Battery forming composition, secondary battery member, secondary battery, and laminate

Abstract

Provided is a battery forming composition which has improved adhesiveness. Specifically provided is a battery forming composition which contains a binder resin and an adhesiveness modifier, the adhesiveness modifier being a polyester represented by general formula (1-1), (1-2), or (1-3) (wherein G represents an aliphatic diol residue having 2-50 carbon atoms, A represents an aromatic dicarboxylic acid residue having 4-18 carbon atoms, X represents a monocarboxylic acid residue having 1-20 carbon atoms, Y represents a monoalcohol residue having 1-30 carbon atoms, and n represents the number of repetitions).

Description

Battery-forming composition, secondary battery component, secondary battery, and laminate

[0001] The present invention relates to a battery-forming composition, a secondary battery component, a secondary battery, and a laminate.

[0002] In recent years, the introduction of electric vehicles (EVs) has been rapidly progressing in various countries in order to achieve reductions in carbon dioxide emissions. EVs generally use lithium-ion batteries (LiB) as their power source, and since the performance of these LiBs determines the driving range of the EV, there is a demand for higher performance LiBs.

[0003] LiB is a laminate containing a positive electrode sheet, a separator, and a negative electrode sheet. Here, the electrode sheets (positive electrode sheet and negative electrode sheet) are usually formed by coating and drying an electrode mixture slurry containing electrode active material, binder resin, etc., onto a current collector such as aluminum foil.

[0004] Improving battery performance requires increasing the density of electrode active material in the electrode mixture. However, this density relatively reduces the binder resin content, leading to insufficient adhesion to the current collector, which was previously ensured by the binder resin. This can cause the electrode sheet to detach from the current collector.

[0005] To address the above issues, a method has been proposed in which the surface of the current collector is treated with a coupling agent (for example, Patent Document 1).

[0006] Japanese Patent Application Publication No. 9-199112

[0007] The problem that this invention aims to solve is to provide a battery forming composition with improved adhesion. The problem that this invention aims to solve is to provide a secondary battery component with improved adhesion. The problem that this invention aims to solve is to provide a secondary battery in which the detachment of the electrode sheet from the current collector is suppressed. The problem that this invention aims to solve is to provide a laminate in which the detachment of the resin layer from the metal layer is suppressed.

[0008] As a result of diligent research to solve the above problems, the inventors of the present invention discovered that an adhesion modifier, which is a polyester having a specific structure, improves the adhesion of the binder resin, and thus completed the present invention.

[0009] In other words, the present invention relates to the following battery-forming compositions, etc. 1. A battery-forming composition comprising a binder resin and an adhesion modifier, wherein the adhesion modifier is a polyester represented by the following general formulas (1-1), (1-2), or (1-3). (In the general formulas (1-1), (1-2), and (1-3) above, G is an aliphatic diol residue having 2 to 50 carbon atoms, A is an aromatic dicarboxylic acid residue having 4 to 18 carbon atoms, X is a monocarboxylic acid residue having 1 to 20 carbon atoms, Y is a monoalcohol residue having 1 to 30 carbon atoms, and n represents the number of repetitions.) 2. The battery-forming composition according to 1, wherein A is one or more selected from phthalic acid residues, isophthalic acid residues, terephthalic acid residues, and naphthalenedicarboxylic acid residues. 3. The battery-forming composition according to 1, wherein G is an aliphatic diol residue having a branched structure having 3 to 20 carbon atoms. 4. The battery-forming composition according to 1, wherein the polyester is an amorphous polyester. 5. The battery-forming composition according to 1, wherein the number-average molecular weight of the polyester is in the range of 400 to 10,000. 6. The battery-forming composition according to 1, wherein the content of the polyester is in the range of 1 to 30 parts by mass per 100 parts by mass of the binder resin. 7. The battery-forming composition according to claim 1, further comprising a metal chelate compound. 8. The battery-forming composition according to claim 1, further comprising an aluminum chelate compound represented by the following general formula (5-1) and / or an aluminum chelate compound represented by the following general formula (5-2). (In the above general formulas (5-1) and (5-2), R ５１１ ~R ５１６ and R ５２１ ~R ５２６Each is independently an alkyl group having 1 to 22 carbon atoms or an alkoxy group having 1 to 22 carbon atoms. ) 9. The battery-forming composition according to 8, wherein the content of the aluminum chelate compound is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the binder resin. 10. The battery-forming composition according to 1, wherein the binder resin is a fluorine-containing resin. 11. The battery-forming composition according to 1, further containing an electrode active material. 12. A secondary battery member comprising the battery-forming composition according to any one of 1 to 11. 13. A secondary battery comprising the secondary battery member according to 12. 14. A laminate in which a resin layer and a metal layer are laminated, wherein the resin layer contains a binder resin, an adhesion modifier, and a metal chelate compound, and the adhesion modifier is a polyester represented by the following general formula (1-1), (1-2) or (1-3). (In the above general formulas (1-1), (1-2) and (1-3), G is an aliphatic diol residue having 2 to 50 carbon atoms, A is an aromatic dicarboxylic acid residue having 4 to 18 carbon atoms, X is a monocarboxylic acid residue having 1 to 20 carbon atoms, Y is a monoalcohol residue having 1 to 30 carbon atoms, and n represents the number of repetitions.) 15. The laminate according to 14, wherein the metal chelate compound is an aluminum chelate compound represented by the following general formula (5-1) and / or an aluminum chelate compound represented by the following general formula (5-2). (In the above general formulas (5-1) and (5-2), R ５１１ ~R ５１６ and are R ５２１ ~R ５２６ Each is independently an alkyl group having 1 to 22 carbon atoms or an alkoxy group having 1 to 22 carbon atoms. ) 16. The laminate according to 14, wherein the metal layer is an aluminum layer. <00�0089> According to the present invention, a battery-forming composition with improved adhesiveness can be provided. According to the present invention, a secondary battery member with improved adhesiveness can be provided. According to the present invention, a secondary battery that suppresses the detachment of the electrode sheet from the current collector can be provided. According to the present invention, a laminate that suppresses the detachment of the resin layer from the metal layer can be provided.

[0011] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the range that does not impair the effects of the present invention. In addition, the compounds in this specification may be derived from fossil resources or may be derived from biological resources.

[0012] [Battery-forming composition] The battery-forming composition of the present invention is a composition containing a binder resin and an adhesion modifier. Hereinafter, each component contained in the battery-forming composition of the present invention will be described.

