All-solid-state battery binder using conjugated diene polymer, positive electrode layer, negative electrode layer, and electrolyte layer using the binder, and all-solid-state battery including these

Abstract

This all solid state battery binder contains a conjugated diene-based polymer that includes a polymer block having a vinyl aromatic monomer unit as a main component, and that has a weight average molecular weight of 40,000-2,000,000.

Description

[Technical Field]

[0001] The present invention relates to an all-solid-state battery binder using a conjugated diene polymer, a positive electrode layer, a negative electrode layer, an electrolyte layer using the binder, and an all-solid-state battery including these. [Background technology]

[0002] Lithium-ion secondary batteries are characterized by their light weight, high energy content, and long life, and are widely used as power sources for portable electronic devices such as notebook computers, mobile phones, digital cameras, video cameras, etc. Furthermore, with the transition to a society with a low environmental impact, they are attracting attention as power sources for hybrid electric vehicles (HEVs) and plug-in hybrid electric vehicles (PHEVs), as well as in the field of power storage, such as residential energy storage systems.

[0003] Conventionally, an organic electrolyte solution in which a lithium salt is dissolved in an organic solvent has been used as the electrolyte for lithium ion secondary batteries, and there have been safety concerns associated with leakage.

[0004] All-solid-state batteries, which use a solid electrolyte instead of a liquid electrolyte and have solid cathode, electrolyte, and anode materials, are proposed as a technology that eliminates the need for flammable electrolytes and dramatically improves safety.

[0005] As a solid electrolyte for use in an all-solid-state battery, for example, a technology using a sulfide-based material due to its high lithium ion conductivity has been disclosed.

[0006] However, sulfide-based materials have poor chemical stability, and when exposed to air, their reaction with moisture generates hydrogen sulfide, impairing electrolyte performance. Therefore, when using these electrolytes, it is desirable to eliminate moisture as much as possible from the battery manufacturing process. Conventional lithium-ion batteries use polyvinylidene fluoride (PVDF) as a binder, which is dissolved in the polar solvent N-methylpyrrolidone (NMP), mixed with electrode components such as electrode active materials and conductive additives, and then applied to a current collector to form electrodes. However, due to its hydrophilic nature, NMP is not suitable for use in the manufacture of all-solid-state batteries using sulfide-based solid electrolytes. Therefore, an electrode manufacturing process using a nonpolar solvent with low hydrophilicity is desirable, but PVDF is insoluble in nonpolar solvents, so the development of a new binder that dissolves in nonpolar solvents is needed. Patent Document 1 proposes a binder that is soluble in nonpolar solvents.

[0007] Since conjugated diene polymers dissolve in non-polar solvents, Patent Document 2 proposes an all-solid-state battery using a butadiene-based rubber binder as the all-solid-state battery binder. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2018-125260 A [Patent Document 2] Special Publication No. 2019-525427 Summary of the Invention [Problem to be solved by the invention]

[0009] The conjugated diene polymers of the prior art are excellent in terms of removing moisture from the production process because they enable the use of non-polar solvents, but are still insufficient in terms of binder performance, such as the strength to bind the constituent components of the electrode active material layer together or the solid electrolyte, and the strength to adhere the electrode active material layer to the current collector.

[0010] Therefore, the present invention has been made in consideration of the above problems, and an object of the present invention is to provide an all-solid-state battery binder that has excellent solubility in non-polar solvents and also has excellent binder performance, and a positive electrode layer, a solid electrolyte layer, an anode layer, and an all-solid-state battery that use the same. [Means for solving the problem]

[0011] As a result of intensive investigations to solve the above-mentioned problems of the conventional art, the present inventors have found that the above-mentioned problems can be solved by a conjugated diene-based polymer having a modifying group and a specific polymer structure, and have thereby completed the present invention.

[0012] That is, the present invention is as follows. [1] The polymer contains a conjugated diene polymer having a polymer block mainly composed of vinyl aromatic monomer units and a weight average molecular weight of 40,000 to 2,000,000. Solid-state battery binder. [2] the conjugated diene-based polymer has a modifying group, and the modifying group is at least one selected from the group consisting of an acid anhydride group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group, an amide group, a urethane group, a urea group, an isocyanate group, and an ionic group; The all-solid-state battery binder according to [1]. [3] The weight average molecular weight of the conjugated diene polymer is 200,000 to 800,000. [1] The all-solid-state battery binder according to [2]. [4] the content of the polymer block is 40% by weight or less based on the total amount of the conjugated diene-based polymer; [1] The all-solid-state battery binder according to any one of [1] to [3]. [5] the amount of vinyl bonds in the conjugated diene monomer units before hydrogenation is 20 mol % to 60 mol % relative to 100 mol % in total of the conjugated diene monomer units; [4] The binder for an all-solid-state battery according to any one of [1] to [4]. [6] The conjugated diene polymer has a toluene-insoluble content of 10 wt% or less. [1] The all-solid-state battery binder according to any one of [1] to [5]. [7] the modifying group is present in an amount of 0.10 mmol or more and 0.50 mmol or less in 100 g of the conjugated diene polymer; [6] The all-solid-state battery binder according to any one of [2] to [6]. [8] the modifying group is a primary amino group or a secondary amino group; [2] to [7], the all-solid-state battery binder according to any one of [2] to [7]. [9] an end or a coupling portion of the conjugated diene polymer has the modifying group; [2] to [8]. The all-solid-state battery binder according to any one of [2] to [8].

[10] having a polymer block mainly composed of the conjugated diene monomer unit, [1] The all-solid-state battery binder according to any one of [1] to [9].

[11] The conjugated diene polymer is hydrogenated.

[10] The all-solid-state battery binder according to any one of [1] to

[10] .

[12] the butylene amount and / or propylene amount of the conjugated diene monomer units is 20 mol % to 60 mol % relative to 100 mol % in total of the conjugated diene monomer units; the conjugated diene polymer has a polymer block mainly composed of a conjugated diene monomer unit;

[11] The all-solid-state battery binder according to any one of [1] to

[11] .

[13] The conjugated diene polymer has a loose bulk density of 0.15 g / cm 3 or more, the compression degree is less than 30, and the powder or crumb shape is [1] The all-solid-state battery binder according to any one of [1] to

[12] .

[14] the total content of the transition metal element and Al, Li, Fe, Zn, and Mg in the conjugated diene polymer is 200 ppm or less in terms of atoms relative to the conjugated diene polymer;

[14] The all-solid-state battery binder according to any one of [1] to

[13] .

[15] The conjugated diene polymer and a phosphorus compound are contained, and the phosphorus atom content is 10 ppm or more relative to the conjugated diene polymer.

[14] The all-solid-state battery binder according to any one of [1] to

[14] .

[16] The polymer is selected from the group consisting of silica, higher fatty acid metal salts, polyolefins, and fatty acid amides.

[16] The all-solid-state battery binder according to any one of [1] to

[15] .

[17] The conjugated diene polymer has isoprene as a conjugated diene polymer unit.

[16] The binder for an all-solid-state battery according to any one of [1] to

[16] .

[18] The moisture content is 200 ppm or less.

[17] The all-solid-state battery binder according to any one of [1] to

[17] .

[19] A slurry containing the all-solid-state battery binder according to any one of [1] to

[18] , having a water content of 200 ppm or less.

[20] [1] to

[18] , and the all-solid-state battery binder according to any one of [1] to

[18] . a positive electrode active material, A positive electrode layer having a moisture content of 200 ppm or less. 〔twenty one〕 [1] to

[18] , and the all-solid-state battery binder according to any one of [1] to

[18] . an ion-conducting solid electrolyte; A solid electrolyte layer with a moisture content of 200 ppm or less. 〔twenty two〕 [1] to

[18] , and the all-solid-state battery binder according to any one of [1] to

[18] . a negative electrode active material, A negative electrode layer having a moisture content of 200 ppm or less. 〔twenty three〕

[20] The cathode layer according to

[21] , the solid electrolyte layer according to

[21] , and the anode layer according to

[22] are included. All-solid-state battery. 〔twenty four〕 The moisture content is 200 ppm or less.

[23] The all-solid-state battery according to

[23] . 〔twenty five〕 a step of preparing a slurry containing a conjugated diene polymer having a conjugated diene monomer unit, a polymer block mainly composed of a vinyl aromatic monomer unit, and a modifying group, the conjugated diene polymer having a water content of 1 wt % or less, and a solvent; and applying the slurry to a substrate and drying the slurry. A method for manufacturing at least one layer of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer, the layer including an all-solid-state battery binder having a moisture content of 200 ppm or less. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide an all-solid-state battery binder that has excellent solubility in non-polar solvents and excellent binder performance, and a positive electrode layer, a solid electrolyte layer, an anode layer, and an all-solid-state battery that use the same. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an all-solid-state battery according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0016] In this specification, the term "polymer" includes both a polymer made of a single type of monomer unit and a copolymer having multiple types of monomer units.

[0017] [All-solid-state battery binder] (Conjugated diene polymer) The all-solid-state battery binder of this embodiment has a polymer block mainly composed of vinyl aromatic monomer units, and contains a conjugated diene polymer having a weight-average molecular weight of 40,000 to 2,000,000.

[0018] In this embodiment, the conjugated diene polymer preferably has a modifying group. The "modifying group" refers to a group capable of binding to the constituent components of the electrode active material layer or the solid electrolyte and / or a group capable of adhering to the current collector, and refers to a functional group containing an element other than carbon and hydrogen. The structure of the "modifying group" can be confirmed by analyzing the conjugated diene polymer and, if necessary, the expected modifier, using various analytical chemistry techniques such as NMR, spectroscopic analysis, electroanalysis, separation analysis, mass spectrometry, and titration. A method for identifying the modifying group generally includes a combination of NMR, IR, GC-MS, etc. For example, maleic anhydride and succinic anhydride, which are acid anhydrides, have a peak at 1750 cm in IR. -1 Since the conjugated diene polymer has an absorption peak near , it can be identified by analyzing the conjugated diene polymer. Furthermore, by analyzing the conjugated diene polymer by chromatography using a column that is adsorbent for the modifying group, it is possible to identify modifying groups such as amine-modified groups. For other functional groups, by analyzing the conjugated diene polymer by NMR, it is possible to identify the modifying group based on the chemical shift specific to the functional group. Furthermore, it is also possible to identify the modifying group or modifying agent by selecting candidates for the modifying group or modifying agent from various analyses and literature, and then identifying the modifying group or modifying agent based on the match between the chemical shifts of the candidate modifying group and the chemical shifts of the modified group in the conjugated diene polymer.

[0019] (conjugated diene monomer units) The conjugated diene monomer constituting the conjugated diene polymer is a diolefin having a pair of conjugated double bonds. Examples of such diolefins include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-cyclopentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, and farnesene. Among these, 1,3-butadiene and isoprene are preferred from the viewpoints of availability and productivity, and 1,3-butadiene is more preferred from the viewpoint of thermal stability. The conjugated diene polymer may be composed of one type of conjugated diene monomer unit, or two or more types of conjugated diene monomer units.

[0020] The conjugated diene polymer may contain a polymer block mainly composed of conjugated diene monomer units. When the conjugated diene polymer contains a polymer block mainly composed of conjugated diene monomer units, the content of the conjugated diene monomer units contained in this polymer block is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, from the viewpoint of increasing entanglement of polymer chains in the block, in order to improve the binding between components of the all-solid-state battery binder, such as the electrode active material, conductive additive, and solid electrolyte of the electrode active material layer and electrolyte layer, and the adhesiveness (also referred to as adhesion) to the current collector. Here, the term "polymer block mainly composed of conjugated diene monomer units" refers to a polymer block in which the content of the conjugated diene monomer units exceeds 70% by mass of the entire polymer block.

[0021] The upper limit of the content of the conjugated diene monomer units contained in the polymer block is not particularly limited, and may be 100% by mass or less, or 99% by mass or less, based on the total amount of conjugated diene monomer units contained in the conjugated diene-based polymer.

[0022] In this embodiment, the binder performance refers to the binding ability of the all-solid-state battery binder to bind together components such as the electrode active material, conductive additive, and solid electrolyte of the electrode active material layer and electrolyte layer, as well as the adhesiveness to the current collector.

[0023] The conjugated diene polymer may be hydrogenated. In the conjugated diene polymer of this embodiment, from the viewpoint of the solubility of the conjugated diene polymer in solvents with low hydrophilicity, such as non-polar solvents, and the binding and adhesive properties of an all-solid-state battery binder containing the conjugated diene polymer, the vinyl bond content of the conjugated diene monomer units before hydrogenation is preferably 20 mol% or more, more preferably 25 mol% or more, even more preferably 30 mol% or more, and still more preferably 35 mol% or more, relative to 100 mol% of the total of the conjugated diene monomer units. In particular, when hydrogenated, if the vinyl bond content is too low, the conjugated diene polymer may crystallize, resulting in a significant decrease in solubility in non-polar solvents.

[0024] The upper limit of the vinyl bond content of the conjugated diene monomer units before hydrogenation may be 100 mol% or less, or 99 mol% or less, preferably 80 mol% or less, and more preferably 70 mol% or less, relative to 100 mol% in total of the conjugated diene monomer units, and from the viewpoint of rubber elasticity, is preferably 60 mol% or less, 50 mol% or less, or 40 mol% or less.

[0025] Furthermore, even when the conjugated diene polymer contains a polymer block mainly composed of conjugated diene monomer units, the preferred range of the vinyl bond content before hydrogenation is the same as above.

[0026] "Amount of vinyl bonds before hydrogenation" refers to the amount (molar ratio) of 1,2-bonds relative to the total amount of 1,4-bonds (cis and trans) and 1,2-bonds resulting from conjugated diene monomer units in a conjugated diene polymer before hydrogenation. However, when the conjugated diene monomer units are incorporated into the polymer via 3,4-bonds, this refers to the total amount (molar ratio) of 1,2-bonds and 3,4-bonds relative to the total amount of 1,4-bonds, 1,2-bonds, and 3,4-bonds. That is, although the term "before hydrogenation" is used for the definition, this is because hydrogenation results in a state that cannot be called a "vinyl bond." However, since it is possible to distinguish between 1,4-bonds, 1,2-bonds, and 3,4-bonds even after hydrogenation, this is an indicator that can be similarly quantified for a polymer after hydrogenation.

[0027] The butylene and / or propylene content of the conjugated diene polymer is preferably 20 mol% or more, more preferably 25 mol% or more, even more preferably 30 mol% or more, and even more preferably 35 mol% or more. The upper limit of the butylene and / or propylene content of the conjugated diene polymer may be 100 mol% or less, or may be 99 mol% or less, preferably 80 mol% or less, even more preferably 70 mol% or less, and from the viewpoint of rubber elasticity, is preferably 60 mol% or less, 50 mol% or less, or 40 mol% or less. By having the butylene and / or propylene content within the above ranges, solubility in nonpolar solvents and binder performance tend to be further improved.

[0028] Here, "amount of butylene and / or propylene" refers to the amount (molar ratio) of 1,2-bonds relative to the total amount of 1,4-bonds (cis and trans) and 1,2-bonds resulting from conjugated diene monomer units in the conjugated diene polymer after hydrogenation. However, when the conjugated diene monomer units are incorporated into the polymer via 3,4-bonds, the amount refers to the total amount (molar ratio) of 1,2-bonds and 3,4-bonds relative to the total amount of 1,4-bonds, 1,2-bonds, and 3,4-bonds. The amount of butylene and / or propylene can be controlled by the amount of vinyl bonds before hydrogenation and the hydrogenation rate.

[0029] The vinyl bond amount and butylene amount and / or propylene amount of the conjugated diene polymer before hydrogenation can be measured using a nuclear magnetic resonance (NMR) spectrometer or the like, and specifically, can be measured by the method described in the examples below.

[0030] The conjugated diene polymer after hydrogenation was used as a sample for proton nuclear magnetic resonance ( 1 The vinyl bond amount before hydrogenation can also be measured by H-NMR. This method will be specifically described using a conjugated diene polymer in which the vinyl aromatic monomer unit is styrene and the conjugated diene monomer unit is 1,3-butadiene as an example.

[0031] The measurement is performed under the following conditions using an ECS400 (product name manufactured by JEOL) as the measuring device, deuterated chloroform as the solvent, and a sample concentration of 50 mg / mL. (Measurement conditions) Observation frequency: 400MHz Chemical shift reference: chloroform (7.26 ppm) Pulse delay: 3 seconds Number of scans: 256 Pulse width: 45° Measurement temperature: 26℃

[0032] The amount of vinyl bonds before hydrogenation can be determined using the area value of signals in the chemical shift range of 10.0 ppm to 0.0 ppm in the obtained NMR spectrum. More specifically, it can be determined by the following formulas (1) to (6). (area value per proton of styrene monomer unit) =(X2-X1) / 5 (1) (Area value per proton of unhydrogenated 1,2-bonded butadiene monomer unit) =X3 / 2 (2) (Area value per proton of unhydrogenated 1,4-bonded butadiene monomer unit) =(X4-(X3 / 2)) / 2 (3) (area value per proton of hydrogenated 1,2-bonded butadiene monomer unit) =X5 / 3 (4) (area value per proton of hydrogenated 1,4-bonded butadiene monomer unit) =(X6-(1)×3-(2)×3-(3)×4-(4)×8-X7) / 8 (5) (Amount of vinyl bonds before hydrogenation (mol%)) =((2)+(4)) / ((2)+(3)+(4)+(5))×100 (6)

[0033] In the above formulas (1) to (5), the symbols X1, X2, X3, X4, X5, X6, and X7 are defined as follows: X1: The area value of the range surrounded by the line connecting the positions of the smallest signal intensity in the 7.26 ppm to 7.25 ppm section and the 7.27 ppm to 7.26 ppm section, with 7.26 ppm as the center, and the NMR spectrum. X2: Area value of the range enclosed by the line connecting the signal positions of 8.0 ppm and 6.0 ppm and the NMR spectrum X3: The area value between the chemical shift of the position with the smallest signal intensity between 5.2 ppm and 4.9 ppm and 4.0 ppm, among the area values ​​enclosed by the line connecting the signal positions of 6.0 ppm and 4.0 ppm and the NMR spectrum. X4: The area value between the chemical shift of the position with the smallest signal intensity between 5.2 ppm and 4.9 ppm and 6.0 ppm, among the area values ​​enclosed by the line connecting the signal positions of 6.0 ppm and 4.0 ppm and the NMR spectrum. X5: The area enclosed by the line connecting the signal positions of 4.0 ppm and 0.3 ppm and the NMR spectrum, the area within a range of 0.3 ppm from the chemical shift of the position with the smallest signal intensity among the valleys of the NMR spectrum between 1.05 ppm and 0.85 ppm (however, if there is no valley between 1.05 ppm and 0.85 ppm, the area within a range of 0.3 ppm from the chemical shift of the position with the smallest signal intensity among the valleys of the NMR spectrum between 1.05 ppm and 0.85 ppm is used). X6: The area enclosed by the line connecting the signal positions at 4.0 ppm and 0.3 ppm and the NMR spectrum X7: The area value of the range surrounded by the line connecting the positions of the smallest signal intensity in each of the sections from 1.49 ppm to 1.50 ppm and from 1.50 ppm to 1.51 ppm, with 1.50 ppm as the center, and the NMR spectrum (however, if the line connecting the positions of the smallest signal intensity is above the NMR spectrum, it is set to 0).

