Dispersant polymer for nonaqueous secondary battery, composition for nonaqueous secondary battery, all-solid-state secondary battery and sheet for all-solid-state secondary battery, and method for manufacturing all-solid-state secondary battery and sheet for all-solid-state secondary battery

Abstract

Provided are: a dispersant polymer for a nonaqueous secondary battery, the dispersant polymer having a constituent component (X) that has a viscosity of 0.10-10,000 Pa·s at a temperature of 25°C and a shear rate of 1 s-1, contains a polymer chain, and has a molecular weight of 400 or more; a composition for a nonaqueous secondary battery, the composition containing the dispersant polymer for a nonaqueous secondary battery; an all-solid-state secondary battery and a sheet for the all-solid-state secondary battery; and a method for manufacturing the all-solid-state secondary battery and the sheet for the all-solid-state secondary battery.

Description

Dispersant polymer 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 dispersant polymer for non-aqueous secondary batteries, a composition for non-aqueous secondary batteries, a sheet for all-solid-state secondary batteries and an all-solid-state secondary battery, and a method for manufacturing the sheet for all-solid-state secondary batteries 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] Constituent layers in nonaqueous electrolyte secondary batteries (electrode layers of anode active material layer and cathode active material layer) and constituent layers in all-solid-state secondary batteries (solid electrolyte layer, anode active material layer, cathode active material layer, etc.) are typically formed using compositions (constituent layer-forming materials) containing raw material compounds constituting each layer, such as active material and inorganic solid electrolyte, as well as a dispersant for dispersing the raw material compounds and a binder for binding the raw material compounds, in consideration of improving productivity, etc. For this reason, studies on dispersants, binders, and constituent layer-forming materials have been ongoing. For example, Patent Document 1 describes a (meth)acrylic polymer having a hydroxy group that improves the dispersibility of graphene used in combination with a cathode active material, and a graphene dispersion containing the same, with the aim of improving the battery life of lithium-ion batteries. That is, Patent Document 1 describes a method for dispersing 100 parts by weight of graphene having an average thickness of 0.3 nm to 10 nm inclusive and a dispersion medium at a temperature of 25° C. and a shear rate of 1.0 s －１ Patent Document 2 describes a graphene dispersion containing 10 parts by weight or more and 300 parts by weight or less of a (meth)acrylic polymer having a hydroxy group and a viscosity at 1000 kJ / cm2 of 0.1 Pa·s or more and 100 Pa·s or less. Specifically, the (meth)acrylic polymer described is (meth)acrylic polymer-10 obtained by copolymerizing 2-hydroxyethyl methacrylate, Blemmer PME-200, ethylhexyl acrylate, and acrylic acid. Patent Document 2 describes "an inorganic solid electrolyte-containing composition containing an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a polymer binder, and a dispersion medium, wherein the polymer binder contains a graft polymer having a mass average molecular weight of 1,000 to 30,000 and including a component (A) containing at least one functional group selected from an amide group, an imide group, and a sulfonamide group in the molecular chain that serves as a side chain of the polymer, and the inorganic solid electrolyte-containing composition is soluble in the dispersion medium."

[0004] JP 2022-071849 A International Publication No. 2023 / 068237

[0005] As described above, 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.), which restricts the interfacial contact state between the solid particles and between the solid particles and the current collector, 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 decrease 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, constituent layer-forming materials are required to stably maintain the excellent dispersibility (initial dispersibility) of the solid particles immediately after preparation (initial), and to be able to redisperse the solid particles to the excellent dispersion state immediately after preparation even if they aggregate or precipitate (dispersion stability, also referred to as storage stability in the present invention). Here, the dispersibility of the solid particles can be improved by increasing the dispersion energy applied when dispersing the solid particles in the dispersion medium, more specifically, by extending the processing time (dispersion time) when dispersing the solid particles in the dispersion medium. Furthermore, from the viewpoint of improving productivity and reducing manufacturing costs, constituent layer-forming materials with increased solid content (thickened slurry) of solid particles and the like are desired. However, in order to improve the dispersibility of solid particles in constituent layer-forming materials with increased solid content, the dispersion energy must be further increased, necessitating a longer dispersion time. However, if the dispersion time is extended, a large load is placed on the solid particles during dispersion, which may cause damage such as deterioration and decomposition of the solid particles, resulting in an increase in the interfacial resistance.

[0007] Furthermore, in recent years, research and development into improving the performance and practical application of electric vehicles has progressed rapidly, and the performance required of nonaqueous secondary batteries has also increased, so there is a need for dispersants that improve the initial dispersibility and dispersion stability of solid particles (hereinafter sometimes referred to as "dispersion characteristics") while reducing the dispersion energy or load during dispersion for constituent layer-forming materials. However, with regard to conventional constituent layer-forming materials and dispersants, no study has been conducted on reducing the load acting on solid particles during mixing from the above-mentioned perspective.

[0008] An object of the present invention is to provide a non-aqueous secondary battery dispersant polymer that can prepare a non-aqueous secondary battery composition that has excellent solid particle dispersion properties while shortening the solid particle dispersion time, and a non-aqueous secondary battery composition containing this non-aqueous secondary battery dispersant polymer. Another object of the present invention is to provide an all-solid-state secondary battery sheet 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 an all-solid-state secondary battery sheet and an all-solid-state secondary battery using the non-aqueous secondary battery composition.

[0009] The present inventors have conducted extensive research into constituent layer forming materials and dispersants for solid particles, and as a result, have found that a dispersant to be used in combination with solid particles when preparing a constituent layer forming material is a dispersant containing a polymer chain and a constituent component (X) having a molecular weight of 400 or more, and dispersing the dispersant at a temperature of 25° C. and a shear rate of 1 s －１ They found that by employing a polymer having a viscosity in the range of 0.10 to 10,000 Pa s at 2000 kJ / s, it is possible to shorten the dispersion time required to achieve the desired dispersion characteristics of solid particles. They also found that by using a nonaqueous secondary battery composition containing this specific polymer as a material for forming a constituent layer, it is possible to realize a nonaqueous secondary battery sheet having a constituent layer with low resistance, and further a nonaqueous secondary battery with low resistance and excellent cycle characteristics. The present invention was completed through further investigation based on these findings.

[0010] That is, the above-mentioned problems were solved by the following means: <1> Temperature 25°C and shear rate 1 s －１<2> The nonaqueous secondary battery dispersant polymer according to <1>, which comprises a component (X) that contains a polymer chain and has a molecular weight of 400 or more, and has a viscosity of 0.10 to 10,000 Pa·s at 100°C. <2> The nonaqueous secondary battery dispersant polymer according to <1>, which comprises a component (A) that has at least one polar functional group selected from the following functional group group (a): (Functional group group (a)) sulfonic acid group, phosphate 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. <3> The nonaqueous secondary battery dispersant polymer has a polymer chain SP value of 15.0 to 25.0 MPa. １／２ <4> The dispersant polymer for a non-aqueous secondary battery according to any one of <1> to <3>, which has a multi-branched structure having a core portion and at least three polymeric arm portions. <5> The dispersant polymer for a non-aqueous secondary battery according to any one of <1> to <4>, which is a multi-branched polymer represented by the following formula (1): In formula (1), L represents an n-valent linking group. １ represents a polymer chain, and n P １may be the same or different. n is an integer of 3 or more. <6> A composition for a non-aqueous secondary battery, containing the dispersant polymer for a non-aqueous secondary battery according to any one of <1> to <5> above. <7> The composition for a non-aqueous secondary battery according to <6>, containing an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table. <8> The composition for a non-aqueous secondary battery according to <7>, in which the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte. <9> The composition for a non-aqueous secondary battery according to any one of <6> to <8>, containing an active material. <10> 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 <6> to <9> above. <12> An all-solid-state secondary battery having 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 non-aqueous composition for a secondary battery according to any one of <6> to <9>. <13> A method for producing a sheet for an all-solid-state secondary battery, comprising forming a film of the non-aqueous composition for a secondary battery according to any one of <6> to <9> above. <14> A method for producing an all-solid-state secondary battery, comprising producing an all-solid-state secondary battery via the method according to <13> above.

[0011] The present invention provides a non-aqueous secondary battery dispersant polymer that can prepare a non-aqueous secondary battery composition that has excellent solid particle dispersion properties while shortening the solid particle dispersion time, and a non-aqueous secondary battery composition containing this non-aqueous secondary battery dispersant polymer. 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.

[0012] 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.

[0013] 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 expressed using "to", the upper and lower limits forming the numerical range are not limited to the specific combination 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 expressed 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.

[0014] 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.

[0015] [Dispersant polymer for non-aqueous secondary batteries] The dispersant polymer for non-aqueous secondary batteries of the present invention (hereinafter sometimes simply referred to as "polymer of the present invention") has a polymer chain and a constituent component (X) having a molecular weight of 400 or more, and is dispersible at a temperature of 25°C and a shear rate of 1 s －１ The viscosity at 10000 Pa·s is 0.10 to 10,000 Pa·s. The polymer of the present invention can disperse solid particles in a dispersion medium in a short time, even when the solid content of the non-aqueous secondary battery composition (constituent layer-forming material) to be prepared is high, and can reduce the dispersion energy and load acting on the solid particles during dispersion, thereby suppressing damage to the solid particles, such as deterioration and decomposition. As a result, the polymer of the present invention can realize a non-aqueous secondary battery composition that has excellent solid particle dispersion characteristics and, more preferably, has a moderate viscosity, high fluidity, and excellent handling properties, allowing the formation of a good coating film. Furthermore, when this excellent non-aqueous secondary battery composition is used as a constituent layer-forming material, it can realize a non-aqueous secondary battery sheet having a constituent layer that is low in resistance (high in conductivity) and, more preferably, flat and has good surface properties, and further a non-aqueous secondary battery that exhibits low resistance and excellent cycle characteristics.

