TW202104494A - Adhesive for nonaqueous batteries and adhesive tape for nonaqueous batteries - Google Patents

Abstract

The present invention provides: an adhesive for nonaqueous batteries, which exhibits excellent adhesiveness in a nonaqueous electrolyte solution, while being less sticky, and which is prevented from protruding beyond the adhesive tape edge if applied to an adhesive tape; and an adhesive tape which comprises this adhesive. An adhesive for nonaqueous batteries according to the present invention exhibits adhesiveness by means of compression, and contains an acrylic polymer that has an acid functional group and a crystalline resin that has a melting point of 25 DEG C or higher. In one embodiment of the present invention, the adhesive for nonaqueous batteries exhibits adhesiveness by means of heating.

Description

Adhesive for non-aqueous battery and adhesive tape for non-aqueous battery

The present invention relates to an adhesive for non-aqueous batteries and an adhesive tape for non-aqueous batteries.

In non-aqueous batteries formed by encapsulating non-aqueous electrolytes such as lithium-ion batteries, adhesive tapes are used for the purpose of improving the loading of the electrodes in the battery case and preventing short circuits between the electrodes. For this kind of adhesive tape, it is required to have the reliability of adhesion in the non-aqueous electrolyte. The use of adhesives with higher hydrophobicity (acrylic adhesives, rubber adhesives) is being studied to make the adhesives contain acid components, A method of adding additives such as an adhesion-imparting resin to the adhesive (for example, Patent Document 1).

However, the adhesives formed to improve the reliability of bonding in the non-aqueous electrolyte are usually soft. The stickiness of the adhesive, the overflow of the adhesive from the end surface of the adhesive tape, etc. cause problems in the battery assembly process and One of the main reasons for reduced operability. In order to prevent this problem, consider methods such as increasing the degree of crosslinking of the base polymer constituting the adhesive, making the thickness of the adhesive layer thinner, and reducing the amount of additives such as adhesion imparting resins. However, these methods all reduce the reliability of bonding in non-aqueous electrolytes. That is, there is a trade-off between ensuring the bonding reliability in the non-aqueous electrolyte and improving the operability in the battery assembly step. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2013-140765

[The problem to be solved by the invention]

The present invention was made in order to solve the previous problems, and its object is to provide an adhesive for non-aqueous batteries, and an adhesive tape containing the adhesive, the adhesive for non-aqueous batteries has excellent adhesion to non-aqueous electrolytes, It is less sticky and can prevent overflow from the end surface of the adhesive tape when it is applied to the adhesive tape. [Technical means to solve the problem]

The adhesive for non-aqueous batteries of the present invention is an adhesive that exhibits adhesiveness by pressure bonding, and includes an acrylic polymer having an acid functional group and a crystalline resin with a melting point of 25° C. or higher. In one embodiment, the adhesive for non-aqueous batteries described above exhibits adhesiveness by heating. In one embodiment, the above-mentioned acrylic polymer having an acid functional group contains a structural unit a derived from an alkyl (meth)acrylate having a linear or branched alkyl group with a carbon number of 4 or more. In one embodiment, the content ratio of the structural unit a is 50 parts by weight or more relative to 100 parts by weight of the acrylic polymer having an acid functional group. In one embodiment, the crystalline resin is a polyolefin resin. In one embodiment, the above-mentioned polyolefin-based resin is a maleic anhydride-modified polyolefin-based resin, a maleic acid-modified polyolefin-based resin, or an acrylic-modified polyolefin-based resin. In one embodiment, the adhesive for non-aqueous batteries includes a C5-based petroleum resin and/or a C9-based petroleum resin. According to another aspect of the present invention, an adhesive tape for a non-aqueous battery is provided. This adhesive tape for non-aqueous batteries contains the above-mentioned adhesive for non-aqueous batteries. In one embodiment, the adhesive tape for non-aqueous batteries includes a substrate and an adhesive layer disposed on at least one side of the substrate, and the adhesive layer includes the adhesive for non-aqueous batteries. In one embodiment, the above-mentioned substrate is selected from polyacrylate, polyurethane, polyimide, polyaramide, polyamide, ethylene-vinyl alcohol copolymer, polyetherimide, At least one of polyvinylidene fluoride, polyester, polypropylene, polyethylene, and polyphenylene sulfide is formed. In one embodiment, a release film is provided on the side of the adhesive layer opposite to the base material. In one embodiment, the adhesive layer is arranged on one side of the substrate, and the other adhesive layer is arranged on the other side of the substrate. According to another aspect of the present invention, a non-aqueous battery is provided. The non-aqueous battery includes the above-mentioned adhesive tape for the non-aqueous battery. [Effects of Invention]

According to the present invention, an adhesive for non-aqueous batteries and an adhesive tape containing the adhesive can be provided. The adhesive for non-aqueous batteries has excellent adhesion to non-aqueous electrolytes and is less sticky, and is applied to adhesive tapes It can prevent overflow from the end surface of the adhesive tape.

A. Adhesive for non-aqueous batteries The adhesive for non-aqueous batteries of the present invention is an adhesive that exhibits adhesiveness by crimping, and contains an acrylic polymer with an acid functional group and a crystal with a melting point of 25°C or higher性resin. In the present invention, by using the acrylic polymer with acid functional group in combination with the above-mentioned crystalline resin, it is possible to obtain less stickiness (specifically, with an appropriate probe viscosity value), and even in non-aqueous systems. Adhesive that exhibits excellent adhesiveness in the electrolyte, and the adhesiveness is difficult to decrease over time. If such an adhesive is used, an adhesive tape with excellent internal short-circuit prevention functionality and excellent operability in the battery assembly step can be obtained. In addition, the above-mentioned adhesive tape can be preferably used for joining members (for example, separators, electrodes, and exterior materials (metal cans, bags, etc.)) used in non-aqueous electrolytes. In addition, the above-mentioned adhesive tape can be configured as a double-sided adhesive tape, which can be preferably used for joining metal materials and metal materials, joining non-metal materials and non-metal materials, and joining metal materials and non-metal materials. Furthermore, in the adhesive of the present invention, by adjusting the structure of the acrylic polymer having acid functional groups (e.g., monomer components, molecular weight), the structure of the crystalline resin, the acrylic polymer having acid functional groups, and The content ratio of crystalline resin, etc., can easily control the balance of stickiness and bonding reliability.