[0034] Furthermore, (1) to (5) in the formulas (5) and (6) are values ​​obtained from the above formulas (1) to (5), respectively.

[0035] The vinyl bond amount, butylene amount, and / or propylene amount can be controlled within the above-mentioned ranges by adding a Lewis base, such as an ether or an amine compound, as a vinyl bond amount adjuster (hereinafter referred to as a vinylating agent) during production of the conjugated diene polymer, or by controlling the temperature during production. Generally, the vinyl bond amount tends to increase by increasing the amount of the vinyl bond amount adjuster or lowering the temperature during production.

[0036] (vinyl aromatic monomer unit) In the conjugated diene polymer of this embodiment, from the viewpoints of the solubility of the conjugated diene polymer in hydrocarbon solvents and the binding and adhesive properties of an all-solid-state battery binder containing the conjugated diene polymer, the content of the vinyl aromatic monomer unit is preferably 80% by mass or less relative to the total amount of the conjugated diene polymer. From the same viewpoint, and from the viewpoint of further improving flexibility, the content is more preferably 5% by mass or more and 60% by mass or less. From the viewpoint of further improving the low-temperature cracking resistance of each layer containing the binder, the content is even more preferably 10% by mass or more, more preferably 12% by mass or more. From the viewpoint of suppressing deterioration of battery performance due to gaps caused by shrinkage of the solid electrolyte or electrode active material caused by repeated charge and discharge, the content is preferably 15% by mass or more, and more preferably 20% by mass or more. The upper limit is more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less.

[0037] The content of vinyl aromatic monomer units in conjugated diene polymers can be measured by ultraviolet spectrophotometry or proton nuclear magnetic resonance ( 1 It can be measured by H-NMR. Specifically, it can be measured by the method described in the Examples.

[0038] In the conjugated diene polymer of this embodiment, from the viewpoints of the solubility of the conjugated diene polymer in nonpolar solvents and the binding properties, adhesiveness, and heat resistance of the all-solid-state battery binder containing the conjugated diene polymer, the content of the polymer block mainly composed of vinyl aromatic monomer units is preferably 40% by mass or less relative to the total amount of the conjugated diene polymer. From the same viewpoint, and from the viewpoint of further improving flexibility, the content is more preferably 5% by mass or more and 35% by mass or less. From the viewpoint of further improving the low-temperature cracking resistance of each layer containing the binder, the content is even more preferably 10% by mass or more and 33% by mass or less. From the viewpoint of suppressing deterioration of battery performance due to gaps caused by shrinkage of the solid electrolyte or electrode active material caused by repeated charge and discharge, the content is preferably 15% by mass or more, more preferably 20% by mass or more.

[0039] Furthermore, from the viewpoint of heat resistance and strength, the polymer block mainly composed of vinyl aromatic monomer units is preferably present in the main chain of the conjugated diene polymer, and is preferably present in the first or second block counting from the end of the polymer chain.

[0040] The content of polymer blocks mainly composed of vinyl aromatic monomer units in a conjugated diene polymer can be calculated using the mass of polymer blocks mainly composed of vinyl aromatic monomer units (excluding vinyl aromatic monomer units having an average degree of polymerization of about 30 or less) determined by a method in which a copolymer before hydrogenation is oxidatively decomposed with t-butyl hydroperoxide using osmium tetroxide as a catalyst (the method described in I. M. Kolthoff, et al., Polym. Sci. 1, 429 (1946)) (hereinafter also referred to as the "osmium tetroxide decomposition method").

[0041] The content of polymer blocks mainly composed of vinyl aromatic monomer units in the conjugated diene polymer after hydrogenation can be measured by nuclear magnetic resonance (NMR) using the conjugated diene polymer after hydrogenation (hydrogenated copolymer (b)) according to the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981) (hereinafter also referred to as the "NMR method").

[0042] The NMR method will be specifically explained using an example in which the vinyl aromatic monomer unit is styrene and the conjugated diene monomer unit is 1,3-butadiene. 30 mg of the hydrogenated conjugated diene polymer is dissolved in 1 g of deuterated chloroform, and the content (Ns value) of the polymer block (in this case, the polystyrene block) mainly composed of vinyl aromatic monomer units is measured by H-NMR using the sample. The Ns value is calculated from the ratio of the integrated value of the chemical shift from 6.9 ppm to 6.3 ppm to the total integrated value. Block styrene strength (b-St strength) = (integrated value of 6.9 ppm to 6.3 ppm) / 2 Random styrene strength (r-St strength) = (integrated value of 7.5 ppm to 6.9 ppm) - 3 × (b-St) Ethylene-butylene strength (EB strength) = Total integrated value - 3 × {(b-St intensity) + (r-St intensity)} / 8 Polystyrene block content (Ns value) obtained by NMR method =104×(b-St strength) / [104×{(b-St strength)+(r-St strength)}+56×(EB strength)]

[0043] Here, there is a correlation represented by the following formula between the content of polymer blocks mainly composed of vinyl aromatic monomer units in a conjugated diene polymer before hydrogenation measured by the osmium tetroxide decomposition method (referred to as the "Os value") and the content of polymer blocks mainly composed of vinyl aromatic monomer units in a conjugated diene polymer after hydrogenation measured by the NMR method (referred to as the "Ns value"). Specifically, it can be measured by the method described in the examples. Os value = -0.012 (Ns value)² + 1.8 (Ns value) -13.0

[0044] A "polymer block mainly composed of vinyl aromatic monomer units" refers to a polymer block in which the content of the vinyl aromatic monomer units exceeds 70% by mass relative to the entire polymer block. From the viewpoint of the binding and adhesive properties of an all-solid-state battery binder containing a conjugated diene polymer, the content of the vinyl aromatic monomer units in the polymer block mainly composed of vinyl aromatic monomer units is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. Within the above range, the polymer block mainly composed of vinyl aromatic monomer units has high cohesion and serves as a physical crosslinking point. The upper limit of the content of the vinyl aromatic monomer units in the polymer block mainly composed of vinyl aromatic monomer units is not particularly limited, but may be 100% by mass or less, or 99% by mass or less.

[0045] The vinyl aromatic monomer is not particularly limited, and examples thereof include vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Among these, from the viewpoints of availability and productivity, styrene, α-methylstyrene, and p-methylstyrene are preferred, and styrene is more preferred. The polymer block mainly composed of a vinyl aromatic compound may be composed of one type of vinyl aromatic monomer, or two or more types.

[0046] (modifying group) When the conjugated diene polymer has a modifying group, it is preferably a group capable of binding to the components of the electrode active material layer or the solid electrolyte and / or a group capable of adhering to the current collector. Examples of such modifying groups include, but are not limited to, acid anhydride groups, hydroxyl groups, carbonyl groups, thiocarbonyl groups, acid halide groups, carboxyl groups, thiocarboxylic acid groups, aldehyde groups, thioaldehyde groups, carboxylic acid ester groups, amide groups, imide groups, sulfonate ester groups, phosphate ester groups, amino groups, imino groups, cyano groups, urethane groups, urea groups, pyridyl groups, quinoline groups, epoxy groups, thioepoxy groups, sulfide groups, isocyanate groups, isothiocyanate groups, silicon halide groups, silanol groups, alkoxysilane groups, tin halide groups, alkoxytin groups, phenyltin groups, and ionic groups. The conjugated diene polymer may have one or more of the above modifying groups alone or in combination. Examples of the ionic group include a sulfonic acid group, a sulfonimide group, a sulfate group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and an ammonium group or a salt thereof.

[0047] Among these, in the case of a battery using a sulfide-based solid electrolyte or an oxide-based solid electrolyte, from the viewpoint of further improving the binding strength between the components of the electrode active material layer or between the solid electrolyte or the adhesion to the current collector, the modifying group of the conjugated diene polymer is preferably one or more selected from the group consisting of an acid anhydride group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group, an amide group, a urethane group, a urea group, an isocyanate group, and an ionic group.

[0048] Furthermore, among these, from the viewpoints of availability and suppression of hydrogen sulfide generation due to reaction with sulfide-based solid electrolytes, acid anhydride groups, carboxyl groups, amino groups, epoxy groups, alkoxysilane groups, and hydroxyl groups are more preferred as modifying groups. Furthermore, from the viewpoints of suppression of alcohol generation, acid anhydride groups, carboxyl groups, amino groups, epoxy groups, and hydroxyl groups are even more preferred as modifying groups. Furthermore, from the viewpoints of productivity (ease of adjusting the modification rate and safety), amino groups, hydroxyl groups, carboxyl groups, and acid anhydride groups are more preferred as modifying groups. Furthermore, from the viewpoints of bond formation by chemical reaction with functional groups on the surface of a current collector or a battery component, and hydrogen bonding properties acting as a donor and acceptor, amino groups, hydroxyl groups, and carboxyl groups are preferred as modifying groups. In particular, from the viewpoints of hydrogen bonding and bond formation with materials having carboxyl groups as surface functional groups, such as conductive additives, amino groups are preferred as modifying groups. Among amino groups, primary amino groups or secondary amino groups are preferred from the viewpoint of bond formation by chemical reaction and hydrogen bonding properties acting as donors and acceptors to functional groups on the surface of the current collector or the surface of the battery components.

[0049] When a conjugated diene polymer has a functional group that does not correspond to a binding group for the constituent components of the electrode active material layer or the solid electrolyte or an adhesive group for the current collector, the adhesiveness of the conjugated diene polymer to the constituent components of the electrode active material layer, the solid electrolyte, or the current collector can be further improved by reacting the functional group of the conjugated diene polymer with another compound that can interact with the functional group and with any of the constituent components of the electrode active material layer, the solid electrolyte, or the current collector. That is, the functional group of the conjugated diene polymer interacts with the other compound through intermolecular forces or chemical bonds, and the other compound interacting with the functional group interacts with the constituent components of the electrode active material layer, the solid electrolyte, or the current collector through intermolecular forces or chemical bonds, thereby further improving the binding and adhesiveness of the conjugated diene polymer.

[0050] Such other compounds are not particularly limited, but examples thereof include carbodiimide compounds, amide condensing agents such as diphenylphosphoric acid azide, alkoxysilane compounds, amino compounds, hydroxy compounds, isocyanate compounds, and epoxy compounds. The other compounds may be used alone or in combination of two or more.

[0051] The carbodiimide compound is not particularly limited, but examples thereof include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.

[0052] The alkoxysilane compound is not particularly limited, but examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0053] The amine compound is not particularly limited, but examples thereof include diaminobutane, diaminopentane, diaminohexane, diaminoheptane, and diaminooctane.

[0054] The hydroxy compound is not particularly limited, but examples thereof include dihydroxybutane, dihydroxypentane, dihydroxyhexane, dihydroxyheptane, and dihydroxyoctane.

[0055] The isocyanate compound is not particularly limited, but examples thereof include hexanemethylene diisocyanate, 1,4-phenylene diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate.

[0056] The epoxy compound is not particularly limited, but examples thereof include ethylene glycol diglycidyl ether and 1,4-butanediol diglycidyl ether.

[0057] These compounds can also be used for the components of the electrode active material layer or for conjugated diene polymers having binding groups for the solid electrolyte or adhesive groups for the current collector.

[0058] The content of the modifying groups in the conjugated diene polymer described above is not particularly limited, but from the viewpoint of further improving binding strength and adhesiveness, it is preferably 0.5 groups / chain or more. From the same viewpoint, it is more preferably 0.7 groups / chain or more, even more preferably 1.0 groups / chain or more, and even more preferably 2.0 groups / chain or more. When the content of the modifying groups is 0.5 groups / chain or more, the modifying groups can more sufficiently interact with the constituent components of the electrode active material layer, the solid electrolyte, or the current collector, thereby further improving adhesiveness. On the other hand, from the viewpoint of dispersibility of the conductive additive when made into a slurry, it is 50 groups / chain or less, more preferably 20 groups / chain or less, even more preferably 10 groups or less, more preferably 2.0 groups / chain or less, and even more preferably 1.0 groups or less.

[0059] In addition, the content of the modifying group is preferably 300 or less per chain, from the viewpoint of further preventing problems such as gelation of the all-solid-state battery binder containing the conjugated diene polymer. Here, the "chain" refers to one polymer molecule such as a conjugated diene polymer, and in the case of a polymer structure branched by chemical bonds, one branched chain is counted as one molecular chain.

[0060] The conjugated diene polymer may have a functional group or polymer chain that improves ionic conductivity in addition to the modifying group described above. Examples of such functional groups and polymer chains include, but are not limited to, an ether group, a crown ether, a polyethylene glycol, a boronic acid group, a boronic acid ester group, an ionic group containing a lithium ion electrolyte used in a lithium ion battery, and an ionic group containing an ionic liquid.

[0061] (Hydrogenation) The conjugated diene polymer is preferably hydrogenated. The hydrogenation rate relative to a total of 100 mol% of conjugated diene monomer units is preferably 30 mol% or more from the viewpoint of electrochemical stability of the conjugated diene polymer, more preferably 50 mol% or more from the viewpoint of thermal stability, even more preferably 70 mol% or more from the viewpoint of further improving adhesiveness, and particularly preferably 90 mol% or more from the viewpoint of improving the strength of the electrode film by entanglement of polymer chains.

[0062] The hydrogenation rate of the conjugated diene polymer can be measured using a nuclear magnetic resonance (NMR) spectrometer or the like, and specifically, can be measured by the method described in the examples.

[0063] The hydrogenation rate can be controlled within the above range by adjusting the amount of hydrogen or catalyst used during hydrogenation.

[0064] (Toluene insolubles) The toluene insoluble content of the conjugated diene polymer is preferably 10 wt% or less, more preferably 5 wt% or less, even more preferably 3 wt% or less, and particularly preferably 1 wt% or less. The lower limit of the toluene insoluble content is not particularly limited, but is 0 wt%. By keeping the toluene insoluble content at 10 wt% or less, the smoothness of the coating film tends to be further improved. The toluene insoluble content can be measured by the method described in the Examples.

[0065] (random copolymer block) The conjugated diene polymer used in the all-solid-state battery binder of this embodiment may further have a random copolymer block of conjugated diene monomer units and vinyl aromatic monomer units. By forming the random structure, the affinity between the conjugated diene polymer and the components of the electrode active material layer or the solid electrolyte can be improved, thereby improving the binding property, and the viscoelasticity can be controlled to impart vibration damping properties in the operating temperature range of the battery, thereby improving the durability of the battery.

[0066] Examples of the vinyl aromatic monomer and the conjugated diene monomer that can be contained in the random copolymer block of a conjugated diene compound and a vinyl aromatic compound include those exemplified as those that can be contained in the block mainly composed of a vinyl aromatic polymer and the block mainly composed of a conjugated diene polymer described above.

[0067] The distribution of the vinyl aromatic monomer units in the random copolymer block is not particularly limited, and the vinyl aromatic monomer units may be distributed uniformly or in a tapered pattern. In addition, there may be a plurality of portions where the vinyl aromatic monomer units are distributed uniformly and / or a plurality of portions where the vinyl aromatic monomer units are distributed in a tapered pattern, and there may be a plurality of segments with different contents of the vinyl aromatic monomer units.

[0068] In the conjugated diene polymer of this embodiment, in addition to the conjugated diene monomer and the vinyl aromatic monomer, other monomers copolymerizable with the conjugated diene monomer and the vinyl aromatic monomer can also be used.

[0069] (Structure of conjugated diene polymer) The structure of the conjugated diene polymer of the present embodiment is not particularly limited, but examples thereof include those having a structure represented by the following formula in part or those having a structure represented by the following formula: In the following formula, the description of the modifying group may be omitted in some cases.

[0070] (ab) n , b-(ab) n , a-(ba) n , (ab) m -X, (ba) m -X, [(ab) n ] m -X, [(ba) n ] m -X, [b-(ab) n ] m -X, [a-(ba) n ] m -X, [(ab) n -a] m -X, [(ba) n -b] m -X, (ac) n , c-(ac) n , a-(ca) n , (ac) m -X, (ca) m -X, [(ac) n ] m -X, [(ca) n ] m -X, [c-(ac) n ] m -X, [a-(ca) n ] m -X, [(ac) n -a] m -X, [(ca) n -c] m -X, c-(ba) n , c-(ab) n , c-(aba) n , c-(bab) n , ac-(ba) n , ac-(ab) n , ac-(ba)n -b、[(a-b-c) n ] m -X、[a-(b-c) n ] m -X、[(a-b) n -c] m -X、[(a-b-a) n -c] m -X、[(b-a-b) n -c] m -X、[(c-b-a) n ] m -X、[c-(b-a)n] m -X、[c-(a-b-a) n ] m -X、[c-(b-a-b) n ] m -X、a-(b-c) n 、a-(c-b) n 、a-(c-b-c) n 、a-(b-c-b) n 、c-a-(b-c) n 、c-a-(c-b) n 、c-a-(b-c) n -b、[(c-b-a) n ] m -X、[c-(b-a) n ] m -X、[(c-b) n -a] m -X、[(c-b-c) n -a] m -X、[(b-c-b) n -a] m -X、[(a-b-c) n ] m -X、[a-(b-c) n ] m -X、[a-(c-b-c) n ] m -X、[a-(b-c-b) n ] m -X、b-(a-c) n 、b-(c-a) n 、b-(c-a-c) n 、b-(a-c-a) n 、c-b-(a-c) n 、c-b-(c-a) n, cb-(ac) n -a, [(cab) n ] m -X, [c-(ab) n ] m -X, [(ca) n -b] m -X, [(cac) n -b] m -X, [(bac) n ] m -X, [b-(ac) n ] m -X, [b-(cac) n ] m -X, [b-(aca) n ] m -X, (b1-b2) n -a, (b1-b2-b) n -a, (b1-b2-a) n , (b1-b2-a) n -b, (b1-b2-ab) n , (b1-b2-a) m -X, (b1-b2-ab) m -X.

[0071] In the above formulas, a represents a vinyl aromatic polymer block mainly composed of vinyl aromatic monomer units, b represents a conjugated diene polymer block mainly composed of conjugated diene monomer units, b1 and b2 represent conjugated diene polymer blocks mainly composed of conjugated diene monomer units (provided that the vinyl bond amount in b1 is smaller than the vinyl bond amount in b2), and c represents a random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer. When all of b1, b2, and b are present, the vinyl bond amount in b is not particularly limited. n represents an integer of 1 or more, preferably an integer of 1 to 5. m represents an integer of 2 or more, preferably an integer of 2 to 11. X represents a residue of a coupling agent or a residue of a polyfunctional initiator.