[0016] As described above, the polymer of the present invention functions as a dispersant that disperses solid particles in a dispersion medium while shortening the dispersion time and reducing the load acting on the solid particles in the preparation of a non-aqueous secondary battery composition. That is, the non-aqueous secondary battery dispersant polymer of the present invention has a constituent component (X) that includes a polymer chain and has a molecular weight of 400 or more, and disperses the solid particles in a dispersion medium at a temperature of 25° C. and a shear rate of 1 s －１ The polymer of the present invention can be said to be a dispersant containing a polymer having a viscosity of 0.10 to 10,000 Pa·s at 200°C. Furthermore, in a constituent layer formed from a composition for a non-aqueous secondary battery, the polymer of the present invention can adsorb to solid particles to bind the solid particles, and can also function as a binder to bind the solid particles to a current collector. In the composition for a non-aqueous secondary battery, the polymer of the present invention may or may not have the function of binding the solid particles. The adsorption of the polymer of the present invention to solid particles includes not only physical adsorption but also chemical adsorption (adsorption by chemical bond formation, adsorption by electron transfer, etc.). The polymer of the present invention, which exhibits the above-described excellent effects, can be preferably used as a material for forming a constituent layer of a non-aqueous secondary battery sheet (including an electrode sheet for a non-aqueous secondary battery) or a non-aqueous secondary battery.

[0017] <Polymer of the Invention> First, the constituent components of the polymer of the invention will be described. The polymer of the invention has a constituent component (X) that contains a polymer chain and has a molecular weight of 400 or more.

[0018] - Constituent Component (X) - The constituent component (X) contained in the polymer of the present invention is a constituent component containing a polymer chain and having a molecular weight of 400 or more. In the present invention, when a constituent component having a molecular weight of 400 or more has a polymer chain and a polar functional group included in the functional group group (a) defined as constituent component (A) described below, this constituent component is referred to as constituent component (X). This constituent component (X) is preferably a constituent component that does not have a polar functional group, and in one preferred embodiment, for example, a constituent component that does not have a polar functional group in a partial structure other than the polymer chain. By containing constituent component (X) in the polymer of the present invention, the excluded volume effect between the polymers of the present invention can be enhanced, and the dispersibility of solid particles can be improved, thereby achieving excellent dispersion properties even when the dispersion time is shortened.

[0019] In the component (X), the polymer chain may be present in the partial structure that will form the main chain of the polymer of the present invention, but it is preferably present in the molecular chain that will form the side chain of the polymer of the present invention. For example, it is more preferable that the polymer chain be incorporated into the interior or end of the molecular chain that will form the side chain of the polymer of the present invention. Such a component (X) can incorporate a graft structure into the chemical structure of the polymer of the present invention, thereby enhancing the above-mentioned excluded volume effect. In the present invention, the molecular chain that will form the side chain of the polymer of the present invention refers to the molecular chain that constitutes the side chain of the polymer of the present invention in which the component (X) is incorporated. This molecular chain is a molecular chain other than the molecular chain that constitutes the main chain of the polymer of the present invention, usually a molecular chain bonded to the molecular chain (atomic group) that constitutes the main chain. The type of polymer chain that one component (X) has may be at least one type, and preferably one or two types. Furthermore, the number of polymer chains that one component (X) has is not particularly limited, but is usually one.

[0020] Examples of this constituent component (X) include a constituent component derived from a polycondensation compound having a polycondensable group and a polymer chain. The polycondensable group is appropriately determined depending on the main chain structure of the polymer of the present invention. For example, when the polymer of the present invention is a step-polymerization polymer, a condensable functional group is selected, and when the polymer of the present invention is a chain-polymerization polymer, a polymerizable group (ethylenically unsaturated group) is selected. When the polymer of the present invention is a multi-branched polymer having a core portion as described below, examples of the polycondensable group include, in addition to the above, groups reactive with sulfanyl groups, such as ethylenically unsaturated groups capable of undergoing an ene-thiol reaction or radical polymerization, carboxyl groups capable of condensation reaction, or halogenated alkyl groups capable of thioetherification. Examples of the ethylenically unsaturated group include vinyl groups. 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-polymerized 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, and copolymers thereof, with (meth)acrylic polymers being preferred. Examples of (meth)acrylic polymers include polymers made of (co)polymers containing 50% by mass or more of a component derived from the (meth)acrylic compound (M1) described below. Examples of vinyl polymers include polymers made of copolymers containing 50% by mass or more of a component derived from the vinyl compound (M2) described below (provided that the content of the component derived from the (meth)acrylic compound (M1) is less than 50% by mass). In the present invention, the term "polymer chain of carbon-carbon double bonds" refers to a polymer chain formed by polymerization of carbon-carbon double bonds (ethylenically unsaturated groups), and specifically refers to a polymer chain formed by polymerization (homopolymerization or copolymerization) of a monomer having a carbon-carbon unsaturated bond. The polymer chain is a molecular chain in which two or more repeating units of one or more types are bonded together. Such polymer chains are not particularly limited, and chains made of ordinary polymers, such as the above-mentioned step-polymerized polymers or chain-polymerized polymers, can be used without any particular limitations.In the present invention, the following formula (L. 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.

[0021]

[0022] 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 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] The above formula (L Ｐ ) includes, for example, a chain made of a chain-polymerized polymer, a chain made of a step-polymerized polymer, etc. 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, and from the viewpoints of shortening the dispersion time and improving the dispersion characteristics, a polymer chain made of polysiloxane is more preferred.

[0027] 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 Examples of the group bonded to the end of the polymer chain include alkyl groups (having preferably 1 to 20 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms) from the viewpoint of dispersion characteristics. This group may further have a substituent, but is preferably unsubstituted.

[0028] 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.

[0029] The polymer chain made of polysiloxane is -(Si(R Ｓ ２ 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:

[0030] The polysiloxane structure is preferably a polysiloxane structure having a chemical structure represented by the following formula 4A.

[0031] 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 １６ and 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.

[0032] 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.

[0033] 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 set appropriately. 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.

[0034] 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 not a group corresponding to each polar functional group defined in the component (A) described later. 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 moiety 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 moiety is bonded to a structural moiety derived from a (meth)acrylic compound (M1) that reacts with the chain transfer agent.

[0035] 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. Ａ１ The 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.

[0036] 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:

[0037]

[0038] 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. １６ represents 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 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. １６Particularly 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.

[0039] Z represents a group represented by the following formula (Z).

[0040] 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 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.

[0041] 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.

[0042] The constituent component (X) is not particularly limited, but is preferably a constituent 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 such as 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.

[0043] 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) described below, 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 below, 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 not corresponding to component (A)).

[0044] Specific examples of the component (X) include those shown below, 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.

[0045] 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, enabling a reduction in dispersion time and improved dispersion characteristics. The molecular weight of the component (X) is appropriately determined taking into consideration the molecular weight of the polymer of the present invention, the content of the component (X), etc., and the like. For example, from the viewpoint of achieving both a reduction in dispersion time and improved dispersion characteristics, the molecular weight 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 achieving both a reduction in dispersion time and improved dispersion characteristics, the molecular weight 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 of the present invention.

[0046] 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 the polymer of the present invention, etc. The degree of polymerization of all structural units forming the polymer chain is, for example, preferably 2 to 1000, more preferably 2 to 200, and even more preferably 6 to 80. The SP value of the constituent component (X) is not particularly limited, and is determined appropriately taking into consideration the SP value of the polymer of the present invention, which will be described later.

[0047] - Constituent Component (A) - The polymer of the present invention preferably contains a constituent component (A) having at least one polar functional group selected from the following functional group group (a), in that this strengthens the adsorptivity or adhesion to solid particles and improves the dispersion characteristics of solid particles without impairing the effect of shortening the dispersion time. When the molecular weight of this constituent component (A) is 400 or more, it is preferably a constituent component that does not have a polymer chain defined by constituent component (X) in its molecular structure, and more preferably a constituent component that does not have a polymer chain defined by constituent component (X) in its molecular structure, regardless of molecular weight.

[0048] In component (A), the polar functional group is preferably present in the molecular chain that will become the side chain of the polymer of the present invention, and more preferably, for example, incorporated into the interior or terminal of the molecular chain that will become the side chain of the polymer of the present invention. In the present invention, the molecular chain that will become the side chain of the polymer of the present invention refers to the molecular chain that constitutes the side chain of the polymer of the present invention into which component (A) has been incorporated, and is a molecular chain other than the molecular chain that constitutes the main chain of the polymer of the present invention, usually a molecular chain bonded to the molecular chain (atomic group) that constitutes the main chain. For example, when the polycondensable compound that derives component (A) is acrylamide, the molecular chain (-CONH ２ )

[0049] 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 polymer of the present invention is not particularly limited and is determined appropriately depending on the number of polar functional groups in component (A) itself, the content of component (A), the molecular weight of the polymer of the present invention, and the like.

[0050] 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) is preferably a compound that does not have a repeating structure in a partial structure other than the polycondensable group.

[0051] The polycondensable group has the same meaning as the polycondensable group in the above-mentioned component (X). 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 that makes the molecular weight of the component (X) less than 400. Such polymer chains (however, the number average molecular weight is limited to those that make the molecular weight of the component (A) less than 400) are not particularly limited, and examples thereof include the above-mentioned 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 links the polycondensable group and the polymer chain in the component (X) is Ａ１ can be applied without any particular restrictions.

[0052] <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

[0053] 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.

[0054] 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 polymer of the present invention, but it is preferable that the bond * is bonded to the main chain side of the polymer of the present invention. However, the ester group does not include a partial structure that forms the main chain of the polymer of the present invention when component (A) is incorporated into the polymer of the present invention, such as an ester group that is directly bonded to the polymer chain of the carbon-carbon double bond.

[0055] 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 used as the terminal group include groups selected from the substituent Z described below. Among these, alkyl groups (including cycloalkyl groups), aryl groups, and heterocyclic groups are preferred, and alkyl groups or aryl groups are more preferred. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 12, and even more preferably 3 to 8. The number of carbon atoms in the aryl group can be selected from R ＮＡ１ In the present invention, the number of carbon atoms in the aryl group can be the same as that of the aryl group ＮＡ１When either the terminal group or the group has a hydrogen atom, this hydrogen atom is ＮＡ１ Interpret as follows.

[0056] 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.

