ましくは１１０℃～１４０℃であり、さらに好ましくは１１５℃～１３５℃である。 The softening point of the tackifier is preferably 100 ° C to 150 ° C, more preferably 110 ° C to 140 ° C, and further preferably 115 ° C to 135 ° C.
　上記熱溶着型粘着剤において、上記粘着付与剤の含有割合は、熱溶着型粘着剤中のベースポリマー１００重量部に対して、好ましくは５重量部～５０重量部であり、より好ましくは１０重量部～３０重量部であり、さらに好ましくは１５重量部～３０重量部である。このような範囲であれば、比較的低温（例えば、５０℃～１５０℃）での加熱であっても、粘着性を示し得る粘着テープを得ることができる。 In the above heat welding adhesive, the content of the tackifier is preferably 5 to 50 parts by weight, more preferably 10 parts by weight with respect to 100 parts by weight of the base polymer in the heat welding adhesive. Part to 30 parts by weight, more preferably 15 parts to 30 parts by weight. Within such a range, it is possible to obtain an adhesive tape that can exhibit adhesiveness even when heated at a relatively low temperature (eg, 50 ° C. to 150 ° C.).
　上記感圧型粘着剤は、本発明の効果が得られる限りにおいて、任意の適切な粘着性ベースポリマーを含む。感圧型粘着剤に含まれるベースポリマーとしては、例えば、アクリル系樹脂、ゴム系樹脂、シリコーン系樹脂等が挙げられる。 The pressure-sensitive adhesive contains any appropriate adhesive base polymer as long as the effects of the present invention can be obtained. Examples of the base polymer contained in the pressure-sensitive adhesive include acrylic resins, rubber resins, and silicone resins.
　上記アクリル系樹脂としては、例えば、（メタ）アクリル酸アルキルエステルを含むモノマー成分を重合して得られるアクリル系樹脂が挙げられる。（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシルなどのアルキル基の炭素数が４～２０の直鎖または分岐鎖状のアルキル基を有する（メタ）アクリル酸アルキルエステル等を挙げることができる。これらの中でも、被着体に対する接着性や貼り合せ作業性の観点から、アルキル基の炭素数が５～１２の（メタ）アクリル酸アルキルエステルが好ましく、より好ましくは、アクリル酸ｎ－ブチルまたはアクリル酸２－エチルヘキシル（２ＥＨＡ）である。 Examples of the acrylic resin include an acrylic resin obtained by polymerizing a monomer component containing a (meth) acrylic acid alkyl ester. Examples of the (meth) acrylic acid alkyl ester include n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and (meth) acrylic. Pentyl acid, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth) Nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, (meth) acrylic Acid tetradecyl, (meth) acrylic acid pentadecyl, (meth) acrylic Linear or branched alkyl groups having 4 to 20 carbon atoms such as hexadecyl, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters having Among these, from the viewpoint of adhesion to the adherend and workability for bonding, (meth) acrylic acid alkyl ester having an alkyl group having 5 to 12 carbon atoms is preferable, and more preferably n-butyl acrylate or acrylic acid. The acid 2-ethylhexyl (2EHA).
　上記（メタ）アクリル酸アルキルエステルの含有割合は、アクリル系樹脂の重合に用いるモノマー成分１００重量部に対して、好ましくは５０重量部～１００重量部であり、より好ましくは７０重量部～１００重量部である。 The content ratio of the alkyl (meth) acrylate is preferably 50 to 100 parts by weight, more preferably 70 to 100 parts by weight with respect to 100 parts by weight of the monomer component used for the polymerization of the acrylic resin. Part.
　上記アクリル系樹脂は、凝集力、耐熱性、架橋性等の改質を目的として、必要に応じて、上記（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマー由来の構成単位を含んでいてもよい。このような他のモノマーとして、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、カルボキシエチルアクリレートなどのカルボキシル基含有モノマー；無水マレイン酸、無水イコタン酸などの酸無水物基含有モノマー；（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチルなどのヒドロキシル基含有モノマー；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メチロールプロパン（メタ）アクリルアミドなどのアミド系モノマー；ビニルエステル系モノマー；スチレン系モノマー；ビニルエーテル系モノマー；アクリロニトリル、メタクリロニトリルなどのシアノアクリレート系モノマー；（メタ）アクリル酸グリシジルなどのエポキシ基含有アクリル系モノマー；オレフィン系モノマー；ジエン系モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチルなどのアミノ基含有モノマー；（メタ）アクリル酸アルコキシアルキル系モノマー；Ｎ－ビニルピロリドン、Ｎ－メチルビニルピロリドン、Ｎ－ビニルピリジン、Ｎ－ビニルピペリドンなどの窒素原子含有環を有するモノマー；Ｎ－ビニルカルボン酸アミド類；スチレンスルホン酸、アリルスルホン酸などのスルホン酸基含有モノマー；２－ヒドロキシエチルアクリロイルホスフェートなどのリン酸基含有モノマー；マレイミド系モノマー；イタコンイミド系モノマー；Ｎ－（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ－（メタ）アクルロイル－６－オキシヘキサメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－８－オキシオクタメチレンスクシンイミドなどのスクシンイミド系モノマー；グリコール系アクリルエステルモノマー；（メタ）アクリル酸テトラヒドロフルフリルなどの酸素原子含有複素環を有するモノマー；フッ素系（メタ）アクリレートなどのフッ素原子を含有するアクリル酸エステル系モノマー；シリコーン系（メタ）アクリレートなどのケイ素原子を含有するアクリル酸エステル系モノマー；ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、多官能エポキシアクリレート、多官能ポリエステルアクリレート、多官能ポリウレタンアクリレート、ジビニルベンゼン、ブチルジ（メタ）アクリレート、ヘキシルジ（メタ）アクリレートなどの多官能モノマー等が挙げられる。これらの単量体成分は、単独で、または２種以上組み合わせて用いてもよい。なかでも、ヒドロキシル基またはカルボキシル基含有モノマーが好ましく用いられ、より好ましくは、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸ヒドロキシブチル又はアクリル酸（ＡＡ）である。 The acrylic resin contains structural units derived from other monomers copolymerizable with the alkyl (meth) acrylate as necessary for the purpose of modifying cohesive strength, heat resistance, crosslinkability and the like. May be. Examples of such other monomers include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and carboxyethyl acrylate; acid anhydrides such as maleic anhydride and itaconic anhydride Group-containing monomers; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide Amide monomers such as N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc .; vinyl ester monomers; styrene monomers; vinyl ether monomers; Cyanoacrylate monomers such as methacrylonitrile, epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; olefin monomers; diene monomers; aminoethyl (meth) acrylate, (meth) acrylic acid N, Amino group-containing monomers such as N-dimethylaminoethyl and t-butylaminoethyl (meth) acrylate; alkoxymethacrylate monomers (meth) acrylate; N-vinylpyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N A monomer having a nitrogen atom-containing ring such as vinylpiperidone; an N-vinylcarboxylic amide; a sulfonic acid group-containing monomer such as styrenesulfonic acid or allylsulfonic acid; a phosphate group-containing monomer such as 2-hydroxyethylacryloyl phosphate; Succinimide monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide A glycol-based acrylic ester monomer; a monomer having an oxygen atom-containing heterocycle such as tetrahydrofurfuryl (meth) acrylate; an acrylic ester monomer containing a fluorine atom such as fluorine-based (meth) acrylate; Acrylic acid ester monomers containing silicon atoms such as acrylate; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol Rudi (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, many Examples thereof include polyfunctional monomers such as functional epoxy acrylate, polyfunctional polyester acrylate, polyfunctional polyurethane acrylate, divinylbenzene, butyl di (meth) acrylate, and hexyl di (meth) acrylate. These monomer components may be used alone or in combination of two or more. Among them, a hydroxyl group- or carboxyl group-containing monomer is preferably used, and more preferably 2-hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate or acrylic acid (AA).