[0072] From the viewpoint of the binding and adhesive properties of an all-solid-state battery binder containing the conjugated diene polymer, the conjugated diene polymer of this embodiment preferably mainly contains a structure having a b, b1, or b2 block. Furthermore, from the viewpoint of improving mechanical strength, the conjugated diene polymer is more preferably a polymer represented by at least one structural formula selected from the group consisting of ab, aba, abab, b1-b2-a, b1-b2-ab, and b1-b2-ba, and coupling products thereof. From the viewpoint of the solubility of the conjugated diene polymer in nonpolar solvents and the binding and adhesive properties of an all-solid-state battery binder containing the conjugated diene polymer, a structure having two or more a blocks in the molecular chain is preferred.

[0073] Furthermore, it is preferable that the terminal or coupling portion of the conjugated diene polymer has a modifying group, which tends to further improve the balance of adhesiveness, binding ability, and dispersibility of the conductive additive.

[0074] (Weight average molecular weight and molecular weight distribution) From the viewpoints of the binding property and adhesiveness of the all-solid-state battery binder containing a conjugated diene polymer, and its solubility in nonpolar solvents, the weight-average molecular weight (Mw) (hereinafter also referred to as "Mw") of the conjugated diene polymer is preferably 40,000 to 2,000,000, more preferably 60,000 to 1,500,000, even more preferably 100,000 to 1,000,000, and even more preferably 200,000 to 800,000. The lower limit of Mw is more preferably 200,000 or more, more preferably 250,000 or more. The upper limit is more preferably 500,000 or less, even more preferably 450,000 or less. Adjusting Mw within a preferred range is important from the viewpoints of storage stability and coatability, since the solvent used in preparing the slurry does not volatilize immediately during storage of the solution containing the conjugated diene polymer and the solvent used in preparing the slurry, or when applied to a current collector. From the viewpoint of vapor pressure reduction by the polymer solution, a higher molecular weight of the conjugated diene polymer increases the degree of vapor pressure reduction and makes it possible to suppress solvent volatilization. Despite these benefits of using high-molecular-weight binders, conventional lithium-ion batteries use N-methyl-2-pyrrolidone (NMP) as the solvent, making the use of high-molecular-weight conjugated diene polymers difficult due to their low solubility. In all-solid-state batteries, nonpolar solvents, such as hydrocarbon solvents, are preferred, and the excellent solubility of conjugated diene polymers in hydrocarbon solvents allows the use of high-molecular-weight binders. Furthermore, NMP has a lower vapor pressure than hydrocarbon solvents and other nonpolar solvents, making the need for high-molecular-weight binders less important due to their volatility. However, nonpolar solvents have a higher vapor pressure than NMP, making the volatility issue more pronounced, necessitating the need for higher-molecular-weight binders. On the other hand, when using battery manufacturing methods that minimize the use of solvents, conjugated diene polymers without modifying groups are preferred due to their excellent solubility in nonpolar solvents.

[0075] A weight-average molecular weight (Mw) of 30,000 or more tends to improve the entanglement of polymer chains and the cohesive strength of vinyl aromatic polymer blocks, leading to improved binding and adhesive strength. In particular, a weight-average molecular weight (Mw) of 2,000,000 or less tends to lower the viscosity when dissolved in a nonpolar solvent, improving the film-forming properties of each layer during electrode production.

[0076] Furthermore, depending on the application, heat resistance is required for all-solid-state batteries, and there is a concern that binder flow at high temperatures may reduce battery performance. In such cases, a high weight-average molecular weight (Mw) of the conjugated diene polymer is preferable in order to suppress flow. The required heat resistance depends on the specifications of the device, so there are no particular restrictions on the applications requiring heat resistance. However, examples of applications requiring heat resistance include power supplies for automobiles and automobile motors installed in the engine compartment, power supplies for motors installed in large industrial machinery, power supplies for medical equipment that require sterilization heating, and small power supplies directly mounted on home appliances or automotive printed wiring boards. Heat resistance may also be required when a solder reflow process is performed, such as when directly mounting on a printed wiring board.

[0077] The weight-average molecular weight (Mw) of the conjugated diene polymer is the weight-average molecular weight (Mw) determined from the molecular weight of the peak in a chromatogram obtained by gel permeation chromatography (GPC) measurement, based on a calibration curve determined from measurements of commercially available standard polystyrene. The calibration curve may be prepared using the peak molecular weight of the standard polystyrene.

[0078] The molecular weight distribution of the conjugated diene polymer before modification can also be determined by GPC measurement, and the molecular weight distribution can be determined from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

[0079] The single-peak molecular weight distribution of the conjugated diene polymer measured by GPC is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and even more preferably 2.5 or less. The lower limit of the molecular weight distribution is not particularly limited, but may be 1.0 or more, or 1.1 or more.

[0080] (moisture content) The all-solid-state battery binder preferably does not contain moisture, and the moisture content of the all-solid-state battery binder is preferably 200 ppm or less, more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 10 ppm or less, and particularly preferably 1 ppm or less. The moisture contained in the all-solid-state battery binder may be removed by drying in a dryer at normal or reduced pressure, or by storing in a dehumidified environment. In this case, the binder may be heated or heated and pressurized with a press or roll, etc.

[0081] In this case, the moisture content of the all-solid-state battery binder before drying or dehumidification may be 200 ppm or more. Furthermore, from the viewpoint of moisture removal efficiency, the moisture content of the conjugated diene polymer used in the all-solid-state battery binder is preferably 1 wt % or less, more preferably 0.5 wt % or less, even more preferably 0.1 wt % or less, even more preferably 0.05 wt % or less, and particularly preferably 0.02 wt % or less. The moisture contained in the conjugated diene polymer may be removed by drying in a dryer under normal or reduced pressure, or by storing in a dehumidified environment. This may be done under heating, or under both heating and pressure using a press or roll.

[0082] The conjugated diene polymer may be in the form of pellets, but when the water content of the polymer is reduced before preparing the slurry, a form with a large specific surface area is preferred from the viewpoint of water removal efficiency, and crumbs or powder are preferable. The conjugated diene polymer-containing slurry preferably has a water content of 1 wt% or less. However, since the slurry is diluted with solvents and other components in addition to the polymer, it is possible to prepare a slurry with a water content of 1 wt% or less even if the water content of the polymer exceeds 1 wt%. In other words, since the water derived from the conjugated diene polymer is also diluted, the water content of the conjugated diene polymer may be 1 wt% or more. Since the water content of the binder is preferably 200 ppm or less, it is a preferred embodiment to use a solvent that forms an azeotrope with water in the slurry when the water content of the slurry is high, thereby increasing the efficiency of water removal by solvent removal.

[0083] When a conjugated diene polymer is fed through a feeder, if the polymer is compressed in the feeder and fed as a lump, the feeding becomes unstable, causing variations in the blending amount and affecting the battery characteristics. From the viewpoint of stable feeding, the degree of compression measured by the method described in the examples is preferably less than 30, more preferably 20 or less, even more preferably 15 or less, and more preferably 10 or less.

[0084] In addition, the loose bulk density is preferably 0.15 g / cm from the viewpoint of filling a large amount of the conjugated diene polymer into a feeder of a fixed volume. 3 More preferably, it is 0.20 g / cm or more. 3 More preferably, it is 0.22 g / cm 3 The preferred upper limit is 0.30 g / cm 3 or less, more preferably 0.25 g / cm 3 The following is the result.

[0085] The total content of the transition metal elements, Al, Li, Zn, and Mg in the conjugated diene polymer is preferably 200 ppm or less in terms of atoms relative to the conjugated diene polymer. Transition metals include V, Ti, Mn, Fe, Co, and Ni.

[0086] Generally, the metal atom-containing compound contained in the polymerization initiator when producing a block copolymer by anionic living polymerization, the hydrogenation catalyst in the hydrogenation reaction, and / or the moisture in the air in the solvent removal step of polymerization react to generate a metal-containing compound, which will be described later, and may remain in the conjugated diene polymer.

[0087] The compound containing a transition metal element (e.g., Ti, Ni, Co) and / or Li in the conjugated diene polymer is not particularly limited, and examples thereof include oxides of each atom such as titanium oxide, amorphous titanium oxide, orthotitanic acid, metatitanic acid, titanium hydroxide, nickel hydroxide, nickel monoxide, lithium oxide, lithium hydroxide, cobalt oxide, and cobalt hydroxide, and composite oxides of each atom with a different metal such as lithium titanate, barium titanate, strontium titanate, nickel titanate, and nickel-iron oxide. In addition, metals such as Al, Li, Zn, Fe, and Mg remain in the conjugated diene polymer as metal residues.

[0088] Here, the atomic equivalent generally refers to the mass per metal atom calculated from the residual weight and molecular weight of the compound containing the metal atom. However, if the compound containing the metal atom can be identified, the calculation may be performed by the above method, but in many cases, such identification is difficult. Therefore, the total content of the metal atoms relative to the total amount in the conjugated diene polymer is determined in atomic equivalent mass by the method described in the Examples.

[0089] By keeping the total content of transition metal elements and Al, Li, Zn, Fe, and Mg in the conjugated diene polymer at 200 ppm or less, calculated on an atomic basis, the thermal stability of the conjugated diene polymer is maintained and the deterioration of heat aging resistance of all-solid-state batteries using the conjugated diene polymer as a binder is suppressed. The detailed mechanism of this phenomenon is unknown and is not limited to the following. It is generally known that when a polymer is exposed to high temperatures, carbon radicals are generated, which react with oxygen in the air to generate hydroperoxides. In the presence of the metal compounds, decomposition into free radicals via a redox reaction is promoted. Furthermore, the hydrogenated block copolymer itself reacts with the metal compounds to generate free radicals. Alternatively, metal ions derived from the metal compounds and oxygen in the air generate charge-transfer complexes and / or active oxygen, and these active species react with the hydrogenated block copolymer to generate carbon radicals. Although the reaction mechanism is not limited to these, according to the above-mentioned reaction mechanism, when the amount of the above-mentioned metal is large, there tends to be a large amount of free radicals derived from the metal compound, and as a result, active species such as carbon radicals and hydroperoxides are generated in the hydrogenated block copolymer. These active species cause bonding between radicals and the generation of further radicals, which leads to deterioration of the polymer and causes bonding between hydrogenated block copolymers, which raises concerns about cracking of the layer using the binder, reduced adhesion and binding properties, and reduced impact resistance due to hardening.

[0090] The total content is preferably 200 ppm or less, more preferably 100 ppm or less, even more preferably 70 ppm or less, and particularly preferably 50 ppm or less. The lower limit of the total content is not particularly limited, but is 0 ppm.

[0091] Known methods can be used to reduce the total content to 200 ppm or less. For the sole purpose of deactivating and neutralizing the hydrogenation catalyst, methods such as adding water and carbon dioxide gas after the hydrogenation reaction of a block copolymer to neutralize the hydrogenation catalyst residue, or adding water, carbon dioxide gas, and an acid to neutralize the hydrogenation catalyst residue, are used. However, for the purpose of reducing the total metal content, neutralization alone is insufficient, so it is preferable to further remove the metals using decantation or a centrifuge. More specifically, the method described in Patent Application No. 2014-557427 can be mentioned. When removing metal residues by contacting a polymer solution with water after hydrogenation, adding an acid such as sulfuric acid, hydrochloric acid, or nitric acid to the conjugated diene polymer solution makes it easier to extract the metal residues into the aqueous phase when mixed with water. To further remove the metal residues, the stirring intensity (P / V value) can be increased when contacting the polymer solution with water to disrupt the interaction between the polymer and the metal residues, thereby further extracting the metal residues into the aqueous phase. Furthermore, by separating the decantation and centrifugation steps, more metal residues can be removed.

[0092] [Method for producing conjugated diene polymer] The method for producing the conjugated diene polymer of the present embodiment is not particularly limited, and may include, for example, a polymerization step, a modification step, and a hydrogenation step as described below.

[0093] The polymerization step is not particularly limited, but is, for example, a step of polymerizing a conjugated diene compound and a vinyl aromatic compound in an organic solvent using an organic alkali metal compound as a polymerization initiator to obtain a random copolymer and / or a block copolymer as represented by the above structure.

[0094] The hydrogenation step is not particularly limited, but is, for example, a step of hydrogenating the conjugated diene polymer obtained in the polymerization step.

[0095] The modification step is not particularly limited, but is, for example, a step of reacting a conjugated diene polymer with a modifier to carry out a modification reaction to obtain a conjugated diene polymer.

[0096] The order of the hydrogenation step and the modification step is not particularly limited. That is, the order may be polymerization step, hydrogenation step, and modification step, or polymerization step, modification step, and hydrogenation step. From the viewpoint of more easily obtaining the above-mentioned conjugated diene-based polymer, the order is preferably polymerization step, hydrogenation step, and modification step. Furthermore, the modification step may be performed in parallel with the polymerization step, as described below.

[0097] (Polymerization process) The polymerization step is, for example, a step of polymerizing a conjugated diene compound and a vinyl aromatic compound in an organic solvent using an organic alkali metal compound as a polymerization initiator to obtain a random copolymer and / or a block copolymer.

[0098] The polymerization may be performed by batch polymerization, continuous polymerization, or a combination thereof. From the viewpoint of making the size of the dispersed phase in the all-solid-state battery binder containing the conjugated diene-based polymer, which affects the impact resistance and toughness, constant, it is preferable to use a batch polymerization method, which narrows the molecular weight distribution.

[0099] The reaction temperature in the polymerization step may be 0° C. or higher and 180° C. or lower. From the viewpoint of more easily obtaining the conjugated diene-based polymer of the present embodiment, the reaction temperature is preferably 20° C. or higher and 160° C. or lower, and more preferably 30° C. or higher and 150° C. or lower.

[0100] The reaction time in the polymerization step varies depending on the target polymer, but may be within 48 hours. From the viewpoint of more easily obtaining the conjugated diene-based polymer of the present embodiment, the reaction time is preferably from 0.1 to 10 hours. From the viewpoint of obtaining a conjugated diene-based polymer having a narrow molecular weight distribution and high strength, the reaction time is more preferably from 0.5 to 5 hours.

[0101] The atmosphere of the polymerization system in the polymerization step is not particularly limited as long as it is in a pressure range sufficient to maintain nitrogen and the solvent in a liquid phase. It is preferable that the polymerization system does not contain impurities that may inactivate the polymerization initiator and the living polymer, such as water, oxygen, and carbon dioxide gas.

[0102] Furthermore, at the end of the polymerization step, a required amount of a bifunctional or higher coupling agent may be added to carry out a coupling reaction. As the bifunctional coupling agent, a conventionally known one can be used, and is not particularly limited, but examples thereof include alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane, dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

[0103] Furthermore, as the polyfunctional coupling agent having three or more functionalities, conventionally known ones can be used, and there is no particular limitation. For example, polyalcohols having three or more functionalities, epoxidized soybean oil, polyfunctional epoxy compounds such as diglycidyl bisphenol A and 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane, and compounds having the general formula R4-nSiX n (wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 to 4), for example, methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and bromides thereof, and silicon halide compounds represented by the general formula R4-nSnX n (wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 to 4), for example, polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Dimethyl carbonate, diethyl carbonate, etc. may also be used.

[0104] The organic solvent is not particularly limited, but examples thereof include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, xylene, toluene, and ethylbenzene.

[0105] The organic alkali metal compound serving as the polymerization initiator is preferably an organic lithium compound, and the organic lithium compound is not particularly limited, but examples thereof include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound.

[0106] The organolithium compound is not particularly limited, and examples thereof include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isopropenyldilithium, and lithium piperidide. When an organolithium compound containing a nitrogen atom, such as lithium piperidide, is used as the polymerization initiator, a conjugated diene polymer having a nitrogen atom is obtained.

[0107] These polymerization initiators may be used alone or in combination of two or more. Among these, n-butyllithium, sec-butyllithium, and lithium piperidide are preferred as the polymerization initiator from the viewpoint of improving the polymerization activity.

[0108] The amount of the organic alkali metal compound used as the polymerization initiator depends on the molecular weight of the target conjugated diene polymer, but is typically in the range of 0.01 phm to 1.5 phm (here, phm indicates parts by mass per 100 parts by mass of monomer; the same applies hereinafter), more preferably in the range of 0.02 phm to 0.3 phm, and even more preferably in the range of 0.03 phm to 0.2 phm.

[0109] The vinyl bond content of the conjugated diene polymer can be controlled by adding a Lewis base, such as an ether or an amine, as a vinyl bond content regulator (hereinafter referred to as a "vinylating agent"). The amount of the vinylating agent used can be adjusted depending on the desired vinyl bond content.

[0110] The vinylating agent is not particularly limited, but examples thereof include ether compounds and tertiary amine compounds.

[0111] The ether compound is not particularly limited, but examples thereof include linear ether compounds and cyclic ether compounds.

[0112] The linear ether compound is not particularly limited, but examples thereof include dialkyl ether compounds of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether, and dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

[0113] Furthermore, the cyclic ether compound is not particularly limited, but examples thereof include alkyl ethers such as tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and furfuryl alcohol.

[0114] The tertiary amine compound is not particularly limited, but examples thereof include trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N",N"-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, pyridine, tetramethylpropanediamine, and bis[2-(N,N-dimethylamino)ethyl]ether.

[0115] The tertiary amine compound is preferably a compound having two amines. Among them, the tertiary amine compound is more preferably one having a symmetrical structure within the molecule, and more preferably N,N,N',N'-tetramethylethylenediamine, bis[2-(N,N-dimethylamino)ethyl]ether, and 1,2-dipiperidinoethane. These vinylating agents may be used alone or in combination of two or more.

[0116] In the polymerization step, a conjugated diene monomer may be polymerized alone, or a conjugated diene monomer may be polymerized with a vinyl aromatic monomer in the coexistence of an alkali metal alkoxide in addition to the vinylating agent and organolithium compound described above.

[0117] Here, alkali metal alkoxide is a compound represented by the general formula MOR (wherein M represents an alkali metal and R represents an alkyl group). The presence of an alkali metal alkoxide in the polymerization step tends to facilitate control of the vinyl bond amount, molecular weight distribution, polymerization rate, block ratio, etc.

[0118] The alkali metal of the alkali metal alkoxide is preferably sodium or potassium, from the viewpoint of obtaining a high vinyl bond content, a narrow molecular weight distribution, a high polymerization reaction rate, and a high block rate.