[0057] 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 methylene group (-CH) in which the carbon atom bonded to the main chain side of the polymer of the present invention is not substituted with a fluorine atom is preferred. 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 polymer of the present invention, is substituted with a fluorine atom is more preferred. ２ -CH ２ -) or propylene group (-CH ２ -CH ２ -CH ２In 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, a perfluoroalkyl group such as the one described below with respect to R ｆ The group may have a substituent (excluding a fluorine atom) that can be taken as follows:

[0058] 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.

[0059] The polar substituent of 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 viewpoint of shortening the dispersion time and improving the dispersion characteristics, an amide group, a hydroxy group, or the like is more preferable. When component (A) has two or more polar functional groups, the combination thereof is not particularly limited and can be determined appropriately. For example, a combination including an amide group is preferable, and specifically, a combination of an amide group and a dicarboxylic acid group can be mentioned.

[0060] The polar substituent possessed by component (A) is usually constituted by 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, it is preferable that component (A) has one polar substituent.

[0061] 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.

[0062] 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 ＮＡ１Alternatively, 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.

[0063] 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. 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.

[0064] As the component (A), a component represented by the following formula (A1) is particularly preferred from the viewpoint of shortening the dispersion time and improving the dispersion characteristics.

[0065] 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.

[0066] 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 can be applied without any particular limitation. 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).

[0067] 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.

[0068] 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.

[0069] 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.

[0070] The molecular weight of the constituent component (A) is not particularly limited and is appropriately determined taking into consideration the molecular weight of the polymer of the present invention, the content of the constituent component (A), etc. The SP value of the constituent component (A) is not particularly limited and is appropriately determined taking into consideration the SP value of the polymer of the present invention described below.

[0071] In the present invention, the component (X) and the component (A) are different from each other, which enables a reduction in dispersion time and an improvement in dispersion characteristics.

[0072] - Other Components - The polymer of the present invention may contain other components in addition to the above-mentioned components (X) and (A). The other components may be any components that do not fall under the category of the above-mentioned components, and 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 compound (M1) or vinyl-based compound (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 components derived from (meth)acrylic acid aryl group-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 carbon number of the long-chain unsubstituted alkyl group can be, for example, 4 to 20, preferably 4 to 16, and more preferably 6 to 14. As other constituent components, a constituent component derived from an acrylate compound of a short-chain unsubstituted alkyl group and a constituent component derived from an acrylate compound of a short-chain alkyl group substituted with an aryl group are also another more preferred embodiment. The number of carbon atoms in the short-chain alkyl group is preferably, for example, 1 to 3. It is preferred that the polymer of the present invention does not contain other constituent components.

[0073] The polymer of the present invention may contain one or more of the above-mentioned components. The content of each component in the polymer of the present invention is not particularly limited and is determined taking into appropriate consideration the physical properties of the polymer as a whole, and is set, for example, within the following range. The content of each component in the polymer of the present invention is set, for example, within the following range so that the total content of all components is 100% by mass. When the polymer contains two or more components corresponding to a specific component, the total content of these components is used.

[0074] The total content of component (X) in the polymer of the present invention is not particularly limited and can be determined appropriately taking into consideration shortening the dispersion time, improving the dispersion properties, and the like. The total content of component (X) is, for example, preferably 50 to 99 mass% relative to the total content of all components. From the viewpoint of shortening the dispersion time and improving the dispersion properties, it is more preferably 55 to 95 mass%, even more preferably 60 to 90 mass%, and particularly preferably 65 to 80 mass%. The total content of component (A) in the polymer of the present invention is not particularly limited and can be determined appropriately taking into consideration shortening the dispersion time, improving the dispersion properties, and the like. Generally, the viscosity of the polymer of the present invention tends to increase as the total content of component (A) increases. The total content of component (A) is preferably, for example, 0 to 50 mass% relative to the total content of all components, from the viewpoint of easily setting the viscosity of the nonaqueous secondary battery composition in the range described below. From the viewpoint of shortening dispersion time and improving dispersion characteristics, it is more preferably 1 to 50 mass%, even more preferably 5 to 45 mass%, particularly preferably 10 to 40 mass%, and most preferably 20 to 35 mass%. In the polymer of the present invention, 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, 1.0 to 99. From the viewpoint of shortening dispersion time and improving dispersion 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 50 mass%, more preferably 0 to 30 mass%, and even more preferably 0 to 10 mass% relative to the total content of all components.

[0075] The polymer of the present invention may have a substituent other than the polar functional group included in the substituent group (a). Examples of the substituent that the polymer of the present invention may have include the substituent Z (excluding polar functional groups) described below. In one preferred embodiment, the polymer of the present invention does not have a hydroxy group among the polar functional groups and substituents.

[0076] The molecular structure of the polymer of the present invention will now be described. The molecular structure of the polymer of the present invention is not particularly limited as long as it contains the above-mentioned component (X). However, it typically has a branched or multi-branched structure in which the polymer chain of component (X) serves as a branched chain (side chain). In the present invention, a 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. Here, a graft structure typically refers to a polymer in which a single main chain does not have a core, but in which multiple polymer chains (as side chains) are bonded in a branched manner. A star structure typically refers to a polymer in which a core has multiple, typically three or more, polymeric arms bonded to the core. The polymeric arms constituting the star structure may be linear or graft. Here, a polymeric arm refers to a partial structure containing a polymer chain that forms the arm of a multi-branched polymer by bonding to the core. The primary structures of the main chain and graft chains in the graft structure (bonding mode of the constituent components) and the primary structure of the polymeric arm portions in the star structure (bonding mode of the constituent components) are not particularly limited and may be any bonding mode such as a random structure, a block structure, an alternating structure, etc. The polymer of the present invention preferably has a graft structure or a star structure.

[0077] When the polymer of the present invention has a graft structure, it can be synthesized by homopolymerizing or copolymerizing the compound leading to the above-mentioned component (X).

[0078] When the polymer of the present invention has a star structure, the polymer of the present invention is preferably a hyperbranched polymer represented by the following formula (1). In formula (1), L represents an n-valent linking group. １ represents a polymer chain as a polymer arm, and n P １ may be the same or different, and n is an integer of 3 or more.

[0079] (L in Formula (1)) In Formula (1), L is an n-valent linking group, and is usually a linking group (organic linking group) made of an organic group containing a skeleton in which carbon atoms are linked by covalent bonds, and a linking group further containing an oxygen atom is preferred. The molecular weight of this linking group is not particularly limited, and is preferably, for example, 200 or more, and more preferably a molecular weight of 300 or more. The upper limit of the molecular weight is preferably 5000 or less, more preferably 4000 or less, and particularly preferably 3000 or less. It is preferable that this linking group does not contain only one tetravalent carbon atom. The valence of this linking group is trivalent to decavalent, and is the same as n described below, and the preferred range is also the same.

[0080] The linking group preferably has a group represented by the following formula 1a. The number of groups represented by formula 1a that the linking group L has is preferably the same as the valence, n, of L. When the linking group has a plurality of such groups, they may be the same or different. -(CR ｆ ２ ) ｎ -O(C=O)-(CR ｆ ２ ) ｎ - (Formula 1a) In formula (1a), n is an integer of 0 to 10, preferably an integer of 1 to 6, and more preferably 1 or 2. Two n's may be the same or different. R ｆ represents a hydrogen atom or a substituent, and a hydrogen atom is preferred. ｆThe 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.

[0081] The linking group L is preferably a linking group represented by the following formula 1A or 1B.

[0082] In both formulas, R ｆ and n is R in formula 1a above. ｆ The meanings and preferred meanings of n are the same as those of n. * indicates the bond to the sulfur atom in Formula 1. In Formula 1A, R １Ａ represents a hydrogen atom or a substituent. １Ａ The substituents that can be adopted as R are not particularly limited, and examples thereof include ｆ Examples of the substituents that can be taken as R include the above-mentioned substituents, and further include the group represented by the above formula 1a. Among these, an alkyl group or a group represented by the above formula 1a is preferred. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. １Ａ The substituent that can be adopted as R may further have one or more substituents, and the substituent that may further have is not particularly limited, and examples thereof include R ｆExamples of the substituents that can be used as R include the above-mentioned substituents. Among them, a hydroxy group is preferred. Examples of the substituent that may further have one or more substituents include a hydroxyalkyl group (having the same number of carbon atoms as above), and specifically, hydroxymethyl is preferred. In Formula 1B, R １Ｃ represents a linking group. １Ｃ The linking group that can be used as the linking group is not particularly limited, and examples thereof include an alkylene group having 1 to 30 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, a heteroarylene group having 3 to 12 carbon atoms, an ether group (—O—), a sulfide group (—S—), a phosphinidene group (—PR—: R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a silylene group (—SiR Ｓ１ R Ｓ２ -:R Ｓ１ , R Ｓ２ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a carbonyl group, an imino group (—NR Ｎ -:R Ｎ is preferably a bonding site, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or a linking group formed by combining two or more of these (preferably 2 to 10 groups). Among these, an alkylene group, an ether group, a sulfide group, or a carbonyl group, or a linking group formed by combining two or more of these (preferably 2 to 5 groups), is preferred, and an ether group is more preferred. １Ｂ represents a hydrogen atom or a substituent, and a hydrogen atom is preferred. １Ｂ The substituents that can be adopted as R are not particularly limited, and examples thereof include R ｆ In Formula 1A and Formula 1B, groups represented by the same symbol may be the same or different.

[0083] In addition to the above-mentioned linking groups, the linking group L may be, for example, a group in which one or more groups represented by the above formula 1a in the above formula 1B are R ｆ A linking group substituted with any of the above substituents that can be taken as the substituent, particularly hydroxymethyl, is also a preferred embodiment.

[0084] Linking group R １is also preferably a linking group represented by any one of the following formulae 1C to 1H: In each formula, * indicates the bond to S in formula 1.

[0085]

[0086] In formulas 1C to 1H, T is a linking group, preferably a group represented by any of formulas T1 to T6 below, or a linking group formed by combining two or more (preferably two or three) of these groups. Examples of combined linking groups include a linking group (-OCO-alkylene group) formed by combining a linking group represented by formula T6 with a linking group represented by formula T1. In the groups represented by formulas T1 to T6, any of the bonding moieties bonded to the sulfur atom in formula 1 above may be present, but when T is an oxyalkylene group (a group represented by formulas T2 to T5) or an -OCO-alkylene group, it is preferable that the terminal carbon atom (bonding moiety) be bonded to the sulfur atom in formula 1 above. Multiple Ts present in each of the above formulas may be the same or different. In formulas 1C to 1H, n is an integer, preferably an integer of 0 to 14, more preferably an integer of 0 to 5, and particularly preferably an integer of 1 to 3.

