Composition for all-solid-state secondary battery, sheet for all-solid-state secondary battery, and all-solid-state secondary battery

Abstract

Provided are: a composition for an all-solid-state secondary battery, the composition containing an inorganic solid electrolyte (SE), an active material AC, a dispersion medium D, and a polymer A that dissolves in the dispersion medium D, the composition being such that Aa calculated using formula 1 below satisfies the relationship 1≤Aa≤100; a sheet for an all-solid-state secondary battery in which the composition for an all-solid-state secondary battery is used; and an all-solid-state secondary battery. Formula 1: Aa = (adsorption rate of polymer A to active material AC)2×[((polymer A content / total solid content) / molecular weight of polymer A) / (total specific surface area of active material AC)3 / 2]×1010. In formula 1, the total specific surface area of the active material AC is a value that is calculated from the specific surface area of the active material AC multiplied by the active material AC content divided by the total solid content.

Description

Composition for all-solid-state secondary battery, sheet for all-solid-state secondary battery, and all-solid-state secondary battery

[0001] The present invention relates to a composition for an all-solid-state secondary battery, a sheet for an all-solid-state secondary battery, and an all-solid-state secondary battery.

[0002] All-solid-state secondary batteries, in which the negative electrode, electrolyte, and positive electrode are all solid, can significantly improve the safety and reliability that are issues with batteries that use organic electrolytes. It is also believed that they can achieve longer life. Furthermore, all-solid-state secondary batteries can be configured with electrodes and electrolytes directly arranged in series. This allows for higher energy density than secondary batteries that use organic electrolytes, and they are expected to be used in electric vehicles, large-scale storage batteries, and other applications.

[0003] The constituent layers (e.g., solid electrolyte layer, negative electrode active material layer, positive electrode active material layer) of all-solid-state secondary batteries are typically formed as layers composed of solid particles using materials in which solid particles such as inorganic solid electrolytes, active materials, and conductive additives are dispersed in a dispersion medium. However, if the solid particles locally aggregate and exist in a non-uniform state (uneven distribution) in the constituent layers, current concentration and / or ion concentration locally occur in the inorganic solid electrolyte and / or active material during charge / discharge, making the inorganic solid electrolyte and / or active material more susceptible to deterioration, resulting in a decrease in battery performance (also referred to as battery characteristics) such as life characteristics, output, and rate characteristics (charge / discharge characteristics). For this reason, techniques for improving the dispersibility of solid particles in materials forming the constituent layers have been investigated.

[0004] Methods for improving the dispersibility of solid particles include increasing the content of the dispersion medium (reducing the solid content concentration) and increasing the dispersion time (mixing time). However, these methods have manufacturing disadvantages, such as a longer drying time after coating the material that forms the constituent layer, an increased environmental load, and a rise in manufacturing costs. In recent years, with the rapid progress of research and development into the practical application of electric vehicles, in order to eliminate the above-mentioned disadvantages in the manufacture of all-solid-state secondary batteries, materials with a higher solid content concentration, such as solid particles, have been investigated. For example, Patent Document 1 describes "an electrode composition containing an inorganic solid electrolyte SE having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, an active material AC, a conductive assistant CA, a polymer binder (B), and a dispersion medium D, wherein the polymer binder (B) contains a polymer binder (B1) that dissolves in the dispersion medium D, and the polymer binder (B1), the inorganic solid electrolyte SE, the active material AC, and the conductive assistant CA satisfy the following conditions (1) to (4)." ２ (3) The content of the polymer binder (B1) in the total solid content is 1.5 mass % or less. (4) The sum of the products of the specific surface areas and the content mass fractions of the inorganic solid electrolyte SE, the active material AC, and the conductive assistant CA is 5.0 to 15.0 m ２ / g"

[0005] International Publication No. 2022 / 202902

[0006] The electrode composition described in Patent Document 1 is said to have excellent dispersion characteristics (initial dispersibility and dispersion stability) and coatability (surface properties and adhesion) even when the solid content concentration is increased. However, Patent Document 1 does not consider not only the improvement of dispersibility but also the shortening of preparation time when the solid content concentration is increased.

[0007] An object of the present invention is to provide a composition for an all-solid-state secondary battery that can be prepared in a short time while suppressing the generation of aggregates even when the solid content is increased, and that desirably contributes to improving battery performance. Another object of the present invention is to provide a sheet for an all-solid-state secondary battery and an all-solid-state secondary battery that use this composition for an all-solid-state secondary battery.

[0008] The present inventors have conducted various studies on materials for forming constituent layers, focusing on polymers present in the materials that are adsorbed or can be adsorbed to the active material or inorganic solid electrolyte, after using a polymer that dissolves in a dispersion medium in combination with the solid particles. They have found that when the value Aa or Ab calculated by Equation 1 or Equation 2 described below is within a specific range, the solid particles can be dispersed without agglomeration and in a short time, even when the solid content is increased. Furthermore, they have found that because the material for forming the constituent layers has excellent solid particle dispersibility, an all-solid-state secondary battery including a layer formed using this material can achieve high battery performance. The present invention was completed through further studies based on these findings.

[0009] That is, the above-mentioned problems have been solved by the following means: <1> A composition for an all-solid-state secondary battery, comprising an inorganic solid electrolyte SE having conductivity for ions of a metal belonging to Group 1 or 2 of the periodic table, an active material AC, a dispersion medium D, and a polymer A dissolved in the dispersion medium D, wherein Aa calculated by the following formula 1 satisfies 1≦Aa≦100. Formula 1: Aa=(adsorption rate of polymer A to active material AC) ２ × [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​active material AC)] ３／２ ] x 10 １０ In formula 1, the total specific surface area of ​​the active material AC is a value calculated from the specific surface area of ​​the active material AC × the content of the active material AC / the total solid content. <2> The composition for an all-solid-state secondary battery according to <1>, wherein Aa calculated by the above formula 1 satisfies 2≦Aa≦30. <3> The composition for an all-solid-state secondary battery according to <1> or <2>, wherein Ab calculated by the following formula 2 satisfies 2≦Ab≦500. Formula 2: Ab=(adsorption rate of polymer A to inorganic solid electrolyte SE)２ × [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​inorganic solid electrolyte SE)] ３／２ ] x 10 １０ In formula 2, the total specific surface area of ​​the inorganic solid electrolyte SE is a value calculated from the specific surface area of ​​the inorganic solid electrolyte SE × the content of the inorganic solid electrolyte SE / the total solid content. <4> The composition for an all-solid-state secondary battery according to <3>, wherein Ab calculated by the above formula 2 satisfies 2≦Ab≦300. <5> The composition for an all-solid-state secondary battery according to <3> or <4>, wherein Ac calculated by the following formula 3 satisfies 3≦Ac≦100. Formula 3: Ac=[Aa×(content of active material AC / total solid content)]+[Ab×(content of inorganic solid electrolyte SE / total solid content)] <6> The weight-average molecular weight of polymer A is 2.0×10 ４ The composition for an all-solid-state secondary battery according to any one of <1> to <5>, wherein the active material AC contains Si, and Aa calculated by the above formula 1 satisfies 2≦Aa≦15.

[0010] <8> A composition for an all-solid-state secondary battery, comprising an inorganic solid electrolyte SE having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, a dispersion medium D, and a polymer A dissolved in the dispersion medium D, wherein Ab calculated by the following formula 2 satisfies 2≦Ab≦500. Formula 2: Ab=(adsorption rate of polymer A to inorganic solid electrolyte SE). ２ × [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​inorganic solid electrolyte SE)] ３／２ ] x 10 １０ In formula 2, the total specific surface area of ​​the inorganic solid electrolyte SE is a value calculated from the specific surface area of ​​the inorganic solid electrolyte SE × the content of the inorganic solid electrolyte SE / the total solid content. <9> The composition for an all-solid-state secondary battery according to <8>, wherein Ab calculated by formula 2 satisfies 2≦Aa≦300. <10> The composition for an all-solid-state secondary battery according to <8> or <9>, which contains an active material AC and wherein Aa calculated by formula 1 below satisfies 1≦Aa≦100. Formula 1: Aa=(adsorption rate of polymer A to active material AC) ２× [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​active material AC)] ３／２ ] x 10 １０ In formula 1, the total specific surface area of ​​the active material AC is a value calculated from the specific surface area of ​​the active material AC × the content of the active material AC / the total solid content. <11> The composition for an all-solid-state secondary battery according to <10>, wherein Aa calculated by the above formula 1 satisfies 2≦Aa≦30. <12> The composition for an all-solid-state secondary battery according to <10> or <11>, wherein Ac calculated by the following formula 3 satisfies 3≦Ac≦100. Formula 3: Ac=[Aa×(content of the active material AC / total solid content)]+[Ab×(content of the inorganic solid electrolyte SE / total solid content)] <13> The weight-average molecular weight of the polymer A is 2.0×10 ４ <14> The composition for an all-solid-state secondary battery according to any one of <10> to <13>, wherein the active material AC contains Si, and Aa calculated by the above formula 1 satisfies 2≦Aa≦15. <15> A sheet for an all-solid-state secondary battery, having a layer formed using the composition for an all-solid-state secondary battery according to any one of <1> to <14> above. <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, wherein at least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer formed using the composition for an all-solid-state secondary battery according to any one of <1> to <14>.

[0011] The present invention provides a composition for an all-solid-state secondary battery that can be prepared in a short time while suppressing the generation of aggregates even when the solid content is increased, and that desirably contributes to improving battery performance. The present invention also provides a sheet for an all-solid-state secondary battery and an all-solid-state secondary battery that use this composition for an all-solid-state secondary battery. The above and other features and advantages of the present invention will become more apparent from the following description, with reference to the accompanying drawings as appropriate.

[0012] Fig. 1 is a longitudinal cross-sectional view schematically showing an all-solid-state secondary battery according to a preferred embodiment of the present invention. Fig. 2 is a longitudinal cross-sectional view schematically showing a coin-type all-solid-state secondary battery produced in an example. Fig. 3 is a graph in which the Aa and Ab values ​​for each of the compositions for all-solid-state secondary batteries of Examples 1 to 5 are plotted on a coordinate system in which the horizontal axis represents Aa calculated by Equation 1 and the vertical axis represents Ab calculated by Equation 2. Fig. 4 is a graph in which the Aa and Ab values ​​for each of the compositions for all-solid-state secondary batteries of Examples 6 to 9 are plotted on a coordinate system in which the horizontal axis represents Aa calculated by Equation 1 and the vertical axis represents Ab calculated by Equation 2.

[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 combination of the specific upper and lower limits written before and after "to" as a specific numerical range, but can be a 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.

[0014] In the present invention, the expression "compound" (for example, when referring to a compound by adding "compound" to the end of its name) refers to the compound itself, as well as its salts and ions. It also includes derivatives that have been partially modified, such as by introducing a substituent, as long as the effects of the present invention are not impaired. In the present invention, "(meth)acrylic" refers to one or both of acrylic and methacrylic. The same applies to (meth)acrylate. In the present invention, for 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, even when simply referring to a YYY group in the present invention, this YYY group encompasses not only an embodiment in which it has no substituent, but also an embodiment in which it 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, unless otherwise specified, when a plurality of substituents or the like are adjacent to each other, they may be linked to each other or condensed to form a ring.

[0015] In the present invention, polymer refers to a polymer, and is synonymous with so-called polymeric compounds. In the present invention, the main chain of a polymer 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 this depends on the weight-average molecular weight of the molecular chains considered as branched or pendant chains, typically, the longest chain among the molecular chains constituting the polymer is the main chain. However, terminal groups at the polymer ends are not included in the main chain. In contrast, the side chain of a polymer refers to molecular chains other than the main chain, and includes short molecular chains and long molecular chains (graft chains). Examples of terminal groups include hydrogen atoms, alkyl groups, aryl groups, hydroxy groups, and even residues of polymerization initiators.

[0016] In the present invention, the term "all-solid-state secondary battery composition" refers to a composition for forming an active material layer or a solid electrolyte layer, which is a constituent layer of an all-solid-state secondary battery. The term "all-solid-state secondary battery composition" encompasses electrode compositions containing an inorganic solid electrolyte, an active material, a polymer, and a dispersion medium, and used as a material for forming the active material layer of an all-solid-state secondary battery (active material layer-forming material), and inorganic solid electrolyte-containing compositions containing an inorganic solid electrolyte, a polymer, and a dispersion medium, and used as a material for forming the solid electrolyte layer of an all-solid-state secondary battery (solid electrolyte layer-forming material). The term "inorganic solid electrolyte-containing composition" may optionally contain an active material, and encompasses electrode compositions. Furthermore, in the present invention, the term "electrode composition" encompasses positive electrode compositions containing a positive electrode active material and used as a material for forming a positive electrode active material layer, and negative electrode compositions containing a negative electrode active material and used as a material for forming a negative electrode active material layer. Furthermore, in the present invention, either or both of the positive electrode active material layer and the negative electrode active material layer may be collectively referred to simply as the active material layer or the electrode active material layer, and either or both of the positive electrode active material and the negative electrode active material may be collectively referred to simply as the active material or the electrode active material.

[0017] [Composition for All-Solid State Secondary Battery] When the composition for an all-solid state secondary battery of the present invention is an electrode composition (hereinafter sometimes referred to as the electrode composition of the present invention), it contains an inorganic solid electrolyte SE having conductivity for ions of a metal belonging to Group 1 or 2 of the periodic table, an active material AC, a dispersion medium D, and a polymer A dissolved in the dispersion medium D, and at least one of Aa calculated by the following formula 1 and Ab calculated by the following formula 2 is within the following range. In order to further enhance the dispersibility of solid particles in the electrode composition of the present invention, it is preferable that Aa calculated by the following formula 1 is within the following range, and it is more preferable that Aa calculated by the following formula 1 and Ab calculated by the following formula 2 are both within the following ranges. When the composition for an all-solid state secondary battery of the present invention is an inorganic solid electrolyte-containing composition (hereinafter sometimes referred to as the inorganic solid electrolyte-containing composition of the present invention), it contains an inorganic solid electrolyte SE having conductivity for ions of a metal belonging to Group 1 or 2 of the periodic table, a dispersion medium D, and a polymer A dissolved in the dispersion medium D, and Ab calculated by the following formula 2 is within the following range. When the inorganic solid electrolyte-containing composition of the present invention further contains an active material AC, it is preferable that Aa calculated by the following formula 1 also be within the following range, in order to further enhance the dispersibility of the solid particles. As described above, the composition for an all-solid-state secondary battery of the present invention encompasses two embodiments, namely, an embodiment (first embodiment) that satisfies Aa calculated by formula 1, and an embodiment (second embodiment) that satisfies Ab calculated by formula 2, regardless of the inclusion of the active material AC.

[0018] [Equation 1] Aa=(adsorption rate of polymer A to active material AC) ２ × [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​active material AC) ３／２ ] x 10 １０ In Formula 1, the total specific surface area of ​​the active material AC is a value calculated from the specific surface area of ​​the active material AC × the content of the active material AC / the total solid content. Range satisfied by Aa calculated by Formula 1: 1 to 100 [Formula 2] Ab = (adsorption rate of polymer A to inorganic solid electrolyte SE) ２ × [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​inorganic solid electrolyte SE) ３／２ ] x 10 １０In Formula 2, the total specific surface area of ​​the inorganic solid electrolyte SE is a value calculated from the specific surface area of ​​the inorganic solid electrolyte SE × the content of the inorganic solid electrolyte SE / the total solid content. Range satisfied by Ab calculated by Formula 2: 2 to 500

[0019] The composition for an all-solid-state secondary battery of the present invention having the above configuration can disperse the solid particles in the dispersion medium D while suppressing the generation of agglomerates, even if the solid content concentration of the solid particles is increased (even if the composition is concentrated), and further, can disperse the solid particles in the dispersion medium D without agglomeration, even if the preparation time (dispersion and mixing time) is short. That is, the present invention can prepare a composition for an all-solid-state secondary battery having a high solid content concentration and suppressing the generation of agglomerates in a short time. As a result, by using the composition for an all-solid-state secondary battery of the present invention as a constituent layer-forming material, it is possible to form a constituent layer in which localized aggregation of solid particles and even uneven distribution (localized presence state) of solid particles are suppressed, and by incorporating this constituent layer, it is possible to realize an all-solid-state secondary battery with excellent battery performance.

[0020] The present inventors have conducted extensive research into the dispersibility of compositions for all-solid-state secondary batteries, and have come up with the idea that, with respect to a polymer A capable of dissolving in a dispersion medium D and functioning as a dispersant, a high level of dispersibility of the inorganic solid electrolyte SE, the active material AC, etc. may be achieved by adjusting the proportion (number of molecules) of the polymer A coexisting with the inorganic solid electrolyte SE and the active material AC in the composition that is adsorbed to the inorganic solid electrolyte SE and the active material AC. Based on this idea, the present inventors have continued their research and experiments, and have found, through numerous experiments and trial and error, that, as shown in the examples described below, when the inorganic solid electrolyte SE, the polymer A, and the active material AC are combined so that the value Aa or Ab calculated by the following formula 1 or formula 2 falls within a predetermined range, the inorganic solid electrolyte SE and the active material AC can be dispersed in dispersibility D while suppressing the occurrence of aggregation, even if the solid content concentration is increased or the preparation time is shortened, and have thus completed the present invention.

[0021] Although the details of why the present invention exhibits the above-described excellent effects are not yet clear, it is believed to be as follows. When the composition for an all-solid-state secondary battery satisfies Aa or Ab calculated by the above formula 1 or formula 2, the proportion (number of molecules) of polymer A that can be adsorbed onto the active material AC or inorganic solid electrolyte SE among the polymer A present in the composition falls within a suitable range, and polymer A dissolved in dispersion medium D effectively functions as a dispersant for the active material AC or inorganic solid electrolyte SE. As a result, the active material AC, inorganic solid electrolyte SE, and polymer A are dispersed in a balanced manner in dispersion medium D, and the active material AC or inorganic solid electrolyte SE can be highly dispersed in dispersion medium D. As a result, it is believed that even if the content of active material AC or inorganic solid electrolyte SE is increased (without increasing the amount of dispersion medium D used) or the mixing time (preparation time) is shortened, the active material AC or inorganic solid electrolyte SE can be dispersed in dispersion medium D while suppressing aggregation of the active material AC or inorganic solid electrolyte SE. When the composition for an all-solid-state secondary battery of the present invention having such excellent dispersibility is used, a constituent layer is formed while maintaining the excellent dispersibility of the composition for an all-solid-state secondary battery, and therefore, in the resulting constituent layer, the active material AC or the inorganic solid electrolyte SE is present with local aggregation suppressed and uneven distribution suppressed. As a result, it is believed that when this constituent layer is incorporated, an all-solid-state secondary battery exhibiting excellent battery performance can be realized.