The above-mentioned adhesive may be an adhesive that exhibits adhesiveness at room temperature (25°C), or an adhesive that exhibits adhesiveness by heating (for example, 100°C to 200°C). Adhesives that exhibit adhesiveness by heating can exhibit adhesiveness after being heated and cooled to room temperature.

A-1. Acrylic polymer having an acid functional group As an acrylic polymer having an acid functional group, for example, including one or more structural units derived from alkyl (meth)acrylate, and Acrylic polymers derived from structural units of monomers with acid functional groups.

In the above-mentioned adhesive, the content ratio of the acrylic polymer with acid functional group relative to 100 parts by weight of the solid content in the adhesive is preferably 7 parts by weight to 95 parts by weight, more preferably 15 parts by weight to 90 parts by weight Parts by weight are more preferably 20 parts by weight to 85 parts by weight, and particularly preferably 40 parts by weight to 85 parts by weight. The content of the acrylic polymer with acid functional group can be set to an appropriate amount according to the required probe viscosity value, adhesiveness, etc. Furthermore, in addition to the acrylic polymer having an acid functional group, the above-mentioned adhesive may include an acrylic polymer without an acid functional group, or may not include an acrylic polymer without an acid functional group.

The content ratio of the structural unit derived from the above-mentioned alkyl (meth)acrylate relative to 100 parts by weight of the acrylic polymer having an acid functional group is preferably 50 parts by weight to 99 parts by weight, more preferably 70 parts by weight to 98 parts by weight, more preferably 80 parts by weight to 98 parts by weight.

Preferably, the above-mentioned (meth)acrylic acid alkyl ester has a linear or branched carbon number of 1 to 24 (more preferably 3 to 20, still more preferably 4 to 12, and particularly preferably 4 to 8). alkyl.

Examples of the alkyl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth) ) Amyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylic acid Eicosyl ester and so on.

In one embodiment, the above-mentioned acrylic polymer having an acid functional group contains a linear or branched alkyl group derived from a carbon number of 4 or more (preferably 4-12, more preferably 4-8) The structural unit a of the alkyl (meth)acrylate, the content ratio of the structural unit a relative to 100 parts by weight of the acrylic polymer having acid functional groups is 50 parts by weight or more (preferably 50 parts by weight to 99 parts by weight Parts, more preferably 70 parts by weight to 98 parts by weight, still more preferably 80 parts by weight to 98 parts by weight). If an acrylic polymer containing the structural unit a in a specific amount or more and having an acid functional group is used, an adhesive with excellent adhesion reliability in a non-aqueous electrolyte can be obtained.

In one embodiment, an alkyl (meth)acrylate having a branched alkyl group is used as the alkyl (meth)acrylate. If an alkyl (meth)acrylate having a branched alkyl group is used, the effect of the present invention becomes particularly remarkable. The carbon number of the branched alkyl group is preferably 4 or more, more preferably 4-12, and still more preferably 4-8. The alkyl (meth)acrylate having a linear alkyl group and the alkyl (meth)acrylate having a branched alkyl group can also be used in combination. In addition, as the alkyl (meth)acrylate, an alkyl (meth)acrylate having a branched alkyl group may be used alone.

In one embodiment, in the acrylic polymer having an acid functional group, the content ratio of the structural unit derived from the alkyl (meth)acrylate having a branched alkyl group is relative to the content of the structural unit derived from the (meth)acrylic acid 100 parts by weight of the structural unit of the alkyl ester (that is, 100 parts by weight of the total amount of the alkyl (meth)acrylate having a linear alkyl group and the alkyl (meth)acrylate having a branched alkyl group) , Preferably 50 parts by weight to 100 parts by weight, more preferably 70 parts by weight to 100 parts by weight, and still more preferably 80 parts by weight to 100 parts by weight.

Examples of alkyl (meth)acrylates having branched alkyl groups include isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, 2-ethylbutyl (meth)acrylate , 2-methylbutyl (meth)acrylate, etc. Among them, preferred is 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate or isodecyl (meth)acrylate, and more preferred is (methyl) ) 2-Ethylhexyl acrylate. If 2-ethylhexyl (meth)acrylate is used, an adhesive with particularly excellent adhesion reliability in a non-aqueous electrolyte can be obtained.

As an acid functional group which the acrylic polymer which has an acid functional group has, a carboxyl group, an acid anhydride group, a phosphoric acid group, a sulfonic acid group etc. are mentioned, for example. Therefore, as a monomer having the above-mentioned acid functional group, for example, a carboxyl group-containing monomer, an acid anhydride group-containing monomer, a phosphoric acid group-containing monomer, a sulfonic acid group-containing monomer, and the like can be cited. Among them, carboxyl group-containing monomers are preferred. If a carboxyl group-containing monomer is used, it has the following characteristics: easy to express adhesion to metal plates, easy to copolymerize with other acrylic monomers in terms of design and production, and easy to form polymers by copolymerization Cross-linked.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. Among them, acrylic acid is preferred.

The content ratio of the structural unit derived from the monomer having an acid functional group relative to 100 parts by weight of the acrylic polymer having an acid functional group is preferably 1.5 parts by weight to 20 parts by weight, more preferably 1.8 parts by weight to 15 parts by weight Parts by weight are more preferably 2 parts by weight to 10 parts by weight.