[0087]

[0088] Z Ｄ is a linking group, and is preferably a group represented by Z1 or Z2 below. In formulas T1 and Z1, m is an integer of 1 to 8, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. In formula Z2, Z ３ is a linking group, which is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably a 2,2-propanediyl group.

[0089] Specific examples of the linking group L are listed below, but the present invention is not limited to these. In each specific example, * indicates the bond to the sulfur atom in Formula 1.

[0090]

[0091] (P in Equation (1) １ ) P in Equation (1) １is a polymer chain that forms a polymer arm portion of the star structure. １ In the multi-branched polymer represented by formula (1) (hereinafter, sometimes simply referred to as "polymer (1)"), n polymer chains P １ Each of the n polymer chains P contains the above-mentioned component (X), preferably the above-mentioned component (A), and may optionally contain other components described above, or may contain the component (X) or the component (A), and optionally contain other components. １ may be the same or different, and in terms of shortening the dispersion time and dispersion characteristics, at least one polymer chain P １ The polymer chain containing the above-mentioned component (X) (hereinafter referred to as "polymer chain P １Ｘ ") and at least one other polymer chain P １ is a polymer chain containing the above-mentioned component (A) (hereinafter referred to as "polymer chain P １Ａ It is preferable that the polymer chain P １Ｘ From the viewpoint of shortening the dispersion time and dispersion characteristics, it is preferable that the polymer chain P does not contain the above-mentioned component (A), and may contain other components, but it is more preferable that it does not contain any other components, that is, it is a homopolymer chain of the component (X), further preferably a homopolymer chain of a component having a polymer chain made of polysiloxane, and particularly preferably a homopolymer chain of a (meth)acrylic compound (M1) having a polymer chain made of polysiloxane. １Ａ In terms of shortening the dispersion time and dispersion characteristics, it is preferable that the polymer chain P does not contain the above-mentioned component (X), and although it may contain other components, it is more preferable that it does not contain any other components, that is, it is a homopolymer chain of the component (A), and a homopolymer chain of a (meth)acrylamide compound is particularly preferable. １Ｘ and polymer chain P １ＡThe number of is determined appropriately within the range indicated by n in the above formula (1), and can be set to the same as nA and mX in the formula (2) described below, for example.

[0092] The polymer chain P １ When the polymer chain P １ The primary structure of the polymer chain P is not particularly limited, and may be any bonding pattern such as a random structure, a block structure, or an alternating structure, but a random structure or a block structure is preferred. １ The group bonded to the terminal of is not particularly limited, and as described above, an appropriate group can be selected depending on the polymerization method, etc.

[0093] Polymer chain P １Ｘ The content of the component (X) therein is not particularly limited, but from the viewpoint of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or more, more preferably 75% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass is also one of the preferred embodiments. １Ｘ The content of the component (A) therein is not particularly limited, but from the viewpoint of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less, and 0% by mass is also one of the preferred embodiments. １Ｘ The content of other constituent components therein is not particularly limited, but from the viewpoint of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 10% by mass or less, and 0% by mass is also one of the preferred embodiments.

[0094] Polymer chain P １Ａ The content of the component (A) therein is not particularly limited, but from the viewpoint of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or more, more preferably 75% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass is also one of the preferred embodiments. １ＡThe content of the component (X) therein is not particularly limited, but from the viewpoint of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less, and 0% by mass is also one of the preferred embodiments. １Ａ The content of other constituent components therein is not particularly limited, but from the viewpoint of shortening the dispersion time and dispersion characteristics, it is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 10% by mass or less, and 0% by mass is also one of the preferred embodiments.

[0095] Polymer chain P １ Weight average molecular weight Mw Ｐ１ (n polymer chains P １ The weight average molecular weight of the polymer chain P is not particularly limited and is appropriately set in consideration of the weight average molecular weight of the polymer (1), which is an example of the polymer of the present invention, and is preferably 500 to 20,000, more preferably 1,000 to 10,000. １ The degree of polymerization of all components (n polymer chains P １ The average degree of polymerization of the polymer chain P is not particularly limited, but is preferably 5 to 300, and more preferably 8 to 150. １Ｘ Weight average molecular weight Mw Ｐ１Ｘ (All polymer chains P １Ｘ The weight average molecular weight of the polymer chain P is not particularly limited and is appropriately set in consideration of the weight average molecular weight of the polymer (1) described below, which is an example of the polymer of the present invention. For example, it is preferably 400 to 50,000, more preferably 1,000 to 20,000. １Ｘ The degree of polymerization of all components (all polymer chains P １Ｘ The average degree of polymerization of the polymer chain P is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. １Ａ Weight average molecular weight Mw Ｐ１Ａ (All polymer chains P １ＡThe weight average molecular weight of the polymer chain P is not particularly limited and is appropriately set in consideration of the weight average molecular weight of the polymer (1) described below, which is an example of the polymer of the present invention. For example, it is preferably 100 to 10,000, more preferably 200 to 3,000. １Ａ The degree of polymerization of all components (all polymer chains P １Ａ The average degree of polymerization of the copolymer (the average value of the ...

[0096] In the polymer represented by formula (1), polymer chain A １Ｘ and polymer chain A １Ａ The combination of the polymer chain A is not particularly limited. １Ｘ The constituent component (X) and the polymer chain A １Ｘ The polymer chain A can be appropriately combined with the component (A) constituting the polymer chain A. １Ｘ and polymer chain A １Ａ As the combination of (A), a combination of a suitable component that can be used as the component (X) and a suitable component that can be used as the component (A) is preferred, and examples thereof include the combinations in the polymers shown in the examples.

[0097] (n in formula (1)) In formula (1), n ​​is an integer of 3 or more, preferably an integer of 3 to 10, more preferably an integer of 3 to 8, even more preferably an integer of 3 to 6, and particularly preferably an integer of 4 to 6.

[0098] The content of the core part L in the polymer (1) is not particularly limited, but can be 1 to 40% by mass in total with "S" in the polymer (1), and from the viewpoint of shortening the dispersion time and improving the dispersion characteristics, it is preferably 2 to 30% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass. １The total content of the polymer chain P in the polymer (1) is not particularly limited, but can be 60 to 99% by mass, and from the viewpoint of shortening the dispersion time and improving the dispersion characteristics, it is preferably 70 to 98% by mass, more preferably 80 to 98% by mass, and even more preferably 90 to 97% by mass. １Ｘ The total content of the polymer chain P １ The total content of the polymer chain P can be appropriately determined in consideration of the total content of the polymer chain P. １ The total content of the polymer chain P in the polymer (1) is preferably the same as the total content of the component (X) in the polymer of the present invention. １Ａ The total content of the polymer chain P １ The total content of the polymer chain P can be appropriately determined in consideration of the total content of the polymer chain P. １ In the polymer (1), the total content of the polymer chain P is preferably the same as the total content of the constituent component (A) in the polymer of the present invention. １Ａ The total content of polymer chains P １Ｘ The ratio of the total content of polymer chains P １Ｘ Total content of polymer chain P １Ａ The total content of the constituent component (X) is not particularly limited, and is preferably the same as the ratio of the total contents in the polymer of the present invention [total content of the constituent component (X) / total content of the constituent component (A)].

[0099] The hyperbranched polymer represented by the above formula (1) is preferably represented by the following formula (2). In formula (2), L represents a (nA+mX)-valent linking group and is the same as L in formula (1). １Ａ is the polymer chain P containing the above-mentioned component (A). １Ａ and nA P １Ａ may be the same or different. １Ｘ is the polymer chain P containing the above-mentioned component (X). １Ｘ and nX P １Ｘ may be the same or different.

[0100] In the above formula (1), nA is an integer of 1 to 8, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1 or 2. mX is an integer of 2 to 9, preferably an integer of 2 to 5, and more preferably an integer of 3 to 5. However, nA+mX is an integer of 3 to 10, preferably an integer of 3 to 8, more preferably an integer of 3 to 6, and even more preferably an integer of 4 to 6.

[0101] The proportions of L and P in the polymer (1) １Ａ and P １Ｘ The contents of L and P in the above formula (1) are １Ａ and P １Ｘ The content is the same as each of the above.

[0102] Specific examples of the polymer represented by formula (1) or formula (2) include the polymers synthesized in the examples described below, but the present invention is not limited to these.

[0103] The polymer of the present invention can be a commercially available product or a synthetic product. Polymer (1) can be synthesized by selecting raw material compounds using known methods. For example, it can be synthesized by condensation, homopolymerization, or copolymerization using a surfactant, emulsifier, or dispersant, a polycondensation compound that derives component (X), a polycondensation compound that derives component (A), or a polycondensation compound that derives other components, using a conventional synthesis method. Furthermore, the hyperbranched polymer represented by formula (1) or formula (2) can be synthesized, for example, by addition reaction of the above raw material compounds with a polyvalent thiol compound corresponding to the core portion L. Specifically, it can be synthesized by the method described in the Examples below. The method for incorporating a polar functional group into the polymer of the present invention 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 having (or generating) the functional group, a method utilizing a polymer reaction, an ene reaction to a double bond, an ene-thiol reaction, or an ATRP (Atom Transfer Radical Polymerization) polymerization method using a copper catalyst. Alternatively, the 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, the 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.

[0104] - 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.

