TWI806306B - All-solid battery adhesive using conjugated diene polymer, positive electrode layer, negative electrode layer, electrolyte layer using the same, and all-solid battery including the same - Google Patents

All-solid battery adhesive using conjugated diene polymer, positive electrode layer, negative electrode layer, electrolyte layer using the same, and all-solid battery including the same Download PDF

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TWI806306B
TWI806306B TW110148596A TW110148596A TWI806306B TW I806306 B TWI806306 B TW I806306B TW 110148596 A TW110148596 A TW 110148596A TW 110148596 A TW110148596 A TW 110148596A TW I806306 B TWI806306 B TW I806306B
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conjugated diene
polymer
mass
diene polymer
group
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TW202234735A (en
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助川敬
近藤知宏
酒向謙太朗
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日商旭化成股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

本發明係一種全固體電池黏著劑，其含有共軛二烯系聚合物，該共軛二烯系聚合物具有以乙烯基芳香族單體單元作為主體之聚合物嵌段，且重量平均分子量為4～200萬。The invention is an all-solid battery adhesive, which contains a conjugated diene polymer, the conjugated diene polymer has a polymer block mainly composed of vinyl aromatic monomer units, and the weight average molecular weight is 4 to 2 million.

Description

使用共軛二烯系聚合物之全固體電池黏著劑及使用該黏著劑之正極層、負極層、電解質層、及包含該等之全固體電池All-solid battery adhesive using conjugated diene polymer, positive electrode layer, negative electrode layer, electrolyte layer using the same, and all-solid battery including the same

本發明係關於一種使用共軛二烯系聚合物之全固體電池黏著劑及使用該黏著劑之正極層、負極層、電解質層、及包含該等之全固體電池。 The present invention relates to an all-solid battery adhesive using a conjugated diene polymer, a positive electrode layer, a negative electrode layer, an electrolyte layer using the adhesive, and an all-solid battery comprising the same.

鋰離子二次電池之較大特徵在於輕量、高能量及長壽命，例如被廣泛用作筆記型電腦、行動電話、數位相機、攝錄影機等攜帶用電子機器之電源。又，隨著向低環境負荷社會過渡，於油電混合車(HEV，Hybrid Electric Vehicle)及插電式HEV(PHEV，Plug-in Hybrid Electric Vehicle，插電式油電混合車)之電源、進而住宅用蓄電系統等電力儲存領域亦受到關注。 Lithium-ion secondary batteries are characterized by light weight, high energy and long life. For example, they are widely used as power sources for portable electronic devices such as notebook computers, mobile phones, digital cameras, and video recorders. Also, with the transition to a society with a low environmental load, power supplies for hybrid electric vehicles (HEV, Hybrid Electric Vehicle) and plug-in HEV (PHEV, Plug-in Hybrid Electric Vehicle, plug-in hybrid electric vehicle), and Power storage fields such as residential power storage systems are also attracting attention.

然，先前鋰離子二次電池之電解質使用了鋰鹽溶解於有機溶劑而成之有機電解液，有伴隨漏液之安全性之虞。 However, the electrolyte of the previous lithium-ion secondary battery used an organic electrolyte solution obtained by dissolving lithium salt in an organic solvent, and there was a risk of safety associated with leakage.

作為無需可燃性電解液而使安全性飛躍性地提高之技術，提出有一種全固體電池，其藉由使用固體電解質作為電解液而使正極材、電解質及負極材均為固體。 As a technique for drastically improving safety without requiring a flammable electrolyte, an all-solid battery has been proposed in which a positive electrode material, an electrolyte, and a negative electrode material are all solid by using a solid electrolyte as the electrolyte solution.

作為用於全固體電池之固體電解質，例如基於較高之鋰離子傳導性考慮，揭示有一種使用硫化物系材料之技術。 As a solid electrolyte for an all-solid battery, for example, a technology using a sulfide-based material is disclosed based on the consideration of high lithium ion conductivity.

然而，硫化物系材料由於化學穩定性不足，於大氣暴露下會因與水分反應而產生硫化氫，損壞電解質性能，故於使用該電解質時較理想為於電池製造過程中儘量去除水分。先前之鋰離子電池係於黏著劑中使用聚偏二氟乙烯(PVDF)，使其溶解於作為極性溶劑之N-甲基吡咯啶酮(NMP)中，與電極活性物質或導電助劑等電極構成材料混合，塗佈於集電體，藉此製作電極，但NMP由於具有親水性，故並不適宜用於使用硫化物系固體電解質之全固體電池之製造。因此，較理想為使用親水性較低之無極性溶劑之電極製作過程，但由於PVDF在無極性溶劑中不溶解，故要求開發一種於無極性溶劑中溶解之新穎之黏著劑。專利文獻1中提出有一種可溶解於無極性溶劑之黏著劑。 However, due to the insufficient chemical stability of sulfide-based materials, hydrogen sulfide will be produced by reacting with moisture under atmospheric exposure, which will damage the performance of the electrolyte. Therefore, it is ideal to remove moisture as much as possible during the battery manufacturing process when using this electrolyte. Previous lithium-ion batteries used polyvinylidene fluoride (PVDF) in the adhesive, which was dissolved in N-methylpyrrolidone (NMP) as a polar solvent, and used with electrodes such as electrode active materials or conductive additives. The constituent materials are mixed and coated on the current collector to make electrodes. However, NMP is not suitable for the manufacture of all-solid batteries using sulfide-based solid electrolytes because of its hydrophilicity. Therefore, it is ideal to use non-polar solvents with low hydrophilicity in the electrode production process. However, since PVDF is insoluble in non-polar solvents, it is required to develop a novel adhesive that can be dissolved in non-polar solvents. Patent Document 1 proposes an adhesive that can be dissolved in a non-polar solvent.

由於共軛二烯系聚合物在無極性溶劑中溶解，故專利文獻2中提出有一種使用丁二烯系橡膠黏著劑作為全固體電池黏著劑之全固體電池。 Since the conjugated diene polymer is dissolved in a nonpolar solvent, Patent Document 2 proposes an all-solid battery using a butadiene-based rubber adhesive as an all-solid battery adhesive.

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Document]

[專利文獻1] 日本專利特開2018-125260號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2018-125260

[專利文獻2] 日本專利特表2019-525427號公報 [Patent Document 2] Japanese Patent Application Publication No. 2019-525427

先前文獻之共軛二烯系聚合物由於能夠使用無極性溶劑，故就於製造過程中去除水分之方面而言優異，但就將電極活性物質層之構成成分彼此或固體電解質黏結之力或將電極活性物質層接著於集電體之力等黏著劑性能方面而言尚不充分。 The conjugated diene-based polymer of the previous literature is excellent in removing moisture during the production process because it can use a non-polar solvent, but it may be difficult to bind the constituent components of the electrode active material layer or the solid electrolyte. The electrode active material layer is not yet sufficient in terms of binder performance such as current collector strength.

因此，本發明係鑒於上述問題而完成者，其課題在於提供一種於無極性溶劑中之溶解性優異、進而黏著劑性能亦優異之全固體電池黏著劑、及使用其之正極層、固體電解質層、負極層、以及全固體電池。 Therefore, the present invention was made in view of the above-mentioned problems, and its object is to provide an all-solid battery adhesive having excellent solubility in nonpolar solvents and excellent adhesive properties, and a positive electrode layer and a solid electrolyte layer using the same. , negative electrode layer, and all-solid-state battery.

本發明者等人為了解決上述先前技術之課題而進行了銳意研究，結果發現，藉由具有改性基且具有特定之聚合物結構之共軛二烯系聚合物可解決上述課題，從而完成了本發明。 The inventors of the present invention conducted earnest research to solve the above-mentioned problems of the prior art, and as a result, found that the above-mentioned problems can be solved by a conjugated diene polymer having a modifying group and having a specific polymer structure, and completed the this invention.

即，本發明如下所述。 That is, the present invention is as follows.

[1] [1]

一種全固體電池黏著劑，其含有共軛二烯系聚合物，該共軛二烯系聚合物具有以乙烯基芳香族單體單元作為主體之聚合物嵌段，且重量平均分子量為4~200萬。 An all-solid battery adhesive, which contains a conjugated diene polymer, the conjugated diene polymer has a polymer block mainly composed of vinyl aromatic monomer units, and has a weight average molecular weight of 4 to 200 Ten thousand.

[2] [2]

如[1]所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物具有改性基，上述改性基為選自由酸酐基、羥基、羰基、羧基、胺基、環氧基、烷 氧基矽烷基、醯胺基、胺基甲酸酯基、脲基、異氰酸基、及離子性基所組成之群中之一種以上。 The all-solid battery adhesive as described in [1], wherein the above-mentioned conjugated diene polymer has a modification group, and the above-mentioned modification group is selected from an acid anhydride group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, alkyl One or more of the group consisting of oxysilyl group, amido group, urethane group, urea group, isocyanate group, and ionic group.

[3] [3]

如[1]或[2]所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物之重量平均分子量為20~80萬。 The all-solid battery adhesive described in [1] or [2], wherein the weight average molecular weight of the conjugated diene polymer is 200,000 to 800,000.

[4] [4]

如[1]至[3]所記載之全固體電池黏著劑，其中上述聚合物嵌段之含量相對於上述共軛二烯系聚合物之總量為40重量%以下。 The all-solid battery adhesive described in [1] to [3], wherein the content of the above-mentioned polymer block is 40% by weight or less relative to the total amount of the above-mentioned conjugated diene-based polymer.

[5] [5]

如[1]至[4]所記載之全固體電池黏著劑，其中共軛二烯單體單元之氫化前之乙烯基鍵量相對於共軛二烯單體單元之合計100mol%為20mol%~60mol%，上述共軛二烯系聚合物具有以共軛二烯單體單元作為主體之聚合物嵌段。 The all-solid battery adhesive as described in [1] to [4], wherein the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is 20 mol% to the total 100 mol% of the conjugated diene monomer unit 60 mol%, the conjugated diene polymer has a polymer block mainly composed of conjugated diene monomer units.

[6] [6]

如[1]至[5]所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物之甲苯不溶分量為10wt%以下。 The all-solid battery adhesive described in [1] to [5], wherein the toluene-insoluble content of the above-mentioned conjugated diene polymer is 10 wt % or less.

[7] [7]

如[2]至[6]所記載之全固體電池黏著劑，其中上述改性基於上述共軛二烯系聚合物100g中為0.10mmol以上0.50mmol以下。 The all-solid battery adhesive described in [2] to [6], wherein the above-mentioned modification is 0.10 mmol to 0.50 mmol based on 100 g of the above-mentioned conjugated diene-based polymer.

[8] [8]

如[2]至[7]中任一項所記載之全固體電池黏著劑，其中上述改性基為一級胺基或二級胺基。 The all-solid battery adhesive as described in any one of [2] to [7], wherein the above-mentioned modifying group is a primary amino group or a secondary amino group.

[9] [9]

如[2]至[9]中任一項所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物之末端或偶合部具有改性基。 The all-solid battery adhesive described in any one of [2] to [9], wherein the terminal or coupling portion of the above-mentioned conjugated diene polymer has a modifying group.

[10] [10]

如[1]至[8]中任一項所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物具有以上述共軛二烯單體單元作為主體之聚合物嵌段。 The all-solid battery adhesive according to any one of [1] to [8], wherein the conjugated diene polymer has a polymer block mainly composed of the conjugated diene monomer unit.

[11] [11]

如[1]至[10]中任一項所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物為經氫化者。 The all-solid battery adhesive described in any one of [1] to [10], wherein the conjugated diene polymer is hydrogenated.

[12] [12]

如[1]至[11]中任一項所記載之全固體電池黏著劑，其中上述共軛二烯單體單元之丁烯量及/或丙烯量相對於共軛二烯單體單元之合計100mol%為20mol%~60mol%， 上述共軛二烯系聚合物具有以共軛二烯單體單元作為主體之聚合物嵌段。 The all-solid battery adhesive as described in any one of [1] to [11], wherein the amount of butene and/or propylene in the above-mentioned conjugated diene monomer units is relative to the total amount of the conjugated diene monomer units 100mol% is 20mol%~60mol%, The above-mentioned conjugated diene polymer has a polymer block mainly composed of conjugated diene monomer units.

[13] [13]

如[1]至[12]中任一項所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物之鬆裝比重為0.15g/cm3以上，壓縮度未達30，且為粉末、或屑粒形狀。 The all-solid battery adhesive as described in any one of [1] to [12], wherein the above-mentioned conjugated diene polymer has a bulk specific gravity of 0.15 g/cm 3 or more, a degree of compression of less than 30, and is Powder, or crumb shape.

[14] [14]

如[1]至[13]中任一項所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物中之過渡金屬元素與Al、Li、Fe、Zn、及Mg之合計含量以原子換算計，相對於共軛二烯系聚合物為200ppm以下。 The all-solid battery adhesive as described in any one of [1] to [13], wherein the total content of the transition metal element and Al, Li, Fe, Zn, and Mg in the above-mentioned conjugated diene polymer is at least In atomic conversion, it is 200 ppm or less relative to the conjugated diene-based polymer.

[15] [15]

如[1]至[14]中任一項所記載之全固體電池黏著劑，其包含上述共軛二烯系聚合物及磷化合物，且磷化合物之含量以磷原子換算計，相對於共軛二烯系聚合物為10ppm以上。 The all-solid battery adhesive as described in any one of [1] to [14], which includes the above-mentioned conjugated diene polymer and a phosphorus compound, and the content of the phosphorus compound is calculated in terms of phosphorus atoms, relative to the conjugated diene polymer. The diene-based polymer is 10 ppm or more.

[16] [16]

如[1]至[15]所記載之全固體電池黏著劑，其包含選自由二氧化矽、高級脂肪酸金屬鹽、聚烯烴、及脂肪醯胺所組成之群中之高分子。 The all-solid battery adhesive as described in [1] to [15], which includes a polymer selected from the group consisting of silicon dioxide, higher fatty acid metal salts, polyolefins, and aliphatic amide.

[17] [17]

如[1]至[16]所記載之全固體電池黏著劑，其中上述共軛二烯系聚合物具有異戊二烯作為共軛二烯系聚合物單元。 The all-solid battery adhesive described in [1] to [16], wherein the conjugated diene polymer has isoprene as a unit of the conjugated diene polymer.

[18] [18]

如[1]至[17]中任一項所記載之全固體電池黏著劑，其中水分量為200ppm以下。 The all-solid battery adhesive described in any one of [1] to [17], wherein the moisture content is 200 ppm or less.

[19] [19]

一種漿料，其包含如[1]至[18]中任一項所記載之全固體電池黏著劑，且水分量為200ppm以下。 A slurry comprising the all-solid battery adhesive described in any one of [1] to [18], and having a moisture content of 200 ppm or less.

[20] [20]

一種正極層，其包含：如[1]至[18]中任一項所記載之全固體電池黏著劑、及正極活性物質，且水分量為200ppm以下。 A positive electrode layer, comprising: the all-solid battery adhesive described in any one of [1] to [18], and a positive electrode active material, and the moisture content is 200ppm or less.

[21] [twenty one]

一種固體電解質層，其包含：如[1]至[18]中任一項所記載之全固體電 池黏著劑、及離子傳導性之固體電解質，且水分量為200ppm以下。 A solid electrolyte layer, comprising: the all-solid electrolyte as described in any one of [1] to [18] Cell adhesive, and ion-conductive solid electrolyte, and the moisture content is below 200ppm.

[22] [twenty two]

一種負極層，其包含：如[1]至[18]中任一項所記載之全固體電池黏著劑、及負極活性物質，且水分量為200ppm以下。 A negative electrode layer, which includes: the all-solid battery adhesive described in any one of [1] to [18], and a negative electrode active material, and the moisture content is 200ppm or less.

