WO2014136813A1

WO2014136813A1 - Coating film composition for battery electrodes or separators, battery electrode or separator provided with coating film obtained by using same, and battery provided with battery electrode or separator

Info

Publication number: WO2014136813A1
Application number: PCT/JP2014/055554
Authority: WO
Inventors: 嘉人清水; 太一上村
Original assignee: 協立化学産業株式会社
Priority date: 2013-03-05
Filing date: 2014-03-05
Publication date: 2014-09-12
Also published as: KR102009736B1; KR20150125700A; TWI644472B; TW201440293A; JPWO2014136813A1; CN105027328A; JP6058783B2; CN105027328B

Abstract

The problem of the present invention is to provide a coating film composition for battery electrodes or separators that is capable of forming a coating film which has high heat resistance and for which the occurrence of curling is suppressed. The present invention is a coating film composition for battery electrodes or separators which includes a binding agent, a solvent, and viscoelastic particles.

Description

Battery electrode or separator coating film composition, battery electrode or separator having a coating film obtained by using the same, and battery having this battery electrode or separator

The present invention relates to a battery electrode or separator coating film composition, a battery electrode or separator having a coating film obtained by using the composition, and a battery having the battery electrode or separator.

Lithium ion secondary batteries that are lightweight, have high voltage and large capacity have been put into practical use as power sources for mobile devices such as mobile phones and laptop computers, power tools and power tools such as cars. However, conventional batteries have low safety resulting from poor heat resistance and pressure collapse resistance, and there is a problem that conductive foreign substances that enter at the manufacturing stage penetrate the separator and cause a short circuit. Further, the lithium ion secondary battery has high internal resistance, charging and discharging characteristics at a high rate are not practically sufficient, charging and discharging capacities are not sufficient, and the active material layer is greatly deteriorated when used for a long time.

As described above, one reason why lithium ion secondary batteries cannot provide sufficient safety is that the insulation by the separator is broken due to contamination of conductive foreign matter, dent light, battery damage, etc. In this case, the mechanism for preventing the thermal runaway from proceeding and the heat resistance are insufficient.

As an improvement measure for the above problem, a method for protecting the active material from falling off the electrode by forming a porous film made of alumina powder or silica powder on the active material coating layer applied to the current collector has been devised. (Patent Document 1). Such a porous protective film suppresses the generation of dentite, and the porous film also functions as a layer for holding the electrolyte solution. The porous protective film serves as an ion supply source to lower internal resistance, and at a high rate. It also contributes to the improvement of discharge characteristics. In addition, the porous protective film buffers and accelerates local degradation resulting from concentration of electrode reactions due to electrode surface non-uniformity, thereby preventing deterioration of the active material layer when used for a long period of time. There is also an effect.

On the other hand, in a battery in which an electrode and a separator are bonded with an adhesive layer, a method has been devised in which a porous porous protective layer is formed using a path when the solvent is evaporated and the adhesive layer is a porous resin layer. (Patent Document 2). By holding the liquid electrolyte in the through-holes of the porous resin layer, good ion conductivity at the electrode electrolyte interface can be ensured.

JP-A-7-220759 WO1999 / 026307

However,

Patent Documents

1 and 2 have a problem that curling occurs in the porous resin layer formed on the electrode or the separator. In the method described in Patent Document 1, curling occurs due to the generation of stress from the difference between the elastic modulus and the linear expansion coefficient between the electrode and the porous protective film. Further, in the method described in Patent Document 2, curling occurs due to stress generated between the separator and the porous resin layer because the solvent evaporates and the coating film shrinks. This curl not only deteriorates handling during assembly, but also causes wrinkles. When wrinkles occur, the distance between the electrodes changes locally. As a result, localization of the electrochemical reaction occurs, and there is a problem that the charge / discharge characteristics and life of the battery are reduced.

Therefore, an object of the present invention is to provide a battery electrode or separator coating film composition that can suppress the occurrence of curling and can form a coating film having high heat resistance.

The present inventor has studied to solve the above-mentioned problems of the prior art, and by using viscoelastic particles as a component contained in the composition forming the coating film, the occurrence of curling of the coating film can be suppressed and high. A battery having a heat resistance and a battery electrode and / or a separator having a coating film obtained by using the coating film composition has a high heat resistance, a low internal resistance, and a charge and discharge cycle characteristic. The present inventors have found that it is excellent, has a large charge and discharge capacity, has a small deterioration in the active material layer after long-term multicycle charge and discharge, and has a long life.

The gist of the present invention is as follows.
The present invention 1 is a battery electrode or separator coating film composition comprising a binder, a solvent, and viscoelastic particles.
The present invention 2 is the battery electrode or separator coating film composition of the present invention 1 in which the viscoelastic modulus of the viscoelastic particles is lower than the viscoelastic modulus of the binder.
The present invention 3 is the battery electrode or separator coating film composition of the

present invention

1 or 2, wherein the viscoelastic particles have shape anisotropy.
The present invention 4 is a battery electrode or separator having a coating film obtained by using the battery electrode or separator coating film composition of any one of the present inventions 1 to 3.
Invention 5 is a battery according to Invention 4, wherein the viscoelastic particles have shape anisotropy, and the longest axis of the viscoelastic particles is oriented in parallel to the shrinkage direction of the base material of the battery electrode or separator. It is an electrode or a separator.
The present invention 6 is a battery having the battery electrode and / or separator of the present invention 5.

According to the present invention, there is provided a battery electrode or separator coating film composition in which curling is suppressed and a battery electrode or separator coating film having high heat resistance is obtained. By using the battery electrode or separator having the coating film of the present invention for the battery, it is possible to prevent the positive and negative electrodes from being short-circuited due to the battery crushing due to an accident, mixing of conductive foreign matters, melting of the separator due to thermal runaway, etc. .

In addition, since the coating film of the present invention becomes an electrolyte holding layer on the electrode or separator surface or a desolvation layer of ions in the electrolyte, the ion conduction resistance is reduced. There is an effect that it is possible to prevent the deterioration of the battery characteristics after the multi-cycle charge and discharge for a period of time or when the battery is left at a high temperature in the charged state. Therefore, the battery of the present invention has high heat resistance, low internal resistance, excellent charge and discharge cycle characteristics, large charge and discharge capacity, and small deterioration of the active material layer after long-term multicycle charge and discharge. Long life.

On the other hand, as a method of suppressing the occurrence of curling, there is a method of lowering the viscoelastic modulus of the binder. However, the binder has a structure in which a porous structure is maintained by binding particles. Therefore, the stress relaxation ability of the binder is relatively weaker and the heat resistance is lower than when the particles are provided with a function of relaxing stress. On the other hand, the method of the present invention using viscoelastic particles makes it difficult for the viscoelastic particles to be deformed beyond the deformation amount of the viscoelastic particles, so compared to the method of reducing the viscoelastic modulus of the binder, It is possible to obtain a coating film in which the occurrence of curling is suppressed and the heat resistance is high.
The coating film of the present invention can also be used as a solid electrolyte film or a gel electrolyte film by impregnating a porous structure with a solid or gel having ion conductivity.

FIG. 1 is a cross-sectional view of a battery electrode having a battery electrode or a separator coating film. FIG. 2 is a cross-sectional view of a separator having a battery electrode or a separator coating film. FIG. 3 is an optical micrograph of a separator having the coating film of Example 8. Arrows indicate the conveyance direction of the substrate.

The battery electrode or separator coating film composition has (1) viscoelastic particles, (2) a binder, and (3) a solvent.

[Viscoelastic particles]
The (1) viscoelastic particles of the present invention will be described. In the present invention, the “viscoelastic particle” is a particle having a property of irreversibly plastically deforming with respect to stress and a property of reversibly elastically deforming. When the battery electrode or the separator coating film composition contains viscoelastic particles, the particles can be irreversibly deformed in the coating film, and the viscoelastic modulus of the resulting coating film is lowered. Thereby, the stress with a battery electrode or a separator base material can be reduced. When using a gravure coater or the like in the production of a battery and applying with roll-to-roll, the base material is applied with tension applied and wound while being dried. When the wound base material is cut out in a later process, the tension at the time of coating is released, which causes curling. Since the viscoelastic particles in the coating film can reduce the occurrence of curling by relieving the stress with the base material, it is easy to handle even when manufacturing batteries by means of roll-to-roll. Occurrence is suppressed. Thereby, a high quality battery can be provided.

As the material of the viscoelastic particles, various polymers such as polyethylene, polypropylene, polystyrene, polycarbonate, polyacetal, polyphenylene sulfide, liquid crystal polymer, polyvinyl chloride, celluloid, polyvinyl alcohol, polyester, polyvinyl acetate, a polymer having a polyethylene glycol structure, Polymer having carbonate group, polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, polyisoprene, chloroprene rubber, acrylic rubber, polymer having cyano group, urethane rubber, ethylene propylene rubber, epichlorohydrin rubber, butadiene rubber, Fluoro rubber, ethylene-vinyl alcohol copolymer, acrylic-vinyl alcohol copolymer, epoxy resin, oxetane resin, urethane resin , Acrylic resins, polysaccharides, polyimide, polyamide-imide, silicone, polymer having a carbonyl group (e.g., a polymer having a β- diketone structure) and copolymers thereof can be exemplified.

As the polymer derivative having a cyano group, specifically, cyanoethylated vinyl alcohol, cyanoethylated carboxymethylcellulose, cyanoethylated pullulan, cyanoethylated cellulose, cyanoethylated starch, cyanoethylated esterified starch, cyanoethylated dextrin, cyanoethylated collagen, And nitrile rubber and the like. Specific examples of the polymer derivative having a polyethylene glycol structure include a polyethylene glycol acrylic acid amide styrene copolymer, a polyethylene glycol polylactic acid copolymer, and polyvinyl alcohol pendant with a polyethylene glycol chain. As an example of a polymer having a carbonyl group, there can be illustrated, for example, Nippon Polyvinyl acetate, PVA; D polymer (PVA having a carbonyl group); As a polymer having a β-diketone structure, specifically, a polyacrylic compound having a β-diketone structure that can be prepared by radical copolymerization of a vinyl compound having a β-diketone structure such as allyl acetoacetate and an acrylate ester. Examples thereof include ester copolymers and polyvinyl alcohol copolymerized with vinyl acetate. Specific examples of the polymer having a carbonate group include polycarbonate and CO ₂ -philic Co-polymer (CO ₂ amphiphilic copolymer). As the material of the viscoelastic particles, urethane resin and polyethylene are preferable.

Viscoelastic particles may be used singly or in combination. The viscoelastic particles may be in the form of a dispersion dispersed in a dispersion medium (for example, water).

The average particle diameter of the viscoelastic particles is preferably in the range of 0.001 to 100 μm, more preferably in the range of 0.01 to 50 μm, and still more preferably in the range of 0.05 to 10 μm. Since the porosity of the coating film can be further increased, it is preferable that the particle size distribution of the viscoelastic particles is narrow. That is, when the average particle diameter of viscoelastic particles is 1/5 times A and 5 times B, particles having a particle diameter in the range of A to B are 80% by volume of viscoelastic particles. It is preferable that the amount is 90% by volume or more. The average particle size and particle size distribution can be measured by, for example, a laser diffraction / scattering particle size distribution measuring apparatus, and specifically, LA-920 manufactured by Horiba, Ltd. can be used. Viscoelastic particles can be produced by various known methods, and can be produced by pulverization, emulsion polymerization, recrystallization, spraying, or using a forced thin film microreactor.

The shape of the viscoelastic particles is not particularly limited. Examples of the viscoelastic particles include viscoelastic particles having shape isotropy or shape anisotropy. In the present invention, the viscoelastic particles preferably have shape anisotropy.

When the viscoelastic particles have shape anisotropy, when the electrode battery or separator coating film composition containing the viscoelastic particles having shape anisotropy is applied to the battery electrode or separator substrate, The shearing force can orient viscoelastic particles having shape anisotropy in the coating flow direction. Further, by applying a magnetic field, an electric field or the like, the viscoelastic particles can be oriented so that the longest axis is parallel to the contraction direction of the battery electrode or the separator substrate. Thereby, while being able to improve the stress relaxation ability accompanying deformation | transformation of this particle | grain, the pore in a coating layer can be orientated and a battery characteristic can be improved more.

Examples of the shape of the viscoelastic particles having isotropy include a cubic shape and a spherical shape. Examples of the shape of the viscoelastic particles having shape anisotropy include a flat shape (for example, a plate shape which is a rectangular parallelepiped), a fiber shape, a bent fiber shape, and a coil shape. When the separator has a direction that tends to shrink, the viscoelastic particles can be oriented in a direction effective to relieve the shrinkage stress. Of the viscoelastic particles of flat shape, plate-like viscoelastic particles can be prepared by tapping and crushing the particles, thinly slicing the fibers, or making it plate-like by self-organization. it can. The fibrous particles can be produced by cutting a spun polymer shortly or by an electrospinning method. Short fibers that can be used as particles having shape anisotropy can be produced by cutting the fibrous particles into short pieces or making short fibers by turning on and off the electric field when spinning by the electrospinning method.