The above-mentioned acrylic polymer with acid functional group can also be used for modification of cohesive force, heat resistance, cross-linking property, etc., and optionally contains derived from the above-mentioned alkyl (meth)acrylate and/or with acid functional group. The structural unit of other monomers for copolymerization of the monomers. Examples of such other monomers include: hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, (meth) ) Hydroxy-containing monomers such as hydroxyoctyl acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl methacrylate, etc.; (meth)acrylic acid Amine, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane (meth)acrylamide, (N-substituted) amide-based monomers such as acrylamide; aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylic acid third Amino alkyl (meth)acrylate monomers such as butylaminoethyl; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, etc. (meth)acrylic acid alkoxy Alkyl ester monomers; N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenyl cis Maleic imine monomers such as butylene diimide; N-methyl iconimidin, N-ethyl iconimines, N-butyl iconimines, N- Ikonimines such as octyl Ikonimines, N-2-ethylhexyl Ikonimines, N-cyclohexyl Ikonimines, N-Lauryl Ikonimines, etc.; N-(meth)acryloyloxymethylene succinimide, N-(meth)acryloyl-6-oxyhexamethylene succinimide, N-(meth)propylene Amino-8-oxyoctamethylene succinylidene-based monomers such as succinylidene imine; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone , Vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperidine, vinyl pyridine, vinyl pyrrole, vinyl imidazole, vinyl azole, vinyl pyridine, N-vinyl carboxamide Vinyl monomers such as styrene, α-methylstyrene and N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; glycidyl (meth)acrylate, etc. Acrylic monomers containing epoxy groups; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy glycol (meth) acrylate, methoxy polypropylene glycol (meth) Glycol-based acrylate monomers such as acrylate; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, polysiloxane (meth)acrylate, etc. have heterocycles, halogen atoms, and silicon atoms Acrylic monomers such as hexamethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate (Meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy Multifunctional monomers such as acrylate, polyester acrylate, and urethane acrylate; olefin-based monomers such as isoprene, butadiene, and isobutylene; vinyl ether, etc. Vinyl ether monomers, etc. These monomer components can be used individually or in combination of 2 or more types.

The content ratio of the structural unit derived from the above-mentioned other monomers is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and more preferably 5 parts by weight relative to 100 parts by weight of the acrylic polymer having acid functional groups the following.

The weight average molecular weight of the acrylic polymer having acid functional groups is preferably 300,000 to 2 million, more preferably 500,000 to 1.5 million. The weight average molecular weight can be measured by GPC (Gel Permeation Chromatography) (solvent: THF (Tetrahydrofuran)).

A-2. As described above the crystalline resin, the adhesive of the present invention comprises a crystalline resin. The so-called crystalline resin refers to a resin with a clear endothermic peak (with a half-value width within 15°C) in the differential calorie curve measured by a differential scanning calorimeter (DSC).

In the adhesive, the content ratio of the crystalline resin relative to 100 parts by weight of the solid content in the adhesive is preferably 3 parts by weight to 90 parts by weight, more preferably 10 parts by weight to 85 parts by weight, and still more preferably 15 parts by weight to 80 parts by weight.

The melting point of the crystalline resin is 25°C or higher, more preferably 40°C or higher, still more preferably 60°C to 120°C, and particularly preferably 60°C to 100°C. If it is in this range, an adhesive with less stickiness can be obtained. The melting point can be determined by differential scanning calorimetry (DSC).

The weight average molecular weight of the crystalline resin is preferably 50,000 to 1.5 million, more preferably 70,000 to 1 million.

The crystallinity of the above-mentioned crystalline resin is preferably 10% or more, more preferably 20% or more. Typically, the degree of crystallinity can be measured by differential scanning calorimetry (DSC).

In one embodiment, the crystalline resin is a polyolefin resin. Examples of the polyolefin resin include ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene -1-heptene copolymer, ethylene-1-octene copolymer, ethylene-1-nonene copolymer, ethylene-1-decene copolymer, ethylene-1-undecene copolymer, ethylene-1- Dodecene copolymer, ethylene-1-tridecene copolymer, ethylene-1-tetradecene copolymer, ethylene-1-pentadecene copolymer, ethylene-1-hexadecene copolymer , Ethylene-1-heptadecene copolymer, ethylene-1-octadecene copolymer, ethylene-1-nonadecene copolymer, ethylene-1-eicosene copolymer and other ethylene-α-olefins Copolymers; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer and ethylene-vinyl propionate copolymer; ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate Copolymers, ethylene-unsaturated carboxylic acid alkyl ester copolymers such as ethylene-butyl acrylate copolymers; propylene-based resins, etc.

In one embodiment, a crystalline polypropylene-based resin is used as the crystalline resin. The crystalline polypropylene resin may be a homopolymer or a copolymer obtained from propylene and a monomer copolymerizable with propylene. Examples of monomers that can be copolymerized with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene , 3-methyl-1-pentene and other α-olefins. In the crystalline polypropylene resin, the content ratio of the propylene-derived structural unit is preferably 60 mol% to 99 mol%, more preferably 65 mol% to 99 mol%, and more preferably 70 mol% Ear%～99mol%. In the crystalline polypropylene resin, the content ratio of the structural unit derived from α-olefin is preferably 1 mol% to 15 mol%, more preferably 1 mol% to 10 mol%.

In one embodiment, a modified polyolefin-based resin is used as the crystalline resin. If a modified polyolefin resin is used, the phase separation between the crystalline resin and the acrylic polymer having acid functional groups can be suppressed, there is less exudation, and an adhesive layer with excellent transparency can be formed. As the modified polyolefin-based resin, a maleic anhydride-modified polyolefin-based resin, a maleic acid-modified polyolefin-based resin, an acrylic-modified polyolefin-based resin, etc. can be preferably used. Specifically, the above-mentioned polyolefin resin is modified by maleic anhydride, modified with maleic acid, or modified with acrylic acid. Among them, maleic anhydride polyolefin resins are preferred, and maleic anhydride modified propylene resins are more preferred. As a specific example of the maleic anhydride-modified propylene-based resin, a resin obtained by modifying the above-mentioned crystalline polypropylene-based resin with maleic anhydride can be cited. The modification rate of the modified polyolefin resin is preferably 1% by weight to 5% by weight, more preferably 1.5% by weight to 2% by weight.

A-3. Additives The above-mentioned adhesive may optionally contain any appropriate additives. Examples of the additives include: crosslinking agents, adhesion-imparting agents, plasticizers (for example, trimellitate-based plasticizers, pyromellitic acid-based plasticizers), pigments, dyes, and fillers , Anti-aging agents, conductive materials, ultraviolet absorbers, light stabilizers, stripping regulators, softeners, surfactants, flame retardants, antioxidants, solvents, etc. In addition, the above-mentioned adhesive may contain any appropriate solvent.