[0013] (Adhesion modifier) The adhesion modifier contained in the battery-forming composition of the present invention is a polyester represented by the following general formula (1-1), (1-2) or (1-3). Hereinafter, the polyester which is the adhesion modifier may be referred to as "the polyester of the present invention".

[0014] (In the general formulas (1-1), (1-2) and (1-3), G is an aliphatic diol residue having 2 to 50 carbon atoms, A is an aromatic dicarboxylic acid residue having 4 to 18 carbon atoms, X is a monocarboxylic acid residue having 1 to 20 carbon atoms, Y is a monoalcohol residue having 1 to 30 carbon atoms, and n represents the number of repetitions.)

[0015] It is presumed that when the battery-forming composition contains the polyester of the present invention, the viscoelastic behavior of the binder resin is changed and the adhesion of the battery-forming composition is improved.

[0016] In the present invention, the "diol residue" and the "alcohol residue" refer to the remaining organic groups obtained by removing the hydroxyl group from the diol and the alcohol. In the present invention, the "carboxylic acid residue" refers to the remaining organic group obtained by removing the carboxyl group from the carboxylic acid. Regarding the number of carbon atoms of the carboxylic acid residue, the carbon atom in the carboxyl group is not included.

[0017] The fatty chain of aliphatic diol residues of G having 2 to 50 carbon atoms may be linear or branched, and may contain alicyclic structures and / or ether bonds. Furthermore, the fatty chain of aliphatic diol residues of G may be saturated or unsaturated, having carbon-carbon unsaturated bonds.

[0018] The aliphatic diol residue of G having 2 to 50 carbon atoms preferably includes an aliphatic diol residue having a branched structure with 3 to 20 carbon atoms, and more preferably includes a diol residue of a diol represented by the following general formula (G-1). (In the general formula (G-1) above, p is an integer of 1 or more, q is an integer of 0 or more, r is an integer of 1 or more, R is a hydrogen atom or an alkyl group having 1 or more carbon atoms, at least one of the r Rs is an alkyl group having 1 or more carbon atoms, and the sum of the number of carbon atoms of p, q, r, and R is an integer in the range of 3 to 20.)

[0019] The aliphatic diol residue of G having 2 to 50 carbon atoms is preferably an alkylene glycol residue having 2 to 50 carbon atoms and / or an oxyalkylene glycol residue having 2 to 50 carbon atoms.

[0020] Examples of alkylene glycol residues of G with 2 to 50 carbon atoms include ethylene glycol residues, 1,2-propylene glycol residues, 1,3-propanediol residues, 1,2-butanediol residues, 1,3-butanediol residues, 2-methyl-1,3-propanediol residues, 1,4-butanediol residues, 1,5-pentanediol residues, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) residues, 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane) residues, and 2 Examples include -n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane) residues, 3-methyl-1,5-pentanediol residues, 1,6-hexanediol residues, 2,2,4-trimethyl-1,3-pentanediol residues, 2-ethyl-1,3-hexanediol residues, 2-methyl-1,8-octanediol residues, 1,9-nonanediol residues, 1,10-decanediol residues, 1,12-dodecanediol residues, 1,2-tetradecanediol residues, and 1,2-dodecanediol residues.

[0021] The alkylene glycol residue of G having 2 to 50 carbon atoms is preferably an alkylene glycol residue having 2 to 20 carbon atoms.

[0022] The aliphatic diol residue of G having 2 to 50 carbon atoms may include an alicyclic structure. Examples of aliphatic diol residues having 2 to 20 carbon atoms including such an alicyclic structure include 1,3-cyclopentanediol residue, 1,2-cyclohexanediol residue, 1,3-cyclohexanediol residue, 1,4-cyclohexanediol residue, 1,2-cyclohexanedimethanol residue, and 1,4-cyclohexanedimethanol residue.

[0023] The oxyalkylene glycol residue of G having 2 to 50 carbon atoms is an alkylene glycol residue containing one or more ether bonds (-O-). Examples of such oxyalkylene glycol residues having 2 to 50 carbon atoms include diethylene glycol residues, triethylene glycol residues, tetraethylene glycol residues, dipropylene glycol residues, trippropylene glycol residues, polyethylene glycol residues, and polypropylene glycol residues.

[0024] The aromatic dicarboxylic acid residue of A having 4 to 18 carbon atoms is a dicarboxylic acid residue in which two carboxyl groups are substituted on an aromatic ring, and the aromatic ring may be further substituted with substituents (for example, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms).

[0025] Examples of aromatic dicarboxylic acid residues of A having 4 to 18 carbon atoms include 2,5-franjic acid, phthalic acid residues, isophthalic acid residues, terephthalic acid residues, 1,4-naphthalenedicarboxylic acid residues, 1,5-naphthalenedicarboxylic acid residues, 2,3-naphthalenedicarboxylic acid residues, 2,6-naphthalenedicarboxylic acid residues, 4,4'-biphenyldicarboxylic acid, 1,5-anthracenedicarboxylic acid, 2,3-anthracenedicarboxylic acid residues, and 9,10-anthracenedicarboxylic acid.

[0026] Furthermore, in this specification, "aromatic dicarboxylic acid residue" includes those in which an aromatic ring is further substituted with a substituent (for example, an alkyl group having 1 to 6 carbon atoms). For example, "terephthalic acid residue" also includes dimethyl terephthalate residue, and the above-mentioned "2,6-naphthalenedicarboxylic acid residue" also includes dimethyl 2,6-naphthalenedicarboxylic acid residue.

[0027] The aromatic dicarboxylic acid residue of A having 4 to 18 carbon atoms is preferably an aromatic dicarboxylic acid residue having 6 to 18 carbon atoms, and more preferably includes one or more selected from phthalic acid residues, isophthalic acid residues, terephthalic acid residues, and naphthalenedicarboxylic acid residues.

[0028] The monocarboxylic acid residue X having 1 to 20 carbon atoms may be, for example, an aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms or an aromatic monocarboxylic acid residue having 4 to 20 carbon atoms, and is preferably an aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms.

[0029] If X is an aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms, the fatty chain of the aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms may be linear or branched, and may contain an alicyclic structure and / or ether bonds. Furthermore, the fatty chain of the aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms may be a saturated fatty chain or an unsaturated fatty chain having carbon-carbon unsaturated bonds.