[23] [twenty three]

一種全固體電池，其包含：如[20]所記載之正極層、如[21]所記載之固體電解質層、及如[22]所記載之負極層中之至少一層。 An all-solid battery, comprising: at least one of the positive electrode layer described in [20], the solid electrolyte layer described in [21], and the negative electrode layer described in [22].

[24] [twenty four]

如[23]所記載之全固體電池，其中水分量為200ppm以下。 The all-solid battery as described in [23], wherein the moisture content is 200ppm or less.

[25] [25]

一種製造包含全固體電池黏著劑之正極層、固體電解質層、及負極層中之至少一層之方法，上述全固體電池黏著劑之水分量為200ppm以下，上述製造方法具有如下步驟：製備包含共軛二烯系聚合物及溶劑之漿料，該共軛二烯系聚合物具有共軛二烯單體單元、以乙烯基芳香族單體單元作為主體之聚合物嵌段、及改性基，且水分量為1wt%以下；以及將上述漿料塗佈於基材並加以乾燥。 A method for manufacturing at least one layer of positive electrode layer, solid electrolyte layer, and negative electrode layer comprising an all-solid battery adhesive, the moisture content of the above-mentioned all-solid battery adhesive is below 200ppm, and the above-mentioned manufacturing method has the following steps: preparing A slurry of a diene polymer and a solvent, the conjugated diene polymer having a conjugated diene monomer unit, a polymer block mainly composed of a vinyl aromatic monomer unit, and a modifying group, and The water content is less than 1wt%; and the above slurry is coated on the substrate and dried.

根據本發明，可提供一種於無極性溶劑中之溶解性優異、黏著劑性能亦優異之全固體電池黏著劑、及使用其之正極層、固體電解質層、負極層、以及全固體電池。 According to the present invention, an all-solid battery adhesive having excellent solubility in nonpolar solvents and excellent adhesive performance, a positive electrode layer, a solid electrolyte layer, a negative electrode layer, and an all-solid battery using the same can be provided.

100:全固體電池 100: All solid battery

110:固體電解質層 110: solid electrolyte layer

140:正極層 140: Positive electrode layer

150:負極層 150: Negative electrode layer

160:正極集電體 160: Positive electrode collector

170:負極集電體 170: Negative electrode collector

180:外裝 180: Exterior

圖1係表示本實施方式之全固體電池之一例之概略剖視圖。 FIG. 1 is a schematic cross-sectional view showing an example of an all-solid-state battery according to this embodiment.

以下，對本發明之實施方式(以下稱為「本實施方式」)進行詳細說明。以下之本實施方式係用以說明本發明之例示，並非意在將本發明限定於以下內容。本發明可於其主旨之範圍內適當變化而實施。 Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate changes within the scope of the gist.

再者，本說明書中，所謂「聚合物」，包括由單種單體單元構成之聚合物、及具有複數種單體單元之共聚物之任一情形。 In addition, in this specification, the term "polymer" includes both a polymer composed of a single monomer unit and a copolymer having a plurality of monomer units.

[全固體電池黏著劑] [All solid battery adhesive] (共軛二烯系聚合物) (conjugated diene polymer)

本實施方式之全固體電池黏著劑含有共軛二烯系聚合物，該共軛二烯系聚合物具有以乙烯基芳香族單體單元作為主體之聚合物嵌段，且重量平均分子量為4~200萬。 The all-solid battery adhesive of this embodiment contains a conjugated diene polymer having a polymer block mainly composed of a vinyl aromatic monomer unit, and has a weight average molecular weight of 4~ 2 million.

本實施方式中，共軛二烯系聚合物較佳為具有改性基。「改性基」係指對電極活性物質層之構成成分或固體電解質之黏結性基及/或對集電體之接著性基，係指包含碳及氫以外之元素之官能基。「改性基」之結構可藉由 使用NMR(Nuclear Magnetic Resonance，核磁共振)、光譜分析、電氣分析、分離分析、質譜分析、滴定等各種分析化學方法對共軛二烯系聚合物及視需要假定之改性劑進行分析而確認。作為特定出改性基之方法，一般可例舉NMR或IR(Infrared Radiation紅外線輻射)、GC-MS(Gas Chromatography-Mass Spectrometry，氣相層析-質譜法)等之組合之方法。例如，作為酸酐之順丁烯二酸酐或琥珀酸酐在IR下於1750cm-1附近具有吸收峰，因此可藉由對共軛二烯系聚合物進行分析而特定。又，藉由使用對改性基具有吸附性之管柱之層析法對共軛二烯系聚合物進行分析，藉此例如能特定出胺改性基等改性基。關於其他官能基，亦可藉由利用NMR對共軛二烯系聚合物進行分析，而特定出官能基固有之化學位移改性基。又，根據各種分析及文獻等，可舉出候選之改性基或改性劑，根據其等之化學位移與源於共軛二烯系聚合物之改性基之化學位移之一致，亦可特定出改性基或改性劑。 In this embodiment, the conjugated diene polymer preferably has a modifying group. "Modification group" refers to the constituent components of the electrode active material layer or the binding group of the solid electrolyte and/or the adhesive group to the current collector, and refers to a functional group containing elements other than carbon and hydrogen. The structure of the "modifier" can be determined by using various analytical chemical methods such as NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance), spectral analysis, electrical analysis, separation analysis, mass spectrometry, titration, etc. The putative modifier is confirmed by analysis. As a method for specifying a modifying group, generally, a combination method of NMR, IR (Infrared Radiation), GC-MS (Gas Chromatography-Mass Spectrometry, etc.) can be exemplified. For example, maleic anhydride or succinic anhydride, which are acid anhydrides, has an absorption peak around 1750 cm −1 in IR, and thus can be identified by analyzing a conjugated diene polymer. Furthermore, by analyzing the conjugated diene polymer by chromatography using a column having adsorption properties for the modifying group, for example, modifying groups such as amine modifying groups can be identified. Regarding other functional groups, the chemical shift modification group inherent in the functional group can also be identified by analyzing the conjugated diene polymer by NMR. In addition, according to various analyzes and documents, candidate modifiers or modifiers can be mentioned, and based on the coincidence of their chemical shifts with the chemical shifts of the modifiers derived from conjugated diene polymers, it is also possible to Specify the modifying group or modifying agent.

(共軛二烯單體單元) (conjugated diene monomer unit)

構成共軛二烯系聚合物之共軛二烯單體係具有一對共軛雙鍵之二烯烴。作為此種二烯烴，並無特別限制，例如可例舉：1,3-丁二烯、2-甲基-1,3-丁二烯(異戊二烯)、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、1,3-環戊二烯、2-甲基-1,3-戊二烯、1,3-己二烯、1,3-環己二烯、及法呢烯。該等中，就獲取性及生產性之觀點而言，較佳為1,3-丁二烯及異戊二烯，就熱穩定性之觀點而言，更佳為1,3-丁二烯。共軛二烯系聚合物可包含1種共軛二烯單體單元，亦可包含2種以上之共軛二烯單體單元。 The conjugated diene monomer constituting the conjugated diene polymer is a diene with a pair of conjugated double bonds. Such dienes are not particularly limited, and examples include: 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 preferable from the viewpoint of availability and productivity, and 1,3-butadiene is more preferable from the viewpoint of thermal stability. . The conjugated diene polymer may contain one kind of conjugated diene monomer unit, or may contain two or more kinds of conjugated diene monomer units.

共軛二烯系聚合物亦可包含以共軛二烯單體單元作為主體之聚合物嵌段。於共軛二烯系聚合物包含以共軛二烯單體單元作為主體之聚合物嵌段之情形時，關於該聚合物嵌段中所含之共軛二烯單體單元之含量，就為了提高全固體電池黏著劑之將電極活性物質層或電解質層之電極活性物質、導電助劑、固體電解質等構成成分彼此黏合之黏結性及對集電體之接著性(亦稱為密接性)而增加嵌段之聚合物鏈之纏結的觀點而言，較佳為80質量%以上，更佳為90質量%以上，進而較佳為95質量%以上。此處所謂「以共軛二烯單體單元作為主體之聚合物嵌段」，意指該共軛二烯單體單元之含量相對於該聚合物嵌段整體超過70質量%之聚合物嵌段。 The conjugated diene polymer may also include a polymer block mainly composed of conjugated diene monomer units. In the case where the conjugated diene polymer includes a polymer block mainly composed of a conjugated diene monomer unit, the content of the conjugated diene monomer unit contained in the polymer block is as follows: Improve the adhesiveness of the all-solid battery adhesive to bond the electrode active material layer or the electrode active material layer of the electrolyte layer, the conductive additive, the solid electrolyte, and the adhesion to the current collector (also called adhesion) From the viewpoint of increasing entanglement of the polymer chains of the blocks, it is preferably at least 80% by mass, more preferably at least 90% by mass, and still more preferably at least 95% by mass. Here, "a polymer block mainly composed of conjugated diene monomer units" means a polymer block in which the content of the conjugated diene monomer unit exceeds 70% by mass relative to the entire polymer block .

再者，聚合物嵌段中所含之共軛二烯單體單元之含量之上限並無特別限制，相對於共軛二烯系聚合物中所含之共軛二烯單體單元之總量，可為100質量%以下，亦可為99質量%以下。 Furthermore, the upper limit of the content of the conjugated diene monomer unit contained in the polymer block is not particularly limited, relative to the total amount of the conjugated diene monomer unit contained in the conjugated diene polymer , may be 100% by mass or less, or 99% by mass or less.

本實施方式中，將全固體電池黏著劑之將電極活性物質層或電解質層之電極活性物質、導電助劑、固體電解質等構成成分彼此黏合之黏結性、及對集電體之接著性統稱為黏著劑性能。 In this embodiment, the adhesiveness of the all-solid battery adhesive to bind the constituent components such as the electrode active material layer or the electrolyte layer, the conductive additive, and the solid electrolyte, and the adhesiveness to the current collector are collectively referred to as Adhesive properties.

共軛二烯系聚合物亦可為經氫化者。本實施方式之共軛二烯系聚合物中，就共軛二烯系聚合物於親水性較低之溶劑、例如無極性溶劑中之溶解性及含有共軛二烯系聚合物之全固體電池黏著劑之黏結性及接著性之觀點而言，共軛二烯單體單元之氫化前之乙烯基鍵量相對於共軛二烯單體單元之合計100mol%，較佳為20mol%以上，更佳為25mol%以上，進而較 佳為30mol%以上，進而更佳為35mol%以上。尤其於氫化之情形時，若乙烯基鍵量過低，則有共軛二烯系聚合物結晶化而導致於無極性溶劑中之溶解性明顯降低之情況。 The conjugated diene polymer may also be hydrogenated. Among the conjugated diene polymers of this embodiment, the solubility of the conjugated diene polymer in solvents with low hydrophilicity, such as non-polar solvents, and the all-solid-state battery containing the conjugated diene polymer From the viewpoint of adhesiveness and adhesion of the adhesive, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is preferably 20 mol% or more relative to the total 100 mol% of the conjugated diene monomer unit, and more preferably Preferably more than 25mol%, and then more Preferably, it is 30 mol% or more, More preferably, it is 35 mol% or more. Especially in the case of hydrogenation, if the amount of vinyl bonds is too low, the conjugated diene-based polymer may crystallize and the solubility in nonpolar solvents may be remarkably lowered.

再者，共軛二烯單體單元之氫化前之乙烯基鍵量之上限相對於共軛二烯單體單元之合計100mol%，可為100mol%以下，可為99mol%以下，較佳為80mol%以下，進而較佳為70mol%以下，就橡膠彈性之觀點而言，較佳為60mol%以下、50mol%以下、40mol%以下。 In addition, the upper limit of the amount of vinyl bonds of the conjugated diene monomer unit before hydrogenation is 100 mol% or less, 99 mol% or less, preferably 80 mol with respect to the total 100 mol% of the conjugated diene monomer unit % or less, more preferably 70 mol% or less, and from the viewpoint of rubber elasticity, preferably 60 mol% or less, 50 mol% or less, and 40 mol% or less.

又，於共軛二烯系聚合物包含以共軛二烯單體單元作為主體之聚合物嵌段之情形時，氫化前之乙烯基鍵量之較佳範圍亦與上述相同。 Also, when the conjugated diene polymer includes a polymer block mainly composed of a conjugated diene monomer unit, the preferable range of the amount of vinyl bonds before hydrogenation is the same as above.

「氫化前之乙烯基鍵量」係指進行氫化之前的共軛二烯系聚合物中相對於源於共軛二烯單體單元之1,4-鍵(順式及反式)及1,2-鍵之合計量的1,2-鍵之量(mol比)。其中，於共軛二烯單體單元以3,4-鍵組入至聚合物之情形時，係指相對於1,4-鍵、1,2-鍵、及3,4-鍵之合計量的1,2-鍵、及3,4-鍵之合計量(mol比)。即，雖然使用「氫化前」之用語進行定義，但其原因在於藉由氫化會成為不能稱之為「乙烯基鍵」之狀態，於氫化後亦可區分1,4-鍵、1,2-鍵或3,4-鍵，因此為於氫化後之聚合物中亦可同樣地定量之指標。 "The amount of vinyl bonds before hydrogenation" refers to the 1,4-bonds (cis and trans) and 1,4-bonds (cis and trans) and 1,4-bonds derived from conjugated diene monomer units in the conjugated diene polymer before hydrogenation. The amount of 1,2-bonds to the total amount of 2-bonds (mol ratio). Here, when the conjugated diene monomer unit is incorporated into the polymer with 3,4-bonds, it refers to the total amount of 1,4-bonds, 1,2-bonds, and 3,4-bonds The total amount (mol ratio) of 1,2-bonds and 3,4-bonds. That is, although the term "before hydrogenation" is used for definition, the reason is that hydrogenation will cause a state that cannot be called "vinyl bond", and after hydrogenation, 1,4-bond and 1,2-bond can be distinguished. Bonds or 3,4-bonds are therefore equally quantifiable indicators in polymers after hydrogenation.

共軛二烯系聚合物之丁烯量及/或丙烯量較佳為20mol%以上，更佳為25mol%以上，進而較佳為30mol%以上，進而更佳為35mol%以上。 又，共軛二烯系聚合物之丁烯量及/或丙烯量之上限可為100mol%以下，可為99mol%以下，較佳為80mol%以下，進而較佳為70mol%以下，就橡膠彈性之觀點而言，較佳為60mol%以下、50mol%以下、40mol%以下。藉由使丁烯量及/或丙烯量為上述範圍內，有於無極性溶劑中之溶解性及黏著劑性能進一步提昇之傾向。 The amount of butene and/or propylene in the conjugated diene polymer is preferably at least 20 mol%, more preferably at least 25 mol%, still more preferably at least 30 mol%, even more preferably at least 35 mol%. In addition, the upper limit of the amount of butene and/or propylene in the conjugated diene polymer may be 100 mol% or less, may be 99 mol% or less, preferably 80 mol% or less, and more preferably 70 mol% or less. From the standpoint, it is preferably 60 mol% or less, 50 mol% or less, and 40 mol% or less. When the amount of butene and/or the amount of propylene are within the above-mentioned ranges, the solubility in a nonpolar solvent and the adhesive performance tend to be further improved.