[0119] The alkali metal alkoxide is not particularly limited, and examples thereof include sodium alkoxides, lithium alkoxides, and potassium alkoxides having an alkyl group with 2 to 12 carbon atoms. Preferred alkali metal alkoxides are sodium alkoxides and potassium alkoxides having an alkyl group with 3 to 6 carbon atoms, and more preferred are sodium t-butoxide, sodium t-pentoxide, potassium t-butoxide, and potassium t-pentoxide. Of these, sodium t-butoxide and sodium t-pentoxide are even more preferred.

[0120] (Hydrogenation process) The hydrogenation step is a step of hydrogenating a conjugated diene polymer or a conjugated diene polymer. The hydrogenation method in the hydrogenation step is not particularly limited, and examples thereof include a method in which hydrogen gas is supplied to the conjugated diene polymer obtained in the polymerization step in the presence of a hydrogenation catalyst to hydrogenate it. When the method for producing a conjugated diene polymer includes such a hydrogenation step, residual double bonds in the conjugated diene monomer units are hydrogenated, and a more thermally stable hydrogenated conjugated diene polymer can be obtained.

[0121] The hydrogenation rate can be controlled, for example, by the amount of catalyst used during hydrogenation or the supply of hydrogen gas (hereinafter also referred to as "feed"). The hydrogenation rate can be controlled, for example, by the amount of catalyst used during hydrogenation, the amount of hydrogen gas supplied, the pressure, the temperature, etc. The hydrogenation step is preferably carried out at a timing after the termination of the production reaction of the conjugated diene polymer in the polymerization step.

[0122] After the hydrogenation reaction is completed, a stabilizer may be added. The stabilizer is not particularly limited, but examples thereof include octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.

[0123] If necessary, the catalyst residue may be removed from the solution of the conjugated diene polymer obtained as described above, and the conjugated diene polymer may be separated from the solvent.

[0124] Examples of methods for separating the solvent include a method in which a polar solvent that is a poor solvent for the hydrogenated copolymer, such as acetone or alcohol, is added to the reaction solution after hydrogenation to precipitate and recover the polymer; a method in which the reaction solution is poured into hot water with stirring and the solvent is removed by steam stripping to recover the polymer; and a method in which the polymer solution is directly heated to distill off the solvent. When poured into hot water, moisture is mixed into the polymer, so moisture can also be removed by a heat extrusion process or the like. Note that various stabilizers, such as phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers, can be added to the hydrogenated copolymer.

[0125] (Denaturation process) The modification step is not particularly limited as long as it is a step of obtaining a conjugated diene polymer having a modifying group, and is, for example, a step of obtaining a conjugated diene polymer by reacting a conjugated diene polymer and / or a hydrogenated conjugated diene polymer with a modifying agent, whereby the obtained conjugated diene polymer has a modifying group.

[0126] The modification step may be carried out in parallel with the polymerization step described above. Such a modification reaction method is not particularly limited, but examples include a method using a polymerization initiator having a binding group for the constituent components of the electrode active material layer or the solid electrolyte, or an adhesive group for the current collector, in the polymerization reaction in the polymerization step; and a method using an unsaturated monomer having a binding group for the constituent components of the electrode active material layer or the solid electrolyte, or an adhesive group for the current collector, in the polymerization reaction in the polymerization step. Furthermore, as a modification reaction method, a method may be used in which a modifier that forms or contains a binding group for the constituent components of the electrode active material layer or the solid electrolyte, or an adhesive group for the current collector, is added to the living end of the conjugated diene polymer obtained by the polymerization reaction in the polymerization step.

[0127] The position at which the modifying group is introduced into the conjugated diene polymer is not particularly limited. For example, the modifying group may be at the end of the conjugated diene polymer, or may be arranged in a block, random, or tapered configuration on a portion of the main chain of the conjugated diene polymer. When introducing the modifying group quantitatively and with high regioselectivity, it is preferable to copolymerize a monomer having the modifying group or a monomer to which the modifying group can be introduced in a subsequent step, or to introduce the modifying group into the polymer end. The concentration of the modifying group can be controlled depending on the amount of the monomer having the modifying group, the amount of the monomer to which the modifying group can be introduced in a subsequent step, or the amount of the modifying agent reacted with the polymer end. Furthermore, when reacting the polymer end with a modifying agent, the amount of the modifying group can also be reduced by increasing the molecular weight of the polymer and reducing the number of polymer ends. Introduction into the polymer end is suitable for introducing a small amount of the modifying group. Furthermore, a coupling agent having a modifying group or a modifying group precursor can also be used for introduction into the polymer end. In this case, the modifying group will be present at the coupling moiety.

[0128] To keep the amount of modifying groups at 3 mmol or less per 100 g of conjugated diene polymer, a method of reacting the polymer terminal with a modifying agent is suitable, particularly for polymers with a molecular weight of 35,000 or more. When the polymer terminal reacts with the modifying agent in a 1:1 ratio, the amount of modifying groups can be controlled depending on the molecular weight: 2.9 mmol or less for a molecular weight of 35,000, 1.0 mmol or less for a molecular weight of 100,000, 0.5 mmol or less for a molecular weight of 200,000, 0.33 mmol or less for a molecular weight of 300,000, 0.2 mmol or less for a molecular weight of 500,000, and 0.14 mmol or less for a molecular weight of 700,000.

[0129] The amount of the modifying group is not particularly limited as long as it does not cause practical problems, but when adhesiveness due to the interaction of the modifying group with different materials is expected, the amount of the modifying group is preferably 0.10 mmol or more, and preferably 0.15 mmol or more, per 100 g of conjugated diene-based polymer. Furthermore, from the viewpoint of conductive additive dispersibility, the amount of the modifying group is preferably 20 mmol or less, more preferably 5 mmol or less, even more preferably 1.5 mmol or less, and even more preferably 0.10 mmol or more to 0.50 mmol or less, per 100 g of conjugated diene-based polymer. In particular, for polymers with a molecular weight of 200,000 or more, when the modification amount is 3.0 mmol or less, the balance between conductive additive dispersibility and adhesiveness can be improved due to the molecular weight entanglement effect in addition to the interaction between the modifying group and the conductive additive.

[0130] The "polymerization initiator having a binding group for the constituent components of the electrode active material layer or the solid electrolyte or an adhesive group for the current collector" is not particularly limited, and examples thereof include 3-lithio-1-[N,N-bis(trimethylsilyl)]aminopropane, 2-lithio-1-[N,N-bis(trimethylsilyl)]aminoethane, 3-lithio-2,2-dimethyl-1-[N,N-bis(trimethylsilyl)]aminopropane, 2,2,5,5-tetramethyl-1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane, 2,2,5, 5-tetramethyl-1-(3-lithio-2,2-dimethyl-propyl)-1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1-(2-lithioethyl)-1-aza-2,5-disilacyclopentane, 3-lithio-1-[N-(tert-butyl-dimethylsilyl)-N-trimethylsilyl]aminopropane, 3-lithio-1-(N-methyl-N-trimethylsilyl)aminopropane, 3-lithio-1-(N-ethyl-N-trimethylsilyl)aminopropane, and lithium piperidide.

[0131] The "unsaturated monomer having a binding group for the constituent components of the electrode active material layer or the solid electrolyte, or an adhesive group for the current collector" is not particularly limited, and examples thereof include p-[N,N-bis(trimethylsilyl)amino]styrene, p-[N,N-bis(trimethylsilyl)aminomethyl]styrene, p-{2-[N,N-bis(trimethylsilyl)amino]ethyl}styrene, m-[N,N-bis(trimethylsilyl)amino]styrene, p-(N-methyl-N-trimethylsilylamino)styrene, and p-(N-methyl-N-trimethylsilylaminomethyl)styrene.

[0132] The "modifier that forms or contains binding groups for the components of the electrode active material layer or the solid electrolyte, or adhesive groups for the current collector" is not particularly limited, but examples thereof include tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and N-methylpyrrolidone.

[0133] Another method for introducing a modifying group includes, for example, reacting a conjugated diene polymer with an organic alkali metal compound such as an organic lithium compound (metallation reaction) to obtain a polymer having an organic alkali metal added thereto, and then adding the above-mentioned modifying agent to the polymer having an organic alkali metal added thereto.

[0134] Further, as another method for introducing a modifying group, for example, a method of grafting an atomic group having a binding group for the constituent components of the electrode active material layer or the solid electrolyte, or an adhesive group for the current collector, to the conjugated diene-based polymer can be mentioned.

[0135] Such a method may be a method of directly grafting onto a conjugated diene polymer, or a method of reacting a conjugated diene polymer into which a primary modifying group has been introduced with an atomic group having a binding group for a component of an electrode active material layer or a solid electrolyte or an adhesive group for a current collector (secondary modification).

[0136] The "atomic group having a binding group for the constituent components of the electrode active material layer or the solid electrolyte, or an adhesive group for the current collector" is not particularly limited, but examples thereof include a molecular unit containing an α,β-unsaturated carboxylic acid or a derivative thereof. Examples of α,β-unsaturated carboxylic acids or derivatives thereof include maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid, and the like, and anhydrides of these dicarboxylic acids, acrylic acid, methacrylic acid, crotonic acid, and the like, and esters of these monocarboxylic acids (e.g., 2-hydroxyethyl acrylate, methyl methacrylate, glycidyl methacrylate, and 3-(trimethoxysilyl)propyl methacrylate), and alkoxysilane compounds (e.g., vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrippropoxysilane, vinyltributoxysilane, vinyldimethoxymethylsilane, vinyldiethoxyethylsilane, vinyldipropoxypropylsilane, and vinyldibutoxybutylsilane). Among these, acrylic acid, anhydride, glycidyl methacrylate, vinyltrimethoxysilane, and vinyltriethoxysilane are preferred, and from the viewpoint of further enhancing adhesiveness, maleic anhydride is more preferred.

[0137] The amount of molecular units containing an α,β-unsaturated carboxylic acid or a derivative thereof added is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the conjugated diene polymer. From the viewpoint of binding strength to the constituent components of the electrode active material layer, the solid electrolyte, etc., or adhesion to the current collector, the amount added is preferably 0.1 parts by mass or more. On the other hand, from the viewpoint of improving the fluidity of the all-solid-state battery binder containing the conjugated diene polymer, the amount added is preferably 20 parts by mass or less.

[0138] Examples of the grafting method include a method of reacting a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof in a solution containing these; a method of reacting a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof under heating to melt or while not melted; a method of reacting a conjugated diene polymer and a compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof under heating to melt or while not melted; a method of reacting a compound that reacts with both compounds containing an α,β-unsaturated carboxylic acid or a derivative group thereof to form a bond with a conjugated diene polymer to which a compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof has been grafted in a solution containing these; and a method of reacting a compound that reacts with both compounds containing an α,β-unsaturated carboxylic acid or a derivative group thereof to form a bond with a conjugated diene polymer to which a compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof has been grafted under heating to melt or while not melted. In either case, graft addition by ene addition without the use of a radical initiator may also be used.

[0139] A method in which a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid group or a derivative thereof are reacted under heating and melting, under heating and not melting, or in a solution is preferred, and a method in which they are reacted under heating and melting is more preferred. In any of the above preferred cases, graft addition by ene addition without using a radical initiator may also be used.

[0140] Examples of a method for reacting a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid group or a derivative thereof under heating and melting include a method of melt-kneading each component using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder. From the viewpoints of cost and production stability, a method using a single-screw, twin-screw, or multi-screw extruder is preferred, and a method using a twin-screw extruder is more preferred.

[0141] The radical initiator, the conjugated diene polymer, and the compound containing an α,β-unsaturated carboxylic acid group or a derivative thereof may be dry-blended and added all at once, or each raw material may be fed separately, or the same raw material may be added in multiple batches.

[0142] The screw rotation speed is preferably 50 rpm or more and 400 rpm or less, more preferably 100 rpm or more and 350 rpm or less, from the viewpoint of uniformly adding the compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof to the conjugated diene polymer. Furthermore, from the viewpoint of suppressing deterioration of the resin due to shear and uniformly adding the compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof to the conjugated diene polymer, the rotation speed is preferably 150 rpm or more and 300 rpm or less.

[0143] The kneading temperature is not particularly limited as long as it is a temperature at which the conjugated diene polymer melts and at which radicals are generated from the radical initiator, but is preferably 100° C. or higher and 350° C. or lower. From the viewpoints of controlling the addition amount of the compound containing an α,β-unsaturated carboxylic acid or a derivative thereof and suppressing deterioration of the resin due to heat, the kneading temperature is more preferably 120° C. or higher and 300° C. or lower, and even more preferably 150° C. or higher and 250° C. or lower.

[0144] In order to prevent deactivation of radical active species by oxygen, the mixture may be melted and kneaded in an atmosphere of an inert gas such as nitrogen.

[0145] The amount of the modifying group in the conjugated diene polymer is preferably low from the viewpoint of suppressing moisture absorption, as long as the adhesiveness, binding ability, volatility, and dispersibility of the conductive additive are sufficient. It is preferably 20 mmol or less per 100 g of polymer, more preferably 15 mmol or less, even more preferably 10 mmol or less, 4 mmol or less, or 2 mmol or less. In particular, when the molecular weight is 200,000 or more, the amount is 15 mmol or less, even more preferably 10 mmol or less, 4 mmol or less, or 2 mmol or less. As the molecular weight increases, the entanglement between the polymers increases, and the interaction between the modifying group and the conductive additive deteriorates the dispersibility of the conductive additive. Therefore, it is preferable to reduce the amount of modification while satisfying the adhesiveness, binding ability, and volatility requirements. Among the above-mentioned modifying groups, a small amount of the modifying group is preferred for functional groups with affinity for water molecules, such as acid anhydride groups, carboxyl groups, amino groups, epoxy groups, alkoxysilane groups, and hydroxyl groups. Conductive additives are mainly made of carbon, and since there are quite a few functional groups such as COOH and OH on their surfaces, it is thought that there will be an interaction with the conjugated diene polymer regardless of the type of conductive additive.

[0146] The radical initiator used in the graft addition is not particularly limited, and examples thereof include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. Among these, radical initiators whose one-minute half-life temperature is within the kneading temperature range are preferred. More preferably, it is a radical initiator having a one-minute half-life temperature of 150°C or higher and 250°C or lower. Examples of such radical initiators include 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylauric acid, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5- Examples of peroxyl groups include di(benzoylperoxy)hexane, t-butyl peroxyacetate, 2,2-di-(t-butylperoxy)butane, t-butyl peroxybenzoate, n-butyl-4,4-di-(t-butylperoxy)valerate, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-methane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0147] From the viewpoint of improving compatibility with conjugated diene polymers, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are preferred, of which 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are more preferred.

[0148] The mol equivalent of the compound containing an α,β-unsaturated carboxylic acid or a derivative thereof relative to the radical initiator is preferably 300 mol equivalents or less, more preferably 200 mol equivalents or less, and even more preferably 100 mol equivalents or less. When the mol equivalent is within the above range, the compound containing an α,β-unsaturated carboxylic acid or a derivative thereof can be more easily added in an amount of more than 0 to about 10 parts by mass per 100 parts by mass of the conjugated diene polymer.

[0149] The reaction method for secondarily modifying a conjugated diene polymer into which a primary modifying group has been introduced with an atomic group having adhesiveness to a component of an electrode active material layer, a solid electrolyte, or a current collector is not particularly limited, and known methods can be used. For example, there is a method in which the primary conjugated diene polymer and the modifier are dry-blended, and then the components are melt-kneaded using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder, and a method in which the components are dissolved or dispersed and mixed in a solvent, and then the solvent is removed by heating.

[0150] Among these, the melt-kneading method using an extruder is preferred from the viewpoint of improving productivity and good kneading properties.

[0151] The shape of the conjugated diene polymer of the present embodiment is not particularly limited, and examples thereof include pellets, sheets, strands, chips, powder, and crumbs. After melt-kneading, the polymer may be directly molded into a product, or may be produced in chip, powder, or crumb form. From the viewpoint of the efficiency of removing moisture contained in the conjugated diene polymer, a shape with a large specific surface area is preferred, and crumbs and powder forms are more preferred than pellets.

[0152] Examples of pelletization methods include a method in which a conjugated diene polymer is extruded in the form of a strand from a single- or twin-screw extruder and cut underwater with a rotary blade installed in front of the die (underwater cutting, etc.); a method in which a conjugated diene polymer is extruded in the form of a strand from a single- or twin-screw extruder, water-cooled or air-cooled, and then cut with a strand cutter; and a method in which a conjugated diene polymer is melt-mixed in an open roll or Banbury mixer, molded into a sheet with a roll, and then cut into strips and cut into cubic pellets with a pelletizer. In the underwater cutting method, moisture is mixed on the polymer surface, so moisture can be removed by a subsequent process such as centrifugal dehydration or pneumatic transport. In addition, in the method in which the polymer is cut with a strand cutter, moisture can be removed by a subsequent process such as air blowing, suction-type draining, or pneumatic transport during the air-cooling step.

[0153] The size and shape of the pellets are not particularly limited, but from the viewpoint of preventing the pellets from adhering to each other, pellets that are nearly spherical are preferable to cylindrical pellets obtained by cutting the strands perpendicular to their longitudinal axes, because the adhesive surface between the pellets can be kept small. Typical methods for producing nearly spherical pellets include, for example, underwater cutting and center hot cutting.

[0154] The pellets of the conjugated diene polymer may contain an anti-blocking agent for the purpose of suppressing pellet blocking.

[0155] The conjugated diene polymer may contain a phosphorus compound. The content of the phosphorus compound, calculated as phosphorus atoms, relative to the conjugated diene copolymer is preferably 10 ppm or more, more preferably 20 ppm or more, and even more preferably 50 ppm or more. The upper limit is preferably 250 ppm or less, more preferably 120 ppm or less.

[0156] The anti-blocking agent is not particularly limited, but examples thereof include higher fatty acid metal salts, polyolefins, fatty acid amides, talc, and silica. Specific examples include calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica. From the viewpoint of low bleeding, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, talc, and amorphous silica are preferred. From the viewpoint of slipperiness during addition to a hopper, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, and amorphous silica are more preferred. From the viewpoint of reduced dusting, polyethylene or amorphous silica is even more preferred, and amorphous silica is most preferred.

[0157] From the viewpoint of the components of the resulting electrode active material layer and adhesion to the solid electrolyte or current collector, calcium stearate, polyethylene, polypropylene, and ethylene bisstearylamide are preferred as the anti-blocking agent.

[0158] The amount of the antiblocking agent used is preferably 500 ppm or more and 8000 ppm or less relative to the conjugated diene polymer. From the viewpoint of suppressing pellet blocking during long-term storage of conjugated diene polymer pellets and from the viewpoint of reducing scattering of the antiblocking agent when the conjugated diene polymer pellets are used, the amount of the antiblocking agent used is more preferably 1000 ppm or more and 7000 ppm or less relative to the conjugated diene polymer. The antiblocking agent is preferably blended in a state where it is attached to the pellet surface, but may also be contained inside the pellet.

