TWI860352B - Adhesive for non-aqueous battery and adhesive tape for non-aqueous battery - Google Patents

Abstract

The present invention provides an adhesive for non-aqueous batteries and an adhesive tape containing the adhesive. The adhesive for non-aqueous batteries has excellent adhesion in non-aqueous electrolytes and is less sticky. When applied to adhesive tapes, it can prevent overflow from the end surface of the adhesive tape. The adhesive for non-aqueous batteries of the present invention is an adhesive that exhibits adhesion by compression, and includes an acrylic polymer having an acid functional group and a crystalline resin having a melting point of 25°C or above. In one embodiment, the adhesive for non-aqueous batteries exhibits adhesion by 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 such as lithium-ion batteries that are sealed with non-aqueous electrolytes, adhesive tapes are used for the purpose of improving the loading properties of electrodes in the battery case and preventing short circuits between electrodes. Such adhesive tapes are required to have adhesion reliability in non-aqueous electrolytes, and methods such as using highly hydrophobic adhesives (acrylic adhesives, rubber adhesives), making the adhesive contain acid components, and adding additives such as adhesive-imparting resins to the adhesive are being studied (for example, Patent Document 1).

However, the adhesive formed to improve the bonding reliability in non-aqueous electrolytes is usually soft, and the stickiness of the adhesive and the overflow of the adhesive from the end surface of the adhesive tape are one of the main causes of the occurrence of defects and reduced operability in the battery assembly step. In order to prevent such adverse conditions, methods such as increasing the degree of crosslinking of the base polymer constituting the adhesive, thinning the thickness of the adhesive layer, and reducing the amount of additives such as adhesion-imparting resins are considered. However, these methods all reduce the bonding reliability in non-aqueous electrolytes. That is, ensuring the bonding reliability in non-aqueous electrolytes and improving the operability in the battery assembly step become a trade-off. [Prior Art Literature] [Patent Literature]

Patent document 1: Japanese Patent Publication No. 2013-140765

[The problem the invention is trying to solve]

The present invention is made to solve the previous problem. Its purpose 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 in non-aqueous electrolytes and is less sticky. When used in adhesive tapes, it can prevent overflow from the end surface of the adhesive tape. [Technical means for solving the problem]

The non-aqueous battery adhesive of the present invention is an adhesive that exhibits adhesion by compression, and comprises an acrylic polymer having an acid functional group, and a crystalline resin having a melting point of 25°C or more. In one embodiment, the non-aqueous battery adhesive exhibits adhesion by heating. In one embodiment, the 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 polyolefin resin is a maleic anhydride-modified polyolefin resin, a maleic acid-modified polyolefin resin or an acrylic acid-modified polyolefin resin. In one embodiment, the non-aqueous battery adhesive comprises a C5-based petroleum resin and/or a C9-based petroleum resin. According to another aspect of the present invention, a non-aqueous battery adhesive tape is provided. The non-aqueous battery adhesive tape comprises the non-aqueous battery adhesive. In one embodiment, the non-aqueous battery adhesive tape comprises a substrate and an adhesive layer disposed on at least one side of the substrate, the adhesive layer comprising the non-aqueous battery adhesive. In one embodiment, the substrate is formed by at least one selected from polyacrylate, polyurethane, polyimide, polyarylamide, polyamide, ethylene-vinyl alcohol copolymer, polyetherimide, polyvinylidene fluoride, polyester, polypropylene, polyethylene, and polyphenylene sulfide. In one embodiment, a peeling film is provided on the side of the adhesive layer opposite to the substrate. 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 form of the present invention, a non-aqueous battery is provided. The non-aqueous battery includes the adhesive tape for the non-aqueous battery. [Effect of the invention]

According to the present invention, a non-aqueous battery adhesive and an adhesive tape containing the adhesive can be provided. The non-aqueous battery adhesive has excellent adhesion in a non-aqueous electrolyte and is less sticky. When used in an adhesive tape, 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 adhesion by compression bonding, and comprises an acrylic polymer having an acid functional group, and a crystalline resin having a melting point of 25°C or above. In the present invention, by using an acrylic polymer having an acid functional group and the above-mentioned crystalline resin in combination, an adhesive with less stickiness (specifically, having an appropriate probe viscosity value) can be obtained, and an adhesive that exhibits excellent adhesion even in non-aqueous electrolytes and whose adhesion is unlikely to decrease over time can be obtained. 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 components used in non-aqueous electrolytes (for example, separators, electrodes, and exterior materials (metal cans, bags, etc.)). 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 to metal materials, joining non-metal materials to non-metal materials, and joining metal materials to non-metal materials. Furthermore, in the adhesive of the present invention, by adjusting the structure of the acrylic polymer with acid functional groups (for example, monomer composition, molecular weight), the structure of the crystalline resin, the content ratio of the acrylic polymer with acid functional groups and the crystalline resin, etc., the balance between the degree of adhesion and the reliability of bonding can be easily controlled.