[0022] As described above, in the composition for an all-solid-state secondary battery, the polymer A is dissolved in the dispersion medium D and is adsorbed to the active material AC or the inorganic solid electrolyte SE or interposed between solid particles, and is thought to function as a dispersant that disperses the active material AC or the inorganic solid electrolyte SE in the dispersion medium D. On the other hand, in the constituent layer, the polymer A is thought to preferably function as a binder that adsorbs to the active material AC or the inorganic solid electrolyte SE and binds them together. Here, the adsorption of the polymer A to the active material AC or the inorganic solid electrolyte SE is not particularly limited, but includes not only physical adsorption but also chemical adsorption (adsorption by chemical bond formation, adsorption by electron transfer, etc.). The polymer A may also function as a binder that binds the current collector and solid particles together.

[0023] In the present invention, polymer A has the property of dissolving (solubility) in dispersion medium D contained in the composition for an all-solid-state secondary battery of the present invention, and polymer A in the composition for an all-solid-state secondary battery is preferably present in a state dissolved in dispersion medium D in the composition for an all-solid-state secondary battery, although this depends on its solubility, content, etc. When polymer A is dissolved, it stably exhibits the function of dispersing solid particles in dispersion medium D, and the dispersion state of the solid particles in the composition for an all-solid-state secondary battery can be further improved. In the present invention, "polymer A being dissolved in dispersion medium D" is not limited to an embodiment in which all of polymer A is dissolved in dispersion medium D. For example, as long as the solubility in dispersion medium D described below is 80 mass % or more, a portion of polymer A may be present in an insoluble state in the composition for an all-solid-state secondary battery. The solubility is measured as follows. That is, a specified amount of polymer A to be measured is weighed into a glass bottle, and 100 g of the same type of dispersion medium D as the dispersion medium D contained in the composition for an all-solid-state secondary battery is added thereto. The mixture is stirred for 24 hours at 25°C on a mix rotor at a rotation speed of 80 rpm. 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 (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 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 In the present invention, the solubility of polymer A in dispersion medium D can be appropriately imparted by the structure, composition (type and content of constituent components), weight average molecular weight of polymer A, and further combination with dispersion medium D, etc.

[0024] In a first embodiment of the composition for an all-solid-state secondary battery of the present invention, Aa calculated by the following formula 1 satisfies 1≦Aa≦100. The first embodiment is a normal electrode composition, and when Aa is within this range, the dispersibility of the solid particles, particularly the active material AC, is increased, and even if the concentration is increased or the preparation time is shortened, the solid particles can be dispersed in the dispersion medium D while suppressing the occurrence of aggregation. [Formula 1] Aa=(adsorption rate of polymer A to active material AC) ２× [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​active material AC) ３／２ ] x 10 １０ In Equation 1, the total specific surface area of ​​the active material AC is a value calculated from the specific surface area of ​​the active material AC × the content of the active material AC / the total solid content. In Equation 1, (content of polymer A / total solid content) / molecular weight of polymer A) is a parameter related to the number (number of moles) of polymer A present, and (total specific surface area of ​​the active material AC) ３／２ is a parameter related to the surface area of ​​the active material AC. That is, [((content of polymer A) / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​active material AC) ３／２ ] represents the number of polymer A present per unit specific surface area of ​​active material AC. On the other hand, (adsorption rate of polymer A to active material AC) ２ represents the proportion of polymer A adsorbed to active material AC. As described above, Equation 1 is an experimentally discovered calculation formula weighted by the adsorption rate of polymer A to function as a dispersant (the proportion of polymer A adsorbed to active material AC), and represents the number of molecules of polymer A adsorbed or capable of being adsorbed to active material AC per unit total specific surface area of ​​active material AC.

[0025] In the present invention, the adsorption rate (%) of polymer A to active material AC is a value measured using active material AC and dispersion medium D contained in a composition for an all-solid-state secondary battery, and is an index showing the degree to which polymer A is adsorbed to active material AC in this dispersion medium D. Here, the adsorption of polymer A to active material (AC) includes not only physical adsorption but also chemical adsorption, as described above. Adsorption rate A of polymer A to active material AC ＡＣ(%) is measured by the method described in the Examples below. Here, when the composition for an all-solid-state secondary battery contains multiple types of active materials AC, the adsorption rate is taken as the adsorption rate for active materials AC having the same composition (type and content) as the active material composition in the composition for an all-solid-state secondary battery. Similarly, when the composition for an all-solid-state secondary battery contains multiple types of dispersion medium D, the adsorption rate is measured using a dispersion medium D having the same composition (type and content) as the dispersion medium in the composition for an all-solid-state secondary battery. When the composition for an all-solid-state secondary battery contains multiple types of polymer A, the adsorption rate of the polymer A may be measured for each polymer A, but is usually measured using a polymer A having the same composition (type and content) as the polymer A in the composition for an all-solid-state secondary battery.

[0026] In the present invention, the adsorption rate A of the polymer A to the active material AC is ＡＣ can be appropriately set depending on the type and composition (type and content of constituent components) of polymer A, the type or content of functional groups possessed by polymer A, etc.

[0027] The specific surface area of ​​the active material AC is a value measured by the following method. In the present invention, the specific surface area refers to the BET specific surface area, and is a value calculated by the BET (single-point) method using the nitrogen adsorption method. Specifically, the value is measured using the following measuring device under the following conditions. Specific surface area / pore distribution measuring device: Measurement is performed by the gas adsorption method (nitrogen gas) using a BELSORP MINI (trade name, manufactured by Microtrac-Bell). 0.3 g of each component is packed into a sample tube with an inner diameter of 3.6 mm, and dried by flowing nitrogen at 80°C for 6 hours before use. Measurement is performed under the following measurement conditions. Note that in the present invention, the specific surface areas of the inorganic solid electrolyte SE and the conductive additive are also values ​​measured in the same manner as the specific surface area of ​​the active material AC. - Measurement conditions - Measurement temperature: -196°C Purge gas: He (helium gas) Adsorption gas: N2 (nitrogen gas) Sample tube inner diameter: 3.6 mm

[0028] Using the value calculated as described above and the content in the all-solid-state secondary battery composition, Aa is calculated according to Equation 1. In the present invention, Aa calculated by Equation 1 is in the range of 1 to 100. When Aa is within this range, the dispersibility of the solid particles, particularly the active material AC, is improved, and even if the concentration is increased or the preparation time is shortened, the solid particles can be dispersed in the dispersion medium D while suppressing the occurrence of aggregation. In order to achieve a higher degree of dispersion of the solid particles, particularly the active material AC, Aa is preferably in the range of 1.5 to 50, more preferably in the range of 2 to 30, and even more preferably in the range of 3 to 30. To explain Aa in more detail, when the active material AC is a negative electrode active material, particularly containing Si, Aa is more preferably in the range of 1.5 to 20, even more preferably in the range of 2 to 15, and particularly preferably in the range of 3 to 15. On the other hand, when the active material AC is a positive electrode active material, Aa is preferably in the range of 2 to 50, more preferably in the range of 2 to 30, and even more preferably in the range of 3 to 30.

[0029] In the composition for an all-solid-state secondary battery of the first aspect of the present invention, Ab calculated by the following formula 2 preferably satisfies 2≦Ab≦500. When Ab is within the above range, the dispersibility of the inorganic solid electrolyte SE in addition to the active material AC can be further increased, and the dispersibility of the solid particles containing the active material AC and the inorganic solid electrolyte SE can be increased, and even if the concentration is increased or the preparation time is shortened, the particles can be dispersed in the dispersion medium D while suppressing the occurrence of aggregation.

[0030] [Equation 2] Ab = (adsorption rate of polymer A to inorganic solid electrolyte SE) ２ × [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​inorganic solid electrolyte SE) ３／２ ] x 10 １０ In Equation 2, the total specific surface area of ​​the inorganic solid electrolyte SE is a value calculated from the specific surface area of ​​the inorganic solid electrolyte SE × the content of the inorganic solid electrolyte SE / the total solid content. In Equation 2, (content of polymer A / the total solid content) / (molecular weight of polymer A) is a parameter related to the number (number of moles) of polymer A present, and (total specific surface area of ​​the inorganic solid electrolyte SE) ３／２is a parameter related to the surface area of ​​the inorganic solid electrolyte SE, i.e., [((content of polymer A) / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​inorganic solid electrolyte SE) ３／２ ] represents the number of polymer A present per unit specific surface area of ​​the inorganic solid electrolyte SE. On the other hand, (adsorption rate of polymer A to the inorganic solid electrolyte SE) ２ represents the proportion of polymer A adsorbed to the inorganic solid electrolyte SE. As described above, Equation 2 is an experimentally found calculation formula weighted by the adsorption rate of polymer A to function as a dispersant (the proportion of polymer A adsorbed to the inorganic solid electrolyte SE), and represents the number of molecules of polymer A adsorbed or capable of being adsorbed to the inorganic solid electrolyte SE per unit total specific surface area of ​​the inorganic solid electrolyte SE.

[0031] In the present invention, the adsorption rate (%) of polymer A to inorganic solid electrolyte SE is a value measured using inorganic solid electrolyte SE and dispersion medium D contained in the composition for an all-solid-state secondary battery, and is an index showing the degree to which polymer A is adsorbed to inorganic solid electrolyte SE in dispersion medium D. Here, the adsorption of polymer A to inorganic solid electrolyte SE includes not only physical adsorption but also chemical adsorption, as described above. Adsorption rate A of polymer A to inorganic solid electrolyte SE ＳＥ (%) is measured by the method described in the Examples below. Here, when the composition for an all-solid-state secondary battery contains multiple types of inorganic solid electrolyte SE, the adsorption rate is taken as the adsorption rate for inorganic solid electrolyte SE having the same composition as the active material composition (type and content) in the composition for an all-solid-state secondary battery. Similarly, when the composition for an all-solid-state secondary battery contains multiple types of dispersion medium D, the adsorption rate is measured using a dispersion medium D having the same composition as the dispersion medium (type and content) in the composition for an all-solid-state secondary battery. When the composition for an all-solid-state secondary battery contains multiple types of polymer A, the adsorption rate of the polymer A may be measured for each polymer A, but is usually measured using a polymer A having the same composition as the composition (type and content) of the polymer A in the composition for an all-solid-state secondary battery.

[0032] In the present invention, the adsorption rate A of polymer A to inorganic solid electrolyte SE is ＳＥcan be appropriately set depending on the type and composition (type and content of constituent components) of polymer A, the type or content of functional groups possessed by polymer A, etc.

[0033] Using the value calculated as described above and the content in the composition for an all-solid-state secondary battery, Ab is calculated according to Equation 2. In the composition for an all-solid-state secondary battery of the first embodiment of the present invention, Ab calculated by Equation 2 is preferably in the range of 2 to 500. In order to achieve a higher degree of dispersion of solid particles, particularly inorganic solid electrolyte SE, Ab is more preferably in the range of 2 to 300, even more preferably in the range of 3 to 250, and particularly preferably in the range of 5 to 200. To explain Ab in more detail, when the inorganic solid electrolyte SE is a sulfide-based inorganic solid electrolyte, Ab is more preferably in the range of 2 to 300, even more preferably in the range of 4 to 200, and particularly preferably in the range of 8 to 170. On the other hand, when the inorganic solid electrolyte SE is an oxide-based inorganic solid electrolyte, Ab is more preferably in the range of 2 to 300, even more preferably in the range of 3 to 250, and particularly preferably in the range of 5 to 200.

[0034] In the composition for an all-solid-state secondary battery of the first aspect of the present invention, it is more preferable that Ac calculated by the following formula 3 satisfies 3≦Ac≦100. When Ac is within the above range, the dispersibility of the active material AC and the inorganic solid electrolyte SE can be improved in a balanced manner, and even if the concentration is increased or the preparation time is shortened, the active material AC and the inorganic solid electrolyte SE can be highly dispersed in the dispersion medium D while suppressing the occurrence of aggregation.

[0035] [Formula 3] Ac = [Aa × (content of active material AC / total solid content)] + [Ab × (content of inorganic solid electrolyte SE / total solid content)] Formula 3 is the sum of the products of the mass fractions of Aa and Ab, and is a calculation formula that was experimentally found to be able to improve the dispersibility of the active material AC by Aa and the dispersibility of the inorganic solid electrolyte SE by Ab in a balanced manner.

[0036] In the present invention, Ac calculated by Equation 3 is more preferably in the range of 5 to 75, and even more preferably in the range of 10 to 50, in order to achieve a well-balanced dispersibility between the active material AC and the inorganic solid electrolyte SE and to further increase the dispersibility to a higher level.

[0037] In a second embodiment of the composition for an all-solid-state secondary battery of the present invention, Ab calculated by the following formula 2 satisfies 2≦Ab≦500. The composition for an all-solid-state secondary battery of the second embodiment is usually an inorganic solid electrolyte composition, but also includes an electrode composition. In the composition for an all-solid-state secondary battery of the second embodiment, when Aa is within this range, even in the coexistence of an active material AC, the dispersibility of the solid particles, particularly the inorganic solid electrolyte SE, is improved, and even if the concentration is increased or the preparation time is shortened, the solid particles can be dispersed in the dispersion medium D while suppressing the occurrence of aggregation. In order to achieve a higher degree of dispersion of the solid particles, particularly the inorganic solid electrolyte SE, Ab is more preferably within the range of 2 to 300, even more preferably within the range of 3 to 250, and particularly preferably within the range of 5 to 200. The details of Ab (such as a more preferable range depending on the type of inorganic solid electrolyte) are the same as the details of A in the composition for an all-solid-state secondary battery of the first embodiment of the present invention. The technical meaning of the following formula 2 is as described above. [Formula 2] Ab=(adsorption rate of polymer A to inorganic solid electrolyte SE) ２ × [((content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​inorganic solid electrolyte SE) ３／２ ] x 10 １０ In formula 2, the total specific surface area of ​​the inorganic solid electrolyte SE is a value calculated from the specific surface area of ​​the inorganic solid electrolyte SE×the content of the inorganic solid electrolyte SE / the total solid content.

[0038] When the composition for an all-solid-state secondary battery of the second aspect of the present invention contains an active material (corresponding to an electrode composition), it is preferable that Aa calculated by the following formula 1 satisfies 1≦Aa≦100. That is, when the composition for an all-solid-state secondary battery of the second aspect of the present invention contains an active material, it is the same as the preferred embodiment of the composition for an all-solid-state secondary battery of the first aspect of the present invention, which satisfies Aa calculated by formula 1 and Ab calculated by formula 2, and therefore a description thereof will be omitted. Furthermore, when the composition for an all-solid-state secondary battery of the second aspect of the present invention contains an active material, it is a further preferred embodiment that Ac calculated by formula 3 above is satisfied, which is also the same as the preferred embodiment of the composition for an all-solid-state secondary battery of the first aspect of the present invention, which satisfies Aa calculated by formula 1 and Ab calculated by formula 2, and therefore a description thereof will be omitted.

[0039] The composition for an all-solid-state secondary battery of the present invention exhibits the above-mentioned excellent properties and can therefore be preferably used as a material for forming a constituent layer of an all-solid-state secondary battery sheet and an all-solid-state secondary battery, and in particular as a material for forming a negative electrode active material layer.

[0040] The composition for an all-solid-state secondary battery of the present invention is preferably a slurry in which an inorganic solid electrolyte SE and an active material AC are dispersed in a dispersion medium D. The composition for an all-solid-state secondary battery of the present invention is preferably a non-aqueous composition. In the present invention, the non-aqueous composition includes not only an embodiment that does not contain water, but also an embodiment in which the water content (also referred to as water content) is preferably 500 ppm or less. In a 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 composition for an all-solid-state secondary battery is a non-aqueous composition, deterioration of the inorganic solid electrolyte SE can be suppressed. The water content refers to the amount of water contained in the composition for an all-solid-state secondary battery (mass ratio relative to the electrode composition), and is specifically a value measured by filtering through a 0.02 μm membrane filter and using Karl Fischer titration.

[0041] Components contained in the composition for an all-solid-state secondary battery of the present invention and components that can be contained therein will be described below. Note that each component contained in the composition for an all-solid-state secondary battery of the present invention may be one type, or two or more types.

[0042] <Inorganic Solid Electrolyte SE> The composition for an all-solid-state secondary battery of the present invention contains an inorganic solid electrolyte SE. 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). In addition, 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 solid electrolytes (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 The inorganic solid electrolyte is not particularly limited as long as it has ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and generally does not have electronic conductivity.

[0043] The inorganic solid electrolyte may be selected from solid electrolyte materials typically 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. Sulfide-based inorganic solid electrolytes are preferred because they can form a better interface between the active material and the inorganic solid electrolyte. When the all-solid-state secondary battery of the present invention is a lithium-ion battery, the inorganic solid electrolyte preferably has ionic conductivity for lithium ions.

[0044] (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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] (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.

[0051] 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.

[0052] (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.

[0053] (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.

[0054] The inorganic solid electrolyte is preferably particulate in the composition for an all-solid-state secondary battery. The particle shape is not particularly limited and may be flat, amorphous, or the like, but is preferably spherical or granular. When the inorganic solid electrolyte is particulate, the particle diameter (volume average particle diameter) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and more preferably 0.5 μm or more. The upper limit is preferably 100 μm or less, more preferably 50 μm or less, and more preferably 10 μm or less. The particle diameter of the inorganic solid electrolyte is measured by the following procedure. The inorganic solid electrolyte particles are diluted with water (or heptane in the case of a substance unstable in water) in a 20 mL sample bottle to prepare a 1 mass % dispersion. The diluted dispersion sample is irradiated with 1 kHz ultrasound for 10 minutes and used for testing immediately thereafter. Using this dispersion sample, a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA) is used to acquire data 50 times at a temperature of 25°C using a quartz cell for measurement, to obtain the volume average particle diameter. For other detailed conditions, etc., refer to the description in Japanese Industrial Standards (JIS) Z 8828:2013 "Particle size analysis - dynamic light scattering method" as necessary. Five samples are prepared for each level, and the average value is used.

