Slurry composition for adhesive layer of non-aqueous secondary battery, adhesive layer for non-aqueous secondary battery and method for manufacturing the same, component for non-aqueous secondary battery, and non-aqueous secondary battery

Abstract

Provided is a slurry composition that is for a nonaqueous secondary battery adhesive layer and that contains at least two kinds of particulate polymers, a water-soluble macromolecule, and a dispersion medium. The at least two kinds of polymers include a particulate polymer A having a glass transition temperature of 30-100°C, and a particulate polymer B having a glass transition temperature of 20°C or less. The solid component concentration of the slurry composition for the nonaqueous secondary battery adhesive layer is 1-25 mass%.

Description

[Technical Field]

[0001] The present invention relates to a slurry composition for adhesive layers of non-aqueous secondary batteries, an adhesive layer for non-aqueous secondary batteries and a method for producing the same, a component for non-aqueous secondary batteries, and a non-aqueous secondary battery. [Background technology]

[0002] Non-aqueous secondary batteries, such as lithium-ion secondary batteries (hereinafter sometimes abbreviated as "secondary batteries"), are small, lightweight, have high energy density, and can be repeatedly charged and discharged, making them suitable for a wide range of applications. Secondary batteries generally consist of battery components such as a positive electrode, a negative electrode, and a separator that isolates the positive and negative electrodes to prevent short circuits between them.

[0003] In recent years, secondary batteries have incorporated battery components that include porous film layers to improve heat resistance and strength, and adhesive layers to improve adhesion between battery components. Specifically, electrodes are used as battery components, which are formed by providing an electrode composite layer on a current collector and then forming an adhesive layer on an electrode substrate, and separators are formed by forming an adhesive layer on a separator substrate. This adhesive layer is usually formed by supplying a slurry-like non-aqueous secondary battery adhesive layer composition (hereinafter sometimes abbreviated as "adhesive layer composition") containing a binder component and a dispersion medium such as water onto a suitable substrate such as an electrode substrate or a separator substrate and drying it (see, for example, Patent Document 1).

[0004] Patent Document 1 proposes a composition for a non-aqueous secondary battery adhesive layer that includes organic particles and a water-soluble polymer whose viscosity when prepared as a 1% by mass aqueous solution is within a predetermined range, and that satisfies predetermined shear viscosity conditions. Patent Document 2 proposes a separator for a secondary battery having an adhesive layer containing a particulate polymer with a glass transition temperature of 10 to 100°C. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2017 / 090242 [Patent Document 2] International Publication No. 2013 / 151144 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, the adhesive layers formed using the adhesive layer compositions described in the above-mentioned Patent Documents 1 and 2 still have room for further improvement in uniformity, and consequently, there is room for further reduction in the internal resistance of the resulting non-aqueous secondary battery.

[0007] Therefore, the present invention aims to provide a slurry composition for an adhesive layer of a non-aqueous secondary battery that has excellent uniformity and can form an adhesive layer that can reduce the internal resistance of the resulting non-aqueous secondary battery. Furthermore, the present invention aims to provide an adhesive layer for non-aqueous secondary batteries that exhibits excellent uniformity and can reduce the internal resistance of non-aqueous secondary batteries, as well as a method for manufacturing the same. Furthermore, the present invention aims to provide a component for a non-aqueous secondary battery that can provide a non-aqueous secondary battery with low internal resistance. Furthermore, the present invention aims to provide a non-aqueous secondary battery with low internal resistance. [Means for solving the problem]

[0008] In view of these points, the inventors conducted extensive research and focused on the fact that the constituent components and solid content concentration of the slurry composition for the adhesive layer have a significant effect on the uniformity of the resulting adhesive layer and the internal resistance of a non-aqueous secondary battery equipped with such an adhesive layer, thereby completing the present invention.

[0009] [1] That is, the present invention aims to advantageously solve the above problems, and the slurry composition for a non-aqueous secondary battery adhesive layer of the present invention is a slurry composition for a non-aqueous secondary battery adhesive layer comprising at least two types of particulate polymers, a water-soluble polymer, and a dispersion medium, wherein the at least two types of polymers include particulate polymer A having a glass transition temperature of 30°C or more and 100°C or less, and particulate polymer B having a glass transition temperature of 20°C or less, and the solid content concentration of the slurry composition for a non-aqueous secondary battery adhesive layer is 1% by mass or more and 25% by mass or less. Such a slurry composition for a non-aqueous secondary battery adhesive layer has excellent uniformity and can form an adhesive layer that can reduce the internal resistance of the resulting non-aqueous secondary battery. In this specification, the glass transition temperature of a polymer can be measured by the method described in the examples. In this specification, a polymer is said to be "water-soluble" if, at 25°C, 0.5 g of the substance is dissolved in 100 g of water and the insoluble content is less than 1.0% by mass.

[0010] [2] The slurry composition for the adhesive layer of a non-aqueous secondary battery described in [1] above preferably contains (meth)acrylic acid ester monomer units in the particulate polymer A. If the particulate polymer A contains (meth)acrylic acid ester monomer units, swelling of the resulting non-aqueous secondary battery can be suppressed. In this specification, (meth)acrylic means acrylic and / or methacrylic. In this specification, "contains monomer units" means "the polymer obtained using the monomer contains monomer-derived structural units."

[0011] [3] Furthermore, in the slurry composition for the adhesive layer of a non-aqueous secondary battery according to [1] or [2] above, it is preferable that the particulate polymer B is a styrene-based polymer or an acrylic-based polymer. If the particulate polymer B is a styrene-based polymer or an acrylic-based polymer, the uniformity will be even better, and the internal resistance of the resulting non-aqueous secondary battery will be further reduced.

[0012] [4] Furthermore, it is preferable that any of the non-aqueous secondary battery adhesive layer slurry compositions of [1] to [3] above contain acid group-containing monomer units in a proportion of 5% by mass or more and 50% by mass or less of the water-soluble polymer. If the water-soluble polymer contains acid group-containing monomer units, the uniformity of the resulting adhesive layer can be further improved. Note that the proportion of monomer units is 1 It can be measured using nuclear magnetic resonance (NMR) methods such as 1H-NMR.

[0013] [5] Furthermore, it is preferable that any of the slurry compositions for the adhesive layer of the non-aqueous secondary battery according to the present invention, as described in [1] to [4] above, have a pH of 7 or higher and 9 or lower. A pH of 7 or higher and 9 or lower provides even better uniformity and makes it possible to further reduce the internal resistance of the resulting non-aqueous secondary battery.

[0014] [6] Furthermore, any of the non-aqueous secondary battery adhesive layer slurry compositions described in [1] to [5] above may contain at least one of a preservative and an antifoaming agent. This allows the slurry composition to be given desired attributes.

[0015] [7] Furthermore, it is preferable that any of the non-aqueous secondary battery adhesive layer slurry compositions described in [1] to [6] above contain particulate polymer A having a core-shell structure, with 30.0% by mass or more of (meth)acrylic acid ester monomer units, where 100% by mass is the total repeating units constituting the shell portion. If particulate polymer A is a core-shell polymer having a shell portion that satisfies these compositional conditions, the electrolyte injection properties and cycle durability of the resulting secondary battery can be improved.

[0016] [8] Furthermore, in the slurry composition for an adhesive layer of a non-aqueous secondary battery according to any one of the above [1] to [7], the particulate polymer A has a core-shell structure, and the shell portion contains methyl methacrylate units and methyl acrylate units serving as (meth)acrylic acid ester monomer units, and a monomer unit having a carboxylic acid group serving as an acid group-containing monomer unit, as repeating units. If the particulate polymer A is a core-shell polymer having a shell portion satisfying such composition conditions, the electrolyte injection property and cycle durability of the obtained secondary battery can be improved.

[0017] [9] Furthermore, an object of the present invention is to advantageously solve the above problem, and the adhesive layer for a non-aqueous secondary battery of the present invention is characterized by being formed using the slurry composition for an adhesive layer of a non-aqueous secondary battery according to any one of the above [1] to [8]. Such an adhesive layer for a non-aqueous secondary battery is excellent in uniformity and can reduce the internal resistance of the non-aqueous secondary battery.

[0018]

[10] Furthermore, an object of the present invention is to advantageously solve the above problem, and the method for producing an adhesive layer for a non-aqueous secondary battery of the present invention is characterized by comprising an application step of applying the slurry composition for an adhesive layer of a non-aqueous secondary battery according to any one of the above [1] to [8] onto a substrate by gravure coating or slot die coating. According to such a production method, the adhesive layer for a non-aqueous secondary battery of the present invention can be produced efficiently.

[0019]

[11] Furthermore, an object of the present invention is to advantageously solve the above problem, and the member for a non-aqueous secondary battery of the present invention is characterized by comprising the adhesive layer for a non-aqueous secondary battery according to the above [9] on a substrate. Use of such a member for a non-aqueous secondary battery makes it possible to provide a non-aqueous secondary battery with low internal resistance.

[0020]

[12] Here, in the member for non-aqueous secondary battery according to

[11] above, the base material includes an organic separator material, and the adhesive layer for non-aqueous secondary battery is disposed adjacent to at least one surface of the organic separator material, or is preferably disposed adjacent to a surface of a heat-resistant layer provided on at least one surface of the organic separator material. Use of such a member for a non-aqueous secondary battery makes it possible to provide a non-aqueous secondary battery with even lower internal resistance.

[0021]

[13] Furthermore, the present invention aims to advantageously solve the above problem, and the non-aqueous secondary battery according to

[11] or

[12] above is characterized by comprising the above-described member for a non-aqueous secondary battery. Thus, by including the member for a non-aqueous secondary battery of the present invention in a secondary battery, the internal resistance of the secondary battery can be reduced. Effects of the Invention

[0022] According to the present invention, there can be provided a slurry composition for a non-aqueous secondary battery adhesive layer, which is capable of forming an adhesive layer that is excellent in uniformity and enables reduction of the internal resistance of the obtained non-aqueous secondary battery. Furthermore, according to the present invention, there can be provided an adhesive layer for a non-aqueous secondary battery that is excellent in uniformity and enables reduction of the internal resistance of a non-aqueous secondary battery, and a method for producing the same. Furthermore, according to the present invention, there can be provided a member for a non-aqueous secondary battery that is capable of providing a non-aqueous secondary battery with low internal resistance. Furthermore, according to the present invention, there can be provided a non-aqueous secondary battery with low internal resistance. Mode for Carrying Out the Invention

[0023] Hereinafter, embodiments of the present invention will be described in detail. Here, the slurry composition for a non-aqueous secondary battery adhesive layer of the present invention is used for the purpose of forming an adhesive layer for mutually bonding battery members such as a separator and an electrode, or for mutually bonding constituent elements of a battery member such as a separator base material and a heat-resistant layer. Furthermore, the adhesive layer for non-aqueous secondary batteries of the present invention is formed using the above-mentioned slurry composition for adhesive layers for non-aqueous secondary batteries, preferably according to the method for manufacturing the adhesive layer for non-aqueous secondary batteries of the present invention. The component for non-aqueous secondary batteries of the present invention comprises at least the adhesive layer for non-aqueous secondary batteries of the present invention. Furthermore, the non-aqueous secondary battery of the present invention comprises at least the component for non-aqueous secondary batteries of the present invention.

[0024] (Slurry composition for non-aqueous secondary battery adhesive layer) The slurry composition for the adhesive layer of non-aqueous secondary batteries contains at least two types of particulate polymers, a water-soluble polymer, and a dispersion medium, and optionally contains other components. More specifically, the slurry composition contains particulate polymer A having a glass transition temperature of 30°C to 100°C, particulate polymer B having a glass transition temperature of 20°C or less, and a water-soluble polymer. Furthermore, the slurry composition is characterized by having a solid content concentration of 1% by mass to 25% by mass. Furthermore, the adhesive layer formed using the non-aqueous slurry composition for secondary battery adhesive layers of the present invention exhibits excellent uniformity and can reduce the internal resistance of a secondary battery equipped with such an adhesive layer. A secondary battery with low internal resistance has excellent rapid charging performance.