The adhesive may be an adhesive that exhibits adhesion at room temperature (25° C.), or an adhesive that exhibits adhesion by heating (e.g., 100° C. to 200° C.). An adhesive that exhibits adhesion by heating may exhibit adhesion when cooled to room temperature after heating.

A-1. Acrylic polymers having acid functional groups Examples of acrylic polymers having acid functional groups include acrylic polymers containing one or more structural units derived from (meth) alkyl acrylates and structural units derived from monomers having acid functional groups.

In the above adhesive, the content ratio of the acrylic polymer having an acid functional group is preferably 7 to 95 parts by weight, more preferably 15 to 90 parts by weight, further preferably 20 to 85 parts by weight, and particularly preferably 40 to 85 parts by weight relative to 100 parts by weight of the solid content in the adhesive. The content of the acrylic polymer having an acid functional group can be set to an appropriate amount according to the required probe viscosity value, adhesion, etc. Furthermore, the above adhesive may include an acrylic polymer without an acid functional group in addition to the acrylic polymer having 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 (meth)acrylic acid alkyl ester is preferably 50 to 99 parts by weight, more preferably 70 to 98 parts by weight, and further preferably 80 to 98 parts by weight, relative to 100 parts by weight of the acrylic polymer having an acid functional group.

The (meth)acrylic acid alkyl ester preferably has a linear or branched alkyl group having 1 to 24 carbon atoms (more preferably 3 to 20, further preferably 4 to 12, and particularly preferably 4 to 8).

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and eicosyl (meth)acrylate.

In one embodiment, the 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 4 or more carbon atoms (preferably 4 to 12, more preferably 4 to 8), and the content ratio of the structural unit a is 50 parts by weight or more (preferably 50 to 99 parts by weight, more preferably 70 to 98 parts by weight, and further preferably 80 to 98 parts by weight) relative to 100 parts by weight of the acrylic polymer having an acid functional group. If an acrylic polymer having an acid functional group and containing a specific amount of the structural unit a or more is used, an adhesive having excellent bonding 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 above-mentioned alkyl (meth)acrylate. If an alkyl (meth)acrylate having a branched alkyl group is used, the effect of the present invention becomes particularly significant. The carbon number of the above-mentioned branched alkyl group is preferably 4 or more, more preferably 4 to 12, and further preferably 4 to 8. An alkyl (meth)acrylate having a straight-chain alkyl group and an alkyl (meth)acrylate having a branched alkyl group may also be used together. In addition, as the alkyl (meth)acrylate, an alkyl (meth)acrylate having a branched alkyl group may also be used alone.

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

Examples of the (meth)acrylic acid alkyl ester having a branched alkyl group include isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, and 2-methylbutyl (meth)acrylate. Among them, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, or isodecyl (meth)acrylate is preferred, and 2-ethylhexyl (meth)acrylate is more preferred. If 2-ethylhexyl (meth)acrylate is used, an adhesive having particularly excellent bonding reliability in a non-aqueous electrolyte can be obtained.

Examples of the acid functional groups of the acrylic polymer having an acid functional group include carboxyl, anhydride, phosphoric acid, and sulfonic acid groups. Therefore, examples of monomers having the above acid functional groups include carboxyl-containing monomers, anhydride-containing monomers, phosphoric acid-containing monomers, and sulfonic acid-containing monomers. Among them, carboxyl-containing monomers are preferred. If carboxyl-containing monomers are used, the following features are achieved: adhesion to metal plates is easily exhibited, and copolymerization with other acrylic monomers is also easy in terms of design and production, and the polymer formed by copolymerization is easily crosslinked.

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

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

The acrylic polymer having an acid functional group may optionally contain structural units derived from other monomers copolymerizable with the (meth)acrylate and/or the monomer having an acid functional group for the purpose of improving cohesion, heat resistance, crosslinking properties, etc. Examples of such other monomers include hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)methyl methacrylate; (N-substituted)amide monomers such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, and N-hydroxymethylpropane (meth)acrylamide; aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate; (meth) acrylate aminoalkyl ester monomers; (meth) acrylate alkoxyalkyl ester monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; N-cyclohexyl succinimidyl diimide, N-isopropyl succinimidyl diimide, N-lauryl succinimidyl diimide, N-phenyl succinimidyl diimide and other succinimidyl diimide monomers; N-methyl iconamide Iconimide monomers such as iconimide, N-ethyliconimide, N-butyliconimide, N-octyliconimide, N-2-ethylhexyliconimide, N-cyclohexyliconimide, and N-lauryliconimide; N-(meth)acryloyloxymethylenebutanediamide, N-(meth)acryloyl-6-oxyhexamethylenebutanediamide, N- dimethicone monomers such as (meth)acryl-8-oxyoctamethylene dimethicone; vinyl monomers such as vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methylvinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperidine, vinyl pyrrolidine, vinyl pyrrole, vinyl imidazole, vinyl pyrazole, vinyl pyrrolidine, N-vinyl carboxamides, styrene, α-methylstyrene, and N-vinyl caprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; acrylic monomers containing epoxy groups such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate; The present invention can be used to prepare the present invention in accordance with the present invention. The present invention can be used to prepare the present invention in accordance with the present invention. The present invention can be used to prepare the present invention in accordance with the present invention. The present invention can be used to prepare the present invention in accordance with the present invention. The present invention can be used to prepare the present invention in accordance with the present invention. The present invention can be used to prepare the present invention in accordance with the present invention. The present invention can be used to prepare the present invention in accordance with the present invention.