此處，「丁烯量及/或丙烯量」係指氫化後之共軛二烯系聚合物中相對於源於共軛二烯單體單元之1,4-鍵(順式及反式)及1,2-鍵之合計量的1,2-鍵之量(mol比)。其中，於共軛二烯單體單元以3,4-鍵組入至聚合物之情形時，係指相對於1,4-鍵、1,2-鍵及3,4-鍵之合計量的1,2-鍵及3,4-鍵之合計量(mol比)。丁烯量及/或丙烯量可藉由氫化前之乙烯基鍵量及氫化率進行控制。 Here, "the amount of butene and/or the amount of propylene" refers to the 1,4-bond (cis and trans) derived from the conjugated diene monomer unit in the conjugated diene polymer after hydrogenation and the total amount of 1,2-bonds (mol ratio). Here, when the conjugated diene monomer unit is incorporated into the polymer with 3,4-bonds, it refers to the total amount of 1,4-bonds, 1,2-bonds, and 3,4-bonds The total amount of 1,2-bond and 3,4-bond (mol ratio). The amount of butene and/or propylene can be controlled by the amount of vinyl bonds and hydrogenation rate before hydrogenation.

共軛二烯系聚合物之氫化前之乙烯基鍵量及丁烯量及/或丙烯量可使用核磁共振裝置(NMR)等進行測定，具體而言，可藉由後述實施例所記載之方法進行測定。 The vinyl bond amount, butene amount, and/or propylene amount of the conjugated diene polymer before hydrogenation can be measured using a nuclear magnetic resonance device (NMR) or the like. Specifically, it can be measured by the method described in the examples below. To measure.

再者，亦可以氫化後之共軛二烯系聚合物作為試樣，藉由質子核磁共振(1H-NMR)法測定氫化前之乙烯基鍵量。關於該方法，例舉乙烯基芳香族單體單元為苯乙烯，共軛二烯單體單元為1,3-丁二烯的共軛二烯系聚合物為例進行具體說明。 Furthermore, the conjugated diene polymer after hydrogenation may be used as a sample, and the amount of vinyl bonds before hydrogenation may be measured by a proton nuclear magnetic resonance ( 1 H-NMR) method. This method will be specifically described by taking, as an example, a conjugated diene-based polymer in which the vinyl aromatic monomer unit is styrene and the conjugated diene monomer unit is 1,3-butadiene.

使用ECS400(JEOL製，製品名)作為測定機器，使用氘代氯仿作為溶 劑，樣品濃度設為50mg/mL，於以下條件下進行測定。 ECS400 (manufactured by JEOL, product name) was used as a measurement device, and deuterated chloroform was used as a solvent. agent, the sample concentration was set to 50 mg/mL, and the determination was carried out under the following conditions.

(測定條件) (measurement conditions)

觀測頻率：400MHz Observation frequency: 400MHz

化學位移基準：氯仿(7.26ppm) Chemical shift benchmark: Chloroform (7.26ppm)

脈衝延遲：3秒 Pulse delay: 3 seconds

掃描次數：256次 Number of scans: 256 times

脈衝寬度：45° Pulse width: 45°

測定溫度：26℃ Measuring temperature: 26°C

氫化前之乙烯基鍵量可使用所獲得之NMR光譜中之化學位移為10.0ppm~0.0ppm之範圍之訊號之面積值來求出。更詳細而言，可藉由下述式(1)~(6)求出。 The amount of vinyl bonds before hydrogenation can be calculated using the area value of the signal in the range of the chemical shift of 10.0 ppm to 0.0 ppm in the obtained NMR spectrum. More specifically, it can be calculated|required by following formula (1)-(6).

(苯乙烯單體單元之每1質子之面積值) (area per 1 proton of styrene monomer unit)

=(X2-X1)/5 (1) =(X 2 -X 1 )/5 (1)

(未氫化1,2鍵丁二烯單體單元之每1質子之面積值) (area per proton of unhydrogenated 1,2-bond butadiene monomer unit)

=X3/2 (2) =X 3 /2 (2)

(未氫化1,4鍵丁二烯單體單元之每1質子之面積值) (area value per proton of unhydrogenated 1,4 bond butadiene monomer unit)

=(X4-(X3/2))/2 (3) =(X 4 -(X 3 /2))/2 (3)

(氫化1,2鍵丁二烯單體單元之每1質子之面積值) (area value per proton of hydrogenated 1,2-bond butadiene monomer unit)

=X5/3 (4) =X 5 /3 (4)

(氫化1,4鍵丁二烯單體單元之每1質子之面積值) (area value per proton of hydrogenated 1,4-bond butadiene monomer unit)

=(X6-(1)×3-(2)×3-(3)×4-(4)×8-X7)/8 (5) =(X 6 -(1)×3-(2)×3-(3)×4-(4)×8-X 7 )/8 (5)

(氫化前之乙烯基鍵量(mol%)) (Vinyl bonds before hydrogenation (mol%))

=((2)+(4))/((2)+(3)+(4)+(5))×100 (6) =((2)+(4))/((2)+(3)+(4)+(5))×100 (6)

其中，上述式(1)~(5)中之記號X1、X2、X3、X4、X5、X6、及X7之定義如下。 Wherein, the symbols X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , and X 7 in the above formulas (1) to (5) are defined as follows.

X1：以7.26ppm為中心，於7.26ppm~7.25ppm區間及7.27ppm~7.26ppm區間之各區間將訊號強度最小之位置彼此連結之線與NMR光譜所包圍之範圍之面積值 X 1 : Taking 7.26ppm as the center, the area value of the area surrounded by the line connecting the positions of the minimum signal intensity and the NMR spectrum in the intervals of 7.26ppm~7.25ppm and 7.27ppm~7.26ppm

X2：將8.0ppm及6.0ppm之訊號位置彼此連結之線與NMR光譜所包圍之範圍之面積值 X 2 : the area value of the range surrounded by the line connecting the signal positions of 8.0ppm and 6.0ppm and the NMR spectrum

X3：將6.0ppm及4.0ppm之訊號位置彼此連結之線與NMR光譜所包圍之面積值中，5.2ppm~4.9ppm之間訊號強度最小之位置之化學位移至4.0ppm之範圍之面積值 X 3 : In the area surrounded by the line connecting the signal positions of 6.0ppm and 4.0ppm and the NMR spectrum, the area value of the chemical shift of the position with the smallest signal intensity between 5.2ppm and 4.9ppm to 4.0ppm

X4：將6.0ppm及4.0ppm之訊號位置彼此連結之線與NMR光譜所包圍之面積值中，5.2ppm~4.9ppm之間訊號強度最小之位置之化學位移至6.0ppm之範圍之面積值 X 4 : In the area surrounded by the line connecting the signal positions of 6.0ppm and 4.0ppm and the NMR spectrum, the area value of the chemical shift of the position with the smallest signal intensity between 5.2ppm and 4.9ppm to 6.0ppm

X5：將4.0ppm及0.3ppm之訊號位置彼此連結之線與NMR光譜所包圍之面積值中，位於1.05ppm~0.85ppm之間的NMR光譜之谷中訊號強度最小之位置之化學位移至0.3ppm之範圍之面積值(其中，於1.05ppm~0.85ppm之間不存在谷之情形時，設為將4.0ppm及0.3ppm之訊號位置彼此連結之線與NMR光譜所包圍之面積值中，1.05ppm~0.85ppm之間訊號強度最小之位置之化學位移至0.3ppm之範圍之面積值) X 5 : In the area surrounded by the line connecting the signal positions of 4.0ppm and 0.3ppm and the NMR spectrum, the chemical shift of the position with the smallest signal intensity in the valley of the NMR spectrum between 1.05ppm and 0.85ppm is to 0.3ppm The area value of the range (where there is no valley between 1.05ppm and 0.85ppm, it is set as 1.05ppm in the area surrounded by the line connecting the signal positions of 4.0ppm and 0.3ppm and the NMR spectrum The chemical shift of the position with the smallest signal intensity between ~0.85ppm and the area value in the range of 0.3ppm)

X6：將4.0ppm及0.3ppm之訊號位置彼此連結之線與NMR光譜所包圍之範圍之面積值 X 6 : The area value of the area surrounded by the line connecting the signal positions of 4.0ppm and 0.3ppm and the NMR spectrum

X7：以1.50ppm作為中心，於1.49ppm~1.50ppm區間及1.50ppm~1.51ppm區間之各區間，將訊號強度最小之位置彼此連結之線與NMR光譜所包圍之範圍之面積值(其中，於將該訊號強度最小之位置彼此連結之線存在於較NMR光譜更上部之情形時，設為0) X 7 : Taking 1.50ppm as the center, the area value of the area surrounded by the line connecting the position of the minimum signal intensity and the range surrounded by the NMR spectrum in the intervals of 1.49ppm~1.50ppm and 1.50ppm~1.51ppm When the line connecting the positions of the minimum signal intensity exists in the upper part of the NMR spectrum, it is set to 0)

又，式(5)及(6)中之(1)~(5)分別為由上述式(1)~(5)獲得之值。 Moreover, (1)-(5) in formula (5) and (6) are the values obtained from said formula (1)-(5), respectively.

上述乙烯基鍵量、或丁烯量及/或丙烯量可藉由在共軛二烯系聚合物之製造時，添加路易斯鹼、例如醚、及胺等化合物作為乙烯基鍵量調整劑(以下表述為乙烯化劑)，或控制製造時之溫度而控制為上述數值範圍。一般而言，藉由增加乙烯基鍵量調整劑之量、或降低製造時之溫度，有乙烯基鍵量增加之傾向。 The above-mentioned amount of vinyl bonds, or the amount of butene and/or the amount of propylene can be obtained by adding compounds such as Lewis bases, ethers, and amines as vinyl bond amount regulators (hereinafter Expressed as vinylating agent), or control the temperature during manufacture to control the above numerical range. Generally, there exists a tendency for the amount of vinyl bonds to increase by increasing the amount of a vinyl bond amount regulator, or lowering the temperature at the time of manufacture.

(乙烯基芳香族單體單元) (vinyl aromatic monomer unit)

就共軛二烯系聚合物於烴溶劑中之溶解性及含有共軛二烯系聚合物之全固體電池黏著劑之黏結性及接著性之觀點而言，本實施方式之共軛二烯系聚合物中，乙烯基芳香族單體單元之含量相對於共軛二烯系聚合物之總量，較佳為80質量%以下。就相同之觀點、及進一步提高柔軟性之觀點而言，其含量更佳為5質量%以上60質量%以下。就進一步提高包含黏著劑之各層之低溫抗裂性之觀點而言，其含量進而較佳為10質量%以上，更佳為12質量%以上，就抑制因反覆充放電導致之固體電解質或電極活性物質之收縮而產生間隙，造成電池性能降低之觀點而言，較佳為15質量%以上，更佳為20質量%以上。更佳之 上限為40質量%以下，進而較佳為35質量%以下，尤佳為30質量%以下。 From the viewpoint of the solubility of the conjugated diene polymer in hydrocarbon solvents and the adhesiveness and adhesiveness of the all-solid battery adhesive containing the conjugated diene polymer, the conjugated diene polymer of the present embodiment In the 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-based polymer. From the same viewpoint and the viewpoint of further improving flexibility, the content is more preferably from 5% by mass to 60% by mass. From the viewpoint of further improving the low-temperature crack resistance of each layer including the adhesive, the content is further preferably 10% by mass or more, more preferably 12% by mass or more, in order to suppress the solid electrolyte or electrode activity caused by repeated charging and discharging. From the viewpoint of causing gaps due to shrinkage of the substance and causing degradation in battery performance, it is preferably at least 15% by mass, more preferably at least 20% by mass. better The upper limit is 40% by mass or less, more preferably 35% by mass or less, particularly preferably 30% by mass or less.

再者，共軛二烯系聚合物中之乙烯基芳香族單體單元之含量可藉由紫外分光光度計法或質子核磁共振(1H-NMR)法進行測定。具體而言，可藉由實施例所記載之方法進行測定。 Furthermore, the content of the vinyl aromatic monomer unit in the conjugated diene polymer can be measured by ultraviolet spectrophotometry or proton nuclear magnetic resonance ( 1 H-NMR) method. Specifically, it can be measured by the method described in the examples.

本實施方式之共軛二烯系聚合物中，就共軛二烯系聚合物於無極性溶劑中之溶解性及含有共軛二烯系聚合物之全固體電池黏著劑之黏結性及接著性及耐熱性之觀點而言，以乙烯基芳香族單體單元作為主體之聚合物嵌段之含量相對於共軛二烯系聚合物之總量，較佳為40質量%以下。就相同之觀點、及進一步提高柔軟性之觀點而言，其含量更佳為5質量%以上35質量%以下。就進一步提高包含黏著劑之各層之低溫抗裂性之觀點而言，其含量進而較佳為10質量%以上33質量%以下。就抑制因反覆充放電導致之固體電解質或電極活性物質之收縮而產生間隙，造成電池性能降低之觀點而言，較佳為15質量%以上，更佳為20質量%以上。 Among the conjugated diene polymers of this embodiment, the solubility of the conjugated diene polymer in non-polar solvents and the adhesiveness and adhesiveness of the all-solid battery adhesive containing the conjugated diene polymer From the viewpoint of heat resistance, the content of the polymer block mainly composed of vinyl aromatic monomer units is preferably 40% by mass or less with respect to the total amount of the conjugated diene-based polymer. From the same viewpoint and the viewpoint of further improving flexibility, the content is more preferably from 5% by mass to 35% by mass. From the viewpoint of further improving the low-temperature crack resistance of each layer including the adhesive, the content is further preferably from 10% by mass to 33% by mass. It is preferably at least 15% by mass, more preferably at least 20% by mass, from the viewpoint of suppressing the generation of gaps due to shrinkage of the solid electrolyte or electrode active material due to repeated charging and discharging, resulting in degradation of battery performance.

又，就耐熱性及強度之觀點而言，以乙烯基芳香族單體單元作為主體之聚合物嵌段較佳為存在於共軛二烯系聚合物之主鏈中，較佳為存在於從聚合物鏈末端數起第1個或第2個嵌段。 Also, 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 main chain of the conjugated diene polymer. The first or second block from the end of the polymer chain.

再者，共軛二烯系聚合物中之以乙烯基芳香族單體單元作為主體之聚合物嵌段之含量可以如下方式算出，即，藉由以四氧化鋨作為觸媒，利用第三丁基過氧化氫使氫化前之共聚物氧化分解之方法(I.M.KOLTHOFF, et al.,Polym.Sci.1,429(1946)所記載之方法)(以下亦稱為「四氧化鋨分解法」)求出以乙烯基芳香族單體單元作為主體之聚合物嵌段之質量(但平均聚合度約30以下之乙烯基芳香族單體單元除外)。 Furthermore, the content of the polymer block mainly composed of vinyl aromatic monomer units in the conjugated diene polymer can be calculated as follows, that is, by using osmium tetroxide as a catalyst and using tertiary Method for oxidative decomposition of copolymers before hydrogenation based on hydrogen peroxide (I.M.KOLTHOFF, et al., Polym.Sci.1, 429 (1946)) (hereinafter also referred to as "osmium tetroxide decomposition method") to obtain the mass of the polymer block mainly composed of vinyl aromatic monomer units ( However, vinyl aromatic monomer units with an average degree of polymerization of about 30 or less are excluded).

又，氫化後之共軛二烯系聚合物中以乙烯基芳香族單體單元作為主體之聚合物嵌段之含量可使用氫化後之共軛二烯系聚合物(氫化共聚物(b))，藉由Y.Tanaka,et al.,RUBBER CHEMISTRY and TECHNOLOGY 54,685(1981)所記載之方法，利用核磁共振裝置(NMR)進行測定(以下亦稱為「NMR法」)。 In addition, the hydrogenated conjugated diene polymer (hydrogenated copolymer (b)) can be used for the content of the polymer block mainly composed of vinyl aromatic monomer units in the hydrogenated conjugated diene polymer. , by the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981), using a nuclear magnetic resonance device (NMR) to measure (hereinafter also referred to as "NMR method").