　上記ヒドロキシル基含有モノマーの含有割合は、アクリル系樹脂の重合に用いるモノマー成分１００重量部に対して、好ましくは１０重量部未満であり、より好ましくは５重量部以下であり、さらに好ましくは２重量部以下である。上記カルボキシル基含有モノマーの含有割合は、アクリル系樹脂の重合に用いるモノマー成分１００重量部に対して、好ましくは２０重量部未満であり、より好ましくは５重量部以下である。 The content ratio of the hydroxyl group-containing monomer is preferably less than 10 parts by weight, more preferably 5 parts by weight or less, and further preferably 2 parts by weight with respect to 100 parts by weight of the monomer component used for the polymerization of the acrylic resin. Or less. The content of the carboxyl group-containing monomer is preferably less than 20 parts by weight and more preferably 5 parts by weight or less with respect to 100 parts by weight of the monomer component used for the polymerization of the acrylic resin.
　上記アクリル系樹脂の重量平均分子量は、好ましくは５万～５００万であり、より好ましくは１０万～２００万、さらに好ましくは２０万～１５０万である。重量平均分子量が５万未満の場合、粘着剤成分が非水系電解液中に溶出するおそれがある。また、重量平均分子量が５００万を超える場合、十分な接着性を発現できなくなるおそれがある。上記重量平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定される。測定条件は下記の通りである。なお、重量平均分子量はポリスチレン換算により算出した。
　測定装置：ＨＬＣ－８１２０ＧＰＣ（製品名、東ソー社製）
　カラム：ＴＳＫｇｅｌ　ＧＭＨ－Ｈ（Ｓ）×２（品番、東ソー社製）
　流量：０．５ｍｌ／ｍｉｎ
　注入量：１００μｌ
　カラム温度：４０℃
　溶離液：ＴＨＦ
　注入試料濃度：０．１重量％
　検出器：示差屈折計 The acrylic resin preferably has a weight average molecular weight of 50,000 to 5,000,000, more preferably 100,000 to 2,000,000, and still more preferably 200,000 to 1,500,000. When the weight average molecular weight is less than 50,000, the pressure-sensitive adhesive component may be eluted in the non-aqueous electrolyte solution. Moreover, when a weight average molecular weight exceeds 5 million, there exists a possibility that sufficient adhesiveness may not be expressed. The weight average molecular weight is measured by GPC (gel permeation chromatography). The measurement conditions are as follows. The weight average molecular weight was calculated in terms of polystyrene.
Measuring device: HLC-8120GPC (product name, manufactured by Tosoh Corporation)
Column: TSKgel GMH-H (S) x 2 (product number, manufactured by Tosoh Corporation)
Flow rate: 0.5ml / min
Injection volume: 100 μl
Column temperature: 40 ° C
Eluent: THF
Injection sample concentration: 0.1% by weight
Detector: Differential refractometer
　上記ゴム系樹脂としては、天然ゴム系樹脂；イソプレンゴム、ポリイソブチレンゴム、ブチルゴム、エチレン・プロピレンゴム、スチレン・ブタジエンゴム、スチレン・イソプレンゴム、スチレン・エチレン・プロピレン・スチレンゴム、スチレン・イソプレン・スチレンブロック共重合体、スチレン・ブタジエン・スチレンブロック共重合体、スチレン・エチレン・ブチレン・スチレンブロック共重合体、スチレン・エチレン・プロピレン・スチレンブロック共重合体、スチレン・エチレン・プロピレンブロック共重合体、再生ゴムや、これらの変性体等の合成ゴム系樹脂（ブロック共重合体、及びランダム共重合体を含む）等を挙げることができる。これらのゴム系樹脂は、単独で、または２種以上組み合わせて用いてもよい。なかでも、電解液成分との反応性が低く、電解液の劣化を引き起こしにくいという点で、ブチルゴム又はポリイソブチレンゴムが好ましい。 Natural rubber resins: isoprene rubber, polyisobutylene rubber, butyl rubber, ethylene / propylene rubber, styrene / butadiene rubber, styrene / isoprene rubber, styrene / ethylene / propylene / styrene rubber, styrene / isoprene / styrene Block copolymer, styrene / butadiene / styrene block copolymer, styrene / ethylene / butylene / styrene block copolymer, styrene / ethylene / propylene / styrene block copolymer, styrene / ethylene / propylene block copolymer, recycled Examples thereof include rubber and synthetic rubber resins (including block copolymers and random copolymers) such as modified products thereof. These rubber resins may be used alone or in combination of two or more. Of these, butyl rubber or polyisobutylene rubber is preferable in that it has low reactivity with the electrolytic solution component and hardly causes deterioration of the electrolytic solution.
　上記シリコーン系樹脂としては、例えば、オルガノポリシロキサンを主成分とするシリコーンゴムやシリコーンレジン、または、これらにシロキサン系架橋剤、過酸化物系架橋剤などの架橋剤を添加して架橋・重合したもの等が挙げられる。 As the silicone resin, for example, silicone rubber or silicone resin mainly composed of organopolysiloxane, or a crosslinking agent such as a siloxane crosslinking agent or a peroxide crosslinking agent is added to the silicone rubber or the silicone resin. And the like.
　１つの実施形態においては、上記粘着剤層を構成する粘着剤として、電解液（例えば、電解質としてＬｉＰＦ６および／またはＬｉＢＦ４を含み、溶媒としてエチレンカーボネート、プロピレンカーボネート等の環状炭酸エステル、ジエチルカーボネート、エチルメチルカーボネートなどの鎖状炭酸エステルを任意の適切な割合で混合して得られた溶媒を含む電解液）に膨潤し得る粘着剤が用いられる。電解液に膨潤し得る粘着剤を用いてセパレーターと電極とから構成される電極部材を形成すれば、該電極部材は、電池に用いられた際、粘着剤層が電解液中で膨潤することにより、制振性に優れる。このような効果は、パターン化された粘着剤層を被着体に転写する形態、すなわち、被着体面の全面には粘着剤層を形成しない形態において、特に有用である。電解液に膨潤し得る粘着剤としては、例えば、側鎖に炭素数４以下のアルキル基を持つアクリル系粘着剤、ウレタン系粘着剤、シリコーン系粘着剤等の非水系電解液と親和性が高い粘着剤が挙げられる。 In one embodiment, as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, an electrolytic solution (for example, LiPF 6 and / or LiBF 4 as an electrolyte and cyclic carbonates such as ethylene carbonate and propylene carbonate as solvents, diethyl carbonate An adhesive that can swell in an electrolytic solution containing a solvent obtained by mixing a chain carbonate such as ethyl methyl carbonate at any appropriate ratio is used. If an electrode member composed of a separator and an electrode is formed using a pressure-sensitive adhesive that can swell in the electrolyte solution, the electrode member will swell in the electrolyte solution when used in a battery. Excellent vibration control. Such an effect is particularly useful in a form in which the patterned pressure-sensitive adhesive layer is transferred to the adherend, that is, in a form in which the pressure-sensitive adhesive layer is not formed on the entire surface of the adherend. Examples of the adhesive that can swell in the electrolytic solution have a high affinity with non-aqueous electrolytic solutions such as acrylic adhesives, urethane adhesives, and silicone adhesives having an alkyl group having 4 or less carbon atoms in the side chain. An adhesive is mentioned.