The content ratio of the structural units derived from the above other monomers is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight or less, based on 100 parts by weight of the acrylic polymer having an acid functional group.

The weight average molecular weight of the acrylic polymer having an acid functional group is preferably 300,000 to 2,000,000, more preferably 500,000 to 1,500,000. The weight average molecular weight can be measured by GPC (Gel Permeation Chromatography) (solvent: THF (tetrahydrofuran)).

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

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

The melting point of the crystalline resin is 25°C or higher, more preferably 40°C or higher, further preferably 60°C to 120°C, and particularly preferably 60°C to 100°C. Within this range, a less sticky adhesive can be obtained. The melting point can be measured by differential scanning calorimetry (DSC).

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

The crystallinity of the crystalline resin is preferably 10% or more, more preferably 20% or more. The 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 homopolymers, ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-1-heptene copolymers, ethylene-1-octene copolymers, ethylene-1-nonene copolymers, ethylene-1-decene copolymers, ethylene-1-undecene copolymers, ethylene-1-dodecene copolymers, ethylene-1-tridecene copolymers, ethylene-1-tetradecene copolymers, ethylene-1-pentadecene copolymers, ethylene-1 Ethylene-α-olefin copolymers such as ethylene-hexadecene copolymer, ethylene-1-heptadecene copolymer, ethylene-1-octadecene copolymer, ethylene-1-nonadecene copolymer, and ethylene-1-eicosene copolymer; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer and ethylene-vinyl propionate copolymer; ethylene-unsaturated carboxylic acid alkyl ester copolymers such as ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer; acrylic resins, etc.

In one embodiment, a crystalline polypropylene resin is used as the above-mentioned crystalline resin. The crystalline polypropylene resin may be a homopolymer or a copolymer obtained by using propylene and a monomer copolymerizable with propylene. Examples of monomers copolymerizable 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 structural unit derived from propylene is preferably 60 mol% to 99 mol%, more preferably 65 mol% to 99 mol%, and further preferably 70 mol% to 99 mol%. In the crystalline polypropylene resin, the content 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 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 an acid functional group is suppressed, the oozing out is less, and an adhesive layer having excellent transparency can be formed. As the modified polyolefin resin, preferably, maleic anhydride-modified polyolefin resin, maleic acid-modified polyolefin resin, acrylic acid-modified polyolefin resin, etc. can be used. Specifically, resins obtained by modifying the above-mentioned polyolefin resins with maleic anhydride, maleic acid or acrylic acid can be cited. Among them, maleic anhydride polyolefin resins are preferred, and maleic anhydride-modified propylene resins are more preferred. As a specific example of maleic anhydride-modified propylene resins, resins obtained by modifying the above-mentioned crystalline polypropylene resins with maleic anhydride can be cited. The modification rate of the modified polyolefin resin is preferably 1% to 5% by weight, and more preferably 1.5% to 2% by weight.

A-3. Additives The above-mentioned adhesive may contain any appropriate additives as needed. Examples of such additives include: crosslinking agents, adhesive imparting agents, plasticizers (e.g., trimellitic acid ester plasticizers, pyromellitic acid ester plasticizers), pigments, dyes, fillers, anti-aging agents, conductive materials, ultraviolet absorbers, light stabilizers, stripping modifiers, softeners, surfactants, flame retardants, antioxidants, solvents, etc. In addition, the above-mentioned adhesive may also contain any appropriate solvents.

Any appropriate adhesive imparting agent can be used as the adhesive imparting agent. For example, an adhesive imparting resin can be used as the adhesive imparting agent. Specific examples of the tackifier resin include rosin-based tackifier resins (e.g., unmodified rosin, modified rosin, rosin phenol-based resins, rosin ester-based resins, etc.), terpene-based tackifier resins (e.g., terpene-based resins, terpene phenol-based resins, styrene-modified terpene-based resins, aromatic-modified terpene-based resins, hydrogenated terpene-based resins), hydrocarbon-based tackifier resins (e.g., aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aromatic hydrocarbon resins (e.g., For example, styrene-based resins, xylene-based resins, etc.), aliphatic-aromatic petroleum resins, aliphatic-aliphatic cyclopentane petroleum resins, hydrogenated hydrocarbon resins, lavender-based resins, lavender-indene-based resins, etc.), phenol-based adhesive-imparting resins (for example, alkylphenol-based resins, xylene formaldehyde-based resins, soluble phenolic resins, phenolic varnishes, etc.), ketone-based adhesive-imparting resins, polyamide-based adhesive-imparting resins, epoxy-based adhesive-imparting resins, elastic system adhesive-imparting resins, etc.