關於NMR法，以乙烯基芳香族單體單元為苯乙烯、共軛二烯單體單元為1,3-丁二烯之情形為例進行具體說明。 Regarding the NMR method, a case where the vinyl aromatic monomer unit is styrene and the conjugated diene monomer unit is 1,3-butadiene will be specifically described as an example.

將氫化後之共軛二烯系聚合物30mg溶解於氘代氯仿1g而獲得試樣，使用該試樣測定1H-NMR，由化學位移6.9ppm~6.3ppm之累計值相對於總累計值之比率，求出以乙烯基芳香族單體單元作為主體之聚合物嵌段(於此情形時成為聚苯乙烯嵌段)之含量(Ns值)。 A sample obtained by dissolving 30 mg of hydrogenated conjugated diene polymer in 1 g of deuterated chloroform was used to measure 1H-NMR, and the ratio of the cumulative value of the chemical shift from 6.9 ppm to 6.3 ppm to the total cumulative value , to obtain the content (Ns value) of the polymer block mainly composed of vinyl aromatic monomer units (in this case, polystyrene block).

嵌段苯乙烯強度(b-St強度) Block styrene strength (b-St strength)

=(6.9ppm~6.3ppm之累計值)/2 =(cumulative value of 6.9ppm~6.3ppm)/2

無規苯乙烯強度(r-St強度) Random Styrene Strength (r-St Strength)

=(7.5ppm~6.9ppm之累計值)-3×(b-St) =(cumulative value of 7.5ppm~6.9ppm)-3×(b-St)

乙烯-丁烯強度(EB強度) Ethylene-Butene Strength (EB Strength)

=總累計值-3×{(b-St強度)+(r-St強度)}/8 =Total cumulative value-3×{(b-St intensity)+(r-St intensity)}/8

藉由NMR法獲得之聚苯乙烯嵌段含量(Ns值) Polystyrene block content (Ns value) obtained by NMR method

=104×(b-St強度) =104×(b-St intensity)

/[104×{(b-St強度)+(r-St強度)}+56×(EB強度)] /[104×{(b-St intensity)+(r-St intensity)}+56×(EB intensity)]

此處，藉由四氧化鋨分解法測定之氫化前之共軛二烯系聚合物中之以乙烯基芳香族單體單元作為主體之聚合物嵌段之含量(稱為「Os值」)與藉由NMR法測定之氫化後之共軛二烯系聚合物中之以乙烯基芳香族單體單元作為主體之聚合物嵌段之含量(稱為「Ns值」)之間存在下述式所示之相關關係。具體而言，可藉由實施例所記載之方法進行測定。 Here, the content of the polymer block mainly composed of vinyl aromatic monomer units (referred to as "Os value") in the conjugated diene polymer before hydrogenation measured by the osmium tetroxide decomposition method and The content of the polymer block mainly composed of vinyl aromatic monomer units (referred to as "Ns value") in the hydrogenated conjugated diene polymer measured by the NMR method exists between the following formulas: show the relevant relationship. Specifically, it can be measured by the method described in the examples.

Os值=-0.012(Ns值)2+1.8(Ns值)-13.0 Os value=-0.012(Ns value)2+1.8(Ns value)-13.0

「以乙烯基芳香族單體單元作為主體之聚合物嵌段」意指該乙烯基芳香族單體單元之含量相對於該聚合物嵌段整體超過70質量%之聚合物嵌段。就包含共軛二烯系聚合物之全固體電池黏著劑之黏結性及接著性之觀點而言，以乙烯基芳香族單體單元作為主體之聚合物嵌段之乙烯基芳香族單體單元之含量較佳為80質量%以上，更佳為90質量%以上，進而較佳為95質量%以上。於上述範圍中，以乙烯基芳香族單體單元作為主體之聚合物嵌段之凝聚力較高，發揮作為物理交聯點之作用。以乙烯基芳香族單體單元作為主體之聚合物嵌段之乙烯基芳香族單體單元之含量之上限並無特別限制，可為100質量%以下，亦可為99質量%以下。 "A polymer block mainly composed of a vinyl aromatic monomer unit" means a polymer block in which the content of the vinyl aromatic monomer unit exceeds 70% by mass relative to the entire polymer block. From the viewpoint of adhesiveness and adhesiveness of an all-solid battery adhesive containing a conjugated diene polymer, the vinyl aromatic monomer unit of the polymer block mainly composed of a vinyl aromatic monomer unit The content is preferably at least 80% by mass, more preferably at least 90% by mass, further preferably at least 95% by mass. Within the above range, the cohesive force of the polymer block mainly composed of vinyl aromatic monomer units is relatively high, and functions as physical crosslinking points. The upper limit of the content of the vinyl aromatic monomer unit in the polymer block mainly composed of the vinyl aromatic monomer unit is not particularly limited, and may be 100% by mass or less, or 99% by mass or less.

作為乙烯基芳香族單體，並無特別限制，例如可例舉：苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、二乙烯基苯、1,1-二苯乙烯、N,N-二甲基-對胺基乙基苯乙烯、及N,N-二乙基-對胺基乙基苯乙烯等乙烯基芳香族化合物。 該等中，就獲取性及生產性之觀點而言，較佳為苯乙烯、α-甲基苯乙烯、及對甲基苯乙烯，更佳為苯乙烯。以乙烯基芳香族化合物作為主體之聚合物嵌段可包含1種乙烯基芳香族單體，亦可包含2種以上之乙烯基芳香族單體。 The vinyl aromatic monomer is not particularly limited, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N -Vinyl aromatic compounds such as dimethyl-p-aminoethylstyrene and N,N-diethyl-p-aminoethylstyrene. Among these, styrene, α-methylstyrene, and p-methylstyrene are preferable from the viewpoint of availability and productivity, and styrene is more preferable. The polymer block mainly composed of a vinyl aromatic compound may contain one type of vinyl aromatic monomer, or may contain two or more types of vinyl aromatic monomers.

(改性基) (Modifier)

於共軛二烯系聚合物具有改性基之情形時，較佳為對電極活性物質層之構成成分或固體電解質之黏結性基及/或對集電體之接著性基。作為此種改性基，並無特別限制，例如可例舉：酸酐基、羥基、羰基、硫羰基、醯鹵化物基、羧基、硫羧酸基、醛基、硫醛基、羧酸酯基、醯胺基、醯亞胺基、磺酸酯基、磷酸酯基、胺基、亞胺基、氰基、胺基甲酸酯基、脲基、吡啶基、喹啉基、環氧基、硫環氧基、硫基、異氰酸基、異硫氰酸酯基、鹵化矽基、矽烷醇基、烷氧基矽烷基、鹵化錫基、烷氧基錫基、苯基錫基、及離子性基等。共軛二烯系聚合物可具有單獨1種如上所述之改性基，或組合具有2種以上之如上所述之改性基。作為離子性基，例如可例舉：磺酸基、磺醯亞胺基、硫酸基、膦酸基、磷酸基、羧酸基、及銨基或其等之鹽。 When the conjugated diene polymer has a modification group, it is preferably a constituent of the electrode active material layer, an adhesive group for the solid electrolyte, and/or an adhesive group for the current collector. Such a modifying group is not particularly limited, and examples thereof include an acid anhydride group, a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acyl halide group, a carboxyl group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, and a carboxylate group. , amido group, imide group, sulfonate group, phosphate group, amine group, imine group, cyano group, carbamate group, urea group, pyridyl group, quinoline group, epoxy group, Thiolyl group, thiol group, isocyanate group, isothiocyanate group, silicon halide group, silanol group, alkoxysilyl group, tin halide group, alkoxytin group, phenyltin group, and ionic groups, etc. The conjugated diene-based polymer may have one of the above-mentioned modifying groups alone, or may have two or more of the above-mentioned modifying groups in combination. As an ionic group, a sulfonic acid group, a sulfonimide group, a sulfuric acid group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, an ammonium group, or salts thereof are mentioned, for example.

其中，於使用硫化物系固體電解質或氧化物系固體電解質之電池之情形時，就進一步提高電極活性物質層之構成成分彼此或固體電解質之黏結性或對集電體之接著性之觀點而言，共軛二烯系聚合物具有之改性基較佳為選自由酸酐基、羥基、羰基、羧基、胺基、環氧基、烷氧基矽烷基、醯胺基、胺基甲酸酯基、脲基、異氰酸基、及離子性基所組成之群中之一種以上。 Among them, 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 adhesion between the components of the electrode active material layer or the solid electrolyte or the adhesion to the current collector , The modified group of the conjugated diene polymer is preferably selected from acid anhydride group, hydroxyl group, carbonyl group, carboxyl group, amine group, epoxy group, alkoxysilane group, amido group, urethane group , urea group, isocyanate group, and one or more of the group consisting of ionic groups.

進而，其中，就獲取性及抑制因與硫化物系固體電解質之反應導致之硫化氫之產生之觀點而言，改性基更佳為酸酐基、羧基、胺基、環氧基、烷氧基矽烷基、羥基。又，就抑制醇之產生之觀點而言，改性基進而較佳為酸酐基、羧基、胺基、環氧基、羥基。進而，就生產性(改性率之調整容易性或安全性)之觀點而言，改性基更佳為胺基或羥基、羧基、酸酐基。又，就對於集電體表面或電池構件表面之官能基的利用化學反應之鍵形成性、或作為供體及受體發揮作用之氫鍵性之觀點而言，改性基較佳為胺基或羥基、羧基。尤其就與導電助劑等具有羧基作為表面官能基之材料之氫鍵性或鍵形成性之觀點而言，改性基較佳為胺基。胺基中，就對於集電體表面或電池構件表面之官能基的利用化學反應之鍵形成性或作為供體及受體發揮作用之氫鍵性之觀點而言，較佳為一級胺基或二級胺基。 Furthermore, among these, the modifying group is more preferably an acid anhydride group, carboxyl group, amine group, epoxy group, or alkoxy group from the viewpoint of availability and suppression of hydrogen sulfide generation due to reaction with a sulfide-based solid electrolyte. Silyl groups, hydroxyl groups. Moreover, the modifying group is further preferably an acid anhydride group, a carboxyl group, an amine group, an epoxy group, or a hydroxyl group from the viewpoint of suppressing the generation of alcohol. Furthermore, the modifying group is more preferably an amino group, a hydroxyl group, a carboxyl group, or an acid anhydride group from the viewpoint of productivity (ease of adjustment of the modification ratio or safety). In addition, the modifying group is preferably an amine group from the viewpoint of bond formation by chemical reaction or hydrogen bonding function as a donor and acceptor to the functional group on the surface of the current collector or the surface of the battery member. Or hydroxyl, carboxyl. In particular, the modifying group is preferably an amine group from the viewpoint of hydrogen bonding or bond forming properties with a material having a carboxyl group as a surface functional group such as a conductive additive. Among the amine groups, preferred are primary amine groups or secondary amine groups.

於共軛二烯系聚合物具有不屬於對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基的官能基之情形時，藉由使與該官能基及電極活性物質層之構成成分、固體電解質或集電體均可相互作用之其他化合物與共軛二烯系聚合物之官能基進行反應，可進一步提昇與共軛二烯系聚合物之電極活性物質層之構成成分、固體電解質或集電體之接著性。即，共軛二烯系聚合物所具有之官能基與該其他化合物藉由分子間力或化學鍵而相互作用，與該官能基相互作用之該其他化合物與電極活性物質層之構成成分、固體電解質或集電體藉由分子間力或化學鍵而相互作用，藉此，可進一步提昇共軛二烯系聚合物之黏結性及接著性。 In the case where the conjugated diene polymer has a functional group that is not a constituent of the electrode active material layer or an adhesive group for the solid electrolyte or an adhesive group for the current collector, by using the functional group and Other compounds that can interact with the constituents of the electrode active material layer, solid electrolyte or current collector react with the functional groups of the conjugated diene polymer to further enhance the electrode active material with the conjugated diene polymer The composition of the layer, the adhesion of the solid electrolyte or the current collector. That is, the functional group of the conjugated diene polymer interacts with the other compound through intermolecular force or chemical bond, and the other compound that interacts with the functional group interacts with the constituent components of the electrode active material layer and the solid electrolyte. Or the current collectors interact through intermolecular forces or chemical bonds, thereby further improving the adhesiveness and adhesiveness of the conjugated diene polymer.

作為此種其他化合物，並無特別限制，例如可例舉：碳二醯亞胺化合物、疊氮磷酸二苯酯等醯胺縮合劑、或烷氧基矽烷化合物、胺基化合物、羥基化合物、異氰酸酯化合物、及環氧化合物。其他化合物可單獨使用1種或組合2種以上使用。 Such other compounds are not particularly limited, and examples thereof include carbodiimide compounds, amide condensing agents such as diphenylphosphoryl azide, alkoxysilane compounds, amino compounds, hydroxyl compounds, and isocyanates. compounds, and epoxy compounds. Other compounds can be used alone or in combination of two or more.

作為碳二醯亞胺化合物，並無特別限制，例如可例舉：N,N'-二環己基碳二醯亞胺、N,N'-二異丙基碳二醯亞胺、及1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺。 The carbodiimide compound is not particularly limited, for example, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, and 1- (3-Dimethylaminopropyl)-3-ethylcarbodiimide.

作為烷氧基矽烷化合物，並無特別限制，例如可例舉：四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四異丙氧基矽烷、四丁氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、及2-(3,4-環氧環己基)乙基三乙氧基矽烷。 The alkoxysilane compound is not particularly limited, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

作為胺化合物，並無特別限制，例如可例舉：二胺基丁烷、二胺基戊烷、二胺基己烷、二胺基庚烷、及二胺基辛烷。 It does not specifically limit as an amine compound, For example, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, and diaminooctane are mentioned.

作為羥基化合物，並無特別限制，例如可例舉：二羥基丁烷、二羥基戊烷、二羥基己烷、二羥基庚烷、及二羥基辛烷。 It does not specifically limit as a hydroxy compound, For example, dihydroxybutane, dihydroxypentane, dihydroxyhexane, dihydroxyheptane, and dihydroxyoctane are mentioned.

作為異氰酸酯化合物，並無特別限制，例如可例舉：己烷亞甲基二異氰酸酯、1,4-伸苯基二異氰酸酯、及二環己基甲烷4,4'-二異氰酸酯。 It does not specifically limit as an isocyanate compound, For example, hexane methylene diisocyanate, 1, 4- phenylene diisocyanate, and dicyclohexyl methane 4, 4'- diisocyanate are mentioned.

作為環氧化合物，並無特別限制，例如可例舉：乙二醇二縮水甘油醚、及1,4-丁二醇二縮水甘油醚。 Although it does not specifically limit as an epoxy compound, For example, ethylene glycol diglycidyl ether, and 1, 4- butanediol diglycidyl ether are mentioned.

該等化合物亦可用於具有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基之共軛二烯系聚合物。 These compounds can also be used for conjugated diene-based polymers having an adhesive group for constituent components of an electrode active material layer or a solid electrolyte, or an adhesive group for a current collector.

上述共軛二烯系聚合物具有之改性基之含量並無特別限制，就進一步提昇黏結性及接著性之觀點而言，較佳為0.5個/鏈以上。就相同之觀點而言，更佳為0.7個/鏈以上，進而較佳為1.0個/鏈以上，進而較佳為2.0個/鏈以上。藉由使改性基之含量為0.5個/鏈以上，改性基可與電極活性物質層之構成成分、固體電解質或集電體更充分地相互作用，接著性進一步提昇。另一方面，就製成漿料時之導電助劑之分散性之觀點而言，為50個/鏈以下，更佳為20個/鏈以下，進而較佳為10個以下，更佳為2.0個/鏈以下，進而較佳為1.0個以下。 The content of the modifying group in the above-mentioned conjugated diene polymer is not particularly limited, but it is preferably 0.5 or more per chain from the viewpoint of further improving the adhesiveness and adhesiveness. From the same viewpoint, it is more preferably at least 0.7/chain, more preferably at least 1.0/chain, and still more preferably at least 2.0/chain. By making the content of the modifying group 0.5 or more per chain, the modifying group can more fully interact with the constituents of the electrode active material layer, the solid electrolyte, or the current collector, and the adhesiveness can be further improved. On the other hand, from the viewpoint of the dispersibility of the conductive auxiliary agent when it is made into a slurry, it is 50 pieces/chain or less, more preferably 20 pieces/chain or less, further preferably 10 pieces/chain or less, more preferably 2.0 No./chain or less, and more preferably 1.0 or less.