As the above-mentioned adhesion-imparting agent, any suitable adhesion-imparting agent can be used. As the adhesion-imparting agent, for example, an adhesion-imparting resin can be used. Specific examples of adhesion-imparting resins include: rosin-based adhesion-imparting resins (for example, unmodified rosin, modified rosin, rosin-phenol resin, rosin ester-series resins, etc.), terpene-based adhesion-imparting resins (for example, terpene Olefin resins, terpene phenol resins, styrene modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins), hydrocarbon adhesion-imparting resins (for example, aliphatic hydrocarbon resins, aliphatic Cyclic hydrocarbon resins, aromatic hydrocarbon resins (for example, styrene resins, xylene resins, etc.), aliphatic-aromatic petroleum resins, aliphatic-alicyclic petroleum resins, hydrogenated hydrocarbon resins, Grass carba resins, lavender carbo-indene resins, etc.), phenolic adhesion-imparting resins (for example, alkylphenol resins, xylene formaldehyde resins, resol resins, novolacs, etc.), ketone-based adhesion-imparting resins , Polyamide-based adhesion imparting resin, epoxy-based adhesion imparting resin, elastic system adhesion imparting resin, etc.

In one embodiment, the above-mentioned adhesive uses a C5-based petroleum resin and/or a C9-based petroleum resin as an adhesive imparting agent. If these adhesive imparting agents are used, an adhesive with high reliability in non-aqueous electrolytes can be obtained.

The softening point of the adhesion imparting agent is preferably 70°C to 200°C, more preferably 80°C to 190°C. If it is in this range, an adhesive layer with the storage elastic modulus and loss elastic modulus adjusted appropriately can be obtained.

The content ratio of the above-mentioned adhesion imparting agent is 100 parts by weight of the total amount of the acrylic polymer having an acid functional group and the crystalline resin having a melting point of 25° C. or higher, preferably 5 parts by weight to 50 parts by weight, more preferably 10 Parts by weight ~ 40 parts by weight.

Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, and urea-based crosslinking agents, metal alkoxides Material-based cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, carbodiimide-based cross-linking agent, azoline-based cross-linking agent, aziridine-based cross-linking agent, amine-based Crosslinking agent, etc. Among them, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or a metal chelate-based crosslinking agent is preferred.

Specific examples of the above-mentioned isocyanate-based crosslinking agent include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophor Alicyclic isocyanates such as ketone diisocyanate; aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane/toluene diisocyanate Isocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry, trade name "Coronate L") Coronate HL"), isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry, trade name "Coronate HX") and other isocyanate adducts. The content of the isocyanate-based crosslinking agent can be set to any appropriate amount according to the required adhesive force and elastic modulus, relative to the total amount of the acrylic polymer with acid functional groups and the crystalline resin with a melting point of 25°C or higher 100 parts by weight, typically 0.1 parts by weight to 20 parts by weight, more preferably 0.5 parts by weight to 10 parts by weight.

Examples of the epoxy-based crosslinking agent include: N,N,N',N'-tetraglycidyl metaxylylenediamine, diglycidylaniline, 1,3-bis(N,N-glycidyl Glycerylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C"), 1,6-hexanediol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 1600") ), neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Chemical Company, trade name "Epolight 1500NP"), ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Company, trade name "Epolight 40E"), propylene glycol Diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 70P"), polyethylene glycol diglycidyl ether (manufactured by Nippon Oil & Fat Co., Ltd., trade name "Epiol E-400"), polypropylene glycol diglycidyl ether (Manufactured by Nippon Oil & Fat Co., Ltd., trade name "Epiol P-200"), sorbitol polyglycidyl ether (manufactured by Nagase ChemteX, trade name "DENACOL EX-611"), glycerol polyglycidyl ether (manufactured by Nagase ChemteX, Trade name "DENACOL EX-314"), pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether (manufactured by Nagase ChemteX, trade name "DENACOL EX-512"), sorbitan polyglycidyl ether, trimethylol Propane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl tris (2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, bisphenol S-Diglycidyl ether, epoxy resin having two or more epoxy groups in the molecule, etc. The content of epoxy crosslinking agent can be set to any appropriate amount according to the required adhesive force and elastic modulus, relative to the total of acrylic polymer with acid functional group and crystalline resin with melting point above 25℃ The amount is 100 parts by weight, typically 0.01 parts by weight to 10 parts by weight, more preferably 0.03 parts by weight to 5 parts by weight.

As the metal chelate crosslinking agent, for example, a metal chelate compound in which the metal atom is aluminum, zirconium, titanium, zinc, iron, tin, or the like can be used. Among them, an aluminum chelate compound or a titanium chelate compound is preferred.

As the aluminum chelating compound, for example, diisopropoxy aluminum monoacetate oleyl acetate, monoisopropoxide aluminum diacetate oleyl acetate, monoisopropoxy aluminum monooleate monoacetate acetic acid Ethyl acetate, diisopropoxy aluminum monoacetate lauryl acetate, diisopropoxy aluminum monoacetate stearyl acetate, diisopropoxy aluminum monoacetate isostearyl acetate, monoisopropoxy Aluminum Mono-N-Lauryl-β-Aluminum Hydride (alanate) Monoacetyl Lauryl Acetate, Tris (Acetylpyruvate) Aluminum, Acetylpyruvate Aluminum Double (Acetyl Acetate), Monoacetate Aluminum pyruvate bis(isobutyl acetylacetate) chelate, aluminum monoacetylpyruvate bis(2-ethylhexyl acetylacetate) chelate, aluminum acetopyruvate bis(acetylacetate ten Dialkyl ester) chelate, aluminum monoacetylpyruvate bis(oleyl acetate) chelate, and the like.

As the titanium chelate compound, for example, diisopropoxy bis(acetylpyruvate) titanium, tetra-n-butyric acid titanium, tetrakis(2-ethylhexanoic acid) titanium, tetraacetyl pyruvate titanium, diisopropyl Titanium propoxylate bis (ethyl acetylacetate), titanium octanediol, and the like.

Examples of other metal chelate compounds include zirconium tetraacetylpyruvate, zirconium tributoxymonoacetylpyruvate, and the like.