In one embodiment, the adhesive uses C5 petroleum resin and/or C9 petroleum resin as an adhesive agent. If such adhesive agents are used, an adhesive having a highly reliable adhesive force in a non-aqueous electrolyte can be obtained.

The softening point of the above-mentioned adhesive agent is preferably 70° C. to 200° C., and more preferably 80° C. to 190° C. Within this range, an adhesive layer having appropriately adjusted storage elastic modulus and loss elastic modulus can be obtained.

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

As the above-mentioned crosslinking agent, for example, there can be listed: isocyanate crosslinking agent, epoxy crosslinking agent, melamine crosslinking agent, peroxide crosslinking agent, and in addition, there can be listed: urea crosslinking agent, metal alkoxide crosslinking agent, metal chelate crosslinking agent, metal salt crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, etc. Among them, isocyanate crosslinking agent, epoxy crosslinking agent or metal chelate crosslinking agent is preferred.

Specific examples of the isocyanate crosslinking agent include: low-order aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate; aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate; trihydroxymethylpropane/toluene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), trihydroxymethylpropane/hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate The content of the isocyanate crosslinking agent can be set to any appropriate amount according to the required adhesion and elastic modulus, and is typically 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the total amount of the acrylic polymer having an acid functional group and the crystalline resin having a melting point of 25°C or above.

Examples of the epoxy crosslinking agent include N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N-glycidylaminomethyl)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 Co., Ltd., trade name "Epolight 1500NP"), ethylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 40E"), propylene glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolight 70P"), polyethylene glycol diglycidyl ether (manufactured by NOF Corporation, trade name "Epiol E-400"), polypropylene glycol diglycidyl ether (manufactured by NOF Corporation, 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, trihydroxymethylpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, tri(2-hydroxyethyl)isocyanuric acid triglycidyl ester, resorcinol diglycidyl ether, bisphenol S-diglycidyl ether, epoxy resins having two or more epoxy groups in the molecule, etc. The content of the epoxy crosslinking agent can be set to any appropriate amount according to the required adhesion and elastic modulus, and is typically 0.01 to 10 parts by weight, and more preferably 0.03 to 5 parts by weight, relative to 100 parts by weight of the total amount of the acrylic polymer having an acid functional group and the crystalline resin having a melting point of 25°C or above.

As the metal chelate crosslinking agent, for example, a metal chelate compound whose metal atom is aluminum, zirconium, titanium, zinc, iron, tin, etc. Among them, aluminum chelate compounds or titanium chelate compounds are preferred.

Examples of the aluminum chelate compound include diisopropoxyaluminum monoacetate oleyl acetate, monoisopropoxyaluminum diacetate oleyl acetate, monoisopropoxyaluminum monooleate ethyl acetate, diisopropoxyaluminum monoacetate lauryl acetate, diisopropoxyaluminum monoacetate stearyl acetate, diisopropoxyaluminum monoacetate isostearyl acetate, monoisopropoxyaluminum mono-N-lauryl-β-aluminum hydroxide (a lanate) monoacetylacetate, aluminum tri(acetylacetonate), aluminum acetylacetonate bis(ethyl acetylacetate), aluminum monoacetylacetonate bis(isobutyl acetylacetate) chelate, aluminum monoacetylacetonate bis(2-ethylhexyl acetylacetate) chelate, aluminum monoacetylacetonate bis(dodecyl acetylacetate) chelate, aluminum monoacetylacetonate bis(oleyl acetylacetate) chelate, etc.

Examples of the titanium chelate compound include titanium diisopropoxybis(acetylacetonate), titanium tetra-n-butyrate, titanium tetra(2-ethylhexanoate), titanium tetraacetylacetonate, titanium diisopropoxybis(ethylacetylacetate), and titanium octanediol.

As other metal chelate compounds, there can be mentioned: zirconium tetraacetylpyruvate, zirconium tributoxymonoacetylpyruvate, etc.

The above-mentioned metal chelate crosslinking agents may be used alone or in combination of two or more.

The content of the metal chelate crosslinking agent can be set to any appropriate amount according to the required adhesion and elastic modulus, and is typically 0.01 to 10 parts by weight, more preferably 0.03 to 7 parts by weight, and further preferably 0.05 to 5 parts by weight, relative to 100 parts by weight of the total amount of the acrylic polymer having an acid functional group and the crystalline resin having a melting point of 25°C or above.

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

FIG2 is a schematic cross-sectional view of an adhesive tape for non-aqueous batteries according to another embodiment of the present invention. The adhesive tape 200 comprises a substrate 10, an adhesive layer 20 disposed on one surface of the substrate 10, and another adhesive layer 30 disposed on the other surface of the substrate. The adhesive layer 20 comprises the adhesive described in item A above. The other adhesive layer 30 comprises any appropriate adhesive other than the adhesive described in item A (e.g., an acrylic adhesive, a rubber adhesive). Although not shown, the adhesive tape may also be provided with a release film on the outer side of the adhesive layer and/or another adhesive layer (i.e., the surface of the adhesive layer and/or another adhesive layer opposite to the substrate) in order to protect the adhesive surface before use.