[0025] <Particulate polymer A> The particulate polymer A contained in the slurry composition must have a glass transition temperature of 30°C or higher and 100°C or lower. Particulate polymer A plays the role of providing adhesion to the adhesive layer formed using the slurry composition for non-aqueous secondary battery adhesive layers. Here, it is preferable that particulate polymer A contains (meth)acrylic acid ester monomer units. If particulate polymer A contains (meth)acrylic acid ester monomer units, swelling of the resulting non-aqueous secondary battery can be effectively suppressed. Furthermore, particulate polymer A may also contain acid group-containing monomer units. If particulate polymer A contains acid group-containing monomer units, the coatability of the slurry composition for non-aqueous secondary battery adhesive layers can be improved. If the slurry composition for adhesive layers has excellent coatability, the occurrence of streaks and unevenness in the formed coating film can be suppressed.

[0026] [(meth)acrylic acid ester monomer unit] Examples of (meth)acrylic acid ester monomers that can form (meth)acrylic acid ester monomer units include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl acrylate. These may be used individually or in combination of two or more in any ratio.

[0027] The content of (meth)acrylic acid ester monomer units in particulate polymer A is preferably 15% by mass or more, more preferably 30% by mass or more, even more preferably 60% by mass or more, preferably 99.0% by mass or less, and more preferably 95.0% by mass or less, when the total monomer units contained in particulate polymer A are taken as 100% by mass. If the content of (meth)acrylic acid ester monomer units in particulate polymer A is above the above lower limit, swelling of the resulting non-aqueous secondary battery can be suppressed.

[0028] [Acid group-containing monomer unit] Examples of acid group-containing monomers that can form acid group-containing monomer units include monomers having acid groups, such as monomers having carboxylic acid groups, monomers having sulfonic acid groups, monomers having phosphate groups, and monomers having hydroxyl groups.

[0029] Examples of monomers having a carboxylic acid group include monocarboxylic acids and dicarboxylic acids. Examples of monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid. Examples of dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid. Examples of monomers having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth)allyl sulfonic acid, ethyl (meth)acrylate-2-sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, and 3-alyloxy-2-hydroxypropanesulfonic acid. Furthermore, examples of monomers having a phosphate group include 2-(meth)acryloyloxyethyl phosphate, methyl-2-(meth)acryloyloxyethyl phosphate, and ethyl-(meth)acryloyloxyethyl phosphate. Examples of monomers having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. In this invention, (meth)allyl means allyl and / or methallyl, and (meth)acryloyl means acryloyl and / or methacryloyl. These may be used individually, or two or more may be combined in any ratio.

[0030] The content of acid group-containing monomer units in particulate polymer A is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, preferably 4.5% by mass or less, and more preferably 4.0% by mass or less, when the total monomer units contained in particulate polymer A are taken as 100% by mass. If the content ratio of acid group-containing monomer units in particulate polymer A is above the lower limit above, the uniformity of the resulting adhesive layer can be further improved. Furthermore, if the content ratio of acid group-containing monomer units in particulate polymer A is below the upper limit above, the internal resistance of the resulting secondary battery can be further reduced.

[0031] [Other monomeric units] Furthermore, particulate polymer A may contain monomer units other than the (meth)acrylic acid ester monomer units and acid group-containing monomer units described above, without any particular limitations. Examples of monomers that can form such monomer units include aromatic vinyl monomers and crosslinkable monomers. Examples of aromatic vinyl monomers include styrene, α-methylstyrene, styrene sulfonic acid, butoxystyrene, vinylnaphthalene, etc. These may be used individually or in combination of two or more types in any ratio. A crosslinkable monomer is a monomer that can form a crosslinked structure during or after polymerization by heating or irradiation with energy rays. More specifically, an example of a crosslinkable monomer is a polyfunctional monomer having two or more polymerization-reactive groups in the monomer. Examples of such polyfunctional monomers include divinyl compounds such as divinylbenzene and allyl methacrylate; di(meth)acrylic acid ester compounds such as diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and 1,3-butylene glycol diacrylate; tri(meth)acrylic acid ester compounds such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate; and ethylenically unsaturated monomers containing epoxy groups such as allyl glycidyl ether and glycidyl methacrylate. These may be used individually or in combination of two or more in any ratio.

[0032] Furthermore, when preparing particulate polymer A, the combination and blending ratio of the above-mentioned monomers can be arbitrarily changed depending on the intended use of the slurry composition.

[0033] —Structure of particulate polymer A— The particulate polymer A may have any structure, for example, a core-shell structure comprising a core portion and a shell portion covering the outer surface of the core portion. The shell portion may also partially cover the outer surface of the core portion. That is, the shell portion of the particulate polymer A may cover the outer surface of the core portion, but not the entire outer surface of the core portion. Furthermore, the particulate polymer A may have a heterogeneous structure in which the polymer composition differs between the central part and the surface. Whether or not the particulate polymer A has a core-shell structure can be confirmed by observing the particulate polymer with a scanning electron microscope.

[0034] Furthermore, when particulate polymer A has a core-shell structure, it may also have any other components besides the core and shell portions described above. For example, particulate polymer A may have a portion inside the core made of a different polymer from the core. Specifically, when particulate polymer A is produced by a seed polymerization method, seed particles used may remain inside the core.

[0035] When particulate polymer A is a so-called core-shell polymer having a core-shell structure, it is preferable that the (meth)acrylic acid ester monomer units be contained in 30.0% by mass or more, more preferably 45.0% by mass or more, even more preferably 60.0% by mass or more, preferably 99.0% by mass or less, and more preferably 95.0% by mass or less, with the total repeating units constituting the shell portion being 100% by mass. If the content of (meth)acrylic acid ester monomer units in the shell is above the lower limit, the electrolyte injection properties and cycle durability of the resulting secondary battery can be improved. Furthermore, if the content of (meth)acrylic acid ester monomer units in the shell is below the upper limit, the adhesion of the resulting non-aqueous secondary battery adhesive layer can be improved.

[0036] The (meth)acrylic acid ester monomer units included in the shell are preferably methyl methacrylate units and methyl acrylate units. Furthermore, it is more preferable that the shell contains both of these. If the shell contains both of these, the electrolyte pourability and cycle durability of the resulting secondary battery can be improved.

[0037] Furthermore, when particulate polymer A is a so-called core-shell polymer having a core-shell structure, it is preferable that the shell portion contains repeating units of methyl methacrylate units and methyl acrylate units as (meth)acrylic acid ester monomer units, and monomer units having a carboxylic acid group as an acid group-containing monomer unit. If particulate polymer A is a core-shell polymer having a shell portion that satisfies these compositional conditions, the electrolyte injection properties and cycle durability of the resulting secondary battery can be improved.

[0038] In particular, the monomer units having a carboxylic acid group contained in the shell portion together with methyl methacrylate units and methyl acrylate units as (meth)acrylic acid ester monomer units are preferably monomer units derived from the monocarboxylic acid described above, more preferably monomer units derived from acrylic acid or methacrylic acid, and even more preferably monomer units derived from methacrylic acid.

[0039] The content of monomer units having a carboxylic acid group in the shell portion is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, even more preferably 0.90% by mass or more, preferably 4.50% by mass or less, and even more preferably 4.00% by mass or less. If the content of monomer units having a carboxylic acid group in the shell portion is above the lower limit, the uniformity of the resulting adhesive layer can be further improved. Also, if the content of monomer units having a carboxylic acid group in the shell portion is below the upper limit, the adhesiveness of the resulting secondary battery can be improved.

[0040] Furthermore, when the particulate polymer A is a so-called core-shell polymer having a core-shell structure, the proportion of polymer constituting the shell portion is preferably 40% by mass or less, more preferably 35% by mass or less, preferably 15% by mass or more, and more preferably 20% by mass or more, based on the total mass of the core portion and the shell portion being 100% by mass. If the proportion of polymer constituting the shell portion is below the above upper limit, the adhesion of the resulting adhesive layer can be further improved. Also, if the proportion of polymer constituting the shell portion is above the above lower limit, the electrolyte injection properties and cycle durability of the resulting secondary battery can be further improved.

[0041] —Volume-average particle diameter of particulate polymer A— The particulate polymer A preferably has a volume-average particle diameter of 300 nm or more, more preferably 450 nm or more, more preferably 900 nm or less, and more preferably 750 nm or less. From the viewpoint of achieving a good balance between the adhesion and blocking resistance (resistance to blocking) of the adhesive layer, it is preferable that the volume-average particle diameter of particulate polymer A is larger than the volume-average particle diameter of particulate polymer B, which will be described later. If the volume-average particle diameter of particulate polymer A is above the lower limit above, the blocking resistance of the adhesive layer can be improved. Also, if the volume-average particle diameter of particulate polymer A is below the upper limit above, the adhesion of the adhesive layer can be improved. The volume-average particle diameter of particulate polymer A can be measured by the method described in the examples.

[0042] —Glass transition temperature of particulate polymer A— The particulate polymer A must have a glass transition temperature of 30°C or higher and 100°C or lower, more preferably 40°C or higher, more preferably 55°C or higher, preferably 90°C or lower, and more preferably 80°C or lower. If the glass transition temperature of particulate polymer A is above the lower limit, it is possible to suppress mutual adhesion and blocking when secondary battery components having an adhesive layer on their surface are stored stacked. Furthermore, if the glass transition temperature of particulate polymer A is below the upper limit, the adhesion of the adhesive layer can be improved, and swelling of the resulting secondary battery can be suppressed. Note that in cases where particulate polymer A has the core-shell structure described above, multiple glass transition temperatures may be detected when the glass transition temperature is measured by the method described in the examples of this specification. In such cases, the lowest glass transition temperature value shall be taken as the glass transition temperature of particulate polymer A. Furthermore, the glass transition temperature of particulate polymer A can be adjusted to a desired temperature by changing the composition of particulate polymer A.

[0043] —Method for preparing particulate polymer A— Particulate polymer A can be prepared by known polymerization methods without particular limitations. The polymerization method is not particularly limited, and any of the following methods can be used, for example, solution polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization. Any of the polymerization methods can be used, for example, ionic polymerization, radical polymerization, or living radical polymerization. In emulsion polymerization, seed polymerization using seed particles may also be employed. Furthermore, when preparing particulate polymer A having a core-shell structure, a stepwise polymerization method can be employed, such as a continuous multi-step suspension polymerization method or a multi-step suspension polymerization method in which the polymer formed in an earlier step is sequentially coated with the polymer formed in a later step.

[0044] Furthermore, the emulsifiers, dispersants, polymerization initiators, and polymerization aids used in polymerization can be those commonly used, and the amounts used can also be those commonly used.

[0045] <Particulate polymer B> The particulate polymer B contained in the slurry composition must have a glass transition temperature of 20°C or lower. Particulate polymer B, together with the particulate polymer A described above, plays a role in providing adhesion to the adhesive layer formed using the slurry composition for non-aqueous secondary battery adhesive layers. Particulate polymer B is not particularly limited as long as it is dispersible in a dispersion medium such as water, and can be any polymer, but among them, styrene polymers and acrylic polymers are preferred as particulate polymer B. This is because it is possible to further improve uniformity and further reduce the internal resistance of the resulting non-aqueous secondary battery. Examples of styrene polymers include polymers in which the proportion of styrene units is 50% by mass or more, preferably more than 60% by mass, of the total repeating units. Specifically, examples of styrene polymers include styrene-butadiene copolymers (SBRs), and among them, polar group-containing SBRs are preferred. Examples of polar group-containing SBRs include polymers obtained by modifying SBR with polar groups such as acid groups. Examples of monomers that can be used to modify SBR with acid groups include the acid group-containing monomers described in the section on particulate polymer A. Furthermore, an acrylic polymer refers to a polymer containing 50% by mass or more, preferably 60% by mass or more, of (meth)acrylic acid ester monomer units of the total repeating units. Here, the (meth)acrylic acid ester monomers that can form (meth)acrylic acid ester monomer units are the same as those described in the section on particulate polymer A. In particular, among acrylic polymers, polymers containing 50% by mass or more and 95% by mass or less of (meth)acrylic acid ester monomer units having 8 or more carbon atoms (especially 2-ethylhexyl acrylate units having 8 carbon atoms) are preferred. The inclusion of (meth)acrylic acid ester monomer units having 8 or more carbon atoms can improve the adhesion between the electrode and the separator. Furthermore, particulate polymer B may be used alone or in combination of two or more types.