The degree of elastic deformation of the viscoelastic particles can be expressed by an elastic modulus h3 determined by the following measurement method 1. In the present invention, h3 of the viscoelastic particles is preferably 0.95 or less, and more preferably 0.9 or less. The h3 of the viscoelastic particles is not particularly limited, but can be 0.5 or more, and preferably 0.6 or more. The degree of plastic deformation of the viscoelastic particles can be expressed by the plastic deformation rate h6 determined by the following measurement method 2. In the present invention, h6 is preferably 0.85 or less, and more preferably 0.75 or less. Further, h6 of the viscoelastic particles is not particularly limited, but is preferably 0.5 or more, and more preferably 0.6 or more. If h3 and h6 of the viscoelastic particles are equal to or less than the upper limit value, the stress relaxation ability is increased and curling can be effectively suppressed. If h3 and h6 of the viscoelastic particles are equal to or higher than the lower limit, the heat resistance is further improved. h3 and h6 are both parameters indicating ease of deformation, and both of them are easier to deform when the numerical value is smaller. Therefore, when h3 and h6 are smaller, curling is further suppressed. However, deformation due to elastic deformation leaves deformation stress. On the other hand, deformation due to plastic deformation does not leave deformation stress. Here, the deformation stress is a force that can cause curling. Therefore, the smaller the plastic deformation rate: h6, the more curling can be suppressed compared to the case where the elastic deformation rate: h3 is small.

[Measurement method 1]
(1) Step of obtaining test particles, (2) Packing the test particles obtained in step (1) into an acrylic cylinder having an inner diameter of 10 mm, an outer diameter of 110 mm, and a height of 150 mm so as to have a height of 100 mm. Step of pushing in an iron bar having a length of 10 mm and a length of 200 mm using an autograph, (3) Measuring height h1 when pushed in with 1 kgf and height h2 when pushing in with 0.5 kgf after loosening the pushing force. Step (4) A step of obtaining the elastic modulus h3 of the viscoelastic particles by h1 / h2 = h3.

[Measurement method 2]
(1) Step of obtaining test particles, (2) Packing of test particles into an acrylic cylinder having an inner diameter of 10 mm, an outer diameter of 110 mm, and a height of 150 mm so that the height is 100 mm, and made of iron having an outer diameter of 10 mm and a length of 200 mm Step of pushing the bar using an autograph, (3) After applying a weight of 1 kgf, obtain the height h4 when the load is returned to 0.5 kgf, then push the iron bar with 100 kgf, The height h5 when returned to 0.5 kgf is obtained. (4) A step of obtaining a plastic deformation rate: h6 of the viscoelastic particles by h5 / h4 = h6.

When the average particle diameter of the viscoelastic particles is 50 μm or more, the test object viscoelastic particles are sieved with a sieve having an opening of 50 μm to obtain test particles. In addition, particles that are likely to be clogged are made into test particles by filtering in an aqueous dispersion.

The content of viscoelastic particles is 0.1 to 99.9% by weight or more of the components contained in the coating film composition excluding the solvent, preferably 0.5 to 99.5% by weight, more preferably Is from 1 to 99% by weight. If it is such a range, the stress relaxation ability accompanying deformation | transformation of a viscoelastic particle and low elastic modulus will become high, and it can suppress curl effectively. The solvent includes a solvent for a binder described later and a dispersion medium when the viscoelastic particles are in the form of a dispersion.

[Binder]
The (2) binder of the present invention will be described. The battery electrode or separator coating film composition of the present invention contains a binder. Examples of the binder include a solid (for example, particulate) binder or a liquid binder. The binder can be in a state dispersed in a solvent, a state dissolved in a solvent, a state dispersed in a solvent, and a state dissolved in a solvent.

[Solid binder]
Various known solid binders can be used as the solid binder. Examples of the solid binder include thermoplastic organic particles, organic crystals, and organic particles that crosslink during heat fusion. The average particle size of the solid binder is not particularly limited, and can be 0.01 to 500 μm. Further, the solid binder does not include particles (that is, viscoelastic particles) having a property of plastically irreversibly with respect to stress and a property of elastically deforming reversibly.

The thermoplastic organic particles are not particularly limited as long as they can be bonded by hot-melting the particles with a hot melt, and examples thereof include thermoplastic polymer particles.

Examples of thermoplastic polymers include viscoelastic particle materials. The thermoplastic organic particles may be used alone or in combination of two or more. As thermoplastic organic particles, polymer derivative particles having a cyano group, polymer derivative particles having a polyethylene glycol structure, and polymer derivatives having a carbonyl group are easy to interact with ions and from the viewpoint of ion conduction. Particles (preferably, polymer particles having a β-diketone structure), and polymer particles having a carbonate group are preferable, particles of a polymer derivative having a cyano group, particles of a polymer having a polyethylene glycol structure, and Polymer particles having a carbonate group are more preferable.

Thermoplastic organic particles can be adjusted in molecular weight and crosslinking density to such an extent that they have a melting point and softening point in the range of -40 to 300 ° C.

The thermoplastic organic particles can be used as a dry powder, or can be used as an aqueous emulsion by forming protective colloid particles using a surfactant or a water-soluble polymer. Further, for the purpose of adjusting the melting point, it is also possible to use a solvent with a high boiling point solvent having a boiling point of 80 ° C. or higher, such as ethylene glycol, glycerin, diethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide, and isophorone.

[Organic crystals]
Examples of organic crystals include hydrazide crystals, acid anhydride crystals, amine crystals, imidazole crystals, triazine crystals, and mixed crystals thereof. The melting point of the organic crystal is preferably 40 ° C. or higher, more preferably 50 to 300 ° C.

As hydrazide crystals, adipic acid dihydrazide (melting point: 177 to 180 ° C.), 1,3-bis (hydrazinecarbonoethyl) -5-isopropylhydantoin (melting point: 120 ° C.), 7,11-octadecadien-1,18-di Examples thereof include carbohydrazide (melting point: 160 ° C.). Examples of acid anhydride crystals include maleic anhydride (melting point 53 ° C.), phthalic anhydride (melting point 131 ° C.), pyromellitic anhydride (melting point 286 ° C.), and the like. Examples of amine crystals include urea (melting point: 132 ° C.) and dicyandiamide (melting point: 208 ° C.). Examples of imidazole crystals include imidazole (melting point 89 to 91 ° C.), 2-methylimidazole (melting point 140 to 148 ° C.), phenyl imidazole (melting point 174 to 184 ° C.), and the like. Examples of triazine crystals include 2,4-diamino-6-vinyl-S-triazine (melting point 240 ° C.), 2,4-diamino-6-methacryloyloxyethyl-S-triazine (melting point 170 ° C.), and the like. Organic crystals can be used in the form of a solid solution by mixing two or more kinds for the purpose of adjusting the melting point and the softening point.

[Organic particles that crosslink during thermal fusion]
The organic particles that are crosslinked at the time of heat fusion are various known latent curable solid resin particles. Examples of latent curable solid resins include epoxy resins, mixtures of epoxy resins and oxirane compounds, (meth) acrylic acid esters, and prepolymers having active hydrogen groups. Therefore, as a particle of an organic substance that crosslinks at the time of heat fusion, a particle in which a latent thermal initiator is blended with a solid epoxy resin; a particle in which a latent thermal initiator is blended in a mixture of a solid epoxy resin and an oxirane compound Particles that are a system containing a solid (meth) acrylic acid ester and a curing agent or an initiator; and particles that are a combination of a prepolymer having an active hydrogen group and a crosslinking agent. In the present invention, (meth) acrylic acid ester refers to acrylic acid ester and methacrylic acid ester.

As a solid epoxy resin, manufactured by DIC Corporation; EPICLON 1050 (bisphenol A type epoxy resin having a softening point of 64 to 74 ° C.), manufactured by DIC Corporation; EPICLON N-660 (cresol novolac type epoxy having a softening point of 62 to 70 ° C. Resin), manufactured by DIC Corporation; EPICLON N-770 (phenol novolac type epoxy resin having a softening point of 65 to 75 ° C.), manufactured by DIC Corporation; HP-7200HH (dicyclopentadiene type epoxy resin having a softening point of 88 to 98 ° C.) EPICLON HP-4700 (a naphthalene type epoxy resin having a softening point of 85 to 95 ° C.), manufactured by Nagase ChemteX Corporation; EX-721 (a monofunctional solid epoxy phthalimide skeleton having a melting point of 94 to 96 ° C.), Nagase Made by Chemtex Co., Ltd .; EX- 71 (melting point 40 ° C. of lauryl alcohol (EO) 15 glycidyl ether) and the like. In the present specification, “EO” refers to ethylene oxide, and “PO” refers to propylene oxide.

Examples of oxirane compounds include oxetane compounds. Specific examples of the oxirane compound include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-Ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ) Ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) Ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclo Pentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl ( 3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Roxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl- 3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa- Nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) Methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmeth) Xyl) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl- 3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl- 3-Oxetanylmethoxy) hexane, pen Erythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexas ( 3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylo Rupropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO Modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ) Ether, oxetanylsilsesquioxane and the like.

Potential thermal initiators for epoxy resins and oxirane compounds are catalysts for cationic polymerization, such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluoro). Phenyl) borate, bis (dodecylphenyl) iodonium / hexafluorophosphate, bis (dodecylphenyl) iodonium / hexafluoroantimonate, bis (dodecylphenyl) iodonium / tetrafluoroborate, bis (dodecylphenyl) iodonium / tetrakis (pentafluorophenyl) ) Borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluo Phosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium / tetrakis (pentafluorophenyl) borate, 4-methoxydiphenyliodonium / hexafluorophosphate, bis (4-methylphenyl) iodonium / hexafluorophosphate, bis (4-t-butylphenyl) iodonium Hexafluorophosphates, iodonium salts such as bis (dodecylphenyl) iodonium, tolylcumyl iodonium hexafluorophosphate;
Sulfonium salts such as triallylsulfonium hexafluoroantimonate;
Phosphonium salts such as triphenylpyrenylmethylphosphonium salts;
(Η6-benzene) (η5-cyclopentadienyl) iron (II) hexafluoroantimonate;
a combination of o-nitrobenzylsilyl ether and aluminum acetylacetonate;
A combination of silsesquioxane and aluminum acetylacetonate;
Etc. can be illustrated.

The amount of the thermal initiator is preferably 0.001 to 50 parts by weight, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the solid epoxy resin or the mixture of the solid epoxy resin and the oxirane compound. More preferably, the amount is 0.1 to 10 parts by weight.

Solid epoxy resin blended with latent thermal initiator, and solid epoxy resin and oxirane compound blended with latent thermal initiator, carboxylic acid, carboxylic anhydride, amine , And hardener particles such as hydrazide. Thereby, a crosslinking reaction can also be advanced at the time of heat fusion. By blending the curing agent particles, the cross-linking reaction can proceed simultaneously with the heat fusion, so that a mutually cross-linked and cross-linked structure can be obtained. The blending amount of the curing agent is preferably 1 to 500 parts by weight, more preferably 2 to 200 parts by weight, based on 100 parts by weight of solid prepolymer particles described later.

Particles that are blended with a latent heat initiator in a solid epoxy resin, or particles that are blended with a latent heat initiator in a mixture of a solid epoxy resin and an oxirane compound are the solid epoxy resin. Producing solid prepolymer particles by mixing a resin or a mixture of the solid epoxy resin and oxirane compound, a latent thermal initiator, and optionally a curing agent, and then grinding. Can do. Alternatively, solid epoxy resin particles or particles of a mixture of the solid epoxy resin and the oxirane compound, initiator particles, and curing agent particles may be mixed to obtain solid prepolymer particles.

As a system including a solid (meth) acrylic acid ester and a curing agent or an initiator, a mixture of a methacrylic acid ester and a thermal initiator (EBECRYL 767 (manufactured by Daicel Cytec Co., Ltd.)) as a thermosetting system: Perhexa HC (manufactured by NOF Corporation) = 100: 5 mixture) can be exemplified, and as a photocurable system, a mixture of a methacrylic ester and a photoinitiator (EBECRYL 740-40TP (manufactured by Daicel Cytec Co., Ltd.): 1 -Hydroxy-cyclohexyl-phenyl-ketone = 100: 5) and the like.