The adhesive tape may be one that exhibits adhesiveness at room temperature (25° C.) or one that exhibits adhesiveness by heating. The adhesive tape that exhibits adhesiveness by heating may exhibit adhesiveness after being cooled to room temperature after being heated.

The adhesive force at 25°C when the adhesive layer of the adhesive tape of the present invention is attached to an aluminum foil is preferably 0.5 N/10 mm or more, more preferably 0.8 N/10 mm to 20 N/10 mm, and further preferably 1 N/10 mm to 10 N/10 mm. If it is within this range, an adhesive tape suitable for non-aqueous batteries can be made. In this specification, the so-called adhesive force refers to the adhesive force measured by the method according to JIS Z 0237:2000, which is measured by attaching the adhesive tape to an aluminum foil by one back and forth movement of a 2 kg roller, leaving it at 25°C for 30 minutes, and then peeling the adhesive tape at a peeling angle of 180° and a peeling speed (tensile speed) of 300 mm/min. Furthermore, in the case where the adhesive tape exhibits adhesiveness by heating, the adhesive tape and the aluminum foil are bonded by a bonding operation at a temperature at which the adhesive tape exhibits adhesiveness (e.g., 130°C, 0.4 MPa, 5 seconds) and the adhesive force measured after cooling 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 further preferably 30 μm to 100 μm.

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

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

The probe viscosity value of the adhesive layer at 25°C is preferably 500 g or less, more preferably 400 g or less, further preferably 340 g or less, and particularly preferably 10 g to 300 g. The method for measuring the probe 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, polyarylamide, polyamide, ethylene-vinyl alcohol copolymer, polyetherimide, polyvinylidene fluoride, polyester, polypropylene, polyethylene, polyphenylene sulfide, etc. These resins can be used alone or in combination of two or more.

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 further preferably 15 μm to 50 μm.

In one embodiment, a non-aqueous battery is provided that includes the above-mentioned adhesive tape for non-aqueous batteries. The adhesive tape for non-aqueous batteries can be used, for example, to improve the loading performance of electrodes in a battery case, to prevent short circuits between electrodes, etc. [Example]

The present invention is specifically described below by way of examples, but the present invention is not limited to these examples. The evaluation method in the examples is as follows. In addition, in the examples, "parts" and "%" are based on weight unless otherwise specified.

(1) Adhesion The adhesive tapes obtained in the examples and comparative examples were attached to the surface of an aluminum foil under the following conditions to obtain test pieces. The adhesive tapes of Examples 10, 11, 13, 14, Comparative Examples 6 and 7 were heat-bonding type adhesive tapes, and thus were only pressed at a temperature of 130°C. The other adhesive tapes were pressed at room temperature (25°C) and at a temperature of 130°C. The force (N/10 mm) required to peel the adhesive tape from the aluminum foil surface was measured for the test pieces obtained using a precision universal testing machine (trade name "Autograph AG-I", manufactured by Shimadzu Corporation) under the following conditions, and this was taken as the adhesion of the adhesive tape. (Compression bonding conditions) Compression bonding at room temperature: Press bonding is performed with a 2 kg roller in one reciprocating motion. Heated compression bonding: Press bonding is performed at 0.4 MPa × 5 seconds with the surface temperature of the bonding device set to 130°C. (Peeling conditions) Temperature: Room temperature (25°C) Peeling speed: 300 mm/min Peeling angle: 180°

(2) Adhesion in non-aqueous electrolyte The test piece prepared in (1) above was immersed in an electrolyte containing 1.0 mol/L lithium hexafluorophosphate as an electrolyte and ethylene carbonate and diethyl carbonate mixed in a volume ratio of 1:2 (ethylene carbonate: diethyl carbonate) at 80°C for 72 hours, and the presence of bulging or peeling of the adhesive tape was visually observed. Thereafter, the test piece without the adhesive tape peeled off was lifted out of the electrolyte, washed with ethanol, and the force (N/10 mm) required to peel the adhesive tape off the aluminum foil surface was measured in the same manner as in (1) above, which was taken as the adhesion in the 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. The probe viscosity value was measured using a tacking tester (manufactured by Rhesca) under the following conditions. (Measurement conditions) Temperature: 25°C Probe material: SUS Probe shape: cylindrical (5 mmφ) Pressure (compression) speed: 30 mm/min Measurement (detachment) speed: 30 mm/min Preload: 100 gf Pressure (compression) time: 1 second

(4) Mist value Use a mist meter (model: HM-150, manufactured by Murakami Color Laboratory) to irradiate incident light from the adhesive layer side to measure the mist value of the adhesive tape.