[0046] —Glass transition temperature of particulate polymer B— The particulate polymer B must have a glass transition temperature of 20°C or lower, preferably 10°C or lower, preferably -50°C or higher, and more preferably -40°C or higher. If the glass transition temperature of particulate polymer B is below the above upper limit, the adhesion of the adhesive layer can be ensured. It is preferable that the particulate polymer B has one glass transition temperature.

[0047] —Volume-average particle diameter of particulate polymer B— The particulate polymer B preferably has a volume-average particle diameter of 80 nm or more, more preferably 100 nm or more, more preferably 400 nm or less, and more preferably 200 nm or less. If the volume-average particle diameter of particulate polymer B is above the lower limit, the internal resistance of the resulting secondary battery can be further reduced. Furthermore, if the volume-average particle diameter of particulate polymer B is below the upper limit, the blocking resistance of the adhesive layer can be improved. The volume-average particle diameter of particulate polymer B can be measured by the method described in the examples.

[0048] Examples of methods for producing particulate polymer B include solution polymerization, suspension polymerization, and emulsion polymerization. Among these, emulsion polymerization and suspension polymerization are preferred because polymerization can be carried out in water, and the aqueous dispersion containing particulate polymer B can be suitably used directly as a material for the slurry composition of the adhesive layer. Furthermore, when producing the polymer as particulate polymer B, it is preferable that the reaction system contains a dispersant. Particulate polymer B is usually formed substantially from the polymers that constitute it, but it may also contain any components such as additives used during polymerization.

[0049] <Mixing ratio of particulate polymers A and B> The blending ratio of particulate polymer A and particulate polymer B in the slurry composition is preferably such that the amount of particulate polymer B is 3 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less, per 100 parts by mass of particulate polymer A. If the blending ratio of particulate polymer A and B is within the above range, the adhesion of the adhesive layer can be made good, and the occurrence of blocking can be effectively suppressed.

[0050] <Water-soluble polymer> The water-soluble polymer contained in the slurry composition for the adhesive layer of a non-aqueous secondary battery plays a role in adjusting the viscosity of the slurry composition to improve its coatability. Preferably, the water-soluble polymer has adhesive and electrolyte resistance properties and plays a role in assisting the adhesion between components in the adhesive layer and between battery components in the secondary battery.

[0051] —Types of water-soluble polymers— Here, the water-soluble polymers are not particularly limited, but examples include natural polymers, semi-synthetic polymers, and synthetic polymers.

[0052] [Natural polymer] Examples of natural polymers include polysaccharides and proteins derived from plants or animals, as well as fermentation products of these by microorganisms, and heat treatment products of these. These natural polymers can be classified into plant-derived natural polymers, animal-derived natural polymers, and microorganism-derived natural polymers, among others. Examples of plant-derived natural polymers include gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed, archecolloid (gasso extract), starch (derived from rice, corn, potato, wheat, etc.), and glycyrrhizin. Examples of animal-derived natural polymers include collagen, casein, albumin, and gelatin. Examples of microorganism-produced natural polymers include xanthan gum, dextran, succinoglucan, and pullulan.

[0053] [Semi-synthetic polymer] Examples of semi-synthetic polymers include cellulose-based semi-synthetic polymers. These can be further classified into nonionic cellulose-based semi-synthetic polymers, anionic cellulose-based semi-synthetic polymers, and cationic cellulose-based semi-synthetic polymers.

[0054] Examples of nonionic cellulosic semi-synthetic polymers include alkylcelluloses such as methylcellulose, methylethylcellulose, ethylcellulose, and microcrystalline cellulose; and hydroxyalkylcelluloses such as hydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose stearoxy ether, carboxymethylhydroxyethylcellulose, alkylhydroxyethylcellulose, and nonoxynylhydroxyethylcellulose.

[0055] Examples of anionic cellulose-based semi-synthetic polymers include substituted products obtained by substituting the above-mentioned nonionic cellulose-based semi-synthetic polymers with various derivative groups, and their salts (sodium salts, ammonium salts, etc.). Specifically, examples include sodium cellulose sulfate, methylcellulose, methylethylcellulose, ethylcellulose, carboxymethylcellulose (CMC), and their salts.

[0056] Examples of cationic cellulose-based semi-synthetic polymers include low-nitrogen hydroxyethylcellulose dimethyldiallylammonium chloride (Polyquaternium-4), O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride (Polyquaternium-10), and O-[2-hydroxy-3-(lauryldimethylammonio)propyl]hydroxyethylcellulose chloride (Polyquaternium-24).

[0057] [Synthetic polymer] The synthetic polymers are not particularly limited, but include, for example, synthetic polymers containing acid group-containing monomer units in a proportion of 5% to 50% by mass, vinyl acetate polymers such as polyvinyl alcohol, special ammonium polyacrylate salts (e.g., Aron® A6114 manufactured by Toagosei Co., Ltd.), acrylic acid / sulfonic acid monomer copolymers (e.g., Aquaric® GL366 manufactured by Nippon Shokubai Co., Ltd.), and compounds known as polyethylene glycol type nonionic surfactants or propylene oxide / ethylene oxide copolymers (e.g., Noptex® ED052 manufactured by Sunnopco Corporation).

[0058] Here, the acid group-containing monomers used to form the acid group-containing monomer units can be those described above. These may be used individually or in combination of two or more types in any ratio.

[0059] Furthermore, the monomer composition used in the preparation of the synthetic polymer preferably contains 5% by mass or more, more preferably 25% by mass or more, preferably 50% by mass or less, and more preferably 45% by mass or less, of the above-mentioned acid group-containing monomers. By keeping the proportion of acid group-containing monomers in the monomer composition used in the preparation of the synthetic polymer within the above range, the uniformity of the resulting adhesive layer can be further improved. For the same reason, the content of acid group-containing monomer units in the synthetic polymer synthesized using such monomer composition is preferably 5% by mass or more, more preferably 25% by mass or more, preferably 50% by mass or less, and more preferably 45% by mass or less, with the total repeating units constituting the synthetic polymer being 100% by mass.

[0060] Furthermore, the above monomer composition may contain other compounds copolymerizable with the acid group-containing monomer. Specifically, examples of other compounds include the (meth)acrylic acid ester monomers mentioned above, the crosslinkable monomers mentioned above, amide group-containing monomers such as (meth)acrylamide, and nitrile group-containing monomers such as acrylonitrile.

[0061] Examples of additives used in the monomer composition for the preparation of synthetic polymers include known additives that can be used in polymerization reactions, such as crosslinking agents like ethylene glycol dimethacrylate, polymerization initiators like potassium persulfate, and polymerization accelerators like tetramethylethylenediamine. The type and amount of additives can be arbitrarily selected depending on the polymerization method.

[0062] Furthermore, as the polymerization solvent to be incorporated into the monomer composition used in the preparation of synthetic polymers, any known solvent capable of dissolving or dispersing the aforementioned monomers can be used, depending on the polymerization method. Among these, water is preferred as the polymerization solvent. However, an aqueous solution of any compound or a mixed solution of a small amount of organic medium and water may also be used as the polymerization solvent.

[0063] The synthetic polymer can be obtained by, for example, radical polymerization of a monomer composition obtained by mixing the above-mentioned monomers, crosslinking agent, additives, and polymerization solvent in a known manner. The solution containing the synthetic polymer and polymerization solvent obtained by polymerizing the above monomer composition may be used as is for preparing the slurry composition for the adhesive layer, or it may be used for preparing the slurry composition for the adhesive layer after solvent substitution or the addition of any components.

[0064] Here, known polymerization methods for synthetic polymers include aqueous solution polymerization, slurry polymerization, suspension polymerization, and emulsion polymerization. However, aqueous solution polymerization using water as the polymerization solvent is preferred because it does not require solvent removal, the solvent is highly safe, and there is no problem of surfactant contamination. In aqueous solution polymerization, the monomer composition is adjusted to a predetermined concentration, the dissolved oxygen in the reaction system is sufficiently replaced with an inert gas, a radical polymerization initiator is added, and the polymerization reaction is carried out by heating or light irradiation such as ultraviolet light as necessary.

[0065] Furthermore, when water is used as the polymerization solvent and the monomer composition described above is polymerized in water to prepare an aqueous solution containing the synthetic polymer, it is preferable to adjust the pH of the aqueous solution to 8 or higher and 9 or lower after polymerization.

[0066] —Weight-average molecular weight of water-soluble polymers— The water-soluble polymer preferably has a weight-average molecular weight of 300 or more, more preferably 500 or more, more preferably 3 million or less, and more preferably 2.5 million or less. Furthermore, if the slurry composition of the present invention contains two or more water-soluble polymers, it is preferable to use in combination those with different weight-average molecular weights.

[0067] The weight-average molecular weight of the water-soluble polymer (hereinafter sometimes referred to as water-soluble polymer A), which has a relatively large weight-average molecular weight, is preferably 100,000 or more, more preferably 150,000 or more, even more preferably 200,000 or more, preferably 500,000 or less, more preferably 450,000 or less, and even more preferably 400,000 or less. If the weight-average molecular weight of water-soluble polymer A is above the lower limit, the uniformity of the resulting adhesive layer can be further improved. If the weight-average molecular weight of water-soluble polymer A is below the upper limit, the resulting adhesiveness can be improved.

[0068] The weight-average molecular weight of the water-soluble polymer (hereinafter sometimes referred to as water-soluble polymer B), which has a relatively small weight-average molecular weight, is preferably 300 or more, more preferably 400 or more, even more preferably 500 or more, preferably 90,000 or less, and more preferably 80,000 or less. If the weight-average molecular weight of water-soluble polymer B is above the lower limit, the uniformity of the resulting adhesive layer can be further improved. If the weight-average molecular weight of water-soluble polymer B is below the upper limit, the resulting adhesiveness can be improved.

[0069] Furthermore, by using water-soluble polymer A and water-soluble polymer B in combination, the uniformity of the resulting adhesive layer can be further improved.

[0070] —Composition ratio of water-soluble polymers— In the slurry composition for the adhesive layer of a non-aqueous secondary battery, the blending ratio of the water-soluble polymer is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, per 100 parts by mass of particulate polymer A. By setting the blending ratio of the water-soluble polymer within the above range, the coatability of the slurry composition is improved, thereby increasing the uniformity of the resulting adhesive layer and further reducing the internal resistance of the resulting secondary battery. When the slurry composition contains the above-mentioned water-soluble polymers A and B as water-soluble polymers, it is preferable that their total amount be within the above range.

[0071] <Other ingredients> The slurry composition for the adhesive layer of non-aqueous secondary batteries may contain any other components in addition to the particulate polymers A and B described above, and the water-soluble polymer. However, compounds corresponding to the water-soluble polymer described above are excluded from the other components. Examples of these other components include preservatives and defoamers. These other components may be used individually or in combination of two or more. By optionally incorporating other components such as preservatives and defoamers, desired attributes can be imparted to the slurry composition for the adhesive layer.

[0072] In particular, isothiazoline compounds such as Navisite P40 and Actiside MBS can be suitably incorporated as preservatives. Furthermore, DF6351 manufactured by Seikoh PMC Co., Ltd. can be suitably incorporated as an antifoaming agent. The amounts of these additives can be adjusted as appropriate depending on the application. For example, the total amount of these additives is preferably in the range of 1000 ppm to 3000 ppm per 100 parts by mass of particulate polymer A.

[0073] <Dispersion medium> Water can be used as the dispersion medium. The dispersion medium is not particularly limited as long as it can disperse the particulate polymers A and B and dissolve at least a portion of the water-soluble polymer, and may be a mixed solvent of water and an organic solvent. From the viewpoint of coating properties, it is preferable that the dispersion medium is water.

[0074] <Method for producing a slurry composition for non-aqueous secondary battery adhesive layers> A method for producing a slurry composition for adhesive layers includes a step of mixing particulate polymers A and B, a water-soluble polymer, and a dispersion medium, along with other components as needed. The mixing method is not particularly limited, but in order to efficiently disperse each component, a disperser is usually used as the mixing device. A disperser is preferably a device capable of uniformly dispersing and mixing the above components. Examples include ball mills, sand mills, pigment dispersers, grinders, ultrasonic dispersers, homogenizers, and planetary mixers. Furthermore, from the viewpoint of applying high shear force during dispersion, high-dispersion devices such as bead mills, roll mills, and film mixers are also suitable.