[0105] - Physical properties or characteristics of the polymer of the present invention - The polymer of the present invention was melt-melted at a temperature of 25°C and a shear rate of 1 s －１ The viscosity of the polymer of the present invention is 0.10 to 10,000 Pa·s. When the viscosity of the polymer of the present invention is within the above range, it becomes liquid at 25°C, making it easy to disperse solid particles in a dispersion medium and shortening the dispersion time of the solid particles. Furthermore, even if the dispersion time of the solid particles is shortened, the solid particles can be dispersed in a dispersion medium and excellent dispersion properties can be achieved. The viscosity of the polymer of the present invention is preferably 0.50 to 9,000 Pa·s from the viewpoint of shortening the dispersion time and improving the dispersion properties. When the polymer of the present invention has a graft structure, its viscosity is more preferably 10 to 8,000 Pa·s, and even more preferably 105 to 6,000 Pa·s, within the above range. On the other hand, when the polymer of the present invention has a multibranched structure, its viscosity is more preferably 10 to 9,000 Pa·s, even more preferably 100 to 8,000 Pa·s, particularly preferably 1,500 to 7,500 Pa·s, and most preferably 2,000 to 6,300 Pa·s, within the above range. The viscosity of the polymer of the present invention was measured using a rheometer at a temperature of 25°C and a shear rate of 1 s －１ In the present invention, the viscosity is measured using a rheometer, RheoStress RS6000 (trade name, manufactured by HAAKE Co., Ltd.). The viscosity of the polymer of the present invention can be appropriately adjusted by changing the molecular structure of the polymer, the type and content of the polycondensable compound, the weight average molecular weight, etc.

[0106] The polymer of the present invention preferably has the following physical properties or characteristics: From the viewpoint of shortening the dispersion time and improving the dispersion characteristics, the polymer of the present invention has an SP value of the polymer chain of 15.0 to 25.0 MPa. １／２It is preferable that the temperature is 17.0 to 22.0 MPa. １／２ More preferably, 17.5 to 20.0 MPa １／２ It is even more preferable that the SP value of the polymer chain is calculated from all constituent components derived from the polycondensable compound that constitutes the polymer of the present invention, ignoring compounds that lead to partial structures other than the polymerizable compound. For example, the SP value is calculated excluding the terminal groups of the polymer chain and the core portion of a hyperbranched polymer. In the present invention, the SP values ​​of the constituent components and the polymer of the present invention are values ​​calculated by the Okitsu method. The Okitsu method is described in detail, for example, in Journal of the Adhesion Society of Japan, 1993, Vol. 29, No. 6, pp. 249-259, and Journal of Sen'i Gakkaishi, 1994, Vol. 50, No. 6, pp. 273-277. The SP value of the constituent components is calculated based on the structure in which the constituent components are incorporated into the polymer of the present invention. The SP value of the polymer of the present invention is calculated from the SP value of each constituent component and the mass fraction of the constituent component. The SP value of the polymer of the present invention can be adjusted appropriately by changing the type and content of the polycondensable compound.

[0107] The weight-average molecular weight of the polymer of the present invention is not particularly limited, and is, for example, preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more. The upper limit of the weight-average molecular weight is substantially 100,000 or less, but is preferably 50,000 or less. From the viewpoint of shortening the dispersion time and improving the dispersion characteristics, it is more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 15,000 or less. When the polymer 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. On the other hand, when the polymer of the present invention has a multibranched 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 5,000 to 70,000, and more preferably 10,000 to 30,000. The weight average molecular weight of the polymer of the present invention can be appropriately adjusted by changing the type and content of the polymerization initiator, polymerization time, polymerization temperature, etc.

[0108] - Molecular Weight Measurement - In the present invention, unless otherwise specified, the molecular weight of a polymer or polymer chain refers to a 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 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

[0109] The polymer of the present invention preferably has no flash point. When the polymer of the present invention has no flash point, a high dispersing effect can be obtained, although the detailed mechanism is unknown. In the present invention, the polymer of the present invention having no flash point means that the flash point is 250°C or higher. In other words, the polymer of the present invention preferably has a flash point of 250°C or higher. The fact that the polymer of the present invention has no flash point can be confirmed by measuring the flash point according to Japanese Industrial Standards (JIS) K 2265-1, ASTM D3278, JIS K 2265-3, etc., usually JIS K 2265-1.

[0110] The polymer of the present invention contains the component (A) having the polar functional group, and preferably has a small acid value, more preferably 3 mgKOH / g or less. It is believed that an acid value of 3 mgKOH / g or less can suppress excessive aggregation and precipitation of the polymer of the present invention and solid particles. The acid value of the polymer of the present invention is more preferably 2 mgKOH / g or less, particularly preferably 1 mgKOH / g or less, and even more preferably 0.5 mgKOH / g or less. The lower limit of the acid value of the polymer of the present invention is preferably 0 mgKOH / g. The acid value of the polymer of the present invention indicates the number of milligrams of potassium hydroxide required to neutralize the acidic groups present in 1 g of the polymer of the present invention, and can be measured by the following method. The acidic group is not particularly limited as long as it can be neutralized with potassium hydroxide, and examples thereof include a carboxylic acid group (carboxy group), a sulfonic acid group (sulfo group), a phosphoric acid group (phospho group), a phosphonic acid group, a phosphinic acid group, or salts thereof. (Measuring Method) 1 g of the polymer of the present invention is dissolved in 25 g of tetrahydrofuran, and the solution is titrated with a 0.01 N KOH solution using a potentiometric titrator to determine the content.

[0111] The polymer of the present invention contains the component (A) having the polar functional group, and preferably has a small base number, for example, 2 mgKOH / g or less. A base number of 2 mgKOH / g or less is believed to prevent excessive aggregation and precipitation of the polymer of the present invention and solid particles. The base number of the polymer of the present invention is more preferably 1 mgKOH / g or less, and even more preferably 0.5 mgKOH / g or less. The lower limit of the base number of the polymer of the present invention is preferably 0 mgKOH / g. The base number of the polymer of the present invention is expressed as the number of milligrams of potassium hydroxide equivalent to the number of moles of acid required to neutralize the basic groups present in 1 g of the polymer of the present invention, and can be measured by the following method. The basic group is not particularly limited as long as it can be neutralized with HCl. Examples of the basic group include groups having a basic nitrogen atom, preferably groups having a basic nitrogen atom bonded to a hydrogen atom. Specific examples include amino groups, pyridyl groups, imino groups, amidine groups, and the above-mentioned urea or urethane groups having a hydrogen atom bonded to a nitrogen atom. (Measurement Method) 1 g of the polymer of the present invention is dissolved in 25 g of tetrahydrofuran, and the solution is titrated with 1N-HCl solution using a potentiometric titrator. The number of moles of HCl required for neutralization can be calculated by converting it into milligrams of potassium hydroxide.

[0112] The acid value and base value of the polymer of the present invention may be within the above ranges, but it is more preferable that the acid value is 0.5 mg KOH / g or less and the base number is 0.5 mg KOH / g or less.

[0113] The polymer of the present invention may be a non-crosslinked polymer or a crosslinked polymer. Furthermore, when crosslinking of the polymer of the present invention progresses due to heating or application of voltage, the molecular weight may be larger than the above-mentioned molecular weight. Preferably, the polymer of the present invention has a weight-average molecular weight within the above-mentioned range at the start of use of the all-solid-state secondary battery.

[0114] The polymer of the present invention 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 of the present invention is preferably 100 ppm (by mass) or less. The polymer of the present invention may be crystallized and dried, or the polymer dispersion may be used as is.

[0115] <Other Components> The polymer of the present invention usually comprises the above-described polymer of the present invention, but may also contain components used during polymerization, such as a polymerization initiator, or decomposition products thereof, etc. Furthermore, the polymer of the present invention can also be used as a polymer liquid of the present invention, dissolved or dispersed in a dispersion medium, etc., which will be described later.

[0116] [Nonaqueous Secondary Battery Composition] The nonaqueous secondary battery composition of the present invention is a composition containing the polymer 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 of the present invention, appropriate components depending on the intended use. For example, a nonaqueous electrolyte secondary battery electrode composition contains the polymer 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 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 of the present invention do not need to be present integrally as the polymer of the present invention, and the components may be present independently (separately).

[0117] As described above, even when the solid content of the nonaqueous secondary battery composition of the present invention is increased, solid particles such as inorganic solid electrolytes are dispersed with excellent dispersion properties without being damaged. The solid content is not uniquely determined by changes in the temperature of the composition, the type of solid particles, etc., but can be, for example, 40% by mass or more at 25°C, and even 50% by mass or more. When used as a material for forming constituent layers of nonaqueous secondary batteries, the nonaqueous secondary battery composition of the present invention exhibiting the above-described properties can be used to realize a nonaqueous secondary battery sheet having a low-resistance constituent layer, and a nonaqueous secondary battery with low resistance (high conductivity) and excellent cycle characteristics. Therefore, the nonaqueous secondary battery composition of the present invention can be preferably used as a material for forming constituent layers of nonaqueous secondary batteries (including electrode sheets for nonaqueous secondary batteries).

[0118] In the non-aqueous secondary battery composition of the present invention, the polymer 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 the polymer be soluble. That is, the polymer of the present invention is preferably present in a dissolved state in the dispersion medium in the non-aqueous secondary battery composition, depending on the content. When the polymer of the present invention is dissolved, it stably exhibits the function of dispersing solid particles in the dispersion medium, further improving the dispersion characteristics of the solid particles in the non-aqueous secondary battery composition. In the present invention, the dissolution of the polymer of the present invention in the dispersion medium is not limited to an embodiment in which the entire polymer of the present invention is dissolved in the dispersion medium. For example, as long as the solubility in the dispersion medium is 80% or more, as described below, a portion of the polymer of the present invention may be insoluble in the non-aqueous secondary battery composition. The solubility can be measured as follows. That is, a specified amount of the polymer of the present invention to be measured is weighed into a glass bottle, 100 g of the same type of dispersion medium as the dispersion medium contained in the nonaqueous secondary battery composition is added thereto, and the mixture is stirred for 24 hours at a temperature of 25°C and 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 binder dissolved (the above-specified amount), and the upper limit concentration X (mass %) at which the transmittance becomes 99.8% is defined as the solubility of the polymer binder 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

[0119] When the polymer of the present invention is particulate (insoluble in the dispersion medium contained in the non-aqueous secondary battery composition), its shape is not particularly limited and may be flat, amorphous, etc., but is preferably spherical or granular. In this case, the average particle size of the particulate polymer of the present invention 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 size of the polymer of the present invention can be measured in the same manner as the particle size of the inorganic solid electrolyte. The average particle size of the polymer of the present invention can be adjusted, for example, by the type of dispersion medium, the composition of the polymer, etc.