(5) Adhesive overflow test The adhesive tape cut into 10 mm squares was pressed onto a SUS plate under the same conditions as in (1) above. Then, the adhesive tape was pressurized under the following conditions to evaluate the amount of adhesive overflowing from the end surface of the adhesive tape. Pressure conditions: Pressurization was performed at 0.4 MPa × 6 hours with the surface temperature of the hot press device set to 130°C.

[Example 1] Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, 2-ethylhexyl acrylate/acrylic acid (95 parts by weight/5 parts by weight), 0.2 parts by weight of benzoyl peroxide as an initiator, and 120 parts by weight of ethyl acetate were added, and nitrogen was introduced while slowly stirring. The liquid temperature in the flask was maintained at approximately 60°C, and a polymerization reaction was carried out for about 6 hours to obtain an acrylic copolymer (1) with a weight average molecular weight of 1.3 million. 25 parts by weight of 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) and 2 parts by weight of isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added as modified olefin resin to 75 parts by weight of acrylic copolymer (1), and diluted with toluene to prepare an adhesive (1) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY Co., Ltd., trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape (1). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

[Example 2] Acrylic acid copolymer (1) was obtained in the same manner as in Example 1. To 75 parts by weight of acrylic acid copolymer (1), 25 parts by weight of 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) as a modified olefin resin, 30 parts by weight of a hydrogenated derivative of a C9-based petroleum resin (manufactured by Arakawa Chemical Industries, Ltd., trade name "Arkon P-125", hydrogenation rate: 95%, softening point: 125°C), and 2 parts by weight of an isocyanate crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L") were added as a modified olefin resin, and diluted with toluene to prepare an adhesive (2) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying was 10 μm, thereby obtaining an adhesive tape (2). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

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

[Example 4] An acrylic copolymer (1) was obtained in the same manner as in Example 1. To 85 parts by weight of the acrylic copolymer (1), 15 parts by weight of a maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight: 75,000, melting point: 90°C) and 2 parts by weight of an isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added as a modified olefin resin, and the mixture was diluted with toluene to prepare an adhesive (4) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 12 μm) in such a manner that the thickness of the adhesive layer after drying was 5 μm, thereby obtaining an adhesive tape (4). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

[Example 5] A 6 μm thick polyester film (manufactured by DuPont Hongji Films Foshan Co. Ltd., trade name "KLBD") was used as the substrate, and the thickness of the adhesive layer was set to 3 μm. An adhesive tape (5) was prepared in the same manner as in Example 4. The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

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

[Example 7] Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, add 2-ethylhexyl acrylate/acrylic acid (90 parts by weight/10 parts by weight), 0.2 parts by weight of benzoyl peroxide as an initiator, and 120 parts by weight of ethyl acetate. While slowly stirring, introduce nitrogen. Keep the liquid temperature in the flask at around 60°C and carry out a polymerization reaction for about 6 hours to obtain an acrylic copolymer (2) with a weight average molecular weight of 1.2 million. 15 parts by weight of 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) and 2 parts by weight of isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added as modified olefin resins to 85 parts by weight of acrylic copolymer (2), and diluted with toluene to prepare an adhesive (6) having a solid content of 15%. The obtained adhesive was applied to a substrate (polyimide film, manufactured by TORAY Co., Ltd., trade name "Kapton 100H", thickness: 25 μm) in such a manner that the thickness of the adhesive layer after drying became 10 μm, thereby obtaining an adhesive tape (7). The obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.

[Example 8] Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, 2-ethylhexyl acrylate/acrylic acid (100 parts by weight/2 parts by weight), 0.2 parts by weight of benzoyl peroxide as an initiator, and 230 parts by weight of ethyl acetate were added, and nitrogen was introduced while slowly stirring. The liquid temperature in the flask was maintained at approximately 60°C, and a polymerization reaction was carried out for about 6 hours to obtain an acrylic copolymer (3) with a weight average molecular weight of 650,000. 30 parts by weight of 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) and 2 parts by weight of isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added as modified olefin resins to 70 parts by weight of acrylic copolymer (3), and diluted with toluene to prepare an adhesive (7) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY Co., Ltd., trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying became 10 μm, thereby obtaining an adhesive tape (8). The obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.

[Example 9] Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, add n-butyl acrylate/acrylic acid (95 parts by weight/5 parts by weight), 0.2 parts by weight of 2,2'-azobisisobutyronitrile as an initiator, and 233 parts by weight of ethyl acetate. While slowly stirring, introduce nitrogen. Keep the liquid temperature in the flask at around 60°C and carry out a polymerization reaction for about 6 hours to obtain an acrylic copolymer (4) with a weight average molecular weight of 700,000. 15 parts by weight of 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) and 2 parts by weight of isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added as modified olefin resins to 85 parts by weight of acrylic copolymer (4), and diluted with toluene to prepare an adhesive (8) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY Co., Ltd., trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape (9). The obtained adhesive tape was subjected to the evaluations (1) to (5) above. The results are shown in Table 1.