[0075] <pH of slurry composition for non-aqueous secondary battery adhesive layer> The slurry composition for the adhesive layer preferably has a pH of 7 or higher, more preferably 8 or higher, and most preferably 9 or lower. If the pH of the slurry composition for the adhesive layer is within the above range, uniformity will be further improved, and the internal resistance of the resulting non-aqueous secondary battery will be further reduced.

[0076] <Solid content concentration of slurry composition for non-aqueous secondary battery adhesive layer> The slurry composition for the adhesive layer must have a solid content concentration of 1% by mass or more and 25% by mass or less, preferably 20% by mass or less, more preferably 12% by mass or less, even more preferably 8% by mass or less, and particularly preferably 5% by mass or less. If the solid content concentration is within the above range, it becomes possible to uniformly manufacture an adhesive layer with a thin thickness and low basis weight. As a result, the internal resistance of the resulting secondary battery can be reduced, and the rapid charging performance can be improved.

[0077] (Adhesive layer for non-aqueous secondary batteries and component for non-aqueous secondary batteries equipped therewith) An adhesive layer can be formed on a suitable substrate using the slurry composition for non-aqueous secondary battery adhesive layers described above. Specifically, an adhesive layer for non-aqueous secondary battery adhesive layers can be formed by drying the slurry composition for non-aqueous secondary battery adhesive layers on a suitable substrate. That is, the adhesive layer for non-aqueous secondary battery adhesive layers of the present invention consists of the dried product of the slurry composition for non-aqueous secondary battery adhesive layers described above, and usually contains the above-mentioned particulate polymers A and B, and a water-soluble polymer, and optionally contains the above-mentioned other components. If the above-mentioned particulate polymers A and B, and the water-soluble polymer contain crosslinkable monomer units, such crosslinkable monomer units may be crosslinked during drying of the slurry composition or during heat treatment optionally performed after drying (i.e., the adhesive layer for non-aqueous secondary battery adhesive layers may contain crosslinked products of the above-mentioned particulate polymer A, particulate polymer B, and / or water-soluble polymer). The preferred abundance ratio of each component contained in the adhesive layer for non-aqueous secondary battery is the same as the preferred abundance ratio of each component in the slurry composition for non-aqueous secondary battery adhesive layers. Furthermore, particulate polymers A and B, which exist as particles in the slurry composition for the adhesive layer of non-aqueous secondary batteries, may maintain their original particle shape or be deformed within the adhesive layer. In addition, when particulate polymer A having a core-shell structure is incorporated into the slurry composition for the adhesive layer, it is preferable that the core-shell structure itself is maintained, even if the overall shape of particulate polymer A changes from the original particle shape. Furthermore, the adhesive layer for non-aqueous secondary batteries of the present invention exhibits excellent uniformity and can reduce the internal resistance of the resulting non-aqueous secondary battery. Furthermore, the non-aqueous secondary battery component equipped with the adhesive layer for non-aqueous secondary batteries of the present invention can reduce the internal resistance of the resulting non-aqueous secondary battery.

[0078] <Base material> The substrate on which the adhesive layer is formed is not particularly limited. For example, when the adhesive layer is used as a component constituting part of a separator, a separator substrate can be used as the substrate. When the adhesive layer is used as a component constituting part of an electrode, an electrode substrate formed by forming an electrode composite layer on a current collector can be used as the substrate. Furthermore, there are no particular restrictions on how the adhesive layer formed on the substrate is used. For example, the adhesive layer may be formed on a separator substrate and used as is as a battery component such as a separator, or the adhesive layer may be formed on an electrode substrate and used as an electrode, or the adhesive layer formed on a release substrate may be peeled off the substrate and attached to another substrate to be used as a battery component. However, from the viewpoint of improving the manufacturing efficiency of battery components by omitting the step of peeling the release substrate from the adhesive layer, it is preferable to use a separator substrate or an electrode substrate as the substrate.

[0079] [Separator substrate] The separator substrate is not particularly limited, and for example, a separator substrate can be used in which an arbitrary heat-resistant layer (for example, a layer containing heat-resistant fillers such as inorganic particles) is disposed on the surface of an organic separator material which is a microporous membrane made of polyolefin resins such as polyethylene, polypropylene, polybutene, and polyvinyl chloride. In other words, the component for a non-aqueous secondary battery has a structure in which the adhesive layer for a non-aqueous secondary battery is disposed directly adjacent to at least one surface of the organic separator material, or is disposed adjacent to the surface of a heat-resistant layer provided on at least one surface of the organic separator material.

[0080] [Electrode base material] The electrode substrates (positive electrode substrate and negative electrode substrate) that form the adhesive layer are not particularly limited, but examples include electrode substrates in which an electrode composite layer is formed on a current collector. Here, known methods can be used for the current collector, the components in the electrode composite layer (for example, electrode active materials (positive electrode active material, negative electrode active material) and binders for the electrode composite layer (binder for the positive electrode composite layer, binder for the negative electrode composite layer), etc.), and the method for forming the electrode composite layer on the current collector, for example, the method described in Japanese Patent Application Publication No. 2013-145763 can be used. Furthermore, the electrode substrate may include, in part, any layer other than the adhesive layer that has the desired function.

[0081] [Release base material] The release substrate used to form the adhesive layer is not particularly limited, and any known release substrate can be used.

[0082] <Weight of the adhesive layer> The adhesive layer has a basis weight of 0.2 g / m². 2 Preferably, it is 0.15 g / m 2 It is more preferable that the following is the case: 0.11 g / m 2 It is even more preferable that the basis weight of the adhesive layer is below the above upper limit. If the basis weight of the adhesive layer is below the above upper limit, the internal resistance of the resulting secondary battery can be further reduced, and the rapid charging performance of the secondary battery can be improved. The lower limit of the basis weight of the adhesive layer is not particularly limited, but is usually 0.05 g / m². 2 That is all that is possible.

[0083] (Method for manufacturing adhesive layers for non-aqueous secondary batteries) The following methods can be used to form an adhesive layer on substrates such as the separator substrate and electrode substrate mentioned above: 1) A method of applying an adhesive layer slurry composition to the surface of a separator substrate or electrode substrate (in the case of an electrode substrate, the surface on the electrode composite layer side, the same applies hereinafter) by gravure coating or slot die coating, and then drying; 2) A method of applying an adhesive layer slurry composition onto a release substrate by gravure coating or slot die coating, drying it to produce an adhesive layer, and transferring the obtained adhesive layer to the surface of a separator substrate or electrode substrate. Among these, method 1) is particularly preferred because it can improve uniformity while reducing the thickness of the adhesive layer. Method 1) comprises, in detail, a step of applying an adhesive layer slurry composition onto a separator substrate or electrode substrate by gravure coating or slot die coating (coating step), and a step of drying the adhesive layer slurry composition applied onto the separator substrate or electrode substrate to form an adhesive layer (drying step).

[0084] In the drying process, the method for drying the slurry composition for the adhesive layer on the substrate is not particularly limited and known methods can be used, such as drying with hot air, hot air, low humidity air, vacuum drying, and drying by irradiation with infrared rays or electron beams. The drying conditions are not particularly limited, but the drying temperature is preferably 30 to 80°C and the drying time is preferably 30 seconds to 10 minutes.

[0085] The thickness of the adhesive layer formed on the substrate is preferably 0.1 μm or more, more preferably 0.3 μm or more, even more preferably 0.5 μm or more, preferably 3.0 μm or less, more preferably 1.5 μm or less, and even more preferably 1.0 μm or less. By having an adhesive layer thickness greater than or equal to the lower limit of the above range, sufficient strength of the adhesive layer can be ensured, and by having an adhesive layer thickness less than or equal to the upper limit of the above range, the internal resistance of the secondary battery can be further reduced.

[0086] (Non-aqueous secondary battery) The non-aqueous secondary battery of the present invention comprises the non-aqueous secondary battery components of the present invention described above. More specifically, in the non-aqueous secondary battery of the present invention, at least one of the positive electrode, negative electrode, and separator is a non-aqueous secondary battery component of the present invention. The non-aqueous secondary battery of the present invention has low internal resistance because it is equipped with the non-aqueous secondary battery component of the present invention. Therefore, the non-aqueous secondary battery of the present invention has excellent rapid charging performance.

[0087] <Positive and negative electrodes> As described above, the secondary battery of the present invention is a component for a non-aqueous secondary battery of the present invention in which at least one of the positive electrode, negative electrode, and separator comprises the adhesive layer of the present invention. That is, an electrode can be used in which an adhesive layer is provided on an electrode substrate which has an electrode composite layer formed on a current collector. The electrode substrate and separator substrate can be the same as those listed in the section on "adhesive layer for non-aqueous secondary battery". Furthermore, the positive and negative electrodes, which do not have an adhesive layer, are not particularly limited, and electrodes made of the electrode substrates described above can be used.

[0088] <Electrolyte> Typically, an organic electrolyte is used as the electrolyte, which is obtained by dissolving a supporting electrolyte in an organic solvent. For example, in lithium-ion secondary batteries, lithium salts are used as the supporting electrolyte. Examples of lithium salts include LiPF6, LiAsF6, LiBF4, LiSbF6, LiAlCl4, LiClO4, CF3SO3Li, C4F9SO3Li, CF3COOLi, (CF3CO)2NLi, (CF3SO2)2NLi, and (C2F5SO2)NLi. Among these, LiPF6, LiClO4, and CF3SO3Li are preferred because they are easily soluble in solvents and exhibit a high degree of dissociation. Note that one type of electrolyte may be used alone, or two or more types may be used in combination. Generally, the lithium ion conductivity tends to increase as the supporting electrolyte with a higher degree of dissociation is used, so the lithium ion conductivity can be adjusted by the type of supporting electrolyte.

[0089] The organic solvent used in the electrolyte is not particularly limited as long as it can dissolve the supporting electrolyte. However, in lithium-ion secondary batteries, for example, carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), and methyl ethyl carbonate (MEC); esters such as γ-butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; and sulfur-containing compounds such as sulfolane and dimethyl sulfoxide are preferably used. Mixtures of these solvents may also be used. Among these, carbonates are preferred because they have a high dielectric constant and a wide stable potential range. Generally, the lower the viscosity of the solvent used, the higher the lithium ion conductivity tends to be, so the lithium ion conductivity can be adjusted by the type of solvent used. The concentration of the electrolyte in the electrolyte solution can be adjusted as appropriate. Furthermore, known additives may be added to the electrolyte solution.

[0090] <Manufacturing method for non-aqueous secondary batteries> Non-aqueous secondary batteries can be manufactured, for example, by stacking a positive electrode and a negative electrode with a separator in between, placing the resulting positive electrode-separator-negative electrode laminate into a battery container as is, or by rolling or folding it as needed, and then injecting an electrolyte into the battery container and sealing it. Here, the battery container may optionally contain expanded metal, fuses, overcurrent protection elements such as PTC elements, lead plates, etc., to prevent pressure rise inside the battery and overcharging / discharging. The shape of the battery may be any of the following: coin type, button type, sheet type, cylindrical type, prismatic type, flat type, etc. [Examples]

[0091] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" used to express quantities refer to mass unless otherwise specified. Furthermore, in polymers produced by copolymerizing multiple types of monomers, the proportion of a structural unit formed by polymerizing a certain monomer in the polymer is, unless otherwise specified, usually equal to the ratio of that particular monomer to the total monomers used in the polymerization of the polymer (the starting ratio). In the examples and comparative examples, the measurement and evaluation of various attributes were carried out according to the following methods.

[0092] <Glass transition temperature> The glass transition temperatures of particulate polymers A and B prepared in the examples and comparative examples were determined by measuring the DSC curves using a differential thermal analysis analyzer (EXSTAR DSC6220, manufactured by SII Nanotechnology Co., Ltd.) in accordance with JIS K6240. Specifically, 10 mg of the dried sample was weighed into an aluminum pan, and an empty aluminum pan was used as a reference. The DSC curve was measured at a heating rate of 20 °C / min within the measurement temperature range of -100 °C to 200 °C. The temperature of the endothermic peak of the differential signal (DDSC) during this heating process was determined and used as the glass transition temperature of particulate polymers A and B. In all examples and comparative examples, two glass transition temperatures were detected for particulate polymer A and the particulate polymer used in its place; however, the lower temperature was adopted as the glass transition temperature of particulate polymer A.