[0030] When X is an aromatic monocarboxylic acid residue having 4 to 20 carbon atoms, the aromatic monocarboxylic acid residue is preferably an aromatic monocarboxylic acid residue having 6 to 20 carbon atoms. Furthermore, the aromatic ring of the aromatic monocarboxylic acid residue may be further substituted with substituents (for example, alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 6 carbon atoms).

[0031] Examples of monocarboxylic acid residues of X having 1 to 20 carbon atoms include acetic acid residues, propionic acid residues, butanoic acid residues, hexanoic acid residues, octanoic acid residues, octic acid residues, benzoic acid residues, dimethylbenzoic acid residues, trimethylbenzoic acid residues, tetramethylbenzoic acid residues, ethylbenzoic acid residues, propylbenzoic acid residues, butylbenzoic acid residues, cuminic acid residues, para-tertrialybutylbenzoic acid residues, orthotoluic acid residues, metatoluic acid residues, paratoluic acid residues, ethoxybenzoic acid residues, propoxybenzoic acid residues, anisic acid residues, and the like.

[0032] The monoalcohol residue of Y having 1 to 30 carbon atoms may be, for example, an aliphatic monoalcohol residue having 1 to 30 carbon atoms or an aromatic monoalcohol residue having 4 to 30 carbon atoms, and is preferably an aliphatic monoalcohol residue having 1 to 30 carbon atoms.

[0033] When Y is an aliphatic monoalcohol residue having 1 to 30 carbon atoms, the fatty chain of the aliphatic monoalcohol residue having 1 to 30 carbon atoms may be linear or branched, and may contain an alicyclic structure and / or ether bonds. Furthermore, the fatty chain of the aliphatic monoalcohol residue having 1 to 30 carbon atoms may be a saturated fatty chain or an unsaturated fatty chain having carbon-carbon unsaturated bonds.

[0034] When Y is an aromatic monoalcohol residue having 4 to 20 carbon atoms, the aromatic monoalcohol residue is preferably an aromatic monoalcohol residue having 6 to 20 carbon atoms. Furthermore, the aromatic ring of the aromatic monoalcohol residue may be further substituted with substituents (for example, alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 6 carbon atoms).

[0035] The monoalcohol residue of Y having 1 to 30 carbon atoms is preferably an alkylalcohol residue having 1 to 10 carbon atoms or an alcohol residue of a polyalkylene glycol monoalkyl ether having 5 to 30 carbon atoms.

[0036] Examples of alkyl alcohol residues of Y having 1 to 10 carbon atoms include methanol residues, ethanol residues, propanol residues, butanol residues, pentanol residues, hexanol residues, cyclohexanol residues, heptanol residues, octanol residues, nonanol residues, decanol residues, and the like.

[0037] Examples of alcohol residues in polyalkylene glycol alkyl ethers with 5 to 30 carbon atoms in Y include polyethylene glycol alkyl ethers such as diethylene glycol monomethyl ether and triethylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as polypropylene glycol monomethyl ether and polypropylene glycol monoethyl ether; and alcohol residues such as (polyethylene glycol / polypropylene glycol) monoalkyl ether.

[0038] The average number of repeats of n is preferably in the range of 0.1 to 20, more preferably in the range of 0.2 to 15, and more preferably in the range of 0.5 to 10. The average number of repeats of n can be calculated from the number-average molecular weight of the polyester of the present invention.

[0039] The number-average molecular weight (Mn) of the polyester of the present invention has a lower limit of, for example, 300 or more, 400 or more, 500 or more, 1,000 or more, or 1,500 or more, and an upper limit of, for example, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, or 4,000 or less. The number-average molecular weight (Mn) of the polyester of the present invention is, for example, in the range of 300 to 20,000, preferably in the range of 400 to 10,000, and more preferably in the range of 450 to 8,000. The above number-average molecular weight (Mn) is a value converted to polystyrene based on gel permeation chromatography (GPC) measurement, and is measured by the method described in the examples.

[0040] The acid value of the polyester of the present invention has a lower limit of, for example, 0.001 mg KOH / g or more, 0.01 mg KOH / g or more, 0.1 mg KOH / g or more, or 1 mg KOH / g or more, and an upper limit of, for example, 10 mg KOH / g or less, 5 mg KOH / g or less, 3 mg KOH / g or less, or 1 mg KOH / g or less. The acid value of the polyester of the present invention is, for example, in the range of 0.001 to 3 mg KOH / g. The acid value of the above polyester is confirmed by the method described in the examples.

[0041] The hydroxyl value of the polyester of the present invention is, for example, in the range of 0.1 to 400 mgKOH / g, preferably in the range of 0.1 to 200 mgKOH / g, and more preferably in the range of 0.1 to 100 KOH / g. The hydroxyl value of the polyester is confirmed by the method described in the examples.

[0042] The polyester of the present invention is preferably amorphous polyester. Here, "amorphous" means that the polyester does not show a clear endothermic peak in differential scanning calorimetry (DSC). Specifically, an amorphous polyester is a polyester that does not show a clear endothermic peak when differential scanning calorimetry is performed as described in the examples. Being amorphous makes the polyester more easily soluble in binder resins and solvents, thereby enhancing the modification effect of the polyester.

[0043] The polyester of the present invention may be any polyester that satisfies the above general formula (1-1), (1-2), or (1-3), and may be used as a mixture of two or more polyesters with different structures.

[0044] The lower limit of the polyester content of the present invention is, for example, 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, 2.5 parts by mass or more, or 3.0 parts by mass or more, per 100 parts by mass of the binder resin. The upper limit of the polyester content of the present invention is, for example, 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, or 7.5 parts by mass or less, per 100 parts by mass of the binder resin. The range of the polyester content of the present invention is, for example, in the range of 1 to 50 parts by mass, preferably in the range of 1 to 30 parts by mass, and more preferably in the range of 1 to 20 parts by mass, per 100 parts by mass of the binder resin.

[0045] The polyester of the present invention is obtained using reaction raw materials comprising an aliphatic diol, an aromatic dicarboxylic acid, a monoalcohol and / or a monocarboxylic acid (however, the production of the polyester represented by general formula (1-3) does not require a monoalcohol and / or a monocarboxylic acid. The monoalcohol and / or a monocarboxylic acid are optional components). Here, "reaction raw materials" means the raw materials that constitute the polyester of the present invention, and does not include solvents or catalysts that do not constitute the polyester. The method for producing the polyester of the present invention is not particularly limited and can be produced by known methods, or by the production method described later.