　電解液に膨潤し得る粘着剤は、非水系電解液に対する膨潤度が、５～２００％であることが好ましく、１０～１００％であることがより好ましく、３０～１５０％であることがさらに好ましい。なお、本明細書において、膨潤度とは、１．４モル濃度のＬｉＰＦ６を含むエチレンカーボネート／ジエチルカーボネート混合溶媒［エチレンカーボネート／ジエチルカーボネート（体積比）＝１／１］を用い、液温６０℃、浸漬時間８時間における粘着剤の厚み変化を意味する。 The pressure-sensitive adhesive that can swell in the electrolytic solution has a degree of swelling with respect to the non-aqueous electrolytic solution of preferably 5 to 200%, more preferably 10 to 100%, and even more preferably 30 to 150%. . In this specification, the degree of swelling refers to an ethylene carbonate / diethyl carbonate mixed solvent [ethylene carbonate / diethyl carbonate (volume ratio) = 1/1] containing LiPF 6 at a 1.4 molar concentration, and a liquid temperature of 60 It means the change in the thickness of the pressure-sensitive adhesive at 8 ° C. for 8 hours.
　上記粘着剤層は、必要に応じて、任意の適切な添加剤を含み得る。該添加剤としては、例えば、架橋剤、粘着付与剤、可塑剤（例えば、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤）、顔料、染料、充填剤、老化防止剤、導電材、紫外線吸収剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤、溶剤等が挙げられる。 The pressure-sensitive adhesive layer may contain any appropriate additive as necessary. Examples of the additive include a crosslinking agent, a tackifier, a plasticizer (for example, trimellitic acid ester plasticizer, pyromellitic acid ester plasticizer), pigment, dye, filler, anti-aging agent, conductive material. , Ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, solvents and the like.
Ｃ．第１の基材
　上記第１の基材は、上記粘着剤層が剥離可能に形成され得る限りにおいて、任意の適切な材料から構成され得る。第１の基材としては、例えば、織布、不織布等の繊維系基材；紙系基材；樹脂フィルム等のプラスチック系基材等が挙げられる。また、発泡シート等の発泡体を基材として用いてもよい。さらに、複層構成の基材であってもよい。基材が複層の形態を有する場合、各層は同一の基材であってもよく、異なる基材を組み合わせてもよい。 C. 1st base material The 1st base material may be comprised from arbitrary appropriate materials, as long as the said adhesive layer can be formed so that peeling is possible. Examples of the first substrate include fiber-based substrates such as woven fabric and nonwoven fabric; paper-based substrates; plastic-based substrates such as resin films. Moreover, you may use foams, such as a foam sheet, as a base material. Furthermore, the base material may be a multilayer structure. When a base material has a form of a multilayer, each layer may be the same base material and may combine a different base material.
　上記第１の基材の厚みは、好ましくは２５μｍ～７５μｍである。このような範囲であれば、被着体に粘着剤層を転写する際の作業性に優れる粘着テープを得ることができる。 The thickness of the first base material is preferably 25 μm to 75 μm. If it is such a range, the adhesive tape excellent in workability | operativity at the time of transferring an adhesive layer to a to-be-adhered body can be obtained.
Ｄ．第２の基材
　上記第２の基材を構成する材料としては、任意の適切な材料が用いられ得る。第２の基材としては、例えば、織布、不織布等の繊維系基材；紙系基材；樹脂フィルム等のプラスチック系基材等が挙げられる。なかでも、電解液に溶解しにくく、電解液の劣化を引き起こしにくい点でプラスチック系基材を用いることが好ましく、特に、ポリイミド、ポリフェニレンサルファイド、またはポリオレフィン（例えば、ポリプロピレン等）から形成されるプラスチック系基材を用いることが好ましい。また、安価である点で、ポリプロピレンから形成されるプラスチック系基材を用いることが好ましい。第２の基材は、複層構成の基材であってもよい。基材が複層の形態を有する場合、各層は同一の基材であってもよく、異なる基材を組み合わせてもよい。 D. Second Base Material Any appropriate material can be used as the material constituting the second base material. Examples of the second substrate include fiber-based substrates such as woven fabrics and nonwoven fabrics; paper-based substrates; plastic-based substrates such as resin films. Among them, it is preferable to use a plastic base material in that it is difficult to dissolve in the electrolytic solution and cause deterioration of the electrolytic solution, and in particular, a plastic type formed from polyimide, polyphenylene sulfide, or polyolefin (for example, polypropylene). It is preferable to use a substrate. Moreover, it is preferable to use a plastic base material formed from polypropylene because it is inexpensive. The second substrate may be a multilayer substrate. When a base material has a form of a multilayer, each layer may be the same base material and may combine a different base material.
　上記第２の基材の厚みは、例えば、１０～５０μｍである。 The thickness of the second base material is, for example, 10 to 50 μm.
Ｅ．粘着テープの製造方法
　上記粘着テープは、任意の適切な方法により製造され得る。例えば、上記粘着テープは、第１の基材上に、粘着剤層形成用組成物を塗工して得ることができる。また、第２の基材の両面に、粘着剤層形成用組成物を塗工して、粘着剤層を形成し、一方の粘着剤層と第１の基材を貼り合わせることにより、粘着テープを製造してもよい。粘着剤層形成用組成物は、上記粘着剤、および任意の適切な添加剤を含む。 E. Manufacturing method of adhesive tape The said adhesive tape may be manufactured by arbitrary appropriate methods. For example, the pressure-sensitive adhesive tape can be obtained by applying a pressure-sensitive adhesive layer forming composition on the first substrate. Moreover, the adhesive tape is formed by coating the adhesive layer forming composition on both surfaces of the second substrate to form an adhesive layer, and bonding the one adhesive layer and the first substrate together. May be manufactured. The composition for forming a pressure-sensitive adhesive layer contains the above pressure-sensitive adhesive and any appropriate additive.
　粘着剤層形成用組成物の塗工方法としては、任意の適切な方法が採用され得る。例えば、スクリーン印刷、スプレー塗工、グラビア塗工、フレキソ塗工、ダイコーター等の方法により、粘着剤層形成用組成物を塗工して、パターン化された粘着剤層が形成される。 Arbitrary appropriate methods may be employ | adopted as a coating method of the composition for adhesive layer formation. For example, the pressure-sensitive adhesive layer-forming composition is applied by a method such as screen printing, spray coating, gravure coating, flexographic coating, or die coater to form a patterned pressure-sensitive adhesive layer.