[0055] 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.

[0056] The specific surface area of ​​the inorganic solid electrolyte is not particularly limited and is determined appropriately taking into consideration Aa or Ab calculated by Equation 1 or Equation 2. The specific surface area of ​​the inorganic solid electrolyte SE is usually 0.1 to 100 m ２ / g, and in that case, a range of 0.5 to 15 m is preferred because it improves the balance with the amount of polymer A present, thereby enhancing the dispersibility of solid particles, and also makes it easier to set Ab calculated by formula 2 within the above range. ２ / g, and 1 to 10 m ２ / g, and more preferably in the range of 1 to 5m ２ The specific surface area of ​​the inorganic solid electrolyte SE can be adjusted to the above range by changing the above-mentioned particle size adjustment method (conditions) and micronization conditions (for example, mechanical milling conditions in the examples).

[0057] The composition for an all-solid-state secondary battery may contain one or more inorganic solid electrolytes. The content of the inorganic solid electrolyte SE in the composition for an all-solid-state secondary battery is not particularly limited and may be determined appropriately. For example, in terms of dispersibility and binding ability, the content 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 composition for an all-solid-state secondary battery contains an active material AC described below, the content of the inorganic solid electrolyte in the composition for an all-solid-state secondary battery is preferably such that the total content of the active material AC and the inorganic solid electrolyte SE is within the above range.

[0058] When the composition for an all-solid-state secondary battery contains an active material AC described later, the content of the inorganic solid electrolyte SE alone is appropriately determined taking into consideration the total content with the active material AC, and is, for example, preferably 5 to 70 mass%, more preferably 10 to 60 mass%, and even more preferably 10 to 50 mass% in 100 mass% solid content. The ratio of the content of the inorganic solid electrolyte SE to the content of the active material AC described later [content of inorganic solid electrolyte SE:content of active material AC] in 100 mass% solid content of the composition for an all-solid-state secondary battery is not particularly limited, but is, for example, preferably 1:1 to 1:6, and more preferably 1:1.2 to 1:5.

[0059] In the present invention, the solid content (solid components) refers to components that do not volatilize or evaporate when the composition for an all-solid-state secondary battery is dried at 150°C for 6 hours under a nitrogen atmosphere at an atmospheric pressure of 1 mmHg. Typically, this refers to components other than the dispersion medium D described below. The content in the total solid content refers to the content in 100% by mass of the total mass of the solid content.

[0060] <Active Material AC> The electrode composition of the present invention contains an active material AC capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table. On the other hand, the inorganic solid electrolyte-containing composition of the present invention may appropriately contain the active material AC. Examples of the active material AC include a positive electrode active material and a negative electrode active material, as described below.

[0061] (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.

[0062] (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], also known as [NCM]) 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 ８ Examples of the (MC) lithium-containing transition metal phosphate compound include LiFePO ４ and Li ３ Fe ２ (P.O. ４ ) ３ Olivine-type iron phosphate salts such as LiFeP ２ O ７ Iron pyrophosphates such as LiCoPO ４ Cobalt phosphates such as Li ３ V ２ (P.O. ４ ) ３ (MD) Examples of lithium-containing transition metal halide phosphate compounds include, for example, Li ２FePO 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.

[0063] The positive electrode active material obtained by the baking method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.

[0064] The positive electrode active material contained in the electrode composition of the present invention is preferably in a particulate form in the electrode composition. The shape of the particles is not particularly limited and may be flat, amorphous, or the like, but is preferably spherical or granular. When the positive electrode active material is in a particulate form, the particle size (volume average particle size) of the positive electrode active material is not particularly limited, but is preferably 0.1 to 50 μm, and more preferably 0.5 to 10 μm, for example. The particle size of the positive electrode active material particles can be adjusted in the same manner as the particle size of the inorganic solid electrolyte, and can be measured in the same manner as the particle size of the inorganic solid electrolyte.

[0065] The electrode composition of the present invention may contain one or more positive electrode active materials. The content of the positive electrode active materials in the electrode composition is not particularly limited and may be determined appropriately. For example, the content 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.

[0066] (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.

[0067] 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.

[0068] 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 element that has 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] The negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is one commonly used as a negative electrode active material for secondary batteries. Such active materials undergo significant expansion and contraction during charging and discharging of all-solid-state secondary batteries, accelerating the deterioration of battery performance. However, the composition for all-solid-state secondary batteries of the present invention contains the polymer A described below and has Aa or Ab calculated by Equation 1 or Equation 2, thereby suppressing the deterioration of battery performance. Examples of such active materials include (negative electrode) active materials (alloys, etc.) containing silicon or tin, and metals such as Al and In. Negative electrode active materials containing silicon (silicon-containing active materials) that enable higher battery capacity are preferred, and silicon-containing active materials with a silicon content of 50 mol% or more of the total constituent elements are 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 store more Li ions than carbon negative electrodes (e.g., graphite and acetylene black). That is, the amount of Li ions absorbed per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, there is an advantage 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 ２and 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.

[0073] 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.

[0074] The negative electrode active material contained in the electrode composition of the present invention is preferably in a particulate form in the electrode composition. The shape of the particles is not particularly limited and may be flat, amorphous, or the like, but is preferably spherical or granular. When the negative electrode active material is in a particulate form, the particle size (volume average particle size) of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 μm, and more preferably 0.5 to 10 μm, for example. The particle size of the negative electrode active material particles can be adjusted in the same manner as the particle size of the inorganic solid electrolyte, and can be measured in the same manner as the particle size of the inorganic solid electrolyte.

[0075] The electrode composition of the present invention may contain one or more negative electrode active materials. The content of the negative electrode active materials in the electrode composition is not particularly limited and may be determined appropriately. For example, the content 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.

[0076] The specific surface area of ​​the active material AC is not particularly limited and is determined appropriately taking into consideration Aa or Ab calculated by Equation 1 or Equation 2. The specific surface area of ​​the active material AC is usually 0.1 to 100 m ２ / g, and in that case, a range of 0.3 to 50 m is preferred because it improves the balance with the amount of polymer A present, thereby enhancing the dispersibility of solid particles, and also makes it easier to set Aa calculated by formula 1 within the above range. ２ / g, and preferably in the range of 2 to 35m ２When the active material AC is a positive electrode active material, the specific surface area thereof is preferably in the range of 0.3 to 20 m / g. ２ / g, and more preferably in the range of 0.5 to 10 m ２ On the other hand, when the active material AC is a negative electrode active material, the specific surface area thereof is more preferably in the range of 2 to 100 m / g. ２ / g, and preferably in the range of 2 to 35m ２ The specific surface area of ​​the active material AC can be adjusted to the above range by changing the above-mentioned particle size adjustment method (conditions) and micronization conditions (for example, mechanical milling conditions in the examples).

[0077] In the present invention, the negative electrode active material layer can also be formed by charging the secondary battery. In this case, ions of a metal belonging to Group 1 or Group 2 of the periodic table that are generated in the all-solid-state secondary battery can be used instead of the negative electrode active material. The negative electrode active material layer can be formed by bonding these ions with electrons and depositing them as a metal.

[0078] 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.

[0079] (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. Examples include titanate spinel, tantalum oxide, niobium oxide, and lithium niobate compounds. Specific examples include Li 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 TiO３ , 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.

[0080] <Polymer A> The polymer A used in the present invention is soluble in at least the dispersion medium D. The solubility of the polymer A in the dispersion medium D is as described above. Adsorption rate A of the polymer A to the active material AC ＡＣ There are no particular limitations on the adsorption rate A (%), but if it is too small, the active material AC will not be adsorbed and will not be able to be dispersed in the dispersion medium D. ＡＣ If the adsorption rate A is too large, the particles are excessively adsorbed to the active material AC and tend to aggregate. ＡＣ is preferably 2 to 50%, more preferably 3 to 40%, and even more preferably 4 to 35%, in that polymer A can be appropriately adsorbed to active material AC and function as a dispersant to enhance dispersibility in dispersion medium D. When active material AC is a positive electrode active material, the adsorption ratio A of polymer A to the positive electrode active material is ＡＣ is more preferably 3 to 40%, further preferably 5 to 30%, and particularly preferably 5 to 20% within the above range. ＡＣWithin the above range, the adsorption rate A is preferably 2 to 50%, more preferably 3 to 40%, and even more preferably 4 to 35%. ＡＣ The meaning is as described above.

[0081] Adsorption rate A of polymer A to inorganic solid electrolyte SE ＳＥ Although there are no particular limitations on the adsorption rate A (%), if it is too small, the inorganic solid electrolyte SE will not be adsorbed and the inorganic solid electrolyte SE will not be able to be dispersed in the dispersion medium D. ＳＥ If the adsorption rate A is too large, the inorganic solid electrolyte SE is excessively adsorbed and tends to aggregate. ＳＥ is preferably 1 to 70%, more preferably 2 to 50%, and even more preferably 5 to 40%, in that the polymer A can be appropriately adsorbed to the inorganic solid electrolyte SE to enhance dispersibility in the dispersion medium D. When the inorganic solid electrolyte SE is a sulfide-based inorganic solid electrolyte, the adsorption ratio A of the polymer A to the sulfide-based inorganic solid electrolyte ＳＥ In the above range, the adsorption ratio A of the polymer A to the inorganic solid electrolyte is preferably 1 to 70%, more preferably 2 to 50%, and even more preferably 5 to 40%. ＳＥ Within the above range, the adsorption rate A is preferably 1 to 70%, more preferably 5 to 50%, and even more preferably 7 to 50%. ＡＣ The meaning is as described above.

[0082] The molecular weight (meaning the weight average molecular weight) of the polymer A is not particularly limited, and is 1.0 × 10 ３ ~1.0 x 10 ５ In the present invention, the number of molecules of polymer A per unit mass can be increased to effectively function as a dispersant, and Aa and Ab calculated by Equation 1 and Equation 2 can be easily set within the above ranges, so that 2.0 × 10 ３ ~7.0 x 10 ４ It is preferable to set the value to 3.0 × 10 ３ ~6.0 x 10 ４ More preferably, it is 2.0 × 10 ４More preferably, it is 4.0 × 10 or less. ３ ~2.0 x 10 ４ It is particularly preferable to set the following.

[0083] The weight average molecular weight of polymer A can be adjusted appropriately by changing the type and amount of polymerization initiator, polymerization time, polymerization temperature, etc.

[0084] In the present invention, unless otherwise specified, the molecular weight of polymer A refers to the weight average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene. Examples of the measurement method include a method set basically under the following condition 1 or condition 2 (priority). In the present invention, the weight average molecular weight or number average molecular weight of the polymer chain (polymer chain) and macromonomer refers to the weight average molecular weight or number average molecular weight in terms of standard polystyrene measured in the same manner as the above-mentioned method for measuring the molecular weight of polymer A, unless otherwise specified. However, depending on the types of polymer A, polymer chain, macromonomer, etc., 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

[0085] As the polymer A, any polymer that dissolves in the dispersion medium D from among various polymers used in all-solid-state secondary batteries can be used without particular limitation. Preferred examples of the polymer A include polymers having at least one bond selected from a urethane bond, a urea bond, an amide bond, an imide bond, and an ester bond, or a polymer chain of a carbon-carbon double bond in the main chain. In the present invention, a polymer chain of a carbon-carbon double bond refers to a polymer chain formed by polymerization of a carbon-carbon double bond (ethylenically unsaturated group), and specifically refers to a polymer chain formed by polymerization (homopolymerization or copolymerization) of a monomer having a carbon-carbon unsaturated bond. More specifically, examples of polymers having a urethane bond, urea bond, amide bond, imide bond, or ester bond in the main chain include step-growth polymerization (polycondensation, polyaddition, or addition-condensation) polymers such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, and polycarbonate. Furthermore, examples of polymers having a polymer chain of carbon-carbon double bonds in the main chain include chain-polymerized polymers such as fluoropolymers (fluorine-containing polymers), hydrocarbon polymers, vinyl polymers, and (meth)acrylic polymers. The polymerization mode of these polymers is not particularly limited, and they may be any of block copolymers, alternating copolymers, and random copolymers. Among these, chain-polymerized polymers are preferred, with hydrocarbon polymers, vinyl polymers, and (meth)acrylic polymers being more preferred, and (meth)acrylic polymers being even more preferred.

[0086] The composition for an all-solid-state secondary battery of the present invention may contain one or more types of polymer A. When two or more types of polymers are contained, it is preferable that at least one polymer is a chain-polymerized polymer, and it is more preferable that all of the polymers are chain-polymerized polymers.

[0087] (Preferred Polymer A of First Aspect) The polymer A (sometimes referred to as the preferred polymer A of the first aspect) preferably used in the present invention includes a polymer containing at least one of a component having a substituent having 8 or more carbon atoms as a side chain and a component having a functional group selected from functional group (a). This polymer exhibits an appropriate adsorption rate for the active material AC and the inorganic solid electrolyte SE, contributing to improved dispersibility. The preferred polymer A of the first aspect preferably does not contain the component (X) in the preferred polymer A of the second aspect (the content in the polymer A is 0.2 mass% or less). Furthermore, the molecular structure of the preferred polymer A of the first aspect is not particularly limited, but it preferably does not have a star structure (multi-branched structure).

[0088] - Constituent Having a Substituent Having 8 or More Carbon A Carbons in the Side Chain - Polymer A preferably contains a constituent having a substituent having 8 or more carbon atoms in the side chain. This constituent reduces the polarity of polymer A and increases its solubility in the dispersion medium, thereby contributing to improved dispersibility. This constituent may be any constituent that forms polymer A, and the substituent having 8 or more carbon atoms is introduced into a side chain of polymer A or as a part thereof. This constituent preferably has a substituent having 8 or more carbon atoms in a partial structure that is incorporated into the main chain of polymer A, either directly or via a linking group.

[0089] The partial structure incorporated into the main chain of polymer A is appropriately selected depending on the type of polymer A, and examples thereof include a carbon chain (carbon-carbon bond) when polymer A is a chain-polymerized polymer. The substituent having 8 or more carbon atoms is not particularly limited, and examples include the substituent Z described below, which has 8 or more carbon atoms. When a constituent component contains a polymer chain as a side chain, the substituent having 8 or more carbon atoms includes the substituent having 8 or more carbon atoms possessed by each constituent component constituting the polymer chain, but the entire polymer chain is not considered to be a single substituent and is therefore considered a substituent having 8 or more carbon atoms. Specific examples of the substituent having 8 or more carbon atoms include long-chain alkyl groups having 8 or more carbon atoms, cycloalkyl groups having 8 or more carbon atoms, aryl groups having 8 or more carbon atoms, aralkyl groups having 8 or more carbon atoms, and heterocyclic groups having 8 or more carbon atoms, with long-chain alkyl groups having 8 or more carbon atoms being preferred. The number of carbon atoms in this substituent may be 8 or more, preferably 10 or more, and more preferably 12 or more. The upper limit is not particularly limited, and is preferably 24 or less, more preferably 20 or less, and even more preferably 16 or less. The number of carbon atoms in a substituent refers to the number of carbon atoms constituting this substituent, and when this substituent has further substituents, the number of carbon atoms constituting the further substituents is included in the calculation.

[0090] The linking group is 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. As the linking group, 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, and a group formed by combining an alkylene group, an arylene group, a carbonyl group, an oxygen atom, and an imino group is more preferred, and a -CO-O- group, -CO-N(RＮ )-group (R Ｎ is as defined above. ) is more preferred, and a group containing a —CO—O— group or a —CO—N(R Ｎ )-group (R Ｎ is as described above. ) is particularly preferred, and a -CO-O- group is most preferred. The number of atoms constituting the linking group and the number of linking atoms are as follows: In the present invention, the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, even more preferably 1 to 12, and particularly preferably 1 to 6. The number of linking atoms in the linking group is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more. The number of linking atoms refers to the minimum number of atoms connecting specified structural moieties. For example, in the case of -C(=O)-O-, the number of atoms constituting the linking group is 3, but the number of linking atoms is 2.

[0091] The partial structure incorporated into the main chain, the linking group, and the substituent having 8 or more carbon atoms may each have a substituent. Such a substituent is not particularly limited and includes, for example, a group selected from the substituent Z described below, and is preferably a group other than a functional group selected from the functional group group (a).

[0092] The constituent having a substituent having 8 or more carbon atoms can be constituted by appropriately combining the partial structure incorporated into the main chain, the substituent having 8 or more carbon atoms, and further the linking group, and for example, a constituent represented by the following formula (1-1) is preferred.

[0093] In formula (1-1), R １ represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms). １ The alkyl group may have a substituent. The substituent is not particularly limited, but examples thereof include the above-described substituent Z, and is preferably a group other than the functional groups selected from the functional group group (a), such as a halogen atom.

[0094] R ２represents a group having a substituent having 8 or more carbon atoms. In the present invention, the group having a substituent is a group consisting of the substituent itself (the substituent is １ is bonded directly to the carbon atom in the above formula to which R ２ a group consisting of a linking group connecting the carbon atom in the above formula to which R is bonded and the substituent, and a substituent (wherein the substituent is R １ is bonded to the carbon atom in the above formula via a linking group. ２ a substituent having 8 or more carbon atoms which R ２ The linking group that may be possessed by R is as described above. ２ As the group, —C(═O)—O-a long-chain alkyl group having 8 or more carbon atoms is particularly preferred. １ The carbon atom adjacent to the carbon atom to which is bonded has two hydrogen atoms, but in the present invention, it may have one or two substituents. The substituent is not particularly limited, but examples thereof include the substituent Z described below, and a group other than a functional group selected from the functional group group (a) is preferred.