[0046] The reaction raw materials for the polyester of the present invention may include an aliphatic diol, an aromatic dicarboxylic acid, a monoalcohol and / or a monocarboxylic acid, and may also include other raw materials. Preferably, the reaction raw materials for the polyester of the present invention consist of an aliphatic diol, an aromatic dicarboxylic acid, a monoalcohol and / or a monocarboxylic acid in an amount of 90% by mass or more of the total amount of reaction raw materials, and more preferably consist only of aliphatic diol, an aromatic dicarboxylic acid, a monoalcohol and / or a monocarboxylic acid.

[0047] The aliphatic diol used in the production of the polyester of the present invention is an aliphatic diol corresponding to an aliphatic diol residue of G having 2 to 50 carbon atoms, and the aliphatic diol used may be used alone or in combination of two or more types. The aromatic dicarboxylic acid used in the production of the polyester of the present invention is an aromatic dicarboxylic acid corresponding to an aromatic dicarboxylic acid residue of A having 4 to 18 carbon atoms, and the aromatic dicarboxylic acid used may be used alone or in combination of two or more types. The monocarboxylic acid used in the production of the polyester of the present invention is a monocarboxylic acid corresponding to a monocarboxylic acid residue of X having 1 to 20 carbon atoms, and the monocarboxylic acid used may be used alone or in combination of two or more types. The monoalcohol used in the production of the polyester of the present invention is a monoalcohol corresponding to a monoalcohol residue of Y having 1 to 30 carbon atoms, and the monoalcohol used may be used alone or in combination of two or more types.

[0048] Hydrogenated vegetable oil fatty acids may be used as the monocarboxylic acid in the production of the polyester of the present invention. Examples of such hydrogenated vegetable oil fatty acids include hydrogenated coconut oil fatty acid, hydrogenated palm kernel oil fatty acid, hydrogenated palm oil fatty acid, hydrogenated olive oil fatty acid, hydrogenated castor oil fatty acid, and hydrogenated rapeseed oil fatty acid. These are obtained by hydrolysis and hydrogenation of oils obtained from coconut, palm kernel, palm, olive, castor, and rapeseed, respectively, and are all mixtures of two or more long-chain aliphatic monocarboxylic acids containing aliphatic monocarboxylic acids with 8 to 21 carbon atoms. In addition, the above vegetable oil fatty acids that have not been hydrogenated may be used as the monocarboxylic acid in the production of the polyester of the present invention, as long as they do not impair the effects of the present invention. Furthermore, the vegetable oil fatty acids are not limited to those listed above.

[0049] When the polyester of the present invention is a polyester reacted with an aliphatic diol, an aromatic dicarboxylic acid, and a hydrogenated vegetable oil fatty acid, the resulting polyester is obtained as a mixture of two or more polyesters represented by the general formula (1-1).

[0050] The aliphatic diols, aromatic dicarboxylic acids, monoalcohols, and monocarboxylic acids used in the production of the polyester of the present invention can all be derivatives thereof. Examples of such derivatives include esterified compounds, acid chlorides, acid anhydrides, and cyclic esters. For example, since epoxy compounds undergo ring-opening to form diols when reacted with carboxylic acids, aliphatic epoxy compounds may be used as derivatives of aliphatic diols used as reaction raw materials in the present invention.

[0051] The polyester represented by the general formula (1-1) can be produced, for example, by reacting an aliphatic diol, an aromatic dicarboxylic acid, and a monocarboxylic acid all at once, with the equivalent amount of carboxyl groups being greater than the equivalent amount of hydroxyl groups. Alternatively, the polyester represented by the general formula (1-1) can also be produced, for example, by reacting an aliphatic diol and an aromatic dicarboxylic acid in any equivalent ratio, and then reacting the terminal hydroxyl groups of the resulting polyester with a monocarboxylic acid to encapsulate the hydroxyl groups with carboxylic acid residues.

[0052] The polyester represented by the general formula (1-2) can be produced, for example, by reacting an aliphatic diol, an aromatic dicarboxylic acid, and a monoalcohol all at once, with the equivalent amount of carboxyl groups being greater than the equivalent amount of hydroxyl groups. Alternatively, the polyester represented by the general formula (1-2) can also be produced, for example, by reacting an aliphatic diol and an aromatic dicarboxylic acid in any equivalent ratio, and then reacting the ends of the resulting polyester with a monoalcohol.

[0053] The polyester represented by the general formula (1-3) can be produced, for example, by reacting an aliphatic diol and an aromatic dicarboxylic acid in a single charge, with the equivalent amount of hydroxyl groups being greater than the equivalent amount of carboxyl groups. Alternatively, the polyester represented by the general formula (1-3) can also be produced, for example, by reacting an aliphatic diol and an aromatic dicarboxylic acid in any equivalent ratio, and then reacting the ends of the resulting polyester with an aliphatic diol.

[0054] In the production of polyester according to the present invention, the reaction of the reaction raw materials may be carried out in the presence of an esterification catalyst as needed, for example, at a temperature range of 170 to 250°C for 10 to 25 hours. The temperature, time, and other conditions of the esterification reaction are not particularly limited and may be set as appropriate.

[0055] Examples of the esterification catalysts include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; zinc-based catalysts such as zinc acetate; tin-based catalysts such as tin octoate and dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.

[0056] The amount of esterification catalyst used can be set as appropriate, but it is usually used in the range of 0.0001 to 0.1 parts by mass per 100 parts by mass of the total amount of reaction raw materials.

[0057] (Metal Chelate Compound) The battery-forming composition of the present invention preferably contains a metal chelate compound. By containing a metal chelate compound in the battery-forming composition, the adhesiveness of the battery-forming composition can be improved. Here, the "metal chelate compound" is a general term for compounds in which metal ions serve as electron acceptors and coordinate-bond with electron donors to form a cyclic structure. Examples of such metals include titanium, copper, nickel, cobalt, aluminum, iron, and the like.

[0058] The metal chelate compound contained in the battery-forming composition of the present invention is preferably an aluminum chelate compound, and more preferably one or more selected from the compounds represented by the following general formula (5-1) and the compounds represented by the following general formula (5-2).