　以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。実施例における評価方法は以下のとおりである。また、実施例において、特に明記しない限り、「部」および「％」は重量基準である。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The evaluation methods in the examples are as follows. In Examples, unless otherwise specified, “parts” and “%” are based on weight.
［実施例１］
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコにアクリル酸２－エチルヘキシル／アクリル酸（９５重量部／５重量部）、開始剤として過酸化ベンゾイル０．２重量部、酢酸エチル１２０重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６０℃付近に保って約６時間重合反応を行い、重量平均分子量１３０万のアクリル系共重合体（１）を得た。
　アクリル系共重合体（１）１００重量部を含む樹脂組成物（２）に、イソシアネート系架橋剤（日本ポリウレタン社製、商品名「コロネートＬ」）２重量部、酢酸エチルを添加し、固形分１０％の粘着剤（１）を調整した。
　粘着剤組成物（１）をポリエステル樹脂から構成される第１の基材（東レフィルム加工（株）社製、商品名「セラピールＭＤ」、厚み：３８μｍ）に、上記粘着剤（１）をドット状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でドット状にパターン化して形成された粘着剤層（厚み：５μｍ、第１の基材の面積に対する粘着剤層の合計面積の割合（以下、粘着剤層の面積割合ともいう）：２５％、ドットの間隔：３０ｍｍ）とを備える粘着テープ（１）を得た。 [Example 1]
4-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 inlet tube, and condenser, and 0.2 parts by weight of benzoyl peroxide as an initiator Then, 120 parts by weight of ethyl acetate was added, nitrogen gas was introduced while gently stirring, and the polymerization temperature was kept at around 60 ° C. for about 6 hours to carry out a polymerization reaction, and an acrylic copolymer having a weight average molecular weight of 1.3 million Combined (1) was obtained.
To the resin composition (2) containing 100 parts by weight of the acrylic copolymer (1), 2 parts by weight of an isocyanate-based crosslinking agent (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) and ethyl acetate are added to obtain a solid content. A 10% pressure-sensitive adhesive (1) was prepared.
Dot the pressure-sensitive adhesive composition (1) on a first base material (made by Toray Film Processing Co., Ltd., trade name “Therapy MD”, thickness: 38 μm) composed of a polyester resin. It was applied to the shape. Thereafter, the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed in a dot pattern on the first base material (thickness: 5 μm, adhesive to the area of the first base material) A pressure-sensitive adhesive tape (1) having a ratio of the total area of the agent layers (hereinafter also referred to as an area ratio of the pressure-sensitive adhesive layer): 25% and a dot interval: 30 mm was obtained.
［実施例２］
　粘着剤層の厚みを３０μｍとしたこと以外は、実施例１と同様にして、粘着テープ（２）を得た。 [Example 2]
An adhesive tape (2) was obtained in the same manner as in Example 1, except that the thickness of the adhesive layer was 30 μm.
［実施例３］
　水添スチレン系熱可塑性エラストマー（旭化成ケミカルズ（株）社製、商品名「タフテックＭ１９１３」重量平均分子量：１１万）１００重量部に、脂環族飽和炭化水素樹脂（荒川化学工業（株）社製、商品名「アルコンＰ１２５」）３０重量部、トルエンを添加して、固形分１０％の熱溶着型粘着剤（１）を得た。
　ポリエステル樹脂から構成される第１の基材東レフィルム加工（株）社製、商品名「セラピールＭＤ」、厚み：３８μｍ）に、上記熱溶着型粘着剤（１）をドット状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でドット状にパターン化して形成された粘着剤層（厚み：１μｍ、粘着剤層の面積割合：５０％、ドットの間隔：５ｍｍ）とを備える粘着テープ（３）を得た。 [Example 3]
Hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Chemicals Co., Ltd., trade name “Tuftec M1913” weight average molecular weight: 110,000) 100 parts by weight, alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Ltd.) , Trade name "Alcon P125") and 30 parts by weight of toluene were added to obtain a heat-welded pressure-sensitive adhesive (1) having a solid content of 10%.
The said heat welding type adhesive (1) was apply | coated to the 1st base material Toray film processing Co., Ltd. product made from a polyester resin, the brand name "Therapy MD", thickness: 38 micrometers) in the shape of a dot. Thereafter, the coating layer is dried, and the first base material and a pressure-sensitive adhesive layer formed by patterning on the first base material in the form of dots (thickness: 1 μm, area ratio of the pressure-sensitive adhesive layer: 50%) , Dot spacing: 5 mm) was obtained.
［実施例４］
　粘着剤層の厚みを３μｍとし、第１の基材の面積に対するドットの合計面積の割合を３０％としたこと以外は、実施例４と同様にして、粘着テープ（４）を得た。 [Example 4]
An adhesive tape (4) was obtained in the same manner as in Example 4 except that the thickness of the adhesive layer was 3 μm and the ratio of the total area of dots to the area of the first substrate was 30%.
［実施例５］
　ポリオレフィン系粘着剤（東洋紡社製、商品名「トーヨータック　ＰＭＡ－Ｌ」重量平均分子量８万）１００重量部に、脂環族飽和炭化水素樹脂（荒川化学工業（株）社製、商品名「アルコンＰ１２５」）３０重量部とトルエンを添加して、固形分１０％の熱溶着型粘着剤（２）を得た。
　ポリエステル樹脂から構成される第１の基材（東レフィルム加工（株）社製、商品名「セラピール」、厚み：３８μｍ）に、上記熱溶着型粘着剤をドット状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でドット状にパターン化して形成された粘着剤層（厚み：１μｍ、粘着剤層の面積割合：５０％、ドットの間隔：５０ｍｍ）とを備える粘着テープ（５）を得た。 [Example 5]
100 parts by weight of polyolefin pressure-sensitive adhesive (manufactured by Toyobo Co., Ltd., trade name “Toyotac PMA-L”, weight average molecular weight 80,000) and alicyclic saturated hydrocarbon resin (produced by Arakawa Chemical Industries, Ltd., trade name “Arcon”) P125 ") and 30 parts by weight of toluene were added to obtain a heat-welded pressure-sensitive adhesive (2) having a solid content of 10%.
The said heat welding adhesive was apply | coated to the 1st base material (Toray Film Processing Co., Ltd. make, brand name "Therapy", thickness: 38 micrometers) comprised from a polyester resin in the shape of a dot. Thereafter, the coating layer is dried, and the first base material and a pressure-sensitive adhesive layer formed by patterning on the first base material in the form of dots (thickness: 1 μm, area ratio of the pressure-sensitive adhesive layer: 50%) , Dot spacing: 50 mm) was obtained.
［実施例６］
　粘着剤層の厚みを３μｍとしたこと以外は、実施例５と同様にして、粘着テープ（６）を得た。 [Example 6]
An adhesive tape (6) was obtained in the same manner as in Example 5 except that the thickness of the adhesive layer was 3 μm.