Examples of the crosslinking agent in the combination of the prepolymer having an active hydrogen group and the crosslinking agent include carboxylic acid, carboxylic acid anhydride, and metal chelate. Examples of combinations of prepolymers having active hydrogen groups and crosslinking agents include boric acid such as a mixture of polyvinyl alcohol and polycarboxylic acid and derivatives thereof, a mixture of polyvinyl alcohol and derivatives thereof with metal chelates and alkoxides, and the like. Can do. Examples of polycarboxylic acids include citric acid, butanetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, hexahydrophthalic acid, 1,3,3a, 4,5,9b-hexahydro-5 (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione (anhydride), glycerin bisanhydro trimellitate monoacetate (anhydride), 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, ethylene glycol bisanhydrotrimellitate (anhydride), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, ethylene glycol bisanhydro Trimellitate, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, bicyclo [2.2.1] heptane-2,3-di Carboxylic acid, aspartic acid, pyromellitic acid, mellitic acid, phosphorus-containing ester group tetracarboxylic acid, phenyl ethynyl phthalic acid, oxydiphthalic acid, polyacrylic acid, may be mentioned polymethyl methacrylate, and the like derivatives. Of these, aromatic carboxylic acids are preferable from the viewpoint of reactivity, and those having three or more carboxyl groups in one molecule are preferable from the viewpoint of reactivity and crosslinking density. In addition, among the exemplified polycarboxylic acids, those corresponding to acid anhydrides can also be used. As metal chelates, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium diisopropoxy bis (acetylacetonate), titanium tetraacetylacetonate, titanium lactate ammonium salt, titanium diisopropoxy bis (triethanolaminate) Such as titanium chelates and alkoxides, zirconium tetranormal propoxide, zirconium tetraacetyl acetonate, zirconium dibutoxy bis (ethyl acetoacetate), zirconium tributoxy monostearate, such as zirconium chelates and alkoxides, aluminum isopropoxide Various known metal compounds such as aluminum chelate can be exemplified. Moreover, the combination of the prepolymer which has an active hydrogen group, and a crosslinking agent may contain the said hardening | curing agent and thermal initiator depending on the case. Particles that are a combination of a prepolymer having active hydrogen groups and a crosslinker will not react with heat when mixing the prepolymer having active hydrogen groups, the crosslinker, and any hardeners and initiators present. In addition, these are mixed in a good solvent, casted thinly and dried at room temperature, and can be produced by grinding while cooling and used as an organic particle type binder that crosslinks during thermal fusion. Can do.

An electrode battery or separator coating film composition containing organic particles that crosslink at the time of heat fusion as a binder, the composition and the battery electrode or separator are fused by evaporating the solvent after coating the composition. At the same time and / or after fusing, crosslinking can be advanced by heating or irradiation with energy rays. Thereby, a protective film having excellent mechanical strength and high heat resistance can be obtained.

[Liquid binder]
A liquid binder can be used as the binder of the present invention.

As the liquid binder, various known liquid binders can be used. Specific examples of the liquid binder include a mixture of a liquid prepolymer and an initiator; a solid polymer substance dissolved in a solvent; a solid inorganic substance by a sol-gel reaction; and water glass It is done.

(Mixture of liquid prepolymer and initiator)
As a mixture of a liquid prepolymer and an initiator, a combination of a photo radical initiator or a thermal radical generator and a compound having a (meth) acryl group, an allyl group, a vinyl group, a maleimide group, etc .; a photo cation initiator or A combination of a thermal cation initiator and a compound having an epoxy group, an oxirane ring such as an oxetane ring, a vinyl ether, a cyclic acetal, etc .; and a photoanion initiator, a compound having an epoxy group and / or a compound having a cyanoacrylate group And combinations thereof. The (meth) acryl group includes an acryl group and a methacryl group.

A combination of a photo radical initiator or a thermal radical generator and a compound having a (meth) acryl group, an allyl group, a vinyl group, a maleimide group, etc. will be described.

As photo radical initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-Isopropylfeinyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2 Acetophenones such as -hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1; Benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as ter, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-allyl benzoin, α-allyl benzoin aryl ether; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropyl Thioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthate 1-phenyl-1,2-propanedione-2 (O-ethoxycarbonyl) oxime, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, 9,10-phenanthrenequinone, Camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 1- [4- ( 3-mercaptopropylthio) phenyl] -2-methyl-2-morpholin-4-yl-propan-1-one, 1- [4- (10-mercaptodecanylthio) phenyl] -2-methyl-2-morpholine -4-yl-propan-1-one, 1- (4- {2- [2- (2-mercap) -Ethoxy) ethoxy] ethylthio} phenyl) -2-methyl-2-morpholin-4-yl-propan-1-one, 1- [3- (mercaptopropylthio) phenyl] -2-dimethylamino-2-benzyl- Propan-1-one, 1- [4- (3-mercaptopropylamino) phenyl] -2-dimethylamino-2-benzyl-propan-1-one, 1- [4- (3-mercapto-propoxy) phenyl] -2-Methyl-2-morpholin-4-yl-propan-1-one, bis (η5-2,4-cyclopentadien-1-yl) bis [2,6-difluoro-3- (1H-pyrrole-1 -Yl) phenyl] titanium, 1,2-octanedione, 1-4 (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 1,3-bis Examples thereof include (p-dimethylaminobenzylidene) acetone. Among photoradical initiators, electron donors (hydrogen donors) are used for intermolecular hydrogen abstraction type photoinitiators such as benzophenone, Michler ketone, dibenzosuberone, 2-ethylanthraquinone, camphorquinone, and isobutylthioxanthone. ) As a starting aid. Such electron donors include aliphatic amines and aromatic amines having active hydrogen. Specific examples of the aliphatic amine include triethanolamine, methyldiethanolamine, and triisopropanolamine. Specific examples of the aromatic amine include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate.

Thermal radical generators include 4-azidoaniline hydrochloride and azides such as 4,4′-dithiobis (1-azidobenzene); 4,4′-diethyl-1,2-dithiolane, tetramethylthiuram disulfide, And disulfides such as tetraethylthiuram disulfide; octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide Diacyl peroxides such as: di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, and di- (2-ethoxyethyl) B) Peroxydicarbonates such as peroxydicarbonate; t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyoctanoate, octylperoxyoctanoate, t-butylperoxy-3, Peroxyesters such as 5,5-trimethylhexanoate, t-butylperoxyneodecanoate, octylperoxyneodecanoate, t-butylperoxylaurate, and t-butylperoxybenzoate; di-t-butyl Peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (t-butyl) hexyne Dialkyl peroxides such as -3 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, and n- Peroxyketals such as butyl-4,4-bis (t-butylperoxy) valerate; ketone peroxides such as methyl ethyl ketone peroxide; peroxides such as p-menthane hydroperoxide and cumene hydroperoxide; 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'- Azobis (2-methylbutylnitrile), 1,1'-azobis (cyclohexane-1-carbonito Ril), 1-[(1-cyano-1-methylethyl) azo] formamide, and azonitriles such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2′-azobis (2- Methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [N- (4-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (4-phenylmethyl) propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2 -Propenyl) propionamidine] dihydrochloride, 2,2′-azobis (2-methylpropionamid ) Dihydrochloride, 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) ) Propane] dihydrochloride, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis [2- (2- Azoamides such as imidazolin-2-yl) propane]; alkylazo compounds such as 2,2′-azobis (2,4,4-trimethylpentane) and 2,2′-azobis (2-methylpropane); Dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (4-cyanovaleric acid), and 2 Azo compounds such as 2′-azobis [2- (hydroxymethyl) propionate]; bipyridine; initiators with transition metals (eg, copper (I) chloride and copper (II) chloride); methyl 2-bromopropionate; And halogen compounds such as ethyl 2-bromopropionate and ethyl 2-bromoisobutyrate.

A decomposition accelerator can be used in combination with the above thermal radical generator. Examples of the decomposition accelerator include thiourea derivatives, organometallic complexes, amine compounds, phosphate compounds, toluidine derivatives, and aniline derivatives.

As thiourea derivatives, N, N′-dimethylthiourea, tetramethylthiourea, N, N′-diethylthiourea, N, N′-dibutylthiourea, benzoylthiourea, acetylthiourea, ethylenethiourea, N, N′-diethylenethio Examples include urea, N, N′-diphenylthiourea, and N, N′-dilaurylthiourea, preferably tetramethylthiourea or benzoylthiourea. Examples of the organometallic complex include cobalt naphthenate, vanadium naphthenate, copper naphthenate, iron naphthenate, manganese naphthenate, cobalt stearate, vanadium stearate, copper stearate, iron stearate, and manganese stearate. As the amine compound, primary or tertiary alkylamines or alkylenediamines represented by an integer of 1 to 18 carbon atoms of the alkyl group or alkylene group, diethanolamine, triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, Trisdiethylaminomethylphenol, 1,8-diazabicyclo (5,4,0) undecene-7, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0)- Nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7, 2-methylimidazole, 2-ethyl-4-methylimidazole and the like can be exemplified. Examples of the phosphate compound include methacrylic phosphate, dimethycyl phosphate, monoalkyl acid phosphate, dialkyl phosphate, trialkyl phosphate, dialkyl phosphate, and trialkyl phosphate. Examples of toluidine derivatives include N, N-dimethyl-p-toluidine and N, N-diethyl-p-toluidine. Examples of aniline derivatives include N, N-dimethylaniline and N, N-diethylaniline.

A compound having a (meth) acryl group, an allyl group, a vinyl group, or a maleimide group is a liquid prepolymer. Examples of the compound having a (meth) acryl group include butanediol mono (meth) acrylate, t-butylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-diethylaminoethyl (meth). Acrylate, 2-ethoxyethyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxypropyl (meth) acrylate 2-methoxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, pyriethylene glycol 400 di (meth) acrylate, propylene glycol mono (meth) acrylate, polyethylene glycol Cole mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloxyethyl phthalate, N- (meth) acryloxy-N-carboxypiperidine, N- (meth) acryloxy-N, N-dicarboxymethyl -P-phenylenediamine, hydroxynaphthoxypropyl (meth) acrylate, (meth) acryloxyethyl phosphorisphenyl, 4- (meth) acryloxyethyl trimellitic acid, (meth) acryloxyethyl phosphate, long chain aliphatic ( (Meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butanediol mono (meth) acrylate, butoxytriethylene glycol (meth) acrylate, ECH-modified butyl ( ) Acrylate, t-butylaminoethyl (meth) acrylate, caprolactone (meth) acrylate, 3-chloro-2-hydroxypromyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclo Pentanyl (meth) acrylate, cycloaliphatic modified neopentyl glycol (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N , N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethyl Xyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, 2-hydroxy -3- (Meth) acryloxypropyltrimethylammonium chloride, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, γ- (meta ) Acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethyleneglycol (Meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol 1000 (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, morpholine (meth) acrylate, nonylphenoxy Preethylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, octyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) ) Acrylate, phenoxyhexaethylene glycol (meth) acrylate, EO-modified Enoxylated phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, EO modified phosphoric acid (meth) acrylate, EO modified phosphoric acid (meth) acrylate, EO modified phthalic acid (meth) acrylate, EO, PO modified phthalic acid (meta ) Acrylate, polyethylene glycol 90 (meth) acrylate, polyethylene glycol 200 (meth) acrylate, polyethylene glycol 400 (meth) acrylate, polypropylene glycol (meth) acrylate, polypropylene glycol 500 (meth) acrylate, polypropylene glycol 800 (meth) acrylate, Polyethylene glycol / polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, sulfur Sodium ethoxy (meth) acrylate, tetrafluoropropyl (meth) acrylate, tetrahydrofurfuryl (meth) EO modified bisphenol A di (meth) acrylate, acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meta ) Acrylate, allylated cyclohexyl di (meth) acrylate, (meth) acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, EO modified bisphenol A di (meth) acrylate, EO modified bisphenol S di (meth) acrylate, Bisphenol F di (meth) acrylate, EO-modified bisphenol AD di (meth) acrylate, EO-modified bisphenol AF di (meth) acrylate, 1,4-butyl Diol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di ( (Meth) acrylate, dicyclopentanyl di (meth) acrylate, diethylene glycol di (meth) acrylate, ECH (epichlorohydrin) modified diethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxy Penta (meth) acrylate, silsesquioxane (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate Relate, ditrimethylolpropane tetra (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol diacrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Stearic acid modified pentaerythritol di (meth) acrylate, EO modified phosphate di (meth) acrylate, EO modified phosphate (Meth) acrylate, polyethylene glycol 200 di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triethylene glycol (meth) acrylate, triglycerol di (meth) acrylate, neo Pentyl glycol modified trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, Caprolactone-modified tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, zinc di (meth) acrylate , Isocyanatoethyl methacrylate, chlorendic di (meth) acrylate, methoxy ether (meth) acrylate, and 2-like (methacryloyloxy) ethyl trimethyl aminium bis (trifluoromethylsulfonyl) amine anion can be exemplified.

Examples of the compound having a vinyl group include vinyl acetate, chloroethylene, vinyltrimethoxysilane, 1-vinyl-3,4-epoxycyclohexane, vinyl acetate, and the like. Examples of the compound having an allyl group include allyl alcohol, 3-aminopropene, allyl bromide, allyl chloride, diallyl ether, diallyl sulfide, allicin, allyl disulfide, allyl isothiocyanate, and the like. As compounds having a maleimide group, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 4,4′-diphenylmethanemaleimide, m-phenylenemaleimide, bisphenol A diphenylether bismaleimide, 3,3′-dimethyl-5,5′- Examples include diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, and 1,6′-bismaleimide- (2,2,4-trimethyl) hexane. Among these compounds, compounds having a (meth) acryl group and a vinyl group are preferable. These compounds can be cured with an electron beam even in the absence of a photoradical initiator.