[0159] The conjugated diene polymer may also contain other additives, and although not particularly limited, examples thereof include oils, fillers, heat stabilizers, UV absorbers, nucleating agents, antioxidants, weathering agents, light stabilizers, plasticizers, antistatic agents, flame retardants, slip agents, antifogging agents, lubricants, pigments, dyes, dispersants, copper inhibitors, neutralizing agents, bubble inhibitors, weld strength improvers, natural oils, synthetic oils, and waxes. Other elastomers and thermoplastic resins may also be used as additives in any proportion. These may be used alone or in combination of two or more.

[0160] [All-solid-state battery] Next, an embodiment of an all-solid-state battery using the all-solid-state battery binder will be described. The all-solid-state battery of this embodiment includes at least one layer selected from the group consisting of a positive electrode layer containing the all-solid-state battery binder, a solid electrolyte layer containing the all-solid-state battery binder, and a negative electrode layer containing the all-solid-state battery binder.

[0161] 1 is a schematic cross-sectional view showing an example of an all-solid-state battery according to this embodiment. This all-solid-state battery (all-solid-state battery) 100 includes a solid electrolyte layer 110, a positive electrode layer 140 and a negative electrode layer 150 sandwiching the solid electrolyte layer 110 from both sides, a positive electrode current collector 160 (disposed on the outside of the positive electrode) and a negative electrode current collector 170 (disposed on the outside of the negative electrode) sandwiching the laminate, and a battery exterior 180 housing them.

[0162] In this embodiment, by using the all-solid-state battery binder, it becomes possible to produce an all-solid-state battery with a reduced water content, thereby realizing an all-solid-state battery having a high electric capacity as a battery.

[0163] The amount of water contained in the all-solid-state battery is preferably 200 ppm or less, more preferably 100 ppm or less, even more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less. The water may be removed by drying in a dryer under normal or reduced pressure, or by storing in a dehumidified environment.

[0164] [Positive electrode] The positive electrode has a positive electrode current collector and a positive electrode layer formed on the positive electrode current collector. The positive electrode layer contains a positive electrode active material and, as needed, may contain a conductive aid, an all-solid-state battery binder, an inorganic solid electrolyte for enhancing ionic conductivity, a polymer gel electrolyte, a polymer electrolyte, an additive, or the like.

[0165] The positive electrode active material may be any positive electrode active material used in general lithium ion batteries, such as an oxide active material or a sulfide active material.

[0166] Specifically, layered rock salt type positive electrode materials include Li-Co composite oxides such as LiCoO2, Li-Ni composite oxides such as LiNiO2, nickel-based compounds derived from these, LiNi(Co,Al)O2, and ternary compounds such as LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiNi 0.8 Co 0.15 Al 0.05 O2, LiNi, a nickel-manganese compound 0.5 Mn 0.5 O2, lithium-rich compounds Li2MnO3-LiMO2 (M = Co, Ni, Mn), spinel-type positive electrode materials LiMn2O4, LiMn 1.5 Ni 0.5 O4, olivine-based cathode materials LiFeO2, LiCoPO4, LiNiPO4, LiFePO 4、Positive electrode materials that can be used include LiMnPO4, Li2MSiO4 (M is a transition metal), LiMPO4F (M is a transition metal), and high-capacity positive electrode materials such as vanadium oxide and sulfur. The positive electrode active material may be used alone or in combination of two or more.

[0167] The positive electrode is not particularly limited as long as it functions as a positive electrode for a lithium ion secondary battery, and can be obtained, for example, as follows.

[0168] First, the positive electrode active material is mixed with other components (e.g., a conductive additive, a binder, etc.) as needed to prepare a positive electrode mixture, which is dispersed in a solvent to prepare a positive electrode mixture-containing slurry. Next, this positive electrode mixture-containing slurry is applied to a positive electrode current collector (substrate), dried to form a positive electrode layer, and further pressed to adjust the thickness as needed, thereby producing a positive electrode.

[0169] The solid content concentration in the positive electrode mixture-containing slurry is not particularly limited, but is preferably 30 to 80 mass %, and more preferably 40 to 70 mass %.

[0170] The positive electrode current collector is made of, for example, a metal foil such as aluminum, stainless steel, gold, platinum, titanium, tin, copper, zinc, etc. These materials may be coated with carbon, or these materials may be processed into a mesh shape.

[0171] If necessary, a method can be used in which the spaces between the particles are filled with a lithium ion conductive material to maintain lithium ion conductivity with the solid electrolyte. Examples of the lithium ion conductive material include amorphous lithium ion conductive materials, and examples of amorphous lithium ion conductive materials include polymer electrolytes and amorphous inorganic compounds having lithium ion conductivity.

[0172] The amount of water contained in the positive electrode layer is preferably 200 ppm or less, more preferably 100 ppm or less, even more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less. The water may be removed by drying in a dryer under normal or reduced pressure, or by storing in a dehumidified environment.

[0173] [Negative electrode] The negative electrode has a negative electrode current collector and a negative electrode layer formed on the negative electrode current collector. The negative electrode layer contains a negative electrode active material and, as needed, may contain a conductive aid, an all-solid-state battery binder, an inorganic solid electrolyte for enhancing ionic conductivity, a polymer gel electrolyte, a polymer electrolyte, an additive, or the like.

[0174] The negative electrode preferably contains, as a negative electrode active material, one or more materials selected from the group consisting of materials capable of absorbing and releasing lithium ions and metallic lithium. Examples of such materials include metallic lithium, materials containing elements capable of forming an alloy with lithium, and other metal materials, as well as carbon materials typified by amorphous carbon (hard carbon), artificial graphite, natural graphite, graphite, pyrolytic carbon, coke, glassy carbon, baked bodies of organic polymer compounds, mesocarbon microbeads, carbon fiber, activated carbon, graphite, carbon colloid, and carbon black.

[0175] Among these, examples of coke include pitch coke, needle coke, petroleum coke, etc. The calcined body of an organic polymer compound is a carbonized product obtained by calcining a polymer material such as a phenol resin or a furan resin at an appropriate temperature.

[0176] The carbon material may contain, in addition to carbon, heterogeneous compounds containing O, B, P, N, S, SiC, BC, etc. The content of the heterogeneous compounds is preferably 0 to 10 mass % with respect to the total mass of the negative electrode active material.

[0177] The metallic material capable of forming an alloy with lithium may be a metal or semimetal simple substance, an alloy, or a compound, or may have one or more of these phases at least in part. Alternatively, SiOx, Li4Ti5O 12 Known materials such as oxide active materials can be used. The above-mentioned negative electrode active materials may be used alone or in combination of two or more.

[0178] The number average particle size (primary particle size) of the negative electrode active material is preferably 0.1 μm to 100 μm, and more preferably 1 μm to 10 μm.

[0179] The negative electrode can be obtained, for example, as follows. First, the negative electrode active material is mixed with other components (e.g., a conductive additive, a binder, etc.) as needed to form a negative electrode mixture, which is dispersed in a solvent to prepare a negative electrode mixture-containing slurry. Next, this negative electrode mixture-containing slurry is applied to a negative electrode current collector (substrate) and dried to form a negative electrode layer. Further, the thickness is adjusted by applying pressure as needed to produce a negative electrode.

[0180] The negative electrode mixture-containing slurry preferably has a solid content of 30 to 80 mass %, more preferably 40 to 70 mass %. The negative electrode current collector is made of a metal foil such as copper, nickel, stainless steel, gold, platinum, titanium, tin, or zinc.

[0181] If necessary, in order to maintain lithium ion conductivity with the solid electrolyte, a method of filling the spaces between the particles with a lithium ion conductive material can be used. Examples of the lithium ion conductive material include amorphous lithium ion conductive materials, and examples of the amorphous lithium ion conductive material include polymer electrolytes and amorphous inorganic compounds having lithium ion conductivity.

[0182] The amount of water contained in the negative electrode layer is preferably 200 ppm or less, more preferably 100 ppm or less, even more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less. The water may be removed by drying in a dryer under normal or reduced pressure, or by storing in a dehumidified environment.

[0183] 〔slurry〕 The slurry of the present embodiment that can be used as the positive electrode mixture-containing slurry or the negative electrode mixture-containing slurry contains the all-solid-state battery binder, and may also contain a conductive additive, a solvent, the positive electrode active material or the negative electrode active material, etc., as necessary.

[0184] The slurry of this embodiment preferably does not contain water, and the water content of the slurry is preferably 200 ppm or less, more preferably 100 ppm or less, even more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less. The water contained in the all-solid-state battery binder may be removed by drying in a dryer at normal pressure or reduced pressure, or by storing in a dehumidified environment.

[0185] (Conductive additive) The conductive additive of this embodiment is not particularly limited as long as it has electronic conductivity. Examples include graphite; carbon black, such as acetylene black and ketjen black; and carbon fibers, such as vapor-grown carbon fibers and carbon nanotubes. Among these, carbon black is preferred. The number-average particle size (primary particle size) of the conductive additive used in the positive electrode is preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm. The number-average particle size (primary particle size) of the conductive additive used in the negative electrode is preferably 0.1 μm to 100 μm, more preferably 1 μm to 10 μm. These additives may be used alone or in combination of two or more. The use of a conductive additive can ensure an electronic conduction path in each electrode layer, reduce the internal resistance of the all-solid-state battery, and increase the current flow, thereby improving the charge / discharge characteristics of the all-solid-state battery. By selecting the modifying group of the all-solid-state battery binder in accordance with the functional group on the surface of the conductive additive, dispersibility can be controlled through interaction. Since carboxyl groups and hydroxyl groups exist on the surface of the carbon-based conductive additive, the mutual carboxyl groups, hydroxyl groups and amino groups are preferred due to the interaction caused by hydrogen bonding.

[0186] Examples of carbon black include oil furnace black and gas furnace black, which are produced by the furnace method (incomplete combustion method), and acetylene black and thermal black, which are produced by the thermal method (thermal decomposition method). Among these, oil furnace black and acetylene black are preferred from the viewpoint of electronic conductivity. Examples of oil furnace black include Ketjenblack (a product manufactured by Lion Specialty Chemicals Co., Ltd.), and examples of acetylene black include Denka Black (registered trademark) (a product manufactured by Denka Co., Ltd.).

[0187] (binder) The binder of this embodiment is a conjugated diene polymer. Although not particularly limited, polymer materials other than conjugated diene polymers can also be used in combination. Specific examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid, styrene-butadiene rubber, and fluororubber. These may have functional groups due to modification. One or more binders may be used in combination.

[0188] The content of the all-solid-state battery binder contained in the positive electrode is not particularly limited, but from the viewpoint of ionic conductivity and electronic conductivity, when the total weight of the positive electrode (excluding the current collector) is taken as 100 wt%, the content is preferably 10 wt% or less, more preferably 5 wt% or less, even more preferably 3 wt% or less, and particularly preferably 1 wt% or less.

[0189] The content of the all-solid-state battery binder contained in the negative electrode is not particularly limited, but from the viewpoint of ionic conductivity and electronic conductivity, when the total weight of the negative electrode (excluding the current collector) is taken as 100 wt%, the content is preferably 10 wt% or less, more preferably 5 wt% or less, even more preferably 3 wt% or less, and particularly preferably 1 wt% or less.

[0190] The content of the all-solid-state battery binder contained in the solid electrolyte layer is not particularly limited, but from the viewpoint of ionic conductivity and electronic conductivity, it is preferably 10 wt % or less, more preferably 5 wt % or less, even more preferably 3 wt % or less, and particularly preferably 1 wt % or less, when the total weight of the solid electrolyte layer is taken as 100 wt %.

[0191] The all-solid-state battery binder may be distributed uniformly or non-uniformly in each layer, or may be distributed with a gradient, and may also be used for the purpose of bonding the interfaces of each layer as needed.

[0192] In all-solid-state batteries, the concentration distribution of the conductive additive contained in the positive electrode layer is not particularly limited. However, from the viewpoint of electronic conductivity, the concentration of the conductive additive near the positive electrode current collector is preferably higher than that near the solid electrolyte layer. During the charge / discharge process of an all-solid-state battery, the entire current of the positive electrode layer is concentrated near the positive electrode current collector. Therefore, by increasing the concentration of the conductive additive near the positive electrode current collector, it is possible to remove the bottleneck in the electronic conduction path of the positive electrode layer, thereby improving the charge / discharge load characteristics and cycle life characteristics of the battery.

[0193] In the all-solid-state battery according to this embodiment, the concentration of the conductive additive contained in the positive electrode layer is higher near the positive electrode current collector than near the solid electrolyte layer, and preferably the concentration of the conductive additive near the positive electrode current collector is at least 10 times higher than the concentration of the conductive additive near the solid electrolyte layer. During charge and discharge of the all-solid-state battery, electron conduction is more prevalent than lithium ion conduction near the positive electrode current collector. Therefore, it is preferable to increase the concentration of the conductive additive near the positive electrode current collector. This improves the electronic conductivity of the positive electrode layer during charge and discharge, resulting in good charge and discharge characteristics.

[0194] Furthermore, in the all-solid-state battery according to the present embodiment, the concentration distribution of the conductive additive contained in the anode layer is not particularly limited. However, from the viewpoint of electronic conductivity, the concentration of the conductive additive near the anode current collector is preferably higher than that near the solid electrolyte layer. During the charge / discharge process of the all-solid-state battery, the entire current of the anode layer is concentrated near the anode current collector. Therefore, by increasing the concentration of the conductive additive near the anode current collector, it is possible to remove the bottleneck in the electron conduction path of the anode layer, thereby improving the charge / discharge load characteristics and cycle life characteristics of the battery.

[0195] Furthermore, similar to the positive electrode layer, during charge and discharge of the all-solid-state battery, electron conduction is greater than lithium ion conduction near the negative electrode current collector. Therefore, in the negative electrode layer of this embodiment, the concentration of the conductive additive near the negative electrode current collector is preferably higher than that near the solid electrolyte layer, and preferably the concentration of the conductive additive near the negative electrode current collector is at least eight times that of the conductive additive near the solid electrolyte layer. This improves the electronic conductivity of the negative electrode layer during charge and discharge, thereby achieving good charge and discharge characteristics.

[0196] (solvent) The solvent of this embodiment is not particularly limited as long as it does not adversely affect the performance of the solid electrolyte, but examples thereof include non-polar solvents with low hydrophilicity. Examples of non-polar solvents include hydrocarbon solvents such as heptane, xylene, toluene, and hexane, or combinations thereof. From the viewpoint of suppressing decomposition of the solid electrolyte, preferably, a hydrocarbon organic solvent that has been dehydrated to reduce its water content is used. Furthermore, from the viewpoint of productivity, non-polar solvents having a boiling point of 100°C or higher and a melting point of 0°C or lower at atmospheric pressure are preferred, and more preferably, non-polar solvents having a boiling point of 150°C or higher and a melting point of -20°C or lower at atmospheric pressure are preferred.

[0197] [Solid electrolyte layer] The solid electrolyte layer of the present embodiment includes an ion-conductive solid electrolyte and, if necessary, an all-solid-state battery binder. The ion-conductive solid electrolyte is not particularly limited as long as it can be used in all-solid-state batteries, and examples thereof include sulfide-based solid electrolytes and oxide-based solid electrolytes.

[0198] Examples of sulfide-based solid electrolytes include sulfide-based amorphous solid electrolytes such as Li2S-SiS2, LiI-Li2S-SiS2, LiI-Li2S-P2S5, LiI-Li2SP2O5, LiI-Li3PO4-P2S5, and Li2S-P2S5. Examples of sulfide-based glass ceramic solid electrolytes include those containing Li2S and P2S5. Examples of Thio-LISICON-based solid electrolytes include Li 3.25 Ge 0.25 P 0.75 S 4、 Li 10 GeP2S 12 etc.

[0199] Oxide-based solid electrolytes include γ-LiPO4-type oxides, anti-fluorite-type oxides, and NASICON-type oxides. 1.3 Al 0.3 Ti 0.7 (PO4)3, perovskite-type Li 0.5La 0.5 TiO3, garnet-type Li7La3Zr2O 12 Examples of oxide-based amorphous solid electrolytes include LiPON, Li2O-B2O3-P2O5, Li2O-SiO2, etc. These may be used alone or in combination of two or more.

[0200] Among these, from the viewpoint of the balance between performance and production, it is preferable to use a sulfide-based solid electrolyte as the solid electrolyte.

[0201] The shape of the solid electrolyte is not particularly limited, and may be a particulate or thin film shape. In the case of particles, the average particle size is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 40 μm or less. As the particles become finer, the packing density improves and good ion conductivity is obtained. Furthermore, from the viewpoint of the physical strength of the solid electrolyte layer and prevention of short circuits, the particle size is preferably 0.1 μm or more.

[0202] Since solid electrolytes react with water and easily decompose, the amount of water contained in the solid electrolyte layer is preferably 200 ppm or less, more preferably 100 ppm or less, even more preferably 50 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less. Water may be removed by drying in a dryer under normal or reduced pressure, or by storing in a dehumidified environment.

[0203] The method for forming the solid electrolyte layer is not particularly limited, and the solid electrolyte layer can be obtained, for example, by press-molding a mixture containing the solid electrolyte or, if necessary, other components such as an all-solid-state battery binder, or by applying a slurry containing the solid electrolyte or, if necessary, a mixture containing other components such as an all-solid-state battery binder to a substrate, drying the slurry, and further applying pressure as necessary to adjust the thickness, followed by peeling the slurry from the substrate, thereby obtaining a solid electrolyte layer.

[0204] [Battery construction] The all-solid-state battery of this embodiment is fabricated by a known method using the above-described positive electrode, negative electrode, and solid electrolyte layer. For example, the electrode laminate may be fabricated as a laminate having a positive electrode, a negative electrode, and a solid electrolyte layer interposed therebetween, or as a multilayer laminate having an electron conductor interposed between multiple alternately stacked positive and negative electrodes. The electrode laminate is then housed in a battery case (exterior) and sealed, thereby fabricating the all-solid-state battery of this embodiment.

[0205] 0.1 to 4000 kgf / cm during battery production 2 It is preferable to apply a pressure of 0.1 to 100 kgf / cm to the opposing surfaces of the positive electrode and the negative electrode. 2 It is preferable to apply pressure of 0.5 to 15 kgf / cm 2 It is most preferable to apply pressure of 0.1 kgf / cm. 2 By setting the pressure at 4000 kgf / cm or more, the contact state between the electrode active material and the solid electrolyte is improved, and the battery characteristics are improved. 2 The following measures can prevent short circuits caused by internal damage to the battery: The battery can be operated while maintaining the pressurized state it was in when it was manufactured, but it can also be operated without pressurization if there are no problems with the charge / discharge characteristics.