[Example 10] Acrylic copolymer (2) was obtained in the same manner as in Example 7. 75 parts by weight of maleic anhydride-modified propylene-butene copolymer (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight: 75,000, melting point 70°C) and 2 parts by weight of isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added to 25 parts by weight of acrylic copolymer (2), and diluted with toluene to prepare an adhesive (9) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 12 μm) in such a manner that the thickness of the adhesive layer after drying was 3 μm, thereby obtaining an adhesive tape (10). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

[Example 11] An acrylic copolymer (1) was obtained in the same manner as in Example 1. 85 parts by weight of maleic anhydride-modified propylene-butene copolymer (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight: 75,000, melting point: 90°C) and 2 parts by weight of an isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added to 15 parts by weight of the acrylic copolymer (1), and diluted with toluene to prepare an adhesive (10) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying was 10 μm, thereby obtaining an adhesive tape (11). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

[Example 12] Acrylic copolymer (1) was obtained in the same manner as in Example 1. 15 parts by weight of maleic anhydride-modified propylene-butene copolymer (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight 75,000, melting point 70°C) and 0.5 parts by weight of aluminum chelate crosslinking agent (trade name "ALUMI-CHELATE A", manufactured by Kawaken Fine Chemicals Co., Ltd.) were added to 85 parts by weight of acrylic copolymer (1), and diluted with toluene to prepare an adhesive (11) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 12 μm) in such a manner that the thickness of the adhesive layer after drying was 10 μm, thereby obtaining an adhesive tape (12). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

[Example 13] An acrylic copolymer (1) was obtained in the same manner as in Example 1. 85 parts by weight of maleic anhydride-modified propylene-butene copolymer (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight 75,000, melting point 70°C) and 0.2 parts by weight of an aluminum chelate crosslinking agent (trade name "ALUMI-CHELATE A", manufactured by Kawaken Fine Chemicals Co., Ltd.) were added to 15 parts by weight of the acrylic copolymer (1), and diluted with toluene to prepare an adhesive (12) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 12 μm) in such a manner that the thickness of the adhesive layer after drying was 5 μm, thereby obtaining an adhesive tape (13). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

[Example 14] An acrylic copolymer (1) was obtained in the same manner as in Example 1. 75 parts by weight of a maleic anhydride-modified propylene-butene copolymer resin (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-T", weight average molecular weight 75,000, melting point 90°C) and 0.1 parts by weight of an epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C") were added to 25 parts by weight of the acrylic copolymer (1) as a modified olefin resin, and diluted with toluene to prepare an adhesive (13) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 12 μm), and an adhesive tape (14) was obtained. The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 1.

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

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

[Comparative Example 3] Acrylic copolymer (1) was obtained in the same manner as in Example 1. 0.5 parts by weight of epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C") was added to 100 parts by weight of acrylic copolymer (1), and the mixture was diluted with toluene to prepare an adhesive (C3) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape (C3). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 4] Acrylic copolymer (4) was obtained in the same manner as in Example 9. 30 parts by weight of terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., trade name "YS Polystar S-145", softening point: about 145°C), 2 parts by weight of isocyanate crosslinking agent (manufactured by Tosoh Corporation, trade name "Coronate L"), and 0.03 parts by weight of epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C") were added to 100 parts by weight of acrylic copolymer (4), and diluted with toluene to prepare an adhesive (C4) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying was 10 μm, thereby obtaining an adhesive tape (C4). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 5] Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, 2-ethylhexyl acrylate/2-hydroxyethyl acrylate (100 parts by weight/4 parts by weight), 0.2 parts by weight of 2,2'-azobisisobutyronitrile as an initiator, and 233 parts by weight of ethyl acetate were added, and nitrogen was introduced while slowly stirring. The liquid temperature in the flask was maintained at approximately 60°C, and a polymerization reaction was carried out for about 6 hours to obtain an acrylic copolymer (5) with a weight average molecular weight of 550,000. 15 parts by weight of 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) and 2 parts by weight of isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added as modified olefin resins to 85 parts by weight of acrylic copolymer (5), and diluted with toluene to prepare an adhesive (C5) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY Co., Ltd., trade name "Torayfan", thickness 30 μm) in such a manner that the thickness of the adhesive layer after drying became 10 μm, to obtain an adhesive tape (C5). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 6] Acrylic copolymer (5) was obtained in the same manner as in Comparative Example 5. 75 parts by weight of maleic anhydride-modified propylene-butene copolymer (manufactured by Toyobo Co., Ltd., trade name "Toyotac PMA-L", weight average molecular weight: 75,000, melting point: 70°C) and 2 parts by weight of isocyanate crosslinking agent (manufactured by Tosoh Co., Ltd., trade name "Coronate L") were added to 25 parts by weight of acrylic copolymer (5), and diluted with toluene to prepare an adhesive (C6) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY, trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying was 10 μm, thereby obtaining an adhesive tape (C6). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 2.