[0095] Examples of the constituent component having a substituent having 8 or more carbon atoms include, for example, a constituent component derived from a compound having a substituent having 8 or more carbon atoms among the (meth)acrylic compounds (M1) described below, and a constituent component derived from a compound having a substituent having 8 or more carbon atoms among the other polymerizable compounds (M2) described below, and a (meth)acrylic acid long-chain alkyl ester compound (having 8 or more carbon atoms) is preferred. Specific examples of the constituent component having a substituent having 8 or more carbon atoms include, but are not limited to, the polymers shown in the specific examples described below and the polymers synthesized in the examples.

[0096] The content of the constituent component having a substituent having 8 or more carbon atoms in polymer A is not particularly limited and is selected from the range of 0 to 100% by mass. For example, from the viewpoint of dispersibility of polymer A, it is preferably 20 to 99.9% by mass, more preferably 30 to 99.5% by mass, even more preferably 30 to 99% by mass, particularly preferably 50 to 99% by mass, and most preferably 80 to 99% by mass. The content specified in this specification can be a range that appropriately combines the upper and lower limits of each range.

[0097] (Component Having a Functional Group Selected from Functional Group Group (a)) The polymer A of a preferred first embodiment preferably contains a component having a functional group selected from the following functional group group (a). This component improves the adsorption force of the polymer A to the inorganic solid electrolyte SE, the active material AC, and the conductive additive, contributing to improved dispersibility and adhesion. This component may be any component that forms the polymer A. The functional group may be incorporated into the main chain of the polymer or into a side chain. When incorporated into a side chain, the functional group may be directly bonded to the main chain or may be bonded via the above-mentioned linking group. In the chain-polymerized polymer, a component having an ester bond (excluding an ester bond that forms a carboxy group) or an amide bond refers to a component in which an ester bond or an amide bond is not directly bonded to an atom that constitutes the main chain of the chain-polymerized polymer, or to an atom that constitutes the main chain of a polymer chain (e.g., a polymer chain possessed by a macromonomer) incorporated into the chain-polymerized polymer as a branched chain or pendant chain, and does not include, for example, a component derived from a (meth)acrylic acid alkyl ester. A single constituent may have one or more types of functional groups, and when two or more types are present, the functional groups may or may not be bonded to each other.

[0098] <Functional Group (a)> Hydroxy group, amino group, carboxy group, sulfo group, phosphate group, phosphonic acid group, sulfanyl group, ether bond (-O-), imino group (=NR, -NR-), ester bond (-CO-O-), amide bond (-CO-NR-), urethane bond (-NR-CO-O-), urea bond (-NR-CO-NR-), heterocyclic group, aryl group, carboxylic anhydride group, fluoroalkyl group The amino group, sulfo group, phosphate group (phosphoryl group), heterocyclic group, and aryl group contained in the functional group group (a) are not particularly limited, but are synonymous with the corresponding groups of the substituent Z described below. However, the number of carbon atoms in the amino group is more preferably 0 to 12, still more preferably 0 to 6, and particularly preferably 0 to 2. The phosphonic acid group is not particularly limited, but examples thereof include phosphonic acid groups having 0 to 20 carbon atoms. When an amino group, an ether bond, an imino group (—NR—), an ester bond, an amide bond, a urethane bond, a urea bond, or the like is contained in the ring structure, it is classified as a heterocycle. A hydroxy group, an amino group, a carboxy group, a sulfo group, a phosphate group, a phosphonate group, or a sulfanyl group may form a salt. A fluoroalkyl group is a group in which at least one hydrogen atom of an alkyl group or a cycloalkyl group is substituted with a fluorine atom, and preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 3 to 10 carbon atoms. The number of fluorine atoms on the carbon atom may be a partial replacement of the hydrogen atoms, or may be a complete replacement (perfluoroalkyl group). R in each bond represents a hydrogen atom or a substituent, with a hydrogen atom being preferred. The substituent is not particularly limited and is selected from the substituent Z described below, with an alkyl group being preferred.

[0099] The carboxylic acid anhydride group is not particularly limited, but includes a group obtained by removing one or more hydrogen atoms from a carboxylic acid anhydride (e.g., a group represented by the following formula (2a)), as well as a constituent component itself formed by copolymerization of a polymerizable carboxylic acid anhydride as a copolymerizable compound (e.g., a constituent component represented by the following formula (2b)). The group obtained by removing one or more hydrogen atoms from a carboxylic acid anhydride is preferably a group obtained by removing one or more hydrogen atoms from an acyclic carboxylic acid anhydride or a cyclic carboxylic acid anhydride. A carboxylic acid anhydride group derived from a cyclic carboxylic acid anhydride also corresponds to a heterocyclic group, but in the present invention, it is classified as a carboxylic acid anhydride group. Examples include acyclic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride, and cyclic carboxylic acid anhydrides such as maleic anhydride, phthalic anhydride, fumaric anhydride, succinic anhydride, and itaconic anhydride. The polymerizable carboxylic acid anhydride is not particularly limited, but includes a carboxylic acid anhydride having an unsaturated bond in the molecule, preferably a polymerizable cyclic carboxylic acid anhydride. Specific examples include maleic anhydride and itaconic anhydride. Examples of the carboxylic acid anhydride group include a group represented by the following formula (2a) or a component represented by the following formula (2b), but the present invention is not limited thereto. In each formula, * indicates a bonding position. The carboxylic acid anhydride group may also be a dicarboxylic acid group included in the functional group group (a1) described below.

[0100]

[0101] The linking group that connects the functional group to the main chain is not particularly limited, and examples thereof include the linking groups described above. Particularly preferred linking groups are —CO—O— groups or —CO—N(R Ｎ )-group (R Ｎ is as defined above.) and an alkylene group.

[0102] Methods for incorporating functional groups into the polymer chain are discussed below.

[0103] The compound having the functional group is not particularly limited, and examples thereof include compounds having at least one carbon-carbon unsaturated bond and at least one of the functional groups. Examples include compounds in which the carbon-carbon unsaturated bond and the functional group are directly bonded, compounds in which the carbon-carbon unsaturated bond and the functional group are bonded via a linking group, and even compounds in which the functional group itself contains a carbon-carbon unsaturated bond (e.g., the polymerizable cyclic carboxylic acid anhydrides described above). Compounds having the functional group also include compounds capable of introducing a functional group into a polymer component after polymerization through various reactions (e.g., alcohol, amino, mercapto, or epoxy compounds (including polymers) capable of undergoing addition reactions or condensation reactions with components derived from carboxylic acid anhydrides or components having a carbon-carbon unsaturated bond). Compounds having the functional group also include compounds in which a carbon-carbon unsaturated bond is bonded directly or via a linking group to a macromonomer having a functional group incorporated as a substituent in the polymer chain. Examples of macromonomers from which macromonomer components are derived include macromonomers having a polymer chain of a chain-polymerized polymer, as described below. The number-average molecular weight of the macromonomer is not particularly limited, but is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 20,000, in order to further strengthen the binding force of the solid particles and the adhesion to the current collector while maintaining excellent dispersibility and coating suitability. Furthermore, the content of repeating units having functional groups incorporated into the macromonomer is preferably 1 to 100 mol%, more preferably 3 to 80 mol%, and even more preferably 5 to 70 mol%. The content of repeating units not having functional groups is preferably 0 to 90 mol%, more preferably 0 to 70 mol%, and even more preferably 0 to 50 mol%. Any component can be selected from the viewpoint of solubility, etc.

[0104] The constituent component having the functional group is not particularly limited as long as it has the functional group, and examples thereof include the (meth)acrylic compound (M1) or other polymerizable compound (M2) described below, a constituent component represented by any of formulas (b-1) to (b-3) described below, and a constituent component obtained by introducing the functional group into a constituent component represented by formula (1-1) described below. Compounds from which the constituent component having the functional group is derived are not particularly limited, and examples thereof include a polymerizable cyclic carboxylic acid anhydride and a compound obtained by introducing the functional group into a fluoroalkyl group-containing (meth)acrylic acid short-chain alkyl ester compound (short-chain alkyl means an alkyl group having 3 or less carbon atoms). Examples of compounds obtained by introducing the functional group into a polymerizable cyclic carboxylic acid anhydride are as described above, and examples thereof include a dicarboxylic acid monoester compound obtained by subjecting a maleic anhydride compound to an addition reaction (ring-opening reaction) with an alcohol.

[0105] The content of the functional group-containing component in polymer A is preferably 0.01 to 70% by mass, more preferably 0.01 to 50% by mass, even more preferably 0.01 to 30% by mass, particularly preferably 0.1 to 10% by mass, and most preferably 0.3 to 8% by mass, from the viewpoint of the dispersibility and binding properties of polymer A. When polymer A contains multiple functional group-containing components, the content of the functional group-containing components refers to the total amount. Furthermore, when one component has multiple or multiple types of functional groups, the content of the functional group-containing component usually refers to the content of this component. When two or more types of polymer A are contained, the content of the functional group-containing component relative to the total number of moles of all the polymer A components is not particularly limited and is set appropriately depending on the content in each of the polymers.

[0106] (Other Constituents) The polymer A of the first preferred embodiment may contain a constituent (referred to as "other constituent") that does not fall into either the constituent having a substituent having 8 or more carbon atoms or the constituent having a functional group selected from the functional group group (a). The other constituent is not particularly limited as long as it can constitute the polymer A, and can be appropriately selected depending on the type of polymer A, etc. Examples include constituents derived from the (meth)acrylic compound (M1) and other polymerizable compounds (M2) described below that do not have a substituent having 8 or more carbon atoms or the above functional group. The content of the other constituent in the polymer A is not particularly limited and is appropriately determined from a range of 0 to 100% by mass taking into consideration the content of the above constituents. When the polymer A contains other constituents, the content is, for example, preferably 1 to 99% by mass, more preferably 5 to 80% by mass, and even more preferably 8 to 60% by mass.

[0107] The polymer A of the first preferred embodiment is preferably a chain-polymerized polymer, and is preferably a hydrocarbon polymer, a vinyl polymer, or a (meth)acrylic polymer, and more preferably a hydrocarbon polymer or a (meth)acrylic polymer. Suitable chain-polymerized polymers are specifically described below. (Hydrocarbon Polymer) Examples of hydrocarbon polymers include polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene, polystyrene-butadiene copolymers, styrene-based thermoplastic elastomers, polybutylene, acrylonitrile-butadiene copolymers, and hydrogenated polymers thereof. The styrene-based thermoplastic elastomer or its hydrogenated product is not particularly limited, and examples thereof include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), hydrogenated SIS, styrene-butadiene-styrene block copolymer (SBS), hydrogenated SBS, styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (HSBR), and random copolymers corresponding to the above block copolymers such as SEBS. In the present invention, hydrocarbon polymers that do not have unsaturated groups (e.g., 1,2-butadiene constituents) bonded to the main chain are preferred, as they can suppress the formation of chemical crosslinks.

[0108] In addition to the constituent components constituting the hydrocarbon polymer described above (e.g., styrene), the hydrocarbon polymer preferably contains a constituent component having the above-mentioned substituent having 8 or more carbon atoms and a constituent component having the above-mentioned functional group, for example, a constituent component derived from a polymerizable cyclic carboxylic acid anhydride such as maleic anhydride. Furthermore, the constituent component having a functional group also includes, for example, a constituent component obtained by introducing a functional group selected from the above-mentioned functional group group (a) into a copolymerized constituent component through various reactions. The content of the constituent components in the hydrocarbon polymer is not particularly limited and can be selected appropriately, for example, within the following ranges. The content of the constituent components having the above-mentioned substituent having 8 or more carbon atoms in all the constituent components constituting the hydrocarbon polymer is as described above. Regardless of the above range, the content of the constituent component derived from a compound having a functional group selected from the above-mentioned functional group group (a) in all the constituent components constituting the hydrocarbon polymer is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit of the content of the functional group-containing components is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, of all the components constituting the hydrocarbon polymer. When the hydrocarbon polymer contains a plurality of components having functional groups, the content of the components having functional groups is the total amount.

[0109] (Vinyl Polymer) Examples of vinyl polymers include polymers containing, for example, 50% by mass or more of a vinyl monomer other than the (meth)acrylic compound (M1). Examples of vinyl monomers include the vinyl compounds described below. Specific examples of vinyl polymers include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, and copolymers containing these. In addition to the constituent components derived from the vinyl monomer, this vinyl polymer also preferably contains at least one of the constituent components having a substituent having 8 or more carbon atoms, the constituent components having the functional group described above, and further, the constituent components derived from the (meth)acrylic compound (M1) that forms the (meth)acrylic polymer described below. The content of the constituent components in the vinyl polymer is not particularly limited and can be appropriately selected taking into consideration other physical properties, etc., and can be set, for example, within the following range. The content of the constituent components derived from the vinyl monomer among all the constituent components that make up the vinyl polymer is preferably the same as the content of the constituent components derived from the (meth)acrylic compound (M1) in the (meth)acrylic polymer. Here, when the constituent component having a substituent having 8 or more carbon atoms and the constituent component having a functional group are constituent components derived from a vinyl monomer, the contents of these constituent components are included in the content of the constituent component derived from the vinyl monomer. The contents of the constituent component having a substituent having 8 or more carbon atoms and the content of the constituent component having the functional group, in all the constituent components constituting the vinyl polymer, are as described above. The content of the constituent component derived from the (meth)acrylic compound (M1) in the polymer is not particularly limited as long as it is less than 50% by mass, but is preferably 0 to 30% by mass.

[0110] ((Meth)acrylic polymer) The (meth)acrylic polymer is preferably a polymer obtained by copolymerizing at least one (meth)acrylic compound (M1) selected from a (meth)acrylic acid compound, a (meth)acrylic acid ester compound, a (meth)acrylamide compound, and a (meth)acrylonitrile compound, and also preferably a polymer having a constituent derived from this (meth)acrylic compound (M1) and at least one of a constituent having a substituent having 8 or more carbon atoms and a constituent having a functional group. Also preferred is a polymer containing a constituent derived from another polymerizable compound (M2).

[0111] Examples of (meth)acrylic acid ester compounds include (meth)acrylic acid alkyl ester compounds, (meth)acrylic acid aryl ester compounds, (meth)acrylic acid ester compounds with heterocyclic groups, and even polymerized (meth)acrylic acid 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. From the viewpoints of dispersibility and adhesion, it is preferably 3 to 20, more preferably 4 to 16, and even more preferably 8 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 most preferably 6. In the (meth)acrylamide compound, the nitrogen atom of the amide group may be substituted with an alkyl group or an aryl group. The polymerized chain possessed by the (meth)acrylic acid ester compound is not particularly limited, but is preferably an alkylene oxide polymerized chain, and more preferably a polymerized chain composed of an alkylene oxide having 2 to 4 carbon atoms. The degree of polymerization of the polymer chain is not particularly limited and can be set as appropriate. The end of the polymer chain is usually bonded to an alkyl group or an aryl group. The other polymerizable compound (M2) is not particularly limited, and examples thereof include vinyl compounds such as styrene compounds, vinyl naphthalene compounds, vinyl carbazole compounds, allyl compounds, vinyl ether compounds, vinyl ester compounds, dialkyl itaconate compounds, and unsaturated carboxylic acid anhydrides, as well as fluorinated versions thereof. Examples of vinyl compounds include the "vinyl monomers" described in JP 2015-88486 A. The (meth)acrylic compound (M1) and the other polymerizable compound (M2) may have a substituent. The substituent is not particularly limited, and preferably includes a group selected from the substituent Z described below.

[0112] The content of the constituent components in the (meth)acrylic polymer is not particularly limited and may be selected as appropriate, and can be set, for example, within the following range. The content of the constituent component derived from the (meth)acrylic compound (M1) in all the constituent components constituting the (meth)acrylic polymer is not particularly limited and may be set as appropriate within the range of 0 to 100% by mass. The upper limit can be, for example, 95% by mass. Here, when the constituent component having a substituent with 8 or more carbon atoms and the constituent component having a functional group are constituent components derived from the (meth)acrylic compound (M1), the content of these constituent components is included in the content of the constituent component derived from the (meth)acrylic compound (M1). The content of the constituent component having a substituent with 8 or more carbon atoms, the content of the constituent component having the functional group, and the content of the other constituent components in all the constituent components constituting the (meth)acrylic polymer are each as described above. The content of the other polymerizable compound (M2) in all the constituent components constituting the (meth)acrylic polymer is not particularly limited, but can be, for example, less than 50 mass%, preferably 1 to 30 mass%, more preferably 1 to 25 mass%, and even more preferably 3 to 25 mass%.

[0113] The (meth)acrylic compound (M1) and other polymerizable compound (M2) from which the (meth)acrylic polymer and vinyl polymer components are derived are preferably compounds represented by the following formula (b-1): This compound is preferably different from the compounds from which the components having a substituent with 8 or more carbon atoms are derived or the compounds from which the components having the functional groups are derived.

[0114]

[0115] In the formula, R １represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 to 6 carbon atoms), an alkynyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 to 6 carbon atoms), or an aryl group (preferably having 6 to 22 carbon atoms, and more preferably having 6 to 14 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferred, and a hydrogen atom or a methyl group is more preferred.

[0116] R ２ represents a hydrogen atom or a substituent. ２ The substituent that can be adopted as the alkyl group is not particularly limited, but examples thereof include an alkyl group (which may be branched but is preferably straight-chain), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms), and a cyano group. The number of carbon atoms in the alkyl group is the same as the number of carbon atoms in the alkyl group constituting the above-mentioned (meth)acrylic acid alkyl ester compound, but a long-chain alkyl ester having 8 or more carbon atoms or an alkyl ester having 7 or less carbon atoms is preferred.

[0117] L １ is a linking group, and is not particularly limited, but examples thereof include the linking groups in the constituent components having a substituent having 8 or more carbon atoms as described above. Ｎ )-group (R Ｎ is as described above.) is preferred. The linking group may have an arbitrary substituent. The number of atoms constituting the linking group and the number of linking atoms are as described above. Examples of the arbitrary substituent include the substituent Z described below, and examples thereof include an alkyl group or a halogen atom.