[0206] The shape of the all-solid-state battery of this embodiment is not particularly limited, and suitable shapes include, for example, a cylindrical shape, an elliptical shape, a rectangular tube shape, a button shape, a coin shape, a flat shape, a laminate shape, etc. Furthermore, the solid electrolyte of this embodiment can be applied not only to the all-solid-state battery described above, but also to other batteries.

[0207] Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments and can be modified in various ways without departing from the spirit and scope of the present invention. [Example]

[0208] Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present embodiment is not limited in any way by the following examples and comparative examples.

[0209] The structures of the conjugated diene polymers and the methods for measuring and evaluating the physical properties of the conjugated diene polymer binders in the examples and comparative examples are shown below.

[0210] [Measurement and Evaluation of the Structure of Conjugated Diene Polymer and the Physical Properties of Conjugated Diene Polymer Binder] (1) Content of each polymer block in the conjugated diene polymer The content of each polymer block in the conjugated diene polymer before hydrogenation was calculated using the following formula, and the content of each polymer block in the conjugated diene polymer was calculated. Content of each block in the conjugated diene polymer before hydrogenation = [(total amount of monomers fed in each step) / (total amount of monomers)] x 100 (mass%)

[0211] However, it was confirmed that the polymerization rates of the butadiene monomer and the styrene monomer were 100% at each step in the polymerization process of the conjugated diene polymer as follows.

[0212] Approximately 20 mL of the polymer solution was sampled at each step of the polymerization process and injected into a 100 mL bottle containing 0.50 mL of n-propylbenzene (used as an internal standard) and approximately 20 mL of toluene. Each sample was measured using a gas chromatograph (Shimadzu Corporation: GC-14B (product name)) equipped with a backed column loaded with Apiezon grease. The amount of residual monomer in the polymer solution was determined from the previously obtained calibration curves for butadiene monomer and styrene monomer, confirming the absence of residual monomer.

[0213] The temperature conditions for the gas chromatography measurements were a constant 90°C for the polymerization rate of butadiene, and a temperature increase from 90°C (10 minute hold) to 150°C (10°C / min) for the polymerization rate of styrene.

[0214] (2) Amount of vinyl bonds in conjugated diene polymer before hydrogenation The vinyl bond amount of the conjugated diene polymer before hydrogenation was measured by proton nuclear magnetic resonance ( 1 H-NMR was used for the measurement.

[0215] Measurements were performed under the following conditions using an ECS400 (JEOL) measuring instrument, deuterated chloroform as the solvent, and a sample concentration of 50 mg / mL: The amount of vinyl bonds was calculated from the signal ratio between 1,4-bonds and 1,2-bonds after determining the integrated values ​​of the signals attributable to 1,4-bonds and 1,2-bonds in the conjugated diene monomer units. (Measurement conditions) Observation frequency: 400MHz Chemical shift reference: tetramethylsilane Pulse delay: 2.904 seconds Number of scans: 64 Pulse width: 45° Measurement temperature: 26℃

[0216] (3) Hydrogenation rate of conjugated diene polymer The hydrogenation rate of unsaturated bonds based on the conjugated diene monomer units of conjugated diene polymers was measured by proton nuclear magnetic resonance ( 1 The measurement conditions and the method of processing the measurement data were the same as those in (2) above.

[0217] The hydrogenation rate was calculated from the signal ratio obtained by integrating the signals at 4.5 to 5.5 ppm derived from double bonds and the signals derived from hydrogenated conjugated dienes.

[0218] (4) Sum of butylene and propylene contents of conjugated diene polymer The total amount of butylene and propylene relative to the total amount of conjugated diene monomer units (100 mol%) in the conjugated diene polymer was determined by proton nuclear magnetic resonance ( 1 The measurement conditions and data processing methods were the same as those in (2) and (3) above.

[0219] The amount of butylene was calculated from the signal ratio obtained by integrating the signals derived from all conjugated diene monomer units in the conjugated diene polymer after hydrogenation and the signals derived from the butylene portion (hydrogenated 1,2-bond) in the range of 0 to 2.0 ppm in the spectrum.

[0220] (5) Styrene content of conjugated diene polymer Using the copolymer before hydrogenation, calculation was made from the absorption intensity at 262 nm using an ultraviolet spectrophotometer (Shimadzu Corporation, UV-2450). Since the content of all vinyl aromatic compound monomer units does not change significantly before and after hydrogenation, the content of all vinyl aromatic compound monomer units (styrene monomer units) obtained for the copolymer before hydrogenation was taken as the content of all vinyl aromatic compound monomer units (total styrene content) of the hydrogenated copolymer.

[0221] (6) Content of polymer blocks mainly composed of styrene units in conjugated diene polymers (Os value) Using an unmodified conjugated diene polymer before hydrogenation, the content of polymer blocks mainly composed of styrene units in the conjugated diene polymer (hereinafter also referred to as "Os value") was measured by the osmium tetroxide decomposition method described in I. M. Kolthoff, et al., J. Polym. Soi. 1, 429 (1946).

[0222] For decomposition of the unmodified conjugated diene polymer before hydrogenation, a 0.1 g / 125 mL tertiary butanol solution of osmic acid was used.

[0223] (7) Conjugated diene polymer and weight average molecular weight and molecular weight distribution of the conjugated diene polymer The weight average molecular weight and molecular weight distribution of the conjugated diene polymer and the conjugated diene polymer were measured using GPC (GPC apparatus: HLC8220 (product name, manufactured by Tosoh Corporation), column: 4.6 mm × 30 cm TSKgel SUPER-HZM-N (product name, manufactured by Sigma-Aldrich Corporation)). Tetrahydrofuran was used as the solvent.

[0224] The weight-average molecular weight was determined from the peaks in the chromatogram based on a calibration curve obtained using commercially available standard polystyrene. When there were multiple peaks in the chromatogram, the weight-average molecular weight was calculated from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram). Conjugated diene polymers may be adsorbed to the column due to interactions between the modifying group and the column. In such cases, the molecular weight of the unadsorbed portion or the copolymer before modification is measured.

[0225] The molecular weight distribution was calculated from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The conjugated diene polymer may be adsorbed to the column due to the interaction between the modifying group and the column, in which case the molecular weight of the non-adsorbed portion is measured.

[0226] (8) Acid anhydride addition amount of conjugated diene polymer The amount of acid anhydride added to the conjugated diene polymer was calculated by dissolving the conjugated diene polymer after modification with the acid anhydride in toluene and titrating it with a methanol solution of sodium methoxide having a factor of 1±0.05.

[0227] (9) Modification rate of amine-terminated conjugated diene polymer The adsorption property of modified components was utilized in a GPC column packed with silica gel, and a sample solution containing a conjugated diene polymer and a low-molecular-weight internal standard polystyrene was analyzed. The ratio of the conjugated diene polymer to the standard polystyrene in the chromatogram measured in (6) above was compared with the ratio of the conjugated diene polymer to the standard polystyrene in the chromatogram measured using a silica-based column GPC [apparatus: LC-10 (Shimadzu Corporation), column: Zorbax (DuPont)], and the amount of adsorption to the silica-based column was calculated from the difference, and this ratio was taken as the modification rate. It was calculated using the following formula.

[0228]

number

[0229] a: Area (%) of the total polymer measured in polystyrene gel (PLgel) b: Area (%) of low molecular weight internal standard PS measured on polystyrene gel (PLgel). c: Area (%) of total polymer measured on a silica-based column (Zorbax) d: Area (%) of low molecular weight internal standard PS measured on a silica-based column (Zorbax)

[0230] (10) Toluene insolubles 1 g of the conjugated diene polymer was placed in a test tube-shaped container made of 200 mesh wire, and the container was immersed in 100 mL of toluene and shaken for 24 hours or more using a shaker. Once the polymer was fully dissolved, the container was removed, washed with toluene from the outside, and dried in a vacuum dryer for 12 hours at 60° C. Using the weight W1 of the resulting container, the weight W0 of the container before the test, and the weighed value P of the conjugated diene polymer, the toluene-insoluble content was calculated according to the following formula: Insoluble fraction (%)=(W1-W0) / P×100

[0231] (11) Loose bulk density and compressibility The evaluation was carried out using a Powder Tester PT-X (manufactured by Hosokawa Micron Corporation). 3The conjugated diene polymer was poured into a bulk density measuring vessel in such a way that it exceeded the top surface, the excess was removed, and the loose bulk density was calculated from the weight at that time and the volume of the vessel. Furthermore, the pouring of the conjugated diene polymer into a vessel in such a way that it exceeded the top surface and tapping were repeated 180 times to calculate the compacted bulk density. The compressibility was evaluated using the following formula: Compressibility = (tight bulk density - loose bulk density) / tight bulk density x 100

[0232] (12) Solvent solubility when using a mixer 10 g of the conjugated diene polymer and toluene were placed in a glass screw vial having an internal volume of 200 mL, and the mixture was stirred with a magnetic stirrer for 5 minutes, after which the solubility was evaluated. (Evaluation criteria) ○: No residue left behind △: 0% to less than 20% remains undissolved ×: 20% or more remains undissolved

[0233] (13) Thermal stability The polymer was dried at 100°C for 48 hours, and the thermal stability was evaluated from the decrease in peak height in the differential molecular weight distribution of the GPC chart before and after heating. (Evaluation criteria) ○: Less than 0.1% △: 0.1% or more to less than 0.3% ×: 0.3% or more

[0234] (14) Feed Stability Assuming material supply, the error range relative to the set value when discharging all-solid-state battery binder using a single-axis screw feeder was evaluated. All-solid-state battery binder was discharged from the feeder at a set value of 5 kg / h for 5 minutes, and the sum of the absolute values ​​of the error from the set value recorded every 3 seconds was averaged by the number of records, and the percentage of error relative to the set value was evaluated. (Evaluation criteria) ○: Less than 0.5% △: 0.5% or more to less than 1.0% ×: 1.0% or more

[0235] (15) Interfacial peel strength (adhesion) between conjugated diene polymer and aluminum sheet The interfacial peel strength between a conjugated diene polymer and an aluminum sheet was measured by a 180° peel test using a multilayer structure obtained by thermally welding a conjugated diene polymer to an aluminum sheet. Specifically, a 1 mm-thick aluminum sheet and a 2 mm-thick conjugated diene polymer sheet were stacked and fixed in a 2 mm-thick mold, preheated to 200°C for 5 minutes without pressure, then hot-pressed at 200°C for 2 minutes at 10 MPa, and then cold-pressed at 20°C for 3 minutes at 10 MPa to produce a multilayer structure consisting of a 1 mm-thick aluminum sheet and a 1 mm-thick conjugated diene polymer. A 10 mm-wide slit was made in the surface of the resulting multilayer structure facing the conjugated diene polymer, and the edge of the conjugated diene polymer layer was peeled off by several centimeters. The peeled portion of the conjugated diene polymer layer and the aluminum sheet were separately fixed in the chucks of a tensile tester (MinebeaMitsumi Inc., TGE-500N (product name)). The peeled portion of the layer made of conjugated diene polymer and the aluminum sheet were pulled in a direction of 180° at 300 mm / min to peel the two layers apart. The tensile force applied during peeling was taken as the interfacial peel strength (N / cm) of the multilayer body of the conjugated diene polymer and the aluminum sheet, and was evaluated according to the following criteria. (Evaluation criteria) ○:10N / cm or more △: 3N / cm or more and less than 10N / cm ×: Less than 3N / cm

[0236] (16) Adhesion strength per modified group It was calculated using the following formula. Adhesion strength per modified group contained in 1 g of polymer (N cm -1 / g) = Interfacial peel strength (N cm -1 ) / (1g x mass% of modifying group / 100)

[0237] (17) Binding properties of conjugated diene polymer binders 0.15 g of conjugated diene polymer, 0.35 g of acetylene black, and 4.5 g of toluene were stirred at 2000 rpm for 2 minutes, and an appropriate amount of toluene was added to adjust the viscosity to obtain a slurry. This slurry was applied to aluminum foil with an applicator, left to stand on a hot plate, dried at 50°C for 5 minutes, and then further dried at 70°C for 10 hours to obtain an electrode in which the electrode layer and current collector were integrated.

[0238] The electrode was wound around a SUS rod with a diameter of 10 mm, and the state of the curved electrode layer was visually observed to evaluate the binding ability of the binder. (Evaluation criteria) ○: No cracks in the electrode layer, showing strong adhesion △: Cracks occurred in part of the electrode layer, and moderate adhesion was observed ×: Cracks occurred throughout the electrode layer, showing weak adhesion

[0239] (18) Smoothness of the coating film The slurry for evaluating the binding property was applied to an aluminum foil, and the surface irregularities were visually observed and evaluated. (Evaluation criteria) ○: No unevenness △: Some unevenness ×: There are irregularities throughout the surface

[0240] (19) Volatility of Conjugated Diene Polymer Binder Solutions 0.3 g of conjugated diene polymer and 10 mL of toluene were placed in a 30 mL glass screw vial and shaken with a shaker to obtain a homogeneous solution. The vial containing the solution was left uncovered in a draft at 24°C and the weight of the solvent evaporated after 10 hours was measured to evaluate the storage stability of the binder solution. (Evaluation criteria) ◎: Less than 3g, and the composition changes little when stored as a binder solution or slurry ○: 3g or more and less than 5g, and the composition changes during storage as a binder solution or slurry are moderate △: 5g or more but less than 7g, and the composition changes significantly during storage as a binder solution or slurry ×: 7 g or more, and the composition changes significantly during storage as a binder solution or slurry

[0241] (20) Conductive additive dispersibility 0.2 g of conjugated diene polymer, 0.4 g of acetylene black, and 19.4 g of toluene were placed in a 30 mL glass screw vial, shaken for 1 hour using a shaker, and then visually observed while left to stand to evaluate the dispersion state of the acetylene black. (Evaluation criteria) 〇: Acetylene black is dispersed △: Acetylene black aggregates were observed, occupying less than 20% of the vial wall above the liquid surface. ×: Acetylene black was observed to have aggregated, occupying 20% ​​or more of the vial wall above the liquid surface.

[0242] (21) Storage stability of conjugated diene polymer binder Conjugated diene polymers were stored in an environment of 23°C / 50% humidity for one day, and the IR before and after storage was (Evaluation criteria) Yes: There is a change in IR due to functional groups. None: No change in IR due to functional groups.

[0243] (22) Electrochemical stability of electrode layers containing conjugated diene-based polymer binders 0.15 g of conjugated diene polymer, 0.35 g of acetylene black, and 4.5 g of toluene were stirred at 2000 rpm for 2 minutes with a stirrer, and then an appropriate amount of toluene was added to adjust the viscosity, and the mixture was stirred at 2000 rpm for 2 minutes to obtain a slurry. This slurry was applied to platinum foil with an applicator, left to stand on a hot plate, dried at 50°C for 5 minutes, and then further dried at 70°C for 10 hours to obtain an oxidation side evaluation electrode in which the electrode layer and current collector were integrated.

[0244] Separately, 0.5 g of the conjugated diene polymer and 4.5 g of toluene were stirred at 2000 rpm for 2 minutes using a stirrer to obtain a slurry, which was then applied to a platinum foil with an applicator, placed on a hot plate, dried at 50°C for 5 minutes, and further dried at 70°C for 10 hours to obtain an electrode for evaluation on the reduction side, in which the electrode layer and current collector were integrated.

[0245] In a glove box under an argon atmosphere with a dew point controlled to below -60°C, a measurement laminate cell was fabricated by placing a platinum lead connected to an oxidation-side electrode or reduction-side electrode (each 14 mm x 20 mm square) that combined a conjugated diene polymer binder-containing electrode layer and a current collector. A platinum lead was attached to the working electrode, a nickel lead was attached to the lithium metal sheet for current extraction, and a nickel lead was attached to the lithium metal sheet for current extraction. A microporous membrane separator and a laminated sheet of glass nonwoven fabric served as separators between the electrodes. These were then housed in an aluminum laminate sheet case. 1M LiPF6 / (ethylene carbonate / methyl ethyl carbonate (=30 wt% / 70 wt%)) electrolyte was poured into the case, and the case was then sealed to prepare a measurement laminate cell. Measurements were performed using this cell under the following conditions. (conditions) Measurement method: Linear sweep voltammetry Sweep speed; 2mV / sec Voltage range: (oxidation side) 3.0V (initial voltage) - 5.4V (final voltage) vs. Li / Li + / V (Reducing side) 3.0V (initial voltage) - 0.0V (final voltage) vs. Li / Li + / V Electrode area: 2.8cm 2 (14mm x 20mm) Temperature; 25℃

[0246] The electrochemical stability of the electrode layer containing the conjugated diene polymer binder was 3.0 V (vs. Li / Li) on the oxidation side. + / V) or more, the voltage when the current value is 0.0005A / mg or more is 4.6V (vs. Li / Li+ / V) or higher is considered a pass (〇), and the reduction side is considered to be 3.0V (vs. Li / Li + / V), the voltage at which the current value is -0.00005A / mg or less is 0.1V (vs. Li / Li + If it is less than / V, it is considered a pass (〇).

[0247] (23) Water content of conjugated diene polymers Using a Karl Fischer moisture meter, measure the sample weight at 1.50 g, vaporizer temperature at 200°C, and carrier gas (nitrogen) at 250 mL / min. If the moisture content is 200 ppm or less, it is considered to be a pass (◯).

[0248] (Preparation of hydrogenation catalyst) The hydrogenation catalyst used in the hydrogenation reaction of the conjugated diene polymer was prepared by the following method. 1 L of dried and purified cyclohexane was placed in a nitrogen-substituted reaction vessel, and 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. With sufficient stirring, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was allowed to react at room temperature for approximately 3 days to obtain a hydrogenation catalyst.

[0249] [Production of Conjugated Diene Block Copolymer] [Manufacturing Example 1] (Production of conjugated diene block copolymer (a-1)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.13 parts by mass of n-butyllithium was added relative to 100 parts by mass of the total monomers. 0.3 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was also added relative to 1 mol of n-butyllithium.

[0250] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added to the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 68 parts by mass of butadiene was added and polymerized at 70°C for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene was added and polymerized at 70°C for 45 minutes. After the reaction was completed, methanol was added, and a conjugated diene-based block copolymer was obtained as step 1.

[0251] The resulting conjugated diene block copolymer had a styrene content of 32% by mass, a polystyrene block content of 32% by mass, and a vinyl bond content of 36% by mol in the butadiene portion.

[0252] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the titanium-equivalent concentration relative to the conjugated diene block copolymer was 100 ppm, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0253] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer.

[0254] The obtained hydrogenated conjugated diene block copolymer (a-1) had a styrene content of 32 mass %, a butylene content of 36 mol %, a weight average molecular weight of 69,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0255] [Manufacturing Example 2] (Production of conjugated diene block copolymer (a-2)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.12 parts by mass of n-butyllithium was added relative to 100 parts by mass of the total monomers. Furthermore, 0.3 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was added relative to 1 mol of n-butyllithium.