［実施例７］
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに２－エチルヘキシルアクリレート／エチルアクリレート／２－ヒドロキシエチルアクリレート／Ｎ－フェニルマレイミド＝３０重量部：７０重量部：４重量部：１０重量部）開始剤として過酸化ベンゾイル０．２重量部、トルエン２００重量部とを加え、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６０℃付近に保って約６時間重合反応を行い、重量平均分子量５０万のアクリル系共重合体（２）を得た。アクリル系共重合体（２）１００重量部に、ポリイソシアネート系化合物（日本ポリウレタン社製、商品名「コロネートＬ」）２重量部、粘着付与樹脂スミライトレジン１２６０３Ｎ（住友ベークライト（株）製）２０重量部、トルエンを添加して、固形分１０％の熱溶着型粘着剤（３）を得た。
　ポリエステル樹脂から構成される第１の基材（三菱樹脂（株）社製、商品名「ダイアホイルＭＲＦ」、厚み：３８μｍ）に、上記熱溶着型粘着剤（３）を、ドット状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でドット状にパターン化して形成された粘着剤層（厚み：３μｍ、粘着剤層の面積割合：６０％、ドットの間隔：２ｍｍ）とを備える粘着テープ（７）を得た。 [Example 7]
2-ethylhexyl acrylate / ethyl acrylate / 2-hydroxyethyl acrylate / N-phenylmaleimide = 30 parts by weight: 70 parts by weight: 4 parts by weight in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser Part: 10 parts by weight) As an initiator, 0.2 parts by weight of benzoyl peroxide and 200 parts by weight of toluene were added, nitrogen gas was introduced with gentle stirring, and the liquid temperature in the flask was kept at around 60 ° C. A polymerization reaction was carried out for 6 hours to obtain an acrylic copolymer (2) having a weight average molecular weight of 500,000. 100 parts by weight of acrylic copolymer (2), 2 parts by weight of polyisocyanate compound (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.), tackifier resin Sumilite resin 12603N (manufactured by Sumitomo Bakelite Co., Ltd.) 20 Part by weight and toluene were added to obtain a heat-welding pressure-sensitive adhesive (3) having a solid content of 10%.
The said heat welding type adhesive (3) was apply | coated to the 1st base material (Mitsubishi Resin Co., Ltd. make, brand name "Diafoil MRF", thickness: 38 micrometers) comprised from a polyester resin in the shape of a dot. . Thereafter, the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed in a dot pattern on the first base material (thickness: 3 μm, area ratio of the pressure-sensitive adhesive layer: 60%) , Dot spacing: 2 mm) was obtained.
［実施例８］
　ゴム系粘着剤（ＢＡＳＦジャパン（株）製　商品名オパノールＢ８０　重量平均分子量７５万）１００重量部に低分子量成分として（ＢＡＳＦジャパン（株）製　商品名オパノールＢ１２ＳＦＮ　重量平均分子量５万）３０重量部とトルエンを添加して、固形分１０％の粘着剤（２）を得た。
　ポリエステル樹脂から構成される第１の基材（三菱樹脂（株）社製、商品名「ダイアホイルＭＲＦ」、厚み：３８μｍ）に、上記粘着剤（２）を、ストライプ状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でストライプ状にパターン化して形成された粘着剤層（厚み：２５μｍ、粘着剤層の面積の割合：７０％、ストライプの間隔：１００ｍｍ）とを備える粘着テープ（８）を得た。 [Example 8]
100 parts by weight of rubber-based pressure-sensitive adhesive (BASF Japan Co., Ltd., trade name Opanol B80 weight average molecular weight 750,000) as a low molecular weight component (BASF Japan Co., Ltd. trade name Opanol B12SFN, weight average molecular weight 50,000) 30 parts by weight Toluene was added to obtain a pressure-sensitive adhesive (2) having a solid content of 10%.
The said adhesive (2) was apply | coated to the 1st base material (Mitsubishi Resin Co., Ltd. make, brand name "Diafoil MRF", thickness: 38 micrometers) comprised from a polyester resin in stripe form. Thereafter, the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed in a stripe pattern on the first base material (thickness: 25 μm, area ratio of the pressure-sensitive adhesive layer: 70) %, Stripe interval: 100 mm).
［実施例９］
　ゴム系粘着剤（ＢＡＳＦジャパン（株）製　商品名オパノールＢ５０　重量平均分子量３４万）１００重量部に脂環族飽和炭化水素樹脂（荒川化学工業（株）社製、商品名「アルコンＰ１２５」）３０重量部、トルエンを添加して、固形分１５％の粘着剤（３）を得た。
　ポリエステル樹脂から構成される第１の基材（三菱樹脂（株）社製、商品名「ダイアホイルＭＲＦ」、厚み：３８μｍ）に、上記粘着剤（３）を、ドット状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でストライプ状にパターン化して形成された粘着剤層（厚み：１０μｍ、粘着剤層の面積割合：４０％、ストライプの間隔：２０ｍｍ）とを備える粘着テープ（９）を得た。 [Example 9]
Rubber pressure-sensitive adhesive (trade name Opanol B50 manufactured by BASF Japan Ltd., weight average molecular weight 340,000) and 100 parts by weight of an alicyclic saturated hydrocarbon resin (trade name “Alcon P125” manufactured by Arakawa Chemical Industries, Ltd.) 30 By weight, toluene was added to obtain an adhesive (3) having a solid content of 15%.
The said adhesive (3) was apply | coated to the 1st base material (Mitsubishi Resin Co., Ltd. make, brand name "Diafoil MRF", thickness: 38 micrometers) comprised from a polyester resin in the shape of a dot. Thereafter, the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed on the first base material in a stripe pattern (thickness: 10 μm, area ratio of the pressure-sensitive adhesive layer: 40%) , Stripe interval: 20 mm) was obtained.
［実施例１０］
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコにブチルアクリレート／エチルアクリレート／メタクリル酸メチル／アクリル酸＝１００重量部／２５重量部／５重量部／４重量部）開始剤として２,２-アゾジイソブチロニトリル０．２重量部、酢酸エチル１５０重量部とを加え、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６０℃付近に保って約６時間重合反応を行い、重量平均分子量１１０万のアクリル系共重合体（３）を得た。アクリル系共重合体（３）１００重量部に、ポリイソシアネート系化合物（日本ポリウレタン社製、商品名「コロネートＬ」）２重量部、酢酸エチルを添加して、固形分１０％の粘着剤（４）を得た。
　ポリエステル樹脂から構成される第１の基材（東レフィルム加工（株）社製、商品名「セラピールＭＤ」、厚み：３８μｍ）に、上記粘着剤（４）をドット状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でドット状にパターン化して形成された粘着剤層（厚み：３μｍ、粘着剤層の面積割合：１０％、ドットの間隔：１０ｍｍ）とを備える粘着テープ（１０）を得た。 [Example 10]
(Butyl acrylate / ethyl acrylate / methyl methacrylate / acrylic acid = 100 parts by weight / 25 parts by weight / 5 parts by weight / 4 parts by weight) in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser) As an initiator, 0.2 parts by weight of 2,2-azodiisobutyronitrile and 150 parts by weight of ethyl acetate were added, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was kept at around 60 ° C. A polymerization reaction was performed for 6 hours to obtain an acrylic copolymer (3) having a weight average molecular weight of 1.1 million. To 100 parts by weight of the acrylic copolymer (3), 2 parts by weight of a polyisocyanate compound (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) and ethyl acetate are added, and a pressure-sensitive adhesive (4 )
The said adhesive (4) was apply | coated to the 1st base material (Toray Film Processing Co., Ltd. make, brand name "Therapy MD", thickness: 38 micrometers) made from a polyester resin in the shape of a dot. Thereafter, the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed in a dot pattern on the first base material (thickness: 3 μm, area ratio of the pressure-sensitive adhesive layer: 10%) , Dot interval: 10 mm) was obtained.