The above-mentioned metal chelate-based crosslinking agent may be used singly or in combination of two or more kinds.

The content of the metal chelate crosslinking agent can be set to any appropriate amount according to the required adhesive force and elastic modulus, relative to acrylic polymers with acid functional groups and crystalline resins with a melting point of 25°C or higher The total amount of 100 parts by weight is typically 0.01 parts by weight to 10 parts by weight, more preferably 0.03 parts by weight to 7 parts by weight, and still more preferably 0.05 parts by weight to 5 parts by weight.

B. Adhesive tape for non-aqueous batteries Fig. 1 is a schematic cross-sectional view of an adhesive tape for non-aqueous batteries (hereinafter, also simply referred to as adhesive tape) according to one embodiment of the present invention. The adhesive tape 100 includes a substrate 10 and an adhesive layer 20 disposed on at least one side (both sides in the example of the figure) of the substrate 10. The adhesive layer 20 contains the adhesive described in item A above. Although not shown, the adhesive tape may be provided with a release film on the outer side of the adhesive layer (that is, the surface of the adhesive layer opposite to the substrate) in order to protect the adhesive surface during the period before use.

Fig. 2 is a schematic cross-sectional view of an adhesive tape for a non-aqueous battery according to another embodiment of the present invention. The adhesive tape 200 includes a substrate 10, an adhesive layer 20 arranged on one side of the substrate 10, and another adhesive layer 30 arranged on the other side of the substrate. The adhesive layer 20 contains the adhesive described in item A above. The other adhesive layer 30 includes any suitable adhesive (for example, acrylic adhesive, rubber adhesive) other than the adhesive described in item A. Although not shown, the above-mentioned adhesive tape can also be placed on the outside of the adhesive layer and/or another adhesive layer (ie, the adhesive layer and/or another adhesive layer) in order to protect the adhesive surface during the period before use. A release film is provided on the surface of the layer opposite to the substrate.

The adhesive tape may be an adhesive tape that exhibits adhesiveness at room temperature (25° C.), or an adhesive tape that exhibits adhesiveness by heating. The adhesive tape that exhibits adhesiveness by heating can exhibit adhesiveness in a state of being cooled to normal temperature after heating.

When the adhesive layer of the adhesive tape of the present invention is attached to the aluminum foil, the adhesive force at 25°C is preferably 0.5 N/10 mm or more, more preferably 0.8 N/10 mm-20 N/10 mm, and more preferably It is 1 N/10 mm～10 N/10 mm. If it is in this range, it can be made into an adhesive tape suitable for non-aqueous batteries. In this manual, the so-called adhesive force refers to the adhesive force measured by the method according to JIS Z 0237:2000, the adhesive tape is attached to the aluminum foil with 1 round trip of a 2 kg roller, and placed at 25°C After 30 minutes, the adhesive tape was peeled off under the conditions of a peeling angle of 180° and a peeling speed (stretching speed) of 300 mm/min for measurement. Furthermore, when the adhesive tape is an adhesive tape that exhibits adhesiveness by heating, the adhesive tape displays adhesiveness at a temperature (for example, 130°C, 0.4 MPa, 5 seconds) that will adhere The adhesive force measured after the tape and the aluminum foil are cooled to 25°C is equivalent to the above-mentioned adhesive force.

The thickness of the adhesive tape is preferably 5 μm to 200 μm, more preferably 15 μm to 150 μm, and still more preferably 30 μm to 100 μm.

B-1. Adhesive layer The adhesive layer contains the adhesive described in item A above.

The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 3 μm to 80 μm, and still more preferably 5 μm to 50 μm.

The probe viscosity value at 25°C of the adhesive layer is preferably 500 g or less, more preferably 400 g or less, still more preferably 340 g or less, and particularly preferably 10 g to 300 g. The measurement method of the probe viscosity value is described below.

B-2. Substrate As the above-mentioned substrate, a resin film can be preferably used. Examples of the resin constituting the resin film include: polyacrylate, polyurethane, polyimide, polyaramide, polyamide, ethylene-vinyl alcohol copolymer, polyetherimide, poly Vinylidene fluoride, polyester, polypropylene, polyethylene, polyphenylene sulfide, etc. These resins may be used alone or in combination of two or more kinds.

The thickness of the substrate is preferably 1 μm to 100 μm, more preferably 5 μm to 100 μm, more preferably 10 μm to 70 μm, and still more preferably 15 μm to 50 μm.

In one embodiment, a non-aqueous battery including the above-mentioned adhesive tape for non-aqueous battery is provided. The adhesive tape for non-aqueous batteries can be used for purposes such as improving the loading of the electrodes in the battery case and preventing short circuits between the electrodes. [Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited by these examples. The evaluation methods in the examples are as follows. In addition, in the examples, unless otherwise specified, "parts" and "%" are based on weight.

(1) Adhesion The adhesive tapes obtained in the examples and comparative examples were attached to the surface of the aluminum foil under the following conditions to obtain test bodies. Furthermore, the adhesive tapes of Example 10, Example 11, Example 13, Example 14, Comparative Example 6, and Comparative Example 7 are thermal adhesive tapes, so they are only crimped by heating (130°C). The other adhesive tapes were crimped at room temperature (25°C) and heated (130°C). Regarding the obtained test body, using a precision universal testing machine (trade name "Autograph AG-I", manufactured by Shimadzu Corporation), the force required to peel the adhesive tape from the surface of the aluminum foil (N/10 mm) was measured under the following conditions , Set as the adhesive force of the adhesive tape. (Crimping conditions) Normal temperature crimping: crimping is performed with 1 round trip of a 2 kg roller. Heating and crimping: Under the setting that the surface temperature of the laminating device becomes 130°C, the crimping is performed at 0.4 MPa×5 seconds. (Peeling conditions) Temperature: normal temperature (25℃) Peeling speed: 300 mm/min Peel angle: 180°

(2) Adhesion in non-aqueous electrolyte The test body produced in the above (1) contains 1.0 mol/L lithium hexafluoride phosphate as the electrolyte and the volume ratio of ethylene carbonate and diethyl carbonate (ethylene carbonate: diethyl carbonate) The resulting electrolyte was mixed at a ratio of 1:2 and immersed at 80°C for 72 hours, and visually observed whether the adhesive tape swelled or peeled off. After that, the unpeeled test body of the adhesive tape was lifted from the electrolyte, washed with ethanol, and the force (N/10 mm) required to peel the adhesive tape from the surface of the aluminum foil was measured by the same method as the above (1). Set the adhesive force in non-aqueous electrolyte.