A photo radical initiator and a thermal radical generator can be used in combination of two or more. These photoradical initiator and thermal radical generator are 0.01 to 50 parts by weight with respect to 100 parts by weight of a compound having a (meth) acryl group, an allyl group, a vinyl group, or a maleimide group as a liquid prepolymer. It is preferably added, more preferably 0.1 to 20 parts by weight, still more preferably 1 to 10 parts by weight. When the photoradical initiator and the thermal radical generator are used in combination, the above content is the total content of the photoradical initiator and the thermal radical generator. The content of the electron donor is preferably 10 to 500 parts by weight with respect to 100 parts by weight of the photo radical initiator. The content of the decomposition accelerator is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the thermal radical generator.

A combination of a photocationic initiator, a thermal cation initiator or a photoanion initiator and a compound having an epoxy group, an oxirane ring such as an oxetane ring, a vinyl ether, a cyclic acetal or the like will be described.

Examples of the photocationic initiator include compounds other than the combination of silsesquioxane and aluminum acetylacetonate in the latent thermal initiator for the epoxy resin and oxirane compound described above.

A sensitizer can be used in combination with the photocationic initiator. Such sensitizers include 9,10-butoxyanthracene, acridine orange, acridine yellow, benzoflavin, cetoflavin T, perylene, pyrene, anthracene, phenothiazine, 1,2-benzacetracene, coronene, thioxanthone, fluorenone, benzophenone And anthraquinone.

Examples of the thermal cation initiator include latent thermal initiators for the epoxy resins and oxirane compounds described above.

Examples of the photoanion initiator include a 2-nitrobenzyl carbamate compound obtained by blocking a bifunctional or higher isocyanate with an o-nitrobenzyl alcohol compound, and a combination of a quinonediazide sulfonate compound and an N-alkylaziridine compound. The photoanion initiator is used for polymerizing a compound having an epoxy group and a compound having a cyanoacrylate group.

A compound having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro ortho carbonate, or a vinyl ether group is a liquid prepolymer and is crosslinked with a photocationic initiator, a thermal cationic initiator, and / or a photoanionic initiator. It is a compound having a reactive substituent.

Compounds having an epoxy group are (3 ′, 4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate, 4-vinylcyclohexene oxide, 1-methyl-4- (2-methyloxiranyl) -7- 1 of oxabicyclo [4.1.0] heptane, epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) -modified epsilon-caprolactone, epoxidized polybutadiene, 2,2-bis (hydroxymethyl) -1-butanol , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct, 1,2-epoxy-4- (2-oxiranyl) cyclosoxane adduct of 2,2-bis (hydroxymethyl) -1-butanol, 3, 4-epoxycyclohexenylmethyl-3 ', 4'-epoxy Lohexene carboxylate, 3,4-epoxycyclohexylmethyl methacrylate, α-olefin epoxide, epoxidized product of styrene-butadiene block copolymer, epoxidized product of styrene-butadiene block copolymer, bisphenol A type epoxy resin, bisphenol AD Type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol novolak type epoxy resin, bisphenol A novolak type epoxy resin, tetrabromobisphenol A type epoxy resin , Tetraglycidyl diaminodiphenyl methane, dihydroxynaphthalene diglycidyl ether, biphenyl type epoxy resin, silsesqui Xane type epoxy resin, isoprene type epoxy resin, isobonyl skeleton, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, epoxy modified silicone, and epoxy modified silsesqui Examples include oxane and the like.

Examples of the compound having a cyanoacrylate group include methyl cyanoacrylate and ethyl cyanoacrylate.

The compound having episulfide is a compound in which the oxygen atom of the above-mentioned compound having an epoxy group is substituted with a sulfur atom. Ethylene sulfide, propylene sulfide, 1-butene sulfide, 2-butene sulfide, isobutylene sulfide, 1-pentene sulfide 2-pentene sulfide, 1-hexene sulfide, 1-octene sulfide, 1-dodecene sulfide, cyclopentene sulfide, cyclohexene sulfide, styrene sulfide, vinylcyclohexene sulfide, 3-phenylpropylene sulfide, 3, 3, 3 -Trifluoropropylene sulfide, 3-naphthylpropylene sulfide, 3-phenoxypropylene sulfide, 3-naphthoxypropylene sulfide, butadiene monosulfide, and 3-toluene Such as methyl silyl oxypropylene sulfide can be exemplified.

Examples of the compound having an oxetane ring include the oxetane compounds described above.

Examples of the compound having spiro ortho carbonate include spiro glycol diallyl ether and bicycloorthoester.

Compounds having vinyl ether include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, allyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether , 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexane dimeta Over distearate ether, triethylene glycol divinyl ether, trimethyl propane trivinyl ether, and pentaerythritol tetra ether can be exemplified.

The compound having an oxetane ring is preferable as the compound having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro ortho carbonate, or a vinyl ether group.

The photo cation initiator, the thermal cation initiator, and the photo anion initiator can be used in combination of two or more. These photocationic initiator, thermal cationic initiator, and photoanion initiator are based on 100 parts by weight of a compound having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro orthocarbonate, or a vinyl ether group, which is a liquid prepolymer. The addition amount is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 10 parts by weight. When a photocationic initiator, a thermal cation initiator, and a photoanion initiator are used in combination, the above content is the total content of the photocationic initiator, the thermal cation initiator, and the photoanion initiator. The content of the sensitizer is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the photocation initiator.

(Liquid binder with solid polymer dissolved in solvent)
Examples of the liquid binder obtained by dissolving a solid polymer substance in a solvent include those obtained by dissolving the above-described polymer particles in a solvent and those suspended in a solvent. As a solvent, it can select suitably from the solvent which can melt | dissolve a solid polymer, and can mix and use 2 or more.

Examples of solid polymer substances include fully saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray Poval PVA-124, Nippon Vinegar Poval Co., Ltd .; JC-25), partially saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray Poval PVA-235, manufactured by Nihon Ventures & Poval Co., Ltd .; JP-33, etc.) Modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray K Polymer KL-118, Kuraray C Polymer CM-318, Kuraray R Polymer R-1130 Kuraray LM Polymer LM-10HD, manufactured by Nihon Vinegar Poval Co., Ltd .; D Polymer DF-20, anion-modified PVA AF-17, alkyl-modified PVA ZF-15, carboxymethyl cellulose (manufactured by Daicel Industries, Ltd .; H-CMC, DN -100L, 1120, 2200, made in Japan Chemical Co., Ltd .; MAC200HC, etc.), Hydroxyethylcellulose (Daicel Industrial Co., Ltd .; SP-400, etc.), Polyacrylamide (MT Aquapolymer Co., Ltd .; Acoflock A-102), Polyoxyethylene (Maisei Chemical Co., Ltd.) Alcox E-30), epoxy resin (manufactured by Nagase ChemteX Corporation; EX-614, manufactured by Japan Chemtech Co., Ltd .; Epicoat 5003-W55, etc.), polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .; Epomin P-1000) , Polyacrylic acid ester (MT Aquapolymer Co., Ltd .; Acofloc C-502, etc.), and saccharides and derivatives thereof (Wako Pure Chemical Industries, Ltd .; Chitosan 5, Nissho Chemical Co., Ltd .; esterified starch milk powder, glyco Made by Co., Ltd .; cluster dextrin, Li styrene sulfonic acid; a water-soluble polymer such as (manufactured by Tosoh Organic Chemical Co., Ltd. Bolinas PS-100, etc.) may be used in a state dissolved in water.

As solid polymer substances, acrylic ester polymerization emulsion (Showa Denko Co., Ltd .; Polysol F-361, F-417, S-65, SH-502), and ethylene / vinyl acetate copolymer emulsion (Kuraray Co., Ltd.) An emulsion such as Panflex OM-4000NT, OM-4200NT, OM-28NT, OM-5010NT) can be used in a state suspended in water. Further, as a solid polymer substance, polyvinylidene fluoride (manufactured by Kureha Co., Ltd .; Kureha KF Polymer # 1120, Kureha KF Polymer # 9130), modified polyvinyl alcohol (manufactured by Shin-Etsu Chemical Co., Ltd .; cyanoresin CR-V), modified pullulan Polymers such as (Shin-Etsu Chemical Co., Ltd .; cyanoresin CR-S) can be used in a state dissolved in N-methylpyrrolidone.

As a liquid binder obtained by dissolving a solid polymer substance in a solvent, a liquid binder obtained by dissolving a water-soluble polymer in water, and a binder obtained by suspending an emulsion in water are preferable.

A liquid binder obtained by dissolving a solid polymer substance in a solvent can be solidified by removing the solvent by heating and / or reducing the pressure. Such a binder can also improve the ionic conductivity of the coating film by impregnating the electrolytic solution in the coating film to form a gel electrolytic layer.

(Liquid binder that becomes solid inorganic substance by sol-gel reaction)
Liquid binders that become solid inorganic substances by sol-gel reaction include triethoxysilane, trimethoxysilane, aluminum isopropoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxy. Titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethylacetoacetate), titanium diisopropoxybis (triethanol) Aminates), titanium lactate, polyhydroxytitanium stearate, zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetylacetonate , Zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethyl acetoacetate), zirconium dibutoxy bis (ethyl acetoacetate), zirconium tetraacetylacetonate, zirconium tributoxy monostearate, various coupling agents, etc. Can be illustrated. Moreover, the catalyst for sol-gel reaction can be added to these. The catalyst for the sol-gel reaction is not particularly limited as long as it is a catalyst for a reaction in which an inorganic component is hydrolyzed and polycondensed. Such catalysts include acids such as hydrochloric acid; alkalis such as sodium hydroxide; amines; or dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate Organotin compounds such as tin octylate; organotitanate compounds such as isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraalkyl titanate; tetrabutyl zirconate, tetrakis (Acetylacetonato) zirconium, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium, dinaphthoic acid Organic zirconium compounds such as konnium; organoaluminum compounds such as tris (ethyl acetoacetate) aluminum and tris (acetylacetonato) aluminum; organometallic catalysts such as zinc naphthenate, cobalt naphthenate and cobalt octylate . Among these, a dibutyltin compound (SCAT-24 manufactured by Sansha Machinery Chemical Co., Ltd.) can be specifically mentioned as a commercial product. These compounds can be used alone or in combination of two or more.

When the battery electrode or separator coating film composition contains a surfactant described later, the surfactant may form micelles. In this case, a solid inorganic substance can be made into an inorganic porous body using micelles as a template. As the surfactant for forming the inorganic porous material, a quaternary ammonium salt is preferable, and specific examples include butyltrimethylammonium chloride, hexyltrimethylammonium chloride, dibutyldimethylammonium chloride, dihexyldimethylammonium chloride and the like.

(Water glass)
In addition to the liquid binder that becomes a solid inorganic substance by the sol-gel reaction, water glass can be exemplified as the liquid binder from which the solid inorganic substance is obtained. Specifically, No. 1 water glass, No. 2, water glass, No. 3 water glass of JIS standard table K1408, 1 type of sodium metasilicate, 2 types of sodium metasilicate, 1 type of potassium silicate, 2 type of potassium silicate, and Lithium silicate or the like can be used.

The degree of the elastic deformation property and the plastic deformation property of the binder can be expressed by the elastic modulus (h3) and the plastic deformation rate (h6), similarly to the viscoelastic particles. In the present invention, h3 of the binder is preferably 0.95 or less, and more preferably 0.9 or less. The h3 of the binder is not particularly limited, but can be 0.5 or more, and preferably 0.6 or more. In the present invention, h6 of the binder is preferably 0.90 or less, and preferably 0.85 or less. Moreover, although h6 is not specifically limited, It is preferable that it is 0.5 or more, and it is more preferable that it is 0.6 or more. If h3 and h6 of a binder are below the said upper limit, it will be excellent in stress relaxation ability, and will be excellent in the adhesive force when a base material is bent. If h3 and h6 of a binder are more than the said lower limit, mechanical strength and heat resistance will improve more.

In the present invention, it is preferable that the viscoelastic modulus of the viscoelastic particles is lower than the viscoelastic modulus of the binder. In the present invention, “the viscoelastic modulus of the viscoelastic particles is lower than the viscoelastic modulus of the binder” means that the h3 and h6 of the viscoelastic particles are smaller than the h3 and h6 of the binder. . When the viscoelastic modulus of the viscoelastic particles is lower than the viscoelastic modulus of the binder, the strength during heating can be relaxed by the binder, and the curl can be relaxed by the viscoelastic particles. Therefore, it is possible to obtain a coating film having higher heat resistance and further curling is prevented. The difference in h3 between the viscoelastic particles and the binder (Δh3 = h3 _binder −h3 _{viscoelastic particles} ) is preferably 0.01 to 0.3, more preferably 0.05 to 0.2. preferable. If the difference in h3 between the viscoelastic particle and the binder is 0.01 or more, it is possible to efficiently achieve both improved heat resistance and curl generation, and if it is 0.3 or less, the heat resistance is further improved. In addition, the occurrence of curling is further suppressed. The difference between h6 of the viscoelastic particles and the binder (Δh6 = h6 _binder −h6 _{viscoelastic particles} ) is preferably 0.01 to 0.3, and is preferably 0.05 to 0.2. Is more preferable. If the difference in h6 between the viscoelastic particles and the binder is 0.01 or more, it is possible to efficiently achieve both improved heat resistance and curl generation, and if it is 0.3 or less, the heat resistance is further improved. In addition, the occurrence of curling is further suppressed. Note that Δh6 indicating the amount of plastic deformation is more dominant in suppressing the occurrence of curling.