又，就進一步防止包含共軛二烯系聚合物之全固體電池黏著劑之凝膠化等問題之觀點而言，改性基之含量較佳為300個/鏈以下。此處所謂「鏈」係指共軛二烯系聚合物之類的聚合物一分子，至於聚合物結構藉由化學鍵而分支者，將一個支鏈計為一分子鏈。 Also, from the viewpoint of further preventing problems such as gelation of the all-solid battery adhesive containing a conjugated diene polymer, the content of the modifying group is preferably 300 or less per chain. The so-called "chain" here refers to one molecule of a polymer such as a conjugated diene polymer. As for a polymer structure branched by chemical bonds, one branched chain is counted as one molecular chain.

共軛二烯系聚合物可除上述改性基以外，還具有提高離子傳導性之官能基或聚合物鏈。作為此種官能基或聚合物鏈，並無特別限制，例如可例 舉：醚基、冠醚、聚乙二醇、硼酸基、硼酸酯基、包含鋰離子電池中使用之鋰離子電解質之離子性基、包含離子性液體之離子性基等。 The conjugated diene polymer may have, in addition to the above-mentioned modifying groups, a functional group or a polymer chain that improves ion conductivity. As such a functional group or a polymer chain, there is no particular limitation, for example, Examples: ether group, crown ether, polyethylene glycol, boric acid group, borate ester group, ionic group including lithium ion electrolyte used in lithium ion battery, ionic group including ionic liquid, etc.

(氫化) (hydrogenation)

共軛二烯系聚合物較佳為經氫化者。相對於共軛二烯單體單元之合計100mol%之氫化率就共軛二烯系聚合物之電化學穩定性之觀點而言，較佳為30mol%以上，就熱穩定性之觀點而言，更佳為50mol%以上，就進一步提昇接著性之觀點而言，進而較佳為70mol%以上，就藉由聚合物鏈之纏結而提高電極膜之強度之觀點而言，尤佳為90mol%以上。 The conjugated diene polymer is preferably hydrogenated. The hydrogenation rate relative to the total 100 mol% of conjugated diene monomer units is preferably 30 mol% or more from the viewpoint of electrochemical stability of the conjugated diene polymer, and from the viewpoint of thermal stability, More preferably 50 mol% or more, from the viewpoint of further improving adhesiveness, more preferably 70 mol% or more, and especially preferably 90 mol% from the viewpoint of improving the strength of the electrode film by entanglement of polymer chains above.

共軛二烯系聚合物之氫化率可使用核磁共振裝置(NMR)等進行測定，具體而言可藉由實施例所記載之方法進行測定。 The hydrogenation rate of the conjugated diene polymer can be measured using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, it can be measured by the method described in the examples.

又，氫化率例如可藉由調整氫化時之氫量或觸媒量而控制為上述數值範圍。 Also, the hydrogenation rate can be controlled within the above numerical range by, for example, adjusting the amount of hydrogen or the amount of catalyst during hydrogenation.

(甲苯不溶分量) (toluene insoluble content)

共軛二烯系聚合物之甲苯不溶分量較佳為10wt%以下，更佳為5wt%以下，進而較佳為3wt%以下，尤佳為1wt%以下。甲苯不溶分量之下限值並無特別限制，為0wt%。藉由使甲苯不溶分量為10wt%以下，有塗膜之平滑性進一步提高之傾向。再者，甲苯不溶分量可藉由實施例所記載之方法進行測定。 The toluene insoluble content of the conjugated diene polymer is preferably 10 wt % or less, more preferably 5 wt % or less, further preferably 3 wt % or less, especially preferably 1 wt % or less. The lower limit of the toluene insoluble content is not particularly limited, and is 0 wt%. By making the toluene insoluble content 10 wt% or less, there exists a tendency for the smoothness of a coating film to improve further. In addition, the toluene insoluble content can be measured by the method described in an Example.

(無規共聚物嵌段) (random copolymer block)

本實施方式之全固體電池黏著劑中使用之共軛二烯系聚合物亦可進而具有共軛二烯單體單元與乙烯基芳香族單體單元之無規共聚物嵌段。藉由設為無規結構，電極活性物質層之構成成分或固體電解質與共軛二烯系聚合物之親和性提高，從而黏結性提高，或藉由控制黏彈性特性而對電池之作動溫度區域賦予制振性，可提高電池之耐久性。 The conjugated diene polymer used in the all-solid battery adhesive of this embodiment may further have a random copolymer block of a conjugated diene monomer unit and a vinyl aromatic monomer unit. By adopting a random structure, the composition of the electrode active material layer or the affinity between the solid electrolyte and the conjugated diene polymer is improved, thereby improving the adhesion, or controlling the operating temperature range of the battery by controlling the viscoelastic properties. Improving the durability of the battery by imparting vibration damping properties.

作為共軛二烯化合物與乙烯基芳香族化合物之無規共聚物嵌段中可包含之乙烯基芳香族單體及共軛二烯單體，可例舉作為上述以乙烯基芳香族聚合物作為主體之嵌段、及以共軛二烯系聚合物作為主體之嵌段中可包含者例示者。 Examples of the vinyl aromatic monomer and conjugated diene monomer that may be contained in the random copolymer block of a conjugated diene compound and a vinyl aromatic compound include the above-mentioned vinyl aromatic polymer as Examples of what may be included in the main block and the main block of the conjugated diene polymer.

作為無規共聚物嵌段中之乙烯基芳香族單體單元之分佈狀態，並無特別限制，乙烯基芳香族單體單元可均勻地分佈，或亦可呈錐狀分佈。又，乙烯基芳香族單體單元均勻分佈之部分及/或呈錐狀分佈之部分可分別存在複數個，亦可存在複數個乙烯基芳香族單體單元之含量不同之鏈段。 The distribution state of the vinyl aromatic monomer units in the random copolymer block is not particularly limited, and the vinyl aromatic monomer units may be uniformly distributed or may be distributed in a cone shape. In addition, there may be a plurality of portions in which the vinyl aromatic monomer units are uniformly distributed and/or a portion in which the vinyl aromatic monomer units are distributed in a cone shape, or a plurality of segments having different contents of the vinyl aromatic monomer units.

本實施方式之共軛二烯系聚合物中，除共軛二烯單體及乙烯基芳香族單體以外，亦可使用能夠與共軛二烯單體及乙烯基芳香族單體共聚之其他單體。 In the conjugated diene polymer of the present embodiment, other than the conjugated diene monomer and the vinyl aromatic monomer, other compounds that can be copolymerized with the conjugated diene monomer and the vinyl aromatic monomer can also be used. monomer.

(共軛二烯系聚合物之結構) (Structure of Conjugated Diene Polymer)

作為本實施方式之共軛二烯系聚合物之結構，並無特別限制，例如可 例舉：一部分具有下述式所表示之結構者、或為下述式所表示之結構者。再者，下述式中，有時亦省略改性基之記載。 The structure of the conjugated diene polymer of this embodiment is not particularly limited, for example, For example: a part has a structure represented by the following formula, or has a structure represented by the following formula. In addition, in the following formulae, description of a modifying group may be omitted sometimes.

(a-b)n、b-(a-b)n、a-(b-a)n、(a-b)m-X、(b-a)m-X、[(a-b)n]m-X、[(b-a)n]m-X、[b-(a-b)n]m-X、[a-(b-a)n]m-X、[(a-b)n-a]m-X、[(b-a)n-b]m-X、(a-c)n、c-(a-c)n、a-(c-a)n、(a-c)m-X、(c-a)m-X、[(a-c)n]m-X、[(c-a)n]m-X、[c-(a-c)n]m-X、[a-(c-a)n]m-X、[(a-c)n-a]m-X、[(c-a)n-c]m-X、c-(b-a)n、c-(a-b)n、c-(a-b-a)n、c-(b-a-b)n、a-c-(b-a)n、a-c-(a-b)n、a-c-(b-a)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、c-b-(a-c)n-a、[(c-a-b)n]m-X、[c-(a-b)n]m-X、[(c-a)n-b]m-X、[(c-a-c)n-b]m-X、[(b-a-c)n]m-X、[b-(a-c)n]m-X、[b-(c-a-c)n]m-X、[b-(a-c-a)n]m-X、(b1-b2)n-a、(b1-b2-b)n-a、(b1-b2-a)n、(b1-b2-a)n-b、(b1-b2-a-b)n、(b1-b2-a)m-X、(b1-b2-a-b)m-X。 (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, [(abc) n ] m -X, [a-(bc) n ] m -X, [(ab) n -c] m -X, [(aba) n -c] m -X, [ (bab) n -c] m -X, [(cba) n ] m -X, [c-(ba)n] m -X, [c-(aba) n ] m -X, [c-(bab ) n ] m -X, a-(bc) n , a-(cb) n , a-(cbc) n , a-(bcb) n , ca-(bc) n , ca-(cb) n , ca -(bc) n -b, [(cba) n ] m -X, [c-(ba) n ] m -X, [(cb) n -a] m -X, [(cbc) n -a] m -X, [(bcb) n -a] m -X, [(abc) n ] m -X, [a-(bc) n ] m -X, [a-(cbc) n ] m -X, [a-(bcb) n ] m -X, b-(ac) n , b-(ca) n , b-(cac) n , b-(aca) n , cb-(ac) n , cb-( ca) 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, (b 1 -b 2 ) n -a, (b 1 -b 2 -b) n -a, (b 1 -b 2 -a) n , (b 1 -b 2 -a) n -b, (b 1 -b 2 -ab) n , (b 1 -b 2 -a) m -X, (b 1 -b 2 -ab) m -X.

再者，上述各式中，a表示以乙烯基芳香族單體單元作為主體之乙烯基芳香族聚合物嵌段，b表示以共軛二烯單體單元作為主體之共軛二烯聚合物嵌段，b1及b2表示以共軛二烯單體單元作為主體之共軛二烯聚合物嵌段(其中，b1中之乙烯基鍵量小於b2中之乙烯基鍵量)，c表示共軛二烯單體與乙烯基芳香族單體之無規共聚物嵌段。再者，於b1、b2、b均存在之情 形時，b之乙烯基鍵量並無特別限定。n為1以上之整數，較佳為1~5之整數。m為2以上之整數，較佳為2~11之整數。X表示偶合劑之殘基或多官能起始劑之殘基。 Furthermore, in the above formulas, a represents a vinyl aromatic polymer block mainly composed of vinyl aromatic monomer units, and b represents a conjugated diene polymer block mainly composed of conjugated diene monomer units. Segment, b1 and b2 represent the conjugated diene polymer block with conjugated diene monomer unit as the main body (wherein, the amount of vinyl bonds in b1 is less than the amount of vinyl bonds in b2 ), c Indicates a random copolymer block of conjugated diene monomer and vinyl aromatic monomer. In addition, when b 1 , b 2 , and b all exist, the amount of vinyl bonds in b is not particularly limited. n is an integer of 1 or more, preferably an integer of 1-5. m is an integer of 2 or more, preferably an integer of 2-11. X represents the residue of a coupler or the residue of a polyfunctional initiator.

就含有共軛二烯系聚合物之全固體電池黏著劑之黏結性及接著性之觀點而言，本實施方式之共軛二烯系聚合物較佳為主要包含具有b、b1或b2嵌段之結構。又，就提高機械強度之觀點而言，更佳為a-b、a-b-a、a-b-a-b、b1-b2-a、b1-b2-a-b、及b1-b2-b-a及該等之偶合體中之至少1種之結構式所表示之聚合物。就共軛二烯系聚合物於無極性溶劑中之溶解性及含有共軛二烯系聚合物之全固體電池黏著劑之黏結性及接著性之觀點而言，較佳為分子鏈內具有2個以上a嵌段之結構。 From the viewpoint of the adhesiveness and adhesiveness of the all-solid battery adhesive containing a conjugated diene polymer , the conjugated diene polymer of this embodiment preferably mainly contains block structure. Also, from the viewpoint of improving the mechanical strength, ab, aba, abab, b 1 -b 2 -a, b 1 -b 2 -ab, and b 1 -b 2 -ba and their couplings are more preferable. Polymers represented by at least one structural formula among them. In terms of the solubility of the conjugated diene polymer in non-polar solvents and the adhesiveness and adhesiveness of the all-solid battery adhesive containing the conjugated diene polymer, it is preferable to have 2 in the molecular chain. The structure of more than one a block.

又，共軛二烯系聚合物之末端或偶合部較佳為具有改性基。藉此，有接著性、黏結性、導電助劑分散性之平衡性進一步提昇之傾向。 Moreover, it is preferable that the terminal or coupling part of a conjugated diene polymer has a modification group. This tends to further improve the balance of adhesiveness, cohesiveness, and dispersibility of the conductive additive.

(重量平均分子量及分子量分佈) (weight average molecular weight and molecular weight distribution)

就含有共軛二烯系聚合物之全固體電池黏著劑之黏結性及接著性、及於無極性溶劑中之溶解性之觀點而言，共軛二烯系聚合物之重量平均分子量(Mw)(以下亦稱為「Mw」)較佳為4萬以上200萬以下，更佳為6萬以上150萬以下，進而較佳為10萬以上100萬以下，進而更佳為20萬以上80萬以下。Mw之下限更佳為20萬以上，更佳為25萬以上。上限更佳為50萬以下，進而較佳為45萬以下。就儲存性或塗敷性之觀點而言，將Mw調整至較佳之範圍較為重要，使得包含共軛二烯系聚合物及用於漿料調整 之溶劑之溶液於保存期間、或塗敷於集電體時溶劑不會立即揮發，就高分子溶液引起之蒸氣壓下降之觀點而言，共軛二烯系聚合物之分子量越高，蒸氣壓下降程度越大，越能抑制溶劑之揮發。黏著劑之高分子量化雖然具有此種優點，但先前之鋰離子電池中，使用N-甲基-2-吡咯啶酮(NMP)作為溶劑，共軛二烯系聚合物之溶解性較低，因此難以使用高分子量體。全固體電池中，作為溶劑，較佳為以烴溶劑為代表之無極性溶劑，共軛二烯系聚合物於烴溶劑中之溶解性優異，因此可使用高分子量體。又，若將NMP與以烴溶劑為代表之無極性溶劑進行比較，則NMP之蒸氣壓更低，就揮發性之觀點而言，高分子量體之必要性未被重視，但於無極性溶劑中，由於蒸氣壓高於NMP，故上述揮發性問題較為顯著，必須進行高分子量化。另一方面，於採用儘量減少溶劑之使用之電池製造方法之情形時，不具有改性基之共軛二烯系聚合物於無極性溶劑中之溶解性更優異，故較佳。 From the viewpoint of the adhesiveness and adhesiveness of the all-solid battery adhesive containing the conjugated diene polymer, and the solubility in non-polar solvents, the weight average molecular weight (Mw) of the conjugated diene polymer (hereinafter also referred to as "Mw") is preferably from 40,000 to 2 million, more preferably from 60,000 to 1.5 million, more preferably from 100,000 to 1 million, and even more preferably from 200,000 to 800,000 . The lower limit of Mw is more preferably at least 200,000, more preferably at least 250,000. The upper limit is more preferably at most 500,000, and more preferably at most 450,000. From the standpoint of storage and coating properties, it is important to adjust Mw to a better range, so that it contains conjugated diene polymers and is used for slurry adjustment The solution of the solvent will not volatilize immediately during storage or when it is applied to the collector. From the viewpoint of the decrease in the vapor pressure caused by the polymer solution, the higher the molecular weight of the conjugated diene polymer, the higher the vapor pressure. The greater the degree of decrease, the more the volatilization of the solvent can be suppressed. Although the high molecular weight of the binder has such advantages, in the previous lithium-ion batteries, N-methyl-2-pyrrolidone (NMP) was used as a solvent, and the solubility of the conjugated diene polymer was low. It is therefore difficult to use a high molecular weight body. In an all-solid-state battery, the solvent is preferably a non-polar solvent represented by a hydrocarbon solvent, and a conjugated diene polymer has excellent solubility in a hydrocarbon solvent, so a high-molecular-weight material can be used. In addition, if NMP is compared with non-polar solvents represented by hydrocarbon solvents, the vapor pressure of NMP is lower. From the viewpoint of volatility, the necessity of high molecular weight bodies is not taken seriously, but , Since the vapor pressure is higher than that of NMP, the above-mentioned volatility problem is more significant, and it is necessary to increase the molecular weight. On the other hand, in the case of adopting a battery manufacturing method that minimizes the use of solvents, a conjugated diene polymer having no modification group is more excellent in solubility in nonpolar solvents, so it is preferable.