［実施例１１］
　攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコにブチルアクリレート／アクリル酸＝９５重量部／５重量部）開始剤として２,２-アゾジイソブチロニトリル０．２重量部、酢酸エチル１５０重量部とを加え、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を６０℃付近に保って約６時間重合反応を行い、重量平均分子量１２０万のアクリル系共重合体（４）を得た。アクリル系共重合体（４）１００重量部に、ポリイソシアネート系化合物（日本ポリウレタン社製、商品名「コロネートＬ」）２重量部、酢酸エチルを添加して、固形分１０％の粘着剤（５）を得た。
　ポリエステル樹脂から構成される第１の基材（東レフィルム加工（株）社製、商品名「セラピールＭＤ」、厚み：３８μｍ）に、上記粘着剤（４）をドット状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でドット状にパターン化して形成された粘着剤層（厚み：１μｍ、粘着剤層の面積割合：５０％、ドットの間隔：５ｍｍ）とを備える粘着テープ（１１）を得た。 [Example 11]
In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas inlet tube, and condenser, butyl acrylate / acrylic acid = 95 parts by weight / 5 parts by weight) 2,2-azodiisobutyronitrile as an initiator 0.2 weight And 150 parts by weight of ethyl acetate were added, nitrogen gas was introduced while gently stirring, and the polymerization temperature was kept at around 60 ° C. for about 6 hours to carry out a polymerization reaction. A copolymer (4) was obtained. To 100 parts by weight of the acrylic copolymer (4), 2 parts by weight of a polyisocyanate compound (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) and ethyl acetate are added to form a pressure-sensitive adhesive (5 )
The said adhesive (4) was apply | coated to the 1st base material (Toray Film Processing Co., Ltd. make, brand name "Therapy MD", thickness: 38 micrometers) made from a polyester resin in the shape of a dot. Thereafter, the coating layer is dried, and the first base material and a pressure-sensitive adhesive layer formed by patterning on the first base material in the form of dots (thickness: 1 μm, area ratio of the pressure-sensitive adhesive layer: 50%) , Dot interval: 5 mm) was obtained.
［実施例１２］
　粘着剤層の厚みを３μｍとしたこと以外は、実施例１１と同様にして、粘着テープ（１２）を得た。 [Example 12]
An adhesive tape (12) was obtained in the same manner as in Example 11 except that the thickness of the adhesive layer was 3 μm.
［実施例１３］
　アクリル系粘着剤（クラレ（株）製　商品名クラリティＬＡ２１４０　重量平均分子量８万）１００重量部に酢酸エチルを添加して、固形分１５％の熱溶着型粘着剤（４）を得た。
　ポリエステル樹脂から構成される第１の基材（三菱樹脂（株）社製、商品名「ダイアホイルＭＲＦ」、厚み：３８μｍ）に、熱溶着型粘着剤（４）を、ドット状に塗布した。その後、塗布層を乾燥させて、第１の基材と、該第１の基材上でストライプ状にパターン化して形成された粘着剤層（厚み：５μｍ、粘着剤層の面積割合：３０％、ストライプの間隔：５ｍｍ）とを備える粘着テープ（１３）を得た。 [Example 13]
Ethyl acetate was added to 100 parts by weight of an acrylic pressure-sensitive adhesive (trade name Clarity LA2140, weight average molecular weight 80,000 manufactured by Kuraray Co., Ltd.) to obtain a heat-welded pressure-sensitive adhesive (4) having a solid content of 15%.
The heat welding type adhesive (4) was apply | coated to the 1st base material (Mitsubishi Resin Co., Ltd. make, brand name "Diafoil MRF", thickness: 38 micrometers) comprised from a polyester resin in the shape of a dot. Thereafter, the coating layer is dried, and the first base material and the pressure-sensitive adhesive layer formed by patterning on the first base material in a stripe shape (thickness: 5 μm, area ratio of the pressure-sensitive adhesive layer: 30%) , Stripe interval: 5 mm) was obtained.
［実施例１４］
　粘着剤層の厚みを５０μｍとしたこと以外は、実施例１と同様にして、粘着テープ（１４）を得た。 [Example 14]
An adhesive tape (14) was obtained in the same manner as in Example 1 except that the thickness of the adhesive layer was 50 μm.
［実施例１５］
　ドットの面積割合を２％としたこと以外は、実施例１同様にして、粘着テープ（１５）を得た。 [Example 15]
An adhesive tape (15) was obtained in the same manner as in Example 1 except that the dot area ratio was 2%.
［比較例１］
　ドットの面積割合を１００％としたこと以外は、実施例１と同様にして、粘着テープ（１６）を得た。 [Comparative Example 1]
An adhesive tape (16) was obtained in the same manner as in Example 1 except that the dot area ratio was 100%.
［参考例１］
　粘着剤層の厚みを０．２μｍとし、ドットの面積割合を５０％としたこと以外は、実施例１と同様にして、粘着テープ（１７）を得た。 [Reference Example 1]
An adhesive tape (17) was obtained in the same manner as in Example 1 except that the thickness of the adhesive layer was 0.2 μm and the area ratio of dots was 50%.
＜評価＞
　実施例、比較例および参考例で得られた粘着テープを用いて下記の試験体を作製し、該試験体を下記の評価に供した。結果を表１に示す。 <Evaluation>
The following test specimens were produced using the adhesive tapes obtained in Examples, Comparative Examples and Reference Examples, and the specimens were subjected to the following evaluation. The results are shown in Table 1.
