Polymer compound for nonaqueous secondary battery, composition for nonaqueous secondary battery, sheet for all-solid-state secondary battery and all-solid-state secondary battery, and method for manufacturing sheet for all-solid-state secondary battery and all-solid-state secondary battery

Abstract

Provided are: a polymer composition for a nonaqueous secondary battery, which contains a polymer (P) and an oligomer (Ol) having a weight average molecular weight of 1000 or less, wherein the content of the oligomer (Ol) in a total of 100 mass% of the polymer (P) and the oligomer (Ol) is 1-30 mass%; a composition for a nonaqueous secondary battery containing this polymer composition; a sheet for an all-solid-state secondary battery and an all-solid-state secondary battery; and a method for manufacturing the sheet for an all-solid-state secondary battery and the all-solid-state secondary battery.

Description

Polymer composition for non-aqueous secondary battery, composition for non-aqueous secondary battery, sheet for all-solid-state secondary battery and all-solid-state secondary battery, and method for manufacturing sheet for all-solid-state secondary battery and all-solid-state secondary battery

[0001] The present invention relates to a polymer composition for a non-aqueous secondary battery, a composition for a non-aqueous secondary battery, a sheet for an all-solid-state secondary battery, an all-solid-state secondary battery, and a method for manufacturing the sheet for the all-solid-state secondary battery and the all-solid-state secondary battery.

[0002] A nonaqueous electrolyte secondary battery (also referred to as a nonaqueous secondary battery) is a storage battery that has a negative electrode, a positive electrode, and a nonaqueous electrolyte between the negative and positive electrodes. It is capable of charging and discharging by the reciprocating movement of specific metal ions, such as lithium ions, between the two electrodes. Such nonaqueous secondary batteries include nonaqueous electrolyte secondary batteries using an organic electrolyte and all-solid-state secondary batteries using a solid electrolyte layer. In particular, all-solid-state secondary batteries, in which the negative electrode, electrolyte, and positive electrode are all solid, can significantly improve the safety and reliability issues associated with nonaqueous electrolyte secondary batteries. They are also believed to enable longer battery life. Furthermore, all-solid-state secondary batteries can be configured with electrodes and a solid electrolyte directly arranged in series. Therefore, all-solid-state secondary batteries can achieve higher energy densities than nonaqueous electrolyte secondary batteries, and are expected to be used in electric vehicles, large-scale storage batteries, and other applications.

[0003] In consideration of improving productivity, constituent layers in nonaqueous electrolyte secondary batteries (electrode layers of anode active material layers and cathode active material layers) and constituent layers in all-solid-state secondary batteries (solid electrolyte layers, anode active material layers, cathode active material layers, etc.) are typically formed using compositions (constituent layer-forming materials) containing raw material compounds constituting each layer, such as active materials and inorganic solid electrolytes, as well as dispersants for dispersing the raw material compounds and binders for binding the raw material compounds. Therefore, research into dispersants, binders, and constituent layer-forming materials has been ongoing. For example, Patent Document 1 proposes a binder composition for use in the manufacture of nonaqueous electrolyte secondary batteries, which comprises "a polymer for binding active materials together, dissolved or dispersed in an organic solvent or water, and wherein the total content of the following (A) and (B) is 300 ppm or less relative to the binder composition: (A) a monomer for polymerizing a repeating unit contained in the polymer; and (B) an oligomer having a weight-average molecular weight of 3,000 or less, formed by reaction of the monomer."

[0004] JP 2014-146600 A

[0005] Because the constituent layers of nonaqueous electrolyte secondary batteries and all-solid-state secondary batteries are formed of solid particles (active materials, conductive additives, inorganic solid electrolytes, etc.), the interfacial contact state between the solid particles and the current collector is restricted, resulting in an increase in interfacial resistance. This increase in interfacial resistance not only increases the battery resistance of the all-solid-state secondary battery (decreases ionic conductivity), but also causes deterioration of the solid particles due to overcurrent generated during discharge, resulting in a decrease in cycle characteristics.

[0006] The increase in interface resistance, which causes a deterioration in battery performance, is due not only to the interfacial contact state of the solid particles but also to the characteristics of the constituent layer-forming material. Therefore, the constituent layer-forming material is required to stably maintain the excellent dispersibility (initial dispersibility) of the solid particles immediately after preparation (initial) at room temperature (e.g., 15°C or higher but lower than 30°C) and to re-disperse the solid particles to the excellent dispersion state immediately after preparation even if they aggregate or precipitate (also referred to as "room temperature dispersion stability" in the present invention). Meanwhile, the dispersion state of the solid particles in the constituent layer-forming material is easily affected by temperature, and the higher the temperature, the lower the dispersibility tends to be. However, due to factors such as the rapid progress of global warming in recent years, the preparation temperature, storage temperature, and use temperature of the constituent layer-forming material may become high in actual manufacturing sites of nonaqueous secondary batteries. Moreover, energy conservation, reduction in manufacturing costs, and improvement in productivity are also required in the manufacturing of all-solid-state secondary batteries. Given the rapid progress in the development and practical application of electric vehicles in recent years, there are limitations to temperature control at manufacturing sites. It is also required to determine the stability of the dispersed state of solid particles immediately after preparation (initial dispersion stability) in a short period of time. In view of this situation, constituent layer forming materials are now required to have dispersion stability even at high temperatures (for example, 30° C. or higher and 60° C. or lower) (also referred to as "high-temperature dispersion stability" in the present invention, and may be referred to as "dispersion stability" together with room-temperature dispersion stability).

[0007] An object of the present invention is to provide a polymer composition for non-aqueous secondary batteries that can be used to prepare a non-aqueous secondary battery composition having excellent dispersion stability, and a non-aqueous secondary battery composition containing this polymer composition for non-aqueous secondary batteries. Another object of the present invention is to provide a sheet for an all-solid-state secondary battery and an all-solid-state secondary battery using the non-aqueous secondary battery composition. A further object of the present invention is to provide a method for producing the sheet for an all-solid-state secondary battery and the all-solid-state secondary battery using the non-aqueous secondary battery composition.

[0008] The present inventors conducted extensive research into the dispersion stability of constituent layer-forming materials and solid particles, and found that by combining a predetermined amount of a low-molecular-weight oligomer with a polymer used in combination with the solid particles used to prepare the constituent layer-forming material, the function of improving the dispersibility of the solid particles, which is exhibited by the polymer, can be complemented in the constituent layer-forming material, thereby improving dispersibility not only at room temperature but also at high temperatures. Furthermore, they found that by using a non-aqueous secondary battery composition containing a polymer and an oligomer as a constituent layer-forming material, a non-aqueous secondary battery sheet having a low-resistance constituent layer, and further a non-aqueous secondary battery with low resistance and excellent cycle characteristics, can be realized. The present invention was completed through further research based on these findings.

[0009] That is, the above-mentioned problems have been solved by the following means. <1> A polymer composition for a non-aqueous secondary battery, comprising a polymer (P) and an oligomer (Ol) having a weight-average molecular weight of 1,000 or less, wherein the content of the oligomer (Ol) is 1 to 30 mass % relative to 100 mass % of the total of the polymer (P) and the oligomer (Ol). <2> The polymer composition for a non-aqueous secondary battery according to <1>, wherein the polymer (P) contains a constituent component derived from a (meth)acrylic acid ester monomer. <3> The polymer composition for a non-aqueous secondary battery according to <1> or <2>, wherein the polymer (P) contains a constituent component (A) having at least one polar functional group selected from the following functional group group (a): (Functional group (a)) Sulfonic acid group, phosphoric acid group, phosphonic acid group, hydroxy group, carboxy group, oxetane group, epoxy group, dicarboxylic acid group, thiol group, ether group, thioether group, thioester group, ester group, amide group, urethane group, urea group, imide group, fluoroalkyl group, and salts thereof. <4> The polymer composition for a non-aqueous secondary battery according to any one of <1> to <3>, wherein the ratio [Mw / Mn] of the weight average molecular weight Mw to the number average molecular weight Mn of the polymer (P) is 3.0 or less. <5> The polymer composition for a non-aqueous secondary battery according to any one of <1> to <4>, wherein either the polymer (P) or the oligomer (O1) contains at least one component different from the component contained in the other. <6> The polymer composition for a non-aqueous secondary battery according to any one of <1> to <5>, wherein the polymer (P) and the oligomer (O1) contain at least one component that is the same as the other. <7> The polymer composition for a non-aqueous secondary battery according to any one of <1> to <6>, wherein the content of the oligomer (O1) is 3 to 12 mass %. <8> A composition for a non-aqueous secondary battery, comprising the polymer composition for a non-aqueous secondary battery according to any one of <1> to <7> above. <9> The composition for a non-aqueous secondary battery according to <8>, comprising an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table. <10> The composition for a non-aqueous secondary battery according to <9>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte. <11> The composition for a non-aqueous secondary battery according to any one of <8> to <10>, comprising an active material.<12> A sheet for an all-solid-state secondary battery having a layer formed using the composition for a non-aqueous secondary battery according to any one of <8> to <11> above. <13> An all-solid-state secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, wherein at least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer formed using the composition for a non-aqueous secondary battery according to any one of <8> to <11> above. <14> A method for producing a sheet for an all-solid-state secondary battery, comprising forming a film from the composition for a non-aqueous secondary battery according to any one of <8> to <11> above. <15> A method for producing an all-solid-state secondary battery, comprising producing an all-solid-state secondary battery via the method according to <14> above.

[0010] The present invention provides a non-aqueous secondary battery polymer composition capable of preparing a non-aqueous secondary battery composition having excellent dispersion stability, and a non-aqueous secondary battery composition containing this non-aqueous secondary battery polymer composition. The present invention also provides an all-solid-state secondary battery sheet and an all-solid-state secondary battery using the non-aqueous secondary battery composition. Furthermore, the present invention also provides a method for manufacturing an all-solid-state secondary battery sheet and an all-solid-state secondary battery using the non-aqueous secondary battery composition. The above and other features and advantages of the present invention will become more apparent from the following description, taken in conjunction with the accompanying drawings, where appropriate.

[0011] Fig. 1 is a longitudinal sectional view schematically showing an all-solid-state secondary battery according to a preferred embodiment of the present invention, and Fig. 2 is a longitudinal sectional view schematically showing a coin-type all-solid-state secondary battery fabricated in Examples.

[0012] In the present invention, when describing the content, physical properties, etc. of a component by indicating a numerical range, if the upper and lower limits of the numerical range are described separately, any of the upper and lower limits can be appropriately combined to form a specific numerical range. On the other hand, when describing multiple numerical ranges represented using "to", the upper and lower limits forming the numerical range are not limited to the specific combination of upper and lower limits written before and after "to" as a specific numerical range, but can be any numerical range obtained by appropriately combining the upper and lower limits of each numerical range. Note that in the present invention, a numerical range represented using "to" means a range that includes the numerical values ​​written before and after "to" as the upper and lower limits. In the present invention, when a compound is referred to (for example, when "compound" is added to the end), it is used to mean not only the compound itself, but also its salts and ions. It also means derivatives that have been partially modified, such as by introducing a substituent, to the extent that the effects of the present invention are not impaired. In the present invention, "(meth)acrylic" means one or both of acrylic and methacrylic. The same applies to (meth)acrylate. In the present invention, with respect to substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) that are not specified as substituted or unsubstituted, this means that the group may have an appropriate substituent. Therefore, in the present invention, even when simply described as a YYY group, this YYY group includes not only an embodiment in which it has no substituent, but also an embodiment in which it further has a substituent. This also applies to compounds in which substituted or unsubstituted is not specified. A preferred substituent is, for example, the substituent Z described below. In the present invention, when there are multiple substituents, etc., designated by a specific symbol, or when multiple substituents, etc. are specified simultaneously, this means that the respective substituents, etc. may be the same or different from each other. Furthermore, even if not otherwise specified, when multiple substituents, etc., are adjacent, they may be linked to each other or fused to form a ring.

[0013] In the present invention, polymer refers to a polymer. In the present invention, the main chain of a polymer (including a polymer chain) refers to a linear molecular chain in which all other molecular chains constituting the polymer can be considered as branched chains or pendant groups relative to the main chain. Although it depends on the weight-average molecular weight of the branched chains considered as branched chains or pendant groups, typically, the longest chain among the molecular chains constituting the polymer becomes the main chain. However, the terminal groups at the polymer ends are not included in the main chain. In contrast, the side chain of a polymer refers to a branched chain other than the main chain, and includes short chains and long chains (graft chains). The terminal group of a polymer is not particularly limited and can be an appropriate group depending on the polymerization method, etc. Examples of terminal groups include hydrogen atoms, alkyl groups, aryl groups, hydroxy groups, and even residues of polymerization initiators.

[0014] [Polymer Composition for Nonaqueous Secondary Batteries] The polymer composition for nonaqueous secondary batteries of the present invention (hereinafter sometimes simply referred to as the "polymer composition of the present invention") contains a polymer (P) and an oligomer (Ol) having a weight-average molecular weight of 1,000 or less. In the polymer composition of the present invention, the state of inclusion (presence) of the polymer (P) and the oligomer (Ol) is not particularly limited. For example, the polymer (P) and the oligomer (Ol) may be contained (present) separately, or may be contained as a mixture, composite, or the like. The polymer composition of the present invention contains the polymer (P) and the oligomer (Ol), and the content of the oligomer (Ol) is 1 to 30 mass% relative to 100 mass% of the total of the polymer (P) and the oligomer (Ol). The polymer composition of the present invention having the above-described composition can be used as a dispersant together with solid particles in a composition for nonaqueous secondary batteries (constituent layer-forming material) to prepare a composition for nonaqueous secondary batteries that has excellent dispersion stability at both room temperature and high temperature. As a result, the polymer composition of the present invention can realize a non-aqueous secondary battery composition that has excellent dispersion stability of solid particles and, more preferably, has a moderate viscosity, high fluidity, and excellent handling properties, allowing the formation of a good coating film. Furthermore, by using this excellent non-aqueous secondary battery composition as a material for forming a constituent layer, it is possible to realize a non-aqueous secondary battery sheet having a constituent layer that has low resistance (high conductivity), more preferably, a flat and smooth surface, and further a non-aqueous secondary battery that has low resistance and excellent cycle characteristics.

[0015] Although the details of why the polymer composition of the present invention exhibits the above-described excellent effects are not yet clear, it is believed to be as follows. That is, in the non-aqueous secondary battery composition, the oligomer (O1) having a lower molecular weight than the polymer (P) complements the adsorption rate and adsorption stability of the polymer (P) to solid particles. The polymer (P) and the oligomer (O1) function complementarily, which is thought to improve and enhance the overall (overall) adsorption rate and adsorption stability of the solid particles, which are achieved by the combination of the polymer (P) and the oligomer (O1), in a balanced manner. As a result, the non-aqueous secondary battery composition stably maintains its initial dispersibility not only at room temperature but also at high temperatures. Even if the solid particles aggregate or precipitate, they can be re-dispersed to the excellent dispersion state they were in immediately after preparation. This dispersion stability can also be obtained by increasing the solid content of the non-aqueous secondary battery composition.

[0016] As described above, the polymer composition of the present invention functions as a dispersant that disperses solid particles in a dispersion medium during the preparation of a non-aqueous secondary battery composition. That is, the polymer composition of the present invention can be considered a dispersant (composition) containing a polymer (P) and an oligomer (O1). Furthermore, the polymer composition of the present invention can also function as a binder that adsorbs to solid particles in a constituent layer formed from the non-aqueous secondary battery composition to bind the solid particles and further bind the solid particles to a current collector. Note that, in a non-aqueous secondary battery composition, the polymer composition of the present invention may or may not function to bind solid particles. Adsorption to solid particles includes not only physical adsorption but also chemical adsorption (adsorption by chemical bond formation, adsorption by electron transfer, etc.). The polymer composition of the present invention, which exhibits the above-described excellent effects, can be preferably used as a dispersant component in a non-aqueous secondary battery sheet (including a non-aqueous secondary battery electrode sheet) or a constituent layer-forming material for a non-aqueous secondary battery.

[0017] <Polymer (P)> The polymer composition of the present invention contains one or more polymers (P). The polymer (P) contained in the polymer composition of the present invention is not particularly limited, and any appropriate polymer can be used, and various polymers used in non-aqueous secondary batteries can be used without particular limitation. Preferred examples of the polymer (P) include polymers having at least one bond selected from a urethane bond, a urea bond, an amide bond, an imide bond, and an ester bond, or a polymer chain of a carbon-carbon double bond in the main chain. In the present invention, a polymer chain of a carbon-carbon double bond refers to a polymer chain formed by polymerization of a carbon-carbon double bond (ethylenically unsaturated group), and specifically refers to a polymer chain formed by polymerization (homopolymerization or copolymerization) of a monomer having a carbon-carbon unsaturated bond. More specifically, examples of polymers having a urethane bond, urea bond, amide bond, imide bond, or ester bond in the main chain include step-growth polymerization (polycondensation, polyaddition, or addition-condensation) polymers such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, and polycarbonate. Furthermore, examples of polymers having a polymer chain of carbon-carbon double bonds in the main chain include chain-polymerized polymers such as fluoropolymers (fluorine-containing polymers), hydrocarbon polymers, vinyl polymers, and (meth)acrylic polymers. Here, the term "(meth)acrylic polymer" refers to a polymer made of a (co)polymer containing 50% by mass or more of a component derived from a (meth)acrylic compound (M1) described below, for example, and the term "vinyl polymer" refers to a copolymer containing 50% by mass or more of a component derived from a vinyl-based compound (M2) described below (provided that the content of the component derived from the (meth)acrylic compound (M1) is less than 50% by mass). The polymerization mode of these polymers is not particularly limited, and they may be block copolymers, alternating copolymers, or random copolymers. The polymer (P) preferably functions as a dispersant for solid particles in the non-aqueous secondary battery composition and also functions as a binder in the constituent layer formed from the non-aqueous secondary battery composition.Of the above polymers, chain polymerization polymers are preferred, hydrocarbon polymers, vinyl polymers and (meth)acrylic polymers are more preferred, and (meth)acrylic polymers are even more preferred.

[0018] The polymer (P) preferably contains a component derived from a (meth)acrylic acid ester monomer, in order to improve dispersion stability, resistance, and cycle characteristics, together with the oligomer (O1) described below. The (meth)acrylic acid ester monomer is not particularly limited, and examples thereof include the (meth)acrylic compound (M1) described below. The component derived from a (meth)acrylic acid ester monomer is not particularly limited, and examples thereof include the component (X), component (A), and other components derived from a (meth)acrylic acid ester monomer, which are described below. The content of the component derived from a (meth)acrylic acid ester monomer in the polymer (P) can be determined appropriately taking into consideration the dispersion stability, resistance, cycle characteristics, and the like, and is, for example, preferably 50 to 100% by mass, and more preferably 75 to 100% by mass.

[0019] The polymer (P) may contain other components in addition to the components derived from the (meth)acrylic acid ester monomer. Examples include components derived from the vinyl compound (M2) described below. The content of components other than the components derived from the (meth)acrylic acid ester monomer in the polymer (P) is not particularly limited and can be determined appropriately. The polymer (P) containing a component derived from the (meth)acrylic acid ester monomer is preferably a (meth)acrylic polymer.

[0020] (Preferred embodiment of polymer (P)) The polymer (P) can be appropriately selected from the various polymers described above, but one preferred embodiment is one in which the polymer (P) contains the following component (A), which, together with the oligomer (O1) described below, improves dispersion stability and enhances resistance and cycle characteristics. In the present invention, a polymer (P) containing the component (A) may be referred to as a preferred polymer (P).

[0021] - Constituent Component (A) - Constituent Component (A) preferably contained in Polymer (P) is a constituent component having at least one polar functional group selected from the following functional group group (a): When constituent component (A) has a molecular weight of 400 or greater, it is preferably a constituent component having no polymer chain defined as constituent component (X) (excluding alkyleneoxy polymer chains) in its molecular structure, as described below, and more preferably a constituent component having no polymer chain defined as constituent component (X) in its molecular structure, regardless of molecular weight.

[0022] In the constituent component (A), the polar functional group is preferably contained in a molecular chain that will become a side chain of the suitable polymer (P), and more preferably, for example, incorporated into the interior or terminal of the molecular chain that will become a side chain of the suitable polymer (P). In the present invention, the molecular chain that will become a side chain of the suitable polymer (P) refers to a molecular chain that constitutes the side chain of the suitable polymer (P) into which the constituent component (A) is incorporated, and is a molecular chain other than the molecular chain that constitutes the main chain of the suitable polymer (P), usually a molecular chain bonded to the molecular chain (atomic group) that constitutes the main chain. For example, when the polycondensable compound that derives the constituent component (A) is acrylamide, the molecular chain (-CONH ２ )

[0023] The constituent component (A) may have at least one polar functional group, and typically preferably has 1 to 3 polar functional groups. The number of polar functional groups in the suitable polymer (P) is not particularly limited and is determined appropriately depending on the number of polar functional groups in the constituent component (A) itself, the content of the constituent component (A), the molecular weight of the suitable polymer (P), etc.

[0024] This component (A) may have a polar functional group, and examples thereof include a component derived from a polycondensation compound having at least one polar functional group selected from the following functional group group (a): The polycondensation compound may, for example, comprise a polycondensation group, a polar functional group or a substituent having a polar functional group, and optionally a linking group L that links the polycondensation group and the substituent. Ａ２and a compound having the above structure is preferred, and a low molecular weight compound is more preferred. The molecular weight of component (A) is not particularly limited, but a preferred embodiment is one in which it is less than 400. In a preferred embodiment in which component (A) has a molecular weight of less than 400, component (A) may or may not have a repeating structure in a partial structure other than the polycondensable group. On the other hand, in an embodiment in which component (A) has a molecular weight of 400 or more, component (A) may be a compound having a repeating structure such as an alkyleneoxy polymer chain in a partial structure other than the polycondensable group, but is preferably a compound that does not have a repeating structure in a partial structure other than the polycondensable group.

[0025] The polycondensable group has the same meaning as the polycondensable group in the component (X) described below. The substituent forming the substituent having a polar functional group is not particularly limited, and examples thereof include a group selected from the substituent Z described below, and a polymer chain. Preferred examples of the polymer chain that can be used as the substituent include a polymer chain having a number average molecular weight such that the molecular weight of the component (X) is less than 400. Such polymer chains (however, the number average molecular weight is preferably such that the molecular weight of the component (A) is less than 400) are not particularly limited, and examples thereof include the polymer chains of the formula (L Ｐ ) is a polymer chain having a repeating unit represented by the formula (I), a polymer chain made of polyether is preferred, and a polyalkyleneoxy chain is more preferred. The substituent is preferably an alkyl group or a polyalkyleneoxy chain. In the present invention, the substituent forming the substituent having a polar functional group is preferably a linking group L Ａ２ When the linking group L can also correspond to Ａ２ The linking group L , which will be described later, links the polycondensable group in the constituent (X) described later to the polymer chain. Ａ１ can be applied without any particular limitation, and a —CO—O— group is preferred.