藉由使重量平均分子量(Mw)為3萬以上，有聚合物鏈之纏結或乙烯基芳香族聚合物嵌段之凝聚力進一步提昇，黏結力或接著力進一步提昇之傾向。尤其是藉由使重量平均分子量(Mw)為200萬以下，有溶解於無極性溶劑時之黏度變得更低，電極生產時各層之成膜性提昇之傾向。 When the weight average molecular weight (Mw) is 30,000 or more, the entanglement of the polymer chains or the cohesion of the vinyl aromatic polymer block is further improved, and the cohesive force or adhesive force tends to be further improved. In particular, by setting the weight average molecular weight (Mw) to 2 million or less, the viscosity when dissolved in a nonpolar solvent becomes lower, and the film-forming properties of each layer during electrode production tend to be improved.

又，根據用途會對全固體電池要求耐熱性，當變成高溫狀態時有因黏著劑之流動而導致電池性能降低之虞。於此種情形時，就抑制流動之觀點而言，以共軛二烯系聚合物之重量平均分子量(Mw)較高為佳。所要求之耐熱性取決於機器之規格，因此需要耐熱性之用途並無特別限制，作為要求 耐熱性之用途，例如可例舉：搭載於發動機室之汽車用電源或汽車馬達用電源、搭載於大型產業機械之馬達用電源、需要滅菌加熱之醫療用機器電源、直接安裝於家電或汽車印刷配線基板上之小型電源等。於如直接安裝於印刷配線基板上之情形般歷經回流焊步驟之情形時，有時亦需要耐熱性。 Also, heat resistance is required for all solid-state batteries depending on the application, and there is a possibility that the performance of the battery may decrease due to the flow of the binder when it becomes a high-temperature state. In such a case, it is preferable that the weight average molecular weight (Mw) of the conjugated diene polymer is higher from the viewpoint of flow suppression. The required heat resistance depends on the specifications of the machine, so there are no special restrictions on applications that require heat resistance, as a requirement Applications of heat resistance include, for example: power supplies for automobiles or automobile motors mounted in the engine room, power supplies for motors mounted in large industrial machinery, power supplies for medical equipment that require sterilization and heating, direct installation in home appliances or automotive printing Small power supplies on wiring boards, etc. In the case of passing through the reflow process as in the case of direct mounting on a printed wiring board, heat resistance may also be required.

共軛二烯系聚合物之重量平均分子量(Mw)係基於由市售之標準聚苯乙烯之測定求出之校準曲線而求出藉由凝膠滲透層析法(GPC)測定所獲得之層析圖之峰之分子量而獲得的重量平均分子量(Mw)。再者，校準曲線只要使用標準聚苯乙烯之峰值分子量繪製即可。 The weight-average molecular weight (Mw) of the conjugated diene-based polymer was obtained from the layer obtained by gel permeation chromatography (GPC) measurement based on a calibration curve obtained from the measurement of commercially available standard polystyrene. The weight average molecular weight (Mw) obtained by analyzing the molecular weight of the peak in the graph. Furthermore, the calibration curve can be drawn using the peak molecular weight of standard polystyrene.

改性前之共軛二烯系聚合物之分子量分佈亦同樣可由GPC測定求出，分子量分佈可由重量平均分子量(Mw)與數量平均分子量(Mn)之比率(Mw/Mn)求出。 The molecular weight distribution of the conjugated diene polymer before modification can also be obtained by GPC measurement, and the molecular weight distribution can be obtained from the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

共軛二烯系聚合物之由GPC測定之單一峰之分子量分佈較佳為5.0以下，更佳為4.0以下，進而較佳為3.0以下，進而更佳為2.5以下。又，分子量分佈之下限並無特別限制，可為1.0以上，亦可為1.1以上。 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, further preferably 3.0 or less, still more preferably 2.5 or less. Moreover, the lower limit of molecular weight distribution is not specifically limited, It may be 1.0 or more, and may be 1.1 or more.

(水分量) (moisture content)

全固體電池黏著劑較佳為不含水分，全固體電池黏著劑之水分量較佳為200ppm以下，更佳為100ppm以下，進而較佳為50ppm以下，進而更佳為10ppm以下，尤佳為1ppm以下。全固體電池黏著劑中所含之水分可利用常壓或減壓之乾燥機來乾燥去除，亦可保管於除濕環境下而去除。 此時，亦可處於加熱下或者加熱且加壓機或輥等之加壓下。 The all-solid battery adhesive is preferably free of moisture, and the moisture content of the all-solid battery adhesive is preferably less than 200ppm, more preferably less than 100ppm, further preferably less than 50ppm, further preferably less than 10ppm, and especially preferably less than 1ppm the following. The moisture contained in the all-solid battery adhesive can be removed by drying with a normal pressure or reduced pressure dryer, or stored in a dehumidified environment. At this time, it may be under heating or under pressure with a press machine or a roll while heating.

於此情形時，乾燥或除濕前之全固體電池黏著劑之水分量可為200ppm以上。又，就水分去除效率之觀點而言，全固體電池黏著劑中使用之共軛二烯系聚合物之水分量較佳為1wt%以下，更佳為0.5wt%以下，進而較佳為0.1wt%以下，進而更佳為0.05wt%以下，尤佳為0.02wt%以下。共軛二烯系聚合物中所含之水分可利用常壓或減壓之乾燥機來乾燥去除，亦可保管於除濕環境下而去除。此時，亦可處於加熱下或加熱且加壓機或輥等之加壓下。 In this case, the moisture content of the all-solid battery adhesive before drying or dehumidification may be 200 ppm or more. Also, from the viewpoint of moisture removal efficiency, the moisture content of the conjugated diene polymer used in the all-solid battery adhesive is preferably 1 wt % or less, more preferably 0.5 wt % or less, and still more preferably 0.1 wt % % or less, more preferably less than 0.05wt%, especially preferably less than 0.02wt%. The moisture contained in the conjugated diene polymer can be removed by drying it with a dryer at normal pressure or reduced pressure, or by storing it in a dehumidified environment. At this time, it may be under heating or under pressure with a press machine or a roll while heating.

共軛二烯系聚合物之形狀可為顆粒，於漿料製備前減少聚合物之水分之情形時，就水分去除效率之觀點而言，較佳為比表面積較大之形狀，較佳為屑粒或粉末狀。包含共軛二烯系聚合物之漿料較佳為含水量為1wt%以下，但由於漿料中除聚合物以外亦含有溶劑或其他成分而進行了稀釋，故即便聚合物之含水量超過1wt%，亦可製備含水量為1wt%以下之漿料。即，由於源自共軛二烯系聚合物之水分亦被稀釋，故共軛二烯系聚合物之水分量亦可為1wt%以上。再者，黏著劑之水分量較理想為200ppm以下，因此於漿料之含水量較高之情形時，藉由將與水共沸之溶劑用於漿料，而藉由溶劑去除提昇水分去除之效率，為較佳態樣。 The shape of the conjugated diene-based polymer can be pellets. When reducing the moisture content of the polymer before slurry preparation, it is preferably a shape with a large specific surface area, preferably chips, from the viewpoint of moisture removal efficiency. granular or powder. The slurry containing the conjugated diene polymer preferably has a water content of 1wt% or less. However, since the slurry contains solvents or other components besides the polymer, it is diluted, so even if the water content of the polymer exceeds 1wt% %, slurry with water content below 1wt% can also be prepared. That is, since the moisture derived from the conjugated diene polymer is also diluted, the moisture content of the conjugated diene polymer may be 1 wt % or more. Furthermore, the moisture content of the adhesive is preferably less than 200ppm, so when the water content of the slurry is high, by using a solvent that is azeotropic with water for the slurry, the water removal can be improved by solvent removal Efficiency is the best form.

於利用供給進料機供給共軛二烯系聚合物時，若聚合物於進料機中被壓縮，以一部分塊之形式進料，則進料變得不穩定，產生調配量之不均，影響電池特性。就穩定地進料之觀點而言，藉由實施例所記載之方法測定 之壓縮度較佳為未達30，更佳為20以下，進而較佳為15以下，更佳為10以下。 When using a feeder to supply conjugated diene polymers, if the polymer is compressed in the feeder and fed in a part of a block, the feed becomes unstable, causing unevenness in the blending amount, Affect battery characteristics. From the point of view of stable feeding, it is determined by the method described in the examples The degree of compression is preferably less than 30, more preferably less than 20, further preferably less than 15, more preferably less than 10.

又，就於一定容積之供給進料機中填充較多共軛二烯系聚合物之觀點而言，鬆裝比重較佳為0.15g/cm3以上，更佳為0.20g/cm3以上，進而較佳為0.22g/cm3以上。較佳之上限為0.30g/cm3以下，更佳為0.25g/cm3以下。 Also, from the viewpoint of filling a large amount of conjugated diene-based polymer in a feeder with a certain volume, the bulk specific gravity is preferably 0.15 g/cm 3 or more, more preferably 0.20 g/cm 3 or more, Furthermore, it is preferably 0.22 g/cm 3 or more. A preferable upper limit is 0.30 g/cm 3 or less, more preferably 0.25 g/cm 3 or less.

上述共軛二烯系聚合物中之過渡金屬元素與Al、Li、Zn、及Mg之合計含量以原子換算計，相對於共軛二烯系聚合物，較佳為200ppm以下。過渡金屬包含V、Ti、Mn、Fe、Co及Ni。 The total content of the transition metal element and Al, Li, Zn, and Mg in the conjugated diene polymer is preferably 200 ppm or less based on the conjugated diene polymer in terms of atoms. Transition metals include V, Ti, Mn, Fe, Co, and Ni.

一般而言，利用陰離子活性聚合製造嵌段共聚物時之聚合起始劑、氫化反應中之氫化觸媒所含之包含該金屬原子之化合物及/或於聚合之脫溶劑步驟等中與空氣中之水分等發生反應而生成之後述之包含該金屬之化合物，有殘存於共軛二烯系聚合物中之情形。 In general, the compound containing the metal atom contained in the polymerization initiator in the production of block copolymers by anionic living polymerization, the hydrogenation catalyst in the hydrogenation reaction, and/or in the air during the desolventization step of the polymerization, etc. Moisture or the like reacts to form a compound containing the metal described later, which may remain in the conjugated diene polymer.

作為共軛二烯系聚合物中之包含過渡金屬元素(例如Ti、Ni、Co)及/或Li之化合物，並無特別限定，例如可例舉：氧化鈦、非晶性氧化鈦、正鈦酸或間鈦酸、氫氧化鈦、氫氧化鎳、一氧化鎳、氧化鋰、氫氧化鋰、氧化鈷、氫氧化鈷等各原子之氧化物、鈦酸鋰、鈦酸鋇、鈦酸鍶、鈦酸鎳、鎳鐵氧化物等各原子與異種金屬之複合氧化物等。此外，Al、Li、Zn、Fe及Mg等金屬作為金屬殘渣殘存於共軛二烯系聚合物中。 The compound containing transition metal elements (such as Ti, Ni, Co) and/or Li in the conjugated diene polymer is not particularly limited, for example, titanium oxide, amorphous titanium oxide, orthotitanium Acid or meta-titanic acid, titanium hydroxide, nickel hydroxide, nickel monoxide, lithium oxide, lithium hydroxide, cobalt oxide, cobalt hydroxide and other atomic oxides, lithium titanate, barium titanate, strontium titanate, Nickel titanate, nickel iron oxide and other atoms and complex oxides of different metals, etc. In addition, metals such as Al, Li, Zn, Fe, and Mg remain in the conjugated diene-based polymer as metal residues.

此處，所謂原子換算，一般係指由上述包含該金屬原子之化合物之殘存重量與分子量算出之該金屬原子每一個之質量。但是，雖然於可特定出包含該金屬原子之化合物之情形時可藉由上述方法算出，但多數情況下難以進行此種特定，故以原子換算之質量求出相對於共軛二烯系聚合物中之總量的金屬之合計含量之值，因此藉由實施例記載之方法測定該金屬原子之合計含量。 Here, the so-called atomic conversion generally refers to the mass of each metal atom calculated from the residual weight and molecular weight of the above-mentioned compound containing the metal atom. However, when the compound containing the metal atom can be specified, it can be calculated by the above-mentioned method, but in many cases it is difficult to carry out such identification, so the mass relative to the conjugated diene polymer is calculated in terms of atomic mass. Therefore, the total content of the metal atoms is determined by the method described in the examples.

共軛二烯系聚合物中之過渡金屬元素與Al、Li、Zn、Fe及Mg之合計含量以原子換算計，相對於共軛二烯系聚合物，設為200ppm以下，藉此，維持共軛二烯系聚合物之熱穩定性，抑制使用共軛二烯系聚合物作為黏著劑之全固體電池之耐熱老化性之降低。該現象之詳細機制並不明確，不限定於以下，但一般而言，已知若聚合物暴露於高溫下，則會生成碳自由基，空氣中之氧與其反應，藉此生成氫過氧化物，但於上述金屬化合物之存在下，會促進由氧化還原反應引起之向自由基之分解。又，氫化嵌段共聚物本身與上述金屬化合物發生反應，生成自由基。或者，於上述源自金屬化合物之金屬離子與空氣中之氧間生成電荷移動錯合物及/或活性氧，該活性種與氫化嵌段共聚物發生反應，藉此生成碳自由基。不限定於該等反應機制，但根據上述反應機制，若上述金屬量較多，則有源自金屬化合物之自由基較多之傾向，其結果為，於氫化嵌段共聚物中生成碳自由基及氫過氧化物等活性種，由於該活性種，自由基彼此鍵結或進一步產生自由基，由此導致聚合物之劣化，產生氫化嵌段共聚物彼此之鍵結，有使用黏著劑之層破裂、或接著性、黏結性降低、因變硬而導致耐衝擊性降低等擔 憂。 The total content of the transition metal element and Al, Li, Zn, Fe, and Mg in the conjugated diene polymer is calculated on an atomic basis, and is set to 200 ppm or less relative to the conjugated diene polymer. The thermal stability of the conjugated diene polymer suppresses the reduction of the heat aging resistance of the all-solid battery using the conjugated diene polymer as a binder. The detailed mechanism of this phenomenon is not clear and is not limited to the following, but in general, it is known that when a polymer is exposed to high temperature, carbon radicals are generated, and oxygen in the air reacts with them to generate hydroperoxides , but in the presence of the above-mentioned metal compounds, it will promote the decomposition of free radicals caused by redox reactions. Also, the hydrogenated block copolymer itself reacts with the metal compound to generate radicals. Alternatively, charge transfer complexes and/or active oxygen are generated between the metal ions derived from the metal compound and oxygen in the air, and the active species react with the hydrogenated block copolymer to generate carbon radicals. It is not limited to these reaction mechanisms, but according to the above reaction mechanism, if the amount of the above metal is large, there is a tendency that there are many free radicals derived from the metal compound, and as a result, carbon free radicals are generated in the hydrogenated block copolymer And active species such as hydroperoxides, due to the active species, free radicals are bonded to each other or further free radicals are generated, which leads to deterioration of the polymer, and hydrogenated block copolymers are bonded to each other, and there is a layer using an adhesive Cracks, adhesiveness, reduction in cohesion, reduction in impact resistance due to hardening, etc. worry.