（Ｉ）試験体ａの作製
　実施例及び比較例で得られた粘着テープの粘着剤層側を、セパレーター（非水系電池用多孔質膜、ポリプロピレンセパレーター、Ｃｅｌｇａｒｄ社製、商品名「Ｃｅｌｇａｒｄ」、厚み２５μｍ、空孔率４１％）の表面に貼着し、粘着テープとセパレーターとから構成される試験体ａ（第１の基材／粘着剤層／セパレーター）を得た。なお、熱溶着型粘着剤で構成される粘着剤層を用いた実施例および比較例は７０℃で、セパレーターと粘着テープとを圧着し、それ以外の実施例および比較例は２５℃で圧着した。
（ＩＩ）試験体Ａの作製
　上記試験体ａから第１の基材を剥離し、露出した粘着剤層面に、非水系電池用電正極箔（パイオトレック（株）製、活物質：ＬｉＮｉＣｏＭｎＯ２（１．５ｍＡｈ／ｃｍ２））を貼着し、０．４ＭＰａの圧力を２秒間負荷して、試験体Ａ（正極箔／粘着剤層／セパレーター）を得た。なお、熱溶着型粘着剤で構成される粘着剤層を用いた実施例および比較例は７０℃で圧着し、それ以外の実施例および比較例は２５℃で圧着した。
（ＩＩＩ）試験体Ｂの作製
　非水系電池用電正極箔に代えて、活物質がグラファイト（１．６ｍＡｈ／ｃｍ２）である負極箔を用い、上記（ＩＩ）と同様の方法により試験体Ｂ（負極箔／粘着剤層／セパレーター）を作製した。 (I) Preparation of Specimen a The pressure-sensitive adhesive layer side of the pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples was separated from a separator (porous membrane for non-aqueous battery, polypropylene separator, manufactured by Celgard, trade name “Celgard”, thickness A test body a (first substrate / adhesive layer / separator) composed of an adhesive tape and a separator was obtained by adhering to a surface of 25 μm and a porosity of 41%. In addition, the Example and comparative example using the adhesive layer comprised with a heat welding type adhesive are 70 degreeC, and the separator and the adhesive tape were crimped | bonded, and the other Example and comparative example were crimped | bonded at 25 degreeC. .
(II) Preparation of Specimen A The first base material was peeled from the Specimen a, and the exposed pressure-sensitive adhesive layer surface was coated with a non-aqueous battery positive electrode foil (Piotrec Co., Ltd., active material: LiNiCoMnO 2 ( 1.5 mAh / cm 2 )) was applied, and a pressure of 0.4 MPa was applied for 2 seconds to obtain a specimen A (positive electrode foil / adhesive layer / separator). In addition, the Example and comparative example using the adhesive layer comprised with a heat welding type adhesive were crimped | bonded at 70 degreeC, and the other Example and comparative example were crimped | bonded at 25 degreeC.
(III) Preparation of Specimen B Specimen B was prepared in the same manner as in (II) above, using a negative electrode foil whose active material was graphite (1.6 mAh / cm 2 ) instead of the non-aqueous battery positive electrode foil. (Negative foil / adhesive layer / separator) was prepared.
（１）セパレーターの閉塞
　上記試験体ａから第１の基材を剥離し、セパレーター表面を目視により確認した。電池に適用した際に、セパレーターの機能を阻害し、電池性能に悪影響がでるほどにセパレーターの孔が閉塞されている場合を不合格（表１中、×）、セパレーターとしての機能を有しつつ粘着剤層が形成されている場合を合格（表１中、〇）とした。 (1) Closure of the separator The first base material was peeled off from the specimen a, and the surface of the separator was visually confirmed. When applied to a battery, the function of the separator is hindered and the separator hole is blocked to such an extent that the battery performance is adversely affected (in Table 1, x), while having a function as a separator. The case where the pressure-sensitive adhesive layer was formed was regarded as acceptable (O in Table 1).
（２）タック値
　上記試験体ａから第１の基材を剥離し、露出した粘着剤層表面について、プローブタック法により、タック値を測定した。なお、タック値は、タッキング試験機（（株）レスカ製）を使用して、下記条件下で測定した。
　＜測定条件＞
　　温度：２５℃
　　プローブ材質：ＳＵＳ
　　プローブ形状：円柱状（５ｍｍφ）
　　加圧（圧縮）速度：３０ｍｍ／ｍｉｎ
　　測定（離脱）速度：３０ｍｍ／ｍｉｎ
　　プリロード：１００ｇｆ
　　加圧（圧縮）時間：１秒 (2) Tack value The 1st base material was peeled from the said test body a, and the tack value was measured by the probe tack method about the exposed adhesive layer surface. The tack value was measured under the following conditions using a tacking tester (manufactured by Resuka Co., Ltd.).
<Measurement conditions>
Temperature: 25 ° C
Probe material: SUS
Probe shape: cylindrical (5mmφ)
Pressurization (compression) speed: 30 mm / min
Measurement (separation) speed: 30 mm / min
Preload: 100gf
Pressurization (compression) time: 1 second
（３）膨潤度
　１．４モル濃度のＬｉＰＦ６含み、エチレンカーボネートとジエチルカーボネートとの混合溶媒（体積比＝１：１）からなる電解液を調製した。
　上記試験体Ａを、該電解液（温度：６０℃）に、８時間浸漬し、下記式により浸漬前後の厚み変化率から粘着剤層の膨潤度を算出した。
　膨潤度（厚み変化率（％））＝｛（Ｔ２－Ｔ１）／Ｔ１｝×１００
　Ｔ１：浸漬前の粘着剤層厚み
　Ｔ２：浸漬後の粘着剤層厚み (3) include LiPF 6 of swelling 1.4 molar concentration, a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio = 1: 1) electrolyte was prepared consisting of.
The said test body A was immersed in this electrolyte solution (temperature: 60 degreeC) for 8 hours, and the swelling degree of the adhesive layer was computed from the thickness change rate before and behind immersion with the following formula.
Swelling degree (thickness change rate (%)) = {(T2-T1) / T1} × 100
T1: Pressure-sensitive adhesive layer thickness before immersion T2: Pressure-sensitive adhesive layer thickness after immersion
（４）第１の基材の剥離力
　上記試験体ａから第１の基材を剥離する際の剥離力を、精密万能試験機（（株）島津製作所製、商品名「オートグラフＡＧ－Ｉ」）を使用し、温度２５℃、引張速度３００ｍｍ／ｍｉｎ、引張角度１８０°の条件で、測定した。 (4) Peeling force of the first substrate The peeling force when peeling the first substrate from the specimen a was measured using a precision universal testing machine (manufactured by Shimadzu Corporation, trade name “Autograph AG-I”). )), And the temperature was 25 ° C., the tensile speed was 300 mm / min, and the tensile angle was 180 °.
（５）せん断粘着力
　上記試験体Ａについて、精密万能試験機（（株）島津製作所製、商品名「オートグラフＡＧ－Ｉ」を使用し、温度２５℃、引張速度３００ｍｍ／ｍｉｎの条件で、せん断粘着力（正極／セパレーター）を測定した。
　また、試験体Ｂについて、上記と同様の方法により、せん断粘着力（負極／セパレーター）を測定した。
　なお、表１においては、単位粘着面積当たりのせん断粘着力を示している（Ｎ／ｃｍ２）。 (5) Shear adhesive strength With respect to the specimen A, a precision universal testing machine (manufactured by Shimadzu Corporation, trade name “Autograph AG-I”) was used at a temperature of 25 ° C. and a tensile speed of 300 mm / min. Shear adhesive strength (positive electrode / separator) was measured.
Further, for the test specimen B, the shear adhesive strength (negative electrode / separator) was measured by the same method as described above.
In Table 1, the shear adhesive strength per unit adhesive area is shown (N / cm 2 ).
（６）ハンドリング性
　上記試験体Ａおよび試験体Ｂを、手で持ち上げて軽く振った際に、電極箔とセパレーターがずれるかどうかを、以下の基準で評価した。
　〇：電極箔とセパレーターとがずれない
　△：電極箔とセパレーターとがずれるものの、実用上許容可能である
　×：電極箔とセパレーターとが著しくずれ、実用上許容不可である (6) Handling property When the specimen A and specimen B were lifted by hand and shaken lightly, whether or not the electrode foil and the separator were displaced was evaluated according to the following criteria.