[0118] n is 0 or 1, preferably 1. However, -(L １ ) ｎ -R ２ When R represents one type of substituent (for example, an alkyl group), n is 0, and R ２In the above formula (b-1), the carbon atom forming the polymerizable group, R １ A carbon atom to which no H is bonded is an unsubstituted carbon atom (H ２ Although the substituent is represented as C=), it may have a substituent. The substituent is not particularly limited, but for example, R １ Examples of the substituent include the above-mentioned groups which may be substituted. Furthermore, groups which may be substituted, such as alkyl groups, aryl groups, alkylene groups, and arylene groups, may have a substituent within a range that does not impair the effects of the present invention. The substituent is not particularly limited, and examples thereof include groups selected from the substituent Z described below, and specific examples thereof include halogen atoms.

[0119] Preferred examples of the (meth)acrylic compound (M1) include compounds represented by the following formula (b-2) or (b-3): This compound is preferably different from a compound that leads to a constituent having a substituent with 8 or more carbon atoms or a compound that leads to a constituent having the above functional group.

[0120]

[0121] R １ , n has the same meaning as in formula (b-1) above. ３ is R ２ It is synonymous with L. ２ is a linking group, and the above L １ The description of the above can be preferably applied. ３ is a linking group, and the above L １ can be preferably applied, and an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3) is preferred. m is an integer of 1 to 200, preferably an integer of 1 to 100, and more preferably an integer of 1 to 50.

[0122] In the above formulas (b-1) to (b-3), the carbon atom forming the polymerizable group, R １ A carbon atom to which no H is bonded is an unsubstituted carbon atom (H ２ Although the substituent is represented as C=), it may have a substituent. The substituent is not particularly limited, but for example, R １Examples of the substituent include the above groups which may take the form of a substituent. In addition, in formulas (b-1) to (b-3), groups which may take a substituent, such as an alkyl group, an aryl group, an alkylene group, or an arylene group, may have a substituent within a range that does not impair the effects of the present invention. The substituent may be any substituent other than a functional group selected from functional group group (a), and examples thereof include groups selected from the substituent Z described below, and specific examples thereof include a halogen atom.

[0123] The chain-polymerized polymer (each of the constituent components and raw material compounds) may have a substituent. The substituent is not particularly limited and is preferably a group selected from the following substituent Z, and is preferably a group other than the functional groups included in the functional group group (a) described above.

[0124] - 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.

[0125] Chain polymerization polymers can be synthesized by selecting raw material compounds and polymerizing the raw material compounds using known methods. The method for incorporating a functional group is not particularly limited, and examples thereof include a method of copolymerizing a compound having a functional group selected from functional group group (a), 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, a functional group can be introduced using a functional group present in the main chain, side chain, or terminal of a polymer as a reaction site. For example, a functional group selected from functional group group (a) can be introduced by various reactions with a carboxylic acid anhydride group in a polymer chain using a compound having a functional group.

[0126] (Preferred Polymer A of Second Aspect) The polymer A (sometimes referred to as preferred polymer A of the second aspect) preferably used in the present invention includes a polymer having a polymer chain and a constituent (X) having a molecular weight of 400 or more. This polymer exhibits an appropriate adsorption rate for the active material AC and the inorganic solid electrolyte SE, contributing to improved dispersibility. The preferred polymer A of the second aspect preferably does not contain a constituent having a substituent having 8 or more carbon atoms as a side chain in the preferred polymer A of the first aspect (the content of the polymer A is 1% by mass or less).

[0127] - Constituent Component (X) - The constituent component (X) contained in the polymer A of the preferred second embodiment 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 (a1) defined for 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. When the polymer A of the preferred second embodiment contains constituent component (X), the excluded volume effect between the polymers A of the preferred second embodiment can be enhanced, and the dispersibility of solid particles can be improved, thereby achieving excellent dispersibility even when the dispersion time is shortened.

[0128] In the constituent (X), the polymer chain may be present in a partial structure that will become the main chain of polymer A, but it is preferably present in a molecular chain that will become a side chain of polymer A. For example, it is more preferably incorporated into the interior or end of the molecular chain that will become the side chain of polymer A. Such a constituent (X) can incorporate a graft structure into the chemical structure of polymer A, thereby enhancing the excluded volume effect. In the present invention, the molecular chain that will become the side chain of polymer A refers to a molecular chain that constitutes the side chain of polymer A into which constituent (X) has been incorporated. This molecular chain is a molecular chain other than the molecular chain that constitutes the main chain of polymer A, usually a molecular chain bonded to the molecular chain (atomic group) that constitutes the main chain. The type of polymer chain that one constituent (X) has may be at least one type, and preferably one or two types. Furthermore, the number of polymer chains that one constituent (X) has is not particularly limited, but is usually one.

[0129] Examples of this constituent (X) include a constituent derived from a polycondensable compound having a polycondensable group and a polymer chain. The polycondensable group is appropriately determined depending on the main chain structure of polymer A. For example, when polymer A is a step-polymerization polymer, a condensable functional group is selected, and when polymer A is a chain-polymerization polymer, a polymerizable group (ethylenically unsaturated group) is selected. When polymer A is a multibranched 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, polyether, polycarbonate, polysiloxane, and 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. Here, examples of (meth)acrylic polymers include polymers made of (co)polymers containing 50% by mass or more of a component derived from a (meth)acrylic compound (M1A) described below. Examples of vinyl polymers include polymers made of copolymers containing 50% by mass or more of a component derived from a vinyl-based compound (M2A) described below (provided that the content of the component derived from the (meth)acrylic compound (M1A) is less than 50% by mass). The polymer chain of carbon-carbon double bonds is as described above. The polymer chain is a molecular chain in which two or more repeating units of one or more types are bonded together. Such a polymer chain is not particularly limited, and a chain made of a conventional polymer, for example, the above-mentioned step-polymerized polymer or chain-polymerized polymer, can be used without any particular limitation. In the present invention, a polymer represented by 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.

[0130]

[0131] 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 from the viewpoint of dispersibility. 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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 dispersibility, a polymer chain made of polysiloxane is more preferred.

[0136] 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 dispersibility. This group may further have a substituent, but is preferably unsubstituted.

[0137] 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.

[0138] 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:

[0139] The polysiloxane structure is preferably a polysiloxane structure having a chemical structure represented by the following formula 4A.

[0140] 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.

[0141] 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.

[0142] 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 (M1A) 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 (M2A), 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 (M1A) 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.

[0143] 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 (M1A) that reacts with the chain transfer agent.

[0144] 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.

[0145] 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:

[0146]

[0147] 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.

[0148] Z represents a group represented by the following formula (Z).

[0149] 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.

[0150] 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.

[0151] The component (X) is not particularly limited, but is preferably a component derived from a compound obtained by introducing (substituting) a polymer chain into the following polycondensable compound. The polycondensable compound is not particularly limited as long as it is a condensation-polymerizable compound having an ethylenically unsaturated bond, and examples thereof include (meth)acrylic compounds (M1A) such as (meth)acrylic acid compounds, (meth)acrylic acid ester compounds, (meth)acrylamide compounds, and (meth)acrylonitrile compounds; vinyl compounds (M2A) 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, styrene compounds, (meth)acrylic acid compounds, (meth)acrylic acid ester compounds, and (meth)acrylamide compounds are preferred. Examples of (meth)acrylic acid ester compounds include (meth)acrylic acid alkyl ester compounds and (meth)acrylic acid aryl ester compounds, and (meth)acrylic acid alkyl ester compounds are 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, 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.

[0152] 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 (a1) described below, this polar functional group functions as a linking group and is not a polar functional group selected from the functional group group (a1). 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 (a1) 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 that does not correspond to component (A)).

[0153] 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.

[0154] 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 dispersibility. The molecular weight of the component (X) is appropriately determined taking into consideration the molecular weight of the polymer A of the preferred second embodiment, the content of the component (X), etc. For example, from the viewpoint of achieving both a reduction in dispersion time and improved dispersibility, the molecular weight is preferably 600 or more, more preferably 800 or more, even more preferably 2,000 or more, and particularly preferably 3,000 or more. The upper limit is not particularly limited, and from the viewpoint of achieving both a reduction in dispersion time and improved dispersibility, 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 A of the preferred second embodiment.

[0155] 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 preferred second embodiment of polymer A, etc. The degree of polymerization of all structural units forming the polymer chain is, for example, preferably 2 to 1,000, more preferably 2 to 200, and even more preferably 6 to 80.

[0156] - Constituent Component (A) - The polymer A of the second preferred embodiment preferably contains a constituent component (A) having at least one polar functional group selected from the following functional group group (a1), in that this enhances the adsorptivity or adhesion to solid particles and improves the dispersibility 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.

[0157] In the constituent component (A), the polar functional group is preferably contained in the molecular chain that will become the side chain of the polymer A, and more preferably, for example, incorporated into the interior or terminal of the molecular chain that will become the side chain of the polymer A. In the present invention, the molecular chain that will become the side chain of the polymer A refers to the molecular chain that constitutes the side chain of the polymer A into which the constituent component (A) has been incorporated, and is a molecular chain other than the molecular chain that constitutes the main chain of the polymer A, usually a molecular chain bonded to the molecular chain (atomic group) that constitutes the main chain. For example, when the polycondensable compound that derives the constituent component (A) is acrylamide, the molecular chain (-CONH ２ )

[0158] 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 polymer A of the preferred second embodiment 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 polymer A, etc.

[0159] 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 (a1): 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.

[0160] 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.

[0161] <Functional Group (a1)> 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

[0162] The sulfonic acid group, phosphoric acid group, phosphonic acid group, etc. included in the functional group group (a1) are not particularly limited, but each has the same meaning as the corresponding group of the above-mentioned substituent Z. The dicarboxylic acid group is not particularly limited, but includes a group obtained by removing one or more hydrogen atoms from a dicarboxylic acid or its anhydride, and a constituent component itself formed by copolymerization of a polymerizable dicarboxylic acid or its anhydride as a polymerizable compound, and further includes a group obtained by reacting a dicarboxylic acid or its 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 or its anhydride, a group obtained by removing one or more hydrogen atoms from an acyclic dicarboxylic acid or 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 or its anhydride is not particularly limited, but includes a dicarboxylic acid or its anhydride having an unsaturated bond in the molecule, preferably a polymerizable cyclic dicarboxylic acid anhydride. Examples of the polymerizable dicarboxylic acid include maleic acid and itaconic acid, and examples of the polymerizable cyclic dicarboxylic acid anhydride include maleic anhydride and itaconic acid 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 an alcohol compound, an amine compound, and a thiol compound.

[0163] 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 (*-CONRＮＡ１ -**), 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 A of the preferred second embodiment, but it is preferable that the bond * is bonded to the main chain side of the polymer A of the preferred second embodiment. However, the ester group does not include a partial structure that forms the main chain of the polymer A when the constituent component (A) is incorporated into the polymer A, for example, an ester group that is directly bonded to the polymer chain of the carbon-carbon double bond.

[0164] 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 RＮＡ１ In the present invention, the number of carbon atoms in the aryl group can be the same as that of the aryl group ＮＡ１ When either the terminal group or the group has a hydrogen atom, this hydrogen atom is ＮＡ１ Interpret as follows.

[0165] 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.

[0166] 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 a preferred embodiment that the lower limit is 4 or more. In the fluoroalkyl group, some or all of the hydrogen atoms may be substituted with fluorine atoms. In the present invention, a fluoroalkyl group in which some of the hydrogen atoms are substituted with fluorine atoms is preferred, and a preferred second embodiment of the polymer A in which the carbon atom bonded to the main chain side is a methylene group (—CH ) that is not substituted with a fluorine atom. 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 A, is substituted with a fluorine atom is more preferred, and ２ -CH ２ -) or propylene group (-CH２ -CH ２ -CH ２ In such a fluoroalkyl group in which some of the hydrogen atoms are substituted with fluorine atoms, the remaining alkyl groups bonded to carbon atoms that are not substituted with fluorine atoms are preferably perfluoroalkyl groups in which all of the hydrogen atoms are substituted with fluorine atoms. The fluoroalkyl group may have a substituent other than a fluorine atom, and for example, 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:

[0167] 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.

[0168] 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 dispersibility, 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 appropriately determined. For example, a combination including an amide group is preferred, and specifically, a combination of an amide group and a dicarboxylic acid group can be mentioned.

[0169] 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.

[0170] 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.

[0171] 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 below 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 (M1A) 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 the substituent substituting the nitrogen atom of the sulfonamide group may be, for example, R ＮＡ１ Alternatively, a terminal group bonded to the terminal of the amide bond may be mentioned, and an alkyl group is preferred.

[0172] 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.

[0173] 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 dispersibility.

[0174] 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.

[0175] 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).

[0176] Y １ and Y ２ represents a hydrogen atom or a substituent. １ and Y ２ The substituents that can be adopted as R are not particularly limited, and 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.

[0177] 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.

[0178] Specific examples of the component (A) include the components contained in polymer A in the examples, as well as components derived from an acrylamide compound, but the present invention is not limited to these.

[0179] 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 A of the preferred second embodiment, the content of the constituent component (A), etc.

[0180] 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 dispersibility.

[0181] Other Components—The polymer A of the second preferred embodiment may contain other components in addition to the components (X) and (A). The other components may be any components not corresponding to the above-described components, including components that do not have a polymer chain or a polar functional group. For example, a component derived from a low-molecular-weight polycondensable compound having an ethylenically unsaturated group but not a polar functional group may be mentioned. More specifically, a component derived from the above-described (meth)acrylic acid compound (M1A) or vinyl-based compound (M2A) may be mentioned. Components derived from styrene compounds, (meth)acrylic acid ester compounds, and (meth)acrylonitrile compounds are preferred, and components derived from (meth)acrylic acid unsubstituted alkyl ester compounds and (meth)acrylic acid aryl-substituted alkyl ester compounds are preferred. As the other components, a component derived from an acrylic acid ester compound of a long-chain unsubstituted alkyl group is one of the more preferred embodiments. The number of carbon atoms in the long-chain unsubstituted alkyl group may 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. Polymer A of a preferred second embodiment is one of the preferred embodiments that does not contain other constituent components.

[0182] The polymer A of the preferred second embodiment may contain one or more of the above-mentioned constituent components. The content of each constituent component in the polymer A of the preferred second embodiment is not particularly limited and is determined taking into appropriate consideration the physical properties of the polymer A as a whole, and is set, for example, within the following range. The content of each constituent component in the polymer A of the preferred second embodiment is set, for example, within the following range so that the total content of all constituent components is 100 mass%. When the polymer A contains two or more constituent components corresponding to a specific constituent, the total content of these constituent components is used.

[0183] The total content of component (X) in the polymer A of the preferred second embodiment is not particularly limited and can be determined appropriately taking into consideration shortening the dispersion time, improving dispersibility, and the like. The total content of component (X) is, for example, preferably 50 to 99% by mass relative to the total content of all components. From the viewpoint of shortening the dispersion time and improving dispersibility, it is more preferably 55 to 95% by mass, even more preferably 60 to 90% by mass, and particularly preferably 65 to 80% by mass. The total content of component (A) in the polymer A of the preferred second embodiment is not particularly limited and can be determined appropriately taking into consideration shortening the dispersion time, improving dispersibility, and the like. Usually, the viscosity of polymer A tends to increase as the total content of component (A) increases. The total content of component (A) is, for example, preferably 0 to 50% by mass relative to the total content of all components, from the viewpoint of easily setting the viscosity of the composition for an all-solid-state secondary battery within an appropriate range. From the viewpoint of shortening dispersion time and improving dispersibility, it is more preferably 1 to 50% by mass, even more preferably 5 to 45% by mass, particularly preferably 10 to 40% by mass, and most preferably 20 to 35% by mass. In the preferred second embodiment of polymer A, 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 dispersibility, 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 the other constituent 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 constituent components.

[0184] The polymer A of a preferred second embodiment may have a substituent in addition to the polar functional groups included in the substituent group (a). Examples of the substituent that the polymer A may have include the substituent Z (excluding polar functional groups) described below. Among the polar functional groups and substituents, the polymer A is one of the preferred embodiments that does not have a hydroxy group.

[0185] The molecular structure of the polymer A of the preferred second embodiment will now be described. The molecular structure of the polymer A of the preferred second embodiment is not particularly limited as long as it contains the above-mentioned component (X). Typically, the polymer A has a branched or multi-branched structure in which the polymer chain of component (X) is a branched chain (side chain). In the present invention, a "branched structure" refers to a polymer chain of the polymer A having a branched structure, such as a structure in which one or more other 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 having no core, but in which multiple polymer chains (as side chains) are bonded to a single main chain in a branched manner. A "star structure" refers to a polymer having a multi-branched structure in which multiple, typically three or more, polymeric arms are bonded to a core. The polymeric arms constituting the star structure may be linear or graft structures. Here, the polymeric arm refers to a partial structure containing a polymer chain, which forms an arm of a hyperbranched polymer by bonding to a core. The primary structures of the main chain and graft chain in the graft structure (the bonding mode of the constituent components) and the primary structure of the polymeric arm in the star structure (the bonding mode of the constituent components) are not particularly limited and may be any bonding mode such as a random structure, a block structure, or an alternating structure. The polymer A of the second preferred embodiment preferably has a graft structure or a star structure.

[0186] When the polymer A of the second preferred embodiment has a graft structure, it can be synthesized by homopolymerizing or copolymerizing the compound that leads to the above-mentioned component (X).

[0187] When the polymer A of the second preferred embodiment has a star structure, the polymer A 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.

[0188] (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 for example, it is preferably 200 or more, and more preferably a molecular weight of 300 or more. The upper limit of the molecular weight is preferably 5,000 or less, more preferably 4,000 or less, and particularly preferably 3,000 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.

[0189] 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.

[0190] The linking group L is preferably a linking group represented by the following formula 1A or 1B.

[0191] 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.

[0192] 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.

[0193] 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.

[0194]

[0195] 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.

[0196]

[0197] 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.

[0198] 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.

[0199]

[0200] (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 dispersibility, 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 dispersibility, 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 (M1A) having a polymer chain made of polysiloxane. １Ａ In terms of shortening the dispersion time and dispersibility, 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.

[0201] 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.

[0202] 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 dispersibility, 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 dispersibility, 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 dispersibility, 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.

[0203] 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 dispersibility, 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 dispersibility, 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 dispersibility, 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.