[0026] <Functional Group (a)> Sulfonic acid group (sulfo group), phosphoric acid group (phosphoryl group), phosphonic acid group, hydroxy group, carboxy group, oxetane group, epoxy group, dicarboxylic acid group, thiol group (sulfanyl group), ether group, thioether group, thioester group, ester group, amide group, urethane group, urea group, imide group, fluoroalkyl group, and salts thereof

[0027] The sulfonic acid group, phosphoric acid group, phosphonic acid group, etc. included in the functional group group (a) are not particularly limited, but each has the same meaning as the corresponding group of the substituent Z described below. The dicarboxylic acid group is not particularly limited, but includes a group obtained by removing one or more hydrogen atoms from a dicarboxylic acid anhydride, and a constituent component itself formed by copolymerization of a polymerizable dicarboxylic acid anhydride as a polymerizable compound, and further includes a group obtained by reacting a dicarboxylic acid anhydride with an active hydrogen compound to cleave the anhydride group. As the group obtained by removing one or more hydrogen atoms from a dicarboxylic acid anhydride, a group obtained by removing one or more hydrogen atoms from a cyclic dicarboxylic acid anhydride is preferred. Examples of dicarboxylic acid anhydrides include acyclic dicarboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride, and cyclic dicarboxylic acid anhydrides such as maleic anhydride, phthalic anhydride, fumaric anhydride, succinic anhydride, and itaconic anhydride. The polymerizable dicarboxylic acid anhydride is not particularly limited, but includes a dicarboxylic acid anhydride having an unsaturated bond in the molecule, preferably a polymerizable cyclic dicarboxylic acid anhydride. Specific examples include maleic anhydride and itaconic anhydride. The active hydrogen compound is not particularly limited as long as it is a compound that reacts with a dicarboxylic acid anhydride group, and examples thereof include alcohol compounds, amine compounds, and thiol compounds.

[0028] An ether group (-O-), a thioether group (-S-), and a thioester group (*-CO-S-**, *-CS-O-**, *-CS-S-**) each represent the bond shown in parentheses. An ester group (*-CO-O-**), an amide group (*-CONR ＮＡ１ -**), urethane group (*-NR ＮＡ１ —CO—O—**), a urea group (—NR ＮＡ１ -CO-NR ＮＡ１-), imide group (*-CO-NR ＮＡ２ -CO-**) each means the bond shown in the parentheses. Here, * and ** represent the bond, and R ＮＡ１ represents a hydrogen atom or a substituent, and R ＮＡ２ represents a bond, a hydrogen atom or a substituent. ＮＡ１ and R ＮＡ２ The substituents that can be taken as R are not particularly limited, but examples thereof include groups selected from the substituent Z described below, and alkyl groups (including cycloalkyl groups), aryl groups, heterocyclic groups, etc. are preferred. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. The number of carbon atoms in the aryl group is preferably 6 to 26, more preferably 6 to 20, and even more preferably 6 to 12. In addition, when two R ＮＡ１ may be the same or different. ＮＡ１ is preferably a hydrogen atom, and R ＮＡ２ is preferably a bond or a hydrogen atom. In each of the above groups, either of the two bonds * and ** may be bonded to the main chain side of the suitable polymer (P), but it is preferable that the bond * is bonded to the main chain side of the suitable polymer (P). However, the ester group does not include a partial structure that forms the main chain of the suitable polymer (P) when the constituent component (A) is incorporated into the suitable polymer (P), such as an ester group that is directly bonded to the polymer chain of the carbon-carbon double bond.

[0029] The terminal group bonded to each of these groups is not particularly limited and represents a hydrogen atom or a substituent. Examples of the substituent that can be adopted as the terminal group include groups selected from the substituent Z described below. Among them, alkyl groups (including cycloalkyl groups), aryl groups, and heterocyclic groups are preferred, and alkyl groups or aryl groups are more preferred. In one preferred embodiment, the number of carbon atoms in the alkyl group is R ＮＡ１ In another preferred embodiment, the number of carbon atoms in the aryl group is preferably 1 to 20, more preferably 2 to 12, and even more preferably 3 to 8. ＮＡ１In the present invention, the number of carbon atoms in the aryl group can be the same as that of the aryl group ＮＡ１ When either the terminal group or the group has a hydrogen atom, this hydrogen atom is ＮＡ１ Interpret as follows.

[0030] The term "ether group" includes carboxyl group, hydroxyl group, oxetane group, epoxy group, dicarboxylic anhydride group, ester group, etc., but the -O- group contained in these is not considered an ether group. The same applies to thioether group. The term "ester group" includes urethane group, but the -CO-O- group contained therein is not considered an ester group. Furthermore, the term "amide group" includes urethane group, urea group, imide group, etc., but the -CO-N group contained therein is not considered an ether group. ＲＮ The - group is not interpreted as an amide group. The polar functional group may form a cyclic structure. For example, the imide group may form a cyclic imide group, specifically, a cyclic imide group derived from maleimide or phthalimide.

[0031] The fluoroalkyl group is a fluoroalkyl group in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom, and the molecular structure thereof may be linear, branched, or cyclic, with linear or branched being preferred. The number of carbon atoms in the fluoroalkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 12, still more preferably 2 to 8, and particularly preferably 2 to 7. In a preferred embodiment, the lower limit of the number of carbon atoms is 3 or more, and in the case where the fluoroalkyl group is linear, it is also preferred to set the lower limit to 4 or more. In the fluoroalkyl group, some or all of the hydrogen atoms may be substituted with fluorine atoms. In the present invention, a fluoroalkyl group in which some of the hydrogen atoms are substituted with fluorine atoms is preferred, and a preferred polymer (P) in which the carbon atom bonded to the main chain side is a methylene group (-CH) that is not substituted with a fluorine atom is ２ A fluoroalkyl group containing an ethylene group (—CH ) in which none of two or three consecutive carbon atoms, including the carbon atom bonded to the main chain side of the preferred polymer (P), is substituted with a fluorine atom is more preferred. ２ -CH ２ -) or propylene group (-CH ２-CH ２ -CH ２ In such a fluoroalkyl group in which some of the hydrogen atoms are substituted with fluorine atoms, the remaining alkyl groups bonded to carbon atoms that are not substituted with fluorine atoms are preferably perfluoroalkyl groups in which all of the hydrogen atoms are substituted with fluorine atoms. The fluoroalkyl group may have a substituent other than a fluorine atom, and for example, ｆ R may have a substituent (excluding a fluorine atom) that can be ｆ The substituent that can be adopted as (I) is not particularly limited, but examples thereof include the substituent Z described below. Specific examples include halogen atoms (e.g., fluorine, chlorine, iodine, and bromine atoms), alkyl groups (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), alkoxy groups (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and particularly preferably having 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably having 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably having 2 to 5 carbon atoms), hydroxy groups, nitro groups, cyano groups, mercapto groups, amino groups, amide groups, and acidic groups (such as carboxyl groups, phosphate groups, and sulfonic acid groups). The acidic group may be a salt. Examples of counter ions that form salts include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkylammonium ions.

[0032] Groups capable of forming salts, such as sulfonic acid groups (sulfo groups), phosphate groups, phosphonic acid groups, hydroxy groups, carboxy groups, and dicarboxylic acid groups, may form salts with cations. Cations are not particularly limited and include various metal salts, ammonium or amine salts, etc. Amide groups, urethane groups, urea groups, imide groups, etc. may form salts with anions. Anions are not particularly limited and include anions of various inorganic or organic acids, etc.

[0033] The polar functional group contained in component (A) is preferably a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a hydroxy group, a carboxy group, an oxetane group, an epoxy group, a dicarboxylic acid group, an ether group, an amide group, or a salt thereof, and from the viewpoints of dispersion stability, resistance, and cycle characteristics, an amide group, a hydroxy group, or the like is more preferable. When component (A) contains two or more polar functional groups, the combination thereof is not particularly limited and can be determined appropriately. For example, a combination containing an amide group is preferred, and a specific example is a combination of an amide group and a dicarboxylic acid group.

[0034] The polar functional group contained in component (A) is usually one, but two or more polar functional groups may be linked to form a repeating structure as long as the molecular weight is less than 400. In the present invention, as described above, component (A) preferably contains one polar functional group.

[0035] Constituent component (A) is not particularly limited, but is preferably a constituent derived from the above-mentioned polycondensable compound, a constituent derived from a compound obtained by introducing (substituting) the above-mentioned polar functional group into the above-mentioned polycondensable compound, a constituent derived from a compound obtained by introducing the above-mentioned polar functional group into a polymer chain (provided that the molecular weight is less than 400), or a constituent derived from a maleimide compound, an N-vinyl substituted imide compound, or a vinyl succinimide compound; a constituent derived from a (meth)acrylic acid compound, a constituent derived from a compound obtained by introducing the above-mentioned polar functional group into a (meth)acrylic acid ester compound, or a constituent derived from a (meth)acrylamide compound is more preferred, and a compound obtained by introducing the above-mentioned polar functional group into a (meth)acrylic acid alkyl ester, or a constituent derived from a (meth)acrylamide compound is even more preferred.

[0036] Examples of the (meth)acrylamide compound include N-unsubstituted (meth)acrylamide compounds and N-mono- or di-substituted (meth)acrylamide compounds, and more specifically, N-unsubstituted (meth)acrylamide compounds, N-alkyl (meth)acrylamide compounds, N,N-dialkyl (meth)acrylamide compounds, N-aryl (meth)acrylamide compounds, N,N-diaryl (meth)acrylamide compounds, and the like are preferred. Examples of the substituent substituting the nitrogen atom in the acrylamide compound include R ＮＡ１ Alternatively, an end group bonded to the end of the amide bond is exemplified, with an alkyl group or an aryl group being preferred. As the (meth)acrylamide compound, a compound that leads to a group having a chemical structure represented by formula (A1) described later is also preferred. Examples of compounds that lead to the component (A) containing an amide group include, in addition to (meth)acrylamide compounds, vinyl compounds containing an amide group, (meth)acrylate compounds containing an amide group, and (meth)acrylamide compounds containing an amide group. The amide group in the component (A) may be a sulfonamide group. Examples of compounds that lead to the component (A) containing a sulfonamide group include vinyl aromatic sulfonamide compounds and (meth)acrylic compounds (M1) containing a sulfonamide group. Preferred examples include compounds in which a sulfonamide group is introduced into a vinyl aromatic compound such as a styrene compound or a vinyl naphthalene compound, and more preferred examples include vinylbenzenesulfonamide. The compound that leads to the component (A) containing a sulfonamide group may be an N-mono- or di-substituted sulfonamide compound, and examples of the substituent substituting the nitrogen atom of the sulfonamide group include R ＮＡ１ Alternatively, a terminal group bonded to the terminal of the amide bond may be mentioned, and an alkyl group is preferred.

[0037] Examples of (meth)acrylic acid ester compounds from which component (A) is derived include (meth)acrylic acid alkyl ester compounds and (meth)acrylic acid aryl ester compounds, with (meth)acrylic acid alkyl ester compounds being preferred. The number of carbon atoms in the alkyl group constituting the (meth)acrylic acid alkyl ester compound is not particularly limited, but can be, for example, 1 to 24. The number of carbon atoms in the alkyl group is typically preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. From the standpoint of solubility in the dispersion medium, the number of carbon atoms in the alkyl group is preferably 3 to 16, and more preferably 6 to 14. The number of carbon atoms in the aryl group constituting the aryl ester is not particularly limited, but can be, for example, 6 to 24, preferably 6 to 10, and more preferably 6. Suitable examples of compounds having the above-mentioned polar functional group introduced into the polymer chain include compounds having a molecular weight of less than 400 when used as a component, such as compounds obtained by introducing the above-mentioned polymer chain, preferably a polyalkyleneoxy chain, into the above-mentioned polycondensable compound, and further introducing the above-mentioned polar functional group into this polymer chain.

[0038] As the component (A), a component represented by the following formula (A1) is particularly preferred in terms of dispersion stability, resistance, and cycle characteristics.

[0039] In the above formula (A1), X １ represents a hydrogen atom or a substituent. １ The substituent that can be adopted as X is not particularly limited, and examples thereof include groups selected from the substituent Z described below, among which an alkyl group is preferred. １ is preferably a hydrogen atom or a methyl group.

[0040] L １ represents a single bond or a linking group, and a single bond is preferred. １ The linking group that can be taken as the linking group L Ａ２ However, L １ The linking group which can be taken as the linking group does not form a urethane group, a urea group or an imide group together with the amide group in formula (A1).

[0041] Y １ and Y ２ Each of Y represents a hydrogen atom or a substituent. １ and Y ２ The substituents that can be adopted as R ＮＡ１ or has the same meaning as the terminal group bonded to the end of the amide bond, and Y １ is preferably a hydrogen atom, and Y ２ is preferably an alkyl group. １ and Y ２ The substituents that can be taken as Y do not form an imide group together with the amide group in formula (A1). １ and Y ２ may be the same or different. １ and Y ２ When both are alkyl groups, Y １ and Y ２ The alkyl group that can be taken as R ＮＡ１ Alternatively, the alkyl group preferably has the same meaning as the alkyl group that can be used as the terminal group bonded to the terminal of the amide bond, and examples thereof include methyl, ethyl, normal propyl, isopropyl, normal butyl, tertiary butyl, a linear or branched octyl group, and a linear or branched dodecyl group. １ and Y ２ The alkyl group that can be taken as Y may have a substituent, but preferably does not have a hydroxy group, and more preferably does not have the above polar functional group. １ and Y ２ The combination of alkyl groups that can be taken as the alkyl group is not particularly limited, and the alkyl groups listed above can be combined appropriately.

[0042] The constituent represented by formula (A1) may have a substituent. For example, in formula (A1), X １ The carbon atom bonded to the carbon atom having the formula ２ Although the substituent is represented as "-", it may have a substituent. Such a substituent is not particularly limited, but for example, X １ Examples of the substituents that can be taken include the above.

[0043] When the preferred polymer (P) contains two or more types of the constituent components (A), the combination thereof is not particularly limited and can be appropriately determined. For example, a combination containing a constituent component derived from an acrylamide compound is preferred, such as a combination of a constituent component derived from an acrylamide compound with the above-mentioned preferred constituent component having a polar functional group.

[0044] Specific examples of the component (A) include the components contained in the polymers synthesized in the examples, as well as components derived from acrylamide compounds, but the present invention is not limited to these.

[0045] The molecular weight of the constituent component (A) is not particularly limited and is appropriately determined taking into consideration the molecular weight of the suitable polymer (P), the content of the constituent component (A), etc.

[0046] In the present invention, the component (A) and the component (X) described below are different components, which makes it possible to improve dispersion stability.

[0047] - Component (X) - In addition to the component (A), the suitable polymer (P) preferably contains a component (X) that contains a polymer chain and has a molecular weight of 400 or more, since this reinforces the dispersion stability-improving effect of the component (A) and further improves dispersion stability, resistance, and cycle characteristics. In the present invention, when a component having a molecular weight of 400 or more contains a polymer chain and a polar functional group included in the functional group group (a) defined by the component (A), this component is referred to as component (X). This component (X) is preferably a component that does not contain a polar functional group, and in one preferred embodiment, for example, a component that does not contain a polar functional group in a partial structure other than the polymer chain. By including component (X) in the suitable polymer (P), the excluded volume effect between the suitable polymers (P) can be enhanced, improving the dispersibility of solid particles and achieving excellent dispersion stability.

[0048] In the constituent (X), the polymer chain may be present in the partial structure that will form the main chain of the suitable polymer (P), but it is preferable that it be present in the molecular chain that will form the side chain of the suitable polymer (P). For example, it is more preferable that it be incorporated into the interior or end of the molecular chain that will form the side chain of the suitable polymer (P). Such a constituent (X) can incorporate a graft structure into the chemical structure of the suitable polymer (P), thereby enhancing the above-mentioned excluded volume effect. In the present invention, the molecular chain that will form the side chain of the suitable polymer (P) refers to the molecular chain that constitutes the side chain of the suitable polymer (P) into which the constituent (X) is incorporated. This refers to a molecular chain other than the molecular chain that constitutes the main chain of the suitable polymer (P), usually a molecular chain bonded to the molecular chain (atomic group) that constitutes the main chain. The type of polymer chain that one constituent (X) has may be at least one type, and preferably one or two types. The number of polymer chains that one constituent (X) has is not particularly limited, but is usually one.

[0049] Examples of this constituent (X) include a constituent derived from a polycondensable compound having a polycondensable group and a polymer chain. The polycondensable group is appropriately determined depending on the main chain structure of the suitable polymer (P). For example, when the suitable polymer (P) is a step-polymerization polymer, a condensable functional group is selected, and when the suitable polymer (P) is a chain-polymerization polymer, a polymerizable group (ethylenically unsaturated group) is selected. Examples of the ethylenically unsaturated group include a vinyl group. Here, examples of step-polymerization polymers include polymers obtained by polycondensation, polyaddition, or addition-condensation of raw material compounds, such as polyurethane, polyurea, polyamide, polyimide, polyester, polysiloxane, or copolymers thereof. Examples of chain-polymerization polymers include polymers having a polymer chain of carbon-carbon double bonds as the main chain, such as hydrocarbon polymers, vinyl polymers, (meth)acrylic polymers, or copolymers thereof, with (meth)acrylic polymers being preferred. The polymer chain is a molecular chain in which two or more repeating units of one or more types are bonded together. Such a polymer chain is not particularly limited, and a chain made of a normal polymer, for example, the above-mentioned step-polymerized polymer or chain-polymerized polymer, can be applied without any particular limitation. Ｐ ) is preferred, a polymer chain made of polyester, a polymer chain made of polyether, a polymer chain made of polysiloxane, or a polymer chain made of (meth)acrylic polymer is more preferred, and a polymer chain made of polysiloxane is even more preferred.

[0050]

[0051] The above formula (L Ｐ), X represents a divalent substituent, L represents a single bond or a linking group, and n represents the (average) degree of polymerization. The substituent that can be taken as X is not particularly limited, and examples thereof include groups in which one hydrogen atom has been further removed from a group appropriately selected from the substituent Z, etc., which will be described later, and preferably represents a hydrocarbon group or an alkylsilylene group in terms of dispersion stability, resistance, and cycle characteristics. The hydrocarbon group that can be taken as X is not particularly limited, and examples thereof include alkylene groups, alkenyl groups, arylene groups, etc., and alkylene groups are preferred. The alkylene groups, etc. that can be taken as X include groups in which one hydrogen atom has further removed from each group corresponding to the substituent Z, which will be described later. However, the number of carbon atoms in the alkylene group is more preferably 1 to 8. In the above formula (L Ｐ When the repeating unit represented by -Si(R) is an alkyleneoxy group, it is more preferable that the number of carbon atoms in the alkylene group is 1 to 6. The alkylsilylene group that can be taken as X is not particularly limited, and may be any of the alkylsilylene groups represented by -Si(R) in the polymer chain made of polysiloxane described below. Ｓ ２ X may have a substituent.

[0052] L is selected depending on the type of polymer chain; for example, in the case of a chain made of a chain-polymerized polymer, it is a single bond, and in the case of a chain made of a step-polymerized polymer, it is a linking group. The linking group that can be taken as L is not particularly limited as long as it is a group that can bond to another repeating unit, and is appropriately selected depending on the type of polymer chain. This linking group is usually a linking group having a hetero atom, and examples thereof include an ester bond (-CO-O-), an ether bond (-O-), a carbonate bond (-O-CO-), an amide bond (-CO-N(R Ｎ )-), urethane bond (-N(R Ｎ )-CO-), urea bond (-N(R Ｎ )-CO-N(R Ｎ )-), imide bond (—CO—N(R Ｎ In each of the above bonds, R Ｎ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Any bonding portion of the linking group may be bonded to X. As the linking group, an ester bond, an ether bond, a carbonate bond, etc. are more preferred.

[0053] n represents the (average) degree of polymerization, and may be 2 or more, and is appropriately determined taking into consideration the number average molecular weight of the polymer chain, which will be described later. For example, the degree of polymerization n is as described later.

[0054] In the polymer chain, two or more repeating units may be the same or different. When two or more repeating units are different, the bonding mode is not particularly limited and may be random, alternating, or block.

[0055] The above formula (L Ｐ ) includes, for example, a chain made of a chain-polymerized polymer, a chain made of a step-polymerized polymer, and the like. More specifically, preferred examples include a polymer chain made of a (meth)acrylic polymer, a polymer chain made of polystyrene, a polymer chain made of polyether, a polymer chain made of polyester, a polymer chain made of polycarbonate, and a polymer chain made of polysiloxane. In terms of dispersion stability, resistance, and cycle characteristics, a polymer chain made of a (meth)acrylic polymer or a polymer chain made of polysiloxane is more preferred.

[0056] The group bonded to the end of the polymer chain is not particularly limited and may be an appropriate group depending on the polymerization method, etc. Examples thereof include a hydrogen atom, an alkyl group, an aryl group, and a hydroxy group. １６Ａ The group bonded to the terminal of the polymer chain is preferably an alkyl group (having preferably 1 to 20 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms). This group may further have a substituent, but is preferably unsubstituted.

[0057] Examples of the polymer chain made of polyether include a polyalkyleneoxy chain and a polyaryleneoxy chain. Examples of the alkylene group and the arylene group include groups in which one hydrogen atom has been further removed from an alkyl group or an aryl group appropriately selected from the substituent Z described below, and preferred examples include the alkylene group and arylene group that can be taken as the above-mentioned X.

[0058] The polymer chain made of polysiloxane is -(Si(R Ｓ２ A polymer chain having a structure represented by R)-O)ns- is preferred. Ｓ represents a hydrogen atom or a substituent, with a substituent being preferred. The substituent is not particularly limited and may be selected from the substituent Z described below, such as a hydroxy group, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 or 3), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14, and particularly preferably 6 to 10), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14, and particularly preferably 6 to 10), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15, and particularly preferably 7 to 11), and a group represented by the formula Z described below. Among these, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a group represented by the formula Z described below is more preferred, with an alkyl group having 1 to 3 carbon atoms being even more preferred. ns indicates the degree of polymerization (average repeat number) of the siloxane structure, and is appropriately determined taking into consideration the number average molecular weight of the polymer chain and the molecular weight of the constituent (X), which will be described later, and is preferably as described later. The polysiloxane structure has a terminal group bonded to its end. This terminal group is not particularly limited, and examples thereof include a hydrogen atom or a substituent. The substituent that can be used as the terminal group are as described above, and examples thereof include R Ｓ Examples of the substituents that can be taken include:

[0059] The polysiloxane structure is preferably a polysiloxane structure having a chemical structure represented by the following formula 4A.

[0060] In formula 4A, R １５ and R １６ represents an alkyl group or an aryl group, and Z represents a group represented by formula (Z) described below. １５ , R １６ and Z are R in Formula 4 described below. １５ , R １６and Z. In Formula 4A, x1, x2, and x3 are integers of 0 or more, and y1 is an integer of 1 to 30. x1, x2, x3, and y1 in Formula 4A are the same as x1, x2, x3, and y1 in Formula 4 described below, respectively.

[0061] Examples of the polymer chain made of polyester include chains made of known polyesters, such as polyester polymer chains obtained by reacting a polyol such as alkylene glycol with a polybasic acid such as an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid, and polyester polymer chains obtained by ring-opening polymerization of a cyclic ester compound such as a caprolactone monomer.

[0062] Preferred examples of the chain formed from a chain-polymerized polymer include a polymer chain formed from a (meth)acrylic polymer and a polymer chain formed from polystyrene. The polymer chain formed from a (meth)acrylic polymer preferably has a component derived from a (meth)acrylic compound (M1) such as a (meth)acrylic acid compound, a (meth)acrylic acid ester compound, a (meth)acrylamide compound, or a (meth)acrylonitrile compound, as described below, or a component derived from a vinyl-based compound (M2), as described below. Among these, a polymer chain having a component derived from one or more (meth)acrylic acid ester compounds is more preferred, and a polymer chain having a component derived from a (meth)acrylic acid alkyl ester compound is even more preferred. The (meth)acrylic acid alkyl ester compound preferably contains an ester compound of a long-chain alkyl group having 4 or more carbon atoms (preferably 6 or more carbon atoms), and may further contain an ester compound of a short-chain alkyl group having 3 or less carbon atoms. The content of each component in the polymer chain is not particularly limited and may be appropriately determined. For example, the content of the component derived from the (meth)acrylic compound (M1) in the polymer chain is preferably 30 to 100% by mass, and can also be 50 to 80% by mass. The content of the component derived from the (meth)acrylic acid alkyl ester compound is preferably 50 to 100% by mass, and can also be 60 to 80% by mass. Furthermore, when a component derived from a (meth)acrylic acid long-chain alkyl ester compound and a component derived from a (meth)acrylic acid short-chain alkyl ester compound are contained, the content of the component derived from the (meth)acrylic acid long-chain alkyl ester compound is preferably 20 to 100% by mass, and more preferably 50 to 100% by mass, and the content of the component derived from the (meth)acrylic acid short-chain alkyl ester compound is preferably 5 to 80% by mass, and more preferably 5 to 40% by mass.