[0059] (In the above general formulas (5-1) and (5-2), R ５１１ to R ５１６ and are R ５２１ to R ５２６ are each independently an alkyl group having 1 to 22 carbon atoms or an alkoxy group having 1 to 22 carbon atoms.) <00,00191>

[0060] R ５１１ to R ５１６ and are R ５２１ to R ５２６ The alkylene group portions of the alkyl group having 1 to 22 carbon atoms and the alkoxy group having 1 to 22 carbon atoms of R ５１１ to R ５１６ and are R ５２１ ,, to R ５２６ may be linear, branched, or may contain an alicyclic structure. The number of carbon atoms in the alkylene group portions of the alkyl group and the alkoxy group of R

[0061] R ５１１ to R ５１６ and are R ５２１ to R ５２６ The alkyl group having 1 to 22 carbon atoms is preferably a methyl group or an ethyl group.

[0062] R ５１１ to R ５１６ and are R ５２１ to R ５２６The alkoxy group having 1 to 22 carbon atoms is preferably a methoxy group, an ethoxy group, or an oleyloxy group.

[0063] Specific examples of aluminum chelate compounds include aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum monoacetylacetonate bisoleylacetoacetate, ethylacetoacetate aluminum diisopropylate, and alkylacetoacetate aluminum diisopropylate.

[0064] The metal chelate compound contained in the battery-forming composition of the present invention may be a single compound or two or more compounds with different structures.

[0065] The lower limit of the content of the metal chelate compound is, for example, 0.1 parts by mass or more, 1.0 parts by mass or more, 3.0 parts by mass or more, 5.0 parts by mass or more, or 10 parts by mass or more per 100 parts by mass of the binder resin. The upper limit of the content of the metal chelate compound is, for example, 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less per 100 parts by mass of the binder resin. The content of the metal chelate compound is, for example, in the range of 1 to 50 parts by mass per 100 parts by mass of the binder resin, preferably in the range of 5 to 40 parts by mass, and more preferably in the range of 10 to 30 parts by mass.

[0066] Aluminum chelate compounds can be produced by known methods, and commercially available products may also be used. An example of such a commercially available product is DICNATE AL-500 (manufactured by DIC Corporation).

[0067] (Binder Resin) The binder resin of the battery-forming composition of the present invention is not particularly limited as long as it is a resin having binder function (adhesion). Examples of binder resins include polyimide resins; fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene; polyolefin resins such as polyethylene and polypropylene; poly(meth)acrylic acid resins such as polyacrylic acid, polymethacrylic acid, polyacrylic acid esters, and polymethacrylic acid esters; carboxymethylene cellulose; styrene-butadiene rubber, polyvinyl alcohol, and polyvinylpyrrolidone. Of these, the binder resin is preferably a fluorine-containing resin.

[0068] The binder resin can be manufactured by known methods, or a commercially available product may be used.

[0069] (Electrode Active Material) When the battery forming composition of the present invention is, for example, an electrode forming composition (electrode composite material), the battery forming composition of the present invention preferably contains an electrode active material. Depending on whether the battery forming composition is used as the positive electrode or the negative electrode, a positive electrode active material and a negative electrode active material are used as the electrode active material.

[0070] Examples of positive electrode active materials include oxide-based positive electrode active materials and sulfide-based positive electrode active materials.

[0071] Oxide-based cathode active materials include LMO (lithium manganese oxide), LCO (lithium cobalt oxide), NMC (lithium nickel manganese cobalt oxide), NCA (lithium nickel cobalt aluminate), LNCO (lithium nickel cobalt oxide), and lithium-containing olivine-type phosphate (LiMePO). ４ Lithium-containing transition metal composite oxides such as Me (Fe, Co, Ni, Mn) are preferred.

[0072] A specific example of an oxide-based cathode active material is LiCoO ２ LiMnO ２ LiNiO ２ LiVO ２ LiNi ｘ Co ｙ Mn ｚ O ２ rock salt layered active materials such as LiMn２ O ４ Li ４ Ti ５ O １２ , Li(Ni ０．５ Mn １．５ ) O ４ Spinel-type active materials such as LiFePO ４ LiMnPO ４ LiNiPO ４ LiCoPO ４ Lithium iron manganese phosphate (LiMn ｘ Fe １－ｘ PO ４ Examples include olivine-type organisms such as those where 0 < x < 1.

[0073] As a sulfide-based cathode active material, titanium sulfide (TiS) ２ ), molybdenum sulfide (MoS ２ ), iron sulfide (FeS, FeS ２ ), copper sulfide (CuS), nickel sulfide (Ni ３ S ２ Examples include ) and others. Also, niobium selenide (NbSe ３ ) and others can also be used.

[0074] The positive electrode active material may be used alone or in combination of two or more types.

[0075] Examples of negative electrode active materials include carbon materials, chalcogen compounds (e.g., oxides, sulfides), nitrides, metals, or alloys, and materials that can be doped and dedoped with lithium ions at a lower potential than the positive electrode can be used.

[0076] Examples of carbon materials used as negative electrode active materials include graphite such as natural graphite and artificial graphite, coke, carbon black, carbon fibers, and calcined organic polymer compounds.

[0077] As an oxide for the negative electrode active material, SiO ２ , silicon oxides represented by the formula SiOx (where x is a positive real number), such as SiO; SnO ２ , tin oxides represented by the formula SnOx (where x is a positive real number), such as SnO; Li ４ Ti ５ O １２ LiVO ２Examples of metal composite oxides containing lithium and titanium include those mentioned above.

[0078] Examples of metals or alloys used as negative electrode active materials include elemental metals such as lithium metal, silicon metal, and tin metal, as well as alloys containing these metals.

[0079] Among the negative electrode active materials, carbon materials mainly composed of graphite, such as natural graphite or artificial graphite, are preferably used. The reasons for this include the fact that the potential of the negative electrode hardly changes from the uncharged state to the fully charged state during charging (good potential flatness), the average discharge potential is low, and the capacity retention rate when repeatedly charged and discharged is high (good cycle characteristics). The shape of the carbon material may be any of the following: for example, flakes like natural graphite, spheres like mesocarbon microbeads, fibers like graphitized carbon fibers, or aggregates of fine powder.

[0080] The negative electrode active material may be used alone or in combination of two or more types.

[0081] The content of the electrode active material is not particularly limited and should be set appropriately according to the purpose.