[0093] <Volume-average particle diameter> The volume-average particle diameters of particulate polymers A and B prepared in the examples and comparative examples were measured by laser diffraction. Specifically, aqueous dispersions containing the prepared particulate polymers A and B (adjusted to a solid content concentration of 0.1% by mass) were used as samples. The volume-average particle diameter was defined as the particle diameter D50 at which the cumulative volume calculated from the smallest diameter side reached 50% in the particle diameter distribution (volume-based) measured using a laser diffraction particle size distribution analyzer (Beckman Coulter, "LS-13320").

[0094] <Weight-average molecular weight of water-soluble polymers> The aqueous solutions containing the water-soluble polymers used in the examples and comparative examples were diluted to a concentration of 0.5%. Next, the solutions were diluted to 0.025% with the eluent described below to prepare the samples. These samples were analyzed by gel permeation chromatography under the following conditions, and molecular weight distribution curves were created to determine the weight-average molecular weight of the water-soluble polymers. Equipment: Gel permeation chromatograph GPC (Agilent 1260 Infinity II HPLC) Detector: Differential refractive index detector RI (Agilent 1260 Infinity II) Column: TSKgel GMPWXL, 2 pieces (φ7.8mm x 30cm, manufactured by Tosoh) Solvent: For anionic polymers, 0.1 M Tris buffer (with 0.1 M potassium chloride added) Flow rate: 0.7mL / min Column temperature: 40℃ Injection volume: 0.2mL Standard samples: Monodisperse polyethylene oxide (PEO) and polyethylene glycol (PEG) manufactured by Tosoh and Sigma-Aldrich.

[0095] <Weight of the adhesive layer> Ten test pieces, each 10 cm wide and 10 cm long, were cut from the substrates with adhesive layers obtained in the examples and comparative examples, and the average mass W1 (g) of the cut test pieces was measured. In addition, the thickness of each test piece was measured at five locations: the four corners and the center, and the average value was taken as the thickness T1 (μm) of each test piece. Similarly, each substrate used in the examples and comparative examples, before the application of the adhesive layer, was cut out, and its mass W0 (g) and thickness T0 (μm) were measured using the same measurement method. From the obtained values, the density ρ of the adhesive layer was calculated according to the following formula. ρ = (W1 - W0) / (T1 - T0) × 100

[0096] <Coating properties of slurry compositions for adhesive layers (presence or absence of unevenness)> The adhesive layers obtained in Examples and Comparative Examples were visually observed by irradiating light from the base material side on which the adhesive layer was coated. Here, when "streaks" or "unevenness" exist in the adhesive layer, a difference in the amount of transmitted light that is visually distinguishable occurs. As used herein, "streaks" refer to surface irregularities generated due to factors such as the influence of the applicator used when applying the slurry composition for adhesive layers. Further, "unevenness" refers to variations in the layer thickness of the coated adhesive layer. Depending on the distribution pattern of the transmitted light amount, it can be visually determined whether "streaks" or "unevenness" has occurred in the adhesive layer to be observed. The slurry composition for adhesive layers used for forming an adhesive layer that allows uniform light transmission has good coatability, while the slurry composition for adhesive layers used for forming an adhesive layer having "streaks" or "unevenness" has poor coatability. Therefore, the evaluation of coatability of the slurry composition for adhesive layers was performed according to the following criteria. "Good": The formed adhesive layer uniformly transmits light. "Faint streaks generated": Regions where the amount of linear transmitted light changes somewhat clearly occur in the formed adhesive layer. "Streaks generated": Regions where the amount of linear transmitted light changes clearly occur in the formed adhesive layer. "Unevenness generated": Regions with irregularly changing transmitted light amount and unclear boundaries occur in the formed adhesive layer.

[0097] <Evaluation of Low Areal Weight Property> The areal weight of the adhesive layer was calculated from the difference between "the weight of the base material after coating + the adhesive layer" and "the weight of the uncoated base material". Then, the low areal weight property was evaluated according to the following criteria. A smaller difference between "the weight of the base material after coating + the adhesive layer" and "the weight of the uncoated base material" indicates better low areal weight property. SA: The difference between "the weight of the base material after coating + the adhesive layer" and "the weight of the uncoated base material" is 0.1 (g / m 2 ) or less A: The difference between "the weight of the base material after coating + the adhesive layer" and "the weight of the uncoated base material" exceeds 0.1 (g / m 2 ) and is 0.15 (g / m 2 ) or less B: The difference between "the weight of the base material after coating + the adhesive layer" and "the weight of the uncoated base material" exceeds 0.15 (g / m 2 ) and is 0.25 (g / m2 )below C: The difference between the weight of the substrate + adhesive layer after coating and the weight of the uncoated substrate is 0.25 (g / m²). 2 ) super

[0098] <Evaluation of uniformity> The uniformity of the adhesive layer was evaluated by observing the adhesive layer at 2,000x magnification using a SEM (FE-SEM (JSM-7800F Prime)), visually confirming the proportion of primary particles (particulate polymer A existing independently) (the density of the particles), and evaluating it according to the following criteria. A higher proportion of primary particles indicates better uniformity. SA: Primary particle abundance is 80% or higher A: Primary particle abundance is between 60% and less than 80% B: Primary particle abundance is between 40% and less than 60% C: Primary particle abundance is less than 40%

[0099] <Swelling of secondary batteries> The secondary batteries prepared in the examples and comparative examples were left standing for 24 hours at 25°C after electrolyte injection. The thickness of the batteries was measured with calipers. Subsequently, at 25°C, the batteries were charged to 4.2V (cutoff condition: 0.02C) using a constant voltage-constant current (CC-CV) method at a charge rate of 1C, and discharged to 3.0V using a constant current (CC) method at a discharge rate of 1C. The same charge-discharge operation was repeated at 45°C, and the thickness of the batteries after 300 cycles was measured with calipers. The increase in battery thickness after the cycle compared to before the cycle was evaluated as the swelling property of the battery. A smaller increase in battery thickness after the cycle compared to before the cycle indicates better swelling property. A: The percentage increase in battery thickness after the cycle compared to before the cycle is less than 1%. B: The percentage increase in battery thickness after the cycle compared to before the cycle is between 1% and less than 5%. C: The percentage increase in battery thickness after the cycle compared to before the cycle is 5% or more.

[0100] <Internal resistance of a secondary battery> The secondary batteries prepared in the examples and comparative examples were left to stand at 25°C for 5 hours after electrolyte injection. Next, they were charged to a cell voltage of 3.65V using a constant current method at 25°C and 0.2C, and then subjected to an aging treatment at 60°C for 12 hours. Then, they were discharged to a cell voltage of 3.00V using a constant current method at 25°C and 0.2C. After that, CC-CV charging (upper limit cell voltage 4.35V) was performed with a constant current of 0.2C, and CC discharge was performed to a cell voltage of 3.00V with a constant current of 0.2C. This charging and discharging at 0.2C was repeated three times. Next, under a temperature of 25°C, constant current charging and discharging was performed at 0.2C with a cell voltage between 4.2 and 3.00V, and the discharge capacity at this time was defined as C0. Subsequently, CC-CV charging was performed similarly with a constant current of 0.2C, and discharge was performed at a temperature of -10°C with a constant current of 0.5C to 3.0V, and the discharge capacity at this time was defined as C1. Then, the capacity retention rate, expressed as ΔC = (C1 / C0) × 100 (%), was calculated as a rate characteristic and evaluated according to the following criteria. A larger value of this capacity retention rate ΔC indicates lower internal resistance and higher discharge capacity at low temperatures and high currents. A: Capacity retention rate ΔC is 70% or more (resistance: low) B: Capacity retention rate ΔC is 55% or more and less than 70% (resistance: medium) C: Capacity retention rate ΔC is less than 55% (resistance: large)

[0101] <Adhesiveness> A single-layer polyethylene separator (thickness: 12 μm) manufactured by a wet process was prepared as a separator substrate. The slurry compositions prepared in the examples and comparative examples were applied to one side of this separator substrate, and the slurry compositions on the separator substrate were dried at 50°C for 10 minutes to form a functional layer (coating basis weight: 0.2 g / m²). 2 A functional layer was formed. A separator with this functional layer on one side was used as the evaluation separator. Furthermore, a negative electrode was prepared in the same manner as in Example 1 described later and used as the evaluation negative electrode. The evaluation negative electrode and evaluation separator obtained above were each cut into 10 mm x 100 mm rectangles. The negative electrode composite layer of the negative electrode was then placed along the surface of the functional layer of the separator to form a test specimen, and it was placed in a laminate packaging with approximately 400 μL of electrolyte (solvent: ethylene carbonate (EC) / diethyl carbonate (DEC) / vinylene carbonate (VC) (volume ratio) = 68.5 / 30 / 1.5, electrolyte: 1 M LiPF6). After 12 hours, the test specimen, along with the laminate packaging, was pressed at 80°C and a pressure of 1.0 MPa for 10 minutes. Next, the test specimen was removed, and the electrolyte adhering to its surface was wiped off. Then, with the negative electrode current collector side of the specimen facing downwards, cellophane tape was applied to the negative electrode current collector side. The cellophane tape used was the type specified in JIS Z1522. The cellophane tape was fixed to a horizontal test stand. The stress was then measured when one end of the separator was pulled vertically upwards at a pulling speed of 50 mm / min to peel it off. This measurement was performed three times, and the average value of the stress was calculated as the peel strength and evaluated according to the following criteria. A higher peel strength indicates that the functional layer has excellent adhesion after immersion in the electrolyte, and that the separator and electrode (negative electrode) can be firmly bonded in the electrolyte via the functional layer. A: Peel strength of 6.0 N / m or more B: Peel strength of 2.0 N / m or more and less than 6.0 N / m C: Peel strength less than 2.0 N / m

[0102] <Electrolyte injection performance> The lithium-ion secondary batteries prepared in the examples and comparative examples were injected with an electrolyte (solvent: ethylene carbonate (EC) / diethyl carbonate (DEC) / vinylene carbonate (VC) (volume ratio) = 68.5 / 30 / 1.5, electrolyte: 1M LiPF6). The inside of the lithium-ion secondary batteries was then reduced to -100kPa and held at that state for 1 minute. After that, heat sealing was performed. After 10 minutes, the electrode (positive electrode) was disassembled and the state of electrolyte impregnation in the electrode was visually checked. The following criteria were used for evaluation: The greater the area of ​​the electrode that is impregnated with electrolyte, the higher the electrolyte injection efficiency. A: The electrolyte is impregnated into all surfaces of the electrode. B: In the electrode, the portion not impregnated with electrolyte is 1 cm 2 Less than (except for all surfaces being impregnated). C: In the electrode, the portion not impregnated with electrolyte is 1 cm 2 That's all that's left.

[0103] <Cycle durability> The lithium-ion secondary batteries prepared in the examples and comparative examples were left standing for 24 hours at 25°C after electrolyte injection. Subsequently, at 25°C, they were charged to 4.2V (cutoff condition: 0.02C) using a constant voltage-constant current (CC-CV) method at a charge rate of 1C, and discharged to 3.0V using a constant current (CC) method at a discharge rate of 1C. The initial capacity C2 was then measured. Furthermore, the same charge-discharge operation was repeated under a 45°C environment, and the capacity C3 was measured after 300 cycles. The capacity retention rate ΔC = (C3 / C2) × 100 (%) was then calculated and evaluated according to the following criteria. A higher value for this capacity retention rate indicates less decrease in discharge capacity and superior cycle characteristics. A: Capacity retention rate ΔC is 85% or more B: Capacity retention rate ΔC is 75% or more but less than 85% C: Capacity retention rate ΔC is less than 75%

[0104] (Example 1) <Preparation of particulate polymer A> As particulate polymer A, polymer (1-1) having a core-shell structure was prepared. First, to form the core, 45 parts of methyl methacrylate monomer and 21.83 parts of butyl acrylate as (meth)acrylic acid ester monomers; 3.1 parts of methacrylic acid monomer as an acid group-containing monomer; and 0.07 parts of allyl methacrylate as a crosslinkable monomer were added to a 5 MPa pressure-resistant container equipped with a stirrer. Furthermore, 1 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added, and after thorough stirring, the container was heated to 60°C to start polymerization. When the polymerization conversion rate reached 96%, 30 parts of styrene were continuously added to the container to form the shell, and the container was heated to 70°C to continue polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling. This obtained an aqueous dispersion containing polymer (1-1) as particulate polymer A. The glass transition temperature and volume-average particle size of polymer (1-1), obtained as particulate polymer A, were measured according to the method described above. The results are shown in Table 1-1.