[0063] The polymer chain is preferably bonded to the polycondensable group directly or via a linking group. Ａ１is not particularly limited, and examples thereof include an alkylene group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms, and more preferably having 2 to 3 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms, and more preferably having 6 to 10 carbon atoms), an oxygen atom, a sulfur atom, an imino group (—NR Ｎ -:R Ｎ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms; a carbonyl group, a phosphate linking group (-O-P(OH)(O)-O-), a phosphonate linking group (-P(OH)(O)-O-), or a group relating to a combination thereof. However, the linking group L Ａ１ is preferably a group that does not correspond to each polar functional group defined in the above-mentioned component (A). Ａ１ As the linking group L, a group formed by combining an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom, and an imino group is preferred, a group formed by combining an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom, and an imino group is more preferred, and a group containing a -CO-O- group is even more preferred, and examples thereof include a -CO-O- group or a -CO-O-alkylene group. Ａ１ Preferred examples of the linking group include a linking group containing a structural part derived from a chain transfer agent (e.g., 3-mercaptopropionic acid) or a polymerization initiator used in the synthesis of the polymer chain, and further, a linking group in which such a structural part is bonded to a structural part derived from a (meth)acrylic compound (M1) that reacts with the chain transfer agent. Examples thereof include a -CO-O-alkylene group-O-CO-alkylene group-S- group, and specifically, examples of the linking group formed by bonding 3-mercaptopropionic acid and glycidyl (meth)acrylate include -CO-O-CH ２ -CH(OH)-CH ２ —O—CO—CH ２ -CH ２ An example is an —S— group.

[0064] The linking group L Ａ１ The number of atoms constituting the linking group L is preferably 1 to 36, more preferably 1 to 24, and even more preferably 1 to 12. Ａ１The number of linking atoms is preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is 1 or more. The number of linking atoms refers to the minimum number of atoms connecting the predetermined structural parts. For example, -O-C(=O)-CH ２ -CH ２ In the case of -, the number of atoms constituting the linking group is 9, but the number of linking atoms is 4.

[0065] The constituent (X) is preferably a constituent derived from a compound having an ethylenically unsaturated group as a polycondensable group and a polymer chain made of polyester, a polymer chain made of polysiloxane, or a polymer chain made of (meth)acrylic polymer, which contains —C(═O)—O— as a linking group, and more preferably a constituent having a polymer chain made of polysiloxane, which is represented by the following formula 4:

[0066]

[0067] In formula 4, R １１ represents a hydrogen atom or methyl. ２ represents a linking group. ２ The linking group that can be used as the linking group is not particularly limited, but the linking group L Ａ１ Examples of the linking group include those listed as possible linking groups. ２ The linking group as R is preferably an alkylene group, an alkenylene group, an arylene group, an oxygen atom, a sulfur atom, a carbonyl group, or a group relating to a combination thereof, more preferably a group containing a —CO—O— group, and particularly preferably a —CO—O— group or a —CO—O-alkylene group. １５ represents an alkyl group or an aryl group, and an alkyl group is preferable. １５ The alkyl group and aryl group that can be taken as R in the polysiloxane structure are respectively Ｓ The alkyl and aryl groups that can be taken as R are the same as those that can be taken as R, and the preferred groups are also the same. １５ Methyl is particularly preferred. Two R's bonded to the same silicon atom １５ may be the same or different, but preferably all are methyl. １６represents an alkyl group or an aryl group, and an alkyl group is preferred. １６ may be the same or different. １６ The alkyl group and aryl group that can be taken as R in the above polysiloxane structure are respectively Ｓ The alkyl and aryl groups that can be taken as R are the same as those that can be taken as R, and the preferred groups are also the same. １６ Particularly preferably, R is methyl. １６Ａ represents a hydrogen atom or a substituent. １６Ａ The substituents that can be taken as R are not particularly limited, and examples thereof include the substituent Z described below. Ｓ The substituents that can be represented by R are preferred. １６Ａ The substituents which can be taken as the aryl group are preferably an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group, and more preferably an alkyl group.

[0068] Z represents a group represented by the following formula (Z).

[0069] In formula (Z), R １７ and R １８ R represents an alkyl group or an aryl group. １７ and R １８ The alkyl group and aryl group that can be taken as R in the above polysiloxane structure are respectively Ｓ The alkyl and aryl groups that can be taken as R are the same as those that can be taken as R, and the preferred groups are also the same. １７ and R １８ may be the same or different. １９ represents an unsubstituted alkyl group having 1 to 4 carbon atoms. y2 represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 20.

[0070] In the constituent represented by Formula 4, x1, x2, x3, y1, and y2 are appropriately determined taking into consideration the number average molecular weight of the polymer chain and the molecular weight of the constituent (X), as described below. The sum of x1, x2, x3, y1, and y2 (degree of polymerization) is as described below, and it is particularly preferable that the value of (x1 + x2 + x3) × y1 is the same as the degree of polymerization, as described below. For example, in Formula 4, x1, x2, and x3 are each an integer of 0 or greater. x1 is preferably an integer of 0 to 50, more preferably an integer of 0 to 20. x2 is preferably an integer of 0 to 50, more preferably an integer of 0 to 20. x3 is preferably an integer of 1 to 100, more preferably an integer of 1 to 30. The sum of x1, x2, and x3 is an integer of 1 to 100, preferably an integer of 2 to 70, and more preferably an integer of 2 to 50. When x1 and x3 each represent an integer of 2 or more, in Formula 4, two Z or R groups bonded to the same silicon atom １５ may be the same or different. y1 is an integer of 1 to 30, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10. With regard to x1, x2, x3, y1, and y2, it is preferable that x1, x2, and y2 are 0, x3 is an integer of 1 to 100, and y1 is an integer of 1 to 30.

[0071] The component (X) is not particularly limited, but is preferably a component derived from a compound obtained by introducing (substituting) a polymer chain into the following polycondensable compound. The polycondensable compound is not particularly limited as long as it is a condensation-polymerizable compound having an ethylenically unsaturated bond, and examples thereof include (meth)acrylic compounds (M1) such as (meth)acrylic acid compounds, (meth)acrylic acid ester compounds, (meth)acrylamide compounds, and (meth)acrylonitrile compounds; vinyl compounds (M2) such as vinyl aromatic compounds (e.g., styrene compounds, vinyl naphthalene compounds, and vinyl carbazole compounds), allyl compounds, vinyl ether compounds, vinyl ester compounds, cyclic olefin compounds, diene compounds, and vinyl carboxylic acid ester compounds; and further, compounds such as dialkyl itaconate compounds and unsaturated carboxylic acid anhydrides. Among these, preferred are styrene compounds, (meth)acrylic acid compounds, (meth)acrylic acid ester compounds, and (meth)acrylamide compounds. Examples of the (meth)acrylic acid ester compounds include (meth)acrylic acid alkyl ester compounds and (meth)acrylic acid aryl ester compounds, and preferred are (meth)acrylic acid alkyl ester compounds. The number of carbon atoms in the alkyl group constituting the (meth)acrylic acid alkyl ester compound is not particularly limited, but can be, for example, 1 to 24, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms in the aryl group constituting the aryl ester is not particularly limited, but can be, for example, 6 to 24, preferably 6 to 10, and more preferably 6.

[0072] In the present invention, the polymer chain of the component (X) is a linking group, for example, a group represented by the formula (L Ｐ Even if the linking group L of the component (X) contains a polar functional group included in the functional group group (a), this polar functional group functions as a linking group and is not a polar functional group selected from the functional group group (a). In addition, when the component (X) is derived from a compound having the polycondensable group and the polymer chain, the linking group L Ａ１Even if component (X) has a polar functional group included in the functional group group (a) described above, this polar functional group does not fully exhibit the function of adsorbing or adhering to solid particles, and therefore, this is considered to be included in an embodiment in which component (X) does not have a polar functional group (a component that does not correspond to component (A)).

[0073] Specific examples of the component (X) include those shown below and those used in the examples, but the present invention is not limited to these. Ｙ and R Ｚ represents a linking group or a substituent. In the following specific examples, the degree of polymerization of the repeating unit is specifically shown, but in the present invention, it can be changed as appropriate. Furthermore, specific examples of the constituent component (X) represented by the above formula 4 include, for example, terminally (meth)acrylic-modified silicone compounds, specifically those shown in the respective polymers synthesized in the examples described below, but the present invention is not limited to these.

[0074] The component (X) may be any component derived from a macromonomer having a polymer chain, as long as the repeating unit has a degree of polymerization of 2 or more, and has a molecular weight of 400 or more. When the component (X) contains a polymer chain and has a molecular weight of 400 or more, the dispersibility of the solid particles is improved, thereby improving dispersion stability and, ultimately, improving resistance and cycle characteristics. The molecular weight of the component (X) is appropriately determined taking into consideration the molecular weight of a suitable polymer (P), the content of the component (X), etc., and, for example, from the viewpoint of improving dispersion stability, it is preferably 600 or more, more preferably 800 or more, even more preferably 2000 or more, and particularly preferably 3000 or more. The upper limit is not particularly limited, and from the viewpoint of improving dispersion stability, it is preferably 200,000 or less, more preferably 50,000 or less, even more preferably 20,000 or less, particularly preferably 7,000 or less, and most preferably 5,000 or less. In the present invention, the molecular weight of the constituent component (X) means the total molecular weight of the number average molecular weight of the polymer chain and the molecular weight of other partial structures. The number average molecular weight of the polymer chain can be measured as a number average molecular weight converted into standard polystyrene in the same manner as the weight average molecular weight of the polymer (P).

[0075] The number average molecular weight of the polymer chain and the degree of polymerization of all structural units forming the polymer chain are not particularly limited, and are determined appropriately taking into consideration the molecular weight of the constituent component (X), the molecular weight of a suitable polymer (P), etc. The degree of polymerization of all structural units forming the polymer chain is, for example, preferably 2 to 1,000, more preferably 2 to 200, and even more preferably 6 to 80.

[0076] Other Components—Suitable polymers (P) may contain other components in addition to the component (A). The other components may be any that do not fall under either the component (A) or the component (X). Examples of such other components include components that do not have a polymer chain or a polar functional group. For example, components derived from low-molecular-weight polycondensable compounds that have an ethylenically unsaturated group but do not have a polar functional group are included. More specifically, components derived from the above-mentioned (meth)acrylic acid compounds (M1) or vinyl compounds (M2) are included. Components derived from styrene compounds, (meth)acrylic acid ester compounds, and (meth)acrylonitrile compounds are preferred, and components derived from (meth)acrylic acid unsubstituted alkyl ester compounds and (meth)acrylic acid aryl-substituted alkyl ester compounds are preferred. As the other components, a component derived from an acrylic acid ester compound of a long-chain unsubstituted alkyl group is one of the more preferred embodiments. The number of carbon atoms in the long-chain unsubstituted alkyl group can be, for example, 4 to 20, preferably 4 to 16, and more preferably 6 to 14. Other preferred components include a component derived from an acrylate compound of a short-chain unsubstituted alkyl group and a component derived from an acrylate compound of a short-chain alkyl group substituted with an aryl group. The number of carbon atoms in the short-chain alkyl group is preferably 1 to 3, for example.

[0077] A suitable polymer (P) may contain one or more of the above-mentioned components. In one preferred embodiment, the suitable polymer (P) contains the above-mentioned component (A) and at least one of the above-mentioned component (X) and other components.

[0078] The content of each constituent component in the suitable polymer (P) is not particularly limited and may be determined as appropriate, and may be set, for example, within the following ranges. The content of each constituent component in the suitable polymer (P) may be set, for example, within the following ranges so that the total content of all constituent components is 100% by mass. When the polymer (P) contains two or more constituent components corresponding to a specific constituent, the total content of these constituent components is used.

[0079] The total content of component (A) in the suitable polymer (P) is not particularly limited and can be determined appropriately taking into consideration improvements in dispersion stability, resistance, and cycle characteristics, etc. The total content of component (A) is, for example, preferably 1 to 50 mass% relative to the total content of all components. From the viewpoints of dispersion stability, resistance, and cycle characteristics, it is more preferably 3 to 50 mass%, even more preferably 5 to 45 mass%, particularly preferably 10 to 40 mass%, and most preferably 20 to 35 mass%. The total content of component (X) in the suitable polymer (P) is not particularly limited and can be determined appropriately taking into consideration improvements in dispersion stability, resistance, and cycle characteristics, etc. The total content of component (X) is, for example, preferably 0 to 97 mass% relative to the total content of all components. From the viewpoints of dispersion stability, resistance, and cycle characteristics, it is more preferably 55 to 95 mass%, even more preferably 60 to 90 mass%, and particularly preferably 65 to 80 mass%. In a suitable polymer (P), the ratio of the total content of component (X) to the total content of component (A) [total content of component (X) / total content of component (A)] is not particularly limited and can be, for example, 0 to 99. In terms of dispersion stability, resistance, and cycle characteristics, it is preferably 1.2 to 19, more preferably 1.5 to 9.0, and even more preferably 1.9 to 4.0. The total content of other components is not particularly limited, but is preferably 0 to 90% by mass, more preferably 0 to 50% by mass, and even more preferably 0 to 10% by mass, relative to the total content of all components. In one preferred embodiment, the total content of other components is set as follows, depending on the presence or absence of component (X). That is, when component (X) is not present, the total content of other components is preferably 0 to 98% by mass, more preferably 50 to 90% by mass. On the other hand, when component (X) is present, it is preferably 0 to 50% by mass, more preferably 0 to 20% by mass.

[0080] The preferred polymer (P) may have a substituent other than the polar functional group included in the substituent group (a). Examples of the substituent that the preferred polymer (P) may have include the substituent Z (excluding polar functional groups) described below.

[0081] The molecular structure of the polymer (P) is not particularly limited and can be linear, branched, crosslinked (network), etc., with linear and branched being preferred. Examples of branched polymers include polymers with a branched or multi-branched structure in which the polymer chain of the component (X) serves as a branch (side chain). In the present invention, the term "branched structure" refers to a polymer in which the polymer chain has a branched structure, such as a structure in which one or more separate polymer chains (side chains) are bonded to the main chain. Examples of branched structures include a graft structure, a star structure (also called a star-shaped structure), and a dendritic structure. A graft structure in which a single main chain does not typically have a core and multiple polymer chains (as side chains) are bonded in a branched manner. When the polymer (P) contains multiple components, the polymer (P) may be a block polymer, an alternating polymer, etc., but is preferably a random polymer.

[0082] The polymer (P) can be a commercially available product, or a synthetic product. The polymer (P) can be synthesized by selecting raw material compounds using known methods. For example, the polymer (P) can be synthesized by condensation, homopolymerization, or copolymerization using a conventional synthesis method using a surfactant, an emulsifier, or a dispersant, a polycondensation compound that derives the constituent component (A), a polycondensation compound that derives the constituent component (X), or a polycondensation compound that derives other constituent components. Specifically, the polymer can be synthesized by the method described in the examples below. The method for incorporating a polar functional group into the polymer (P) is not particularly limited, and examples thereof include a method of copolymerizing a compound having a functional group, a method using a polymerization initiator or chain transfer agent that has (or generates) the functional group, a method using a polymer reaction, an ene reaction of a double bond, an ene-thiol reaction, or an ATRP (atom transfer radical polymerization) polymerization method using a copper catalyst. Alternatively, a functional group can be introduced by using a functional group present in the main chain, side chain, or terminal of the polymer as a reaction point. For example, a functional group can be introduced by various reactions with a dicarboxylic acid anhydride group in the polymer chain using a compound having a functional group. In the present invention, the synthesized polymer (P) is purified by a known method before use. However, by changing the polymerization conditions, for example, the type and amount of polymerization initiator or chain transfer agent, to by-produce a low-molecular-weight component corresponding to the oligomer (O1) during the synthesis of the polymer (P), a mixture of the polymer (P) and the oligomer (O1), or an oligomer (O1)-containing polymer (P) can also be obtained.

[0083] - Substituent Z - An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, for example, vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, butadiynyl, phenylethynyl, etc.), a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), In the present invention, alkyl groups usually include cycloalkyl groups, but will be described separately here.), aryl groups (preferably aryl groups having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), aralkyl groups (preferably aralkyl groups having 7 to 23 carbon atoms, for example, benzyl, phenethyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5- or 6-membered heterocyclic groups having at least one oxygen atom, sulfur atom, or nitrogen atom. Heterocyclic groups include aromatic heterocyclic groups and aliphatic heterocyclic groups.For example, a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, a pyrrolidone group, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, for example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), a heterocyclic oxy group (a group in which an -O- group is bonded to the above heterocyclic group), an alkoxycarbonyl group (preferably or an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, dodecyloxycarbonyl, etc.), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 26 carbon atoms, for example, phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), a heterocyclic oxycarbonyl group (a group in which an —O—CO— group is bonded to the above heterocyclic group), an amino group (preferably an amino group having 0 to 20 carbon atoms, an alkylamino group, or an arylamino group, for example, amino(—NH ２), N,N-dimethylamino, N,N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl group (preferably a sulfamoyl group having 0 to 20 carbon atoms, for example, N,N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), acyl group (including an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, an arylcarbonyl group, or a heterocyclic carbonyl group, preferably an acyl group having 1 to 20 carbon atoms, for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyl, benzoyl, naphthoyl, nicotinoyl, etc.), acyl Oxy groups (including alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, and heterocyclic carbonyloxy groups, preferably acyloxy groups having 1 to 20 carbon atoms, for example, acetyloxy, propionyloxy, butyryloxy, octanoyloxy, hexadecanoyloxy, acryloyloxy, methacryloyloxy, crotonoyloxy, and nicotinoyloxy), aryloyloxy groups (preferably aryloyloxy groups having 7 to 23 carbon atoms, for example, benzoyloxy and naphthoyloxy), carbamoyl groups (preferably carbamoyl groups having 1 to 20 carbon atoms, for example, N,N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino groups (preferably acylamino groups having 1 to 20 carbon atoms, for example, acetylamino, benzoylamino, etc.), alkylthio groups (preferably alkylthio groups having 1 to 20 carbon atoms, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), heterocyclic thio groups (groups in which an -S- group is bonded to the above heterocyclic group), alkylsulfonyl groups (preferably alkylsulfonyl groups having 1 to 20 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl groups (preferably an arylsulfonyl group having 6 to 22 carbon atoms, for example, benzenesulfonyl; an alkylsilyl group (preferably an alkylsilyl group having 1 to 20 carbon atoms, for example, monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl; an arylsilyl group (preferably an arylsilyl group having 6 to 42 carbon atoms, for example, triphenylsilyl; an alkoxysilyl group (preferably an alkoxysilyl group having 1 to 20 carbon atoms, for example, monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl; an aryloxysilyl group having 6 to 42 carbon atoms, for example, triphenyloxysilyl; an aryloxysilyl group having 6 to 42 carbon atoms, for example, triphenyloxysilyl; a phosphoryl group (preferably a phosphoric acid group having 0 to 20 carbon atoms, for example, -OP(=O)(R, Ｐ ) ２ ), a phosphonyl group (preferably a phosphonyl group having 0 to 20 carbon atoms, for example, —P(═O)(R Ｐ ) ２ ), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for example, —P(R Ｐ ) ２ ), a phosphonic acid group (preferably a phosphonic acid group having 0 to 20 carbon atoms, for example, —PO(OR Ｐ ) ２ ), sulfo group (sulfonic acid group), carboxy group, hydroxy group, sulfanyl group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). Ｐis a hydrogen atom or a substituent (preferably a group selected from the substituent Z). Each of the groups listed as the substituent Z may be further substituted with the substituent Z. The alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and / or alkynylene group may be cyclic or chain-like, and may be linear or branched.

[0084] Physical Properties or Characteristics of Polymer (P) The polymer (P) preferably has the following physical properties or characteristics. The weight-average molecular weight of the polymer (P) is not particularly limited, and is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more. The upper limit of the weight-average molecular weight is essentially 100,000 or less, but is preferably 50,000 or less. From the viewpoints of dispersion stability, resistance, and cycle characteristics, it is more preferably 30,000 or less, even more preferably 20,000 or less, particularly preferably 15,000 or less, and particularly preferably 10,000 or less. When the suitable polymer (P) of the present invention has a graft structure, its weight-average molecular weight can be any weight-average molecular weight within the above range, but in a preferred embodiment, it is preferably 3,000 to 30,000, and more preferably 4,000 to 15,000. The weight average molecular weight of the polymer (P) can be adjusted appropriately by changing the type and content of the polymerization initiator, the polymerization time, the polymerization temperature, and the like.

[0085] In the polymer (P), the ratio [Mw / Mn] of the weight-average molecular weight Mw to the number-average molecular weight Mn (also referred to as molecular weight distribution) is not particularly limited and can be any suitable value. The ratio [Mw / Mn] can be, for example, 3.5 or less. However, from the viewpoints of dispersion stability, resistance, and cycle characteristics, it is preferably 3.0 or less, more preferably 1.3 to 2.5, even more preferably 1.4 to 2.0, and particularly preferably 1.5 to 1.8. The ratio [Mw / Mn] is calculated using the measured values ​​of the weight-average molecular weight Mw and number-average molecular weight Mn of the polymer (P). In the present invention, depending on the weight-average molecular weight and molecular weight distribution, the polymer (P) may contain low-molecular-weight components corresponding to the oligomer (O1) described below. Typically, the polymer (P) is purified after synthesis before use, but low-molecular-weight components by-produced during the synthesis of the polymer (P) can also be used as the oligomer (O1).

[0086] - Measurement of Molecular Weight - In the present invention, unless otherwise specified, the molecular weight of the polymer (P), oligomer (O1), or polymer chain refers to the weight-average molecular weight or number-average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene. Examples of the measurement method include a method set under the following condition 1 or condition 2 (priority). However, depending on the type of polymer (P), oligomer (O1), or polymer chain, an appropriate eluent may be selected and used. (Condition 1) Column: Two TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) connected together Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40°C Carrier flow rate: 1.0 ml / min Sample concentration: 0.1 mass% Detector: RI (refractive index) detector (Condition 2) Column: A column connected together with TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) is used. Carrier: Tetrahydrofuran Measurement temperature: 40°C Carrier flow rate: 1.0 ml / min Sample concentration: 0.1 mass% Detector: RI (refractive index) detector

[0087] The polymer (P) may be a non-crosslinked polymer or a crosslinked polymer. Furthermore, when crosslinking of the polymer (P) progresses due to heating or application of voltage, the polymer (P) may have a molecular weight greater than the above-mentioned range. Preferably, the polymer (P) has a weight-average molecular weight within the above-mentioned range at the start of use of the all-solid-state secondary battery.

[0088] The polymer (P) is preferably amorphous. In the present invention, the term "amorphous" typically means that an endothermic peak due to crystalline melting is not observed when measured at the glass transition temperature. The water concentration of the polymer (P) is preferably 100 ppm (by mass) or less. The polymer (P) may be crystallized and dried, or the polymer solution or dispersion may be used as is.

[0089] <Oligomer (Ol)> The polymer composition of the present invention contains one or more oligomers (Ol). The oligomer (Ol) contained in the polymer composition of the present invention is a low-molecular-weight polymer having a weight-average molecular weight of 1,000 or less. By using an oligomer (Ol) having the above weight-average molecular weight in combination with the polymer (P), the nonaqueous secondary battery composition exhibits excellent dispersion stability at both room temperature and high temperature. The weight-average molecular weight of the oligomer (Ol) is preferably 300 to 1,000, more preferably 500 to 1,000, in order to further improve dispersion stability and achieve excellent resistance and cycle characteristics. The weight-average molecular weight of the oligomer (Ol) is the value measured by the method described for the polymer (P). The weight-average molecular weight of the oligomer (Ol) can be appropriately adjusted by changing the type and content of the polymerization initiator, polymerization time, polymerization temperature, etc.