[0120] In the present invention, the solubility of the polymer of the present invention in a dispersion medium can be appropriately imparted by the structure, composition (type and content of constituent components), weight average molecular weight, and further combination with a dispersion medium of the polymer of the present invention.

[0121] 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 composition but also a composition having a water content (also referred to as water content) of 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, the polymer of the present invention can be dissolved and deterioration of the solid particles, particularly the inorganic solid electrolyte, can be suppressed. 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.

[0122] 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.

[0123] <Polymer of the Present Invention> The non-aqueous secondary battery composition of the present invention contains the above-described polymer of the present invention. The non-aqueous secondary battery composition may contain one or more types of polymer of the present invention. The content of the polymer of the present invention (solid content equivalent) in the non-aqueous secondary battery composition can be determined as appropriate. For example, from the viewpoints of suppressing damage to solid particles and dispersing solid particles, 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 %. For the same reasons, the content of the polymer of the present invention (solid content equivalent) in 100 mass % solids of the non-aqueous secondary battery composition 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 %. In the present invention, at a solid content of 100% by mass, the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the polymer of the present invention [(mass of inorganic solid electrolyte + mass of active material) / (total mass of the polymer of the present invention)] is preferably in the range of 2,000 to 1. This ratio is more preferably 1,000 to 10, and even more preferably 500 to 20.

[0124] <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. The polymer of the present invention can reduce the load acting on the inorganic solid electrolyte during the preparation of a nonaqueous secondary battery composition, thereby suppressing deterioration and decomposition. Therefore, sulfide-based inorganic solid electrolytes, which are 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.

[0125] (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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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 ５ By 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.

[0130] 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-P２ S ５ 、Li ２ S-Li ２ O-P ２ S ５ 、Li ２ S-Li ３ PO 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-P ２ 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 ２S 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 P.O. ４ , Li １０ GeP ２ S １２ However, 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.

[0131] (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.

[0132] 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 ｚｂM 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 ｃｃ is 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 Alumni２ 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 Zn ０．２５ 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.

[0133] (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 ６ Among them, Li ３ YBr ６ , Li ３ YCl ６ is preferred.

[0134] (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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] <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.

[0139] 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.

[0140] 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.).

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] <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).

[0148] (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 M ａ 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.

[0149] (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 , Li ２ CrMn ３ O ８ and Li ２ NiMn ３ O ８Examples 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.

[0150] 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.

[0151] 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.

[0152] (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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] The negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is one that is 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 ion absorption 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 Si, SiO ｘ Silicon materials such as silicon (0<x≦1), as well as 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 active material include silicon and tin-containing active materials such as SiO ｘ can be used as an anode active material (semi-metal oxide) by itself, and can also be used as an anode active material (precursor material) that can be alloyed with lithium because it produces Si during operation of an all-solid-state secondary battery. Examples of anode active materials containing tin 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] (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.

[0165] <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.

[0166] 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.

[0167] <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.

[0168] <Dispersant Other Than the Polymer of the Present Invention> The non-aqueous secondary battery composition of the present invention does not need to contain any dispersant other than the polymer of the present invention because the above-described polymer of the present invention functions as a dispersant. However, it may contain a dispersant other than the polymer of the present invention (referred to as "other dispersant") to reinforce the dispersing function of the polymer of the present invention. As the other dispersant, one that is commonly used in non-aqueous secondary batteries can be appropriately selected and used. Generally, compounds intended for particle adsorption and steric and / or electrostatic repulsion are preferably used. The non-aqueous secondary battery composition of the present invention may contain one or more other dispersants. When the non-aqueous 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 non-aqueous secondary battery composition.

[0169] <Binder> The non-aqueous secondary battery composition of the present invention does not need to contain any binder other than the polymer of the present invention because the polymer of the present invention can also function as a binder in the constituent layers. However, a binder other than the polymer of the present invention may be contained to reinforce the binder function of the polymer of the present invention. Such a binder can be appropriately selected from binders commonly used in non-aqueous secondary batteries. The non-aqueous secondary battery composition of the present invention may contain one or more binders other than the polymer of the present invention. When the non-aqueous secondary battery composition of the present invention contains a binder other than the polymer of the present invention, the content of the binder is appropriately determined. For example, the content of the binder (equivalent to the solid content) in the non-aqueous 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 (solid content equivalent) in 100% by mass of the solid content of the nonaqueous secondary battery composition 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 of the present invention [(mass of inorganic solid electrolyte + mass of active material) / (total mass of binder other than the polymer of the present invention)] is preferably in the range of 1,000 to 1. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.

[0170] <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.

[0171] (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 of the present invention and the above-described 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.

[0172] The mixing time is not particularly limited and can be determined appropriately depending on the dispersibility of the solid particles, and can be, for example, 1 to 180 minutes. Because the polymer of the present invention can disperse solid particles into the dispersion medium to the desired dispersion state in a short time, the mixing time (dispersion time) can be set short, for example, 30 minutes or less, and preferably 5 to 25 minutes. Here, the mixing time shortened by the polymer of the present invention refers to the mixing time when mixing the solid particles, the polymer of the present invention, and the dispersion medium. However, if the components are mixed in multiple stages, the mixing time at each stage can be shortened. By setting the mixing time short in this way, the dispersion energy and load acting on the solid particles during dispersion can be reduced, suppressing damage to the solid particles, thereby achieving a low-resistance component layer and a nonaqueous secondary battery with low resistance and excellent cycle characteristics. Furthermore, because the nonaqueous secondary battery composition of the present invention has excellent solid particle dispersion properties, it can be stored after preparation and does not need to be prepared each time it is used.

[0173] [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.

[0174] <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.

[0175] 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) and the polymer of the present invention are adhered (bound) together in a mixed state. The sheet for an all-solid-state secondary battery can be incorporated into an all-solid-state secondary battery by peeling off the substrate as appropriate, or by incorporating the sheet into an all-solid-state secondary battery as is, thereby achieving low resistance (improved conductivity) and excellent cycle characteristics of the all-solid-state secondary battery.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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 includes a constituent layer having a flat surface and low resistance, to which solid particles containing an inorganic solid electrolyte are bound. By using this constituent layer 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.

[0180] [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.

[0181] 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.

[0182] [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.

[0183] <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.

[0184] 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.

[0185] <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 1,000 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.

[0186] <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.

[0187] 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.

[0188] <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.

[0189] <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.

[0190] <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.

[0191] 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.

[0192] 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.

[0193] (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 electrolytes and the polymers of the present invention 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.

[0194] 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 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 of the present invention, and the optional components described above within the scope of the present invention, and the optional components described above within the scope of the present invention. The negative 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 negative electrode active material, the polymer of the present invention, and the optional components described above within the scope of the present invention, and the optional components described above within the scope of the present invention. In the all-solid-state secondary battery 10, the negative electrode active material layer can be a lithium metal layer. Examples of the lithium metal layer include a layer formed by depositing or molding lithium metal powder, a lithium foil, and a lithium vapor-deposited film. 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.

[0195] 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.

[0196] (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.

[0197] [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.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] <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.

[0202] 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. It may also be pressed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. It may also be pressed at a temperature higher than the glass transition temperature of the polymer of the present invention. However, the temperature is generally not higher than the melting point of the polymer 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.

[0203] 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.

[0204] <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.

[0205] [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.

[0206] 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.

[0207] [Example 1] Synthesis of polymer and preparation of polymer solution or dispersion Polymers shown in the following chemical formula and Table 1 were synthesized as follows, and polymer solutions or dispersions were prepared. 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 following polymer B-01, "Ph" represents a phenyl group. In the following polymers B-01 to B-06, B-21, and T-1 to T-5, the numerical value written to the lower right of each constituent component indicates the content (% by mass) of that constituent component in the polymer.

[0208]

[0209]

[0210]

[0211] [Synthesis Example B-01: Synthesis of Polymer B-01, and Preparation of Polymer Solution B-01] First, 12.6 g of KF-2012 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 5.4 g of benzyl methacrylate, and 2.7 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 81 g of butyl butyrate was dissolved to prepare a monomer solution. Next, 81 g of butyl butyrate was added to a 300 mL three-necked flask, and the mixture was stirred at 85 ° C. under a nitrogen stream. Next, the monomer solution was added dropwise over 2 hours, and after completion of the dropwise addition, the mixture was heated 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. After removing the supernatant, the obtained precipitate 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, a random copolymer polymer B-01 was synthesized, and a polymer solution B-1 (concentration 10% by mass) consisting of this polymer was obtained.

[0212] [Synthesis Examples B-02 to B-06: Synthesis of Polymers B-02 to B-06, and Preparation of Polymer Solutions B-02 to B-06] Random copolymer polymers B-02 to B-06 were synthesized in the same manner as in Synthesis Example B-01, except that in Synthesis Example B-01, compounds were used that would lead to each constituent component so that polymers B-02 to B-06 would have the compositions (types and contents of constituent components) shown in Table 1, and the amount of polymerization initiator was adjusted so that the weight-average molecular weight would be as shown in Table 1, and polymer solutions B-02 to B-06 composed of each polymer were obtained, respectively.