[0082] (Conductive Material) The battery-forming composition of the present invention preferably contains a conductive material. Examples of conductive materials include metals such as aluminum, stainless steel (SUS), silver, gold, copper, and titanium; and carbon fillers such as graphite, carbon black (acetylene black, furnace black, hollow carbon black, channel black, thermal black, Ketjen black, etc.), carbon nanotubes (single-walled carbon nanotubes, multi-walled carbon nanotubes, etc.), graphene, and graphene oxide.

[0083] The conductive material is preferably a carbon filler. The shape of the carbon filler, such as particle size, fiber length, and fiber diameter, is not particularly limited and can be adjusted as appropriate depending on the intended application. For example, carbon nanotubes include single-walled carbon nanotubes, in which one sheet of graphite is wound as a single layer, and multi-walled carbon nanotubes, in which two or more layers of graphite are wound as a multi-walled structure; both can be used. Furthermore, the surface treatment state of the carbon filler is not particularly limited, and the surface may be modified with, for example, saturated fatty acids, depending on the intended application.

[0084] The amount of conductive material is not particularly limited and should be set appropriately according to the purpose.

[0085] The battery-forming composition of the present invention may, for example, contain a solvent and be in the form of a slurry. As the solvent, organic solvents such as aromatic solvents, alcohol solvents, polyhydric alcohol solvents, glycol ether solvents, ester solvents, amine / amide solvents, heterocyclic solvents, and sulfone solvents, or water (purified water, distilled water, pure water, ultrapure water, etc.) can be used.

[0086] Examples of aromatic solvents that can be used include toluene, xylene, benzyl alcohol, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monophenyl ether, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, alkyl sulfonate phenyl ester, butyl phthalate, ethylhexyl phthalate, tridecyl phthalate, ethylhexyl trimellitate, diethylene glycol dibenzoate, and dipropylene glycol dibenzoate.

[0087] Examples of alcohol solvents that can be used include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butyl alcohol, 1-pentanol, isoamyl alcohol, sec-amyl alcohol, 3-pentanol, tert-amyl alcohol, n-hexanol, methylamyl alcohol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, nonanol, n-decanol, undecanol, n-decanol, trimethylnonyl alcohol, tetradecanol, heptadecanol, cyclohexanol, and 2-methylcyclohexanol.

[0088] Examples of polyhydric alcohol solvents that can be used include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, 3-methyl-1,3-buntanediol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, hexylene glycol, octylene glycol, and the like.

[0089] Examples of glycol ether solvents include methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl ether, butyl ether, hexyl ether, 2-ethylhexyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, 3-methyl-3-methoxy-1-butanol, 3-methoxy-1-butanol, and propylene glycol monomethyl ether. You can use propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, etc.

[0090] Examples of ester solvents include propylene glycol methyl ether acetate, propylene glycol diacetate, 3-methyl-3-methoxybutyl acetate, propylene glycol ethyl ether acetate, ethylene glycol ethyl ether acetate, butyl formate, isobutyl formate, isoamyl formate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, isobutyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, methyl isobutyrate, ethyl isobutyrate, and pro Pyryl, methyl valerate, ethyl valerate, propyl valerate, methyl isovalerate, ethyl isovalerate, propyl isovalerate, methyl trimethylacetate, ethyl trimethylacetate, propyl trimethylacetate, methyl caproate, ethyl caproate, propyl caproate, methyl caprylate, ethyl caprylate, propyl caprylate, methyl laurate, ethyl laurate, methyl oleate, ethyl oleate, caprylic triglyceride, tributyl citrate, octyl oxystearate, propylene glycol monolicinolate, methyl 2-hydroxyisobutyrate, 3-methoxybutyl acetate, etc. can be used.

[0091] As amine / amide solvents, for example, amines such as ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, and tetramethylpropylenediamine can be used, as well as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, and N-methylcaprolactam can be used. As heterocyclic solvents, chlorohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone can be used. As sulfone solvents, dimethyl sulfoxide, hexamethylphosphorotriamide, and sulfolane can be used.

[0092] The solvent content is not particularly limited; for example, the amount of solvent used to form the battery-forming composition of the present invention can be appropriately set to a slurry-like consistency.

[0093] The battery composition of the present invention may contain other additives besides those mentioned above, such as dispersants, thickeners, anti-settling agents, wetting agents, emulsifiers, anti-sagging agents, defoaming agents, leveling agents, and plasticizers.

[0094] The battery composition of the present invention does not contain a non-crosslinked polymer having a functional group capable of binding to metal ions of, for example, a metal chelate compound. Here, "functional group capable of binding to metal ions" refers to one or more selected from, for example, a carboxyl group, a sulfonic acid group, a carbonyl group, a hydroxyl group, and an amino group. Furthermore, "non-crosslinked polymer" refers to a polymer that is crosslinkable but has not yet been crosslinked, and is, for example, a polymer having a structure derived from an alkyl (meth)acrylate ester.

[0095] The battery composition of the present invention can be prepared, for example, by dispersing the above components using a known dispersion apparatus. Examples of such dispersion apparatus include mixers such as dispersers, homomixers, rotational mixers, Henschel mixers, and planetary mixers; media-type dispersers such as (high-pressure) homogenizers, paint conditioners, colloid mills, bead mills, cone mills, ball mills, sand mills, attritors, pearl mills, and coball mills; media-less dispersers such as wet jet mills and thin-film swirling high-speed mixers; and other roll mills.

[0096] [Electrodes for Lithium Secondary Batteries] The battery composition of the present invention can be suitably used as an electrode-forming composition for forming electrodes of lithium secondary batteries. Specifically, the electrode-forming composition of the present invention can be applied to a current collector and dried to form electrodes for lithium secondary batteries. The material and shape of the current collector are not particularly limited; for example, the material of the current collector can be a metal or alloy such as aluminum, copper, nickel, titanium, or stainless steel. In terms of shape, a flat foil is generally used, but current collectors with roughened surfaces, perforated foils, and mesh-shaped current collectors can also be used.

[0097] There are no particular limitations on the method for coating the electrode-forming composition onto the current collector, and known methods can be used. Specifically, die coating, dip coating, roll coating, doctor coating, knife coating, spray coating, gravure coating, screen printing, or electrostatic coating methods can be used, and drying methods such as standing drying, forced-air drying, hot-air drying, infrared heating, and far-infrared heating can be used, but are not limited to these.

[0098] In a laminate of electrodes formed using a current collector and an electrode-forming composition, the adhesive modification effect of the polyester of the present invention in the electrodes makes it difficult for the electrodes to detach from the current collector.