[0090] The oligomer (Ol) contained in the polymer composition of the present invention is not particularly limited, and a low-molecular-weight polymer of an appropriate polymer can be used. Low-molecular-weight polymers of various polymers used in non-aqueous secondary batteries can be used without particular limitation. Examples of the appropriate polymer include the polymers described in the polymer (P) having a specific bond or a polymer chain of a carbon-carbon double bond in the main chain, and include the step-growth polymers and chain-growth polymers described above. The oligomer (Ol) is preferably a low-molecular-weight polymer of a polymer that functions as a dispersant for solid particles in the non-aqueous secondary battery composition. The oligomer (Ol) is preferably a low-molecular-weight polymer of a polymer that also functions as a binder in a layer formed from the non-aqueous secondary battery composition. Among the above, the oligomer (Ol) is preferably a low-molecular-weight polymer of a chain-growth polymer, more preferably a low-molecular-weight polymer of a hydrocarbon polymer, a vinyl polymer, or a (meth)acrylic polymer, and even more preferably a low-molecular-weight polymer of a (meth)acrylic polymer.

[0091] In one preferred embodiment, the oligomer (O1) contains at least one of the components (A), (X), and other components described in connection with the polymer (P). In the present invention, the oligomer (O1) containing at least one of the components (A), (X), and other components may be referred to as a preferred oligomer (O1).

[0092] In the constituent component (A) which may be contained in the suitable oligomer (Ol), the polar functional group is preferably contained in the molecular chain which will become the side chain of the suitable oligomer (Ol), and more preferably incorporated, for example, into the interior or terminal of the molecular chain which will become the side chain of the suitable oligomer (Ol), as in the case of the polymer (P). In the present invention, the molecular chain which will become the side chain of the suitable oligomer (Ol) refers to the molecular chain which constitutes the side chain of the suitable oligomer (Ol) into which the constituent component (A) is incorporated, and is a molecular chain other than the molecular chain which constitutes the main chain of the suitable oligomer (Ol), usually a molecular chain bonded to the molecular chain (atomic group) which constitutes the main chain.

[0093] In the constituent (X) that may be contained in the suitable oligomer (Ol), the polymer chain may be present in the partial structure that will become the main chain of the suitable oligomer (Ol), but it is preferable that the polymer chain be present in the molecular chain that will become the side chain of the suitable oligomer (Ol), and more preferably, it is incorporated, for example, into the interior or end of the molecular chain that will become the side chain of the suitable oligomer (Ol). Such a constituent (X) can incorporate a graft structure into the chemical structure of the suitable oligomer (Ol). In the present invention, the molecular chain that will become the side chain of the suitable oligomer (Ol) refers to a molecular chain that constitutes the side chain of the suitable oligomer (Ol) into which the constituent (X) is incorporated, and is a molecular chain other than the molecular chain that constitutes the main chain of the suitable oligomer (Ol), usually a molecular chain bonded to the molecular chain (atomic group) that constitutes the main chain.

[0094] The constituent (X) that may be contained in the suitable oligomer (O1) is the same as the constituent (X) described above for the polymer (P), but its molecular weight is determined taking into account the weight-average molecular weight of the suitable oligomer (O1). The molecular weight of the constituent (X) that may be contained in the suitable oligomer (O1) is, for example, preferably 200 or more, more preferably 400 or more. There is no particular upper limit as long as the weight-average molecular weight of the suitable oligomer (O1) is 1,000 or less, and for example, it is more preferably 800 or less, and even more preferably 600 or less. Furthermore, in the constituent (X), the degree of polymerization of all structural units that form the polymer chain is, for example, preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 5.

[0095] Other constituent components that may be contained in the suitable oligomer (O1) are the same as the other constituent components described above for the polymer (P).

[0096] A suitable oligomer (O1) may contain one or more of the above-mentioned components, and may also contain a fourth component that does not correspond to any of the above-mentioned components. Suitable oligomers (O1) containing any one of the above-mentioned components include, for example, a homopolymer of one type of component (A) or a copolymer of two or more types of component (A), a homopolymer of one type of component (X) or a copolymer of two or more types of component (X), a homopolymer of one type of other component or a copolymer of two or more types of other component, and polymers containing a fourth component in addition to these polymers. Among these, a homopolymer of one type of component (A) or a copolymer of two or more types of component (A) is preferred, and a homopolymer of one type of component (A) is more preferred, in that it can improve dispersion stability together with the polymer (P) and thereby enhance resistance and cycle characteristics.

[0097] Examples of oligomers (O1) containing two or more of the above-mentioned components include copolymers that appropriately combine two or three of the above-mentioned components. Among these, including component (A) is a preferred embodiment because it improves dispersion stability together with polymer (P) and enhances resistance and cycle characteristics. Furthermore, in addition to component (A), component (X) may also be included. When a suitable oligomer (O1) contains component (X), the dispersion stability-improving effect of component (A) can be reinforced. Furthermore, other components may also be included in addition to component (A). Specific examples of oligomers (O1) containing two or more of the above-mentioned components include copolymers containing component (A) and component (X), copolymers containing component (A) and the other component, copolymers containing component (X) and the other component, and copolymers containing component (A), component (X), and the other component.

[0098] Among the above, preferred examples of the suitable oligomer (O1) include a homopolymer of one type of component (A), a copolymer of two or more types of component (A), and a copolymer containing the component (X) and the other component(s) described above. A homopolymer of one type of component (A) is more preferred, and a homopolymer of a component derived from the (meth)acrylamide compound described above is even more preferred.

[0099] The content of each of the above constituent components in the oligomer (O1) containing two or more of the above constituent components is not particularly limited and may be set appropriately. For example, the total content of constituent component (A) in the oligomer (O1) containing two or more of the above constituent components is preferably 5% by mass or more but less than 100% by mass, more preferably 20% by mass or more but less than 100% by mass, and even more preferably 50% by mass or more but less than 100% by mass. The total content of constituent component (X) can be 0 to 100% by mass, and the total content of the other constituent components is preferably 0 to 95% by mass, more preferably 0% by mass or more but less than 80% by mass, and even more preferably 0% by mass or more but less than 50% by mass.

[0100] The oligomer (O1) may be a commercially available product or a synthetic product. The synthesis method is the same as the synthesis method for the polymer (P), but the polymerization conditions can be appropriately changed so that the weight-average molecular weight is 1,000 or less. The oligomer (O1) is usually synthesized separately from the polymer (P) and mixed with the polymer (P). However, as described above, by adjusting and changing the polymerization conditions for the polymer (P), the oligomer (O1) can be by-produced simultaneously with the synthesis of the polymer (P), and the polymer (P) can be used as a mixture of the oligomer (O1).

[0101] The presence and content of oligomer (O1) in the polymer composition of the present invention can be confirmed by conventional analytical methods such as gas chromatography (GC) and gel permeation chromatography (GPC). The content of oligomer (O1) can be determined as the amount mixed with polymer (P) during the preparation of the polymer composition of the present invention, or can be determined as the value obtained by subjecting the polymer composition of the present invention (a mixture of polymer (P) and oligomer (O1)) to the above analytical method. Furthermore, structural analysis of oligomer (O1) can be performed by subjecting oligomer (O1) isolated from the polymer composition of the present invention to conventional analytical methods such as nuclear magnetic resonance spectroscopy, infrared spectroscopy, and mass spectrometry.

[0102] - Physical properties or characteristics of oligomer (Ol) - The oligomer (Ol) preferably has the following physical properties or characteristics. The oligomer (Ol) may be a non-crosslinked polymer or a crosslinked polymer. Furthermore, when crosslinking of the oligomer (Ol) progresses due to heating or application of voltage, the molecular weight may be larger than the above-mentioned molecular weight. Preferably, the oligomer (Ol) has a weight-average molecular weight within the above-mentioned range at the start of use of the all-solid-state secondary battery. The oligomer (Ol) is preferably amorphous. The water concentration of the oligomer (Ol) is preferably 100 ppm (by mass) or less. Furthermore, the oligomer (Ol) may be crystallized and dried, or the oligomer solution or dispersion may be used as is.

[0103] <Polymer (P) and Oligomer (Ol)> The combination of polymer (P) and oligomer (Ol) contained in the polymer composition of the present invention is not particularly limited, and the polymer (P) and oligomer (Ol) can be appropriately selected from those described above. Regarding the combination of polymer (P) and oligomer (Ol), in terms of the type of polymer, a combination of polymers of the same type is preferred in terms of compatibility, a combination of chain-polymerized polymers is more preferred, and a combination of (meth)acrylic polymers is even more preferred. Regarding the combination of polymer (P) and oligomer (Ol), in terms of the type of constituent components, the types of constituent components contained in polymer (P) and the types of constituent components contained in oligomer (Ol) may be all the same or all different, but it is preferable that they are partially the same. In the present invention, regarding the combination of polymer (P) and oligomer (Ol), in a combination of polymers of the same type, it is more preferable that the types of constituent components contained in polymer (P) and the types of constituent components contained in oligomer (Ol) are partially the same.

[0104] In the present invention, when comparing the constituent components contained in the polymer (P) with the constituent components contained in the oligomer (Ol), it is preferable that the types of constituent components contained in the polymer (P) and the types of constituent components contained in the oligomer (Ol) are partially the same, i.e., that one of the polymer (P) and the oligomer (Ol) contains at least one constituent component different from the constituent component contained in the other. Since the polymer (P) and the oligomer (Ol) are not the same polymer, the dispersion stability of each can be complemented, and the dispersion stability exhibited by the polymer composition of the present invention can be highly improved. In the present invention, since the number of constituent components contained in the polymer (P) is usually large, the polymer (P) will contain a constituent component different from the constituent component contained in the oligomer (Ol), i.e., a constituent component other than the constituent component contained in the oligomer (Ol), but this is not limited thereto. The different constituent component may be any of the constituent components described above, but is preferably at least one of the constituent component (X) and another constituent component. The number of different components is not particularly limited, but can be from 1 to 5, and is usually 1 or 2.

[0105] On the other hand, in the present invention, it is preferable that the polymer (P) and the oligomer (Ol) contain at least one of the same constituents. In the present invention, "the same constituent" means that the chemical structure of the compound from which the constituent is derived is the same. For example, if one of the compared compounds has a substituent, the comparison is made based on the chemical structure of the basic skeleton excluding the substituent. A polymer (P) and an oligomer (Ol) containing at least one of the same constituents are different from a simple combination of two different types of polymers, for example, as a binder for an all-solid-state secondary battery; that is, a combination of polymers of the same type is preferable. By using a polymer (P) and an oligomer (Ol) containing at least one of the same constituents in combination, the compatibility of the polymer (P) and the oligomer (Ol) is improved, thereby highly improving the dispersion stability exhibited by the polymer composition of the present invention. The same constituent contained in the polymer (P) and the oligomer (Ol) may be any of the constituents described above, but in terms of dispersion stability, resistance, and cycle characteristics, it is preferably the constituent (A), and more preferably a constituent derived from an acrylamide compound. The number of the same constituent components contained in the polymer (P) and the oligomer (O1) is not particularly limited, but can be 1 to 5, and is usually 1 or 2. In the present invention, the number of types of constituent components contained in the polymer (P) is usually large, and therefore the polymer (P) contains the same constituent components as the constituent components contained in the oligomer (O1) and constituent components different from the constituent components contained in the oligomer (O1).

[0106] In the present invention, when comparing the constituent components contained in polymer (P) with the constituent components contained in oligomer (Ol), the ratio of the number of types of constituent components that are the same as those contained in oligomer (Ol) to the total number of types of constituent components contained in polymer (P) (also referred to as the constituent identity rate) can be 0 to 100%, but from the viewpoint of highly improving the dispersion stability exhibited by the polymer composition of the present invention, it is preferably 20 to 100%, more preferably 25 to 50%, and even more preferably 30 to 50%. For example, Example 1 described below combines "Polymer B-1 containing tBuAAm and LA" as polymer (P) and "Oligomer A containing only tBuAAm" as oligomer (Ol), and therefore, of the two types of total constituent components contained in polymer B-1, one type of constituent, tBuAAm, is the same as the constituent contained in oligomer (Ol). Therefore, the constituent identity rate between polymer (P) and oligomer (Ol) is 50%.

[0107] In the present invention, the above-mentioned differences between the polymer (P) and the oligomer (O1) are focused on the types of constituent components, and the contents of the constituent components are not important.

[0108] <Other Components> The polymer composition of the present invention typically contains the polymer (P) and oligomer (O1), but may also contain components used during polymerization, such as a polymerization initiator, or decomposition products thereof. The polymer composition of the present invention can also be used as a polymer solution of the present invention by dissolving or dispersing it in a dispersion medium or the like. The dispersion medium used in this case is not particularly limited, and examples include water, organic solvents described below, and mixtures of water and organic solvents. It can be appropriately selected depending on the application. For example, when the polymer composition of the present invention is used as a material for forming a constituent layer of an all-solid-state secondary battery, an organic solvent is usually selected. When the polymer composition of the present invention contains a dispersion medium, the content of the dispersion medium is not particularly limited and can be appropriately set. For example, it can be 40 to 99% by mass, and preferably 55 to 95% by mass, of the polymer composition of the present invention. In this case, the total content of the polymer (P) and oligomer (O1) relative to the total mass of the polymer composition including the dispersion medium is preferably 1 to 60% by mass, more preferably 5 to 40% by mass, and even more preferably 8 to 35% by mass. The dispersion medium contained in the polymer composition of the present invention may be the same as or different from the dispersion medium contained in the nonaqueous secondary battery composition of the present invention.

[0109] In the polymer composition of the present invention, the content of the oligomer (Ol) is 1 to 30% by mass relative to the total 100% by mass of the polymer (P) and the oligomer (Ol). When the oligomer (Ol) is contained in this range, the dispersion stability exhibited by the polymer composition of the present invention can be improved, and thus the resistance and cycle characteristics can also be improved. The content of the oligomer (Ol) is preferably 2 to 20% by mass, and more preferably 3 to 12% by mass, in order to further improve the dispersion stability exhibited by the polymer composition of the present invention. The content of the polymer (P) relative to the total 100% by mass of the polymer (P) and the oligomer (Ol) can be appropriately determined taking into account the content of the oligomer (Ol), etc., and can be, for example, 70 to 99% by mass, preferably 80 to 98% by mass, and more preferably 88 to 97% by mass. The total content of the polymer (P) and the oligomer (Ol) in the polymer composition of the present invention can be appropriately determined taking into account the content of the other components. For example, when the polymer composition of the present invention does not contain a dispersion medium, the total content of the polymer (P) and the oligomer (O1) can be 50 to 100 mass% of the total mass of the polymer composition of the present invention (solid components excluding the dispersion medium), and is preferably 80 to 100 mass%. When the polymer composition of the present invention contains a dispersion medium, the total content is appropriately determined taking into consideration the content of the dispersion medium and the content of the solid components in the total mass, as specifically described above. The contents of other components in the polymer composition of the present invention can be appropriately determined.

[0110] [Nonaqueous Secondary Battery Composition] The nonaqueous secondary battery composition of the present invention is a material for forming a constituent layer of a nonaqueous secondary battery, and is a composition containing the polymer composition of the present invention. In the present invention, when the nonaqueous secondary battery composition is used as a material for forming a constituent layer of an all-solid-state secondary battery, it is referred to as an inorganic solid electrolyte-containing composition. When used as a material for forming an electrode layer of a nonaqueous electrolyte secondary battery, it is also referred to as a nonaqueous electrolyte secondary battery electrode composition. The nonaqueous secondary battery composition of the present invention preferably contains, in addition to the polymer composition of the present invention, appropriate components depending on the intended use. For example, a nonaqueous electrolyte secondary battery electrode composition contains the polymer composition of the present invention and an active material, and optionally contains a conductive additive, other components described below, a dispersion medium, etc. On the other hand, an inorganic solid electrolyte-containing composition contains the polymer composition of the present invention and an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and optionally contains an active material, a conductive additive, a dispersion medium, and other components described below. In the present invention, in the nonaqueous secondary battery composition, the components contained in the polymer composition of the present invention do not need to be present integrally as the polymer composition of the present invention, and the components may be present independently (separately).

[0111] As described above, the non-aqueous secondary battery composition of the present invention exhibits excellent dispersion stability of solid particles such as inorganic solid electrolytes. Furthermore, in a preferred embodiment, the composition also exhibits excellent handling properties, such as a moderate viscosity and high fluidity, enabling the formation of a favorable coating film. This dispersion stability and sanding properties can also be achieved by increasing the solid content of the non-aqueous secondary battery composition. The solid content is not uniquely determined by the temperature of the composition, the type of solid particles, and other factors. However, it can be, for example, 40% by mass or more, and even 50% by mass or more, at 25°C. The non-aqueous secondary battery composition of the present invention, which exhibits the above-described properties, can be used as a material for forming constituent layers in non-aqueous secondary batteries to realize non-aqueous secondary battery sheets having low-resistance constituent layers, and non-aqueous secondary batteries with low resistance (high conductivity) and excellent cycle characteristics. Therefore, the non-aqueous secondary battery composition of the present invention can be preferably used as a material for forming constituent layers in non-aqueous secondary battery sheets (including electrode sheets for non-aqueous secondary batteries) or non-aqueous secondary battery sheets.

[0112] In the non-aqueous secondary battery composition of the present invention, the polymer (P) and oligomer (O1) among the components contained in the polymer composition of the present invention may not be soluble in the dispersion medium contained in the non-aqueous secondary battery composition and may be dispersed in a particulate form, but it is preferable that they are soluble. That is, the polymer (P) and oligomer (O1) in the non-aqueous secondary battery composition are preferably present in a dissolved state in the dispersion medium, depending on their contents. When the polymer (P) and oligomer (O1) are dissolved, they stably exhibit the function of dispersing solid particles in the dispersion medium, thereby further improving the dispersion stability of the solid particles in the non-aqueous secondary battery composition. In the present invention, the phrase "polymer (P) and oligomer (O1) dissolved in the dispersion medium" does not necessarily mean that all of the polymer (P) and oligomer (O1) are dissolved in the dispersion medium. For example, as long as the solubility in the dispersion medium is 80% or more, a portion of the polymer (P) and oligomer (O1) may be insoluble in the nonaqueous secondary battery composition. The solubility is measured as follows. Specifically, the measurement object is a polymer (P) and oligomer (O1) having the same composition (type and content ratio) as the polymer (P) and oligomer (O1) in the polymer composition of the present invention. A specified amount of the measurement object is weighed into a glass bottle, to which 100 g of the same type of dispersion medium as the dispersion medium contained in the nonaqueous secondary battery composition is added. The mixture is stirred at 25°C for 24 hours at a rotation speed of 80 rpm on a mix rotor. The transmittance of the mixture thus obtained after 24 hours of stirring is measured under the following conditions. This test (transmittance measurement) is performed by changing the amount of the substance to be measured dissolved (the above-mentioned specified amount), and the upper limit concentration X (mass %) at which the transmittance becomes 99.8% is defined as the solubility of the substance to be measured in the above-mentioned dispersion medium. <Transmittance measurement conditions> Dynamic light scattering (DLS) measurement Apparatus: DLS measurement apparatus DLS-8000 manufactured by Otsuka Electronics Laser wavelength, output: 488 nm / 100 mW Sample cell: NMR tube

[0113] In the present invention, the solubility of the polymer (P) and the oligomer (O1) in a dispersion medium can be appropriately imparted by the structure, composition (type and content of constituent components), weight average molecular weight, and combination with the dispersion medium of each of the polymer (P) and the oligomer (O1).

[0114] When the polymer (P) and oligomer (O1) contained in the polymer composition of the present invention are particulate (insoluble in the dispersion medium contained in the non-aqueous secondary battery composition), their shapes are not particularly limited and may be flat, amorphous, etc., but are preferably spherical or granular. In this case, the average particle diameter of the particulate polymer (P) and oligomer (O1) in the non-aqueous secondary battery composition is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 30 nm or more. The upper limit is preferably 5 μm or less, more preferably 1 μm or less. The average particle diameter of the polymer (P) and oligomer (O1) can be measured in the same manner as the particle diameter of the inorganic solid electrolyte. The average particle diameter of the polymer (P) and oligomer (O1) can be adjusted, for example, by the type of dispersion medium, the composition of the polymer (P) and oligomer (O1), etc.

[0115] The non-aqueous secondary battery composition of the present invention is preferably a slurry in which solid particles such as an inorganic solid electrolyte are dispersed in a dispersion medium. Furthermore, the non-aqueous secondary battery composition of the present invention is preferably a non-aqueous composition. In the present invention, the non-aqueous composition includes not only a water-free embodiment but also a form in which the water content (also referred to as water content) is preferably 500 ppm or less. In the non-aqueous composition, the water content is more preferably 200 ppm or less, even more preferably 100 ppm or less, and particularly preferably 50 ppm or less. When the non-aqueous secondary battery composition is a non-aqueous composition, it can dissolve the polymer (P) and oligomer (O1) and suppress the deterioration and decomposition of solid particles, particularly the inorganic solid electrolyte. The water content refers to the amount of water contained in the non-aqueous secondary battery composition (mass ratio relative to the non-aqueous secondary battery composition), specifically, the value measured by Karl Fischer titration after filtering through a 0.02 μm membrane filter.

[0116] The non-aqueous secondary battery composition of the present invention also includes an embodiment containing an active material and further a conductive additive, etc., in addition to the inorganic solid electrolyte (the composition in this embodiment is referred to as an electrode composition). Components contained in the non-aqueous secondary battery composition of the present invention and components that can be contained therein are described below.

[0117] <Polymer Composition of the Present Invention> The non-aqueous secondary battery composition of the present invention contains the above-described polymer composition of the present invention. The non-aqueous secondary battery composition may contain one or more types of the polymer composition of the present invention (polymer (P) and oligomer (O1)). The content of the polymer composition of the present invention in the non-aqueous secondary battery composition can be determined appropriately. For example, in terms of dispersion stability of the solid particles, resistance, and cycle characteristics, it is preferably 0.1 to 5.0 mass%, more preferably 0.2 to 4.0 mass%, and even more preferably 0.3 to 2.0 mass%. Furthermore, for the same reasons, the content of the polymer composition of the present invention in 100 mass% of the solid content of the non-aqueous secondary battery composition (corresponding to the solid content excluding the dispersion medium) is preferably 0.1 to 6.0 mass%, more preferably 0.2 to 5.0 mass%, and even more preferably 0.3 to 2.5 mass%. The contents of the polymer (P) and oligomer (O1) in the non-aqueous secondary battery composition are determined by the above-mentioned contents of the polymer composition of the present invention and the contents of each component in the polymer composition of the present invention. For example, the content of the polymer (P) in the non-aqueous secondary battery composition is preferably 0.1 to 2.5 mass%, more preferably 0.2 to 2.0 mass%, and even more preferably 0.2 to 1.0 mass%, and the content of the oligomer (O1) in the non-aqueous secondary battery composition is preferably 0.0005 to 0.75 mass%, more preferably 0.0015 to 0.5 mass%, and even more preferably 0.0025 to 0.35 mass%. Furthermore, the content of the polymer (P) in 100% by mass of the solid content of the non-aqueous secondary battery composition (corresponding to the solid content excluding the dispersion medium) is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 4.0% by mass, and even more preferably 0.5 to 2.0% by mass, and the content of the oligomer (O1) in 100% by mass of the solid content of the non-aqueous secondary battery composition (corresponding to the solid content excluding the dispersion medium) is preferably 0.001 to 1.5% by mass, more preferably 0.003 to 1.0% by mass, and even more preferably 0.005 to 0.75% by mass.In the present invention, the mass ratio of the combined mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the polymer composition of the present invention (corresponding to the solid content excluding the dispersion medium) at 100% by mass of solid content [(mass of inorganic solid electrolyte + mass of active material) / (total mass of the polymer composition of the present invention)] is preferably in the range of 2000 to 1. This ratio is more preferably 1000 to 10, and even more preferably 500 to 20.