[0213] Synthesis Example B-07: Synthesis of Polymer B-07, and Preparation of Polymer Solution B-07 First, 80.6 g (89.4 mmol) of X-22-174ASX (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.4 g of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 500 mL graduated cylinder and dissolved in 81 g of butyl butyrate to prepare a monomer solution (X). Next, 152 g of butyl butyrate and 20.0 g of dipentaerythritol hexakis(3-mercaptopropionate) (trade name: DPMP, manufactured by SC Organic Chemical Industry, 25.5 mmol) were added to a 500 mL three-neck flask, and the mixture was stirred at 80°C under a nitrogen stream. An initiator solution prepared by previously mixing and dissolving 0.3 g of polymerization initiator V-601 and 2 g of butyl butyrate was added. After 10 minutes, the monomer solution (X) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 80°C for 1 hour, then heated to 90°C and stirred for 2 hours to obtain a polymer solution. Next, 81.1 g (24.3 g solids) of the polymer solution obtained above, 3.5 g (27.5 mmol) of t-butylacrylamide (tBuAAm), and 0.1 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 20 g of N-methyl-2-pyrrolidone to prepare a monomer solution (A). Next, 33 g of butyl butyrate was added to a 300 mL three-neck flask, and the mixture was stirred at 80°C under a nitrogen stream. An initiator solution prepared by previously mixing and dissolving 0.05 g of polymerization initiator V-601 and 2 g of butyl butyrate was added. Next, after 10 minutes, the monomer solution (A) was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for 2 hours, then heated to 90°C and stirred for 1 hour. The obtained polymerization solution was poured into 800 g of methanol, stirred for 10 minutes, and then allowed to stand for 10 minutes. The supernatant was removed, and the obtained precipitate was dissolved in 60 g of butyl butyrate. The methanol was distilled off by heating at 30 hPa and 80°C for 1 hour. Thus, a polymer chain P consisting of a homopolymer of X-22-174ASX was obtained. １Ｘ and a polymer chain P consisting of a homopolymer of tBuAAm. １Ａ A hyperbranched polymer B-07 having the above as polymeric arm moieties was synthesized, and a polymer solution B-07 (concentration 10% by mass) consisting of this polymer was obtained.

[0214] [Synthesis Examples B-08 to B-20: Synthesis of Polymers B-08 to B-20, and Preparation of Polymer Solutions B-08 to B-20] Hyperbranched polymers B-08 to B-20 were synthesized in the same manner as in Synthesis Example B-07, except that compounds were used to induce each component so that polymers B-08 to B-20 had the compositions shown in Table 1 (types and contents of each component of the constituents and core portion) and the amount of polymerization initiator was adjusted so that the weight-average molecular weight would be as shown in Table 1, and polymer solutions B-08 to B-20 comprising each polymer were obtained, respectively. The polymeric arm portions in each hyperbranched polymer were all polymer chains comprising a homopolymer of constituent component (X) or constituent component (A).

[0215] Synthesis Example B-21: Synthesis of Polymer B-21 and Preparation of Binder Dispersion B-21 First, macromonomer M-7 was synthesized as follows. 150.2 g of methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 380.8 g of dodecyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 5.0 g of mercaptopropionic acid, and 5.0 g of polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a 1 L measuring cylinder, and the mixture was stirred to dissolve uniformly to prepare a monomer solution (M1). 468 g of toluene (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to a 2 L three-neck flask, and the mixture was stirred at 80°C, to which the monomer solution (M1) was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for 2 hours, and then the temperature was raised to 90°C and the mixture was stirred for 2 hours. Next, 480 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 32.8 g of glycidyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 6.5 g of tetrabutylammonium bromide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at 120°C for 3 hours. After allowing the solution to stand at room temperature, it was poured into 1800 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-7. The solids concentration was 40% by mass, and the number average molecular weight was 12,500.

[0216] Next, polymer B-21 was synthesized using macromonomer M-7 as follows. 120.0 g of Blemmer AE-400 (NOF Corporation) and 2.40 g of polymerization initiator V-601 (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 500 mL graduated cylinder and dissolved in 155.8 g of butyl butyrate to prepare monomer solution (M2). 300 g of macromonomer M-7 solution (120.0 g solids) and 225.0 g of butyl butyrate were added to a 2 L three-neck flask and stirred at 80°C, to which the monomer solution (M2) was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 90°C and stirring was continued for 2 hours. In this way, binder dispersion B-21 (concentration 30% by mass) in which polymer B-21 was dispersed in butyl butyrate was obtained. The average particle size of the binder in this dispersion was 100 nm.

[0217] [Synthesis Examples T-1 to T-5: Synthesis of Polymers T-1 to T-5, and Preparation of Polymer Solutions T-1 to T-5] Polymers T-1 to T-5 were synthesized in the same manner as in Synthesis Example B-01, except that in Synthesis Example B-01, compounds were used that would lead to each constituent component so that polymers T-1 to T-5 would have the compositions (types and contents of constituent components) shown in Table 1, and the amount of polymerization initiator was adjusted so that the weight-average molecular weight would be as shown in Table 1, and polymer solutions T-1 to T-5 composed of each polymer were obtained, respectively. Polymers T-1 and T-3 to T-5 are random copolymers.

[0218] [Synthesis Examples T-6 to T-7: Synthesis of Polymers T-6 to T-7, and Preparation of Polymer Solutions T-6 to T-7] Polymers T-6 to T-7 were synthesized in the same manner as in Synthesis Example B-07, except that compounds were used to induce each component so that polymers T-6 to T-7 had the compositions shown in Table 1 (types and contents of each component of the constituent components and core portion) and the amount of polymerization initiator was adjusted so that the weight-average molecular weights would be as shown in Table 1, and polymer solutions T-6 to T-7 composed of each polymer were obtained.

[0219] The acid value and base value of each synthesized polymer were measured by the methods described above. As a result, the acid value of polymer B-06 was 13 mgKOH / g, the acid value of polymer B-19 was 6 mgKOH / g, the acid value of polymer B-20 was 20 mgKOH / g, and the acid value of polymer T-5 was 8 mgKOH / g, and the acid values ​​of the other polymers were 0 mgKOH / g. The base values ​​of polymers B-01 to B-21 and T-1 to T-7 were all 0 mgKOH / g.

[0220] The viscosity and weight-average molecular weight of each synthesized polymer are shown in Table 1. The viscosity and weight-average molecular weight were measured by the above-mentioned method. The viscosity was measured by thoroughly drying the solvent under reduced pressure and preparing a sample of the polymer alone. In addition, the "State" column in Table 1 shows the state of the polymer in each composition described below, determined as "dissolved" or "particles" (not dissolved but dispersed in particulate form) as a result of measuring the solubility in the dispersion medium by the above-mentioned method. Note that none of the synthesized polymers had a flash point (the flash point was 250°C or higher). The "Content (mass%)" in Table 1 is a value calculated from the charge ratio of each compound during preparation.

[0221]

[0222] <Abbreviations in Table 1> In Table 1, a "-" in the constituent column indicates that the corresponding constituent is not present. Note that benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value 20.2) used in the preparation of polymer B-01 and 2-ethylhexyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value 17.3) used in the preparation of polymer T-1 do not correspond to either constituent component (A) or constituent component (X), and therefore are not listed in the constituent component column of Table 1. The "constituent component (X)" column in Table 1 shows the following compound from which the above constituent component (X) is derived. M-1: X-22-174ASX (product number, molecular weight 900, manufactured by Shin-Etsu Chemical Co., Ltd., SP value 16.7) M-2: X-22-174BX (product number, molecular weight 2300, manufactured by Shin-Etsu Chemical Co., Ltd., SP value 16.4) M-3: KF-2012 (product number, molecular weight 4600, manufactured by Shin-Etsu Chemical Co., Ltd., SP value 16.3) M-4: X-22-2404 (product number, molecular weight 400, manufactured by Shin-Etsu Chemical Co., Ltd., SP value 16.8) M-5: Methoxypolyethylene glycol monomethacrylate (Blemmer PME-200, manufactured by NOF Corporation), molecular weight 300, SP value 20.3 M-6: Polyethylene glycol monomethacrylate (Blemmer AE-400, manufactured by NOF Corporation), molecular weight 500, SP value 21.5 M-7: Macromonomer synthesized in Synthesis Example B-21, number average molecular weight 12,500, SP value 18.0

[0223] The column "Component (A)" in Table 1 shows the following compounds from which the component (A) is derived. tBuAAm: N-tert-butylacrylamide (Fujifilm Wako Pure Chemical Industries, Ltd., SP value 24.1) iPrAAm: N-iso-propylacrylamide (Fujifilm Wako Pure Chemical Industries, Ltd., SP value 25.8) MeAAm: N-methylacrylamide (Sigma-Aldrich Corporation, SP value 31.4) PhAAm: N-phenylacrylamide (Fujifilm Wako Pure Chemical Industries, Ltd., SP value 27.9) HEA: 2-hydroxyethyl acrylate (Fujifilm Wako Pure Chemical Industries, Ltd., SP value 23.5) GMA: glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd., SP value 23.7) MEA: methoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd., SP value 20.0) Phosmer PP: Acid Phosphoxy Polyoxy Propylene Glycol Monomethacrylate (Propyleneoxy group polymerization degree 5-6, manufactured by Unichemical Corporation, SP value 19.4) MAA: Methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd., SP value 24.0) HEMA: 2-Ethylhexyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd., SP value 22.9) MA: Maleic anhydride (Fujifilm Wako Pure Chemical Industries, Ltd., SP value 24.1) AA: Acrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd., SP value 25.5)

[0224] The "Core part" column in Table 1 shows the following compounds that lead to "L-(S-)n" in the above formula (1): DPMP: dipentaerythritol hexakis(3-mercaptopropionate), manufactured by SC Organic Chemicals Co., Ltd. PEMP: pentaerythritol tetra(3-mercaptopropionate), manufactured by SC Organic Chemicals Co., Ltd. MUT4: pentaerythritol tetrapropanethiol (trade name: Multiol (registered trademark) Y-4, manufactured by SC Organic Chemicals Co., Ltd. TMMP: trimethylolpropane tris(3-mercaptopropionate), manufactured by SC Organic Chemicals Co., Ltd.

[0225] [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 ５ 3.90 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.

[0226] 2. Each composition shown in Tables 2-1 to 2-4 (collectively referred to as Table 2) was prepared as follows. <Preparation of Inorganic Solid Electrolyte-Containing Compositions> 60 g of zirconia beads with a diameter of 5 mm was placed in a 45 mL zirconia container (manufactured by Fritsch), and 9.85 g of LPS synthesized in Synthesis Example A above, 0.15 g (solid content by mass) of the polymer solution or dispersion shown in Table 2-1 or Table 2-4, and 10 g (total amount) of butyl butyrate as a dispersion medium were then placed in the container. The container was then placed 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-21 and Kc11 to Kc17, respectively.

[0227] <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 the 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 solution or dispersion 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-21 and PKc21 to PKc27, respectively.