上述合計含量較佳為200ppm以下，更佳為100ppm以下，進而較佳為70ppm以下，尤佳為50ppm以下。合計含量之下限並無特別限制，為0ppm。 The above-mentioned total content is preferably at most 200 ppm, more preferably at most 100 ppm, still more preferably at most 70 ppm, particularly preferably at most 50 ppm. The lower limit of the total content is not particularly limited, and is 0 ppm.

作為使上述合計含量為200ppm以下之方法，可應用公知者。於僅以氫化觸媒之失活、中和為目的之情形時，使用在嵌段共聚物之氫化反應後添加水及二氧化碳，中和氫化觸媒殘渣之方法，除水、二氧化碳以外，亦添加酸，中和氫化觸媒殘渣之方法，但以減少金屬之合計含量為目的時，僅中和並不夠，因此較佳為進而藉由使用傾析或離心分離機來去除金屬之方法。更具體而言，可例舉日本專利特願2014-557427所記載之方法。於使氫化後之聚合物溶液與水接觸而去除金屬殘渣之情形時，關於添加至共軛二烯系聚合物溶液中之酸，藉由添加硫酸、鹽酸、及硝酸等，於與水混合時金屬殘渣容易提取至水層，為了進一步消除金屬殘渣，藉由提高使聚合物溶液與水接觸時之攪拌強度(P/V值)，斷開聚合物與金屬殘渣之相互作用，而將金屬殘渣進而提取至水相中。藉由進而分成傾析與離心分離之步驟，可去除更多之金屬殘渣。 Known ones can be applied as a method for setting the above-mentioned total content to 200 ppm or less. When the purpose is only to deactivate and neutralize the hydrogenation catalyst, use the method of adding water and carbon dioxide after the hydrogenation reaction of the block copolymer to neutralize the hydrogenation catalyst residue. In addition to water and carbon dioxide, also add Acid is a method of neutralizing hydrogenation catalyst residues, but neutralization alone is not enough for the purpose of reducing the total content of metals, so a method of further removing metals by using decantation or a centrifuge is preferable. More specifically, the method described in Japanese Patent Application No. 2014-557427 may be mentioned. When the hydrogenated polymer solution is brought into contact with water to remove metal residues, the acid added to the conjugated diene polymer solution is mixed with water by adding sulfuric acid, hydrochloric acid, and nitric acid, etc. Metal residues are easily extracted to the water layer. In order to further eliminate the metal residues, by increasing the stirring intensity (P/V value) when the polymer solution is in contact with water, the interaction between the polymer and the metal residues is broken, and the metal residues are removed. Further extracted into the aqueous phase. By further dividing into steps of decantation and centrifugation, more metal residues can be removed.

[共軛二烯系聚合物之製造方法] [Manufacturing method of conjugated diene polymer]

本實施方式之共軛二烯系聚合物之製造方法並無特別限制，例如可具有如下所述之聚合步驟、改性步驟、及氫化步驟。 The method for producing the conjugated diene polymer of this embodiment is not particularly limited, and may include, for example, a polymerization step, a modification step, and a hydrogenation step as described below.

聚合步驟並無特別限制，例如為如下步驟：於有機溶劑中以有機鹼金屬化合物作為聚合起始劑，使共軛二烯化合物與乙烯基芳香族化合物聚合，藉此，獲得如上述構成所表示之無規共聚物及/或嵌段共聚物。 The polymerization step is not particularly limited, for example, the following step: using an organic alkali metal compound as a polymerization initiator in an organic solvent to polymerize a conjugated diene compound and a vinyl aromatic compound, thereby obtaining the random copolymers and/or block copolymers.

氫化步驟並無特別限制，例如為對藉由聚合步驟獲得之共軛二烯系聚合物進行氫化之步驟。 The hydrogenation step is not particularly limited, and is, for example, a step of hydrogenating the conjugated diene polymer obtained in the polymerization step.

改性步驟並無特別限制，例如為藉由使共軛二烯系聚合物與改性劑進行反應而進行改性反應，獲得共軛二烯系聚合物之步驟。 The modifying step is not particularly limited, and is, for example, a step of obtaining a conjugated diene polymer by reacting the conjugated diene polymer with a modifier to perform a modification reaction.

再者，氫化步驟與改性步驟之順序並無特別限制。即，可為聚合步驟、氫化步驟、改性步驟之順序，亦可為聚合步驟、改性步驟、氫化步驟之順序。就可更容易地獲得上述共軛二烯系聚合物之觀點而言，較佳為聚合步驟、氫化步驟、改性步驟之順序。又，改性步驟亦可如後所述與聚合步驟同時進行。 Furthermore, the order of the hydrogenation step and the modification step is not particularly limited. That is, the sequence of the polymerization step, the hydrogenation step, and the modification step may be used, or the sequence of the polymerization step, the modification step, and the hydrogenation step may be used. The order of the polymerization step, the hydrogenation step, and the modification step is preferable from the viewpoint that the above-mentioned conjugated diene-based polymer can be obtained more easily. In addition, the modification step can also be performed simultaneously with the polymerization step as will be described later.

(聚合步驟) (polymerization step)

聚合步驟例如為如下步驟：於有機溶劑中以有機鹼金屬化合物作為聚合起始劑，使共軛二烯化合物及乙烯基芳香族化合物聚合，藉此獲得無規共聚物及/或嵌段共聚物。 The polymerization step is, for example, the following step: using an organic alkali metal compound as a polymerization initiator in an organic solvent to polymerize a conjugated diene compound and a vinyl aromatic compound, thereby obtaining a random copolymer and/or a block copolymer .

作為聚合之態樣，可為批次聚合，可為連續聚合，亦可為該等之組合。就使包含影響耐衝擊性及韌性之共軛二烯系聚合物之全固體電池黏著劑中 之分散相之尺寸固定之觀點而言，較佳為使用分子量分佈變小之批次聚合方法。 As an aspect of the polymerization, batch polymerization may be used, continuous polymerization may be used, or a combination thereof may be used. For all-solid battery adhesives containing conjugated diene polymers that affect impact resistance and toughness From the viewpoint of the fixed size of the dispersed phase, it is preferable to use a batch polymerization method in which the molecular weight distribution becomes smaller.

聚合步驟中之反應溫度亦可為0℃以上180℃以下。就可更易於獲得本實施方式之共軛二烯系聚合物之觀點而言，反應溫度較佳為20℃以上160℃以下，更佳為30℃以上150℃以下。 The reaction temperature in the polymerization step may be not less than 0°C and not more than 180°C. The reaction temperature is preferably from 20°C to 160°C, more preferably from 30°C to 150°C, from the viewpoint that the conjugated diene polymer of the present embodiment can be obtained more easily.

聚合步驟中之反應時間根據目標之聚合物而有所不同，可為48小時以內。就可更易於獲得本實施方式之共軛二烯系聚合物之觀點而言，反應時間較佳為0.1小時以上10小時以內。就獲得分子量分佈較小且具有高強度之共軛二烯系聚合物之觀點而言，反應時間更佳為0.5小時以上5小時以內。 The reaction time in the polymerization step varies depending on the target polymer, but may be within 48 hours. The reaction time is preferably from 0.1 hour to 10 hours from the viewpoint that the conjugated diene polymer of the present embodiment can be obtained more easily. From the viewpoint of obtaining a conjugated diene polymer having a small molecular weight distribution and high strength, the reaction time is more preferably from 0.5 hour to 5 hours.

聚合步驟中之聚合系之氛圍只要為用以將氮及溶劑維持為液相之充分之壓力之範圍即可，並無特別限制。較佳為於聚合系內不存在使聚合起始劑及活性聚合物失活之雜質、例如水、氧、及二氧化碳。 The atmosphere of the polymerization system in the polymerization step is not particularly limited as long as it is within a pressure range sufficient to maintain nitrogen and a solvent in a liquid phase. It is preferable that impurities such as water, oxygen, and carbon dioxide that deactivate the polymerization initiator and the living polymer are not present in the polymerization system.

又，於上述聚合步驟結束時，可添加所需量之二官能以上之偶合劑進行偶合反應。作為二官能偶合劑，可應用先前公知者，並無特別限制，例如可例舉：三甲氧基矽烷、三乙氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、二甲基二甲氧基矽烷、二乙基二甲氧基矽烷、二氯二甲氧基矽烷、二氯二乙氧基矽烷、三氯甲氧基矽烷、三氯乙氧基矽烷等烷氧基矽烷化合物、二氯乙烷、二溴乙烷、二甲基二氯矽烷、二甲基二溴矽烷等二鹵素化合物、 苯甲酸甲酯、苯甲酸乙酯、苯甲酸苯酯、鄰苯二甲酸酯類等酸酯類等。 In addition, at the end of the above-mentioned polymerization step, a required amount of a coupling agent having more than two functions can be added to carry out the coupling reaction. As the difunctional coupling agent, previously known ones can be used without particular limitation, for example, trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethylsilane Oxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane and other alkoxysilane compounds, di Dihalogen compounds such as ethyl chloride, dibromoethane, dimethyldichlorosilane, dimethyldibromosilane, Esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, phthalates, etc.

又，作為3官能以上之多官能偶合劑，可應用先前公知者，並無特別限制，可例舉：例如3元以上之多元醇類、環氧化大豆油、二縮水甘油基雙酚A、1,3-雙(N-N'-二縮水甘油基胺基甲基)環己烷等多元環氧化合物、通式R4-nSiXn(此處，R表示碳數1~20之烴基，X表示鹵素，n表示3~4之整數)所表示之鹵化矽化合物、例如甲基矽烷基三氯化物、第三丁基矽烷基三氯化物、四氯化矽及該等之溴化物等、通式R4-nSnXn(此處，R表示碳數1~20之烴基，X表示鹵素，n表示3~4之整數)所表示之鹵化錫化合物、例如甲基錫三氯化物、第三丁基錫三氯化物、四氯化錫等多元鹵素化合物。又，亦可使用碳酸二甲酯或碳酸二乙酯等。 Also, as the multifunctional coupling agent with more than three functions, previously known ones can be used without particular limitation, and examples include: polyhydric alcohols with more than three valences, epoxidized soybean oil, diglycidyl bisphenol A, 1 ,3-bis(N-N'-diglycidylaminomethyl)cyclohexane and other polyvalent epoxy compounds, general formula R 4 -nSiX n (here, R represents a hydrocarbon group with 1 to 20 carbons, X Represents halogen, n represents an integer of 3~4) represented by silicon halide compounds, such as methyl silyl trichloride, tertiary butyl silyl trichloride, silicon tetrachloride and their bromides, etc., generally Tin halide compounds represented by the formula R 4 -nSnX n (here, R represents a hydrocarbon group with 1 to 20 carbons, X represents a halogen, and n represents an integer of 3 to 4), such as methyl tin trichloride, tertiary butyl tin Multi-element halogen compounds such as trichloride and tin tetrachloride. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used.

作為有機溶劑，並無特別限制，例如可例舉：正丁烷、異丁烷、正戊烷、正己烷、正庚烷、及正辛烷等脂肪族烴類；環己烷、環庚烷、及甲基環戊烷等脂環式烴類；以及苯、二甲苯、甲苯、及乙基苯等芳香族烴類。 The organic solvent is not particularly limited, and examples include: aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane, cycloheptane , and alicyclic hydrocarbons such as methylcyclopentane; and aromatic hydrocarbons such as benzene, xylene, toluene, and ethylbenzene.

作為聚合起始劑之有機鹼金屬化合物較佳為有機鋰化合物。作為有機鋰化合物，並無特別限制，例如可例舉：有機單鋰化合物、有機二鋰化合物、及有機聚鋰化合物。 The organoalkali metal compound as a polymerization initiator is preferably an organolithium compound. The organic lithium compound is not particularly limited, and examples thereof include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds.

作為有機鋰化合物，並無特別限制，例如可例舉：乙基鋰、正丙基鋰、異丙基鋰、正丁基鋰、第二丁基鋰、第三丁基鋰、正戊基鋰、正己基鋰、戊苄基鋰、苯基鋰、六亞甲基二鋰、丁二烯基鋰、異丙烯基二鋰、及哌啶 鋰。於將如哌啶鋰般含有氮原子之有機鋰化合物作為聚合起始劑之情形時，可獲得具有氮原子之共軛二烯系聚合物。 The organolithium compound is not particularly limited, for example, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, second-butyllithium, third-butyllithium, n-pentyllithium , n-hexyllithium, pentabenzyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isopropenyldilithium, and piperidine lithium. When an organolithium compound containing a nitrogen atom such as lithium piperidine is used as a polymerization initiator, a conjugated diene polymer having a nitrogen atom can be obtained.

該等聚合起始劑可僅單獨使用1種，亦可併用2種以上。該等中，就提高聚合活性之觀點而言，聚合起始劑較佳為正丁基鋰、第二丁基鋰、及哌啶鋰。 These polymerization initiators may be used alone or in combination of two or more. Among these, the polymerization initiator is preferably n-butyllithium, second-butyllithium, and piperidine lithium from the viewpoint of enhancing polymerization activity.

作為聚合起始劑之有機鹼金屬化合物之使用量視目標之共軛二烯系聚合物之分子量而定，典型而言，較佳為0.01phm以上1.5phm以下(此處，phm表示相對於單體每100質量份之質量份；以下同樣)之範圍，更佳為0.02phm以上0.3phm以下之範圍，進而較佳為0.03phm以上0.2phm以下之範圍。 The amount of the organic alkali metal compound used as a polymerization initiator depends on the molecular weight of the target conjugated diene polymer. Typically, it is preferably from 0.01 phm to 1.5 phm (here, phm means relative to the mono The range of mass parts per 100 mass parts of body; hereinafter the same) is more preferably in the range of 0.02 phm to 0.3 phm, and still more preferably in the range of 0.03 phm to 0.2 phm.

共軛二烯系聚合物之乙烯基鍵量可藉由添加路易斯鹼、例如醚、及胺等化合物作為乙烯基鍵量調整劑(以下稱為「乙烯化劑」)來進行控制。又，可根據目標之乙烯基鍵量而調整乙烯化劑之使用量。 The vinyl bond amount of the conjugated diene polymer can be controlled by adding compounds such as Lewis bases, ethers, and amines as vinyl bond amount regulators (hereinafter referred to as "vinylating agents"). Moreover, the usage-amount of a vinylating agent can be adjusted according to the target vinyl bond amount.

作為乙烯化劑，並無特別限制，例如可例舉：醚化合物、及三級胺系化合物。 It does not specifically limit as a vinylating agent, For example, an ether compound and a tertiary amine compound are mentioned.

作為醚化合物，並無特別限制，例如可例舉：直鏈狀醚化合物及環狀醚化合物。 It does not specifically limit as an ether compound, For example, a linear ether compound and a cyclic ether compound are mentioned.