[0118] <Inorganic Solid Electrolyte> The nonaqueous secondary battery composition of the present invention, particularly the inorganic solid electrolyte-containing composition of the present invention, contains an inorganic solid electrolyte. In the present invention, the inorganic solid electrolyte refers to an inorganic solid electrolyte, and the solid electrolyte refers to a solid electrolyte capable of moving ions therein. Since it does not contain an organic substance as the main ion-conducting material, it is clearly distinguished from organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO) and the like, and organic electrolyte salts typified by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and the like). Furthermore, since inorganic solid electrolytes are solid in a steady state, they are not usually dissociated or liberated into cations and anions. In this respect, inorganic electrolyte salts (LiPF ) that are dissociated or liberated into cations and anions in an electrolytic solution or a polymer are not easily dissociated or liberated into cations and anions. ６ , LiBF ４, lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.). The inorganic solid electrolyte is not particularly limited as long as it has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and generally does not have electronic conductivity. When the all-solid-state secondary battery of the present invention is a lithium-ion battery, the inorganic solid electrolyte preferably has ionic conductivity of lithium ions. The inorganic solid electrolyte can be appropriately selected from solid electrolyte materials commonly used in all-solid-state secondary batteries. Examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes, (ii) oxide-based inorganic solid electrolytes, (iii) halide-based inorganic solid electrolytes, and (iv) hydride-based inorganic solid electrolytes. In the present invention, a sulfide-based inorganic solid electrolyte, which is generally prone to deterioration and decomposition, can be used, and a better interface can be formed between the active material and the inorganic solid electrolyte, effectively suppressing an increase in interfacial resistance.

[0119] (i) Sulfide-Based Inorganic Solid Electrolyte The sulfide-based inorganic solid electrolyte preferably contains sulfur atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. The sulfide-based inorganic solid electrolyte preferably contains at least Li, S, and P as elements and has lithium ion conductivity, but may contain elements other than Li, S, and P as appropriate.

[0120] Examples of sulfide-based inorganic solid electrolytes include lithium ion conductive inorganic solid electrolytes having a composition represented by the following formula (S1): ａ１ M ｂ１ P ｃ１ S ｄ１ A ｅ１(S1) In formula (S1), L represents an element selected from Li, Na, and K, and Li is preferred. M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. A represents an element selected from I, Br, Cl, and F. a1 to e1 represent the composition ratio of each element, and a1:b1:c1:d1:e1 satisfies the ratio of 1-12:0-5:1:2-12:0-10. a1 is preferably 1-9, and more preferably 1.5-7.5. b1 is preferably 0-3, and more preferably 0-1. d1 is preferably 2.5-10, and more preferably 3.0-8.5. e1 is preferably 0-5, and more preferably 0-3.

[0121] The composition ratio of each element can be controlled by adjusting the blending amounts of raw material compounds when producing the sulfide-based inorganic solid electrolyte, as described below.

[0122] The sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass-ceramic), or may be only partially crystallized. For example, Li-P-S-based glass containing Li, P, and S, or Li-P-S-based glass-ceramic containing Li, P, and S can be used. The sulfide-based inorganic solid electrolyte may be, for example, lithium sulfide (Li ２ S), phosphorus sulfide (e.g., diphosphorus pentasulfide (P ２ S ５ )), elemental phosphorus, elemental sulfur, sodium sulfide, hydrogen sulfide, lithium halides (e.g., LiI, LiBr, LiCl), and sulfides of the elements represented by M (e.g., SiS ２ , SnS, GeS ２ ) can be produced by reacting at least two or more raw materials.

[0123] Li in Li-P-S glass and Li-P-S glass ceramics ２ S and P ２ S ５ The ratio of Li ２ S:P ２ S ５ The molar ratio of Li is preferably 60:40 to 90:10, more preferably 68:32 to 78:22. ２ S and P ２ S ５By setting the ratio to this range, the lithium ion conductivity can be made high. Specifically, the lithium ion conductivity is preferably set to 1×10 －４ S / cm or more, more preferably 1×10 －３ There is no particular upper limit, but it can be 1 × 10 －１ It is practical to have a viscosity of 200 S / cm or less.

[0124] As a specific example of a sulfide-based inorganic solid electrolyte, a combination of raw materials is shown below. For example, Li ２ S-P ２ S ５ , Li ２ S-P ２ S ５ -LiCl, Li ２ S-P ２ S ５ -H ２ S., Li. ２ S-P ２ S ５ -H ２ S-LiCl, Li ２ S-LiI-P ２ S ５ , Li ２ S-LiI-Li ２ O-P ２ S ５ , Li ２ S-LiBr-P ２ S ５ , Li ２ S-Li ２ O-P ２ S ５ , Li ２ S-Li ３ P.O. ４ -P ２ S ５ , Li ２ S-P ２ S ５ -P ２ O ５ , Li ２ S-P ２ S ５ -SiS ２ , Li ２ S-P ２ S ５ -SiS ２ -LiCl, Li ２ S-P２ S ５ -SnS、Li ２ S-P ２ S ５ -Al ２ S ３ 、Li ２ S-GeS ２ 、Li ２ S-GeS ２ -ZnS、Li ２ S-Ga ２ S ３ 、Li ２ S-GeS ２ -Ga ２ S ３ 、Li ２ S-GeS ２ -P ２ S ５ 、Li ２ S-GeS ２ -Sb ２ S ５ 、Li ２ S-GeS ２ -Al ２ S ３ 、Li ２ S-SiS ２ 、Li ２ S-Al ２ S ３ 、Li ２ S-SiS ２ -Al ２ S ３ 、Li ２ S-SiS ２ -P ２ S ５ 、Li ２ S-SiS ２ -P ２ S ５ -LiI、Li ２ S-SiS ２ -LiI、Li ２ S-SiS ２ -Li ４ SiO ４ 、Li ２ S-SiS ２ -Li ３ PO ４ 、Li １０ GeP ２ S １２However, the mixing ratio of each raw material is not important. As a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition, for example, an amorphization method can be mentioned. Examples of the amorphization method include a mechanical milling method, a solution method, and a melt quenching method. This is because processing at room temperature becomes possible, and the manufacturing process can be simplified.

[0125] (ii) Oxide-based inorganic solid electrolyte The oxide-based inorganic solid electrolyte preferably contains oxygen atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. The oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1×10 －６ S / cm or more, and 5×10 －６ S / cm or more is more preferable, and 1×10 －５ The upper limit is not particularly limited, but it is preferably 1 × 10 －１ It is practical to have a viscosity of 200 S / cm or less.

[0126] Specific examples of the compound include Li ｘａ La ｙａ TiO ３ [xa satisfies 0.3≦xa≦0.7, and ya satisfies 0.3≦ya≦0.7.] (LLT); Li ｘｂ La ｙｂ Zr ｚｂ M ｂｂ ｍｂ O ｎｂ (M ｂｂ is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn. xb satisfies 5≦xb≦10, yb satisfies 1≦yb≦4, zb satisfies 1≦zb≦4, mb satisfies 0≦mb≦2, and nb satisfies 5≦nb≦20; Li ｘｃ B ｙｃ M ｃｃ ｚｃ O ｎｃ (M ｃｃis one or more elements selected from C, S, Al, Si, Ga, Ge, In, and Sn. xc satisfies 0<xc≦5, yc satisfies 0<yc≦1, zc satisfies 0<zc≦1, and nc satisfies 0<nc≦6; Li ｘｄ (Al, Ga) ｙｄ (Ti, Ge) ｚｄ Si ａｄ P ｍｄ O ｎｄ (xd satisfies 1≦xd≦3, yd satisfies 0≦yd≦1, zd satisfies 0≦zd≦2, ad satisfies 0≦ad≦1, md satisfies 1≦md≦7, and nd satisfies 3≦nd≦13); Li （３－２ｘｅ） M ｅｅ ｘｅ D ｅｅ O(xe represents a number between 0 and 0.1, and M ｅｅ represents a divalent metal atom. ｅｅ represents a halogen atom or a combination of two or more halogen atoms; Li ｘｆ Si ｙｆ O ｚｆ (xf satisfies 1≦xf≦5, yf satisfies 0<yf≦3, and zf satisfies 1≦zf≦10); Li ｘｇ S ｙｇ O ｚｇ (xg satisfies 1≦xg≦3, yg satisfies 0<yg≦2, and zg satisfies 1≦zg≦10); Li ３ BO ３ Li ３ BO ３ -Li ２ SO ４ Li ２ Alumni ２ O ３ -P ２ O ５ Li ２ O—SiO ２ Li ６ BaLa ２ Ta ２ O １２ Li ３ P.O. （４－３／２ｗ） N ｗ (w is w<1); Li having a LISICON (Lithium super ionic conductor) type crystal structure ３．５ Zn０．２５ GeO ４ La having a perovskite crystal structure ０．５５ Li ０．３５ TiO ３ LiTi having a NASICON (sodium super ionic conductor) type crystal structure ２ P ３ O １２ Li １＋ｘｈ＋ｙｈ (Al, Ga) ｘｈ (Ti, Ge) ２－ｘｈ Si ｙｈ P ３－ｙｈ O １２ (xh satisfies 0≦xh≦1, and yh satisfies 0≦yh≦1); Li having a garnet-type crystal structure ７ La ３ Zr ２ O １２ (LLZ), etc. Phosphorus compounds containing Li, P, and O are also desirable. For example, lithium phosphate (Li ３ P.O. ４ ) LiPON, in which part of the oxygen element of lithium phosphate is replaced with nitrogen element; LiPOD １ (D １ is preferably one or more elements selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au. １ ON (A １ is one or more elements selected from Si, B, Ge, Al, C and Ga.) can also be preferably used.

[0127] (iii) Halide-based inorganic solid electrolyte The halide-based inorganic solid electrolyte is preferably a compound containing a halogen atom, having ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and having electronic insulation. The halide-based inorganic solid electrolyte is not particularly limited, but examples thereof include LiCl, LiBr, LiI, and Li described in ADVANCED MATERIALS, 2018, 30, 1803075. ３ YBr ６ , Li ３ YCl ６Among them, Li ３ YBr ６ , Li ３ YCl ６ is preferred.

[0128] (iv) Hydride-Based Inorganic Solid Electrolyte The hydride-based inorganic solid electrolyte is preferably a compound that contains hydrogen atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. The hydride-based inorganic solid electrolyte is not particularly limited, but examples thereof include LiBH ４ , Li ４ (BH ４ ) ３ I, 3LiBH ４ -LiCl, etc.

[0129] The inorganic solid electrolyte is preferably in the form of particles in the nonaqueous secondary battery composition. In this case, the particle size (volume-average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more. The upper limit is preferably 100 μm or less, more preferably 50 μm or less. The particle size of the inorganic solid electrolyte is measured by the following procedure. A 1 mass% dispersion of inorganic solid electrolyte particles is prepared by diluting them with water (or heptane in the case of a substance unstable in water) in a 20 mL sample bottle. The diluted dispersion sample is irradiated with 1 kHz ultrasound for 10 minutes and then used for testing immediately thereafter. Using this dispersion sample, data is acquired 50 times using a quartz measurement cell at 25°C using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA Corporation), to obtain the volume-average particle size. For other detailed conditions, etc., refer to the description in Japanese Industrial Standards (JIS) Z 8828:2013 "Particle size analysis - dynamic light scattering method." Five samples are prepared for each level, and the average value is used.

[0130] The method for adjusting the particle size is not particularly limited, and known methods can be applied, such as a method using a conventional pulverizer or classifier. Suitable pulverizers or classifiers include, for example, a mortar, a ball mill, a sand mill, a vibration ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow jet mill, or a sieve. Wet pulverization can be performed in the presence of a dispersion medium such as water or methanol. Classification is preferably performed to obtain the desired particle size. Classification is not particularly limited, and can be performed using a sieve, an air classifier, or the like. Both dry and wet classification methods can be used.

[0131] The non-aqueous secondary battery composition may contain one or more inorganic solid electrolytes. The content of the inorganic solid electrolyte in the non-aqueous secondary battery composition is not particularly limited. However, from the viewpoint of the dispersion state of the solid particles and the resistance, it is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on 100% by mass of the solid content. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less. However, when the non-aqueous secondary battery composition contains an active material described below, the content of the inorganic solid electrolyte in the non-aqueous secondary battery composition is preferably the total content of the active material and the inorganic solid electrolyte within the above range. In the present invention, the solid content (solid components) refers to components that do not volatilize or evaporate when the non-aqueous secondary battery composition is dried at 150°C under a nitrogen atmosphere at an atmospheric pressure of 1 mmHg for 6 hours. Typically, this refers to components other than the dispersion medium described below.

[0132] <Dispersion Medium> The dispersion medium contained in the nonaqueous secondary battery composition of the present invention may be any organic compound that is liquid in the usage environment, and examples thereof include various organic solvents, specifically alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, nitrile compounds, and ester compounds. The dispersion medium may be a nonpolar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a nonpolar dispersion medium is preferred in terms of its excellent dispersibility. A nonpolar dispersion medium generally refers to a dispersion medium that has a low affinity for water. In the present invention, examples of the nonpolar dispersion medium include ester compounds, ketone compounds, ether compounds, aromatic hydrocarbon compounds, and aliphatic hydrocarbon compounds.

[0133] Examples of alcohol compounds include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.

[0134] Examples of the ether compound include alkylene glycols (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol dialkyl ethers (ethylene glycol dimethyl ether, etc.), dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), and cyclic ethers (tetrahydrofuran, dioxane (including 1,2-, 1,3-, and 1,4-isomers), etc.).

[0135] Examples of the amide compound include N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide.

[0136] Examples of amine compounds include triethylamine, diisopropylethylamine, and tributylamine. Examples of ketone compounds include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec-butyl propyl ketone, pentyl propyl ketone, and butyl propyl ketone. Examples of aromatic hydrocarbon compounds include benzene, toluene, xylene, and perfluorotoluene. Examples of aliphatic hydrocarbon compounds include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and diesel. Examples of nitrile compounds include acetonitrile, propionitrile, and isobutyronitrile. Examples of the ester compound include ethyl acetate, propyl acetate, butyl acetate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanoate, pentyl pentanoate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, propyl pivalate, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.

[0137] In the present invention, among these, ether compounds, ketone compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, and ester compounds are preferred, and ester compounds, ketone compounds, aromatic hydrocarbon compounds, and ether compounds are more preferred.

[0138] The number of carbon atoms in the compound constituting the dispersion medium is not particularly limited, and is preferably 2 to 30, more preferably 4 to 20, even more preferably 6 to 15, and particularly preferably 7 to 12.

[0139] The boiling point of the dispersion medium at normal pressure (1 atmosphere: 101,325 Pa) is preferably 50° C. or higher, more preferably 70° C. or higher. The upper limit is preferably 250° C. or lower, more preferably 220° C. or lower.

[0140] The nonaqueous secondary battery composition may contain one or more dispersion media. Examples of dispersion media containing two or more dispersion media include xylene (a mixture of xylene isomers in which the molar ratio of the isomers is ortho-isomer:para-isomer:meta-isomer = 1:5:2), mixed xylenes (a mixture of o-xylene, p-xylene, m-xylene, and ethylbenzene), etc. In the present invention, the content of the dispersion media in the nonaqueous secondary battery composition is not particularly limited and can be set appropriately. For example, the content of the dispersion media in the nonaqueous secondary battery composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass. When a high solids concentration is desired, the content of the dispersion media can be set to 60% by mass or less, or even 50% by mass or less.

[0141] <Active Material> In one preferred embodiment, the nonaqueous secondary battery composition of the present invention contains an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table. Examples of the active material include a positive electrode active material and a negative electrode active material, as described below. In the present invention, a nonaqueous secondary battery composition containing an active material (positive electrode active material or negative electrode active material) may be referred to as an electrode composition (positive electrode composition or negative electrode composition).

[0142] (Positive electrode active material) The positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one that can insert and release lithium ions reversibly. The material is not particularly limited as long as it has the above-mentioned properties, and may be a transition metal oxide, or an element that can be composited with Li, such as an organic substance or sulfur. Among them, it is preferable to use a transition metal oxide as the positive electrode active material, and it is preferable to use a transition metal element Mａ A transition metal oxide containing one or more elements selected from Co, Ni, Fe, Mn, Cu, and V is more preferred. ｂ (Elements of Group 1 (Ia) of the periodic table other than lithium, elements of Group 2 (IIa), Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, B, etc.) may be mixed. ａ The amount of Li / M is preferably 0 to 30 mol % relative to the amount of Li / M (100 mol %). ａ More preferably, the transition metal oxides are synthesized by mixing them so that the molar ratio of the above is 0.3 to 2.2. Specific examples of the transition metal oxide include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD) a lithium-containing transition metal halide phosphate compound, and (ME) a ​​lithium-containing transition metal silicate compound.

[0143] (MA) Specific examples of transition metal oxides having a layered rock salt structure include LiCoO ２ (Lithium cobalt oxide [LCO]), LiNi ２ O ２ (lithium nickel oxide), LiNi ０．８５ Co ０．１０ Al ０．０５ O ２ (nickel cobalt lithium aluminum oxide [NCA]), LiNi １／３ Co １／３ Mn １／３ O ２ (Lithium nickel manganese cobalt oxide [NMC]) and LiNi ０．５ Mn ０．５ O ２ (Lithium manganese nickel oxide). (MB) Specific examples of transition metal oxides having a spinel structure include LiMn ２ O ４ (LMO), LiCoMnO ４ , Li ２ FeMn ３ O ８ , Li ２ CuMn ３ O ８ , Li２ CrMn ３ O ８ and Li ２ NiMn ３ O ８ Examples of the (MC) lithium-containing transition metal phosphate compound include LiFePO ４ and Li ３ Fe ２ (P.O. ４ ) ３ Olivine-type iron phosphate salts such as LiFeP ２ O ７ Iron pyrophosphates such as LiCoPO ４ Cobalt phosphates such as Li ３ V ２ (P.O. ４ ) ３ (MD) Examples of lithium-containing transition metal halide phosphate compounds include, for example, Li ２ FePO ４ Fluorophosphate iron salts such as F, Li ２ MnPO ４ Fluorophosphate manganese salts such as F and Li ２ CoPO ４ Examples of the (ME) lithium-containing transition metal silicate compound include cobalt fluoride phosphates such as Li ２ FeSiO ４ , Li ２ MnSiO ４ , Li ２ CoSiO ４ In the present invention, transition metal oxides having a layered rock salt structure (MA) are preferred, and LCO or NMC are more preferred.

[0144] The shape of the positive electrode active material is not particularly limited, but it is preferably particulate in the nonaqueous secondary battery composition. When the positive electrode active material is particulate, the particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 μm. The particle size of the positive electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte. To achieve the desired particle size, a conventional grinder or classifier is used, as with the inorganic solid electrolyte. The positive electrode active material obtained by the calcination method may be used after washing with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.

[0145] The positive electrode active material content in the nonaqueous secondary battery composition is not particularly limited, and is preferably 10 to 97 mass %, more preferably 30 to 95 mass %, even more preferably 40 to 93 mass %, and particularly preferably 50 to 90 mass %, based on 100 mass % of the solid content.

[0146] (Negative electrode active material) The negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or 2 of the periodic table, and is preferably one that can reversibly insert and release lithium ions. The material is not particularly limited as long as it has the above properties, and examples thereof include carbonaceous materials, metal oxides, metal composite oxides, lithium alone, lithium alloys, and negative electrode active materials that can form an alloy (can be alloyed) with lithium. Among these, carbonaceous materials, metal composite oxides, and lithium alone are preferably used from the viewpoint of reliability. In terms of enabling a large capacity all-solid-state secondary battery, active materials that can be alloyed with lithium are preferred.

[0147] The carbonaceous material used as the negative electrode active material is a material essentially composed of carbon. Examples include carbon black such as petroleum pitch and acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite, etc.), and carbonaceous materials obtained by calcining various synthetic resins such as PAN (polyacrylonitrile)-based resins or furfuryl alcohol resins. Further examples include various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polyvinyl alcohol)-based carbon fibers, lignin carbon fibers, glassy carbon fibers, and activated carbon fibers, as well as mesophase microspheres, graphite whiskers, and flat graphite. These carbonaceous materials can also be divided into difficult-to-graphitize carbonaceous materials (also called hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Furthermore, the carbonaceous material preferably has the interplanar spacing or density and crystallite size described in JP-A-62-22066, JP-A-2-6856, and JP-A-3-45473. The carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, etc. can also be used. As the carbonaceous material, hard carbon or graphite is preferably used, and graphite is more preferably used.

[0148] The oxide of a metal or metalloid element used as the negative electrode active material is not particularly limited as long as it is an oxide capable of absorbing and releasing lithium, and examples thereof include oxides of metal elements (metal oxides), composite oxides of metal elements, or composite oxides of metal elements and metalloid elements (collectively referred to as metal composite oxides), and oxides of metalloid elements (metalloid oxides). Among these oxides, amorphous oxides are preferred, and chalcogenides, which are reaction products of metal elements and elements of Group 16 of the periodic table, are also preferred. In the present invention, the term "metalloid element" refers to an element that exhibits properties intermediate between metal elements and non-metalloid elements, and typically includes six elements: boron, silicon, germanium, arsenic, antimony, and tellurium, and three elements: selenium, polonium, and astatine. Furthermore, "amorphous" refers to an oxide having a broad scattering band with a peak in the 2θ range of 20° to 40° in an X-ray diffraction method using CuKα radiation, and may also have crystalline diffraction lines. The strongest intensity of the crystalline diffraction lines observed at 2θ values ​​of 40° to 70° is preferably 100 times or less, more preferably 5 times or less, the diffraction line intensity at the apex of a broad scattering band observed at 2θ values ​​of 20° to 40°, and it is particularly preferable that the crystal has no crystalline diffraction lines.

[0149] Among the compound group consisting of the amorphous oxides and chalcogenides, amorphous oxides or chalcogenides of metalloid elements are more preferred, and (composite) oxides or chalcogenides consisting of one element selected from Groups 13 (IIIB) to 15 (VB) of the periodic table (e.g., Al, Ga, Si, Sn, Ge, Pb, Sb, and Bi) alone or in combination of two or more elements thereof are particularly preferred. Specific examples of preferred amorphous oxides and chalcogenides include, for example, Ga ２ O ３ , GeO, PbO, PbO ２ , Pb ２ O ３ , Pb ２ O ４ , Pb ３ O ４ , Sb ２ O ３ , Sb ２ O ４ , Sb ２ O ８Bi ２ O ３ , Sb ２ O ８ Si ２ O ３ , Sb ２ O ５ , Bi ２ O ３ , Bi ２ O ４ , GeS, PbS, PbS ２ , Sb ２ S ３ or Sb ２ S ５ Suitable examples of negative electrode active materials that can be used in combination with amorphous oxides mainly containing Sn, Si, or Ge include carbonaceous materials that can occlude and / or release lithium ions or lithium metal, lithium alone, lithium alloys, and negative electrode active materials that can be alloyed with lithium.

[0150] The oxides of metal or semi-metal elements, particularly the metal (composite) oxides and the chalcogenides, preferably contain at least one of titanium and lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics. Examples of the lithium-containing metal composite oxide (lithium composite metal oxide) include composite oxides of lithium oxide and the metal (composite) oxides or the chalcogenides, more specifically, Li ２ SnO ２ The negative electrode active material, for example, a metal oxide, preferably contains titanium element (titanium oxide). Specifically, Li ４ Ti ５ O １２ Lithium titanate (LTO) is preferred because it has small volume fluctuations during absorption and desorption of lithium ions, has excellent rapid charge and discharge characteristics, suppresses electrode deterioration, and can improve the life of the lithium ion secondary battery.