[0099] [Lithium Secondary Battery] The lithium secondary battery of the present invention is a battery equipped with electrodes for the lithium secondary battery of the present invention. The form of the lithium secondary battery of the present invention may be any of the following: a lithium-ion secondary battery in which the electrolyte is liquid and equipped with a separator, an all-solid-state secondary battery in which the electrolyte is solid, or a semi-solid-state secondary battery in which the electrolyte is both solid and liquid.

[0100] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0101] In the embodiments of this application, the values ​​of acid value and hydroxyl value were evaluated by the following methods. [Method for measuring acid value] Measured according to the method in accordance with JIS K0070-1992. [Method for measuring hydroxyl value] Measured according to the method in accordance with JIS K0070-1992.

[0102] In the present embodiment, the number-average molecular weight of the polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows: [GPC Measurement Conditions] Measurement device: Tosoh Corporation high-speed GPC device "HLC-8420GPC" Column: Tosoh Corporation "TSKgel SuperMultiporeHZ-N" x 4 Detector: RI (differential refractometer) Data processing: Tosoh Corporation "EcoSEC Data Analysis Version 1.07" Column temperature: 40°C Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min Sample: 20 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to be used as the sample. Sample injection volume: 20 μl Standard substance: Tosoh Corporation "PStQuick MP-N"

[0103] (Synthesis Example 1: Synthesis of Modifier A) In a 2-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser, 486 g of propylene glycol, 21 g of ethylene glycol, 831 g of terephthalic acid as the dicarboxylic acid component, and 0.08 g of tetraisopropyl titanate as the catalyst were charged. The mixture was heated gradually over 64 hours while stirring under a nitrogen atmosphere until it reached 235°C, and then condensed for 8 hours at 230°C. After the reaction, the mixture was further condensed at 235°C under reduced pressure for 2 hours to remove unreacted raw materials and low-volatile components, thereby obtaining modifier A, which is a polyester.

[0104] The obtained modifier A was solid at room temperature, with an acid value of 1.05 mg KOH / g, a hydroxyl value of 42 mg KOH / g, and a number-average molecular weight of 3,690. Furthermore, no clear endothermic peak was obtained in differential scanning calorimetry, confirming that modifier A is an amorphous polyester.

[0105] The differential scanning calorimetry described above was performed under the following conditions: Measurement device: Mettler Toledo DSC3+ Data processing: STAR software Measurement conditions: (1) Heating from 25°C to 250°C (10°C / min) (2) Cooling from 250°C to 0°C (10°C / min) (3) Holding at 0°C for 5 minutes (4) Heating from 0°C to 250°C (10°C / min) Analysis: In (4), the presence or absence of an endothermic peak was checked.

[0106] (Synthesis Example 2: Synthesis of Modifier B) In a 5-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser, 1635 g of propylene glycol as the glycol component, 3175 g of dimethyl 2,6-naphthalenedicarboxylate as the dicarboxylic acid component, and 0.29 g of zinc acetate dihydrate as the catalyst were charged, and the temperature was gradually increased over 8 hours while stirring under a nitrogen atmosphere until it reached 220°C. At 220°C, 0.29 g of tetraisopropyl titanate was added as the catalyst, and the condensation reaction was carried out for a further 23 hours. The condensation reaction was carried out for a further 4 hours under reduced pressure at 220°C to extend the molecular weight and obtain modifier B, which is a polyester.

[0107] The obtained modifier B was solid at room temperature, with an acid value of 1.40 mg KOH / g, a hydroxyl value of 47.7 mg KOH / g, and a number-average molecular weight of 2,160. Furthermore, no clear endothermic peak was obtained in differential scanning calorimetry, confirming that modifier B is an amorphous polyester.

[0108] (Synthesis Example 3: Synthesis of Modifier C) In a 1-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser, 137.8 g of propylene glycol, 48.2 g of ethylene glycol, and 170.5 g of polyethylene glycol (PEG-200, manufactured by Tokyo Chemical Industry Co., Ltd., polyethylene glycol with a number average molecular weight of 200) were charged as glycol components, 488.5 g of dimethyl 2,6-naphthalenedicarboxylate was charged as a dicarboxylic acid component, and 0.05 g of zinc acetate dihydrate was charged as a catalyst. The mixture was gradually heated to 220°C over 5 hours while stirring under a nitrogen atmosphere, and the reaction was carried out for 10 hours after reaching 220°C. Further, 0.05 g of tetraisopropyl titanate was charged as a catalyst, and the condensation reaction was carried out under reduced pressure at 220°C for a further 3 hours to extend the molecular weight and obtain modifier C, which is a polyester.

[0109] The obtained modifier C was solid at room temperature, with an acid value of 0.72 mg KOH / g, a hydroxyl value of 52.7 mg KOH / g, and a number-average molecular weight of 2,490. Furthermore, no clear endothermic peak was obtained in differential scanning calorimetry, confirming that modifier C is an amorphous polyester.

[0110] (Synthesis Example 4: Synthesis of Modifier D) In ​​a 1-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser, 212.2 g of propylene glycol, 9.7 g of ethylene glycol, and 196.4 g of polyethylene glycol (PEG-1000, manufactured by Tokyo Chemical Industry Co., Ltd., polyethylene glycol with a number average molecular weight of 1,000) were charged as glycol components, 439.7 g of dimethyl 2,6-naphthalenedicarboxylate was charged as a dicarboxylic acid component, and 0.05 g of zinc acetate dihydrate was charged as a catalyst. The mixture was gradually heated to 220°C over 5 hours while stirring under a nitrogen atmosphere, and the reaction was continued for 4 hours after reaching 220°C. Further, 0.05 g of tetraisopropyl titanate was charged as a catalyst, and the reaction was continued at 220°C for 15 hours. Subsequently, the condensation reaction was carried out under reduced pressure at 220°C for a further 3 hours to extend the molecular weight and obtain modifier D, which is a polyester.

[0111] The obtained modifier D was solid at room temperature, with an acid value of 1.23 mg KOH / g, a hydroxyl value of 23.4 mg KOH / g, and a number-average molecular weight of 4,700. Furthermore, no clear endothermic peak was obtained in differential scanning calorimetry, confirming that modifier D is an amorphous polyester.