◯: The electrode foil and the separator do not deviate. Δ: The electrode foil and the separator deviate, but are acceptable for practical use. X: The electrode foil and the separator deviate significantly, and are not practically acceptable.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　表１から明らかなように、本発明の粘着テープを用いれば、セパレーターの閉塞を防止してセパレーターに対する電解液の浸透性を維持させつつ、セパレーターと電極とを良好に固定し得る粘着テープを得ることができる。なお、参考例１の粘着テープは、粘着剤層が、第１の基材上で剥離可能に形成されておらず、電池製造用途には不適であった。 As is apparent from Table 1, when the pressure-sensitive adhesive tape of the present invention is used, a pressure-sensitive adhesive tape capable of satisfactorily fixing the separator and the electrode while preventing the separator from being blocked and maintaining the permeability of the electrolyte to the separator is obtained. be able to. In the pressure-sensitive adhesive tape of Reference Example 1, the pressure-sensitive adhesive layer was not formed so as to be peelable on the first substrate, and was unsuitable for battery manufacturing applications.
　本発明の粘着テープは、２次電池の電極部材において、セパレーターと電極とを固定する粘着テープとして好適に用いられ得る。 The adhesive tape of the present invention can be suitably used as an adhesive tape for fixing a separator and an electrode in an electrode member of a secondary battery.
　１０　　　　　　　第１の基材
　２１、２１’　　　粘着剤層
　２２　　　　　　　第２の基材
　１００、２００　　粘着テープ
　 DESCRIPTION OF SYMBOLS 10 1st base material 21, 21 'adhesive layer 22 2nd base material 100, 200 adhesive tape

Claims (18)

  1. 　第１の基材と、該第１の基材上に剥離可能に形成された粘着剤層とを備え、
    　該粘着剤層が、パターン化して形成されている、
    　粘着テープ。     A first substrate and a pressure-sensitive adhesive layer formed on the first substrate so as to be peelable;
    The pressure-sensitive adhesive layer is formed by patterning,
    Adhesive tape.
  2. 　第１の基材と、該第１の基材上に剥離可能に形成された粘着積層体とを備え、
    　該粘着積層体が、第２の基材と、該第２の基材の両側に形成された粘着剤層とを含み、
    　該粘着剤層が、パターン化して形成されている、
    　粘着テープ。     A first substrate and an adhesive laminate formed on the first substrate so as to be peelable;
    The pressure-sensitive adhesive laminate includes a second base material and a pressure-sensitive adhesive layer formed on both sides of the second base material,
    The pressure-sensitive adhesive layer is formed by patterning,
    Adhesive tape.
  3. 　前記粘着剤層が、熱溶着型粘着剤を含む、請求項１に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1, wherein the pressure-sensitive adhesive layer contains a heat-welding pressure-sensitive adhesive.
  4. 　前記粘着剤層が、熱溶着型粘着剤を含む、請求項２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 2, wherein the pressure-sensitive adhesive layer contains a heat-welding type pressure-sensitive adhesive.
  5. 　前記粘着剤層が、非水系電解液に対する膨潤度が、５～２００％である粘着剤を含む、請求項１に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1, wherein the pressure-sensitive adhesive layer contains a pressure-sensitive adhesive having a degree of swelling of 5 to 200% with respect to the non-aqueous electrolyte solution.
  6. 　前記粘着剤層が、非水系電解液に対する膨潤度が、５～２００％である粘着剤を含む、請求項２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 2, wherein the pressure-sensitive adhesive layer contains a pressure-sensitive adhesive having a degree of swelling of 5 to 200% with respect to the non-aqueous electrolyte solution.
  7. 　前記粘着剤層が、ドット状に形成されている、請求項１に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1, wherein the pressure-sensitive adhesive layer is formed in a dot shape.
  8. 　前記粘着剤層が、ドット状に形成されている、請求項２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 2, wherein the pressure-sensitive adhesive layer is formed in a dot shape.
  9. 　前記粘着剤層の面積割合が、第１の基材の面積に対して、５％～９０％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 area ratio of the pressure-sensitive adhesive layer is 5% to 90% with respect to the area of the first base material.
  10. 　前記粘着剤層の面積割合が、第１の基材の面積に対して、５％～９０％である、請求項２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 2, wherein the area ratio of the pressure-sensitive adhesive layer is 5% to 90% with respect to the area of the first base material.
  11. 　前記粘着剤層の厚みが、１μｍ～３０μｍである、請求項１に記載の粘着テープ。 2. The pressure-sensitive adhesive tape according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 1 μm to 30 μm.
  12. 　前記粘着剤層の厚みが、１μｍ～３０μｍである、請求項２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 2, wherein the pressure-sensitive adhesive layer has a thickness of 1 μm to 30 μm.
  13. 　前記粘着剤層の２５℃におけるタック値が、１０Ｎ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 pressure-sensitive adhesive layer has a tack value at 25 ° C of 10 N or less.
  14. 　前記粘着剤層の２５℃におけるタック値が、１０Ｎ以下である、請求項２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 2, wherein the pressure-sensitive adhesive layer has a tack value at 25 ° C of 10 N or less.
  15. 　前記粘着剤層から前記第１の基材を剥離する際の２３℃における剥離力が、２．００Ｎ／５０ｍｍ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 a peeling force at 23 ° C when peeling the first base material from the pressure-sensitive adhesive layer is 2.00 N / 50 mm or less.
  16. 　前記粘着剤層から前記第１の基材を剥離する際の２３℃における剥離力が、２．００Ｎ／５０ｍｍ以下である、請求項２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 2, wherein a peeling force at 23 ° C when peeling the first substrate from the pressure-sensitive adhesive layer is 2.00 N / 50 mm or less.
  17. 　非水系２次電池製造時に、セパレーターに貼着して用いられる、請求項１に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1, wherein the pressure-sensitive adhesive tape is used by being stuck to a separator when manufacturing a non-aqueous secondary battery.
  18. 　非水系２次電池製造時に、セパレーターに貼着して用いられる、請求項２に記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 2, which is used by sticking to a separator when manufacturing a non-aqueous secondary battery.
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CN110911622A (en) * 2019-10-31 2020-03-24 东莞东阳光科研发有限公司 Coated diaphragm slurry, composite diaphragm and preparation method thereof

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JP2006206657A (en) * 2005-01-25 2006-08-10 Kokuyo S&T Co Ltd Pressure-sensitive adhesive product and transfer tool
JP2010205467A (en) * 2009-03-02 2010-09-16 Nitto Denko Corp Pressure-sensitive adhesive tape for battery and battery using the same
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CN107298951A (en) * 2017-07-14 2017-10-27 东莞市古川胶带有限公司 Novel super-high discharge type point-like glue band and preparation method thereof
CN110911622A (en) * 2019-10-31 2020-03-24 东莞东阳光科研发有限公司 Coated diaphragm slurry, composite diaphragm and preparation method thereof

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