[0151] The lithium alloy used as the negative electrode active material is not particularly limited as long as it is an alloy that is commonly used as a negative electrode active material for secondary batteries, and examples thereof include lithium-aluminum alloys, specifically lithium-aluminum alloys having lithium as the base metal and 10 mass % of aluminum added thereto.

[0152] The negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is one commonly used as a negative electrode active material for secondary batteries. Examples of such active materials include (negative electrode) active materials (alloys, etc.) containing silicon or tin, and metals such as Al and In. A negative electrode active material containing silicon (silicon-containing active material) that enables higher battery capacity is preferred, and a silicon-containing active material having a silicon content of 50 mol% or more of the total constituent elements is more preferred. Generally, negative electrodes containing these negative electrode active materials (e.g., Si negative electrodes containing silicon-containing active materials, Sn negative electrodes containing tin-containing active materials, etc.) can absorb more Li ions than carbon negative electrodes (e.g., graphite and acetylene black). That is, the amount of Li ions absorbed per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, there is an advantage in that the battery operating time can be extended. Examples of silicon-containing active materials include silicon materials such as Si and SiOx (0<x≦1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, etc. (e.g., LaSi ２ , VSi ２ , La—Si, Gd—Si, Ni—Si), or textured active materials (e.g., LaSi ２ / Si), and also SnSiO ３ , SnSiS ３ Examples of the tin-containing negative electrode active material include Sn, SnO, and SnO. SiOx itself can be used as a negative electrode active material (semi-metal oxide), and can also be used as a negative electrode active material (precursor material) that can be alloyed with lithium because it generates Si during operation of the all-solid-state secondary battery. Examples of the tin-containing negative electrode active material include Sn, SnO, and SnO. ２ , SnS, SnS ２ and active materials containing the above silicon and tin elements. Also, composite oxides with lithium oxide, for example, Li ２ SnO ２ It is also possible to cite the following.

[0153] In the present invention, the above-mentioned negative electrode active material can be used without any particular limitation. However, in terms of battery capacity, a negative electrode active material that can be alloyed with lithium is a preferred embodiment. Among these, the above-mentioned silicon material or silicon-containing alloy (alloy containing silicon element) is more preferred, and it is even more preferred that the negative electrode active material contains silicon (Si) or a silicon-containing alloy.

[0154] The chemical formula of the compound obtained by the above calcination method can be measured by inductively coupled plasma (ICP) emission spectroscopy, or simply calculated from the difference in mass of the powder before and after calcination.

[0155] The shape of the negative electrode active material is not particularly limited, but is preferably particulate in the nonaqueous secondary battery composition. When the negative electrode active material is particulate, the particle size of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 μm. The particle size of the negative electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte. To achieve the desired particle size, a conventional grinder or classifier is used, as with the inorganic solid electrolyte.

[0156] The content of the negative electrode active material in the nonaqueous secondary battery composition is not particularly limited, and is preferably 10 to 90 mass %, more preferably 20 to 85 mass %, even more preferably 30 to 80 mass %, and still more preferably 40 to 75 mass %, based on 100 mass % of the solid content.

[0157] In the present invention, when the negative electrode active material layer is formed by charging the secondary battery, ions of a metal belonging to Group 1 or 2 of the periodic table that are generated in the all-solid-state secondary battery can be used instead of the above-mentioned negative electrode active material. The negative electrode active material layer can be formed by bonding these ions with electrons and precipitating them as a metal.

[0158] (Coating of active material) The surfaces of the positive electrode active material and the negative electrode active material may be coated with another metal oxide. Examples of the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si, or Li. Specific examples include titanate spinel, tantalum-based oxides, niobium-based oxides, and lithium niobate-based compounds.４ Ti ５ O １２ , Li ２ Ti ２ O ５ , LiTaO ３ , LiNbO ３ , LiAlO ２ , Li ２ ZrO ３ , Li ２ WO ４ , Li ２ TiO ３ , Li ２ B ４ O ７ , Li ３ P.O. ４ , Li ２ MoO ４ , Li ３ BO ３ , LiBO ２ , Li ２ CO ３ , Li ２ SiO ３ , SiO ２ , TiO ２ , ZrO ２ , Al ２ O ３ , B ２ O ３ The surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus. Furthermore, the particle surfaces of the positive electrode active material or the negative electrode active material may be surface-treated with actinic rays or an active gas (plasma, etc.) before or after the surface coating.

[0159] <Conductive Aid> In one preferred embodiment, the nonaqueous secondary battery composition of the present invention contains a conductive aid. It is preferable to use a conductive aid in combination with an active material. For example, it is preferable to use a silicon-containing active material as the negative electrode active material in combination with a conductive aid. The conductive aid is not particularly limited, and any commonly known conductive aid can be used. For example, the conductive aid may be an electron-conductive material such as graphites (e.g., natural graphite, artificial graphite, etc.), carbon blacks (e.g., acetylene black, ketjen black, furnace black, etc.), amorphous carbon (e.g., needle coke), carbon fibers (e.g., vapor-grown carbon fiber, carbon nanotube, etc.), carbonaceous materials (e.g., graphene, fullerene, etc.), metal powders or fibers (e.g., copper, nickel, etc.), or conductive polymers (e.g., polyaniline, polypyrrole, polythiophene, polyacetylene, polyphenylene derivatives, etc.). In the present invention, when an active material and a conductive additive are used in combination, the conductive additive is one among the above-mentioned conductive additives that does not undergo insertion and release of ions of a metal belonging to Group 1 or Group 2 of the periodic table (preferably Li ions) during charging and discharging of the battery and does not function as an active material. Therefore, among conductive additives, one that can function as an active material in the active material layer during charging and discharging of the battery is classified as an active material rather than a conductive additive. Whether or not a conductive additive functions as an active material during charging and discharging of the battery is not uniquely determined, but is determined by the combination with the active material.

[0160] The conductive additive is preferably in particulate form in the non-aqueous secondary battery composition. When the conductive additive is particulate, the particle size (volume average particle size) of the conductive additive is not particularly limited, but is preferably 0.02 to 1.0 μm, for example. The particle size of the conductive additive can be measured in the same manner as the particle size of the inorganic solid electrolyte. The non-aqueous secondary battery composition may contain one or two types of conductive additives. When the non-aqueous secondary battery composition of the present invention contains a conductive additive, the content of the conductive additive in the non-aqueous secondary battery composition is preferably 0 to 10 mass% based on 100 mass% of the solid content.

[0161] <Lithium Salt> The nonaqueous secondary battery composition of the present invention also preferably contains a lithium salt (supporting electrolyte). The lithium salt is preferably a lithium salt typically used in this type of product, and is not particularly limited. For example, the lithium salts described in paragraphs 0082 to 0085 of JP 2015-088486 A are preferred. When the nonaqueous secondary battery composition of the present invention contains a lithium salt, the content of the lithium salt is preferably 0.1 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the inorganic solid electrolyte. The upper limit is preferably 50 parts by mass or less, and more preferably 20 parts by mass or less.

[0162] <Dispersant Other Than the Polymer Composition of the Present Invention> The nonaqueous secondary battery composition of the present invention does not necessarily contain any dispersant other than the polymer composition of the present invention, because the polymer (P) and / or oligomer (O1) contained in the polymer composition of the present invention can function as dispersants. However, the nonaqueous secondary battery composition of the present invention may contain a dispersant other than the polymer composition of the present invention (referred to as "other dispersant") to reinforce the dispersing function of the polymer composition of the present invention. As the other dispersant, any dispersant commonly used in nonaqueous secondary batteries can be appropriately selected and used. Generally, compounds intended for particle adsorption and steric and / or electrostatic repulsion are preferably used. The nonaqueous secondary battery composition of the present invention may contain one or more other dispersants. When the nonaqueous secondary battery composition of the present invention contains another dispersant, the content of the other dispersant can be appropriately determined and can be, for example, 3 mass % or less based on 100 mass % of the solids content of the nonaqueous secondary battery composition.

[0163] <Binder> The nonaqueous secondary battery composition of the present invention does not necessarily contain any binder other than the polymer composition of the present invention, because the polymer (P) and / or oligomer (O1) contained in the polymer composition of the present invention can function as binders in the constituent layers. However, the nonaqueous secondary battery composition of the present invention may contain a binder other than the polymer composition of the present invention to reinforce the binder function of the polymer composition of the present invention. Such a binder can be appropriately selected from binders commonly used in nonaqueous secondary batteries. The nonaqueous secondary battery composition of the present invention may contain one or more binders other than the polymer composition of the present invention. When the nonaqueous secondary battery composition of the present invention contains a binder other than the polymer composition of the present invention, the content of the binder is appropriately determined. For example, the content of the binder in the nonaqueous secondary battery composition is not particularly limited, but is preferably 0.1 to 4.0 mass %, more preferably 0.2 to 2.0 mass %, and even more preferably 0.5 to 1.5 mass %, in terms of the binding strength of the solid particles. For the same reasons, the content of the binder in 100% by mass of the solid content of the nonaqueous secondary battery composition (equivalent to the solid content) is preferably 0.1 to 5.0% by mass, more preferably 0.3 to 3.0% by mass, and even more preferably 0.5 to 1.5% by mass. For 100% by mass of the solid content, the mass ratio of the combined mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the binder other than the polymer composition of the present invention [(mass of inorganic solid electrolyte + mass of active material) / (total mass of binder other than the polymer composition of the present invention)] is preferably in the range of 1,000 to 1.

[0164] <Other Additives> The nonaqueous secondary battery composition of the present invention may contain, as appropriate, other components in addition to the above-mentioned components, an ionic liquid, a thickener, a crosslinking agent (such as one that undergoes a crosslinking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization), a polymerization initiator (such as one that generates an acid or radical by heat or light), an antifoaming agent, a leveling agent, a dehydrating agent, an antioxidant, etc. The ionic liquid is contained to further improve ionic conductivity, and any known ionic liquid can be used without any particular limitation.

[0165] (Preparation of Non-Aqueous Secondary Battery Composition) The non-aqueous secondary battery composition of the present invention can be prepared as a mixture, preferably as a slurry, by mixing the polymer composition of the present invention and the above-mentioned components according to the intended use, for example, using various commonly used mixers. In the case of an electrode composition, an active material is further mixed. The mixing method is not particularly limited, and can be carried out using known mixers such as a ball mill, bead mill, planetary mixer, blade mixer, roll mill, kneader, disk mill, planetary mixer, or narrow-gap disperser. The components may be mixed all at once or sequentially. The mixing environment is not particularly limited, and examples include dry air (dew point -20°C or lower) or an inert gas (e.g., argon gas, helium gas, or nitrogen gas). The mixing conditions are also not particularly limited and can be set appropriately; for example, the mixing temperature can be 15 to 40°C. The rotation speed of the planetary mixer can be 200 to 3,000 rpm.

[0166] The mixing time is not particularly limited and can be appropriately determined depending on the dispersibility of the solid particles, and can be, for example, 1 to 180 minutes. Since the nonaqueous secondary battery composition of the present invention has excellent dispersion stability of the solid particles, it can be stored after preparation and does not need to be prepared each time it is used. The environmental conditions under which the nonaqueous secondary battery composition of the present invention is stored are not particularly limited, and can be the same as those under which ordinary nonaqueous secondary battery compositions are stored. In particular, the nonaqueous secondary battery composition of the present invention exhibits excellent high-temperature dispersion stability and can therefore be stored even under high-temperature conditions.

[0167] [Nonaqueous Secondary Battery Sheet] A nonaqueous secondary battery sheet can be produced using the nonaqueous secondary battery composition of the present invention. This nonaqueous secondary battery sheet is a sheet-like molded article capable of forming a constituent layer of a nonaqueous secondary battery, and includes various embodiments depending on its application. The constituent layer formed from this nonaqueous secondary battery composition has low resistance and, more preferably, a flat surface. Below, a sheet for an all-solid-state secondary battery, which is a preferred embodiment of the nonaqueous secondary battery sheet, is described, but the following description of this all-solid-state secondary battery sheet can also be applied to the nonaqueous secondary battery sheet.

[0168] <Sheet for All-Solid-State Secondary Battery> The sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded article capable of forming a constituent layer of an all-solid-state secondary battery, and includes various embodiments depending on its application. Examples include a sheet preferably used for a solid electrolyte layer (also referred to as a solid electrolyte sheet for an all-solid-state secondary battery), a sheet preferably used for an electrode, or a laminate of an electrode and a solid electrolyte layer (electrode sheet for an all-solid-state secondary battery), and the like. In the present invention, these various sheets are collectively referred to as a sheet for an all-solid-state secondary battery. In the present invention, each layer constituting the sheet for an all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.

[0169] In the sheet for an all-solid-state secondary battery, the solid electrolyte layer or the active material layer on the substrate is formed from the non-aqueous secondary battery composition of the present invention. Therefore, the layer formed from the non-aqueous secondary battery composition of the present invention is formed from components derived from the non-aqueous secondary battery composition (excluding the dispersion medium), and typically, solid particles (inorganic solid electrolyte, conductive additive, and active material) are adhered (bound) in a mixed state with the polymer (P) and oligomer (O1) contained in the polymer composition of the present invention. The sheet for an all-solid-state secondary battery can be incorporated into an all-solid-state secondary battery by appropriately peeling off the substrate or as is, thereby achieving low resistance (improved conductivity) and excellent cycle characteristics of the all-solid-state secondary battery.

[0170] The solid electrolyte sheet for an all-solid-state secondary battery of the present invention may be any sheet having a solid electrolyte layer. It may be a sheet in which the solid electrolyte layer is formed on a substrate, or a sheet formed from the solid electrolyte layer without a substrate (a sheet from which the substrate has been peeled off). The solid electrolyte sheet for an all-solid-state secondary battery may have other layers in addition to the solid electrolyte layer. Examples of such other layers include a protective layer (release sheet), a current collector, and a coating layer. The solid electrolyte layer of the solid electrolyte sheet for an all-solid-state secondary battery is preferably formed from the non-aqueous secondary battery composition of the present invention (inorganic solid electrolyte-containing composition). The content of each component in this solid electrolyte layer is not particularly limited, but is preferably the same as the content of each component in the solid content of the non-aqueous secondary battery composition of the present invention. The layer thickness of each layer constituting the solid electrolyte sheet for an all-solid-state secondary battery is the same as the layer thickness of each layer described in the all-solid-state secondary battery described below. The solid electrolyte sheet for an all-solid-state secondary battery of the present invention may be, for example, a sheet having, on a substrate, a layer composed of the non-aqueous secondary battery composition of the present invention, a typical solid electrolyte layer, and a protective layer, in this order.

[0171] The substrate is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include sheets (plates) of materials described below in relation to the current collector, organic materials, inorganic materials, etc. Examples of organic materials include various polymers, specifically polyethylene terephthalate, polypropylene, polyethylene, cellulose, etc. Examples of inorganic materials include glass, ceramics, etc.

[0172] The electrode sheet for an all-solid-state secondary battery (also simply referred to as "electrode sheet") of the present invention may be an electrode sheet having an active material layer. It may be a sheet in which the active material layer is formed on a substrate (current collector), or a sheet formed from the active material layer without a substrate (a sheet from which the substrate has been peeled off). This electrode sheet typically has a current collector and an active material layer. However, it also includes an embodiment in which the current collector, active material layer, and solid electrolyte layer are formed in this order, as well as an embodiment in which the current collector, active material layer, solid electrolyte layer, and active material layer are formed in this order. The solid electrolyte layer and active material layer of the electrode sheet are preferably formed from the non-aqueous secondary battery composition (inorganic solid electrolyte-containing composition or electrode composition) of the present invention. The content of each component in this solid electrolyte layer or active material layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the non-aqueous secondary battery composition of the present invention. The layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described below. The electrode sheet may also have other layers as described above. When the solid electrolyte layer or the active material layer is not formed from the nonaqueous secondary battery composition of the present invention, it is formed from a normal constituent layer forming material.

[0173] In the sheet for an all-solid-state secondary battery of the present invention, at least one of the solid electrolyte layer and the active material layer is formed from the nonaqueous composition for a secondary battery of the present invention. Therefore, the sheet for an all-solid-state secondary battery of the present invention has a low-resistance constituent layer in which solid particles containing an inorganic solid electrolyte are bound, and in a preferred embodiment, the surface of the constituent layer is flat. By using a constituent layer formed from the nonaqueous composition for a secondary battery of the present invention as a constituent layer of an all-solid-state secondary battery, low resistance (high conductivity) and excellent cycle characteristics of the all-solid-state secondary battery can be achieved.

[0174] [Method for Manufacturing Sheet for All-Solid-State Secondary Battery] The method for manufacturing the sheet for an all-solid-state secondary battery of the present invention is not particularly limited, and the sheet can be manufactured by forming each of the above-mentioned layers using the nonaqueous composition for a secondary battery of the present invention. For example, a method is preferably used in which a layer (coated and dried) of the nonaqueous composition for a secondary battery is formed on a substrate or a current collector (optionally via another layer) by coating and drying. This method allows for the production of a sheet for an all-solid-state secondary battery having a substrate or a current collector and a coated and dried layer. In particular, when the nonaqueous composition for a secondary battery of the present invention is formed on a current collector to form a film, the adhesion between the current collector and the active material layer can be strengthened. Here, the coated and dried layer refers to a layer formed by coating the nonaqueous composition for a secondary battery of the present invention and drying the dispersion medium (i.e., a layer formed using the nonaqueous composition for a secondary battery of the present invention and consisting of a composition obtained by removing the dispersion medium from the nonaqueous composition for a secondary battery of the present invention). The active material layer and the coated and dried layer may contain a residual dispersion medium as long as the effects of the present invention are not impaired, and the residual amount can be, for example, 3 mass % or less in each layer. In the method for producing a sheet for an all-solid-state secondary battery of the present invention, each step such as coating and drying will be described in the method for producing an all-solid-state secondary battery below.

[0175] In the method for producing a sheet for an all-solid-state secondary battery of the present invention, the coated and dried layer obtained as described above can also be pressed. The pressing conditions and the like will be explained in the method for producing an all-solid-state secondary battery described below. In addition, in the method for producing a sheet for an all-solid-state secondary battery of the present invention, the substrate, the protective layer (particularly the release sheet), and the like can also be peeled off.

[0176] [Non-aqueous secondary battery] The non-aqueous secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and an electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer. The non-aqueous secondary battery of the present invention is not particularly limited in configuration other than that, as long as it has an electrolyte layer between the positive electrode active material layer and the negative electrode active material layer, and for example, a known configuration related to non-aqueous secondary batteries can be adopted.

[0177] <All-Solid-State Secondary Battery> The following describes an all-solid-state secondary battery, which is a preferred embodiment of a nonaqueous secondary battery. The all-solid-state secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer. The all-solid-state secondary battery of the present invention is not particularly limited in its configuration as long as it has a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer, and for example, a known configuration related to all-solid-state secondary batteries can be adopted. The positive electrode active material layer is preferably formed on a positive electrode current collector to constitute the positive electrode. The negative electrode active material layer is preferably formed on a negative electrode current collector to constitute the negative electrode. In the present invention, each constituent layer (including the current collector, etc.) constituting the all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.

[0178] At least one of the negative electrode active material layer, positive electrode active material layer, and solid electrolyte layer is preferably formed from the nonaqueous secondary battery composition of the present invention. Another preferred embodiment is that at least one of the negative electrode active material layer and positive electrode active material layer is formed from the nonaqueous secondary battery composition of the present invention. Another preferred embodiment of the present invention is that all layers are formed from the nonaqueous secondary battery composition of the present invention. In the present invention, forming the constituent layers of an all-solid-state secondary battery from the nonaqueous secondary battery composition of the present invention includes forming the constituent layers from the all-solid-state secondary battery sheet of the present invention (provided that, if a layer other than the layer formed from the nonaqueous secondary battery composition of the present invention is present, the sheet is formed from this layer). The all-solid-state secondary battery of the present invention, in which at least one constituent layer is formed from the nonaqueous secondary battery composition of the present invention, exhibits low resistance (high conductivity) and excellent cycle characteristics. Furthermore, the all-solid-state secondary battery of the present invention exhibits low resistance and high ionic conductivity, allowing for large current extraction. If the active material layer or solid electrolyte layer is not formed from the nonaqueous secondary battery composition of the present invention, known materials can be used. In the present invention, each of the constituent layers (including the current collector and the like) constituting the all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.

[0179] <Positive Electrode Active Material Layer, Solid Electrolyte Layer, Negative Electrode Active Material Layer> The active material layer or solid electrolyte layer formed from the nonaqueous secondary battery composition of the present invention preferably has the same component types and content as the solid content of the nonaqueous secondary battery composition of the present invention. The thicknesses of the negative electrode active material layer, solid electrolyte layer, and positive electrode active material layer are not particularly limited. The thickness of each layer is preferably 10 to 1000 μm, and, taking into account the dimensions of a typical all-solid-state secondary battery, more preferably 20 μm or more and less than 500 μm. In the all-solid-state secondary battery of the present invention, it is even more preferable that the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is 50 μm or more and less than 500 μm.

[0180] <Current Collector> The positive electrode active material layer and the negative electrode active material layer may each have a current collector on the side opposite to the solid electrolyte layer. The positive electrode current collector and the negative electrode current collector are preferably electronic conductors. In the present invention, either the positive electrode current collector or the negative electrode current collector, or both of them together, may be simply referred to as a current collector. Materials for forming the positive electrode current collector include aluminum, aluminum alloys, stainless steel, nickel, titanium, etc., as well as aluminum or stainless steel surfaces treated with carbon, nickel, titanium, or silver (thin films formed thereon), with aluminum and aluminum alloys being more preferred. Materials for forming the negative electrode current collector include aluminum, copper, copper alloys, stainless steel, nickel, titanium, etc., as well as aluminum, copper, copper alloys, or stainless steel surfaces treated with carbon, nickel, titanium, or silver, with aluminum, copper, copper alloys, and stainless steel being more preferred.

[0181] The current collector is usually in the form of a film sheet, but nets, punched materials, lath materials, porous materials, foamed materials, and molded fiber bodies can also be used. The thickness of the current collector is not particularly limited, but is preferably 1 to 500 μm. It is also preferable to make the surface of the current collector uneven by surface treatment.

[0182] <Other Configurations> In the present invention, functional layers or members may be appropriately interposed or disposed between or on the outside of the negative electrode current collector, negative electrode active material layer, solid electrolyte layer, positive electrode active material layer, and positive electrode current collector.

[0183] <Housing> Depending on the application, the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure as it is, but it is preferable to further encapsulate it in an appropriate housing to make it into a dry battery. The housing may be made of metal or resin (plastic). When a metal housing is used, examples include aluminum alloys and stainless steel. The metal housing is preferably divided into a positive electrode housing and a negative electrode housing, and is electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. The positive electrode housing and the negative electrode housing are preferably joined and integrated via a gasket to prevent short circuits.

[0184] <Preferred Embodiment of All-Solid State Secondary Battery> Hereinafter, an all-solid state secondary battery according to a preferred embodiment of the present invention will be described with reference to FIG. 1, but the present invention is not limited thereto.

[0185] FIG. 1 is a cross-sectional view schematically illustrating an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention. The all-solid-state secondary battery 10 of this embodiment has, as viewed from the negative electrode side, a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5, in this order. Each layer is in contact with each other and has an adjacent structure. By adopting such a structure, electrons (e － ) is supplied to the battery, and lithium ions (Li ＋ On the other hand, during discharge, the lithium ions (Li ＋ ) is returned to the positive electrode side, and electrons are supplied to the operating part 6. In the illustrated example, a light bulb is used as a model for the operating part 6, and it is lit by discharge.