[0105] <Preparation of particulate polymer B> In a 5 MPa pressure vessel equipped with a stirrer, 32.5 parts of 1,3-butadiene, 65 parts of styrene, 1 part of methacrylic acid monomer as an acid group-containing monomer, 1 part of 2-hydroxyethyl acrylate, 0.5 parts of allyl methacrylate as a (meth)acrylic acid ester monomer, 0.4 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added and thoroughly stirred. The mixture was then heated to 50°C to start polymerization. When the polymerization conversion rate reached 96%, the mixture was cooled to stop the reaction and a mixture containing polymer (2-1) as particulate polymer B was obtained. A 5% aqueous sodium hydroxide solution was added to the mixture containing polymer (2-1) to adjust the pH to 8. Subsequently, unreacted monomers were removed from the mixture by heated vacuum distillation, and the mixture was cooled to below 30°C to obtain an aqueous dispersion containing the desired polymer (2-1). For polymer (2-1) as particulate polymer B, the glass transition temperature and volume-average particle size were measured according to the method described above. The results are shown in Table 1-1.

[0106] <Preparation of water-soluble polymer A> As water-soluble polymer A, synthetic water-soluble polymer 1 (synthetic WP1) was prepared. In a 5 MPa pressure vessel equipped with a stirrer, 34 parts of methacrylic acid as an acid group-containing monomer, 65 parts of ethyl acrylate as a (meth)acrylic acid ester monomer, 1.0 part of ethylene glycol dimethacrylate as a crosslinkable monomer, 1.0 part of ammonium polyoxyalkylene alkenyl ether sulfate, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added and thoroughly stirred. Then the contents of the vessel were heated to 60°C to start polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain an aqueous dispersion containing synthetic water-soluble polymer 1 (synthetic WP1) as water-soluble polymer A. Next, in a container equipped with a stirrer and containing deionized water, the aqueous dispersion containing the synthesized WP1 and a 5% by mass sodium hydroxide aqueous solution were added, adjusting the proportions so that the pH of the resulting solution would be 8 and the concentration of synthesized WP1 in the solution would be 1% by mass. The mixture was then thoroughly stirred to dissolve the synthesized WP1. In this way, an aqueous solution of water-soluble polymer A was prepared.

[0107] <Preparation of slurry compositions for non-aqueous secondary battery adhesive layers> To a container equipped with a stirrer, 100 parts by mass of particulate polymer A (equivalent to solid content), 10 parts by mass of particulate polymer B (equivalent to solid content), and 2 parts by mass of an aqueous solution of water-soluble polymer A (equivalent to solid content) were added and mixed. To this, 2000 ppm of a preservative (Navisite P40) and 150 ppm of an antifoaming agent (DF6351 manufactured by Seikoh PMC Co., Ltd.) were added, and the mixture was further diluted with deionized water to obtain an adhesive layer slurry composition with a solid content concentration of 1% by mass.

[0108] <Formation of adhesive layer for non-aqueous secondary batteries> The slurry composition for the adhesive layer obtained as described above was applied onto a separator substrate (made of polypropylene, Cellguard 2500) using a gravure coating machine (manufactured by Yasui Seiki) μCoater, and dried at 50°C for 3 minutes. This operation was performed on both sides of the separator substrate to obtain separators with an adhesive layer of 1 μm thickness on each side. The basis weight of the adhesive layer was measured for the obtained separators with the adhesive layer as described above. The results are shown in Table 1-2.

[0109] <Fabrication of the negative electrode> In a 5 MPa pressure vessel equipped with a stirrer, 33 parts 1,3-butadiene, 3.5 parts itaconic acid, 63.5 parts styrene, 0.4 parts sodium dodecylbenzenesulfonate as an emulsifier, 150 parts deionized water, and 0.5 parts potassium persulfate as a polymerization initiator were added and thoroughly stirred. The contents of the vessel were then heated to 50°C to start polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain a mixture containing particulate binder (SBR). To the above mixture containing particulate binder, a 5% by mass aqueous sodium hydroxide solution was added to adjust the pH to 8. After removing unreacted monomers by heated vacuum distillation, the mixture was cooled to below 30°C to obtain an aqueous dispersion containing particulate binder. 100 parts of artificial graphite (average particle size: 15.6 μm) and 1 part of a 2% aqueous solution of carboxymethylcellulose (MAC350HC, manufactured by Nippon Paper Industries Co., Ltd.) as a thickener were mixed with deionized water to a solid content concentration of 68% by mass, and then mixed at 25°C for 60 minutes. The solid content concentration was further adjusted to 62% by mass with deionized water, and then mixed for another 15 minutes at 25°C. To the resulting mixture, 1.5 parts of the above-mentioned particulate binder (in terms of solid content) was added, and deionized water was added to adjust the final solid content concentration to 52% by mass, and then mixed for another 10 minutes. This mixture was defoamed under reduced pressure to obtain a smooth slurry composition for a negative electrode. The anode slurry composition obtained above was applied using a comma coater to a 20 μm thick copper foil current collector, so that the dried film thickness would be approximately 150 μm, and then dried. This drying was performed by transporting the copper foil at a speed of 0.5 m / min in a 60°C oven for 2 minutes. After that, it was heat-treated at 120°C for 2 minutes to obtain a pre-press anode base. This pre-press anode base was rolled using a roll press to obtain a post-press anode with a thickness of 80 μm in the anode active material layer (single-sided anode).

[0110] <Fabrication of the positive electrode> As the positive electrode active material, 100 parts of LiCoO2 with a volume-average particle size of 12 μm, 2 parts of acetylene black (Denka Co., Ltd. "HS-100") as the conductive material, and 2 parts of PVDF (Kureha Corporation, #7208) as the binder (equivalent to solid content) were mixed with N-methyl-2-pyrrolidone (NMP) to adjust the total solid content concentration to 70% by mass. These were mixed using a planetary mixer to prepare a slurry composition for the positive electrode. The slurry composition for the positive electrode obtained as described above was applied using a comma coater to a 20 μm thick aluminum foil current collector, so that the dried film thickness would be approximately 150 μm, and then dried. This drying was performed by transporting the copper foil at a speed of 0.5 m / min in a 60°C oven for 2 minutes. After that, it was heat-treated at 120°C for 2 minutes to obtain a positive electrode base roll before pressing. This positive electrode base roll before pressing was rolled in a roll press to obtain a pressed positive electrode with a positive electrode active material layer thickness of 80 μm (single-sided positive electrode).

[0111] <Manufacturing of lithium-ion secondary batteries> The pressed positive electrode obtained as described above was cut into a 4cm square. The separator with the adhesive layer for non-aqueous secondary batteries obtained as described above was cut into a 5cm square. The square piece of separator was then placed on the positive electrode composite layer side of the cut positive electrode square piece. Furthermore, the pressed negative electrode prepared as described above was cut into a 4.2cm square piece, and this was placed on the square piece of separator so that the negative electrode composite layer side faces the negative electrode square piece. Next, the resulting laminate was pressed at a temperature of 60°C and 0.5 MPa to bond the layers together. Next, the bonded laminate was wrapped in an aluminum packaging material to serve as the battery's casing, and the electrolyte (solvent: ethylene carbonate (EC) / diethyl carbonate (DEC) / vinylene carbonate (VC) (volume ratio) = 68.5 / 30 / 1.5, electrolyte: 1M LiPF6) was injected, ensuring no air remained. Then, the opening of the aluminum packaging material was heat-sealed at 150°C, sealing the aluminum packaging material and manufacturing a 40mAh laminated lithium-ion secondary battery. The obtained stacked lithium-ion secondary battery underwent various evaluations as described above. The results are shown in Table 1-2.

[0112] (Examples 2-4) Except for changing the solid content concentration when preparing the slurry composition for the adhesive layer as shown in Table 1-1, the same procedures, measurements, and evaluations as in Example 1 were performed. The results are shown in Tables 1-1 and 1-2.

[0113] (Example 5) The same procedures, measurements, and evaluations as in Example 1 were performed, except that polymer (1-2) was prepared by changing the composition of particulate polymer A as shown in Table 1-1. The results are shown in Tables 1-1 and 1-2. <Preparation of polymers (1-2)> As particulate polymer A, polymers (1-2) having a core-shell structure were prepared. First, to form the core, 35 parts of 2-ethylhexyl acrylate as a (meth)acrylic acid ester monomer; 31.1 parts of styrene as an aromatic vinyl monomer; 2.8 parts of methacrylic acid monomer as an acid group-containing monomer; and 0.8 parts of ethylene glycol dimethacrylate as a crosslinkable monomer were added to a 5 MPa pressure vessel equipped with a stirrer. Furthermore, 1 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added, and after thorough stirring, the contents of the vessel were heated to 60°C to start polymerization. When the polymerization conversion rate reached 96%, 30 parts of styrene and 0.3 parts of methacrylic acid monomer were continuously added to the above vessel to form the shell, and the contents of the vessel were heated to 70°C to continue polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling. This yielded an aqueous dispersion containing polymer (1-2) as particulate polymer A.

[0114] (Examples 6-7) Except for changing the composition of particulate polymer A as shown in Table 1-1 to prepare polymers (1-3) to (1-4), the same procedures, measurements, and evaluations as in Example 1 were performed. The results are shown in Tables 1-1 and 1-2. The conditions for preparing polymers (1-3) to (1-4) were the same as in Example 5.

[0115] (Example 8) Except for using the polymer (1-2) prepared in Example 5 and changing the pH of the slurry composition for the adhesive layer to 7, the same procedures, measurements, and evaluations as in Example 1 were performed. The results are shown in Tables 1-1 and 1-2.

[0116] (Example 9) The same procedures, measurements, and evaluations as in Example 1 were carried out, except that polymer (2-2) was prepared by changing the composition of particulate polymer B as shown in Table 1-1, according to the following procedure. The results are shown in Tables 1-1 and 1-2. <Preparation of Polymer (2-2)> In a reactor equipped with a stirrer, 90 parts of deionized water, 0.05 parts of sodium dodecylbenzenesulfonate (Kao Chemical Co., Ltd., "Neoperex G-15") as an emulsifier, and 0.23 parts of ammonium persulfate were supplied, the gas phase was replaced with nitrogen gas, and the temperature was raised to 70°C. Meanwhile, in a separate container, 50 parts of deionized water, 0.1 part of sodium dodecylbenzenesulfonate as an emulsifier, 2 parts of methacrylic acid (MAA) as an acid group-containing monomer, 2.5 parts of acrylonitrile (AN) as a nitrile group-containing monomer, and 95 parts of n-butyl acrylate (BA) as a (meth)acrylic acid ester monomer and 0.5 parts of allyl methacrylate (AMA) as a crosslinkable monomer were mixed to obtain a monomer composition. This monomer composition was continuously added to the reactor over 4 hours to carry out polymerization. The reaction was carried out at 80°C during the addition. After the addition was completed, the reaction was further stirred at 80°C for 3 hours to complete the reaction and obtain an aqueous dispersion containing polymer (2-2) as particulate polymer B.

[0117] (Example 10) The same procedures, measurements, and evaluations as in Example 1 were carried out, except that the composition of particulate polymer B was changed as shown in Table 1-1, and polymer (2-3) was prepared according to the following procedure. The results are shown in Tables 1-1 and 1-2. <Preparation of polymers (2-3)> In a reactor equipped with a stirrer, 90 parts of deionized water, 0.05 parts of sodium dodecylbenzenesulfonate (Kao Chemical Co., Ltd., "Neoperex G-15") as an emulsifier, and 0.23 parts of ammonium persulfate were supplied, the gas phase was replaced with nitrogen gas, and the temperature was raised to 70°C. Meanwhile, in a separate container, 50 parts of deionized water, 0.1 part of sodium dodecylbenzenesulfonate as an emulsifier, 3 parts of methacrylic acid (MAA) as an acidic group-containing monomer, 25 parts of styrene, 71.5 parts of 2-ethylhexyl acrylate (2EHA) as a (meth)acrylic acid ester monomer, and 0.5 parts of allyl methacrylate (AMA) as a crosslinkable monomer were mixed to obtain a monomer composition. This monomer composition was continuously added to the reactor over 4 hours to carry out polymerization. The reaction was carried out at 80°C during the addition. After the addition was completed, the reaction was further stirred at 80°C for 3 hours to complete the reaction and obtain an aqueous dispersion containing polymer (2-3) as particulate polymer B.