[0204] 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 A of the second embodiment, and is preferably 500 to 20,000, and 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 A of the second embodiment, and is preferably 400 to 50,000, and 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 preferred polymer A of the second embodiment. 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 ...

[0205] 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 polymer A shown in the specific examples and examples described below.

[0206] (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.

[0207] 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 dispersibility, 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 dispersibility, 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 constituent component (X) in the polymer A of the preferred second embodiment. 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 A of the preferred second embodiment. 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 components (X) is not particularly limited, and is preferably the same as the ratio of the total contents in the polymer A of the preferred second embodiment [total content of constituent component (X) / total content of constituent component (A)].

[0208] 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.

[0209] 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.

[0210] 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.

[0211] Specific examples of the polymer A represented by formula (1) or formula (2) include the polymers synthesized in the specific examples and examples described below, but the present invention is not limited to these.

[0212] The polymer A of the second preferred embodiment 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 A of the second preferred embodiment 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 of 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 site. 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.

[0213] Specific examples of polymer A include those shown below, but the present invention is not limited to these. In the following specific examples A-1 to A-14, the alkyl groups in the (meth)acrylic acid alkyl esters are all linear alkyl groups, and the numbers attached to the bottom right of the constituent components indicate the content in the polymer, expressed in mass %. In the following A-15 to A-32, polymer chain M-1 made of polysiloxane is a polymer chain derived from X-22-174ASX (product number, molecular weight 900, manufactured by Shin-Etsu Chemical Co., Ltd.), M-2 is a polymer chain derived from X-22-174BX (product number, molecular weight 2300, manufactured by Shin-Etsu Chemical Co., Ltd.), and M-3 is a polymer chain derived from KF-2012 (product number, molecular weight 4600, manufactured by Shin-Etsu Chemical Co., Ltd.). The polymerization degrees of the siloxane structures in polymer chains M-1 to M-3 are omitted. In addition, R bonded to the polymer chain made of polysiloxane Ｙ represents a linking group, and R Ｚ indicates a substituent. In the following specific examples A-15 to A-24, the numbers to the lower right of the constituent components indicate the content in the polymer, and the units are % by mass. In the following structural formulas, "Me" indicates a methyl group, and "Ph" indicates a phenyl group.

[0214]

[0215]

[0216]

[0217]

[0218] The polymer A contained in the composition for an all-solid-state secondary battery of the present invention may be one type or two or more types. When two or more types of polymer A are contained, at least one of them has an adsorption rate A in the above-mentioned preferred range. ＡＣ and the adsorption rate A in the above preferred range ＳＥ It is preferable that the polymer satisfies at least one of the above, for example, a polymer selected from the polymer A of the first preferred embodiment and the polymer A of the second preferred embodiment, and all of the polymers have an adsorption rate A in the above preferred range. ＡＣ and the adsorption rate A in the above preferred range ＳＥIt is more preferable that the polymer satisfies at least one of the above-mentioned preferable ranges of adsorption rate A. ＡＣ and the adsorption rate A in the above preferred range ＳＥ As the polymer that does not satisfy one of the above requirements, for example, various polymers that are used as binders or the like in all-solid-state secondary batteries can be used without any particular limitation.

[0219] (Physical properties or characteristics of polymer A) Polymer A preferably has the following physical properties or characteristics. The water concentration of polymer A is preferably 100 ppm (by mass) or less. Polymer A may also be obtained by crystallizing and drying polymer A, or a solution of polymer A may be used as is. Polymer A is preferably amorphous. In the present invention, a polymer being "amorphous" typically means that no endothermic peak due to crystalline melting is observed when measured at the glass transition temperature. Polymer A may be a non-crosslinked polymer or a crosslinked polymer, and is preferably a non-crosslinked polymer. In addition, when crosslinking of the polymer progresses by heating or application of voltage, the molecular weight may be larger than the above-mentioned molecular weight.

[0220] The content of polymer A in the composition for an all-solid-state secondary battery is not particularly limited and can be appropriately set taking into consideration Aa or Ab calculated by Equation 1 or Equation 2, and further Ac calculated by Equation 3, and can be, for example, 0.1 to 20 mass% based on 100 mass% solids. The content of polymer A is preferably low in order to suppress the battery performance of the all-solid-state secondary battery, such as a decrease in battery output and an increase in resistance. On the other hand, if the content of polymer A is low, the number of molecules of polymer A functioning as a dispersant decreases. Therefore, in the present invention, in order to increase the number of molecules of polymer A present in the composition for an all-solid-state secondary battery while reducing the content of polymer A in consideration of battery performance, it is preferable to determine the content in consideration of the weight-average molecular weight. This makes it easy to set Aa or Ab calculated by Equation 1 or Equation 2 within the above range, and it is possible to enhance the dispersibility of solid particles while suppressing a decrease in battery performance. Within the above range, the content of polymer A is preferably 0.1 to 5 mass%, and particularly when the weight-average molecular weight of polymer A is 2.0 × 10 ３~2.0 x 10 ４ In this case, the content is more preferably 0.2 to 3 mass %, and further preferably 0.3 to 2 mass %.

[0221] In the present invention, at a solid content of 100% by mass, the mass ratio of the total mass of the inorganic solid electrolyte SE and the active material AC to the mass of the polymer A [(mass of SE + mass of AC) / (mass of polymer A)] 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. When the composition for an all-solid-state secondary battery contains two or more types of polymer A, the content of the polymer A refers to the total content.

[0222] <Dispersion Medium D> The composition for an all-solid-state secondary battery of the present invention contains a dispersion medium D that disperses or dissolves the above-mentioned components. Such dispersion medium D 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. Dispersion medium D may be either a nonpolar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a nonpolar dispersion medium is preferred because it can exhibit excellent dispersibility. A nonpolar dispersion medium generally refers to a dispersion medium that has low affinity for water. In the present invention, examples thereof include ester compounds, ketone compounds, ether compounds, aromatic hydrocarbon compounds, and aliphatic hydrocarbon compounds.

[0223] 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.

[0224] 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.).

[0225] 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.

[0226] 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.

[0227] 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, and ether compounds are more preferred.

[0228] 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.

[0229] The boiling point of the dispersion medium at normal pressure (1 atmosphere: 101,325 Pa) is not particularly limited, but is preferably 50° C. or higher, and more preferably 70° C. or higher. The upper limit is preferably 250° C. or lower, and more preferably 220° C. or lower.

[0230] The dispersion medium D contained in the composition for an all-solid-state secondary battery of the present invention may be one type or two or more types. Examples of dispersion mediums containing two or more types 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 medium D in the composition for an all-solid-state secondary battery is not particularly limited and can be set appropriately. In the present invention, the excellent dispersibility of the composition for an all-solid-state secondary battery can be utilized to increase the solid content concentration, i.e., to reduce the content of the dispersion medium D. The content of the dispersion medium D in the composition for an all-solid-state secondary battery is, for example, preferably 10 to 60 mass%, more preferably 20 to 50 mass%, and particularly preferably 20 to 40 mass%.

[0231] <Conductive Aid> The all-solid-state secondary battery composition of the present invention, particularly the electrode composition, preferably contains 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 fibers, carbon nanotubes, etc.); carbonaceous materials (e.g., graphene, fullerene, etc.); metal powders or metal 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 aid are used in combination, the conductive aid is one of the above-mentioned conductive aids that does not undergo insertion and release of ions (preferably Li ions) of a metal belonging to Group 1 or Group 2 of the periodic table during charging and discharging of the battery and does not function as an active material. Therefore, among the conductive additives, those that can function as an active material in the active material layer when the battery is charged and discharged are classified as active materials rather than as conductive additives. Whether or not a conductive additive functions as an active material when the battery is charged and discharged is not uniquely determined, but is determined by the combination with the active material.

[0232] The conductive additive contained in the composition for an all-solid-state secondary battery of the present invention is preferably in a particulate form in the composition for an all-solid-state secondary battery. The shape of the particles is not particularly limited and may be flat, amorphous, etc., but is preferably spherical or granular. When the conductive additive is in a particulate form, the particle diameter (volume average particle diameter) of the conductive additive is not particularly limited, but is preferably 0.02 to 1.0 μm, and more preferably 0.03 to 0.5 μm. The particle diameter of the conductive additive can be adjusted in the same manner as the particle diameter of the inorganic solid electrolyte, and can be measured in the same manner as the particle diameter of the inorganic solid electrolyte. The specific surface area of ​​the conductive additive is not particularly limited and can be set appropriately. For example, the specific surface area of ​​the conductive additive is usually 1.0 to 1,500 m ２ / g range, but 5 to 100 m ２ It is preferable that the range is / g.

[0233] The composition for an all-solid-state secondary battery of the present invention may contain one or more conductive additives. The content of the conductive additive in the composition for an all-solid-state secondary battery is not particularly limited and may be determined appropriately. For example, the content is preferably 10% by mass or less, more preferably 1.0 to 5.0% by mass, based on 100% by mass of the solid content.

[0234] <Lithium Salt> The composition for an all-solid-state secondary battery of the present invention may also contain 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 composition for an all-solid-state secondary battery 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, relative to 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.

[0235] <Other Additives> The composition for an all-solid-state secondary battery 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.

[0236] (Preparation of Composition for All-Solid-State Secondary Battery) The composition for all-solid-state secondary batteries of the present invention can be prepared by a conventional method using inorganic solid electrolyte SE, polymer A, and, if necessary, active material AC, and a conductive additive. For example, the inorganic solid electrolyte SE, polymer A, dispersion medium D, and active material AC, as well as the appropriate conductive additive, lithium salt, and any other components, can be prepared as a mixture, preferably as a slurry, by mixing them, for example, with various commonly used mixers. 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, and narrow-gap disperser. The components may be mixed all at once or sequentially. The mixing environment is not particularly limited, but examples include dry air (dew point -20°C or lower) and inert gas (e.g., argon gas, helium gas, nitrogen gas), etc. 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 or the like can be set to 200 to 3,000 rpm (rotation per minute).

[0237] The mixing time is not particularly limited and can be determined appropriately depending on the dispersibility of the solid particles, and can typically be, for example, 1 to 180 minutes. The composition for an all-solid-state secondary battery of the present invention has excellent dispersibility of solid particles, and can highly disperse the solid particles in the dispersion medium D without aggregation even when mixed for a short time, so the mixing time (dispersion time) can be set short, for example, 10 minutes or less, and preferably 1 to 8 minutes. In the present invention, the mixing time refers to the mixing time when mixing the solid particles (inorganic solid electrolyte SE, polymer A, and optionally active material AC, and further conductive additive), polymer A, and dispersion medium.

[0238] In the method for preparing a composition for an all-solid-state secondary battery, the components used are selected so as to satisfy the values ​​calculated by Formula 1 and / or Formula 2, and preferably also the value calculated by Formula 3. Specifically, Aa calculated by Formula 1 is, as is clear from Formula 1, the adsorption rate A of polymer A to active material AC. ＡＣWhen the content of polymer A in the total solid content is increased, when the molecular weight of polymer A is decreased, or when the specific surface area of ​​active material AC is decreased, the adsorption rate A ＡＣ By setting the content of polymer A, the molecular weight of polymer A, and the specific surface area of ​​active material AC within the above-mentioned ranges or preferred ranges thereamong, it becomes easier to adjust Aa calculated by Equation 1 to within the range of 1 to 100. Preferably, (1) the specific surface area of ​​the active material AC to be used is measured, and the content of the active material / total solid content is set (setting the total specific surface area of ​​active material AC). Next, (2-1) for example, if the content of polymer A / total solid content is determined to be 0.005, a polymer A is selected that exhibits an adsorption rate and weight-average molecular weight to active material AC such that Aa is 1 to 100. On the other hand, (2-2) if polymer A is determined (the adsorption rate and weight-average molecular weight to active material AC are fixed), the content of polymer A / total solid content is set such that Aa is 1 to 100.

[0239] Adsorption rate A of polymer A to active material AC ＡＣ can be adjusted by incorporating a group contained in the functional group group (a) or the functional group group (a1) into the polymer A, and the adsorption rate A in a preferred range can be achieved by using the type of functional group contained in the functional group group (a) or the functional group group (a1) as the preferred group described above, or by setting the content of the constituent component having a functional group within the preferred range described above, or by combining these. ＡＣ can be obtained. Furthermore, it is preferable to determine the content of each component while taking into consideration the total solid content so as to satisfy Aa or Ab calculated by the above formula 1 or formula 2. In particular, the content of each of the active material AC, inorganic solid electrolyte SE, and polymer A is appropriately determined from the above content range for each component, taking into consideration the characteristics of each component, etc., but when set in the above-mentioned preferred range, it becomes easy to adjust Aa calculated by formula 1 to a range of 1 to 100. For example, it is preferable to set the content of polymer A to a low value, and in this case, the values ​​Aa and Ab calculated by formula 1 and formula 2 can be reduced.

[0240] Ab calculated by Equation 2 can also be adjusted to within the range of 2 to 500 in the same manner as Aa calculated by Equation 1. Preferably, for example, (1) the specific surface area of ​​the inorganic solid electrolyte SE to be used is measured, and the content / total solid content of the inorganic solid electrolyte SE is set (setting of the total specific surface area of ​​the inorganic solid electrolyte SE). Next, (2-1) for example, if the content / total solid content of the polymer A is determined to be 0.005, select a polymer A that exhibits an adsorption rate to the inorganic solid electrolyte SE and a weight-average molecular weight such that Aa is 1 to 100. On the other hand, (2-2) if the polymer A is determined (the adsorption rate to the inorganic solid electrolyte SE and the weight-average molecular weight are fixed), the content / total solid content of the polymer A such that Aa is 1 to 100 may be set.

[0241] [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 (also referred to as an 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.

[0242] 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 composition for an all-solid-state secondary battery of the present invention. Therefore, the layer formed from the composition for an all-solid-state secondary battery of the present invention is formed from components derived from the composition for an all-solid-state secondary battery (excluding the dispersion medium), and the solid particles are adhered or bound together. In the layer formed from the composition for an all-solid-state secondary battery of the present invention, the dispersion state of the solid particles (inorganic solid electrolyte SE, active material AC if necessary, and a conductive additive) and polymer A is improved, and it is presumed that, for example, the solid particles and polymer A are dispersed or present in a substantially uniform mixed state. In the sheet for an all-solid-state secondary battery of the present invention, at least one of the solid electrolyte layer and active material layer is formed from the composition for an all-solid-state secondary battery of the present invention. Therefore, the sheet for an all-solid-state secondary battery of the present invention includes a constituent layer in which the dispersion state of the solid particles is improved. By using this constituent layer as a constituent layer of an all-solid-state secondary battery, excellent battery performance, such as rate characteristics and battery life, can be achieved. Thus, the sheet for an all-solid-state secondary battery of the present invention is suitable for use as a sheet-like member forming a constituent layer of an all-solid-state secondary battery. The sheet for an all-solid-state secondary battery is incorporated into an all-solid-state secondary battery as a constituent layer by appropriately peeling off the substrate, or as an electrode (a laminate of a current collector and an active material layer) with the substrate attached.

[0243] (Solid Electrolyte Sheet for All-Solid-State Secondary Battery) The solid electrolyte sheet for an all-solid-state secondary battery of the present invention (also simply referred to as a "solid electrolyte sheet") 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 composition for an all-solid-state secondary battery (inorganic solid electrolyte-containing composition) of the present invention. 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 composition for an all-solid-state secondary battery 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 composition for an all-solid-state secondary battery of the present invention, a normal solid electrolyte layer, and a protective layer, in this order.

[0244] 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.

[0245] (Electrode Sheet for All-Solid-State Secondary Battery) The electrode sheet for an all-solid-state secondary battery of the present invention (also simply referred to as "electrode sheet") 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 an 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, but also includes an embodiment in which the electrode sheet has a current collector, an active material layer, and a solid electrolyte layer in this order, as well as an embodiment in which the electrode sheet has a current collector, an active material layer, a solid electrolyte layer, and an active material layer in this order. At least one of the solid electrolyte layer and the active material layer of the electrode sheet is formed from the composition for an all-solid-state secondary battery of the present invention (an inorganic solid electrolyte-containing composition or an electrode composition). The content of each component in a layer formed from the composition for an all-solid-state secondary battery of the present invention is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the composition for an all-solid-state secondary battery 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 have the other layers described above. When the solid electrolyte layer or the active material layer is not formed from the composition for an all-solid-state secondary battery of the present invention, it is formed from a material typically used for forming a constituent layer.

[0246] [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 an inorganic solid electrolyte layer or an active material layer using the composition for an all-solid-state secondary battery of the present invention. For example, a method is preferably used in which the composition for an all-solid-state secondary battery is formed (coated and dried) on a substrate or a current collector (optionally via another layer) to form a layer (coated and dried layer) composed of the composition for an all-solid-state secondary battery. This method allows 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. Here, the coated and dried layer refers to a layer formed by coating the composition for an all-solid-state secondary battery of the present invention and drying the dispersion medium D (i.e., a layer formed using the composition for an all-solid-state secondary battery of the present invention and having a composition obtained by removing the dispersion medium D from the composition for an all-solid-state secondary battery of the present invention). The coated and dried layer and the constituent layers may contain residual dispersion medium as long as it does not impair the effects of the present invention. The residual amount can be, for example, 3% by mass or less in each layer. In the method for manufacturing a sheet for an all-solid-state secondary battery of the present invention, each step, such as coating and drying, is described below in the method for manufacturing an all-solid-state secondary battery.

[0247] In this way, a sheet for an all-solid-state secondary battery having a constituent layer produced by appropriately applying pressure to the coated and dried layer can be produced. The pressure 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.

[0248] [All-Solid-State 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. For example, a known configuration related to all-solid-state secondary batteries can be adopted. The positive electrode active material layer preferably has a positive electrode current collector laminated on the surface opposite the solid electrolyte layer to form a positive electrode, and the negative electrode active material layer preferably has a negative electrode current collector laminated on the surface opposite the solid electrolyte layer to form a negative electrode. In the present invention, each constituent layer (including the current collector, etc.) of the all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.