The h3 and h6 of the binder can be measured in the same manner as that of the viscoelastic particles. That is, after solidifying into a film having a thickness of 50 μm under conditions using a binder, the particles are cooled with liquid nitrogen and then pulverized using a mill (manufactured by IKA; M20 general-purpose mill) to obtain binder particles. be able to. This binder particle can be used as a test target particle in step (1) of [Measurement method 1] and [Measurement method 2]. Thereby, h3 and h6 of a binder can be calculated | required.

The binder content is preferably a practically sufficient addition amount without filling the voids generated between the particles. In the composition of the present invention, the content of the binder is preferably 0.01 to 49 parts by weight, more preferably 0.5 to 30 parts by weight, with respect to 100 parts by weight of the viscoelastic particles. Part by weight is more preferred.

[solvent]
The (3) solvent of the present invention will be described. The battery electrode or separator coating film composition of the present invention has a solvent for generating voids due to transpiration and adjusting fluidity. The solvent can be evaporated by heat drying, vacuum drying, freeze drying, or a combination thereof. In the case where the binder is a resin that is cured with light or an electron beam, it can be made porous using a frosted shape by being lyophilized and then cured with light or an electron beam. Moreover, the electrolyte solution solvent used for a battery can be added in advance to assist the impregnation of the electrolyte. Solvents include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, turpentine oil, pinene, etc.), halogenated hydrocarbons (chlorinated) Methyl, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.), alcohol (methanol, ethanol, n-propanol, (Isopropanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, n-heptanol, 2-octanol, n-dodecanol, nonanol, cyclohexanol, glycidol, etc.) Ether, acetal (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, ethyl benzyl ether, furan, furfural, 2-methyl furan, cineol, methylal), ketone (acetone, methyl ethyl ketone, Methyl-n-propyl ketone, methyl-n-amyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone, acetophenone, etc.), ester (methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, acetic acid-n- Amyl, methyl cyclohexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl stearate, propylene carbonate, diethyl carbonate, ethylene carbonate, vinylene car , Etc.), polyhydric alcohols and derivatives thereof (ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene Glycol monoethyl ether), fatty acids and phenols (formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isovaleric acid, phenol, cresol, o-cresol, xylenol, etc.), nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene, monomethylamine, dimethylamine, trimethylamine, monoethylamine Min, diamylamine, aniline, monomethylaniline, o-toluidine, o-chloroaniline, dicyclohexylamine, dicyclohexylamine, monoethanolamine, formamide, N, N-dimethylformamide, acetamide, acetonitrile, pyridine, α-picoline, 2, 4-lutidine, quinoline, morpholine, etc.), sulfur, phosphorus, other compounds (carbon disulfide, dimethyl sulfoxide, 4,4-diethyl-1,2-dithiolane, dimethyl sulfide, dimethyl disulfide, methanethiol, propane sultone, phosphoric acid Examples thereof include liquids such as triethyl, tophenyl phosphate, diethyl carbonate, ethylene carbonate, and amyl borate), inorganic solvents (liquid ammonia, silicone oil, and the like), and water.

A solvent can be added to the battery electrode or separator coating film composition at an arbitrary ratio in order to adjust the viscosity in accordance with the coating apparatus. The battery electrode or separator coating film composition preferably has a viscosity of 1 to 10,000 mPa · s, more preferably 2 to 5000 mPa · s, and more preferably 3 to 1,000 mPa · s from the viewpoint of coatability. More preferably, the viscosity when the shear rate is 20 seconds ⁻¹ is C, the viscosity when the shear rate is 200 seconds ⁻¹ is D, and when C / D = E, the viscosity is in the range of 1 <E <3. preferable. The kind and content of the solvent for obtaining such a viscosity can be determined as appropriate. In the present invention, the viscosity is a value obtained with a cone plate type rotational viscometer.

The battery electrode or separator coating film composition is within the range not impairing the object of the present invention, other particles, core-shell type foaming agent, salt, ionic liquid, coupling agent, stabilizer, preservative, and interface. An active agent can be included.

[Other particles]
The battery electrode or separator coating film composition may further contain one or more particles selected from the group consisting of organic fillers, carbon-based fillers, and inorganic fillers as other particles. The other particles do not include particles having the property of irreversibly plastically deforming with respect to stress and the property of reversibly elastically deforming (that is, viscoelastic particles).

Specific examples of the organic filler include polymers such as acrylic resin, epoxy resin, and polyimide that are three-dimensionally cross-linked and not substantially plastically deformed, cellulose particles, silicone particles, polyolefin particles, and the like. Examples include fibers and flakes. An organic filler can be used 1 type or in combination of 2 or more types.

Specific examples of the carbon filler include graphite, acetylene black, and carbon nanotube. A carbon type filler can be used combining 1 type or 2 types or more. The carbon-based filler is a particle that can be added to such an extent that the insulating property is not impaired.

Specific examples of inorganic fillers include powders of metal oxides such as alumina, silica, zirconia, beryllia, magnesium oxide, titania, and iron oxide; sols such as colloidal silica, titania sol, alumina sol, talc, kaolinite, and smectite. Clay minerals; carbides such as silicon carbide and titanium carbide; nitrides such as silicon nitride, aluminum nitride and titanium nitride; borides such as boron nitride, titanium boride and boron oxide; complex oxides such as mullite; water Examples include hydroxides such as aluminum oxide, magnesium hydroxide, and iron hydroxide; barium titanate, strontium carbonate, magnesium silicate, lithium silicate, sodium silicate, potassium silicate, and glass. Examples of the inorganic filler that can be added to such an extent that the insulating properties are not impaired include lithium cobaltate and olivine-type lithium iron phosphate. One kind of inorganic filler or two or more kinds of inorganic fillers can be used in appropriate combination.

The inorganic filler is preferably dried at a high temperature of about 200 ° C. for about 1 hour in order to activate the active hydrogen groups on the surface. By activating the active hydrogen group, adhesion to organic particles is improved, mechanical strength and heat resistance are improved, and ion conductivity is improved by stabilizing ions in the electrolyte.

The inorganic filler may be used in powder form, or in the form of a water-dispersed colloid such as silica sol or alumina sol or in a state dispersed in an organic solvent such as organosol. These may be contained in the organic particles to be thermally fused, or may be used in close contact with the surface of the organic particles to be thermally fused, or in a state independent of the organic particles to be thermally fused. May be added.

The size of other particles is preferably in the range of 0.001 to 100 μm, and more preferably in the range of 0.005 to 10 μm. Furthermore, it is also preferable to use a porous body of other particles from the viewpoint of increasing the porosity. Specifically, inorganic fillers such as silica gel, porous alumina, and various zeolites can be used as the other particles.

The surface of other particles can be modified with various coupling agents. Examples of the coupling agent include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane as a fluorine-based silane coupling agent, and (2-bromo) as a bromine-based silane coupling agent. -2-Methyl) propionyloxypropyltriethoxysilane, an oxetane-modified silane coupling agent, a coupling agent manufactured by Toagosei Co., Ltd. (trade name: TESOX), or vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloro Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycine Sidoxypropyltrimethoxysilane (city KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)), β-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyl Examples include silane coupling agents such as trimethoxysilane and cyanohydrin silyl ether.

Titanium coupling agents include triethanolamine titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium lactate, titanium lactate ammonium salt, tetrastearyl titanate, isopropyltricumylphenyl titanate, isopropyltri (N-aminoethyl-aminoethyl) ) Titanate, dicumylphenyloxyacetate titanate, isopropyl trioctanor titanate, isopropyl dimethacrylisostearoyl titanate, titanium lactate ethyl ester, octylene glycol titanate, isopropyl triisostearoyl titanate, triisostearyl isopropyl titanate, isopropyl tridodecyl benzene sulfonyl Titanate, tetra 2-ethylhexyl) titanate, butyl titanate dimer, isopropylisostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl) Phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, tetra- i-propyl titanate, tetra-n-butyl titanate, diisostearoyl ethylene titanate, etc. It is possible.

As coupling agents, titanium coupling agents, vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ- Aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylpropyl Methoxysilane, γ-methacryloxyxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and cyanohydrin silyl ether are preferred. A silane coupling agent and a titanium coupling agent can be used alone or in combination of two or more.

Such a coupling agent can improve adhesion by causing interaction with the battery electrode surface or the separator surface. Also, by coating the surface of other particles with these coupling agents, gaps are created between the other particles due to the exclusion effect of the coupling agent molecules, and ions are conducted between them to improve ion conductivity. You can also. Moreover, since these particles can be hydrophobized by coating the surfaces of inorganic fillers, silicone particles, polyolefin particles and the like with a coupling agent, the defoaming property can be further improved. In addition, the amount of water adsorbed on the surface can be reduced by substituting active hydrogen on the surface of other particles with a silane coupling agent, so that the amount of moisture that causes deterioration of characteristics in the non-aqueous battery can be reduced. it can. The other particles are preferably particles whose surfaces are coated with polymer chains formed by graft polymerization. Examples of the polymer chain include those described in the viscoelastic particle of the present invention, including preferable ones.

Similar effects can be obtained by blending dendrimers. In order to improve ion conductivity, it is preferable to introduce a structure having a cyano group having a high dielectric constant, a polyoxyethylene group having a strong interaction with ions, or the like. Titanium coupling agents can be more preferably applied to inorganic particles having an isoelectric point pH of 7 or more, and silane coupling agents can be more preferably applied to inorganic particles having an isoelectric point pH of less than 7. As the pH of the isoelectric point of the inorganic particles, the value measured by the method defined in JIS R1638 “Method for measuring the isoelectric point of fine ceramic powder” can be used. Silica (pH about 1.8), kaolin (pH about 5.1), mullite (pH about 6.3; the pH of isoelectric point can be controlled by changing the ratio of silicon and aluminum), titania (anatase type) (pH about 6.2), tin oxide (pH About 6.9), boehmite (pH about 7.7), γ-alumina (pH about 7.9), α-alumina (pH about 9.1), beryllia (pH about 10.1), iron hydroxide; Examples thereof include Fe (OH) ₂ (pH about 12.0), manganese hydroxide (pH about 12.0), magnesium hydroxide (pH about 12.4), and the like.

In the battery electrode or separator coating film composition of the present invention, the above-mentioned other particles can be added within a range that does not deteriorate the porosity and the continuity of the voids, and preferably 0 to 100 parts by weight of the viscoelastic particles. Up to 90 parts by weight can be contained, more preferably 0 to 50 parts by weight. In the composition of the present invention, the content of the carbon-based filler and the inorganic filler that can be added to such an extent that the insulating property is not impaired is 0.01 to 10 parts by weight with respect to 100 parts by weight of the viscoelastic particles. The amount is preferably 0.1 to 5 parts by weight.

Other types of particles can be used. A combination of inorganic fillers having a large difference in pH at the isoelectric point is preferable because an acid-base interaction is likely to occur, and the amount of one active hydrogen is increased because the activity of the other active hydrogen is improved. Specifically, silica having a low isoelectric point pH and inorganic fillers having a high isoelectric point pH, γ-alumina, α-alumina, beryllia, iron hydroxide, manganese hydroxide, magnesium hydroxide. A combination is preferable, and a combination of silica and α-alumina or a combination of silica and magnesium hydroxide is more preferable. In the case of a Li-ion battery, the addition amount of silica having a low isoelectric point pH is preferably in the range of 0.1 to 100% by weight with respect to the inorganic filler having a high isoelectric point pH, and is 1 to 10% by weight. The range of is more preferable.

[Core-shell type foaming agent]
The battery electrode or separator coating film composition of the present invention can contain a core-shell type foaming agent. As such a foaming agent, EXPANCEL (made by Nippon Philite Co., Ltd.) etc. can be used. Since the shell is organic, long-term reliability with respect to the electrolyte is poor. Therefore, what coat | covered this core shell type foaming agent with the inorganic substance further can also be used. As such inorganic substances, metal oxides such as alumina, silica, zirconia, beryllia, magnesium oxide, titania and iron oxide; sols such as colloidal silica, titania sol and alumina sol; gels such as silica gel and activated alumina; mullite and the like Complex oxides; hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide: and barium titanate can be exemplified. These inorganic substances can be coated on the surface of the viscoelastic particles by sol-gel reaction or heating. In addition, before coating with an inorganic substance, the surface is treated with a chromate treatment, a plasma treatment, a water-soluble polymer such as PVA, carboxymethyl cellulose, starch, or the like and a compound obtained by adding the above-described polycarboxylic acid to the ester and crosslinking. The adhesion can also be improved.