[0112] (Example 1: Preparation and Evaluation of Battery-Forming Composition) 100 parts by mass of polyvinylidene fluoride (PVDF, Kureha Corporation's "Kureha KF Polymer W#7300") was dissolved in 2375 parts by mass of N-methylpyrrolidone as a binder resin. 16.7 parts by mass of metal chelate compound A was added to the PVDF solution and stirred at 500 rpm at room temperature. 4.7 parts by mass of modifier A was further added and stirred at 500 rpm at room temperature. The resulting mixture was filtered through a 300-mesh wire mesh to obtain a slurry-like battery-forming composition. The adhesive strength was evaluated using the obtained battery-forming composition as described below. The results are shown in Table 1.

[0113] Furthermore, the aforementioned metal chelate compound A is an aluminum chelate compound having the following structure.

[0114] (Adhesion strength evaluation) The obtained battery-forming composition was applied at a coating rate (surface density) of 0.013 to 0.015 mg / cm². ２The aluminum foil was coated using a bar coater to achieve the desired result. After coating, it was dried for 35 minutes in a forced-air dryer set to 90°C. The resulting laminate, consisting of aluminum foil and a PVDF resin layer, was bonded to one side of a double-sided tape (Nitto Denko Corporation's "No. 5015") to prepare a sample for peel strength testing.

[0115] The obtained peel strength test samples were cut into 20 mm widths, and the cut samples were stretched at a tensile speed of 100 mm / min using a Tensilon tensile testing machine (model: RTF-1210, manufactured by A&D Co., Ltd.), and the 180° peel adhesion strength (N / 20 mm) of the PVDF resin layer was measured. The results are shown in Table 1.

[0116] (Examples 2-4 and Comparative Examples 1-3: Preparation and Evaluation of Battery-Forming Compositions) Battery-forming compositions were prepared in the same manner as in Example 1, except that the binder resin, metal chelating compound, and modifier shown in Table 1 were used in the amounts shown in Table 1, and the adhesive strength was evaluated. The results are shown in Table 1. In Table 1, "PVP" is polyvinylpyrrolidone (K-90, manufactured by Tokyo Chemical Industry Co., Ltd.), and "H-NBR" is hydrogenated nitrile rubber (Terban 3406, manufactured by Alantheo), both of which are additives known as carbon dispersants in the battery field.

[0117]

[0118] While metal chelate compounds can improve adhesion, there is a concern that increasing their amount may reduce battery capacity because they are conductive materials, thus creating a need to reduce the amount added. The results from Examples 1 and 2 and Comparative Examples 1 and 2 show that the amount of metal chelate compound added can be reduced by using a combination of metal chelate compounds and polyester. Furthermore, the results from Examples 3-6 and Comparative Examples 3-5 show that sufficient adhesion improvement can be obtained with the polyester of the present invention alone. The polyester of the present invention is sometimes used as a carbon dispersant, but since adhesion improvement effects have not been obtained with the known carbon dispersants "PVP K90" and "H-NBR", it can be seen that the polyester of the present invention functions uniquely as an adhesion modifier.

Claims

1. A battery-forming composition containing a binder resin and an adhesion modifier, wherein the adhesion modifier is a polyester represented by the following general formula (1-1), (1-2) or (1-3). (In the general formulas (1-1), (1-2) and (1-3), G is an aliphatic diol residue having 2 to 50 carbon atoms, A is an aromatic dicarboxylic acid residue having 4 to 18 carbon atoms, X is a monocarboxylic acid residue having 1 to 20 carbon atoms, Y is a monoalcohol residue having 1 to 30 carbon atoms, and n represents the number of repetitions.) 2. The battery-forming composition according to claim 1, wherein A comprises one or more selected from phthalic acid residues, isophthalic acid residues, terephthalic acid residues, and naphthalenedicarboxylic acid residues.

3. The battery-forming composition according to claim 1, wherein G is an alkylene glycol residue having 2 to 50 carbon atoms and / or an oxyalkylene glycol residue having 2 to 50 carbon atoms.

4. The battery-forming composition according to claim 1, wherein the polyester is an amorphous polyester.

5. The battery-forming composition according to claim 1, wherein the number-average molecular weight of the polyester is in the range of 400 to 10,000.

6. The battery-forming composition according to claim 1, wherein the polyester content is in the range of 1 to 30 parts by mass per 100 parts by mass of the binder resin.

7. The battery-forming composition according to claim 1, further comprising a metal chelate compound.

8. The battery-forming composition according to claim 1, further comprising an aluminum chelate compound represented by the following general formula (5-1) and / or an aluminum chelate compound represented by the following general formula (5-2). (In the above general formulas (5-1) and (5-2), R ５１１ ~R ５１６ and R ５２１ ~R ５２６ Each of these is independently an alkyl group having 1 to 22 carbon atoms or an alkoxy group having 1 to 22 carbon atoms.

9. The battery-forming composition according to claim 8, wherein the content of the aluminum chelate compound is in the range of 1 to 50 parts by mass per 100 parts by mass of the binder resin.

10. The battery-forming composition according to claim 1, wherein the binder resin is a fluorine-containing resin.

11. The battery-forming composition according to claim 1, further comprising an electrode active material.

12. A secondary battery component comprising the battery-forming composition according to any one of claims 1 to 11.

13. A secondary battery comprising the secondary battery component described in claim 12.

14. A laminate comprising a resin layer and a metal layer, wherein the resin layer contains a binder resin, an adhesion modifier, and a metal chelate compound, and the adhesion modifier is a polyester represented by the following general formulas (1-1), (1-2), or (1-3). (In the general formulas (1-1), (1-2), and (1-3) above, G is an aliphatic diol residue having 2 to 50 carbon atoms, A is an aromatic dicarboxylic acid residue having 4 to 18 carbon atoms, X is a monocarboxylic acid residue having 1 to 20 carbon atoms, Y is a monoalcohol residue having 1 to 30 carbon atoms, and n represents the number of repetitions.) 15. The laminate according to claim 14, wherein the metal chelate compound is an aluminum chelate compound represented by the following general formula (5-1) and / or an aluminum chelate compound represented by the following general formula (5-2). (In the above general formulas (5-1) and (5-2), R ５１１ ~R ５１６ and R ５２１ ~R ５２６ Each of these is independently an alkyl group having 1 to 22 carbon atoms or an alkoxy group having 1 to 22 carbon atoms.

16. The laminate according to claim 14, wherein the metal layer is an aluminum layer.

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