[0118] (Example 11) Except for changing the composition of particulate polymer B as shown in Table 1-1 and preparing polymer (2-4) in the same manner as in Example 10, the same procedures, measurements, and evaluations as in Example 1 were carried out. The results are shown in Tables 1-1 and 1-2.

[0119] (Example 12) The same procedures, measurements, and evaluations as in Example 1 were performed, except that the composition of the water-soluble polymer was changed as shown in Table 1-1, and synthetic water-soluble polymer 2 (WP2) was prepared according to the following procedure. The results are shown in Tables 1-1 and 1-2. <Preparation of Synthetic Water-Soluble Polymer 2 (Synthetic WP2)> As a water-soluble polymer, synthetic water-soluble polymer 2 (synthetic WP2) was prepared. 550 parts of deionized water and 17 parts of a 2.0% aqueous solution of L-ascorbic acid as a polymerization accelerator were added to a 10 L flask with a septum, heated to 40°C, and the flask was purged with nitrogen gas at a flow rate of 100 mL / min. Next, 75 parts of acrylamide as an amide group-containing monomer and 25 parts of acrylic acid as an acid group-containing monomer were mixed and injected into the flask using a syringe. Subsequently, 17 parts of a 5.0% aqueous solution of ammonium persulfate as a polymerization initiator were added to the flask using a syringe, and the reaction temperature was set to 60°C. After 2 hours, in order to further increase the reaction conversion rate, 10 parts of a 5.0% aqueous solution of ammonium persulfate as a polymerization initiator and 8 parts of a 2.0% aqueous solution of L-ascorbic acid as a polymerization accelerator were added. After another 2 hours, 10 parts of a 5.0% aqueous solution of ammonium persulfate as a polymerization initiator and 8 g of a 2.0% aqueous solution of L-ascorbic acid as a polymerization accelerator were added. After another 2 hours, 3 parts of a 5% aqueous solution of sodium nitrite as a reaction stopper were added to the flask and stirred. The flask was then cooled to 40°C and exposed to air, and the pH of the system was adjusted to 8.0 using an 8% aqueous lithium hydroxide solution to prepare an aqueous solution of water-soluble polymer (synthetic water-soluble polymer 2 (synthetic WP2)).

[0120] (Example 13) The same procedures, measurements, and evaluations as in Example 1 were performed, except that the composition of the water-soluble polymer was changed as shown in Table 1-1, and synthetic water-soluble polymer 3 (WP3) was prepared according to the following procedure. The results are shown in Tables 1-1 and 1-2. <Preparation of Synthetic Water-Soluble Polymer 3 (Synthetic WP3)> As a water-soluble polymer, synthetic water-soluble polymer 3 (synthetic WP3) was prepared. In an autoclave equipped with a stirrer, 164 parts of deionized water, 59 parts of acrylonitrile (AN) as a nitrile group-containing monomer, and 39 parts of acrylic acid as an acid group-containing monomer were mixed. Further, 2 parts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as another monomer were added, along with 0.3 parts of potassium persulfate as a polymerization initiator and 1.2 parts of sodium polyoxyethylene alkyl ether sulfate as an emulsifier. After thorough stirring, the polymerization reaction was carried out at a reaction temperature of 80°C for 5 hours to obtain an aqueous dispersion containing synthetic water-soluble polymer 3 (synthetic WP3).

[0121] (Example 14) Polymers (1-8) were prepared by changing the composition of particulate polymer A as shown in Table 2-1. Furthermore, when preparing the slurry composition for the adhesive layer, the amount of aqueous solution of water-soluble polymer (synthetic WP1) was changed to 1.9 parts in terms of solid content, and 0.1 parts of propylene oxide / ethylene oxide copolymer (Sunopco, Noptex® ED052; weight-average molecular weight: 550-600 (nominal value)) was added as water-soluble polymer B. Except for these points, the same operations, measurements, and evaluations as in Example 1 were carried out. The results are shown in Tables 2-1 and 2-2. <Preparation of polymers (1-8)> As particulate polymer A, polymers (1-8) having a core-shell structure were prepared. First, the core portion was formed in the same manner as in Example 1. When the polymerization conversion rate of the monomer composition for forming the core portion reached 96%, then, in order to form the shell portion, 10 parts of styrene, 0.3 parts of methacrylic acid monomer as an acid group-containing monomer, and 20 parts of methyl methacrylate monomer as a (meth)acrylic acid ester monomer were successively added to the container, and the polymerization was continued by heating the container to 70°C. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling. This yielded an aqueous dispersion containing polymer (1-8) as particulate polymer A.

[0122] (Example 15) Except for using polymer (1-8) prepared in the same manner as in Example 14 as particulate polymer A, the same procedures, measurements, and evaluations as in Example 1 were performed. The results are shown in Tables 2-1 and 2-2.

[0123] (Example 16) Polymers (1-9) were prepared by changing the composition of particulate polymer A as shown in Table 2-1. Furthermore, when preparing the slurry composition for the adhesive layer, the amount of aqueous solution of water-soluble polymer (synthetic WP1) was changed to 1.9 parts in terms of solid content, and 0.1 parts of propylene oxide / ethylene oxide copolymer (Sunopco, Noptex® ED052; weight-average molecular weight: 550-600 (nominal value)) was added as water-soluble polymer B. Except for these points, the same operations, measurements, and evaluations as in Example 1 were carried out. The results are shown in Tables 2-1 and 2-2. <Preparation of polymers (1-9)> As particulate polymer A, polymers (1-9) having a core-shell structure were prepared. First, the core portion was formed in the same manner as in Example 1. When the polymerization conversion rate of the monomer composition for forming the core portion reached 96%, then, in order to form the shell portion, 10 parts of styrene, 0.3 parts of methacrylic acid monomer as an acid group-containing monomer, 10 parts of methyl methacrylate monomer as a (meth)acrylic acid ester monomer, and 10 parts of methyl acrylate monomer were successively added to the container, and the polymerization was continued by heating the container to 70°C. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling. This yielded an aqueous dispersion containing polymer (1-9) as particulate polymer A.

[0124] (Example 17) Polymers (1-10) were prepared by changing the composition of particulate polymer A as shown in Table 2-1. Furthermore, when preparing the slurry composition for the adhesive layer, the amount of aqueous solution of water-soluble polymer (synthetic WP1) was changed to 1.9 parts in terms of solid content, and 0.1 parts of propylene oxide / ethylene oxide copolymer (Sunopco, Noptex® ED052; weight-average molecular weight: 550-600 (nominal value)) was added as water-soluble polymer B. Except for these points, the same operations, measurements, and evaluations as in Example 1 were carried out. The results are shown in Tables 2-1 and 2-2. <Preparation of polymers (1-10)> As particulate polymer A, polymer (1-10) having a core-shell structure was prepared. First, the core portion was formed in the same manner as in Example 1. When the polymerization conversion rate of the monomer composition for forming the core portion reached 96%, then, in order to form the shell portion, 10 parts of styrene, 0.3 parts of methacrylic acid monomer as an acid group-containing monomer, 15 parts of methyl methacrylate monomer as a (meth)acrylic acid ester monomer, and 5 parts of butyl acrylate monomer were successively added to the container, and the polymerization was continued by heating the container to 70°C. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling. This yielded an aqueous dispersion containing polymer (1-10) as particulate polymer A.

[0125] (Example 18) Polymer (1-11) was prepared by changing the composition of particulate polymer A as shown in Table 2-1. Furthermore, when preparing the slurry composition for the adhesive layer, the amount of aqueous solution of water-soluble polymer (synthetic WP1) was changed to 1.9 parts in terms of solid content, and 0.1 parts of propylene oxide / ethylene oxide copolymer (Sunopco, Noptex® ED052; weight-average molecular weight: 550-600 (nominal value)) was added as water-soluble polymer B. Except for these points, the same operations, measurements, and evaluations as in Example 1 were carried out. The results are shown in Tables 2-1 and 2-2. <Preparation of polymers (1-11)> As particulate polymer A, polymer (1-11) having a core-shell structure was prepared. First, the core portion was formed in the same manner as in Example 1. When the polymerization conversion rate of the monomer composition for forming the core portion reached 96%, then, in order to form the shell portion, 10 parts of styrene, 0.3 parts of methacrylic acid monomer as an acid group-containing monomer, 15 parts of methyl methacrylate monomer as a (meth)acrylic acid ester monomer, and 5 parts of acrylonitrile monomer were successively added to the container, and the polymerization was continued by heating the container to 70°C. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling. This yielded an aqueous dispersion containing polymer (1-11) as particulate polymer A.

[0126] (Example 19) Polymer (1-12) was prepared by changing the composition of particulate polymer A as shown in Table 2-1. Furthermore, when preparing the slurry composition for the adhesive layer, the amount of aqueous solution of water-soluble polymer (synthetic WP1) was changed to 1.9 parts in terms of solid content, and 0.1 parts of propylene oxide / ethylene oxide copolymer (Sunopco, Noptex® ED052; weight-average molecular weight: 550-600 (nominal value)) was added as water-soluble polymer B. Except for these points, the same operations, measurements, and evaluations as in Example 1 were carried out. The results are shown in Tables 2-1 and 2-2. <Preparation of polymers (1-12)> As particulate polymer A, polymers (1-12) having a core-shell structure were prepared. First, to form the core, 20 parts of 2-ethylhexyl acrylate as a (meth)acrylic acid monomer; 46.1 parts of styrene as an aromatic vinyl monomer; 2.8 parts of methacrylic acid monomer as an acid group-containing monomer; and 0.8 parts of ethylene glycol dimethacrylate as a crosslinkable monomer were added to a 5 MPa pressure vessel equipped with a stirrer. Furthermore, 1 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added, and after thorough stirring, the contents of the vessel were heated to 60°C to start polymerization. When the polymerization conversion rate reached 96%, 10 parts of styrene, 0.3 parts of methacrylic acid monomer as an acid group-containing monomer, and 20 parts of methyl methacrylate monomer as a (meth)acrylic acid ester monomer were successively added to the container to form the shell portion. The container was heated to 70°C to continue polymerization, and when the polymerization conversion rate reached 96%, it was cooled to stop the reaction. This yielded an aqueous dispersion containing polymer (1-12) as particulate polymer A.

[0127] (Example 20) The same procedures, measurements, and evaluations as in Example 14 were performed, except that water-soluble polymer A was not included. The results are shown in Tables 2-1 and 2-2.

[0128] (Example 21) Except for not incorporating water-soluble polymer A, and instead using 1.9 parts of special ammonium polyacrylate salt (manufactured by Toagosei Co., Ltd., Aron® A6114; weight-average molecular weight: 8000 (nominal value)) and 0.1 parts of propylene oxide / ethylene oxide copolymer (manufactured by Sunopco, Noptex® ED052; weight-average molecular weight: 550-600 (nominal value)) as water-soluble polymer B, the same procedures, measurements, and evaluations as in Example 14 were performed. The results are shown in Tables 2-1 and 2-2.

[0129] (Example 22) Except for the addition of 0.1 parts of a vinyl acetate polymer (polyvinyl alcohol; manufactured by Nippon Vinegar & Poval Co., Ltd., PVA JF-17; weight-average molecular weight: 70,000-80,000 (nominal value)) as the water-soluble polymer B, the same procedure, measurements, and evaluations as in Example 14 were performed. The results are shown in Tables 2-1 and 2-2.

[0130] (Example 23) Except for using the same polymer (2-2) as in Example 9 as particulate polymer B, the same procedures, measurements, and evaluations as in Example 14 were performed. The results are shown in Tables 2-1 and 2-2.

[0131] (Example 24) Except for using the same polymer (2-3) as in Example 10 as particulate polymer B, the same procedures, measurements, and evaluations as in Example 14 were performed. The results are shown in Tables 2-1 and 2-2.