[0249] In the all-solid-state secondary battery of the present invention, at least one of the negative electrode active material layer, positive electrode active material layer, and solid electrolyte layer is formed from the composition for an all-solid-state secondary battery of the present invention. Also, in a preferred embodiment, at least one of the negative electrode active material layer and the positive electrode active material layer is formed from the composition for an all-solid-state secondary battery of the present invention. In this embodiment, it is more preferable that at least the negative electrode active material layer is formed from the composition for an all-solid-state secondary battery of the present invention. In another preferred embodiment of the present invention, all layers are formed from the composition for an all-solid-state secondary battery of the present invention. In the present invention, forming the constituent layers of an all-solid-state secondary battery from the composition for an all-solid-state secondary battery of the present invention includes forming the constituent layers from the sheet for an all-solid-state secondary battery of the present invention (provided that, if a layer other than the layer formed from the composition for an all-solid-state secondary battery of the present invention is present, the sheet is formed from the layer removed). An all-solid-state secondary battery of the present invention in which at least one of the constituent layers is formed from the composition for an all-solid-state secondary battery of the present invention exhibits excellent battery performance. If the active material layer is not formed from the electrode composition of the present invention, the active material layer and the solid electrolyte layer can be prepared using known materials. 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.

[0250] <Positive Electrode Active Material Layer, Solid Electrolyte Layer, Negative Electrode Active Material Layer> The active material layer or solid electrolyte layer formed from the composition for an all-solid-state secondary battery of the present invention preferably has the same component types and their contents as those in the solid content of the composition for an all-solid-state secondary battery 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.

[0251] <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.

[0252] 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.

[0253] <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.

[0254] <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.

[0255] <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.

[0256] 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.

[0257] 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.

[0258] (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 composition for an all-solid-state secondary battery of the present invention. The inorganic solid electrolyte SE and the polymer A 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 assistants 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.

[0259] The solid electrolyte layer contains an inorganic solid electrolyte SE having conductivity for metal ions belonging to Group 1 or 2 of the periodic table, a polymer A, 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 SE having conductivity for metal ions belonging to Group 1 or 2 of the periodic table, a positive electrode active material, a polymer A, preferably a conductive additive, and the optional components described above within the scope of the present invention. The negative electrode active material layer contains an inorganic solid electrolyte SE having conductivity for metal ions belonging to Group 1 or 2 of the periodic table, a negative electrode active material, a polymer A, preferably a conductive additive, 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.

[0260] In the present invention, when the constituent layers are formed from the composition for an all-solid-state secondary battery of the present invention, an all-solid-state secondary battery having excellent battery performance such as life characteristics, output, and rate characteristics can be realized.

[0261] (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 composition for an all-solid-state secondary battery 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.

[0262] [Manufacturing of All-Solid-State Secondary Battery] The all-solid-state secondary battery of the present invention can be manufactured by a conventional method using the all-solid-state secondary battery composition of the present invention. For example, the all-solid-state secondary battery can be manufactured by forming at least one constituent layer using the all-solid-state secondary battery composition of the present invention. Specifically, the all-solid-state secondary battery of the present invention can be manufactured by a method (the method for manufacturing an all-solid-state secondary battery sheet of the present invention) that includes a step of applying the all-solid-state secondary battery composition of the present invention to a suitable substrate (e.g., a metal foil serving as a current collector) to form a coating film (film formation). More specifically, an all-solid-state 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, an all-solid-state 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, an all-solid-state 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.

[0263] Another method includes the following. That is, a positive electrode sheet for an all-solid-state secondary battery is prepared as described above. A composition for an all-solid-state secondary battery containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) to 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 includes the following. 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 from this, a composition for an all-solid-state secondary battery 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.

[0264] 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.

[0265] The solid electrolyte layer or the like can also be formed, for example, by pressure molding an all-solid-state 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 composition for an all-solid-state secondary battery 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 composition for an all-solid-state secondary battery 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. It is preferable to use the composition for an all-solid-state secondary battery of the present invention as at least the negative electrode composition. The composition for an all-solid-state secondary battery 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 composition for an all-solid-state secondary battery 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, a negative electrode active material layer can also be formed by bonding ions of a metal belonging to Group 1 or Group 2 of the periodic table, which have accumulated in the negative electrode current collector during initialization or charging during use (described later), with electrons and depositing the metal on the negative electrode current collector or the like.

[0266] <Formation of Each Layer (Film Formation)> The method for applying the composition for an all-solid-state secondary battery is not particularly limited and can be selected as appropriate. Examples of application (preferably wet application) methods include spray application, spin coating, dip coating, slit coating, stripe coating, and bar coating. The application temperature is not particularly limited and, for example, can be, for example, a temperature range of about room temperature (e.g., 15 to 30°C) without heating. The applied composition for an all-solid-state secondary battery 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 D to be removed and the composition to be in a solid state (coated, dried layer). Furthermore, it is preferable to avoid raising the temperature too high, as this 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. The drying time of the applied composition for an all-solid-state secondary battery is appropriately determined depending on the application amount, application area, etc., but can be shortened in the case of a highly concentrated composition for an all-solid-state secondary battery, and can be set to, for example, 10 minutes or less.

[0267] <Formation of Each Layer (Film Formation)> After coating and drying the composition for an all-solid-state secondary battery, and then 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 a pressurizing method include a hydraulic cylinder press. The pressure is not particularly limited and is generally preferably in the range of 5 to 1500 MPa. The coated composition for an all-solid-state secondary battery 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 polymer A. However, the temperature is generally not higher than the melting point of polymer A. Pressing may be performed after the coating solvent or dispersion medium has been dried in advance, or may be performed while the solvent or dispersion medium remains. The compositions may be applied 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.

[0268] 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.

[0269] In the production of an all-solid-state secondary battery sheet and an all-solid-state secondary battery, when the composition for an all-solid-state secondary battery of the present invention, particularly a highly concentrated composition for an all-solid-state secondary battery, is used, the drying time after application can be set short and the amount of volatilization of the dispersion medium can be reduced, resulting in improved productivity, reduced environmental load, and reduced production costs. Therefore, the composition for an all-solid-state secondary battery of the present invention is also beneficial from the viewpoint of industrial production of an all-solid-state secondary battery sheet and an all-solid-state secondary battery.

[0270] <Initialization> The all-solid-state 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 carrying out initial charge and discharge under an elevated pressure, and then releasing the pressure until the pressure reaches the general operating pressure of an all-solid-state secondary battery.

[0271] [Applications of All-Solid-State Secondary Battery] The all-solid-state 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 movie players, 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 all-solid-state secondary battery can be used for various military and space applications. It can also be combined with solar cells.

[0272] 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. In these examples, Table 1-1 and Table 1-2 are collectively referred to as "Table 1," and Table 2-1 and Table 2-2 are collectively referred to as "Table 2."

[0273] 1. Synthesis of Polymer A Of the polymers A represented by the above chemical formula, the following polymers were synthesized as follows.

[0274] Synthesis Example A-1: ​​Synthesis of Polymer A-1 To a 200 mL volumetric flask, 9.5 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 90.0 g of dodecyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of maleic anhydride, and 3.6 g of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was dissolved in 70 g of diisobutyl ketone (DIBK) to prepare a monomer solution. 40 g of DIBK was added to a 500 mL three-neck flask and stirred at 80°C, to which the above monomer solution was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 90°C and stirred for 2 hours. The resulting solution was dried, and the weight average molecular weight measured by the above measurement method was 1.6 × 10 ４ Polymer A-1 (acrylic polymer) was synthesized.

[0275] In addition, the amount of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was appropriately changed to obtain a polymer having a weight average molecular weight of 6.0 × 10 ３ , 1.2 × 10 ５ , 2.0 × 10 ５ or 4.0 x 10 ５ Polymer A-1 was synthesized.

[0276] Synthesis Example A-2: Synthesis of Polymer A-2 100 g of ion-exchanged water, 48 g of vinylidene fluoride, 30 g of hexafluoropropene, and 22 g of tetrafluoroethylene were added to an autoclave, and 1 g of a polymerization initiator, Peroyl IPP (trade name, chemical name: diisopropyl peroxydicarbonate, manufactured by NOF Corporation), was further added, and the mixture was stirred at 40°C for 24 hours. After stirring, the precipitate was filtered and dried at 100°C for 10 hours. Thus, the weight average molecular weight measured by the above-mentioned measurement method was 8.0 × 10 ５ Polymer A-2 (a random copolymer fluoropolymer) was synthesized. The amounts of the polymerization initiator and ion-exchanged water were changed, and the weight average molecular weight measured by the above measurement method was 6.0 × 10 ４ or 4.0 x 10 ５ Polymer A-2 was synthesized.

[0277] Synthesis Example A-3: Synthesis of Polymer A-3 In Synthesis Example A-1, a compound was used to induce each component so as to have the structure shown in the above chemical formula instead of methyl methacrylate, and the amount of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was appropriately changed to adjust the molecular weight. In the same manner as in Synthesis Example A-1, a polymer A-3 was synthesized, and the weight average molecular weight measured by the above measurement method was 1.6 × 10. ４ In Synthesis Example A-3, the amounts of the polymerization initiator and ion-exchanged water were changed, and the weight average molecular weight measured by the above measurement method was 8.0 × 10 ３ or 4.0 x 10 ５ Polymer A-3 was synthesized.

[0278] Synthesis Example A-5: Synthesis of Polymer A-5 A nitrogen-purged, dried pressure vessel was charged with 300 g of cyclohexane as a solvent and 2.0 mL of sec-butyllithium (1.3 M, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and the temperature was raised to 50 ° C., after which 31 g of styrene was added and polymerized for 2 hours, followed by the addition of 48 g of 1,3-butadiene and 90 g of ethylene and polymerization for 3 hours, after which 31 g of styrene was added and polymerized for 2 hours. The resulting solution was reprecipitated in methanol, and 3 parts by mass of 2,6-di-t-butyl-p-cresol was added to 100 parts by mass of the polymer obtained by drying the resulting solid, and the mixture was allowed to react at 180 ° C. for 5 hours. The resulting solution was reprecipitated in acetonitrile, and the resulting solid was dried at 80 ° C. to obtain a polymer (dry product). Thereafter, the entire amount of the polymer obtained above was dissolved in 400 parts by mass of cyclohexane in a pressure vessel, and then palladium carbon (palladium loading: 5% by mass) was added as a hydrogenation catalyst in an amount of 5% by mass relative to the polymer, and the reaction was carried out for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150° C. After cooling and pressure release, the palladium carbon was removed by filtration, the filtrate was concentrated and further dried in vacuo, and the weight average molecular weight measured by the above measurement method was 1.0×10 ５ Polymer A-5 (hydrocarbon polymer) was synthesized.

[0279] Synthesis Example A-6: Synthesis of Polymer A-6 In Synthesis Example A-1, a polymer A-6 was synthesized in the same manner as in Synthesis Example A-1, except that compounds were used that lead to the respective constituent components so as to have the structure and composition (content of constituent components) shown in the above chemical formula, and the amount of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was appropriately changed to adjust the molecular weight, and a polymer A-6 was synthesized in the same manner as in Synthesis Example A-1, with a weight average molecular weight of 1.2 × 10 measured by the above measurement method. ４ Polymer A-6 (acrylic polymer) was synthesized.

[0280] Synthesis Example A-8: Synthesis of Polymer A-8 In Synthesis Example A-1, except that 33 g of butyl acrylate and 67 g of styrene were used instead of methyl methacrylate, dodecyl acrylate, and maleic anhydride, and the amount of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was appropriately changed to adjust the molecular weight, the same procedure as in Synthesis Example A-1 was repeated to obtain a polymer A-8 having a weight average molecular weight of 1.0 × 10 measured by the above-mentioned measurement method.５ Polymer A-8 (vinyl polymer) was synthesized.

[0281] Synthesis Example A-9: Synthesis of Polymer A-9 In Synthesis Example A-1, a compound was used that leads to each constituent component so that the structure and composition (content of constituent components) shown in the above chemical formula was obtained, and the amount of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was appropriately changed to adjust the molecular weight. In the same manner as in Synthesis Example A-1, a polymer A-9 having a weight average molecular weight of 1.5 × 10 measured by the above measurement method was obtained. ５ Polymer A-9 (acrylic polymer) having a weight average molecular weight of 8.0 × 10 was synthesized by changing the amount of polymerization initiator V-601. ５ Polymer A-9 was synthesized.

[0282] Synthesis Example A-10: Synthesis of Polymer A-10 In Synthesis Example A-1, compounds were used that lead to the respective constituent components so that the structure and composition (content of constituent components) represented by the above chemical formula were obtained, and the amount of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was appropriately changed to adjust the molecular weight. In the same manner as in Synthesis Example A-1, a polymer A-10 having a weight average molecular weight of 4.0 × 10 measured by the above measurement method was obtained. ５ Polymer A-10 (acrylic polymer) was synthesized.

[0283] Synthesis Example A-13: Synthesis of Polymer A-13 In Synthesis Example A-1, compounds were used that lead to the respective constituent components so that the structure and composition (content of constituent components) were as shown in the above chemical formula, and the amount of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was appropriately changed to adjust the molecular weight. In the same manner as in Synthesis Example A-1, a polymer A-13 having a weight average molecular weight of 1.2 × 10 measured by the above measurement method was synthesized. ４ Polymer A-13 (acrylic polymer) was synthesized.

[0284] Synthesis Example A-14: Synthesis of Polymer A-14 In Synthesis Example A-1, a compound was used that leads to each constituent component so that the structure and composition (content of constituent components) shown in the above chemical formula was obtained, and the amount of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was appropriately changed to adjust the molecular weight. In the same manner as in Synthesis Example A-1, a polymer A-14 was synthesized, and the weight average molecular weight measured by the above measurement method was 4.0 × 10.５ Polymer A-14 (acrylic polymer) was synthesized.

[0285] [Synthesis Example A-15: Synthesis of Polymer A-15] First, 14 g of KF-2012 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 6 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 dissolved in 100 g of butyl butyrate to prepare a monomer solution. Next, 300 g of butyl butyrate was added to a 1000 mL three-necked flask and stirred at 85 ° C. under a nitrogen stream. Next, the above monomer solution was added dropwise over 2 hours, and after completion of the dropwise addition, the temperature was raised to 90 ° C. and stirred for 2 hours. The obtained polymerization solution was poured into 800 g of methanol, stirred for 10 minutes, and then allowed to stand for 10 minutes. 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. Thus, the weight average molecular weight measured by the above measurement method was 1.1 × 10 ４ Polymer A-15 (a random copolymer acrylic polymer) was synthesized. The amount of polymerization initiator V-601 was changed to obtain a polymer A-15 having a weight average molecular weight of 1.4 × 10 ４ Polymer A-15 was synthesized.

[0286] Synthesis Example A-16: Synthesis of Polymer A-16 In Synthesis Example A-15, compounds were used to introduce the respective constituent components so that Polymer A-16 would have the composition (types and contents of constituent components) shown in the above chemical formula, and the amount of the polymerization initiator was adjusted so that the weight-average molecular weight would be as shown below. ４ The amount of the polymerization initiator V-601 was changed to obtain a polymer A-16 (a random copolymer acrylic polymer) having a weight average molecular weight of 1.5×10 ４ , 2.0 × 10 ４ or 1.0 x 10 ５ Polymer A-16 was synthesized.

[0287] Synthesis Example A-17: Synthesis of Polymer A-17 In Synthesis Example A-15, compounds were used to introduce the respective constituent components so that Polymer A-17 would have the composition (types and contents of constituent components) shown in the above chemical formula, and the amount of the polymerization initiator was adjusted so that the weight-average molecular weight would be as shown below. ３ Polymer A-17 (a random copolymer acrylic polymer) was obtained. The amount of polymerization initiator V-601 was changed to obtain a polymer A-17 having a weight average molecular weight of 1.0 × 10 ４ or 2.0 x 10 ４ Polymer A-17 was synthesized.

[0288] Synthesis Example A-18: Synthesis of Polymer A-18 In Synthesis Example A-15, compounds were used to introduce the respective constituent components so that Polymer A-18 would have the composition (types and contents of constituent components) shown in the above chemical formula, and the amount of the polymerization initiator was adjusted so that the weight-average molecular weight would be as shown below. The weight-average molecular weight was 1.38 × 10 measured by the above method in the same manner as in Synthesis Example A-15. ４ Polymer A-18 (a random copolymer acrylic polymer) was obtained. The amount of the polymerization initiator V-601 was changed to obtain a polymer A-18 having a weight average molecular weight of 7.0 × 10 ３ Polymer A-18 was synthesized.

[0289] Synthesis Example A-20: Synthesis of Polymer A-20 In Synthesis Example A-15, compounds were used to introduce the respective constituent components so that Polymer A-20 would have the composition (types and contents of constituent components) shown in the above chemical formula, and the amount of the polymerization initiator was adjusted so that the weight-average molecular weight would be as shown below. ４ The amount of the polymerization initiator V-601 was changed to obtain a polymer A-20 (a random copolymer acrylic polymer) having a weight average molecular weight of 1.0 × 10 ４ Polymer A-20 was synthesized.

[0290] Synthesis Example A-25: Synthesis of Polymer A-25 First, 80.6 g (89.4 mmol) of KF-2012 (trade name, molecular weight 4600, 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-necked 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 thereto 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 and heated at 30 hPa and 80°C for 1 hour to distill off the methanol. Thus, a polymer chain P consisting of a homopolymer of KF-2012 was obtained. １Ｘ and a polymer chain P consisting of a homopolymer of tBuAAm. １Ａ Polymer A-25 was obtained as a hyperbranched polymer having as polymeric arm moieties. The weight average molecular weight of polymer A-25 measured by the above method was 2.0 × 10 ４In addition, the amount of the polymerization initiator used in the polymerization of tBuAAm was changed, and the weight average molecular weight measured by the above measurement method was 1.8 × 10 ４ , 2.2 × 10 ４ Polymer A-25 was synthesized.

[0291] [Synthesis Example A-26: Synthesis of Polymer A-26] Polymer A-26, a hyperbranched polymer, was obtained in the same manner as in Synthesis Example A-25, except that compounds were used to induce each component so that Polymer A-26 would have the composition shown in the above chemical formula (type and content of each component of the constituent components and core portion), and the amount of polymerization initiator used during tBuAAm polymerization was adjusted so that the weight-average molecular weight would be as shown below. The weight-average molecular weight of Polymer A-26 measured by the above method was 2.0 × 10 ４ It was.