[0228] <Preparation of negative electrode composition> A 45 mL zirconia container (manufactured by Fritsch) was charged with 60 g of zirconia beads having a diameter of 5 mm, 4.53 g of LPS synthesized in Synthesis Example A, 0.08 g (solid content mass) of the polymer solution or dispersion 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, and negative electrode compositions (slurries) NK-1 to NK-21 and NKc21 to NKc27 were prepared, respectively.

[0229] 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.

[0230] <Evaluation 1: Dispersion Time Test> For each composition prepared as described above, LPS, polymer solution, dispersion medium, active material, and conductive additive were mixed in the same proportions as the composition content and solid content shown in Table 2 under the same conditions as for each composition to prepare a composition for dispersibility evaluation (slurry). Each prepared composition was examined for the presence of solid particle agglomerates using a grindmeter (manufactured by Asahi Research Institute Co., Ltd.). In this test, the particle size at which linear and granular marks occurred was observed using the grindmeter, and a particle size of 5 μm or less was defined as the absence of agglomerates. Each composition was also evaluated for uniformity (at a consistent coating thickness without running out) using a Baker-type applicator (product name: SA-201) at 25°C. This evaluation (presence or absence of agglomerates and applicability) was evaluated by determining whether the dispersion time under each of the preparation conditions for each composition described above was the type condition (Tp). The dispersion time was then extended, and the shortest dispersion time (T) at which a uniform coating was achieved without the occurrence of agglomerates was included in the following evaluation criteria for the type condition. The results are shown in Table 2. In this test, the shorter the shortest dispersion time (T), the more excellent dispersibility of solid particles can be maintained even when the dispersion energy applied to the composition is reduced, and an evaluation standard of "D" or higher is a passing level. - Evaluation standard - A: T≦Tp×1.1 B: Tp×1.1≦T<Tp×1.3 C: Tp×1.3≦T<Tp×1.5 D: Tp×1.5≦T<Tp×2.0 E: Tp×2.0≦T<Tp×3.0 F: Aggregates are present even at a dispersion time 3.0 times Tp.

[0231] <Evaluation 2: Storage Stability Test (Redispersibility)> The dispersion stability of each composition prepared as described above was evaluated based on the redispersibility (storage stability) of the composition, which allows the composition to be redispersed to an excellent dispersion state immediately after preparation (initial). Specifically, for each prepared composition, LPS, a polymer solution, 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 those for 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 aggregates of solid particles was confirmed using a grindmeter (manufactured by Asahi Research Institute Co., Ltd.). The size of the aggregates at this time was designated 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 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 designated 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 likelihood of agglomerate formation (aggregation tendency or sedimentation tendency) was evaluated as the storage stability (solid particle redispersibility) 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 storage 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

[0232] <Evaluation 3: Handling Test> A slurry with a solid content concentration of 72% by mass was prepared in the same manner as each of the prepared compositions, except for the dispersion medium, with the same mixing ratio. A 2 mL plastic dropper (manufactured by Atect Co., Ltd.) was placed vertically so that the tip 10 mm was below the interface of the slurry, and the slurry was sucked at 25°C for 10 seconds, and the mass W of the plastic dropper containing the sucked slurry was measured. The tare weight (weight) of the plastic dropper was W ０ When this is done, the slurry mass W-W ０ If the amount of the slurry was less than 0.1 g, it was determined that the slurry could not be sucked up with a dropper. If the slurry could not be sucked up with a dropper, the upper limit of the solid content concentration that could be sucked up with a dropper was determined by gradually adding the dispersion medium. The handleability of each composition (whether the composition had a viscosity appropriate for forming a flat, well-formed layer) was evaluated based on whether the obtained upper limit of the solid content 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, heating it at 120°C for 2 hours, and distilling off the dispersion medium. In this test, a higher upper limit of the solid content concentration indicated better handleability, and a rating of "D" or higher was considered a passing level. The results are shown in Table 3. - Evaluation criteria - A: Upper limit solid content ≧ 70% B: 70% > upper limit solid content ≧ 65% C: 65% > upper limit solid content ≧ 60% D: 60% > upper limit solid content ≧ 55% E: 55% > upper limit solid content ≧ 50% F: 50% > upper limit solid content

[0233]

[0234]

[0235]

[0236]

[0237] LPS: LPS synthesized in Synthesis Example A NMC: LiNi １／３ Co １／３ Mn １／３ O ２ Si: Silicon (APS 1-5 μm, manufactured by Alfa Aesar) AB: Acetylene black VGCF: Carbon nanofiber

[0238] 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 of 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 121 and c11 to c17, respectively. The film thickness of the solid electrolyte layer was 40 μm.

[0239] <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 221 and c21 to c27, respectively, having a positive electrode active material layer with a film thickness of 70 μm.

[0240] <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 321 and c31 to c37, respectively, having a negative electrode active material layer with a film thickness of 60 μm.

[0241]

[0242]

[0243]

[0244]

[0245] 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.

[0246] - 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 221 and c21 to c27 (cathode active material layer thickness 50 μm) each having a solid electrolyte layer with a thickness of 25 μm.

[0247] - 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 321 and c31 to c37 each having a solid electrolyte layer with a thickness of 25 μm (negative electrode active material layer thickness of 40 μm).

[0248] 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).

[0249] All solid state secondary batteries Nos. 402 to 421 and c101 to c107 were produced as follows. All solid state secondary batteries Nos. 402 to 421 and c101 to c107 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.

[0250] 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 .

[0251] 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.

[0252] All solid state secondary batteries Nos. 502 to 521 and c201 to c207 were produced as follows. All solid state secondary batteries Nos. 502 to 521 and c201 to c207 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.

[0253] <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

[0254] <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 421 and 501 to 521 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

[0255]

[0256]

[0257]

[0258] The results shown in Tables 1 to 4 reveal the following: －１When a polymer other than the polymer having a component (X) with a viscosity of 0.10 to 10,000 Pa·s at 25°C and a molecular weight of 400 or more is used in combination with the solid particles, the dispersion time of the solid particles cannot be shortened, and the resulting inorganic solid electrolyte-containing composition is inferior in dispersion stability and handleability. All-solid-state secondary batteries produced using such inorganic solid electrolyte-containing compositions are inferior in both battery resistance and cycle characteristics. In contrast, when a polymer other than the polymer having a component (X) with a viscosity of 0.10 to 10,000 Pa·s at 25°C and a shear rate of 1 s －１ When the polymer of the present invention, which has a viscosity of 0.10 to 10,000 Pa s at 2000 W / V and which contains a polymer chain and a component (X) having a molecular weight of 400 or more, is used in combination with solid particles, the solid particles can be dispersed in a dispersion medium as desired, despite the fact that the dispersion time of the solid particles can be shortened, and an inorganic solid electrolyte-containing composition having excellent dispersion stability and handleability can be prepared. Furthermore, an all-solid-state secondary battery produced using an inorganic solid electrolyte-containing composition exhibiting such excellent dispersion properties has low battery resistance (conductivity) and excellent cycle characteristics.

[0259] 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.

[0260] This application claims priority based on Japanese Patent Application No. 2023-108490, filed in Japan on June 30, 2023, the contents of which are incorporated herein by reference.

[0261] 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

Claims

1. Temperature 25°C and shear rate 1 s －１ A dispersant polymer for non-aqueous secondary batteries having a viscosity of 0.10 to 10000 Pa·s, containing a polymer chain, and having a constituent component (X) with a molecular weight of 400 or more.

2. The dispersant polymer for non-aqueous secondary batteries according to claim 1, comprising a component (A) having at least one polar functional group from the following functional group group (a). <Functional group group (a)> Sulfonic acid groups, phosphate groups, phosphonic acid groups, hydroxyl groups, carboxyl groups, oxetane groups, epoxy groups, dicarboxylic acid groups, thiol groups, ether groups, thioether groups, thioester groups, ester groups, amide groups, urethane groups, urea groups, imide groups, fluoroalkyl groups, and salts thereof.

3. The dispersant polymer for non-aqueous secondary batteries according to Claim 2, wherein the constituent component (A) has at least one polar functional group selected from a sulfonic acid group, a phosphate group, a phosphonic acid group, a hydroxyl group, an oxetane group, an epoxy group, a thiol group, a thioether group, a thioester group, an amide group, a urethane group, a urea group, an imide group, a fluoroalkyl group, and salts thereof.

4. The dispersant polymer for non-aqueous secondary batteries according to claim 2, wherein the constituent component (A) has an amide group.

5. The SP value of the polymer chain in the aforementioned dispersant polymer for non-aqueous secondary batteries is 15.0 to 25.0 MPa. １／２ The dispersant polymer for non-aqueous secondary batteries according to claim 1.

6. The dispersant polymer for non-aqueous secondary batteries according to claim 1, having a multi-branched structure comprising a core portion and at least three polymeric arm portions.

7. The dispersant polymer for non-aqueous secondary batteries according to claim 1, which is a highly branched polymer represented by the following formula (1). 【Chemistry 1】 In formula (1), L represents an n-valent linking group. P １ represents a polymer chain, and n P １ These may be the same or different. n is an integer greater than or equal to 3.

8. The dispersant polymer for non-aqueous secondary batteries according to claim 1, having a graft structure.

9. A composition for a non-aqueous secondary battery containing the dispersant polymer for non-aqueous secondary batteries described in any one of claims 1 to 8.

10. The composition for a non-aqueous secondary battery according to claim 9, comprising an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table.

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

12. A composition for a non-aqueous secondary battery according to claim 9, comprising an active material.

13. A sheet for an all-solid-state secondary battery having a layer formed using the non-aqueous secondary battery composition described in claim 9.

14. A sheet for an all-solid-state secondary battery having a layer formed using the non-aqueous secondary battery composition described in claim 10.

15. 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, An all-solid-state secondary battery in which 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 non-aqueous secondary battery composition described in claim 9.

16. 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, An all-solid-state secondary battery in which 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 non-aqueous secondary battery composition described in claim 10.

17. A method for producing a sheet for an all-solid-state secondary battery that forms a film of the non-aqueous secondary battery composition described in claim 9.

18. A method for manufacturing an all-solid-state secondary battery, comprising manufacturing an all-solid-state secondary battery via the manufacturing method described in claim 17.

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