(3) Probe viscosity value Regarding the surface of the adhesive layer, the probe viscosity value was measured by the probe viscosity method. In addition, the probe viscosity value was measured under the following conditions using a tacking tester (manufactured by Rhesca). (Measurement conditions) Temperature: 25℃ Probe material: SUS Probe shape: cylindrical (5 mmϕ) Pressurization (compression) speed: 30 mm/min Measurement (detachment) speed: 30 mm/min Preload: 100 gf Pressurization (compression) time: 1 second

(4) Fog value Using a haze meter (model: HM-150, manufactured by Murakami Color Research Institute), incident light is irradiated from the side of the adhesive layer to measure the haze value of the adhesive tape.

(5) Adhesive overflow test The adhesive tape cut into 10 mm squares is crimped on the SUS board under the same conditions as the above (1). After that, the adhesive tape was pressurized under the following conditions to evaluate the amount of adhesive overflow from the end surface of the adhesive tape. Pressing conditions: pressurize at 0.4 MPa×6 hours under the setting where the surface temperature of the hot pressing device becomes 130°C.

[Example 1] Add 2-ethylhexyl acrylate/acrylic acid (95 parts by weight/5 parts by weight) and 0.2 weight of benzyl peroxide as a starting agent to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser. 120 parts by weight of ethyl acetate. While slowly stirring, nitrogen was introduced into the flask. The liquid temperature in the flask was maintained at around 60°C. The polymerization reaction was carried out for about 6 hours to obtain an acrylic copolymer with a weight average molecular weight of 1.3 million (1 ). To 75 parts by weight of acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight) is added as a modified olefin resin 75,000, melting point 70°C) 25 parts by weight, isocyanate crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 2 parts by weight, diluted with toluene to prepare an adhesive with 15% solid content (1) . The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( 1). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 2] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. With respect to 75 parts by weight of acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L"," added as a modified olefin resin, by weight Average molecular weight 75,000, melting point 70°C) 25 parts by weight, hydrogenated derivative of C9 petroleum resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "Arkon P-125", hydrogenation rate: 95%, softening point: 125°C) 30 Part by weight, 2 parts by weight of an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), diluted with toluene to prepare an adhesive (2) with a solid content of 15%. The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( 2). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 3] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. To 75 parts by weight of acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight) is added as a modified olefin resin : 75,000, melting point: 90°C) 25 parts by weight, 2 parts by weight of isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), diluted with toluene to prepare an adhesive with a solid content of 15% ( 3). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 12 μm) so that the thickness of the adhesive layer after drying became 15 μm, to obtain an adhesive tape ( 3). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 4] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. With respect to 85 parts by weight of acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight) is added as a modified olefin resin : 75,000, melting point: 90°C) 15 parts by weight, 2 parts by weight of isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), diluted with toluene to prepare an adhesive with 15% solid content ( 4). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 12 μm) so that the thickness of the adhesive layer after drying became 5 μm, to obtain an adhesive tape ( 4). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 5] A polyester film with a thickness of 6 μm (manufactured by DuPont Hongji Films Foshan Co. Ltd, trade name "KLBD") was used as a substrate, and the thickness of the adhesive layer was set to 3 μm, except that it was the same as in Example 4 The way to make adhesive tape (5). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 6] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. To 75 parts by weight of acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-Lz"," weight average molecular weight is added as a modified olefin resin : 100,000, melting point: 70°C) 25 parts by weight, 2 parts by weight of isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), diluted with toluene to prepare an adhesive with 15% solid content ( 5). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( 6). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 7] Add 2-ethylhexyl acrylate/acrylic acid (90 parts by weight/10 parts by weight) and 0.2 weight of benzyl peroxide as a starting agent to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser 120 parts by weight of ethyl acetate. While slowly stirring, nitrogen was introduced into the flask. The liquid temperature in the flask was maintained at around 60°C. The polymerization reaction was carried out for about 6 hours to obtain an acrylic copolymer with a weight average molecular weight of 1.2 million (2 ). With respect to 85 parts by weight of the acrylic copolymer (2), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L"," weight average molecular weight is added as a modified olefin resin : 75,000, melting point: 70°C) 15 parts by weight, isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 2 parts by weight, diluted with toluene to prepare an adhesive with a solid content of 15% ( 6). The resulting adhesive was coated on a substrate (polyimide film, manufactured by TORAY, trade name "Kapton 100H", thickness: 25 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain Adhesive tape (7). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 8] Add 2-ethylhexyl acrylate/acrylic acid (100 parts by weight/2 parts by weight) and 0.2 weight of benzyl peroxide as a starting agent to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser. 230 parts by weight of ethyl acetate. While slowly stirring, nitrogen was introduced into the flask. The liquid temperature in the flask was maintained at around 60°C. The polymerization reaction was carried out for about 6 hours to obtain an acrylic copolymer with a weight average molecular weight of 650,000 (3 ). To 70 parts by weight of the acrylic copolymer (3), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight) is added as a modified olefin resin : 75,000, melting point: 70°C) 30 parts by weight, isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 2 parts by weight, diluted with toluene to prepare an adhesive with a solid content of 15% ( 7). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( 8). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 9] Add n-butyl acrylate/acrylic acid (95 parts by weight/5 parts by weight) and 2,2'-azobisisobutyl as a starting agent to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser 0.2 parts by weight of nitrile and 233 parts by weight of ethyl acetate. While slowly stirring, nitrogen was introduced. The liquid temperature in the flask was maintained at around 60°C. The polymerization reaction was carried out for about 6 hours to obtain an acrylic copolymer with a weight average molecular weight of 700,000.物(4). With respect to 85 parts by weight of the acrylic copolymer (4), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L",” weight average molecular weight is added as a modified olefin resin : 75,000, melting point: 70°C) 15 parts by weight, isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 2 parts by weight, diluted with toluene to prepare an adhesive with a solid content of 15% ( 8). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( 9). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 10] In the same manner as in Example 7, an acrylic copolymer (2) was obtained. With respect to 25 parts by weight of acrylic copolymer (2), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L"," weight average molecular weight is added as a modified olefin resin : 75,000, melting point 70°C) 75 parts by weight, 2 parts by weight of isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), diluted with toluene to prepare an adhesive with a solid content of 15% (9 ). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 12 μm) so that the thickness of the adhesive layer after drying became 3 μm, to obtain an adhesive tape ( 10). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 11] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. To 15 parts by weight of acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight) is added as a modified olefin resin : 75,000, melting point: 90°C) 85 parts by weight, 2 parts by weight of isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), diluted with toluene to prepare an adhesive with a solid content of 15% ( 10). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( 11). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 12] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. With respect to 85 parts by weight of the acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L"," added as a modified olefin resin, weight Average molecular weight 75,000, melting point 70°C) 15 parts by weight, aluminum chelate crosslinking agent (trade name "ALUMI-CHELATE A", manufactured by Kawaken Fine Chemicals Co., Ltd.) 0.5 parts by weight, diluted with toluene to prepare a solid form 15% adhesive (11). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 12 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( 12). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 13] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. With respect to 15 parts by weight of acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L"," added as a modified olefin resin, weight Average molecular weight 75,000, melting point 70°C) 85 parts by weight, aluminum chelate crosslinking agent (trade name "ALUMI-CHELATE A", manufactured by Kawaken Fine Chemicals Co., Ltd.) 0.2 parts by weight, diluted with toluene to prepare a solid form 15% adhesive (12). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 12 μm) so that the thickness of the adhesive layer after drying became 5 μm, to obtain an adhesive tape ( 13). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Example 14] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. With respect to 25 parts by weight of the acrylic copolymer (1), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-T"," added as a modified olefin resin, by weight Average molecular weight 75,000, melting point 90°C) 75 parts by weight, epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Company, trade name "Tetrad C" 0.1 part by weight, diluted with toluene to prepare 15% solid content adhesive) (13). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 12 μm) so that the thickness of the adhesive layer after drying became 5 μm, to obtain an adhesive tape ( 14). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 1.