[0256] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 9.5 parts by mass of styrene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added to the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 81 parts by mass of butadiene was added and polymerized at 70°C for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 9.5 parts by mass of styrene was added and polymerized at 70°C for 45 minutes. After the reaction was completed, methanol was added, and a conjugated diene-based block copolymer was obtained as step 1.

[0257] The resulting conjugated diene block copolymer had a styrene content of 19% by mass, a polystyrene block content of 19% by mass, and a vinyl bond content of 36% by mol in the butadiene portion.

[0258] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the titanium-equivalent concentration relative to the conjugated diene block copolymer was 100 ppm, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0259] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer.

[0260] The obtained hydrogenated conjugated diene block copolymer (a-2) had a styrene content of 19 mass %, a butylene content of 36 mol %, a weight average molecular weight of 85,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0261] [Manufacturing Example 3] (Production of conjugated diene-based block copolymer (a-3)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.08 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomers. Furthermore, 0.5 mol of TMEDA (tetramethylethylenediamine) was added per 1 mol of n-butyllithium.

[0262] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added to the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 87 parts by mass of butadiene was added and polymerized at 50°C for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene was added and polymerized at 70°C for 45 minutes. After the reaction was completed, methanol was added to obtain a conjugated diene-based block copolymer.

[0263] The obtained conjugated diene block copolymer had a styrene content of 13% by mass, a polystyrene block content of 13% by mass, and a vinyl bond content of 45% by mol in the butadiene part.

[0264] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the titanium-equivalent concentration relative to the conjugated diene block copolymer was 100 ppm, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0265] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer.

[0266] The obtained hydrogenated conjugated diene block copolymer (a-3) had a styrene content of 13 mass %, a butylene content of 45 mol %, a weight average molecular weight of 80,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0267] [Manufacturing Example 4] (Production of conjugated diene block copolymer (a-4)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.11 parts by mass of n-butyllithium per 100 parts by mass of the total monomers was added. Furthermore, 1.5 mol of TMEDA (tetramethylethylenediamine) per 1 mol of n-butyllithium and 0.05 mol of sodium t-pentoxide per 1 mol of n-butyllithium were added.

[0268] Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added, and polymerization was carried out at 70°C for 20 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 9 parts by mass of styrene was added, and polymerization was carried out at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 77 parts by mass of butadiene was added, and polymerization was carried out at 50°C for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 9 parts by mass of styrene was added, and polymerization was carried out at 70°C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer.

[0269] The obtained conjugated diene block copolymer had a styrene content of 18% by mass, a polystyrene block content of 18% by mass, and a vinyl bond content of 73 mol% in the butadiene portion.

[0270] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the titanium-equivalent concentration relative to the conjugated diene block copolymer was 100 ppm, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C. After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce an unmodified, hydrogenated conjugated diene block copolymer (a-4).

[0271] The obtained hydrogenated conjugated diene block copolymer (a-4) had a styrene content of 18 mass %, a butylene content of 73 mol %, a weight average molecular weight of 107,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0272] [Manufacturing Example 5] (Production of conjugated diene block copolymer (a-5)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.07 parts by mass of n-butyllithium per 100 parts by mass of the total monomers was added. Furthermore, 1.8 mol of TMEDA (tetramethylethylenediamine) per 1 mol of n-butyllithium and 0.05 mol of sodium t-pentoxide per 1 mol of n-butyllithium were added.

[0273] Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added, and polymerization was carried out at 70°C for 20 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 7 parts by mass of styrene was added, and polymerization was carried out at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 82 parts by mass of butadiene was added, and polymerization was carried out at 50°C for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6 parts by mass of styrene was added, and polymerization was carried out at 70°C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer.

[0274] The resulting conjugated diene block copolymer had a styrene content of 13% by mass, a polystyrene block content of 13% by mass, and a vinyl bond content of 78 mol% in the butadiene portion.

[0275] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration relative to the block copolymer was 100 ppm, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0276] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer (a-5).

[0277] The obtained hydrogenated conjugated diene block copolymer (a-5) had a styrene content of 13 mass %, a butylene content of 78 mol %, a weight average molecular weight of 160,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0278] [Manufacturing Example 6] (Production of conjugated diene block copolymer (a-6)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.07 parts by mass of n-butyllithium per 100 parts by mass of the total monomers was added. Furthermore, 1.8 mol of TMEDA (tetramethylethylenediamine) per 1 mol of n-butyllithium and 0.05 mol of sodium t-pentoxide per 1 mol of n-butyllithium were added.

[0279] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added, and polymerization was carried out at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 87 parts by mass of butadiene was added, and polymerization was carried out at 50°C for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene was added, and polymerization was carried out at 70°C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer.

[0280] The resulting conjugated diene block copolymer had a styrene content of 13% by mass, a polystyrene block content of 13% by mass, and a vinyl bond content of 78 mol% in the butadiene portion.

[0281] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration relative to the block copolymer was 100 ppm, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0282] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer (a-6).

[0283] The obtained hydrogenated conjugated diene block copolymer (a-6) had a styrene content of 13 mass %, a butylene content of 78 mol %, a weight average molecular weight of 160,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0284] [Manufacturing Example 7] (Production of conjugated diene block copolymer (a-7)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.05 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomers. Furthermore, 0.05 mol of TMEDA (tetramethylethylenediamine) was added per 1 mol of n-butyllithium.

[0285] Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 10 parts by mass of butadiene (relative to 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added, and polymerization was carried out at 65°C for 20 minutes. Next, 1.50 mol of TMEDA per 1 mol of n-butyllithium and 0.05 mol of sodium t-pentoxide per 1 mol of n-butyllithium were added, and then a cyclohexane solution (butadiene concentration: 20% by mass) containing 85 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 70 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 5 parts by mass of styrene was added, and polymerization was carried out at 65°C for 15 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer.

[0286] The obtained conjugated diene block copolymer had a styrene content of 5% by mass, a polystyrene block content of 5% by mass, and a vinyl bond content of 78 mol% in the polymer block mainly composed of conjugated diene monomer units (hereinafter also referred to as the "butadiene portion").

[0287] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene-based block copolymer so that the titanium-equivalent concentration relative to the block copolymer was 100 ppm, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0288] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer (a-7).

[0289] The obtained hydrogenated conjugated diene block copolymer (a-7) had a styrene content of 5 mass %, a butylene content of 78 mol %, a weight average molecular weight of 249,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0290] [Manufacturing Example 8] (Production of conjugated diene block copolymer (a-8)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.10 parts by mass of n-butyllithium per 100 parts by mass of the total monomers was added. Furthermore, 1.8 mol of TMEDA (tetramethylethylenediamine) per 1 mol of n-butyllithium and 0.05 mol of sodium t-pentoxide per 1 mol of n-butyllithium were added.

[0291] Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added, and polymerization was carried out at 70°C for 20 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 21.5 parts by mass of styrene was added, and polymerization was carried out at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 52 parts by mass of butadiene was added, and polymerization was carried out at 50°C for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 21.5 parts by mass of styrene was added, and polymerization was carried out at 70°C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer.

[0292] The obtained conjugated diene block copolymer had a styrene content of 43% by mass, a polystyrene block content of 43% by mass, and a vinyl bond content of 78 mol% in the butadiene portion.

[0293] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained block copolymer so that the concentration in terms of titanium based on the block copolymer was 100 ppm, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0294] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer (a-8).

[0295] The obtained hydrogenated conjugated diene block copolymer (a-8) had a styrene content of 43 mass%, a butylene content of 78 mol%, a weight average molecular weight of 103,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0296] [Manufacturing Example 9] (Production of conjugated diene block copolymers (a-9-1 to a-9-13)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.04 parts by mass of n-butyllithium was added relative to 100 parts by mass of the total monomers. 0.3 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was also added relative to 1 mol of n-butyllithium.

[0297] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added to the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 68 parts by mass of butadiene was added and polymerized at 70°C for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene was added and polymerized at 70°C for 45 minutes. After the reaction was completed, methanol was added, and a conjugated diene-based block copolymer was obtained as step 1.

[0298] The resulting conjugated diene block copolymer had a styrene content of 32% by mass, a polystyrene block content of 32% by mass, and a vinyl bond content of 36% by mol in the butadiene portion.

[0299] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the titanium-equivalent concentration relative to the conjugated diene block copolymer was 100 ppm, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0300] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer.

[0301] The obtained hydrogenated conjugated diene block copolymer (a-9-1) had a styrene content of 32 mass%, a butylene content of 36 mol%, a weight average molecular weight of 285,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0302] Tris(2,4-di-tert-butylphenoxy)phosphine was added to (a-9-1) so that the concentration was 10 ppm, 50 ppm, and 100 ppm in terms of phosphorus atoms, to obtain (a-9-2), (a-9-3), and (a-9-4), respectively.

[0303] The resulting hydrogenated block copolymer solution was subjected to the decalcification procedure described below to reduce the amount of metals originating from the initiator and hydrogenation catalyst. Specifically, after the decalcification, 30 parts by mass of a water / sulfuric acid mixed solution was added to 100 parts by mass of the hydrogenated block copolymer. The amount of sulfuric acid added was adjusted so that the pH of the water removed by decanting in a subsequent process would be 7.0. Most of the water was removed by decanting the solution until the water content was reduced to 3 parts by mass, and 0.4 mol of carbon dioxide gas was added per 1 mol of the metal initiator and mixed. Then, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer. The solution was subjected to the steam stripping method described in JP-B-05-54845 (a method in which most of the solvent is removed in water at 90 to 98°C, and then the aqueous dispersion slurry with a crumb concentration of approximately 5% by weight is fed into a twin-screw extruder to remove the solvent), thereby obtaining hydrogenated block copolymers (a-9-5) and (a-9-6).

[0304] The obtained hydrogenated conjugated diene block copolymer (a-9-1) was freeze-pulverized to obtain (a-9-7) to (a-9-11) each having a loose bulk density and dispersity shown in the table.

[0305] The obtained hydrogenated conjugated diene block copolymer (a-9-1) was freeze-pulverized, and (a-9-12) and (a-9-13) were obtained by adding 1000 ppm of amorphous silica and calcium stearate to the conjugated diene block copolymer having the loose bulk density and dispersity shown in the table.

[0306] [Manufacturing Example 10] (Production of amine-conjugated diene polymer) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.13 parts by mass of n-butyllithium was added relative to 100 parts by mass of the total monomers. Furthermore, 0.3 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was added relative to 1 mol of n-butyllithium.

[0307] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (relative to 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added to the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 68 parts by mass of butadiene was added and polymerized at 70°C for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene was added and polymerized at 70°C for 45 minutes. Next, 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added in an amount equimolar to 1 mol of n-butyllithium, and the mixture was reacted at 70°C for 10 minutes. After the reaction was completed, methanol was added, and a modified conjugated diene-based block copolymer was obtained (step 1). The resulting conjugated diene-based block copolymer had a styrene content of 32% by mass, a polystyrene block content of 32% by mass, and a vinyl bond content of 36 mol% in the butadiene moiety.

[0308] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained modified conjugated diene block copolymer so that the titanium-equivalent concentration relative to the modified conjugated diene block copolymer was 100 ppm, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0309] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the modified conjugated diene block copolymer to produce a hydrogenated modified conjugated diene block copolymer.

[0310] The obtained hydrogenated conjugated diene block copolymer (a-10) had a styrene content of 32 mass%, a butylene content of 36 mol%, a weight-average molecular weight of 75,000, a molecular weight distribution of 1.2, a hydrogenation rate of 72 mol%, and a modification rate of 65% (the number of modifying groups per polymer chain was 0.65).

[0311] [Production of modified conjugated diene block copolymer] A conjugated diene polymer was produced using the following materials. Maleic anhydride (Fuso Chemical Co., Ltd.) Radical initiator: Perhexa 25B (NOF Corporation)

[0312] [Manufacturing Example 11] (Production of modified conjugated diene block copolymer (aa-1)) <Process 3> 100 parts by mass of the pelletized hydrogenated conjugated diene polymer (a-1), 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B were dry blended and melt-kneaded in a twin-screw extruder TEX30 (manufactured by The Japan Steel Works, Ltd.) at a cylinder temperature of 210°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to produce a maleic anhydride conjugated diene polymer (aa-1).

[0313] [Manufacturing Example 12] (Production of modified conjugated diene block copolymer (aa-2a)) <Process 3> A conjugated diene polymer (aa-2a) was produced in the same manner as in Production Example 11, except that 100 parts by mass of the pelletized hydrogenated conjugated diene polymer (a-2), 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B were dry-blended.

[0314] [Manufacturing Example 13] (Production of modified conjugated diene block copolymer (aa-2b)) <Process 3> A maleic anhydride conjugated diene polymer (aa-2b) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of the pelletized hydrogenated conjugated diene polymer (a-2), 4.2 parts by mass of maleic anhydride, and 0.48 parts by mass of Perhexa 25B.

[0315] [Manufacturing Example 14] (Production of modified conjugated diene block copolymer (aa-3)) <Process 3> A maleic anhydride conjugated diene polymer (aa-3) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of pelletized hydrogenated conjugated diene polymer (a-3), 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B.

[0316] [Manufacturing Example 15] (Production of modified conjugated diene block copolymer (aa-4)) <Process 3> A maleic anhydride conjugated diene polymer (aa-4) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of the pelletized hydrogenated conjugated diene polymer (a-4), 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B.

[0317] [Manufacturing Example 16] (Production of modified conjugated diene block copolymer (aa-5)) <Process 3> A maleic anhydride conjugated diene polymer (aa-5) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of pelletized hydrogenated conjugated diene polymer (a-5), 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B.

[0318] [Manufacturing Example 17] (Production of modified conjugated diene block copolymer (aa-6)) <Process 3> A maleic anhydride conjugated diene polymer (aa-6) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of the pelletized hydrogenated conjugated diene polymer (a-6), 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B.

[0319] [Manufacturing Example 18] (Production of modified conjugated diene block copolymer (aa-7)) <Process 3> A maleic anhydride conjugated diene polymer (aa-7) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of the pelletized hydrogenated conjugated diene polymer (a-7), 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B.

[0320] [Manufacturing Example 19] (Production of modified conjugated diene block copolymer (aa-8)) <Process 3> A maleic anhydride conjugated diene polymer (aa-8) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of the pelletized hydrogenated conjugated diene polymer (a-8), 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B.

[0321] [Manufacturing Example 20] (Production of modified conjugated diene block copolymer (aa-9)) <Process 3> A maleic anhydride conjugated diene polymer (aa-9) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of pelletized hydrogenated conjugated diene polymer (a-9), 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B, and the cylinder set temperature was changed to 240°C.

[0322] [Manufacturing Example 21] (Production of conjugated diene block copolymer (a-11)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.04 parts by mass of n-butyllithium was added relative to 100 parts by mass of the total monomers. 0.3 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was also added relative to 1 mol of n-butyllithium.

[0323] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (based on 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added to the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 68 parts by mass of butadiene was added and polymerized at 70°C for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene was added and polymerized at 70°C for 45 minutes. After the reaction was completed, methanol was added, and a conjugated diene-based block copolymer was obtained as step 1.

[0324] The resulting conjugated diene block copolymer had a styrene content of 32% by mass, a polystyrene block content of 32% by mass, and a vinyl bond content of 36% by mol in the butadiene portion.

[0325] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the titanium-equivalent concentration relative to the conjugated diene block copolymer was 100 ppm, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0326] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer.

[0327] The obtained hydrogenated conjugated diene block copolymer (a-11) had a styrene content of 32 mass %, a butylene content of 36 mol %, a weight average molecular weight of 287,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 75 mol %.

[0328] [Manufacturing Examples 22-25] (Production of conjugated diene block copolymers (a-12 to 15)) The production was carried out in the same manner as in Production Example 9, except for adjusting the amounts of n-butyllithium and TMEDA.

[0329] The resulting hydrogenated conjugated diene block copolymer (a-12) had a styrene content of 32% by mass, a butylene content of 36 mol%, a weight-average molecular weight of 190,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%. (a-13-1) had a styrene content of 32% by mass, a butylene content of 36 mol%, a weight-average molecular weight of 351,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%. (a-14) had a styrene content of 32% by mass, a butylene content of 58 mol%, a weight-average molecular weight of 351,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%. (a-15-1) had a styrene content of 32% by mass, a butylene content of 36 mol%, a weight-average molecular weight of 451,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0330] Tris(2,4-di-tert-butylphenoxy)phosphine was added to (a-13-1) so that the concentration was 10 ppm, 50 ppm, and 100 ppm in terms of phosphorus atoms, to obtain (a-13-2), (a-13-3), and (a-13-4), respectively.

[0331] The resulting hydrogenated block copolymer solution was subjected to the decalcification procedure described below to reduce the amount of metals originating from the initiator and hydrogenation catalyst. Specifically, after the decalcification, 30 parts by mass of a water / sulfuric acid mixed solution was added to 100 parts by mass of the hydrogenated block copolymer. The amount of sulfuric acid added was adjusted so that the pH of the water removed by decanting in a subsequent process would be 7.0. Most of the water was removed by decanting the solution until the water content was reduced to 3 parts by mass, and 0.4 mol of carbon dioxide gas was added per 1 mol of the metal initiator and mixed. Then, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer. The solution was subjected to the steam stripping method described in JP-B-05-54845 (a method in which most of the solvent is removed in water at 90 to 98°C, and then the aqueous dispersion slurry with a crumb concentration of approximately 5% by weight is fed into a twin-screw extruder to remove the solvent), thereby obtaining hydrogenated block copolymers (a-13-5) and (a-13-6).

[0332] The obtained hydrogenated conjugated diene block copolymer (a-13-1) was freeze-pulverized to obtain (a-13-7) to (a-13-11), each having a loose bulk density and dispersity as shown in the table.

[0333] The obtained hydrogenated conjugated diene block copolymer (a-13-1) was freeze-pulverized, and (a-13-12) and (a-13-13) were obtained by adding 1000 ppm of amorphous silica and calcium stearate to the conjugated diene block copolymer having the loose bulk density and dispersity shown in the table.

[0334] Tris(2,4-di-tert-butylphenoxy)phosphine was added to (a-15-1) so that the concentration was 10 ppm, 50 ppm, and 100 ppm in terms of phosphorus atoms, to obtain (a-15-2), (a-15-3), and (a-15-4), respectively.

[0335] The resulting hydrogenated block copolymer solution was subjected to the decalcification procedure described below to reduce the amount of metals originating from the initiator and hydrogenation catalyst. Specifically, after the decalcification, 30 parts by mass of a water / sulfuric acid mixed solution was added to 100 parts by mass of the hydrogenated block copolymer. The amount of sulfuric acid added was adjusted so that the pH of the water removed by decanting in a subsequent process would be 7.0. Most of the water was removed by decanting the solution until the water content was reduced to 3 parts by mass, and 0.4 mol of carbon dioxide gas was added per 1 mol of the metal initiator and mixed. Then, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer. The solution was subjected to the steam stripping method described in JP-B-05-54845 (a method in which most of the solvent is removed in water at 90 to 98°C, and then the aqueous dispersion slurry with a crumb concentration of approximately 5% by weight is fed into a twin-screw extruder to remove the solvent), thereby obtaining hydrogenated block copolymers (a-15-5) and (a-15-6).