[Comparative Example 7] 100 parts by weight of 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) as a modified olefin resin was dissolved in toluene to prepare an adhesive (C7) having a solid content of 15%. The obtained adhesive was applied to a substrate (polypropylene film, manufactured by TORAY Co., Ltd., trade name "Torayfan", thickness: 30 μm) in such a manner that the thickness of the adhesive layer after drying became 10 μm, thereby obtaining an adhesive tape (C7). The obtained adhesive tape was subjected to the evaluations of (1) to (5) above. The results are shown in Table 2.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Adhesive composition [parts by weight] Acrylic copolymer (1) 2EHA/AA=95/5 (Mw 1.3 million) 75 75 75 85 85 75 15 85 15 25 (2) 2EHA/AA=90/10 (Mw 1.2 million) 85 25 (3) 2EHA/AA=100/2 (Mw 650,000) 70 (4) BA/AA=95/5 (Mw 700,000) 85 (5) 2EHA/HEA=100/4 (Mw 600,000) 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 series 0.1 Aluminum Chelate 0.5 0.2 Adhesion agents 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 Reviews Adhesion force [N/10 mm] Normal temperature compression 1.47 1.70 1.29 0.80 2.03 1.27 2.73 2.07 1.00 1.50 Heating Pressing 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] Normal temperature compression 1.24 1.35 1.35 1.95 1.15 1.03 1.74 0.57 0.45 2.18 Heating Pressing 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 Fog 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] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparative Example 6 Comparison Example 7 Adhesive composition [parts by weight] Acrylic copolymer (1) 2EHA/AA=95/5 (Mw 1.3 million) 100 100 100 (2) 2EHA/AA=90/10 (Mw 1.2 million) (3) 2EHA/AA=100/2 (Mw 650,000) (4) BA/AA=95/5 (Mw 700,000) 100 (5) 2EHA/HEA=100/4 (Mw 550,000) 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 series 0.5 0.03 Aluminum Chelate Adhesion agents 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 Reviews Adhesion force [N/10 mm] Normal temperature compression 2.87 2.10 0.87 4.03 0.13 Heating Pressing 3.43 2.64 0.90 5.73 0.60 0.30 5.70 Adhesion in non-aqueous electrolyte [N/10 mm] Normal temperature compression 0.92 1.23 ×Peel ×Peel ×Peel Heating Pressing 1.02 1.47 ×Peel ×Peel ×Peel ×Peel 5.90 Probe viscosity value [gf] 508.2 348.7 184.2 251.0 212.0 4.5 0.0 Fog 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: Base material 20,30: Adhesive layer 100,200: Adhesive tape for non-aqueous batteries

FIG1 is a schematic cross-sectional view of an adhesive tape for a non-aqueous battery according to one embodiment of the present invention. FIG2 is a schematic cross-sectional view of an adhesive tape for a non-aqueous battery according to another embodiment of the present invention.

10: Base material

20: Adhesive layer

100: Adhesive tape for non-aqueous batteries

Claims (11)

An adhesive for non-aqueous batteries, which exhibits adhesiveness by compression bonding, and comprises an acrylic polymer having an acid functional group, and a crystalline resin having a melting point of 25°C or above, wherein the crystalline resin is a polyolefin resin, and the polyolefin resin is a maleic anhydride-modified polyolefin resin, a maleic acid-modified polyolefin resin, or an acrylic acid-modified polyolefin resin. For example, the adhesive for non-aqueous batteries in claim 1 exhibits adhesion by heating. As in claim 1 or 2, the non-aqueous battery adhesive, wherein the 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 4 or more carbon atoms. As in claim 3, the non-aqueous battery adhesive, 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. For example, the non-aqueous battery adhesive of claim 1 or 2 contains C5 petroleum resin and/or C9 petroleum resin. An adhesive tape for non-aqueous batteries, comprising an adhesive for non-aqueous batteries as described in any one of claims 1 to 5. The adhesive tape for non-aqueous batteries as claimed in claim 6 comprises a substrate and an adhesive layer disposed on at least one side of the substrate, and the adhesive layer comprises an adhesive for non-aqueous batteries as claimed in any one of claims 1 to 5. As in claim 7, the adhesive tape for non-aqueous batteries, wherein the substrate is formed by at least one selected from polyacrylate, polyurethane, polyimide, polyarylamide, polyamide, ethylene-vinyl alcohol copolymer, polyetherimide, polyvinylidene fluoride, polyester, polypropylene, polyethylene, and polyphenylene sulfide. For example, in the adhesive tape for non-aqueous batteries of claim 7 or 8, a peeling film is provided on the side of the adhesive layer opposite to the substrate. As in the adhesive tape for non-aqueous batteries of claim 7 or 8, the adhesive layer is disposed on one side of the substrate, and the other adhesive layer is disposed on the other side of the substrate. A non-aqueous battery, comprising an adhesive tape for a non-aqueous battery as described in any one of claims 6 to 10.