[Comparative Example 1] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. To 100 parts by weight of the acrylic copolymer (1), 18 parts by weight of modified rosin resin (manufactured by Harima Chemicals, trade name "Hariester KT-3"), isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 2 parts by weight, diluted with toluene to prepare an adhesive (C1) with a solid content of 15%. The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( C1). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 2] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. To 100 parts by weight of the acrylic copolymer (1), 2 parts by weight of an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L") was added and diluted with toluene to prepare an adhesive with a solid content of 15% (C2). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( C2). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 3] In the same manner as in Example 1, an acrylic copolymer (1) was obtained. With respect to 100 parts by weight of the acrylic copolymer (1), 0.5 parts by weight of an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C") was added and diluted with toluene to prepare a solid content of 15% Adhesive (C3). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( C3). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 4] In the same manner as in Example 9, an acrylic copolymer (4) was obtained. With respect to 100 parts by weight of acrylic copolymer (4), 30 parts by weight of terpene phenol resin (manufactured by Yasuhara Chemical Company, trade name "YS Polystar S-145", softening point: about 145°C), isocyanate-based crosslinking agent ( 2 parts by weight of Tosoh Corporation, brand name "Coronate L"), 0.03 parts by weight of epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Company, brand name "Tetrad C"), diluted with toluene to prepare solid component 15 % Of adhesive (C4). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( C4). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 5] Add 2-ethylhexyl acrylate/2-hydroxyethyl acrylate (100 parts by weight/4 parts by weight) to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser, as the starting agent 2. 0.2 parts by weight of 2'-azobisisobutyronitrile and 233 parts by weight of ethyl acetate. While slowly stirring, nitrogen was introduced, and the liquid temperature in the flask was maintained at around 60°C. The polymerization reaction was carried out for about 6 hours to obtain the weight An acrylic copolymer (5) with an average molecular weight of 550,000. With respect to 85 parts by weight of the acrylic copolymer (5), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., brand name "Toyotac PMA-L", weight average molecular weight) is added as a modified olefin resin : 75,000, melting point: 70°C) 15 parts by weight, isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L") 2 parts by weight, diluted with toluene to prepare an adhesive with a solid content of 15% ( C5). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape (C5) ). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 6] In the same manner as in Comparative Example 5, an acrylic copolymer (5) was obtained. With respect to 25 parts by weight of acrylic copolymer (5), maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L"," weight average molecular weight is added as a modified olefin resin : 75,000, melting point: 70°C) 75 parts by weight, 2 parts by weight of isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), diluted with toluene to prepare an adhesive with a solid content of 15% ( C6). The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( C6). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 7] As a modified olefin resin, maleic anhydride modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight: 75,000, melting point: 70°C) 100 parts by weight Toluene was dissolved to prepare an adhesive (C7) with a solid content of 15%. The resulting adhesive was coated on a substrate (polypropylene film, manufactured by TORAY Corporation, trade name "Torayfan", thickness: 30 μm) so that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape ( C7). The obtained adhesive tape was used for the evaluation of (1) to (5) above. The results are shown in Table 2.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Adhesive composition [parts by weight] Acrylic copolymer (1) 2EHA/AA=95/5 (Mw1.3 million) 75 75 75 85 85 75 15 85 15 25 (2) 2EHA/AA=90/10 (Mw1.2 million) 85 25 (3) 2EHA/AA=100/2 (Mw65 million) 70 (4)BA/AA=95/5 (Mw700,000) 85 (5) 2EHA/HEA=100/4 (Mw600,000) Olefin resin PMA-L (softening point 70℃) 25 25 15 30 15 75 PMA-LZ (softening point 70℃) 25 15 85 PMA-T (softening point 90℃) 25 15 15 85 75 Crosslinking agent Polyisocyanate 2 2 2 2 2 2 2 2 2 2 2 Epoxy 0.1 Aluminum chelate 0.5 0.2 Adhesion imparting agent Hariester KT-3 (softening point 180℃) YS Polystar S145 (softening point 145℃) Arkon P125 (softening point 125℃) 30 Adhesive layer thickness [μm] 10 10 15 5 3 10 10 10 10 3 10 10 5 5 Substrate PP PP PP PP PET PP PI PP PP PP PP PP PP PP Substrate thickness [μm] 30 30 12 12 6 30 25 30 30 12 30 12 12 12 Evaluation Adhesion [N/10 mm] Room temperature crimping 1.47 1.70 1.29 0.80 2.03 1.27 2.73 2.07 1.00 1.50 Heated crimping 3.20 3.23 5.24 2.57 3.13 2.73 4.30 2.40 3.63 1.53 2.77 3.10 1.46 1.55 Adhesion in non-aqueous electrolyte [N/10 mm] Room temperature crimping 1.24 1.35 1.35 1.95 1.15 1.03 1.74 0.57 0.45 2.18 Heated crimping 2.62 1.51 4.55 4.10 1.50 1.65 2.90 0.91 1.02 1.25 6.92 1.73 0.65 0.76 Probe viscosity value [gf] 193.3 214.6 284.3 251.5 236.1 264.6 233.6 297.0 152.3 0.0 2.4 201.4 1.2 0.5 Haze value [%] 4.5 7.9 6.8 3.4 4.0 8.5 7.2 9.9 6.9 2.6 16.3 2.9 3.4 3.7 Adhesive overflow test [μm] 141.5 94.2 181.4 49.5 45.1 122.3 120.3 234.3 252.6 67.2 210.3 120.8 78.6 87.4