By using a core-shell type foaming agent that combines a shell that softens at a certain temperature and a core made of a material that expands in volume due to evaporation due to heating, the foaming agent foams when the battery runs out of heat. In addition, the distance between the electrodes can be increased, and thereby the shutdown function can be exhibited. Furthermore, since the shell portion expands greatly, the distance between the electrodes can be increased, thereby preventing a short circuit or the like. Further, since the expanded shell portion maintains its shape even after the heat generation has subsided, it is possible to prevent the electrodes from being narrowed again and short-circuiting again. In addition, by coating the core-shell type foaming agent with an inorganic substance, the influence of electrolysis during charging and discharging can be reduced, and further, the active hydrogen group on the inorganic substance surface becomes a counter ion when conducting ions, thereby improving the ionic conductivity. It can also be increased efficiently.
The battery electrode or separator coating film composition of the present invention preferably contains 1 to 99 parts by weight of the above core-shell type foaming agent with respect to 100 parts by weight of the total of the viscoelastic particles and the binder. More preferably, it is more preferably 20 to 97 parts by weight.

[salt]
The battery electrode or separator protective film composition of the present invention can contain salts serving as various ion sources. Thereby, ion conductivity can be improved. It is also possible to add the electrolyte of the battery used. In the case of a lithium ion battery, as an electrolyte, lithium hydroxide, lithium silicate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (pentafluoro) Ethanesulfonyl) imide and lithium trifluoromethanesulfonate can be exemplified. In the case of a sodium ion battery, sodium hydroxide, sodium perchlorate and the like can be exemplified. In the case of a calcium ion battery, examples of the electrolyte include calcium hydroxide and calcium perchlorate. In the case of a magnesium ion battery, examples of the electrolyte include magnesium perchlorate. In the case of an electric double layer capacitor, examples of the electrolyte include tetraethylammonium tetrafluoroborate, triethylmethylammonium bis (trifluoromethanesulfonyl) imide, and tetraethylammonium bis (trifluoromethanesulfonyl) imide.

The battery electrode or separator coating film composition of the present invention preferably contains 0.1 to 300 parts by weight, preferably 0.5 to 200 parts by weight of the above-mentioned salt with respect to 100 parts by weight as a total of the viscoelastic particles and the binder. More preferably, it is contained in an amount of 1 to 100 parts by weight. The salt may be added as a powder, made porous, or dissolved in a compounding component.

[Ionic liquid]
The battery electrode or separator coating film composition of the present invention can contain an ionic liquid. The ionic liquid may be a solution in which the salt is dissolved in a solvent or an ionic liquid. Examples of the solution in which the salt is dissolved in a solvent include a solution in which a salt such as lithium hexafluorophosphate or tetraethylammonium borofluoride is dissolved in a solvent such as dimethyl carbonate.

Examples of ionic liquids include imidazo such as 1,3-dimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazolium bromide, etc. Pyridinium salt derivatives such as 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide; tetrabutylammonium heptadeca Alkylammonium derivatives such as fluorooctane sulfonate and tetraphenylammonium methanesulfonate; phosphonium salt derivatives such as tetrabutylphosphonium methanesulfonate; Composite conductive agent complex such as a periodate such as lithium can show.

The content of the ionic liquid is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the viscoelastic particles. More preferred is 5 parts by weight.

[Coupling agent]
The battery electrode or separator coating film composition of the present invention can further contain a coupling agent. Examples of the coupling agent include those exemplified above, including preferred ones. The content of the coupling agent is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the viscoelastic particles.

[Stabilizer]
The battery electrode or separator coating film composition of the present invention may contain a stabilizer. Specific examples of such stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-ethyl- Phenol-based antioxidants exemplified by phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine Agents: alkyldiphenylamine, N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine, etc. Aromatic amine antioxidants exemplified by: dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, bis A sulfide hydroperoxide decomposer exemplified by [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-tert-butyl-phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole and the like; (Isodecyl) phosphite, phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate diethyl ester, Phosphorus hydroperoxide decomposers exemplified by sodium bis (4-tert-butylphenyl) phosphate, etc .; salicylate series exemplified by phenyl salicylate, 4-tert-octylphenyl salicylate, etc. Stabilizer; benzophenone light stabilizer exemplified by 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, etc .; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like; Hindered amine light stabilizers exemplified by phenyl-4-piperidinyl carbonate, bis- [2,2,6,6-tetramethyl-4-piperidinyl] sebacate and the like; [2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel- (II) Agent; cyanoacrylate light stabilizer; oxalic anilide-based light stabilizer; fullerenes, fullerene hydrogenated, mention may be made of fullerene-based light stabilizer such as fullerene. These stabilizers can be used alone or in combination of two or more.

The content of the stabilizer is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the viscoelastic particles. More preferably, it is part.

[Preservative]
The battery electrode or separator coating film composition of the present invention can further contain a preservative, whereby the storage stability of the composition can be adjusted.

Preservatives include acids such as benzoic acid, salicylic acid, dehydroacetic acid, sorbic acid, salts such as sodium benzoate, sodium salicylate, sodium dehydroacetate, and potassium sorbate, 2-methyl-4-isothiazoline-3- ON, and isothiazoline-based preservatives such as 1,2-benzisothiazolin-3-one, alcohols such as methanol, ethanol, isopropyl alcohol, and ethylene glycol, parahydroxybenzoates, phenoxyethanol, benzalkonium chloride, And chlorhexidine hydrochloride.

These preservatives can be used alone or in combination of two or more.

The content of the preservative is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight with respect to 100 parts by weight of the viscoelastic particles.

[Surfactant]
The battery electrode or separator coating film composition of the present invention can further contain a surfactant for the purpose of adjusting the wettability and antifoaming property of the composition. In addition, the battery electrode or separator coating film composition of the present invention can contain an ionic surfactant for the purpose of further improving ionic conductivity.

Surfactants include anionic surfactants such as soap, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate (eg, dodecyl benzene sulfonate), polyoxyethylene alkyl ether phosphate, poly Oxyethylene alkyl phenyl ether phosphate, N-acyl amino acid salt, α-olefin sulfonate, alkyl sulfate ester salt, alkyl phenyl ether sulfate ester salt, methyl taurate, trifluoromethane sulfonate, pentafluoroethane sulfonate , Heptafluoropropane sulfonate, nonafluorobutane sulfonate, and the like. As the counter cation, sodium ion, lithium ion, or the like can be used. In the lithium ion battery, a lithium ion type surfactant is more preferable, and in the sodium ion battery, a sodium ion type surfactant is more preferable.

Amphoteric surfactants include alkyldiaminoethylglycine hydrochloride, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amide propyl betaine, fatty acid alkyl betaine, sulfobetaine , Amidoxide and the like.

Nonionic (nonionic) surfactants include alkyl ester compounds such as polyethylene glycol and acetylene glycol, alkyl ether compounds such as triethylene glycol monobutyl ether, ester compounds such as polyoxysorbitan esters, alkylphenol compounds, A fluorine type compound, a silicone type compound, etc. are mentioned.

Surfactant can be used alone or in combination of two or more.

The content of the surfactant is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the viscoelastic particles. More preferred are parts by weight.

The battery electrode or separator coating film composition of the present invention is used to protect the battery electrode or separator. That is, the composition of the present invention is used as a composition for a coating film formed on at least the surface of a battery electrode or a separator, and a part of the composition may enter the battery electrode or the separator.

[Production of battery electrode or separator coating film composition]
The battery electrode or separator coating film composition of the present invention can be prepared by mixing and stirring the above components. In addition, you may mix the viscoelastic particle of this invention in the state disperse | distributed to the solvent. Stirring can be performed using a stirring device such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, an emulsifying homogenizer, and an ultrasonic homogenizer. Moreover, it can also stir, heating or cooling as needed.

In the present invention, the method for producing viscoelastic particles whose surface is coated with a polymer formed by graft polymerization is the following process: mixing the viscoelastic particles of the present invention and a coupling agent having a reactive substituent. A step of obtaining surface-modified viscoelastic particles, and mixing the surface-modified viscoelastic particles with a polymerizable compound that reacts with a reactive substituent of the surface-modified viscoelastic particles, and graft polymerization. To obtain viscoelastic particles whose surface is coated with a polymer formed by graft polymerization.

In the step of obtaining surface-modified viscoelastic particles, a silane coupling agent having a reactive substituent is immobilized on the surface of the viscoelastic particles. After the surface modification, the graft polymerization can be performed using the reactive substituent immobilized on the surface as a reaction starting point. In addition, immobilization means the state chemically bonded to the viscoelastic particle surface or the state physically adsorbed.

Examples of the coupling agent having a reactive substituent at one end include the above-mentioned silane coupling agents and titanium coupling agents, with fluorine-based silane coupling agents and bromine-based silane coupling agents being preferred, (2 -Bromo-2-methyl) propionyloxypropyltriethoxysilane is particularly preferred.

The amount of the coupling agent having a reactive substituent at one end is preferably 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, based on 100 parts by weight of the solid content of the viscoelastic particles. Is more preferable.

In the present invention, after the step of obtaining surface-modified viscoelastic particles, a step of washing the viscoelastic particles using the aforementioned solvent can be included. Thereby, reaction residues, such as an unreacted coupling agent, can be removed. The solvent used in the step of washing the viscoelastic particles is not particularly limited as long as it dissolves the reaction residue and does not peel off the surface-modified polymer, and the amount of the solvent used is an amount that can remove the reaction residue. If it does not specifically limit.

As the polymerizable compound that reacts with the reactive substituent of the surface-modified viscoelastic particle, the above-mentioned compound having a (meth) acryl group, allyl group, vinyl group, maleimide group, oxirane such as epoxy group, oxetane ring, etc. Examples include compounds having a ring, vinyl ether, cyclic acetal, and the like, and those that react with and bind to the reactive substituents of the surface-modified viscoelastic particles can be selected. As such a combination, for example, when the reactive substituent is a (2-bromo-2-methyl) propionyloxy group, a compound having a (meth) acryl group, an allyl group, and a vinyl group as the polymerizable compound Is mentioned. The amount of the polymerizable compound is not particularly limited as long as viscoelastic particles coated with a desired polymer are obtained, and is 100 to 300 parts by weight with respect to 100 parts by weight of viscoelastic particles as a raw material. Is preferred.

Polymerization may be performed in the presence of an initiator. An initiator can be used according to the kind of the polymerizable compound. Examples of such initiators include the latent thermal initiators, photocationic initiators, and thermal cationic initiators described above, and can be used depending on the type of polymerizable compound used. These initiators may be used alone or in combination of two or more. As for the usage-amount of an initiator, content of the latent thermal initiator mentioned above, a photocationic initiator, and a thermal cation initiator can be illustrated.

A step of washing viscoelastic particles coated with the polymer may be included after the step of obtaining viscoelastic particles coated with a polymer whose surface is formed by graft polymerization. The solvent described above can be used for washing.

[Battery electrode or separator surface protection method]
The battery electrode or separator surface protecting method of the present invention is a coating having voids by forming at least one layer of the battery electrode or separator coating film composition on the battery electrode or separator surface and evaporating the solvent. Forming a film. The surface of the battery electrode or separator is protected by the battery electrode or separator coating film of the present invention.

[Method for producing battery electrode or separator coating film]
The present invention also relates to a coating film obtained by using the battery electrode or separator coating film composition of the present invention in the battery electrode or separator surface protecting method. That is, in the method for producing a coating film obtained using the battery electrode or separator coating film composition of the present invention, when the binder is dissolved in a solvent, the battery electrode or separator is formed on the surface of the battery electrode or separator. Including a step of forming at least one coating layer of the coating film composition and a step of evaporating the solvent. In the case where the binder is a solid that does not dissolve in the solvent, a step of forming at least one coating layer of the battery electrode or separator coating film composition on the surface of the battery electrode or separator, a step of evaporating the solvent, and In the case where the solid binder is not heat-sealed under the temperature conditions for evaporating the solvent, a step of heat-sealing the solid binder is included.

[Method of forming coating layer of coating film composition]
In the method for producing a battery electrode or separator coating film of the present invention, a gravure coater, a slit die coater, a spray coater, dipping or the like can be used to form a coating layer of the coating film composition on the battery electrode or separator. The thickness of the coat layer is preferably in the range of 0.01 to 100 μm, and more preferably in the range of 0.05 to 50 μm from the viewpoint of electrical characteristics and adhesion. The battery electrode or separator coating film composition of the present invention may have a structure in which at least a part of the battery electrode or separator is impregnated. When at least a part of the battery electrode or separator coating film composition of the present invention is impregnated inside the battery electrode or separator, curling and deformation during the process and heat can be further suppressed. In the present invention, the dry thickness of the coating layer, that is, the thickness of the coating film is preferably in the range of 0.01 to 100 μm, more preferably in the range of 0.05 to 50 μm. If the thickness of the coating film is 0.01 μm or more, the insulation against electronic conduction is good and the risk of a short circuit is suppressed. If the thickness of the coating film is 100 μm or less, the resistance increases in proportion to the thickness, so the resistance to ion conduction is low, and the charge / discharge characteristics of the battery are improved.