[0132] (Example 25) The same procedures, measurements, and evaluations as in Example 14 were performed, except that polymer (2-6), prepared as described below, was used as particulate polymer B. The results are shown in Tables 2-1 and 2-2. <Preparation of polymers (2-6)> In a reactor equipped with a stirrer, 90 parts of deionized water, 0.05 parts of sodium dodecylbenzenesulfonate (Kao Chemical Co., Ltd., "Neoperex G-15") as an emulsifier, and 0.23 parts of ammonium persulfate were supplied, the gas phase was replaced with nitrogen gas, and the temperature was raised to 70°C. Meanwhile, in a separate container, 50 parts of deionized water, 0.1 parts of sodium dodecylbenzenesulfonate as an emulsifier, 3 parts of methacrylic acid (MAA) as an acidic group-containing monomer, 25 parts of styrene, 71 parts of 2-ethylhexyl acrylate (2EHA) as a (meth)acrylic acid ester monomer, and 1 part of ethylene glycol dimethacrylate (EDMA) as a crosslinkable monomer were mixed to obtain a monomer composition. This monomer composition was continuously added to the reactor over 4 hours to carry out polymerization. The reaction was carried out at 80°C during the addition. After the addition was completed, the reaction was further stirred at 80°C for 3 hours to complete the reaction and obtain an aqueous dispersion containing polymer (2-6) as particulate polymer B.

[0133] (Comparative Example 1) Except for replacing polymer (1-1) as particulate polymer A with particulate polymer (1-5) having the composition shown in Table 3-1 and a glass transition temperature of 110°C, the same procedures, measurements, and evaluations as in Example 1 were carried out according to the following instructions. The results are shown in Tables 3-1 and 3-2. <Preparation of polymers (1-5)> Polymers (1-5) having a core-shell structure were prepared. First, to form the core, 10 parts of 2-ethylhexyl acrylate as a (meth)acrylic acid ester monomer; 56.1 parts of styrene as an aromatic vinyl monomer; 2.8 parts of methacrylic acid monomer as an acid group-containing monomer; and 0.8 parts of ethylene glycol dimethacrylate as a crosslinkable monomer were added to a 5 MPa pressure vessel equipped with a stirrer. Furthermore, 1 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added, and after thorough stirring, the contents of the vessel were heated to 60°C to start polymerization. When the polymerization conversion rate reached 96%, 30 parts of styrene and 0.3 parts of methacrylic acid monomer were continuously added to the vessel to form the shell, and the contents of the vessel were heated to 70°C to continue polymerization. When the polymerization conversion rate reached 96%, the mixture was cooled to stop the reaction. This yielded an aqueous dispersion containing particulate polymers (1-5).

[0134] (Comparative Example 2) Except for replacing polymer (2-1) as particulate polymer B with particulate polymer (2-5) having the composition shown in Table 3-1 and a glass transition temperature of 30°C, the same procedures, measurements, and evaluations as in Example 1 were carried out according to the following instructions. The results are shown in Tables 3-1 and 3-2. <Preparation of polymers (2-5)> In a reactor equipped with a stirrer, 90 parts of deionized water, 0.05 parts of sodium dodecylbenzenesulfonate (Kao Chemical Co., Ltd., "Neoperex G-15") as an emulsifier, and 0.23 parts of ammonium persulfate were supplied, the gas phase was replaced with nitrogen gas, and the temperature was raised to 70°C. Meanwhile, in a separate container, 50 parts of deionized water, 0.1 part of sodium dodecylbenzenesulfonate as an emulsifier, 3 parts of methacrylic acid (MAA) as an acid group-containing monomer, 40 parts of styrene, 56.5 parts of 2-ethylhexyl acrylate (2EHA) as a (meth)acrylic acid ester monomer, and 0.5 parts of allyl methacrylate (AMA) as a crosslinkable monomer were mixed to obtain a monomer composition. This monomer composition was continuously added to the reactor over 4 hours to carry out polymerization. The reaction was carried out at 80°C during the addition. After the addition was completed, the reaction was further stirred at 80°C for 3 hours to finish, and an aqueous dispersion containing particulate polymer (2-5) was obtained.

[0135] (Comparative Example 3) Except for the absence of a water-soluble polymer, the same procedures, measurements, and evaluations as in Example 1 were performed. The results are shown in Tables 3-1 and 3-2.

[0136] (Comparative Example 4) Except for changing the solid content concentration to 0.7% by mass when preparing the slurry composition for the adhesive layer, and changing the number of lines on the gravure roll used during coating so that the basis weight was the same as in Example 1, the same procedures, measurements, and evaluations were performed. The results are shown in Tables 3-1 and 3-2.

[0137] (Comparative Example 5) Except for changing the solid content concentration to 30% by mass when preparing the slurry composition for the adhesive layer, the same procedures, measurements, and evaluations as in Example 1 were performed. The results are shown in Tables 3-1 and 3-2.

[0138] (Comparative Example 6) As particulate polymer A, polymers (1-6) with the composition shown in Table 3-1, prepared according to the following procedure, were blended. Polymers corresponding to particulate polymer B and water-soluble polymers were not blended. Furthermore, the solid content concentration of the slurry composition for the adhesive layer was changed to 20% by mass. Except for these changes, the same procedures, measurements, and evaluations as in Example 1 were performed. The results are shown in Tables 3-1 and 3-2. <Preparation of polymers (1-6)> As particulate polymer A, polymers (1-6) having a core-shell structure were prepared. First, to form the core, 69.2 parts of butyl acrylate as a (meth)acrylic acid ester monomer; 29.7 parts of methacrylic acid monomer as an acid group-containing monomer; and 0.8 parts of ethylene glycol dimethacrylate were added to a 5 MPa pressure vessel equipped with a stirrer. Furthermore, 1 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added, and after thorough stirring, the contents of the vessel were heated to 60°C to start polymerization. When the polymerization conversion rate reached 96%, 30 parts of styrene and 0.3 parts of methacrylic acid monomer were continuously added to the vessel to form the shell, and the contents of the vessel were heated to 70°C to continue polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling. This yielded an aqueous dispersion containing polymer (1-6) as particulate polymer A.

[0139] (Comparative Example 7) Except for replacing particulate polymer A with particulate polymer (1-7) having a glass transition temperature of 105°C and the composition shown in Tables 1-1 and 3-2, prepared according to the following procedure, and using the same polymer (2-2) as in Example 9, and further changing the solid content concentration of the adhesive layer slurry composition to 30% by mass, the same procedures, measurements, and evaluations as in Example 1 were carried out. The results are shown in Tables 3-1 and 3-2. <Preparation of polymers (1-7)> Polymers (1-7) having a core-shell structure were prepared. First, to form the core, 58.5 parts of methyl methacrylate monomer and 8.33 parts of butyl acrylate as (meth)acrylic acid ester monomers; 2.8 parts of methacrylic acid monomer as an acid group-containing monomer; and 0.07 parts of allyl methacrylate as a crosslinkable monomer were added to a 5 MPa pressure vessel equipped with a stirrer. Furthermore, 1 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of deionized water, and 0.5 parts of potassium persulfate as a polymerization initiator were added, and after thorough stirring, the contents of the vessel were heated to 60°C to start polymerization. When the polymerization conversion rate reached 96%, 30 parts of styrene and 0.3 parts of methacrylic acid monomer were continuously added to the above vessel to form the shell, and the contents of the vessel were heated to 70°C to continue polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling. This yielded an aqueous dispersion containing particulate polymers (1-7).

[0140] In addition, in Tables 1-1 to 3-2 shown below, "MMA" refers to methyl methacrylate. "BA" indicates butyl acrylate. "ST" stands for styrene. "MAA" indicates methacrylic acid. "HEA" indicates 2-hydroxyethyl acrylate. "AMA" indicates allyl methacrylate. "EDMA" refers to ethylene glycol dimethacrylate. "2EHA" indicates 2-ethylhexyl acrylate. "EA" stands for ethyl acrylate. "AAm" stands for acrylamide. "AA" indicates acrylic acid. "AN" stands for acrylonitrile. "AMPS" stands for 2-acrylamido-2-methylpropanesulfonic acid. "WP" indicates a water-soluble polymer.

[0141] [Table 1-1]

[0142] [Table 1-2]

[0143] [Table 2-1]

[0144] [Table 2-2]

[0145] [Table 3-1]

[0146] [Table 3-2]

[0147] Examples 1 to 25 show that by using a slurry composition for adhesive layers of non-aqueous secondary batteries, comprising particulate polymer A having a glass transition temperature of 30°C to 100°C, particulate polymer B having a glass transition temperature of 20°C or less, a water-soluble polymer, and a dispersion medium, and having a solid content concentration of 1% to 25% by mass, it is possible to form an adhesive layer that exhibits excellent uniformity and can reduce the internal resistance of the resulting non-aqueous secondary battery. [Industrial applicability]

[0148] According to the present invention, it is possible to provide a slurry composition for an adhesive layer of a non-aqueous secondary battery that can form an adhesive layer with excellent uniformity and that can reduce the internal resistance of the resulting non-aqueous secondary battery. Furthermore, according to the present invention, it is possible to provide an adhesive layer for non-aqueous secondary batteries that has excellent uniformity and can reduce the internal resistance of non-aqueous secondary batteries, as well as a method for manufacturing the same. Furthermore, according to the present invention, it is possible to provide a component for a non-aqueous secondary battery that can provide a non-aqueous secondary battery with low internal resistance. Furthermore, according to the present invention, it is possible to provide a non-aqueous secondary battery with low internal resistance.

Claims

1. A slurry composition for a non-aqueous secondary battery adhesive layer, comprising at least two types of particulate polymers, a water-soluble polymer, and a dispersion medium, The above-mentioned at least two polymers include particulate polymer A having a glass transition temperature of 30°C to 100°C, and particulate polymer B having a glass transition temperature of 20°C or less. The solid content concentration of the aforementioned non-aqueous secondary battery adhesive layer slurry composition is 1% by mass or more and 25% by mass or less. The particulate polymer A satisfies both conditions: it contains (meth)acrylic acid ester monomer units, and the particulate polymer B is a styrene-based polymer or an acrylic-based polymer. Slurry composition for non-aqueous secondary battery adhesive layers.

2. The slurry composition for a non-aqueous secondary battery adhesive layer according to claim 1, wherein the water-soluble polymer contains acid group-containing monomer units in a proportion of 5% by mass or more and 50% by mass or less.

3. A slurry composition for a non-aqueous secondary battery adhesive layer according to claim 1, wherein the pH is 7 or higher and 9 or lower.

4. The slurry composition for a non-aqueous secondary battery adhesive layer according to claim 1, further comprising at least one of a preservative and an antifoaming agent.

5. The slurry composition for a non-aqueous secondary battery adhesive layer according to claim 1, wherein the particulate polymer A has a core-shell structure, and contains 30.0% by mass or more of (meth)acrylic acid ester monomer units, with the total repeating units constituting the shell portion being 100% by mass.

6. The slurry composition for a non-aqueous secondary battery adhesive layer according to claim 1, wherein the particulate polymer A has a core-shell structure, and the shell portion contains repeating units of methyl methacrylate units and methyl acrylate units as (meth)acrylic acid ester monomer units, and monomer units having a carboxylic acid group as an acid group-containing monomer unit.

7. An adhesive layer for a non-aqueous secondary battery, formed using the slurry composition for a non-aqueous secondary battery adhesive layer described in any one of claims 1 to 6.

8. A method for producing an adhesive layer for a non-aqueous secondary battery, comprising a coating step of applying a slurry composition for a non-aqueous secondary battery adhesive layer according to any one of claims 1 to 6 onto a substrate by gravure coating or slot die coating.

9. A component for a non-aqueous secondary battery, comprising a substrate on which the adhesive layer for a non-aqueous secondary battery described in claim 7 is provided.

10. The non-aqueous secondary battery component according to claim 9, wherein the substrate includes an organic separator material, and the non-aqueous secondary battery adhesive layer is disposed adjacent to at least one surface of the organic separator material, or is disposed adjacent to the surface of a heat-resistant layer provided on at least one surface of the organic separator material.

11. A non-aqueous secondary battery comprising the non-aqueous secondary battery component described in claim 9.

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