[Table 2] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Adhesive composition [parts by weight] Acrylic copolymer (1) 2EHA/AA=95/5 (Mw1.3 million) 100 100 100 (2) 2EHA/AA=90/10 (Mw1.2 million) (3) 2EHA/AA=100/2 (Mw65 million) (4)BA/AA=95/5 (Mw700,000) 100 (5) 2EHA/HEA=100/4 (Mw55 million) 85 25 Olefin resin PMA-L (softening point 70℃) 15 75 100 PMA-LZ (softening point 70℃) PMA-T (softening point 90℃) Crosslinking agent Polyisocyanate 2 2 2 2 Epoxy 0.5 0.03 Aluminum chelate Adhesion imparting agent Hariester KT-3 (softening point 180℃) 18 YS Polystar S145 (softening point 145℃) 30 Arkon P125 (softening point 125℃) Adhesive layer thickness [μm] 10 10 10 10 10 10 10 Substrate PP PP PP PP PP PP PP Substrate thickness [μm] 30 30 30 30 30 30 30 Evaluation Adhesion [N/10 mm] Room temperature crimping 2.87 2.10 0.87 4.03 0.13 Heated crimping 3.43 2.64 0.90 5.73 0.60 0.30 5.70 Adhesion in non-aqueous electrolyte [N/10 mm] Room temperature crimping 0.92 1.23 ×Peel off ×Peel off ×Peel off Heated crimping 1.02 1.47 ×Peel off ×Peel off ×Peel off ×Peel off 5.90 Probe viscosity value [gf] 508.2 348.7 184.2 251.0 212.0 4.5 0.0 Haze value [%] 4.2 2.3 2.5 4.7 19.4 10.5 6.5 Adhesive overflow test [μm] 301.3 106.5 98.4 243.1 85.8 116.6 491.3

10: Substrate 20, 30: Adhesive layer 100, 200: Adhesive tape for non-aqueous batteries

Fig. 1 is a schematic cross-sectional view of an adhesive tape for a non-aqueous battery according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view of an adhesive tape for a non-aqueous battery according to another embodiment of the present invention.

10: Substrate

20: Adhesive layer

100: Adhesive tape for non-aqueous batteries

Claims (13)

An adhesive for non-aqueous batteries, which is an adhesive that exhibits adhesiveness by crimping, and Contains an acrylic polymer with an acid functional group and a crystalline resin with a melting point of 25°C or higher. Such as the adhesive for non-aqueous batteries of claim 1, which exhibits adhesiveness by heating. The adhesive for non-aqueous batteries according to claim 1 or 2, wherein the acrylic polymer having an acid functional group contains (meth)acrylic acid derived from a linear or branched alkyl group having a carbon number of 4 or more The structural unit a of the alkyl ester. The adhesive for a non-aqueous battery according to claim 3, wherein the content ratio of the structural unit a is 50 parts by weight or more relative to 100 parts by weight of the acrylic polymer having an acid functional group. The adhesive for non-aqueous batteries according to any one of claims 1 to 4, wherein the crystalline resin is a polyolefin resin. The adhesive for non-aqueous batteries according to claim 5, wherein the polyolefin resin is a maleic anhydride-modified polyolefin-based resin, a maleic acid-modified polyolefin-based resin or an acrylic-modified polyolefin-based resin . The adhesive for a non-aqueous battery according to any one of claims 1 to 6, which comprises a C5 series petroleum resin and/or a C9 series petroleum resin. An adhesive tape for a non-aqueous battery, which contains the adhesive for a non-aqueous battery according to any one of claims 1 to 7. Such as the adhesive tape for non-aqueous battery of claim 8, which has a substrate and an adhesive layer disposed on at least one side of the substrate, and The adhesive layer contains the adhesive for non-aqueous batteries according to any one of claims 1 to 7. The adhesive tape for a non-aqueous battery according to claim 9, wherein the base material is selected from polyacrylate, polyurethane, polyimide, polyaramide, polyamide, ethylene-vinyl alcohol copolymer , At least one of polyetherimide, polyvinylidene fluoride, polyester, polypropylene, polyethylene, polyphenylene sulfide is formed. The adhesive tape for a non-aqueous battery according to claim 9 or 10, wherein a release film is provided on the side of the adhesive layer opposite to the base material. The adhesive tape for a non-aqueous battery according to any one of claims 9 to 11, wherein the adhesive layer is disposed on one side of the substrate, Another adhesive layer is disposed on the other side of the substrate. A non-aqueous battery comprising the adhesive tape for a non-aqueous battery according to any one of claims 8 to 12.

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