When at least a part of the battery electrode or separator coating film composition of the present invention is impregnated in the battery electrode or separator, the amount of impregnation of the composition is an amount that does not completely fill the pore structure of the electrode or separator. That is, it is preferable that the porosity of the electrode or separator is more than 0%, preferably the amount of porosity of the electrode or separator is 50% or more, more preferably the porosity of the electrode or separator is 75% or more. Is the amount.
When the viscoelastic particles are particles having shape anisotropy, the particles having shape anisotropy in the coating direction can be oriented by a shearing force during coating. For example, by coating so that the major axis direction of the fibrous particles is parallel to the major axis direction of the separator, curl derived from shrinkage when releasing the tension of the separator at the time of coating is also applied to the major axis direction. The stress can be relaxed more efficiently than in the case where the oriented fibrous particles are present randomly.

[Method of transpiration of solvent]
The solvent can be obtained by heat drying, vacuum drying, freeze drying, or a combination thereof. Heating and drying can be performed using a hot stove, an infrared heater, a heat roll, or the like. The vacuum drying can be performed by putting a coating film of the coating film composition in a chamber and applying a vacuum. Freeze drying can be employed when a solvent having sublimation properties is used. The heating temperature and heating time in heat drying are not particularly limited as long as the temperature and time at which the solvent evaporates, and can be, for example, 80 to 120 ° C. and 0.1 to 2 hours. By evaporating the solvent, the components excluding the solvent of the battery electrode or separator coating film composition are in close contact with the battery electrode or the separator, and when the binder is hot melt particles, the components of the present invention are thermally fused. A coating film is formed.

[Heating method]
In the method for producing a battery electrode or separator coating film of the present invention, when the binder is used in the form of particles, the binders can be thermally fused to be solidified. In that case, the particles can be solidified by heat fusion at a temperature at which the particles are completely melted, or the surfaces of the organic particles can be melted and welded and cooled in a state of being in close contact with each other. It can also be solidified in a state where it is in close contact with a gap. According to the former heat fusion solidification, there are many portions in a continuous phase, and ion conductivity, mechanical strength, and heat resistance are high. According to the latter heat fusion solidification, since there are few portions in the continuous phase, the ion conductivity, mechanical strength and heat resistance through the fused organic particles are inferior. Impregnation can improve ion conductivity. Further, since the latter has a structure in which gaps are randomly opened, the effect of preventing a short circuit can be enhanced by preventing the linear growth when dentlite is generated. Various known methods such as hot air, hot plate, oven, infrared ray, ultrasonic fusion can be used as the heat fusion method at the time of hot melt, and the density of the protective agent layer can be increased by pressing during heating. it can. In addition to natural cooling, various known methods such as cooling gas and pressing against a heat sink can be used for cooling. Further, when heating to a temperature at which the binder is melted, the heating can be performed at a temperature at which the binder is melted for 0.1 to 1000 seconds.

[Magnetic field and / or electric field orientation]
In the method for producing a battery electrode or separator coating film of the present invention, the compounded material can be solidified in an oriented state using a magnetic field and / or an electric field. Thereby, a coating film having anisotropy in ion conductivity, mechanical strength, and heat resistance can be formed. The stress relaxation ability can be enhanced by fixing the viscoelastic particles in a state in which they are oriented in a direction in which stress relaxation is easy using a magnetic field and / or an electric field. In the case of the above-described polymer material, anisotropy can be imparted to the magnetic susceptibility and / or the dielectric constant by stretching, so that the polymer material can be oriented by a magnetic field and / or an electric field. In addition, fibers having anisotropy such as cellulose can also be used. Ion conductivity can be improved by pulverizing fibers and fibers produced by stretching such a polymer into particles and orienting the major axis so as to stand perpendicular to the electrode surface. As for organic crystals, those having crystal magnetic and / or dielectric anisotropy can be oriented by a magnetic field and / or an electric field, and the effects as described above can be exhibited. The magnetic field and / or electric field may be a static magnetic field and / or an electric field or a time-varying magnetic field and / or an electric field such as a rotating magnetic field and / or an electric field, and the magnetic field and the electric field may be applied simultaneously.

The battery electrode or separator having a coating film on its surface can be obtained by the method for producing a battery electrode or separator coating film of the present invention including the above steps. Note that at least a part of the coating film may be formed so as to enter the inside of the battery electrode or the separator. The porosity of the coating film is 40% or more, preferably 41 to 90%, and more preferably 41 to 80%.

[Battery electrode and / or separator]
The present invention relates to a battery electrode and / or separator having a coating film which is protected by the battery electrode or separator coating film or manufactured by the method for manufacturing the battery electrode or separator coating film.
The battery electrode or separator protected with the battery electrode or separator coating film of the present invention can be produced by coating the battery electrode or separator with the composition of the present invention and then evaporating the solvent. As a battery electrode, the positive electrode and / or negative electrode of a well-known various battery and an electric double layer type capacitor can be illustrated, A battery electrode or a separator coating film composition can be apply | coated or impregnated to at least one surface. Examples of the separator include a porous material made of polypropylene or polyethylene, a nonwoven fabric made of cellulose, polypropylene, polyethylene, or polyester, and can be applied or impregnated on both sides or one side. The battery electrode or separator coating film composition of the present invention can be used in a state of being in close contact with the opposing separator or electrode. After the solvent is not evaporated, the separator and the electrode are in close contact and then dried or after battery assembly. These members can be brought into close contact with each other by hot pressing.

Electrodes and separators may have anisotropy in elastic modulus, linear expansion coefficient, and shrinkage when heated, depending on the application direction of the electrode active material layer, the stretching and winding directions of the separator, and the like. For example, a uniaxially stretched polyethylene separator relieves stress during stretching and increases the amount of shrinkage in the stretching direction when heated, resulting in an anisotropic increase in stress between the coating films. In this case, the viscoelastic particles have shape anisotropy, and the longest axis of the viscoelastic particles is oriented parallel to the contraction direction (that is, the stretching direction) of the battery electrode or the separator base material. A battery electrode or separator having a coating film obtained by using the battery electrode or separator coating film composition of the invention is preferred. Here, the longest axis of the viscoelastic particles refers to a line having the longest straight line connecting the end points of any two points of the viscoelastic particles. Moreover, the base material of a battery electrode or a separator means parts other than the coating film in the battery electrode or separator which have a coating film. When the longest axis of the viscoelastic particles is oriented parallel to the shrinkage direction of the battery electrode or separator substrate, the viscoelastic particles in the coating film are oriented so that the amount of deformation increases in the stretching direction. Yes. Therefore, in the battery electrode or separator having the coating film, the stress relaxation ability between the coating film and the base material of the battery electrode or separator is increased, curling is further suppressed, and the heat resistance is further improved. For example, it is possible to increase the stress relaxation capability by making the polyethylene fiber stretched with viscoelastic particles short and aligning the fiber orientation direction with the separator stretching direction, curling is further suppressed, and heat resistance is improved. More improved.

[battery]
The present invention relates to a battery comprising a battery electrode and / or a separator protected with the battery electrode or separator coating film composition of the present invention. The battery can be manufactured by a known method. In addition, a battery can be manufactured using a coating film impregnated with ion conductivity by impregnating the coating film with an electrolytic solution. Further, the coating film composition itself can have ion conductivity and can be incorporated into a battery as a solid electrolyte film. When the coating film is impregnated with the electrolytic solution, the amount of the binder with respect to the viscoelastic particles can be 20% by weight or less, and the ionic conductivity can be imparted by impregnating the electrolytic solution into the void formed by the volume exclusion effect of the particles. . In the case of a structure having no voids, ion conductivity can be imparted by swelling the electrolyte in the binder.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The indication of the amount added is part by weight or% by weight unless otherwise noted.

[Test Example 1]
The elastic modulus and plastic deformation rate of the viscoelastic particles and binder used in Examples and Comparative Examples described later were evaluated by the following methods. Here, about the viscoelastic particle, the dispersion of the viscoelastic particle to be used was filtered and dried to obtain test particles. The binder was solidified into a film having a thickness of 50 μm under the conditions for using the binder used, cooled with liquid nitrogen, pulverized using a mill (made by IKA; M20 general-purpose mill), A test particle was obtained by sieving with an opening 50 μm sieve.

(Measurement of elastic modulus)
The test particles were packed into an acrylic cylinder having an inner diameter of 10 mm, an outer diameter of 110 mm, and a height of 150 mm so as to have a height of 100 mm, and an iron bar having an outer diameter of 10 mm and a length of 200 mm was pushed in using an autograph. The ratio of the height h1 when pressed at 1 kgf and the height h2 when pressed at 0.5 kgf was loosened and h1 / h2 = h3 was measured as the elastic modulus.

(Measurement of plastic deformation rate)
After applying a weight of 1 kgf in the above measurement, obtain the height h4 when the load is returned to 0.5 kgf, and then push the iron rod with 100 kgf and then return the load to 0.5 kgf The ratio with h5, h5 / h4 = h6, was measured as the plastic deformation rate.

[Test Example 2]
The following characteristics were measured for the lithium ion secondary batteries manufactured in Examples and Comparative Examples described later.

(Initial capacity measurement)
To obtain the initial capacity, the battery was charged at a constant current of 0.005 mA until the voltage reached 4.2 V, and then charged at a constant voltage of 4.2 V for 2 hours. Thereafter, the battery was discharged at a constant current of 0.005 mA until the voltage reached 3.5V. This was repeated three times, and the third discharge capacity was set as the initial capacity.

(Initial internal resistance)
The cell whose initial capacity was measured was set to a potential of 4.2 V, and an impedance of 1 kHz was measured with a voltage change of ± 15 mV with the potential at the center.

(Rate characteristics)
The discharge rate was obtained from the initial capacity, and the discharge capacity for each discharge rate was measured. The charge was increased to 4.2 V with a constant current over 10 hours each time, and then charged with a 4.2 V constant voltage for 2 hours. Thereafter, the battery was discharged at a constant current to 3.5 V over 10 hours, and the discharge capacity at this time was set to a discharge capacity of 0.1 C. Next, after charging in the same manner, the battery was discharged at a current value at which discharge was completed in 1 hour from the discharge capacity determined at 0.1 C, and the discharge capacity at that time was determined to be the discharge capacity at 1 C. Similarly, the discharge dose at 3C, 10C, and 30C was determined, and the capacity retention rate was calculated when the discharge capacity at 0.1C was 100%.

(Cycle life)
A charge and discharge test was performed in which the battery was charged to 4.2 V at 1 C, charged at a constant voltage of 4.2 V for 2 hours, and then discharged to 3.5 V at 1 C. At this time, it was calculated what percentage the discharge capacity was with respect to the first discharge, and the number of times of charging and discharging when the capacity was less than 80% was defined as the lifetime.

(Heat resistance insulation test)
Charge to 4.2V at 1C, charge for 2 hours at a constant voltage of 4.2V and fully charged, then raise the temperature from 25 ° C to 260 ° C in 10 ° C increments per hour, then increase to approximately 25 ° C in 1 hour The test which cools 20 degreeC at a time was implemented, and the resistance after an endurance test was confirmed by the measuring method of the said (initial internal resistance). The evaluation criteria were as follows.
Impedance at 1 kHz is ◎; 10 MΩ or more ○: 100 kΩ to less than 10 MΩ Δ: 1 kΩ to less than 100 kΩ x: less than 1 kΩ

(Heat resistance appearance test)
The test method was the same as the heat-resistant insulation test described above, and the battery after the test was disassembled to confirm the internal state. The evaluation criteria were as follows.
◎: There is no direct touch between the positive electrode and the negative electrode and the insulation state is maintained, and the battery electrode protective layer is in close contact with the electrode and / or the separator. ○: There is no direct touch between the positive electrode and the negative electrode and the insulation state is maintained. Battery electrode protective layer is partially lifted but not peeled △: Desorption progresses and part of positive and negative electrodes is exposed ×: Positive and negative electrodes are touched and short-circuited

[Test Example 3]
The following characteristics were measured in the electrodes or separators produced in Examples and Comparative Examples described later.

(Curl test)
The electrode or separator on which the coating film was formed was cut out at 50 mm square to confirm the curl state. The evaluation criteria were as follows.
◎: Not curled at all ○: The end is turned up at a height of less than 1 mm △: The end is turned up at a height of 1 to 5 mm ×: Curled on the roll

[Example 1]
In Example 1, a negative electrode having a coating film obtained by coating a battery electrode or separator coating film composition comprising a solvent, a binder, and viscoelastic particles on a negative electrode and evaporating the solvent is used for lithium ion secondary. A method for manufacturing the secondary battery will be described.

(Production of composition)
(Preparation of viscoelastic particle slurry 1)
Add 10 L of ion-exchanged water and urethane particles (manufactured by Negami Kogyo Co., Ltd .; 60% water mixture of low-modulus urethane 2 μm particles; Art Pearl MM-120TW) to a 100 L polypropylene tank and stir for 12 hours to obtain a 50% dispersion. Was made. The dispersion was filtered with a nylon mesh having an opening of 20 μm, magnetic foreign substances were removed with a 2T electromagnet, and water removed in the process was added to prepare a dispersion containing 50% viscoelastic particles.