[0292] The polymer shown in the following chemical formula was synthesized as follows: In the following chemical formula, the numbers written to the lower right of each component indicate the content (% by mass).

[0293]

[0294] [Synthesis Example A-33: Synthesis of Polymer A-33 and Preparation of Polymer Dispersion A-33] Polymer A-33 was synthesized in accordance with the method described in JP 2015-088486 A. That is, to a 3 L three-neck flask equipped with a reflux condenser and a gas inlet cock, 7.2 g of a 40 mass % heptane solution of the following macromonomer MC-1, 12.4 g of methyl acrylate, 6.7 g of acrylic acid, 207 g of heptane (manufactured by Wako Pure Chemical Industries, Ltd.), and 1.4 g of azoisobutyronitrile were added, and nitrogen gas was introduced at a flow rate of 200 mL / min for 10 minutes, and then the temperature was raised to 100 ° C. To this was added dropwise a liquid prepared in a separate container (a mixture of 846 g of a 40% by mass heptane solution of macromonomer MC-1, 222.8 g of methyl acrylate, 75.0 g of acrylic acid, 300.0 g of heptane, and 2.1 g of azoisobutyronitrile) over a period of 4 hours. After completion of the addition, 0.5 g of azoisobutyronitrile was added. The mixture was then stirred at 100°C for 2 hours and cooled to room temperature. 1000 g of xylene was added, heated at 100°C, and 1.5 L of the solvent was distilled off, followed by cooling to room temperature. 1000 g of xylene was added again, heated at 100°C, and 1.0 L of the solvent was distilled off. The weight average molecular weight measured by the above measurement method was 1.9 x 10 ４ A xylene dispersion A-33 of polymer A-33 was obtained. The average particle size of polymer A-33 in this dispersion was 160 nm.

[0295] (Synthesis Example of Macromonomer MC-1) A self-condensate of 12-hydroxystearic acid (manufactured by Wako Pure Chemical Industries, Ltd.) (GPC polystyrene standard number average molecular weight: 2.0 × 10 ３ ) was reacted with glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain a macromonomer, which was then polymerized with methyl methacrylate and glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) in a molar ratio of 1:0.99:0.01, and the polymer was reacted with acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) to obtain macromonomer M-1. The number average molecular weight of this macromonomer MC-1 was 1.1 × 10 ４ It was.

[0296] Synthesis Example A-34: Synthesis of Polymer A-34 In Synthesis Example A-33, except that the amount of methyl acrylate was changed from 12.4 g to 12.6 g, the amount of methyl acrylate in the separate vessel was changed from 222.8 g to 256.2 g, the amount of acrylic acid was changed from 6.7 g to 6.8 g, and the amount of acrylic acid in the separate vessel was changed from 75.0 g to 47.0 g, the same procedure was carried out as in Synthesis Example A-33, and a weight average molecular weight of 3.2 × 10 measured by the above-mentioned measurement method was obtained. ４ A xylene dispersion A-34 of polymer A-34 was obtained. The average particle size of polymer A-34 in this dispersion was 180 nm.

[0297] [Synthesis Example A-35: Synthesis of Polymer A-35] Polymer A-35 was synthesized in accordance with the method described in JP 2015-088486 A. That is, to a 3 L three-neck flask equipped with a reflux condenser and a gas inlet cock, 1.5 g of a 40 mass % heptane solution of the following macromonomer MC-2, 12.6 g of methyl acrylate, 6.8 g of acrylic acid, 207 g of heptane (manufactured by Wako Pure Chemical Industries, Ltd.), and 1.4 g of azoisobutyronitrile were added, and nitrogen gas was introduced at a flow rate of 200 mL / min for 10 minutes, followed by heating to 100°C. A liquid prepared in a separate vessel (a mixture of 161.4 g of a 40% by mass heptane solution of macromonomer MC-2, 256.2 g of methyl acrylate, 47.0 g of acrylic acid, 300.0 g of heptane, and 2.1 g of azoisobutyronitrile) was added dropwise thereto over 4 hours. After completion of the dropwise addition, 0.5 g of azoisobutyronitrile was added. The mixture was then stirred at 100°C for 2 hours and cooled to room temperature. 1000 g of DIBK was added, heated at 110°C, the heptane was distilled off, and the mixture was cooled to room temperature. The weight average molecular weight measured by the above measurement method was 1.0 x 10 ４ Thus, a polymer solution A-35 of polymer A-35 was obtained.

[0298] (Synthesis Example of Macromonomer MC-2) A self-condensate of 12-hydroxystearic acid (manufactured by Wako Pure Chemical Industries, Ltd.) (GPC polystyrene standard number average molecular weight: 2.0 × 10 ３ ) was reacted with glycidyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) in a molar ratio of 1:1.01 to obtain macromonomer MC-2. The number average molecular weight of this macromonomer MC-2 was 2.1 × 10３ It was.

[0299] Synthesis Example A-36: Synthesis of Polymer A-36 Into a 200 mL three-neck flask, 4.46 g of polyethylene glycol (trade name: Polyethylene Glycol 200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.17 g of 2,2-bis(hydroxymethyl)butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 6.69 g of NISSO-PB GI-1000 (trade name, manufactured by Nippon Soda Co., Ltd.) were added and dissolved in 74 g of THF (tetrahydrofuran). To this solution, 7.32 g of dicyclohexylmethane-4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 60°C to achieve a uniform solution. To the resulting solution, 560 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60°C for 5 hours to obtain a 20% by mass THF solution of Polymer A-36. Next, 74 g of THF was added to the polymer solution obtained above, and 222 g of xylene was added to the resulting solution, followed by heating at 85°C for 120 minutes. 50 g of xylene was added to the resulting residue, followed by further heating at 85°C for 60 minutes. This procedure was repeated four times to remove THF. The weight average molecular weight measured by the above method was 4.5 x 10 ４ Thus, a polymer solution A-36 of polymer A-36 was obtained.

[0300] Synthesis Example A-37: Synthesis of Polymer A-37 Into a 200 mL three-neck flask, 4.46 g of polyethylene glycol (trade name: Polyethylene Glycol 200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.17 g of 2,2-bis(hydroxymethyl)butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 6.69 g of NISSO-PB GI-1000 (trade name, manufactured by Nippon Soda Co., Ltd.) were added and dissolved in 74 g of THF (tetrahydrofuran). To this solution, 6.98 g of diphenylmethane-4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 60°C to achieve a uniform solution. To the resulting solution, 560 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60°C for 5 hours to obtain a 20% by mass THF solution of Polymer A-37. Next, 74 g of THF was added to the polymer solution obtained above, and 222 g of butyl butyrate was added dropwise over 10 minutes while stirring at 150 rpm to obtain an emulsion of polymer A-37. This emulsion was heated at 85°C for 120 minutes while flowing nitrogen gas. 50 g of butyl butyrate was added to the obtained residue, and the mixture was further heated at 85°C for 60 minutes. This operation was repeated four times, and the THF was removed. The weight average molecular weight measured by the above method was 7.0 × 10 ４ Polymer A-37 was synthesized.

[0301] 2. Preparation of Polymer [SEBS] As a styrene-ethylene-butylene-styrene block copolymer, commercially available SEBS (trade name, weight average molecular weight 1.0 × 10 ５ , Sigma-Aldrich) was prepared.

[0302] 3. Synthesis of sulfide-based inorganic solid electrolyte (specific surface area 5.0 m ２Synthesis of Li-P-S-based glass LPS-1 with a solubility of 0.15g / g The 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 The ratio was 75:25. Next, 66 g of zirconia beads having a diameter of 2 mm was placed in a 45 mL zirconia container (manufactured by Fritsch), and the entire amount of the mixture of lithium sulfide and diphosphorus pentasulfide was placed in the container, which was then completely sealed under an argon atmosphere. The container was placed in a planetary ball mill P-7 (trade name, manufactured by Fritsch), and mechanical milling was carried out at a temperature of 25 ° C. and a rotation speed of 500 rpm for 20 hours to obtain a powder with a specific surface area of ​​5.0 m ２ / g Li-P-S based glass LPS-1 was obtained.

[0303] (specific surface area is 10m ２ Synthesis of Li-P-S-based glass LPS-2 with a specific surface area of ​​10 m / g was prepared in the same manner as in the synthesis of LPS-1, except that the rotation speed in mechanical milling was changed from 500 rpm to 750 rpm. ２ / g Li-P-S based glass LPS-2 was obtained.

[0304] (specific surface area is 1.5m ２Synthesis of Li-P-S-based glass LPS-3 with a specific surface area of ​​1.5 m / g was obtained in the same manner as in the synthesis of LPS-1, except that zirconia beads with a diameter of 5 mm were used instead of the zirconia beads with a diameter of 2 mm in the synthesis of LPS-1, and the rotation speed was changed from 500 rpm to 380 rpm during mechanical milling. ２ / g Li-P-S based glass LPS-3 was obtained.

[0305] (specific surface area is 3.0 m ２ Synthesis of Li-P-S-based glass LPS-4 with a specific surface area of ​​3.0 m / g was prepared in the same manner as in the synthesis of LPS-1, except that zirconia beads with a diameter of 5 mm were used instead of the zirconia beads with a diameter of 2 mm in the synthesis of LPS-1. ２ / g Li-P-S based glass LPS-4 was obtained.

[0306] 4. An active material (with a specific surface area of ​​30 m) was prepared as follows: ２ Preparation of negative electrode active material Si-1 (Aldrich, nonopowder) with a specific surface area of ​​30 m ２ / g of Si-1 was obtained.

[0307] (specific surface area is 25m ２ Preparation of negative electrode active material Si-2 (Aldrich, nonopowder) was classified using a classifier to obtain a negative electrode active material Si-2 having a specific surface area of ​​25 m ２ / g of Si-2 was obtained.

[0308] (specific surface area is 2.8m ２ Preparation of negative electrode active material Si-3 (APS 1-5 micron, manufactured by Thermo Scientific) ２ / g of Si-3 was obtained.

[0309] (specific surface area is 0.5m ２ Preparation of NCM-1, a positive electrode active material of 1000 μg / g) １／３ Co １／３ Mn １／３ O ２To the mixture were added 60 g of lithium niobium ethoxide (manufactured by Toshima Manufacturing Co., Ltd.), 200 mL of ethanol, and 25 mL of a 5% w / v ethanol solution of lithium niobium ethoxide (manufactured by Thermo Scientific). The ethanol was slowly removed using a rotary evaporator at a rotation speed of 5 rpm, a reduced pressure of 500 mmHg, and a water bath temperature of 60°C. The dried powder was heated in a gas replacement furnace at 450°C for 2 hours in an oxygen atmosphere. The powder was then classified using a classifier to obtain a powder with a specific surface area of ​​0.5 m. ２ / g of NCM-1 was obtained.

[0310] (specific surface area is 1.0 m ２ Preparation of NCM-2: In the preparation of NCM-1, the positive electrode active material was classified with a classifier to have a specific surface area of ​​1.0 m ２ / g of NCM-2 was obtained.

[0311] (specific surface area is 5.0 m ２ Preparation of a positive electrode active material NCM-3 having a specific surface area of ​​5.0 m / g: In the preparation of NCM-1, NMC was changed to that manufactured by Aldrich (<0.5 μm), and the material was classified using a classifier in the same manner as in the preparation of NCM-1. ２ / g of NCM-3 was obtained.

[0312] (specific surface area is 1.5m ２ Preparation of positive electrode active material LMO-1 (LiMn ２ O ４ (manufactured by Toshima Manufacturing Co., Ltd.) was classified using a classifier to determine the specific surface area of ​​1.5 m ２ / g of LMO-1 was obtained.

[0313] <Adsorption rate A ＡＣ and adsorption rate A ＳＥ Measurement of adsorption rate A for each prepared polymer with respect to the active material AC used in the preparation of the composition for an all-solid-state secondary battery described later ＡＣ , and the adsorption rate A for the inorganic solid electrolyte SE ＳＥ was measured as follows. ＡＣ Measurement of adsorption rate A of polymer to active material AC ＡＣThe mass of the polymer and active material AC used in the preparation of the compositions for all-solid-state secondary batteries in each Example and Comparative Example was measured as follows: the mass of the polymer and active material AC used in the preparation of each composition for all-solid-state secondary batteries, and the mass of the dispersion medium D so that the solid content was 53 mass % were added to a 30 mL cylindrical container, and the mixture was stirred with a mix roller at 40 rpm for 1 hour. Thereafter, the stirred dispersion was filtered using a membrane filter with a 0.2 μm pore size, and the entire filtrate was dried to solid, and the mass of the polymer remaining in the filtrate (the mass of the polymer not adsorbed to the active material) W Ａ The mass W Ａ and the mass W of the polymer used in the measurement Ｂ The adsorption rate of the polymer to the active material AC was calculated from the following formula: The adsorption rate A of the polymer A to the active material AC in each Example and Comparative Example was calculated by averaging the adsorption rates obtained by performing the above measurement twice. ＡＣ The results are shown in Tables 1 to 3. Adsorption rate (%) = [(W Ｂ -W Ａ ) / W Ｂ ] × 100 As mentioned above, the adsorption rate A ＡＣ In the measurement of the adsorption rate A of Examples 1-9, the inorganic solid electrolyte SE was not present. ＡＣ In the measurement, the weight average molecular weight of the polymer was 2.0 × 10 ４ The adsorption rate A of Comparative Example 1-3 was calculated using a mixture of polymer A-25 and the commercially available SEBS (mass ratio [A-25:SEBS] = 50:50). ＡＣ In the measurement, a mixture of polymers A-8 and A-10 (mass ratio [A-8:A-10]=50:50) was used as the polymer.

[0314] (Adsorption rate A ＳＥ Measurement of the adsorption ...

Claims

1. A composition for an all-solid-state secondary battery, comprising an inorganic solid electrolyte SE having ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, an active material AC, a dispersion medium D, and a polymer A dissolved in the dispersion medium D, wherein Aa calculated by the following formula 1 satisfies 1≦Aa≦100. Formula 1: Aa=(adsorption rate of polymer A to active material AC) ２ × [(content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​active material AC) ３／２ ]×10 １０ In the above formula 1, the total specific surface area of ​​the active material AC is a value calculated from the specific surface area of ​​the active material AC×the content of the active material AC / the total solid content.

2. The composition for an all-solid-state secondary battery according to claim 1, wherein Aa calculated by the formula 1 satisfies 2≦Aa≦30.

3. The composition for an all-solid-state secondary battery according to claim 1, wherein Ab calculated by the following formula 2 satisfies 2≦Ab≦500. Formula 2: Ab=(adsorption rate of polymer A to inorganic solid electrolyte SE) ２ × [((content of polymer A) / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​inorganic solid electrolyte SE) ３／２ ]×10 １０ In the above formula 2, the total specific surface area of ​​the inorganic solid electrolyte SE is a value calculated from the specific surface area of ​​the inorganic solid electrolyte SE×the content of the inorganic solid electrolyte SE / the total solid content.

4. The composition for an all-solid-state secondary battery according to claim 3, wherein Ab calculated by the formula 2 satisfies 2≦Ab≦300.

5. The composition for an all-solid-state secondary battery according to claim 3, wherein Ac calculated by the following formula 3 satisfies 3≦Ac≦100. Formula 3: Ac=[Aa×(content of active material AC / total solid content)]+[Ab×(content of inorganic solid electrolyte SE / total solid content)] 6. The weight average molecular weight of the polymer A is 2.0×10 ４ The composition for an all-solid-state secondary battery according to claim 1 , wherein:

7. The composition for an all-solid-state secondary battery according to claim 1, wherein the active material AC contains Si, and Aa calculated by the formula 1 satisfies 2≦Aa≦15.

8. A composition for an all-solid-state secondary battery, comprising an inorganic solid electrolyte SE having ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a dispersion medium D, and a polymer A soluble in the dispersion medium D, wherein Ab calculated by the following formula 2 satisfies 2≦Ab≦500. Formula 2: Ab=(adsorption rate of polymer A to inorganic solid electrolyte SE) ２ × [((content of polymer A) / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​inorganic solid electrolyte SE) ３／２ ]×10 １０ In the above formula 2, the total specific surface area of ​​the inorganic solid electrolyte SE is a value calculated from the specific surface area of ​​the inorganic solid electrolyte SE×the content of the inorganic solid electrolyte SE / the total solid content.

9. The composition for an all-solid-state secondary battery according to claim 8, wherein Ab calculated by the formula 2 satisfies 2≦Ab≦300.

10. The composition for an all-solid-state secondary battery according to claim 8, which contains an active material AC and has Aa calculated by the following formula 1 satisfying 1≦Aa≦100. Formula 1: Aa=(adsorption rate of polymer A to active material AC) ２ × [(content of polymer A / total solid content) / molecular weight of polymer A) / (total specific surface area of ​​active material AC) ３／２ ]×10 １０ In the above formula 1, the total specific surface area of ​​the active material AC is a value calculated from the specific surface area of ​​the active material AC×the content of the active material AC / the total solid content.

11. The composition for an all-solid-state secondary battery according to claim 10, wherein Aa calculated by the formula 1 satisfies 2≦Aa≦30.

12. The composition for an all-solid-state secondary battery according to claim 10, wherein Ac calculated by the following formula 3 satisfies 3≦Ac≦100. Formula 3: Ac=[Aa×(content of active material AC / total solid content)]+[Ab×(content of inorganic solid electrolyte SE / total solid content)] 13. The weight average molecular weight of the polymer A is 2.0×10 ４ The composition for an all-solid-state secondary battery according to claim 8, wherein:

14. The composition for an all-solid-state secondary battery according to claim 10, wherein the active material AC contains Si, and Aa calculated by the formula 1 satisfies 2≦Aa≦15.

15. A sheet for an all-solid-state secondary battery, comprising a layer formed using the composition for an all-solid-state secondary battery according to any one of claims 1 to 14.

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, 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 all-solid-state secondary battery composition according to any one of claims 1 to 14.

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