[0186] When an all-solid-state secondary battery having the layer structure shown in FIG. 1 is placed in a 2032-type coin case 11 (see, for example, FIG. 2 ), this all-solid-state secondary battery is referred to as a laminated body 12 for an all-solid-state secondary battery, and a battery produced by placing this laminated body 12 for an all-solid-state secondary battery in a 2032-type coin case 11 is sometimes referred to as a (coin-type) all-solid-state secondary battery 13.

[0187] (Positive Electrode Active Material Layer, Solid Electrolyte Layer, Negative Electrode Active Material Layer) In the all-solid-state secondary battery 10, the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are all formed from the nonaqueous secondary battery composition of the present invention. The inorganic solid electrolyte and the polymer composition of the present invention (which in the present invention refers to each component in the constituent layers excluding the dispersion medium, such as the polymer (P) and the oligomer (O1)) contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be the same or different from each other. Furthermore, the conductive additives contained in the positive electrode active material layer 4 and the negative electrode active material layer 2 may be the same or different from each other. In the present invention, either the positive electrode active material layer or the negative electrode active material layer, or both together, may be simply referred to as the active material layer or the electrode active material layer. Furthermore, either the positive electrode active material or the negative electrode active material, or both together, may be simply referred to as the active material or the electrode active material.

[0188] The solid electrolyte layer contains an inorganic solid electrolyte having conductivity for metal ions belonging to Group 1 or 2 of the periodic table, the polymer composition of the present invention, and the optional components described above within the scope of the present invention, and typically does not contain a positive electrode active material and / or a negative electrode active material. The positive electrode active material layer contains an inorganic solid electrolyte having conductivity for metal ions belonging to Group 1 or 2 of the periodic table, a positive electrode active material, the polymer composition of the present invention, and the optional components described above within the scope ... The thickness of the lithium metal layer can be, for example, 1 to 500 μm, regardless of the thickness of the negative electrode active material layer.

[0189] In the present invention, when the constituent layers are formed from the nonaqueous secondary battery composition of the present invention, an all-solid-state secondary battery exhibiting low resistance and excellent cycle characteristics can be realized.

[0190] (Current Collector) The positive electrode current collector 5 and the negative electrode current collector 1 are as described above. When the all-solid-state secondary battery 10 has a constituent layer other than the constituent layer formed from the nonaqueous secondary battery composition of the present invention, a layer formed from a known constituent layer-forming material can also be applied. Furthermore, each layer may be composed of a single layer or multiple layers.

[0191] [Manufacturing of Nonaqueous Secondary Battery] A nonaqueous secondary battery can be manufactured by a conventional method using the nonaqueous secondary battery composition of the present invention. For example, an all-solid-state secondary battery can be manufactured by forming each of the above-mentioned layers using the nonaqueous secondary battery composition of the present invention. Specifically, the all-solid-state secondary battery can be manufactured by a method (a manufacturing method for an all-solid-state secondary battery sheet of the present invention) that includes a step of applying the nonaqueous secondary battery composition of the present invention to a suitable substrate (e.g., a metal foil serving as a current collector) and forming a coating film. More specifically, a nonaqueous secondary battery composition containing a positive electrode active material as a positive electrode material (positive electrode composition) is applied and dried on a metal foil serving as a positive electrode current collector to form a positive electrode active material layer, thereby producing a positive electrode sheet for an all-solid-state secondary battery. Next, a nonaqueous secondary battery composition (an inorganic solid electrolyte-containing composition) for forming a solid electrolyte layer is applied and dried on this positive electrode active material layer to form a solid electrolyte layer. Furthermore, a nonaqueous secondary battery composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) onto the solid electrolyte layer and dried to form a negative electrode active material layer. By overlaying a negative electrode current collector (metal foil) on the negative electrode active material layer, an all-solid-state secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer can be obtained. This can also be enclosed in a casing to form a desired all-solid-state secondary battery. Alternatively, an all-solid-state secondary battery can be manufactured by reversing the method of forming each layer, forming a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer on the negative electrode current collector, and then overlaying the positive electrode current collector.

[0192] Another method is as follows. That is, a positive electrode sheet for an all-solid-state secondary battery is prepared as described above. A nonaqueous secondary battery composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) onto a metal foil serving as a negative electrode current collector and dried to form a negative electrode active material layer, thereby preparing a negative electrode sheet for an all-solid-state secondary battery. Next, a solid electrolyte layer is formed on the active material layer of either of these sheets as described above. Furthermore, the other of the positive electrode sheet for an all-solid-state secondary battery and the negative electrode sheet for an all-solid-state secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. In this manner, an all-solid-state secondary battery can be manufactured. Another method is as follows. That is, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are prepared as described above. Separately, a nonaqueous secondary battery composition is applied to a substrate and dried to prepare a solid electrolyte sheet for an all-solid-state secondary battery comprising a solid electrolyte layer. Furthermore, the solid electrolyte layer peeled from the substrate is sandwiched between the positive electrode sheet for an all-solid-state secondary battery and the negative electrode sheet for an all-solid-state secondary battery. In this way, an all-solid-state secondary battery can be manufactured.

[0193] Furthermore, a positive electrode sheet for an all-solid-state secondary battery or a negative electrode sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are produced as described above. Next, the positive electrode sheet for an all-solid-state secondary battery or the negative electrode sheet for an all-solid-state secondary battery and the solid electrolyte sheet for an all-solid-state secondary battery are overlapped with each other in a state in which the positive electrode active material layer or the negative electrode active material layer is in contact with the solid electrolyte layer, and pressurized. In this way, the solid electrolyte layer is transferred to the positive electrode sheet for an all-solid-state secondary battery or the negative electrode sheet for an all-solid-state secondary battery. Thereafter, the solid electrolyte layer from which the substrate of the solid electrolyte sheet for an all-solid-state secondary battery has been peeled is overlapped with the negative electrode sheet for an all-solid-state secondary battery or the positive electrode sheet for an all-solid-state secondary battery (in a state in which the negative electrode active material layer or the positive electrode active material layer is in contact with the solid electrolyte layer) and pressurized. In this way, an all-solid-state secondary battery can be produced. The pressurization method and pressurization conditions in this method are not particularly limited, and the method and pressurization conditions described in the pressurization step below can be applied.

[0194] The solid electrolyte layer or the like can also be formed, for example, by pressure molding a non-aqueous secondary battery composition or the like on a substrate or an active material layer under pressure conditions described below. In the above-mentioned manufacturing method, the non-aqueous secondary battery composition of the present invention may be used for any one of the positive electrode composition, the inorganic solid electrolyte-containing composition, and the negative electrode composition. It is preferable to use the non-aqueous secondary battery composition of the present invention for the inorganic solid electrolyte-containing composition or at least one of the positive electrode composition and the negative electrode composition. The non-aqueous secondary battery composition of the present invention can also be used for any of the compositions. When forming a solid electrolyte layer or an active material layer using a composition other than the non-aqueous secondary battery composition of the present invention, examples of the material include commonly used compositions. Alternatively, instead of forming a negative electrode active material layer during the manufacturing of an all-solid-state secondary battery, the negative electrode active material layer can be formed by bonding ions of a metal belonging to Group 1 or 2 of the periodic table, which have accumulated in the negative electrode current collector during initialization or charging during use (described below), with electrons and depositing the metal on the negative electrode current collector or the like.

[0195] <Formation of Each Layer (Film Formation)> The method for applying the nonaqueous secondary battery composition is not particularly limited and can be selected appropriately. Examples include coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating, and bar coating. The coating temperature is not particularly limited and can be, for example, unheated, typically in the temperature range of about room temperature (e.g., 15 to 30°C). The applied nonaqueous secondary battery composition is then dried (heat treated). The drying treatment may be performed after applying each composition or after applying multiple compositions in layers. The drying temperature is not particularly limited. The lower limit is preferably 30°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher. The upper limit is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower. Heating within this temperature range allows the dispersion medium to be removed and the composition to be in a solid state (coated, dried layer). Furthermore, not raising the temperature too high is preferable because it avoids damaging the components of the all-solid-state secondary battery. This allows the all-solid-state secondary battery to exhibit excellent overall performance, and to obtain good binding properties and good ionic conductivity.

[0196] After coating and drying the nonaqueous secondary battery composition, after stacking the constituent layers, or after fabricating the all-solid-state secondary battery, it is preferable to pressurize each layer or the all-solid-state secondary battery. It is also preferable to pressurize the layers in a stacked state. Examples of pressurizing methods include a hydraulic cylinder press. The pressure is not particularly limited and is generally in the range of 5 to 1500 MPa. The coated nonaqueous secondary battery composition may be heated simultaneously with pressing. The heating temperature is not particularly limited and is generally in the range of 30 to 300°C. Pressing may also be performed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. Pressing may also be performed at a temperature higher than the glass transition temperature of the polymer composition of the present invention. However, the temperature generally does not exceed the melting point of the polymer composition of the present invention. Pressing may be performed after the coating solvent or dispersion medium has been dried in advance, or while the solvent or dispersion medium remains. The compositions may be coated simultaneously, or coating, drying, and pressing may be performed simultaneously and / or sequentially. After coating on separate substrates, the compositions may be laminated by transfer.

[0197] The atmosphere in the film-forming method (coating, drying, and pressurization (under heating)) is not particularly limited, and may be any of the following: atmospheric air, dry air (dew point -20°C or lower), and inert gas (e.g., argon gas, helium gas, nitrogen gas). High pressure may be applied for a short period of time (e.g., within a few hours), or moderate pressure may be applied for a long period of time (one day or more). In the case of a sheet other than an all-solid-state secondary battery sheet, for example, an all-solid-state secondary battery, a restraining device for the all-solid-state secondary battery (e.g., screw tightening pressure) may be used to continuously apply moderate pressure. The pressing pressure may be uniform or may vary across the pressed portion, such as the sheet surface. The pressing pressure may be varied depending on the area or film thickness of the pressed portion. The same portion may also be subjected to different pressures in stages. The pressing surface may be smooth or roughened.

[0198] <Initialization> The nonaqueous secondary battery produced as described above is preferably initialized after production or before use. The initialization is not particularly limited, and can be performed, for example, by performing initial charge / discharge under an elevated pressure and then releasing the pressure until the pressure reaches the normal operating pressure for nonaqueous secondary batteries.

[0199] [Uses of Nonaqueous Secondary Battery] The nonaqueous secondary battery of the present invention can be used in a variety of applications. While there are no particular limitations on the application, examples of applications include electronic devices such as notebook computers, pen-input PCs, mobile PCs, electronic book players, mobile phones, cordless phone handsets, pagers, handheld terminals, portable fax machines, portable copiers, portable printers, headphone stereos, video camcorders, LCD televisions, handheld vacuum cleaners, portable CD players, mini-discs, electric shavers, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, and backup power supplies. Other consumer applications include automobiles (e.g., electric vehicles), electric vehicles, motors, lighting fixtures, toys, game consoles, road conditioners, clocks, flash devices, cameras, and medical devices (e.g., pacemakers, hearing aids, and shoulder massagers). Furthermore, the battery can be used for various military and space applications. It can also be combined with solar cells.

[0200] The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited thereto. In the following examples, "parts" and "%" representing compositions are based on mass unless otherwise specified. In the present invention, "room temperature" means 25°C.

[0201] [Example 1] 1. Synthesis of polymer and preparation of polymer solution Polymers shown in the following chemical formula and in Table 1 were synthesized as follows to prepare polymer solutions. In the following chemical formula, the degree of polymerization of the siloxane structure in the polymer chain made of polysiloxane is omitted. In addition, the R bonded to the polymer chain made of polysiloxane Ｙ represents a linking group, and R Ｚindicates a substituent. In the polymers below, the numerical value written to the lower right of each constituent component indicates the content (mass %) of that constituent component in the polymer. Polymers B-1 to B-9 and T-1 and T-2 have the same structure except for the content of the constituent components, so the content of the constituent components is not written in the chemical formulas below (see Table 1).

[0202]

[0203]

[0204] [Synthesis Example B-1: Synthesis of Polymer B-1 and Preparation of Polymer Solution B-1] 28.8 g of lauryl acrylate, 7.2 g of t-butylacrylamide, and 1.8 g of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 200 mL graduated cylinder, and dissolved in 28 g of N-methyl-pyrrolidone and 28 g of butyl butyrate to prepare a monomer solution. 28 g of butyl butyrate was added to a 300 mL three-necked flask and stirred at 85 ° C., to which the monomer solution was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 90 ° C. and stirred for 2 hours. The obtained polymerization solution was poured into 800 g of methanol, stirred for 10 minutes, and then allowed to stand for 10 minutes. The precipitate obtained after removing the supernatant was dissolved in 60 g of butyl butyrate, and the methanol was distilled off by heating at 30 hPa and 80 ° C. for 1 hour. In this way, polymer B-1 was synthesized, and a polymer solution B-1 (concentration 10% by mass) consisting of this polymer was obtained.

[0205] [Synthesis Examples B-2 to B-22 and T-1 to T-2: Synthesis of Polymers B-2 to B-22 and Polymers T-1 to T-2, and Preparation of Polymer Solutions B-2 to B-22 and Polymer Solutions T-1 to T-2] Polymers B-2 to B-22 and T-1 to T-2 were synthesized in the same manner as in Synthesis Example B-1, except that in Synthesis Example B-1, compounds were used that lead to each constituent component so that polymers B-2 to B-22 and T-1 to T-2 had the compositions (types and contents of constituent components) shown in the above chemical formulas and Table 1, and the amount of initiator and polymerization concentration were adjusted so that the molecular weights would be as shown in Table 1, and polymer solutions B-2 to B-22 and T-1 to T-2 composed of each polymer were obtained, respectively.

[0206] Macromonomer M-1 was synthesized as follows. 210 g of dodecyl acrylate (Tokyo Chemical Industry Co., Ltd.), 23.3 g of 3-mercaptopropionic acid, 90 g of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.), and 2.1 g of polymerization initiator V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 500 mL graduated cylinder and stirred to dissolve uniformly, preparing a monomer solution. 140 g of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) was added to a 1 L three-neck flask and stirred at 80°C, to which the monomer solution was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 80°C for 2 hours, then heated to 90°C and stirred for 2 hours. Next, 275 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 37.5 g of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 15.6 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at 110°C for 3 hours. After allowing the solution to stand at room temperature, it was poured into 1200 g of methanol, and the supernatant was removed. Butyl butyrate was added thereto, and the methanol was distilled off under reduced pressure to obtain a butyl butyrate solution of macromonomer M-1. The solids concentration was 49% by mass. The following macromonomers M-2 to M-3 were used. <Macromonomer M-2> X-22-174ASX (product number, molecular weight 900, manufactured by Shin-Etsu Chemical Co., Ltd.) <Macromonomer M-3> X-22-174BX: (product number, molecular weight 2300, manufactured by Shin-Etsu Chemical Co., Ltd.) <Macromonomer M-4> KF-2012 (product number, molecular weight 4600, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0207] 2. Synthesis of Oligomer and Preparation of Oligomer Solution The oligomer shown in the following chemical formula was synthesized as follows to prepare an oligomer solution. In the following Oligomer B, the numerical value written to the lower right of each component indicates the content (mass %) of that component in Oligomer B.

[0208] [Synthesis Example OL-1: Synthesis of Oligomer A and Preparation of Oligomer Solution OL-1] 5.4 g of t-butylacrylamide and 4.5 g of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 200 mL graduated cylinder and dissolved in 114 g of diisobutyl ketone to prepare a monomer solution. 114 g of diisobutyl ketone was added to a 500 mL three-necked flask and stirred at 85 ° C., to which the monomer solution was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 90 ° C. and stirred for 2 hours. The diisobutyl ketone was distilled off from the resulting polymerization solution at 30 hPa and 80 ° C. Next, 100 g of butyl butyrate was added to the distilled solution, and the butyl butyrate was distilled off at 30 hPa and 80 ° C. This was repeated once more to replace the solvent with butyl butyrate. In this way, oligomer A was synthesized, and an oligomer solution OL-1 (concentration: 10% by mass) consisting of this oligomer was obtained.

[0209] [Synthesis Examples OL-2 to OL-7: Synthesis of Oligomers B to G, and Preparation of Oligomer Solutions OL-2 to OL-7] Oligomers B to G were synthesized in the same manner as in the Synthesis Example of Oligomer A, except that in the Synthesis Example of Oligomer A, compounds were used that would lead to each component so that Oligomers B to G would have the compositions (types and contents of components) shown in the above chemical formulas, and the amount of initiator and polymerization concentration were adjusted so that the molecular weights would be as shown in Table 1, and oligomer solutions OL-2 to OL-7 composed of the respective oligomers were obtained.

[0210] The number average molecular weight of the synthesized macromonomer M-1, the weight average molecular weight and molecular weight distribution (Mw / Mn) of each synthesized polymer, and the weight average molecular weight of each synthesized oligomer are shown in Table 1. The weight average molecular weight and number average molecular weight were measured by the above-mentioned methods. The "content (% by mass)" of each constituent shown in Table 1 is a value calculated from the charge ratio of each compound at the time of preparation.

[0211] 3. Preparation of Polymer Compositions Compositions S-1 to S-22 and TS-1 to TS-2 shown in Table 1 were prepared as follows. Each polymer composition was prepared by mixing the polymer solution shown in the "Type No." column of the "Polymer (P)" column in Table 1 and the oligomer solution shown in the "No." column of the "Oligomer (O1)" column in Table 1 in the combination shown in the "Polymer composition No." column in Table 1 at room temperature for 2 hours to achieve the content (solid content) shown in the "Content (mass %)" column of the "Oligomer (O1)" column in Table 1.

[0212] In Table 1, the content of oligomer (O1) indicates the content of oligomer (O1) in 100% by mass of the total amount including polymer (P). For each polymer composition, the components contained in polymer (P) were compared with the components contained in oligomer (O1), and the ratio of the number of types of components identical to the components contained in oligomer (O1) to the total number of types of components contained in polymer (P) was calculated, and the results are shown in the "Matching rate (%) with polymer (P)" column in Table 1. Furthermore, the "State" column in Table 1 shows the state of the polymer and oligomer in each composition, as described below, as determined by measuring their solubility in the dispersion medium using the method described above, and determining whether they were "dissolved" or "particles" (dispersed in particulate form without dissolving).

[0213]

[0214] <Abbreviations in Table 1> In Table 1, "-" in the constituent column indicates that the corresponding constituent is not contained. M-1 to M-4 listed in the "constituent (X)" column in Table 1 represent the macromonomers M-1 to M-4 described above. The "constituent (A)" column in Table 1 lists the following compounds from which the constituent (A) described above is derived. tBuAAm: N-tert-butylacrylamide (Fujifilm Wako Pure Chemical Industries, Ltd.) iPrAAm: N-iso-propylacrylamide (Fujifilm Wako Pure Chemical Industries, Ltd.) MeMAm: N-methylmethacrylamide (Tokyo Chemical Industry Co., Ltd.) PhAAm: N-phenylacrylamide (Fujifilm Wako Pure Chemical Industries, Ltd.) HEA: 2-hydroxyethyl acrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) GMA: glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.) MEA: methoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) Phosmer PP: acid phosphoxy polyoxy propylene glycol monomethacrylate (degree of polymerization of propyleneoxy group 5-6, Unichemical Co., Ltd.) MAA: methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) MA: maleic anhydride (Fujifilm Wako Pure Chemical Industries, Ltd.) The "Other components" column in Table 1 shows the following compounds from which the other components are derived: LA: lauryl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0215] [Example 2] 1. Synthesis of sulfide-based inorganic solid electrolyte <Synthesis Example A> A sulfide-based inorganic solid electrolyte was synthesized with reference to the non-patent literature of T. Ohtomo, A. Hayashi, M. Tatsumisago, Y. Tsuchida, S. Hama, K. Kawamoto, Journal of Power Sources, 233, (2013), pp. 231-235, and A. Hayashi, S. Hama, H. Morimoto, M. Tatsumisago, T. Minami, Chem. Lett., (2001), pp. 872-873. Specifically, lithium sulfide (Li ２ S, manufactured by Aldrich, purity >99.98%) 2.42 g and diphosphorus pentasulfide (P ２ S ５3.90 g of Li, manufactured by Aldrich, purity >99%) was weighed out and placed in an agate mortar and mixed for 5 minutes using an agate pestle. ２ S and P ２ S ５ The mixing ratio is Li in molar ratio. ２ S:P ２ S ５ = 75:25. Next, 66 g of zirconia beads having a diameter of 5 mm was added to a 45 mL zirconia container (manufactured by Fritsch), and the entire amount of the mixture of lithium sulfide and diphosphorus pentasulfide was added, and the container was completely sealed under an argon atmosphere. The container was set in a planetary ball mill P-7 (trade name, manufactured by Fritsch), and mechanical milling was performed for 20 hours at a temperature of 25 ° C. and a rotation speed of 510 rpm to obtain 6.20 g of a yellow powder sulfide-based inorganic solid electrolyte (Li-P-S-based glass, hereinafter sometimes referred to as LPS). The particle diameter of the Li-P-S-based glass was 15 μm.

[0216] 2. The compositions shown in Tables 2-1 to 2-4 were prepared as follows. The content of the polymer (P) and oligomer (O1) in each composition and the content of each composition in 100% by mass of the solid content (corresponding to the solid content excluding the dispersion medium) are shown in Table 2-5. In this specification, Tables 2-1 to 2-5 are collectively referred to as Table 2.

[0217] <Preparation of Inorganic Solid Electrolyte-Containing Composition> 60 g of zirconia beads having a diameter of 5 mm were placed in a 45 mL zirconia container (manufactured by Fritsch), and 9.85 g of the LPS synthesized in Synthesis Example A above, 0.15 g (solid content by mass) of a polymer composition shown in Table 2-1 or Table 2-4, and 10 g (total amount) of butyl butyrate as a dispersion medium were placed in the container. The container was then set in a planetary ball mill P-7 (trade name). Mixing was performed for 5 minutes at a temperature of 25°C and a rotation speed of 150 rpm to prepare inorganic solid electrolyte-containing compositions (slurries) K-1 to K-22 and Kc11 to Kc12, respectively.

[0218] <Preparation of Positive Electrode Composition> 60 g of zirconia beads having a diameter of 5 mm were placed in a 45 mL zirconia container (manufactured by Fritsch), and 7.81 g of the LPS synthesized in Synthesis Example A and 6.4 g (total amount) of butyl butyrate as a dispersion medium were placed in the container. The container was set in a planetary ball mill P-7 (trade name), and the mixture was stirred at 25°C and 200 rpm for 15 minutes. Thereafter, 5.44 g of NMC (manufactured by Aldrich Chemical Co.) as a positive electrode active material, 0.24 g of acetylene black (AB) as a conductive additive, and 0.10 g (solid content by mass) of a polymer composition shown in Table 2-2 or Table 2-4 were added to the container, and the container was set in a planetary ball mill P-7 (trade name). Mixing was continued for 15 minutes at a temperature of 25°C and a rotation speed of 200 rpm to prepare positive electrode compositions (slurries) PK-1 to PK-22 and PKc21 to PKc22, respectively.

[0219] <Preparation of negative electrode composition> 60 g of zirconia beads with a diameter of 5 mm was added to a 45 mL zirconia container (manufactured by Fritsch), 4.53 g of LPS synthesized in Synthesis Example A, 0.08 g (solid content by mass) of the polymer composition shown in Table 2-3 or Table 2-4, and 10 g (total amount) of butyl butyrate were added. This container was set in a planetary ball mill P-7 (trade name) and mixed for 30 minutes at a temperature of 25 ° C. and a rotation speed of 300 rpm. Thereafter, 5.0 g of silicon (Si) as a negative electrode active material and 0.40 g of VGCF (manufactured by Showa Denko K.K.) as a conductive additive were added, and similarly, the container was set in a planetary ball mill P-7 (trade name), and mixed for 5 minutes at a temperature of 25 ° C. and a rotation speed of 100 rpm to prepare negative electrode compositions (slurries) NK-1 to NK-22 and NKc21 to NKc22, respectively.