(Composition of composition)
20 kg of water is added to 50 kg of the dispersion, and 200 g of polyoxyethylene (manufactured by Meisei Chemical Co., Ltd .; Alcox E-30) is added and dissolved by stirring for 6 hours to obtain a battery electrode or separator coating film composition. It was. In the composition, the content of viscoelastic particles among the components excluding the solvent was 99.2% by weight.

(Manufacture of positive electrode)
In a 10 L planetary mixer with a cooling jacket, 520 parts of a 15% NMP (N-methylpyrrolidone) solution of PVdF (polyvinylidene fluoride) (manufactured by Kureha; Kureha KF Polymer # 1120), lithium cobaltate (abbreviation: LCO) (Nippon Chemical Industry Co., Ltd .; Cellseed C-5H) 1140 parts, acetylene black (Denki Black HS-100, Denka Black HS-100) 120 parts and NMP 5400 parts were added and cooled so that the liquid temperature did not exceed 30 ° C. The mixture was stirred until uniform. This was coated on a rolled aluminum current collector (manufactured by Nippon Foil Co., Ltd .; width 300 mm, thickness 20 μm) with a width of 180 mm and a thickness of 200 μm, and dried in a 130 ° C. hot air oven for 30 seconds. This was roll-pressed at a linear pressure of 530 kgf / cm. The thickness of the positive electrode active material layer after pressing was 22 μm.

(Manufacture of negative electrode)
To a 10 L planetary mixer with a cooling jacket, add 530 parts of a 15% NMP solution of PVdF (manufactured by Kureha; Kureha KF Polymer # 9130), 1180 parts of graphite (manufactured by Nippon Graphite Co., Ltd .; GR-15), and 4100 parts of NMP. It stirred until it became uniform, cooling, so that temperature might not exceed 30 degreeC. This was coated on a rolled copper foil current collector (manufactured by Nippon Foil Co., Ltd .; width 300 mm, thickness 20 μm) with a width of 180 mm and a thickness of 200 μm, and dried in a 100 ° C. hot air oven for 2 minutes. This was roll-pressed at a linear pressure of 360 kgf / cm. The thickness of the negative electrode active material layer after pressing was 28 μm.

(Manufacture of negative electrode with coating film)
The composition was applied to the negative electrode using a gravure coater so as to have a dry thickness of 5 μm (mucoater manufactured by Yasui Seiki Co., Ltd., cylinder # 100, conveyance speed 1 m / min, cylinder / conveyance speed ratio = 1). ), And heated at 100 ° C. for 60 seconds to produce a negative electrode having a coating film in which the thickness of the battery electrode or the separator coating film is 5 μm.

(Manufacture of lithium ion secondary batteries)
The positive electrode and the negative electrode coated with the coating film are cut at 40 mm × 50 mm so as to include an area where the active material layer is not coated at both ends with a width of 10 mm on the short side, and in a portion where the metal is exposed The positive electrode was joined with an aluminum tab, and the negative electrode was joined with a nickel tab by resistance welding. A separator (manufactured by Celgard Co., Ltd .; # 2400) was cut to a width of 45 mm and a length of 120 mm, folded back into three, and sandwiched so that the positive electrode and the negative electrode faced each other, and an aluminum laminate cell with a width of 50 mm and a length of 100 mm was obtained. The sheet was sandwiched between two parts, and the sealant was sandwiched between the parts where the tabs hit, and then the sealant part and the side perpendicular to it were heat laminated to form a bag. This was put in a vacuum oven at 100 ° C. for 24 hours and then vacuum-dried, and then in a drive lobe box, lithium hexafluorophosphate / EC: DEC = 1: 1 1M electrolyte (manufactured by Kishida Chemical Co., Ltd .; LBG-96533) Was injected and vacuum impregnated, and then the remaining electrolyte was handled and sealed with a vacuum sealer to produce a lithium ion secondary battery.

[Example 2]
In Example 2, a positive electrode having a coating film obtained by coating a battery electrode or separator coating film composition comprising a solvent, a binder, and viscoelastic particles on a positive electrode and evaporating the solvent is used to form a lithium ion catalyst. A method for manufacturing the secondary battery will be described.

(Production of composition)
The same method as in Example 1 was used.

(Manufacture of positive electrode)
Manufactured by the method of Example 1.

(Manufacture of negative electrode)
Manufactured by the method of Example 1.

(Manufacture of positive electrode with coating film)
The positive electrode was manufactured by the method of Example 1.

(Manufacture of lithium ion secondary batteries)
Manufactured by the method of Example 1.

[Example 3]
In Example 3, a battery electrode or separator coating film composition comprising a solvent, a binder and viscoelastic particles is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used to form lithium ion A method for manufacturing the secondary battery will be described.

(Production of composition)
The same method as in Example 1 was used.

(Manufacture of positive electrode)
Manufactured by the method of Example 1.

(Manufacture of negative electrode)
Manufactured by the method of Example 1.

(Manufacture of separator with coating film)
A separator was produced in the same manner as in Example 1.

[Example 4]
In Example 4, a battery electrode or separator coating film composition comprising a solvent, a binder, and viscoelastic particles is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used to form a lithium ion solution. A method for manufacturing the secondary battery will be described.

(Production of composition)
(Preparation of viscoelastic particle slurry 1)
Add 10 L of ion-exchanged water and urethane particles (manufactured by Negami Kogyo Co., Ltd .; 60% water mixture of low-modulus urethane 2 μm particles; Art Pearl MM-120TW) to a 100 L polypropylene tank and stir for 12 hours to obtain a 50% dispersion. Was made. The dispersion was filtered with a nylon mesh having a mesh size of 20 μm, magnetic foreign matter was removed with a 2T electromagnet, and water removed in the process was added to produce a dispersion (viscoelastic particle slurry 1) containing 50% viscoelastic particles. .

(Composition of composition)
2 kg of water was added to 12 kg of the dispersion, 0.1 kg of ethylene / vinyl acetate copolymer emulsion (manufactured by Kuraray Co., Ltd .; Panflex OM-4000NT) was added and dissolved by stirring for 6 hours, and then lithium dodecylbenzenesulfonate was added. 0.01 kg of 55% aqueous solution was added and further stirred for 2 hours to obtain a battery electrode or separator coating film composition. In the composition, the content of viscoelastic particles among the components excluding the solvent was 99.2% by weight.

(Manufacture of positive electrode)
Manufactured by the method of Example 1.

(Manufacture of negative electrode)
Manufactured by the method of Example 1.

(Manufacture of separator with coating film)
Prepared by the method of Example 3.

[Example 5]
In Example 5, a battery electrode comprising a solvent, a binder, and viscoelastic particles or a separator coating film composition is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used to form a lithium ion solution. A method for manufacturing the secondary battery will be described.

(Production of composition)
(Preparation of viscoelastic particle slurry 2)
To a 100 L polypropylene tank, 10 L of ion exchange water and 50 kg of polyethylene particles (manufactured by Unitika Ltd .; 60% water mixture of polyethylene 0.2 μm particles; CD-1200) were added and stirred for 12 hours to prepare a 50% dispersion. The dispersion was filtered with a nylon mesh having an opening of 20 μm, magnetic foreign substances were removed with a 2T electromagnet, and water removed in the process was added to prepare a dispersion (viscoelastic particle slurry 2) containing 50% viscoelastic particles. .
(Composition of composition)
2 kg of water was added to 12 kg of the dispersion, 0.1 kg of ethylene / vinyl acetate copolymer emulsion (manufactured by Kuraray Co., Ltd .; Panflex OM-4000NT) was added and dissolved by stirring for 6 hours, and then lithium dodecylbenzenesulfonate was added. 0.01 kg of 55% aqueous solution was added and further stirred for 2 hours to obtain a battery electrode or separator coating film composition. In the composition, the content of viscoelastic particles among the components excluding the solvent was 99.2% by weight.

(Manufacture of positive electrode)
Manufactured by the method of Example 1.

(Manufacture of negative electrode)
Manufactured by the method of Example 1.

[Example 6]
In Example 6, a separator having a coating film obtained by coating a battery electrode or separator coating film composition comprising a solvent, a binder and viscoelastic particles on a separator and evaporating the solvent, lithium ion A method for manufacturing the secondary battery will be described.

(Production of composition)
(Preparation of inorganic particle dispersed slurry)
To a 100 L polypropylene tank, 50 L of ion exchange water and 100 kg of corundum (manufactured by Showa Denko KK; A-50-F) were added and stirred for 12 hours to prepare a 67% dispersion. While this was cooled, it was circulated and pulverized for 1 week using a bead mill having a vessel volume of 20 L (packed with 80% 0.3 mm zirconia beads, peripheral speed 10 m / s) to prepare a finely pulverized slurry. The finely pulverized slurry is filtered with a nylon mesh having an opening of 5 μm, stored in a 100 L polypropylene tank and allowed to stand for 2 days. Then, the supernatant layer of 1/5 of the volume is removed by a pump, and the remaining 3/5 is removed. An intermediate layer was collected by a pump and stored in a 100 L polypropylene tank, and 1/5 remaining at the bottom of the container was removed as a sedimentation layer. For the 3/5 sampled, the drained water was added to make 67%, then stored in a 50 L polypropylene tank and allowed to stand for 2 days, and the supernatant layer and the sedimented layer were similarly removed. This operation of separating the intermediate layer was repeated three times after changing the capacity of the polypropylene tank to 20 L, and then the magnetic foreign matter was further removed from the finally separated intermediate layer with a 2T electromagnet, which was removed in the process. Ion exchange water was added to prepare an inorganic particle-dispersed slurry containing 67% corundum particles.

(Composition of composition)
Add 1 kg of water to 3 kg of the inorganic particle-dispersed slurry, add 0.03 kg of polyoxyethylene (manufactured by Meisei Chemical Co., Ltd .; Alcox E-30) and stir for 6 hours to dissolve, and then add 100 g of CD-1200. The mixture was stirred for 2 hours to obtain a battery electrode or separator coating film composition. In the composition, the content of viscoelastic particles among the components excluding the solvent was 2.9% by weight.

(Manufacture of positive electrode)
Manufactured by the method of Example 1.

(Manufacture of negative electrode)
Manufactured by the method of Example 1.

(Manufacture of lithium ion secondary batteries)
Manufactured by the method of Example 1.
[Example 7]
In Example 7, a battery electrode comprising a solvent, a binder, and viscoelastic particles or a separator coating film composition is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used to form a lithium ion solution. A method for manufacturing the secondary battery will be described.

(Manufacture of fibrous elastic particles)
A polyethylene fishing line (manufactured by YKG Yotsuami; G-soul Pe 0.3) is cut to a width of 1 mm, and then dispersed in 50 g of water (5 kg). While cooling this, a bead mill (0.3 mm zirconia beads having a vessel volume of 0.6 L) The slurry was circulated and dispersed for one day using 80% filling and a peripheral speed of 10 m / s). Thereafter, the slurry was heated and stirred at 80 ° C. to remove moisture, and the concentration was increased to 60%.
(Production of composition)
A composition was prepared in the same manner as in Example 6 except that the above slurry was added instead of CD-1200 in Example 6.

(Manufacture of positive electrode)
Manufactured by the method of Example 1.

(Manufacture of negative electrode)
Manufactured by the method of Example 1.

[Example 8]
In Example 8, a battery electrode or a separator coating film composition comprising a solvent, a binder, and viscoelastic particles is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used. A method for manufacturing the secondary battery will be described.
(Manufacture of separator with coating film)
Except that the cylinder / conveying speed ratio is set to 2, the cylinder is double the conveying speed, and the fiber is oriented so that the fiber is oriented parallel to the conveying direction of the substrate by the shearing force between the cylinder and the substrate. This was produced by the method of Example 3. The state of fiber orientation was observed with an optical microscope.

[Comparative Example 1]
A lithium ion secondary battery was produced in the same manner as in Example 1 except that a battery electrode or an electrode having no separator coating film and a separator were used.

[Comparative Example 2]
A lithium ion secondary battery was produced in the same manner as in Example 6 except that the viscoelastic particles were not used.

The results are shown in Tables 1 to 3.

According to the battery electrode or separator coating film composition of the present invention, even if the coating film is applied, the substrate electrode or separator suppresses the occurrence of curling and has high heat resistance. Since there is no deterioration in electrochemical durability due to the wrinkles of the base material, a battery with excellent long-term reliability can be provided.

[Explanation of symbols]
1 Battery electrode or separator coating film 2 Active material layer 3 Current collector 4 Separator 5 Substrate transport direction

Claims

A battery electrode or separator coating film composition comprising a binder, a solvent and viscoelastic particles.
The battery electrode or separator coating film composition according to claim 1, wherein the viscoelastic particles have a lower viscoelastic modulus than the viscoelastic modulus of the binder.
The battery electrode or separator coating film composition according to claim 1 or 2, wherein the viscoelastic particles have shape anisotropy.
A battery electrode or separator having a coating film obtained by using the battery electrode or separator coating film composition according to any one of claims 1 to 3.
The battery electrode or separator according to claim 4, wherein the viscoelastic particles have shape anisotropy, and the longest axis of the viscoelastic particles is oriented in parallel to the shrinkage direction of the base material of the battery electrode or separator. .
A battery comprising the battery electrode and / or separator according to claim 4 or 5.