[0336] The obtained hydrogenated conjugated diene block copolymer (a-15-1) was freeze-pulverized to obtain (a-15-7) to (a-15-11), each having a loose bulk density and dispersity as shown in the table.

[0337] The obtained hydrogenated conjugated diene block copolymer (a-15-1) was freeze-pulverized to obtain (a-15-12) and (a-15-13), respectively, in which amorphous silica and calcium stearate were added to the conjugated diene block copolymer with the loose bulk density and dispersity values ​​shown in the table.

[0338] [Manufacturing Example 26] (Production of conjugated diene block copolymer (a-16)) Production was carried out in the same manner as in Production Example 9, except that the amount of n-butyllithium was changed and styrene was introduced in increments of 9.5 parts by mass.

[0339] The obtained hydrogenated conjugated diene block copolymer (a-16) had a styrene content of 19 mass %, a butylene content of 36 mol %, a weight average molecular weight of 352,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0340] [Manufacturing Example 27] (Production of conjugated diene block copolymer (a-17)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.04 parts by mass of n-butyllithium was added relative to 100 parts by mass of the total monomers. 0.3 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was also added relative to 1 mol of n-butyllithium.

[0341] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 15 parts by mass of styrene (relative to 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added to the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution (total concentration of butadiene and isoprene: 20% by mass) containing 35 parts by mass of butadiene and 35 parts by mass of isoprene was added and polymerized at 70°C for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 15 parts by mass of styrene was added and polymerized at 70°C for 45 minutes. After the reaction was completed, methanol was added, and a conjugated diene-based block copolymer was obtained as step 1.

[0342] The resulting conjugated diene block copolymer had a styrene content of 30% by mass, a polystyrene block content of 30% by mass, and a vinyl bond content of 36 mol% in the butadiene / isoprene portion.

[0343] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the titanium-equivalent concentration relative to the conjugated diene block copolymer was 100 ppm, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0344] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer.

[0345] The obtained hydrogenated conjugated diene block copolymer (a-17) had a styrene content of 30 mass %, a butylene content of 36 mol %, a weight average molecular weight of 450,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol %.

[0346] [Manufacturing Example 28] (Production of conjugated diene block copolymer (a-18)) <Process 1> Batch polymerization was carried out using a 10 L tank reactor equipped with a stirrer and a jacket. 1 L of cyclohexane was placed in the reactor, and 0.056 parts by mass of n-butyllithium was added relative to 100 parts by mass of the total monomers. 1.2 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was also added relative to 1 mol of n-butyllithium.

[0347] Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 20 parts by mass of styrene (relative to 100 parts by mass of total monomers; the same applies hereinafter in this paragraph) was added to the reactor and polymerized at 45°C for 30 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 80 parts by mass of butadiene was added and polymerized at 80°C for 1.0 hour. Finally, 0.27 mol of tetramethoxysilane was added per 1 mol of n-butyllithium to carry out a coupling reaction. After the reaction was completed, methanol was added, and a conjugated diene-based block copolymer was obtained as step 1.

[0348] The resulting conjugated diene block copolymer had a styrene content of 20% by mass, a polystyrene block content of 20% by mass, and a vinyl bond content of 63 mol% in the butadiene portion.

[0349] <Process 2> The above-mentioned hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the titanium-equivalent concentration was 100 ppm per 100 parts by mass of the conjugated diene block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

[0350] After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer.

[0351] The obtained hydrogenated conjugated diene block copolymer (a-18) had a styrene content of 20 mass %, a butylene content of 62 mol %, a weight average molecular weight of 434,000, a molecular weight distribution of 2.3, and a hydrogenation rate of 99 mol %.

[0352] [Manufacturing Examples 29-35] (Production of amine-conjugated diene polymers (a-19 to 25)) The production was carried out in the same manner as in Production Example 10, except that the amounts of n-butyllithium, TMEDA, and DMI were changed.

[0353] The obtained hydrogenated conjugated diene block copolymer (a-19) had a styrene content of 32 mass%, a butylene content of 30 mol%, a weight average molecular weight of 180,000, a molecular weight distribution of 1.1, a hydrogenation rate of 87 mol%, and a modification rate of 71% (the number of modifying groups per polymer chain was 0.71).

[0354] The resulting hydrogenated conjugated diene block copolymer (a-20) had a styrene content of 32% by mass, a butylene content of 21 mol%, a weight-average molecular weight of 203,000, a molecular weight distribution of 1.1, a hydrogenation rate of 87 mol%, and a modification rate of 71% (0.71 modified groups per polymer chain). The resulting hydrogenated conjugated diene block copolymer (a-21) had a styrene content of 32% by mass, a butylene content of 30 mol%, a weight-average molecular weight of 203,000, a molecular weight distribution of 1.1, a hydrogenation rate of 87 mol%, and a modification rate of 70% (0.70 modified groups per polymer chain). (a-22) had a styrene content of 32% by mass, a butylene content of 36 mol%, a weight-average molecular weight of 252,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 71% (0.71 modified groups per polymer chain). (a-23) had a styrene content of 32 mass%, a butylene content of 36 mol%, a weight-average molecular weight of 251,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 25% (0.25 modified groups per polymer chain). (a-24) had a styrene content of 32 mass%, a butylene content of 36 mol%, a weight-average molecular weight of 351,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 71% (0.71 modified groups per polymer chain). (a-25) had a styrene content of 32 mass%, a butylene content of 36 mol%, a weight-average molecular weight of 450,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 71% (0.71 modified groups per polymer chain).

[0355] [Manufacturing Example 36] (Production of amine-conjugated diene polymer (a-26)) Production was carried out in the same manner as in Production Example 10, except that the amount of n-butyllithium was changed and styrene was introduced in increments of 19.0 parts by mass.

[0356] The obtained hydrogenated conjugated diene block copolymer (a-26) had a styrene content of 38 mass%, a butylene content of 36 mol%, a weight average molecular weight of 252,000, a molecular weight distribution of 1.1, a hydrogenation rate of 83 mol%, and a modification rate of 70% (the number of modifying groups per polymer chain was 0.70).

[0357] [Manufacturing Example 37] (Production of amine-conjugated diene polymer (a-27)) Production was carried out in the same manner as in Production Example 10, except that the amount of n-butyllithium was changed and styrene was introduced in amounts of 21 parts by mass each.

[0358] The obtained hydrogenated conjugated diene block copolymer (a-27) had a styrene content of 42 mass%, a butylene content of 36 mol%, a weight average molecular weight of 252,000, a molecular weight distribution of 1.1, a hydrogenation rate of 84 mol%, and a modification rate of 75% (the number of modifying groups per polymer chain was 0.75).

[0359] [Manufacturing Example 38] (Production of amine-conjugated diene polymer (a-28)) Production was carried out in the same manner as in Production Example 10, except that the amount of n-butyllithium was changed and styrene was introduced in increments of 6.5 parts by mass.

[0360] The obtained hydrogenated conjugated diene block copolymer (a-28) had a styrene content of 13 mass%, a butylene content of 36 mol%, a weight average molecular weight of 250,000, a molecular weight distribution of 1.1, a hydrogenation rate of 83 mol%, and a modification rate of 75% (the number of modifying groups per polymer chain was 0.75).

[0361] [Manufacturing Example 39] (Production of amine-conjugated diene polymer (a-29)) The production was carried out in the same manner as in Production Example 10, except for adjusting the amounts of n-butyllithium and TMEDA.

[0362] The obtained hydrogenated conjugated diene block copolymer (a-29) had a styrene content of 32 mass%, a butylene content of 59 mol%, a weight average molecular weight of 250,000, a molecular weight distribution of 1.1, a hydrogenation rate of 83 mol%, and a modification rate of 75% (the number of modifying groups per polymer chain was 0.75).

[0363] [Manufacturing Example 40] (Production of amine-conjugated diene polymer (a-30)) The hydrogenated product was prepared in the same manner as in (a-24), except that N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane was used instead of DMI. The modified conjugated diene-based block copolymer (a-30) was then prepared by desilylating the protecting groups.

[0364] The obtained hydrogenated conjugated diene block copolymer (a-30) had a styrene content of 32 mass%, a butylene content of 36 mol%, a weight average molecular weight of 351,000, a molecular weight distribution of 1.1, a hydrogenation rate of 90 mol%, and a modification rate of 90% (the number of modifying groups per polymer chain was 0.9).

[0365] [Manufacturing Example 41] (Production of amine-conjugated diene polymer (a-31)) A modified conjugated diene block copolymer (a-31) was produced in the same manner as in (a-24), except that 1-(4-dimethylaminophenyl)-1-phenylethylene was used instead of DMI.

[0366] The obtained hydrogenated conjugated diene block copolymer (a-31) had a styrene content of 32 mass%, a butylene content of 36 mol%, a weight average molecular weight of 351,000, a molecular weight distribution of 1.1, a hydrogenation rate of 90 mol%, and a modification rate of 90% (the number of modifying groups per polymer chain was 0.9).

[0367] [Manufacturing Example 42] (Production of amine-conjugated diene polymer (a-32)) The same procedures as in Production Example 10 were carried out except that the amount of n-butyllithium, the amount of TMEDA, and the amount of styrene introduced were changed to 6.5 parts by mass each.

[0368] The obtained hydrogenated conjugated diene block copolymer (a-32) had a styrene content of 13 mass%, a butylene content of 36 mol%, a weight average molecular weight of 151,000, a molecular weight distribution of 1.2, a hydrogenation rate of 87 mol%, and a modification rate of 80% (the number of modifying groups per polymer chain was 0.80).

[0369] [Manufacturing Example 43] (Production of amine-conjugated diene polymer (a-33)) This was produced in the same manner as in Production Example 10, except for changing the amount of n-butyllithium.

[0370] The obtained hydrogenated conjugated diene block copolymer (a-33) had a styrene content of 32 mass%, a butylene content of 38 mol%, a weight average molecular weight of 60,000, a molecular weight distribution of 1.2, a hydrogenation rate of 87 mol%, and a modification rate of 72% (the number of modifying groups per polymer chain was 0.72).

[0371] [Manufacturing Example 44] (Production of amine-conjugated diene polymer (a-34)) The same procedures as in Production Example 10 were carried out except that the amount of n-butyllithium was changed, and the amount of TMEDA and styrene were changed so that 12.5 parts by mass were introduced.

[0372] The obtained hydrogenated conjugated diene block copolymer (a-34) had a styrene content of 25 mass%, a butylene content of 54 mol%, a weight average molecular weight of 90,000, a molecular weight distribution of 1.2, a hydrogenation rate of 98 mol%, and a modification rate of 90% (the number of modifying groups per polymer chain was 0.9).

[0373] [Manufacturing Example 45] (Production of modified conjugated diene block copolymer (aa-10)) A maleic anhydride conjugated diene polymer (aa-10) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of pelletized hydrogenated conjugated diene polymer (a-13), 1.5 parts by mass of maleic anhydride, and 0.10 parts by mass of Perhexa 25B, and the cylinder set temperature was changed to 240°C.

[0374] [Manufacturing Example 46] (Production of modified conjugated diene block copolymer (aa-11)) A maleic anhydride conjugated diene polymer (aa-11) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of pelletized hydrogenated conjugated diene polymer (a-13), 2.1 parts by mass of maleic anhydride, and 0.14 parts by mass of Perhexa 25B, and the cylinder set temperature was changed to 240°C.

[0375] [Manufacturing Example 47] (Production of modified conjugated diene block copolymer (aa-12)) A maleic anhydride conjugated diene polymer (aa-12) was produced in the same manner as in Production Example 11, except that the components used in dry blending were changed to 100 parts by mass of pelletized hydrogenated conjugated diene polymer (a-13), 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B, and the cylinder set temperature was changed to 250°C.

[0376] [Manufacturing Example 48] (Production of conjugated diene polymer (a-35)) Except for changing the amount of n-butyllithium, the procedure was the same as in Production Example 1. The resulting hydrogenated conjugated diene block copolymer (a-35) had a styrene content of 32 mass%, a butylene content of 36 mol%, a weight-average molecular weight of 39,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0377] (Polyvinylidene fluoride (a-36)) PVDF (polyvinylidene fluoride, KF-1100, manufactured by Kureha Corporation) was used as the binder (a-36).

[0378] In Examples 1 to 85 and Comparative Examples 1 and 2, electrodes were produced according to the above-mentioned formulations and evaluated.

[0379] [Table 1]

[0380] [Table 2]

[0381]

Table 3

[0382]

Table 4

[0383]

Table 5

[0384]

Table 6

[0385]

Table 7

[0386]

Table 8

[0387]

Table 9

[0388]

Table 10

[0389]

Table 11

[0390] The results in Table 1 indicate that Examples 1 to 85 are conjugated diene-based polymers with excellent adhesive properties and electrochemical stability, as well as low water content, making them suitable as binders for all-solid-state batteries. Among these, high-molecular-weight binders with modified groups exhibited an excellent balance of adhesiveness, binding properties, and volatility. Even high-molecular-weight binders with low modified group equivalents, such as those in Examples 65 to 80, exhibited high binding properties. Furthermore, binders with fewer modified groups were found to exhibit excellent dispersibility of conductive additives even after polymerization. Furthermore, Examples 21-23, 36-38, and 50-52 indicated that binders containing phosphorus compounds exhibited excellent thermal stability. Furthermore, Examples 24-25, 39-40, and 53-54 indicated that binders with fewer metal residues exhibited excellent thermal stability. Thermal stability is an indicator of thermal degradation during pre-drying before use and deterioration of battery performance. Furthermore, Examples 26-30, 41-45, and 55-59 show that binders with low compressibility have excellent feed stability, and Examples 31-32, 46-47, and 60-61 show that binders with an external lubricant added have excellent feed stability. [Industrial Applicability]

[0391] The modified conjugated diene-based block copolymer of the present invention has industrial applicability as a binder for batteries including all-solid-state batteries. [Explanation of symbols]

[0392] 100 solid state battery 110 Solid electrolyte layer 140 Positive electrode layer 150 negative electrode layer 160 Positive electrode current collector 170 Negative electrode current collector 180 Exterior

Claims

1. The polymer block has a polymer block mainly composed of a vinyl aromatic monomer unit, and has a weight average molecular weight of 40,000 to 2,000,000. Contains a conjugated diene polymer, the conjugated diene polymer has a modifying group, and the modifying group is at least one selected from the group consisting of an acid anhydride group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an amide group, a urethane group, a urea group, an isocyanate group, and an ionic group; the modifying group is present in an amount of 0.10 mmol or more and 0.50 mmol or less in 100 g of the conjugated diene polymer; Solid-state battery binder.

2. The all-solid-state battery binder according to claim 1, wherein the conjugated diene polymer has a weight average molecular weight of 200,000 to 800,000.

3. the content of the polymer block is 40% by weight or less based on the total amount of the conjugated diene-based polymer; The all-solid-state battery binder according to claim 1 or 2.

4. the amount of vinyl bonds in the conjugated diene monomer units contained in the conjugated diene polymer before hydrogenation is 20 mol % to 60 mol % relative to 100 mol % in total of the conjugated diene monomer units; The all-solid-state battery binder according to any one of claims 1 to 3.

5. the conjugated diene polymer has a toluene-insoluble content of 10 wt % or less; The all-solid-state battery binder according to any one of claims 1 to 4.

6. the modifying group is a primary amino group or a secondary amino group; The all-solid-state battery binder according to any one of claims 1 to 5.

7. an end or a coupling portion of the conjugated diene polymer has the modifying group; The all-solid-state battery binder according to any one of claims 1 to 6.

8. the conjugated diene polymer has a polymer block mainly composed of a conjugated diene monomer unit; The all-solid-state battery binder according to any one of claims 1 to 7.

9. The conjugated diene polymer is hydrogenated. The all-solid-state battery binder according to any one of claims 1 to 8.

10. the butylene amount and / or propylene amount of the conjugated diene monomer units contained in the conjugated diene polymer is 20 mol % to 60 mol % relative to 100 mol % in total of the conjugated diene monomer units; the conjugated diene polymer has a polymer block mainly composed of a conjugated diene monomer unit; The all-solid-state battery binder according to any one of claims 1 to 9.

11. The loose bulk density of the conjugated diene polymer is 0.15 g / cm 3 or more, the compression degree is less than 30, and the powder or crumb shape is The all-solid-state battery binder according to any one of claims 1 to 10.

12. the total content of the transition metal element and Al, Li, Fe, Zn, and Mg in the conjugated diene polymer is 200 ppm or less in terms of atoms relative to the conjugated diene polymer; The all-solid-state battery binder according to any one of claims 1 to 11.

13. The composition contains the conjugated diene polymer and a phosphorus compound, and the phosphorus atom content is 10 ppm or more relative to the conjugated diene polymer. The all-solid-state battery binder according to any one of claims 1 to 11.

14. containing at least one selected from the group consisting of silica, higher fatty acid metal salts, polyolefins, and fatty acid amides; The all-solid-state battery binder according to any one of claims 1 to 13.

15. The conjugated diene polymer has isoprene as a conjugated diene polymer unit. The all-solid-state battery binder according to any one of claims 1 to 14.

16. The moisture content is 200 ppm or less. The all-solid-state battery binder according to any one of claims 1 to 15.

17. A slurry comprising the all-solid-state battery binder according to any one of claims 1 to 16, having a water content of 200 ppm or less.

18. The all-solid-state battery binder according to any one of claims 1 to 16, a positive electrode active material, A positive electrode layer having a moisture content of 200 ppm or less.

19. The all-solid-state battery binder according to any one of claims 1 to 16, an ion-conducting solid electrolyte; A solid electrolyte layer having a moisture content of 200 ppm or less.

20. The all-solid-state battery binder according to any one of claims 1 to 16, a negative electrode active material, A negative electrode layer having a moisture content of 200 ppm or less.

21. The cathode layer according to claim 18, the solid electrolyte layer according to claim 19, and the anode layer according to claim 20 are included. All-solid-state battery.

22. The moisture content is 200 ppm or less. The all-solid-state battery according to claim 21.

23. a step of preparing a slurry containing a conjugated diene polymer having a conjugated diene monomer unit, a polymer block mainly composed of a vinyl aromatic monomer unit, and a modifying group, the conjugated diene polymer having a water content of 1 wt % or less, and a solvent; and applying the slurry to a substrate and drying the slurry. A method for producing at least one layer of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer, the method comprising the all-solid-state battery binder according to claim 1, the all-solid-state battery binder having a moisture content of 200 ppm or less.

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