[0220] In Table 2, the composition content is the content (mass%) relative to the total mass of the composition, and the solid content is the content (mass%) relative to 100 mass% of the solid content of the composition, and units are omitted in the table.

[0221] <Evaluation 1: Room Temperature Dispersion Stability Test (Redispersibility)> The room temperature dispersion stability of each composition prepared as described above was evaluated by evaluating the redispersibility (storage stability) at room temperature (25°C), which is the ability to redisperse the composition into an excellent dispersion state immediately after preparation (initial). Specifically, for each prepared composition, LPS, a polymer composition, a dispersion medium, an active material, and a conductive additive were mixed under the same conditions as those for each composition in the same proportions as the composition content and solid content shown in Table 2 to prepare a composition (slurry) for dispersibility evaluation. For each prepared composition, the occurrence (presence or absence) of solid particle aggregates was confirmed using a grindmeter (manufactured by Asahi Research Institute Co., Ltd.). The size of the aggregates at this time was defined as X (μm) and used as an index of initial dispersibility. Meanwhile, each prepared composition was left at 25°C for 24 hours and then remixed at a temperature of 25°C using a planetary ball mill P-7 (trade name). The rotation speed and time during remixing were the same as those for the preparation of the inorganic solid electrolyte composition, the positive electrode composition, and the negative electrode composition, respectively. The remixed composition was examined for the presence or absence of solid particle agglomerates using the grind meter. The size of the agglomerates was defined as Y (μm) and used as an index of redispersibility after storage. The size of the agglomerates was determined by the point at which significant spots of coating appeared on the grind meter (see JIS K-5600-2-5 6.6). The ease of agglomerate formation (aggregation tendency or sedimentation tendency) was evaluated as the room-temperature dispersion stability (redispersibility of solid particles) of the solid electrolyte composition depending on whether the agglomerate sizes X and Y were included in the following evaluation criteria. In this test, a smaller agglomerate size X indicates better initial dispersibility, and a smaller agglomerate size Y indicates better room-temperature dispersion stability. In this test, an evaluation criterion of "D" or higher for the agglomerate size Y was considered acceptable, and when the size Y was 8 μm or less (evaluation criterion of "C" or higher), the agglomerate size X was also included in the evaluation. The results are shown in Table 2. - Evaluation criteria - A: Y≦5μm and X≦5μm B: 5μm<Y≦8μm and 5μm<X≦8μm C: 5μm<Y≦8μm and 8μm<X≦12μm D: 8μm<Y≦10μm E: 10μm<Y≦20μm F: 20μm<Y

[0222] <Evaluation 2: High-Temperature Dispersion Stability Test (Redispersibility)> As the high-temperature dispersion stability of each composition prepared as described above, the redispersibility property (storage stability) that allows the composition to be redispersed at a high temperature (40°C) to an excellent dispersion state immediately after preparation (initial) was evaluated. Specifically, as in Evaluation 1 above, for each composition prepared as described above, LPS, a polymer composition, a dispersion medium, an active material, and a conductive additive were mixed under the same conditions as those for preparing each composition in the same proportions as those for the composition content and solid content shown in Table 2 to prepare a composition (slurry) for dispersibility evaluation. Each prepared composition was left at 25°C for 24 hours and then remixed at a temperature of 25°C using a planetary ball mill P-7 (trade name). The rotation speed and time during remixing were the same as those for preparing the inorganic solid electrolyte composition, the positive electrode composition, and the negative electrode composition. The occurrence (presence or absence) of solid particle aggregates was confirmed for the remixed composition using the grind meter. The size of the aggregates at this time was designated Y (μm) and used as an index of redispersibility after storage at room temperature. Meanwhile, each of the prepared compositions was left at 40°C for 24 hours, cooled to 25°C, and remixed at 25°C using a planetary ball mill P-7 (trade name). The rotation speed and time during remixing were the same as those for preparing the inorganic solid electrolyte composition, the positive electrode composition, and the negative electrode composition. The remixed compositions were examined for the occurrence (presence) of solid particle agglomerates using the grind meter. The size of the agglomerates at this time was designated Z (μm) and used as an index of redispersibility after high-temperature storage. The agglomerate size was determined as the point at which significant spots appeared on the coating of the grind meter (see JIS K-5600-2-5 6.6). The tendency for agglomerates to occur (aggregation tendency or sedimentation tendency) was evaluated as the high-temperature dispersion stability (redispersibility of solid particles) of the solid electrolyte composition depending on whether the ratio Z / Y of the agglomerate sizes Y and Z fell within any of the following evaluation criteria. In this test, a smaller agglomerate size ratio Z / Y indicates better high-temperature dispersion stability. In this test, a rating of "D" or higher for the aggregate size ratio Z / Y is considered a pass level. The results are shown in Table 2. Rating criteria: A: Z / Y≦1.2 B: 1.2<Z / Y≦1.5 C: 1.5<Z / Y≦3.0 D: 3.0<Z / Y≦5.0 E: 5.0<Z / Y.

[0223] <Evaluation 3: Handling Test> A slurry with a solids concentration of 72% by mass was prepared in the same manner as each of the prepared compositions, except for the dispersion medium, but with a reduced amount of dispersion medium. A 2 mL plastic dropper (manufactured by Atect Co., Ltd.) was positioned vertically so that its tip was 10 mm below the interface of the slurry. The slurry was aspirated for 10 seconds at 25°C, and the mass W of the plastic dropper containing the aspirated slurry was measured. When the tare weight (weight) of the plastic dropper was W0, if the slurry mass W - W0 was less than 0.1 g, it was determined that the dropper could not aspirate the slurry. If the slurry could not be aspirated with the dropper, the upper limit of the solids concentration that could be aspirated with the dropper was determined by gradually adding dispersion medium. The handleability of each composition (whether it had a viscosity appropriate for forming a flat, smooth layer) was evaluated based on whether the obtained upper limit of the solids concentration fell within any of the following evaluation criteria. The solid content concentration was calculated by placing 0.30 g of the prepared slurry on an aluminum cup and heating it at 120°C for 2 hours to distill off the dispersion medium. In the present invention, this test is a reference test, and in this test, the higher the upper limit solid content concentration, the better the handleability, with evaluation criterion "D" or higher being a preferred level. The results are shown in Table 2. - Evaluation Criteria - A: Upper limit solid content concentration ≧ 70% B: 70% > upper limit solid content concentration ≧ 65% C: 65% > upper limit solid content concentration ≧ 60% D: 60% > upper limit solid content concentration ≧ 55% E: 55% > upper limit solid content concentration ≧ 50% F: 50% > upper limit solid content

[0224]

[0225]

[0226]

[0227]

[0228]

[0229] LPS: LPS synthesized in Synthesis Example A NMC: LiNi １／３ Co １／３ Mn １／３ O ２Si: Silicon (APS 1-5 μm, manufactured by Alfa Aesar) AB: Acetylene black VGCF: Carbon nanofiber

[0230] 3. Preparation of Solid Electrolyte Sheets for All-Solid-State Secondary Batteries <Preparation of Solid Electrolyte Sheets for All-Solid-State Secondary Batteries> Each of the inorganic solid electrolyte-containing compositions shown in the "Solid Electrolyte Composition No." column in Table 3-1 or Table 3-4 obtained above was applied to a 20 μm-thick aluminum foil using a Baker-type applicator (product name: SA-201, manufactured by Tester Sangyo Co., Ltd.) and heated at 80°C for 2 hours to dry the inorganic solid electrolyte-containing composition (removing the dispersion medium). Thereafter, using a heat press, the dried inorganic solid electrolyte-containing composition was heated and pressed at a temperature of 120°C and a pressure of 40 MPa for 10 seconds to prepare solid electrolyte sheets for all-solid-state secondary batteries (referred to as solid electrolyte sheets in Tables 3-1 and 3-4) 101 to 122 and c11 to c12, respectively. The film thickness of the solid electrolyte layer was 40 μm.

[0231] <Preparation of Positive Electrode Sheet for All-Solid State Secondary Battery> Each of the positive electrode compositions shown in the "Electrode Composition No." column in Table 3-2 or Table 3-4 obtained above was applied to a 20 μm-thick aluminum foil using a Baker-type applicator (product name: SA-201), heated at 80°C for 1 hour, and further heated at 110°C for 1 hour to dry the positive electrode composition (removing the dispersion medium). Thereafter, using a heat press, the dried positive electrode composition was pressed (10 MPa, 1 minute) at 25°C to prepare positive electrode sheets for all-solid state secondary batteries (referred to as positive electrode sheets in Tables 3-2 and 3-4) 201 to 222 and c21 to c22, respectively, having a positive electrode active material layer with a film thickness of 70 μm.

[0232] <Preparation of negative electrode sheets for all-solid-state secondary batteries> Each of the negative electrode compositions shown in the "Electrode composition No." column in Table 3-3 or Table 3-4 obtained above was applied to a copper foil having a thickness of 20 μm using a Baker-type applicator (product name: SA-201), heated at 80°C for 1 hour, and further heated at 110°C for 1 hour to dry the negative electrode composition (removing the dispersion medium). Thereafter, using a heat press, the dried negative electrode composition was pressed (10 MPa, 1 minute) at 25°C to prepare negative electrode sheets for all-solid-state secondary batteries (referred to as negative electrode sheets in Tables 3-3 and 3-4) 301 to 322 and c31 to c32, respectively, having a negative electrode active material layer with a film thickness of 60 μm.

[0233]

[0234]

[0235]

[0236]

[0237] 4. Production of All-Solid-State Secondary Battery First, a positive electrode sheet for an all-solid-state secondary battery having a solid electrolyte layer and a negative electrode sheet for an all-solid-state secondary battery having a solid electrolyte layer were produced, to be used in the production of an all-solid-state secondary battery.

[0238] - Preparation of cathode sheets for all solid state secondary batteries having solid electrolyte layer - On the cathode active material layer of each of the cathode sheets for all solid state secondary batteries shown in the "Electrode active material layer (sheet No.)" column of Tables 4-1 and 4-3, the solid electrolyte sheets prepared above and shown in the "Solid electrolyte layer (sheet No.)" column of Tables 4-1 and 4-3 were superimposed such that the solid electrolyte layer was in contact with the cathode active material layer, and the sheets were transferred (laminated) at 25°C and a pressure of 50 MPa using a press, and then pressed at 25°C and 600 MPa to prepare cathode sheets for all solid state secondary batteries Nos. 201 to 222 and c21 to c22 (cathode active material layer thickness 50 μm) each having a solid electrolyte layer with a thickness of 25 μm.

[0239] - Preparation of negative electrode sheets for all solid state secondary batteries having solid electrolyte layer - On the negative electrode active material layer of each negative electrode sheet for all solid state secondary batteries shown in the "Electrode active material layer (sheet No.)" column of Tables 4-2 and 4-3, the solid electrolyte sheet prepared above and shown in the "Solid electrolyte layer (sheet No.)" column of Tables 4-2 and 4-3 was superimposed such that the solid electrolyte layer was in contact with the negative electrode active material layer, and a press was used to transfer (laminate) the sheets at 25°C and a pressure of 50 MPa, followed by pressure at 25°C and 600 MPa to prepare negative electrode sheets for all solid state secondary batteries 301 to 322 and c31 to c32 each having a solid electrolyte layer with a thickness of 25 μm (negative electrode active material layer thickness of 40 μm).

[0240] All-solid-state secondary battery No. 401 having the layer structure shown in FIG. 1 was fabricated as follows. The all-solid-state secondary battery positive electrode sheet No. 201 (the aluminum foil of the solid electrolyte-containing sheet had already been peeled off) provided with the solid electrolyte layer obtained above was cut into a disk shape with a diameter of 14.5 mm and placed in a stainless steel 2032-type coin case 11 incorporating a spacer and a washer (not shown in FIG. 2 ) as shown in FIG. 2 . Next, a lithium foil cut into a disk shape with a diameter of 15 mm was placed on top of the solid electrolyte layer. Stainless steel foil was then placed on top of that, and the 2032-type coin case 11 was then crimped to fabricate all-solid-state secondary battery No. 401 13 shown in FIG. 2 . The all-solid-state secondary battery fabricated in this manner had the layer structure shown in FIG. 1 (where the lithium foil corresponds to the negative electrode active material layer 2 and the negative electrode current collector 1).

[0241] All solid state secondary batteries Nos. 402 to 422 and c101 to c102 were produced as follows. All solid state secondary batteries Nos. 402 to 422 and c101 to c102 were produced in the same manner as in the production of all solid state secondary battery No. 401, except that in the production of all solid state secondary battery No. 401, positive electrode sheets for all solid state secondary batteries having a solid electrolyte layer, represented by the numbers shown in the "Electrode active material layer (sheet No.)" column in Tables 4-1 and 4-3, were used instead of positive electrode sheet No. 201 for all solid state secondary batteries having a solid electrolyte layer.

[0242] All-solid-state secondary battery No. 501 having the layer structure shown in FIG. 1 was fabricated as follows. The solid electrolyte-containing negative electrode sheet No. 301 for all-solid-state secondary batteries obtained above (the aluminum foil of the solid electrolyte-containing sheet had already been peeled off) was cut into a disk shape with a diameter of 14.5 mm and placed in a stainless steel 2032-type coin case 11 incorporating a spacer and a washer (not shown in FIG. 2 ), as shown in FIG. 2 . Next, a positive electrode sheet (positive electrode active material layer) punched to a diameter of 14.0 mm from the positive electrode sheet for all-solid-state secondary batteries fabricated below was placed on top of the solid electrolyte layer. A stainless steel foil (positive electrode current collector) was further placed on top of this to form an all-solid-state secondary battery laminate 12 (a laminate consisting of stainless steel foil-aluminum foil-positive electrode active material layer-solid electrolyte layer-negative electrode active material layer-copper foil). The 2032-type coin case 11 was then crimped to produce all-solid-state secondary battery No. 501 shown in FIG. 2 .

[0243] The positive electrode sheet for a solid secondary battery used in the production of all-solid-state secondary battery No. 501 was prepared as follows. - Preparation of positive electrode composition - 180 zirconia beads with a diameter of 5 mm were placed in a 45 mL zirconia container (manufactured by Fritsch), and 2.7 g of the LPS synthesized in Synthesis Example A above, 0.3 g of KYNAR FLEX 2500-20 (trade name, PVdF-HFP: polyvinylidene fluoride hexafluoropropylene copolymer, manufactured by Arkema) as a solid content mass, and 22 g of butyl butyrate were added. This container was placed in a Fritsch planetary ball mill P-7 (trade name) and stirred at 25°C at 300 rpm for 60 minutes. Thereafter, LiNi was added as a positive electrode active material. １／３ Co １／３ Mn １／３ O ２7.0 g of (NMC) was added, and in the same manner, the container was set in a planetary ball mill P-7, and mixing was continued for 5 minutes at 25 ° C. and 100 rpm, to prepare a positive electrode composition. - Preparation of a positive electrode sheet for a solid secondary battery - The positive electrode composition obtained above was applied to a 20 μm thick aluminum foil (positive electrode current collector) using a Baker applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.), heated at 100 ° C. for 2 hours, and the positive electrode composition was dried (dispersion medium removed). Thereafter, using a heat press, the dried positive electrode composition was pressurized (10 MPa, 1 minute) at 25 ° C. to prepare a positive electrode sheet for an all-solid-state secondary battery having a positive electrode active material layer with a film thickness of 80 μm.

[0244] All solid state secondary batteries Nos. 502 to 522 and c201 to c202 were produced as follows. All solid state secondary batteries Nos. 502 to 522 and c201 to c202 were produced in the same manner as in the production of all solid state secondary battery No. 501, except that in the production of all solid state secondary battery No. 501, negative electrode sheets for all solid state secondary batteries having a solid electrolyte layer, represented by the numbers shown in the "Electrode active material layer (sheet No.)" column in Tables 4-2 and 4-3, were used instead of negative electrode sheet No. 301 for all solid state secondary batteries having a solid electrolyte layer. All solid state secondary batteries Nos. 502 to 522 and c201 to c202 were produced in the same manner as in the production of all solid state secondary battery No. 501.

[0245] <Evaluation 4: Resistance Measurement> The ionic conductivity of each of the manufactured all-solid-state secondary batteries was measured to evaluate the resistance. Specifically, each all-solid-state secondary battery was used as a sample for ionic conductivity measurement, and AC impedance was measured at a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz using a 1255B FREQUENCY RESPONSE ANALYZER (trade name, manufactured by SOLARTRON) in a thermostatic bath at 25°C. The resistance in the layer thickness direction of the sample for ionic conductivity measurement was then determined, and the ionic conductivity was calculated using the following formula (C1). The results are shown in Tables 4-1 to 4-3 (collectively referred to as Table 4). Formula (C1): Ionic conductivity σ (mS / cm) = 1000 × sample layer thickness (cm) / [resistance (Ω) × sample area (cm ２) In formula (C1), the sample layer thickness is the value measured before placing the laminate 12 in the 2032-type coin case 11, and is the value obtained by subtracting the thickness of the current collector (total layer thickness of the solid electrolyte layer and the electrode active material layer). The sample area is the area of ​​a disk-shaped sheet with a diameter of 14.5 mm. It was determined whether the obtained ionic conductivity σ fell within any of the following evaluation criteria. In this test, an ionic conductivity σ of evaluation criterion "D" or higher is considered to be pass level. As is clear from formula (C1) above, a high ionic conductivity σ means a low resistance. - Evaluation Criteria - A: 0.30≦σ B: 0.25≦σ<0.30 C: 0.20≦σ<0.25 D: 0.15≦σ<0.20 E: 0.10≦σ<0.15 F: σ<0.10

[0246] <Evaluation 5: Cycle Characteristics> The discharge capacity retention rate of each of the manufactured all-solid-state secondary batteries was measured using a charge-discharge evaluation device TOSCAT-3000 (trade name, manufactured by Toyo Systems Co., Ltd.). Specifically, each all-solid-state secondary battery was charged at a current density of 0.1 mA / cm in an environment of 25°C. ２ The battery was charged at a current density of 0.1 mA / cm until the battery voltage reached 4.3 V. ２The battery was discharged at 100°C until the battery voltage reached 2.5 V. This one charge and one discharge constituted one charge / discharge cycle, and three charge / discharge cycles were repeated under the same conditions to initialize the battery. The above charge / discharge cycles were then repeated, and the discharge capacity of each all-solid-state secondary battery was measured after each charge / discharge cycle using a charge / discharge evaluation device: TOSCAT-3000 (trade name). The battery characteristics (cycle characteristics) were evaluated based on whether the number of charge / discharge cycles at which the discharge capacity retention rate (discharge capacity relative to the initial discharge capacity) reached 80%, when the discharge capacity (initial discharge capacity) of the first charge / discharge cycle after initialization was taken as 100%, fell within the following evaluation criteria. In this test, the higher the evaluation criteria, the better the battery characteristics (cycle characteristics), and the initial battery characteristics can be maintained even after multiple charge / discharge cycles (even during long-term use). Evaluation criteria of "C" or higher for the cycle characteristics in this test were considered acceptable. The results are shown in Table 4. All-solid-state secondary battery No. The initial discharge capacities of Nos. 401 to 422 and 501 to 522 all showed values ​​sufficient to function as all-solid-state secondary batteries. -Evaluation criteria- A: 600 cycles or more B: 450 cycles or more and less than 600 cycles C: 300 cycles or more and less than 450 cycles D: 150 cycles or more and less than 300 cycles E: 80 cycles or more and less than 150 cycles F: 40 cycles or more and less than 80 cycles

[0247]

[0248]

[0249]

[0250] The results shown in Tables 1 to 4 reveal the following. Non-aqueous secondary battery compositions using polymer compositions containing only polymer (P) without oligomer (Ol), and non-aqueous secondary battery compositions using polymer compositions containing oligomer (Ol) in excessive amounts, inherently exhibit poor room-temperature dispersion stability and insufficient high-temperature dispersion stability. All-solid-state secondary batteries manufactured using such non-aqueous secondary battery compositions exhibit poor battery resistance and cycle characteristics. In contrast, polymer compositions containing polymer (P) and a specific amount of oligomer (Ol) can be used to prepare non-aqueous secondary battery compositions that exhibit excellent room-temperature dispersion stability as well as high-temperature dispersion stability and excellent handleability. Furthermore, all-solid-state secondary batteries manufactured using such non-aqueous secondary battery compositions exhibiting excellent dispersion stability exhibit low battery resistance (conductivity) and excellent cycle characteristics. As described above, the nonaqueous secondary battery composition of the present invention, which has excellent dispersion stability not only at room temperature but also at high temperatures, and the polymer composition of the present invention which can prepare the composition, do not require temperature conditions at the production site to be controlled at around room temperature, and can respond to recent demands for addressing global warming, saving energy, reducing production costs, improving productivity, and the like, and therefore can be said to have a great advantage in actual production.

[0251] REFERENCE SIGNS LIST 1 negative electrode current collector 2 negative electrode active material layer 3 solid electrolyte layer 4 positive electrode active material layer 5 positive electrode current collector 6 operating part 10 all-solid-state secondary battery 11 2032-type coin case 12 laminate for all-solid-state secondary battery 13 coin-type all-solid-state secondary battery

[0252] While the present invention has been described in connection with embodiments thereof, we do not intend to limit our invention to any of the details of the description unless otherwise specified, and believe that the claims should be construed broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

[0253] This application claims priority based on Japanese Patent Application No. 2024-051478, filed on March 27, 2024, the contents of which are incorporated herein by reference as part of the present specification.

Claims

1. A polymer composition for a non-aqueous secondary battery, comprising a polymer (P) and an oligomer (Ol) having a weight-average molecular weight of 1,000 or less, wherein the content of the oligomer (Ol) is 1 to 30 mass % relative to 100 mass % of the total of the polymer (P) and the oligomer (Ol).

2. The polymer composition for a non-aqueous secondary battery according to claim 1, wherein the polymer (P) contains a constituent derived from a (meth)acrylic acid ester monomer.

3. The polymer composition for a non-aqueous secondary battery according to claim 1, wherein the polymer (P) comprises a component (A) having at least one polar functional group selected from the following functional group group (a): <Functional group group (a)> sulfonic acid group, phosphoric acid group, phosphonic acid group, hydroxy group, carboxy group, oxetane group, epoxy group, dicarboxylic acid group, thiol group, ether group, thioether group, thioester group, ester group, amide group, urethane group, urea group, imide group, fluoroalkyl group, and salts thereof.

4. The polymer composition for a non-aqueous secondary battery according to claim 1, wherein the ratio [Mw / Mn] of the weight average molecular weight Mw to the number average molecular weight Mn of the polymer (P) is 3.0 or less.

5. The polymer composition for a non-aqueous secondary battery according to claim 1, wherein either the polymer (P) or the oligomer (O1) contains at least one component different from the component contained in the other.

6. The polymer composition for a non-aqueous secondary battery according to claim 1, wherein the polymer (P) and the oligomer (O1) contain at least one of the same constituent components.

7. The polymer composition for a non-aqueous secondary battery according to claim 1, wherein the content of the oligomer (O1) is 3 to 12 mass %.

8. A composition for a non-aqueous secondary battery, comprising the polymer composition for a non-aqueous secondary battery according to any one of claims 1 to 7.

9. The non-aqueous secondary battery composition according to claim 8, which contains an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table.

10. The composition for a non-aqueous secondary battery according to claim 9, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.

11. The non-aqueous secondary battery composition according to claim 8, which contains an active material.

12. A sheet for an all-solid-state secondary battery, comprising a layer formed using the nonaqueous secondary battery composition according to claim 8.

13. An all-solid-state secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, wherein at least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is formed using the nonaqueous secondary battery composition according to claim 8.

14. A method for producing a sheet for an all-solid-state secondary battery, comprising forming a film from the nonaqueous secondary battery composition according to claim 8.

15. A method for producing an all-solid-state secondary battery, comprising the steps of: producing an all-solid-state secondary battery through the method according to claim 14;

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