作為直鏈狀醚化合物，並無特別限制，例如可例舉：二甲醚、二***、二苯醚、乙二醇二甲醚、乙二醇二***、及乙二醇二丁醚之類的乙二醇之二烷基醚化合物類；以及二乙二醇二甲醚、二乙二醇二***、及二乙二醇二丁醚之類的二乙二醇之二烷基醚化合物類。 The linear ether compound is not particularly limited, and examples thereof include dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Dialkyl ether compounds of ethylene glycol; and dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether .

又，作為環狀醚化合物，並無特別限制，例如可例舉：四氫呋喃、二

Figure 110148596-A0305-02-0038-14
烷、2,5-二甲基氧雜環戊烷、2,2,5,5-四甲基氧雜環戊烷、2,2-雙(2-氧雜環戊烷基)丙烷、及呋喃甲醇之類的烷基醚。 Also, the cyclic ether compound is not particularly limited, for example, tetrahydrofuran, di
Figure 110148596-A0305-02-0038-14
alkane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolyl)propane, and Alkyl ethers such as furanmethanol.

作為三級胺系化合物，並無特別限制，例如可例舉：三甲胺、三乙胺、三丁胺、N,N-二甲基苯胺、N-乙基哌啶、N-甲基吡咯啶、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四乙基乙二胺、1,2-二哌啶基乙烷、三甲基胺基乙基哌

Figure 110148596-A0305-02-0038-15
、N,N,N',N",N"-五甲基伸乙基三胺、N,N'-二辛基-對苯二胺、吡啶、四甲基丙烷二胺、及雙[2-(N,N-二甲基胺基)乙基]醚。 The tertiary amine compound is not particularly limited, for example, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine , N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylamine Ethylpiper
Figure 110148596-A0305-02-0038-15
, N,N,N',N",N"-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, pyridine, tetramethylpropanediamine, and bis[2 -(N,N-Dimethylamino)ethyl]ether.

作為三級胺系化合物，較佳為具有2個胺之化合物。進而，於該等中，作為三級胺系化合物，更佳為分子內具有顯示出對稱性之結構者，進而較佳為N,N,N',N'-四甲基乙二胺、雙[2-(N,N-二甲基胺基)乙基]醚、及1,2-二哌啶基乙烷。 As a tertiary amine type compound, the compound which has two amines is preferable. Furthermore, among these, as the tertiary amine compound, one having a structure showing symmetry in the molecule is more preferable, and N,N,N',N'-tetramethylethylenediamine, bis [2-(N,N-Dimethylamino)ethyl]ether, and 1,2-dipiperidinylethane.

該等乙烯化劑可僅單獨使用1種，亦可併用2種以上。 These vinylating agents may be used alone or in combination of two or more.

聚合步驟中，亦可除上述乙烯化劑、及有機鋰化合物以外，於鹼金屬烷氧化物之共存下，使共軛二烯單體均聚、或使共軛二烯單體與乙烯基芳 香族單體聚合。 In the polymerization step, in addition to the above-mentioned vinylating agent and organic lithium compound, the conjugated diene monomer can be homopolymerized in the presence of an alkali metal alkoxide, or the conjugated diene monomer can be mixed with a vinyl aromatic compound. Polymerization of aromatic monomers.

此處，鹼金屬烷氧化物係指通式MOR(式中，M表示鹼金屬，R表示烷基)所表示之化合物。藉由在聚合步驟中使鹼金屬烷氧化物共存，有變得容易控制乙烯基鍵量、分子量分佈、聚合速度、及嵌段率等之傾向。 Here, the alkali metal alkoxide refers to a compound represented by the general formula MOR (wherein, M represents an alkali metal, and R represents an alkyl group). By allowing the alkali metal alkoxide to coexist in the polymerization step, it tends to be easy to control the amount of vinyl bonds, molecular weight distribution, polymerization rate, block ratio, and the like.

作為鹼金屬烷氧化物之鹼金屬，就可獲得較高之乙烯基鍵量、較小之分子量分佈、較高之聚合反應速度、及較高之嵌段率之觀點而言，較佳為鈉或鉀。 As the alkali metal of the alkali metal alkoxide, it is preferably sodium from the viewpoint of obtaining a higher vinyl bond amount, a smaller molecular weight distribution, a higher polymerization reaction speed, and a higher block ratio. or potassium.

作為鹼金屬烷氧化物，並無特別限制，例如可例舉：具有碳數2~12之烷基之烷氧化鈉、烷氧化鋰、及烷氧化鉀。作為鹼金屬烷氧化物，較佳為具有碳數3~6之烷基之烷氧化鈉及烷氧化鉀，更佳為第三丁氧化鈉、第三戊氧化鈉、第三丁氧化鉀、及第三戊氧化鉀。該等中，進而較佳為第三丁氧化鈉、及第三戊氧化鈉。 The alkali metal alkoxide is not particularly limited, and examples thereof include sodium alkoxide, lithium alkoxide, and potassium alkoxide having an alkyl group having 2 to 12 carbon atoms. As the alkali metal alkoxide, it is preferably sodium alkoxide and potassium alkoxide having an alkyl group with a carbon number of 3 to 6, more preferably sodium tertiary butoxide, sodium tertiary pentoxide, potassium tertiary butoxide, and Potassium pentoxide. Among these, sodium tertiary butoxide and sodium tertiary pentoxide are more preferable.

(氫化步驟) (hydrogenation step)

氫化步驟係指對共軛二烯系聚合物進行氫化之步驟。氫化步驟中之氫化方法並無特別限制，例如可例舉：對於上述聚合步驟中所獲得之共軛二烯系聚合物，於氫化觸媒之存在下，供給氫氣進行氫化之方法。藉由使共軛二烯系聚合物之製造方法具有此種氫化步驟，共軛二烯單體單元中之雙鍵殘基被氫化，可獲得熱性質更穩定之氫化共軛二烯系聚合物。 The hydrogenation step refers to a step of hydrogenating the conjugated diene polymer. The hydrogenation method in the hydrogenation step is not particularly limited, for example, a method of hydrogenating the conjugated diene polymer obtained in the above polymerization step by supplying hydrogen gas in the presence of a hydrogenation catalyst. By including such a hydrogenation step in the production method of the conjugated diene polymer, the double bond residue in the conjugated diene monomer unit is hydrogenated, and a hydrogenated conjugated diene polymer having more stable thermal properties can be obtained .

氫化率例如可藉由氫化時之觸媒量或氫氣之供給(以下亦稱為「進料」)進行控制。又，氫化速度例如可藉由氫化時之觸媒量、氫氣之供給量、壓力及溫度等進行控制。氫化步驟較佳為於上述聚合步驟中之共軛二烯系聚合物之生成反應停止後之時點實施。 The hydrogenation rate can be controlled by, for example, the amount of catalyst or the supply of hydrogen gas (hereinafter also referred to as "feed") during hydrogenation. In addition, the hydrogenation rate can be controlled by, for example, the amount of catalyst, the amount of hydrogen gas supplied, pressure and temperature during hydrogenation. The hydrogenation step is preferably carried out after the formation reaction of the conjugated diene polymer in the above-mentioned polymerization step has stopped.

氫化反應結束後，亦可添加穩定劑。作為穩定劑，並無特別限制，例如可例舉：3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯。 After the hydrogenation reaction is completed, a stabilizer may also be added. The stabilizer is not particularly limited, and for example, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate may be mentioned.

以上述方式獲得之共軛二烯系聚合物之溶液可視需要去除觸媒殘查，將共軛二烯系聚合物從溶劑分離。 The solution of the conjugated diene polymer obtained in the above manner may optionally remove catalyst residues and separate the conjugated diene polymer from the solvent.

作為溶劑之分離方法，例如可例舉：於氫化後之反應液中加入丙酮或醇等作為對氫化共聚物之不良溶劑的極性溶劑，使聚合物沈澱而進行回收之方法；將反應液於攪拌下投入至熱水中，藉由蒸汽汽提去除溶劑後回收之方法；或直接對聚合物溶液進行加熱而將溶劑蒸餾去除之方法等。於投入至熱水中之情形時，於聚合物內會混入水分，因此亦可藉由加熱擠出步驟等去除水分。再者，共聚物之氫化物中可添加各種酚系穩定劑、磷系穩定劑、硫系穩定劑、胺系穩定劑等穩定劑。 As the method of separating the solvent, for example, a polar solvent such as acetone or alcohol is added as a poor solvent for the hydrogenated copolymer to the reaction liquid after hydrogenation, and the polymer is precipitated and recovered; the reaction liquid is stirred Putting it into hot water, removing the solvent by steam stripping and recovering it; or directly heating the polymer solution to distill the solvent away, etc. When pouring into hot water, water will be mixed in the polymer, so the water can also be removed by heating and extruding steps. Furthermore, various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, amine stabilizers and other stabilizers can be added to the hydrogenated copolymer.

(改性步驟) (modification step)

所謂改性步驟，只要是獲得具有改性基之共軛二烯系聚合物之步驟即可，並無特別限制，例如為藉由使共軛二烯系聚合物及/或氫化共軛二烯系 聚合物與改性劑進行反應而獲得共軛二烯系聚合物之步驟。藉此，所獲得之共軛二烯系聚合物會具有改性基。 The so-called modification step is not particularly limited as long as it is a step of obtaining a conjugated diene polymer having a modifying group, for example, by making a conjugated diene polymer and/or hydrogenating a conjugated diene Tie A step in which a polymer is reacted with a modifier to obtain a conjugated diene polymer. Thereby, the obtained conjugated diene polymer has a modifying group.

改性步驟亦可與上述聚合步驟同時進行。作為此種改性反應方法，並無特別限制，例如可例舉：於聚合步驟之聚合反應中，使用具有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基之聚合起始劑的方法；及於聚合步驟之聚合反應中，使用具有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基之不飽和單體的方法。又，作為改性反應方法，亦可使用如下方法：於藉由聚合步驟之聚合反應所獲得之共軛二烯系聚合物之活性末端，加成會形成或含有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基之改性劑。 The modification step can also be carried out simultaneously with the above-mentioned polymerization step. There are no particular limitations on the method of such a modification reaction, for example, in the polymerization reaction in the polymerization step, the use of an adhesive group having a constituent component of the electrode active material layer or a solid electrolyte or an adhesive to the current collector is used. The method of the polymerization initiator of the active group; and in the polymerization reaction of the polymerization step, using an unsaturated monomer having an adhesive group for the constituents of the electrode active material layer or a solid electrolyte or an adhesive group for the current collector Methods. In addition, as a modification reaction method, the following method can also be used: to the active terminal of the conjugated diene polymer obtained by the polymerization reaction in the polymerization step, adding a constituent that will form or contain a counter electrode active material layer Or the modifier of the bonding group of the solid electrolyte or the bonding group of the current collector.

共軛二烯系聚合物中，關於導入改性基之位置，亦無特別限制，例如可為共軛二烯系聚合物之末端，亦可於共軛二烯系聚合物之主鏈之一部分以嵌段、無規或錐狀配置。於定量且位置選擇性較高地導入改性基之情形時，較佳為使具有改性基之單體或後步驟中可導入改性基之單體共聚、或導入至聚合物末端。改性基之濃度可對應於具有改性基之單體之量或後步驟中可導入改性基之單體之量、或與聚合物末端反應之改性劑之量進行控制。又，於使聚合物末端與改性劑反應之情形時，藉由提昇聚合物之分子量，減少聚合物末端數，亦可減少改性基量。向聚合物末端之導入適於導入少量改性基之情況。又，作為向聚合物末端之導入，亦可使用具有改性基或改性基前驅物之偶合劑，於此情形時，於偶合部具有改性基。 In the conjugated diene polymer, there are no special restrictions on the position of the modified group, for example, it can be the terminal of the conjugated diene polymer, or it can be part of the main chain of the conjugated diene polymer In block, random or conical configuration. When introducing a modifying group quantitatively and with high position selectivity, it is preferable to copolymerize a monomer having a modifying group or a monomer capable of introducing a modifying group in a later step, or to introduce it into a polymer terminal. The concentration of the modifying group can be controlled corresponding to the amount of the monomer having the modifying group or the amount of the monomer capable of introducing the modifying group in the subsequent step, or the amount of the modifying agent reacting with the end of the polymer. In addition, when the polymer terminal is reacted with a modifying agent, the amount of modifying groups can also be reduced by increasing the molecular weight of the polymer and reducing the number of polymer terminals. Introduction to the polymer terminal is suitable for the case of introducing a small amount of modifying group. In addition, a coupling agent having a modifying group or a modifying group precursor can also be used as the introduction to the polymer terminal, and in this case, the coupling portion has a modifying group.

於使改性基量相對於共軛二烯系聚合物每100g為3mmol以下之情形時，適宜為使聚合物末端與改性劑反應之方法，尤其適宜為分子量為3.5萬以上之聚合物。於聚合末端與改性劑以1比1反應之情形時，關於改性基量，於分子量為3.5萬時為2.9mmol以下，分子量為10萬時為1.0mmol以下，分子量為20萬時為0.5mmol以下，分子量為30萬時為0.33mmol以下，分子量為50萬時為0.2mmol以下，分子量為70萬時為0.14mmol以下，可對應於分子量進行控制。 When the amount of the modifying group is 3 mmol or less per 100 g of the conjugated diene polymer, a method of reacting the polymer terminal with the modifying agent is suitable, and it is particularly suitable for a polymer having a molecular weight of 35,000 or more. When the polymerization terminal and the modifier react at a ratio of 1:1, the amount of the modifier group is 2.9 mmol or less when the molecular weight is 35,000, 1.0 mmol or less when the molecular weight is 100,000, and 0.5 when the molecular weight is 200,000 When the molecular weight is 300,000, it is 0.33 mmol or less, when the molecular weight is 500,000, it is 0.2 mmol or less, and when the molecular weight is 700,000, it is 0.14 mmol or less. It can be controlled according to the molecular weight.

改性基量於實用中無問題之範圍內並無特別限制，於期待改性基與異種材料之相互作用所獲得之接著性之情形時，改性基之量相對於共軛二烯系聚合物每100g，較佳為0.10mmol以上，較佳為0.15mmol以上。又，改性基之量相對於共軛二烯系聚合物每100g，就導電助劑分散性之觀點而言，較佳為20mmol以下，更佳為5mmol以下，進而較佳為1.5mmol以下，進而更佳為0.10mmol以上0.50mmol以下。尤其是分子量為20萬以上之高分子中，若改性量為3.0mmol以下，則除改性基與導電助劑之相互作用以外，藉由分子量之纏結效應，可改善導電助劑分散性與接著性之平衡。 The amount of the modifying group is not particularly limited within the range of no problem in practice. When expecting the adhesiveness obtained by the interaction between the modifying group and different materials, the amount of the modifying group is relative to the amount of the conjugated diene polymer. Per 100 g of the substance, it is preferably more than 0.10 mmol, more preferably more than 0.15 mmol. Also, the amount of the modifying group is preferably not more than 20 mmol, more preferably not more than 5 mmol, and still more preferably not more than 1.5 mmol, from the viewpoint of the dispersibility of the conductive additive per 100 g of the conjugated diene-based polymer. Still more preferably, it is not less than 0.10 mmol and not more than 0.50 mmol. Especially in polymers with a molecular weight of 200,000 or more, if the modification amount is less than 3.0 mmol, in addition to the interaction between the modified group and the conductive additive, the dispersion of the conductive additive can be improved by the entanglement effect of the molecular weight Balance with Continuity.

作為「具有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基之聚合起始劑」，並無特別限制，例如可例舉：3-鋰-1-[N,N-雙(三甲基矽烷基)]胺基丙烷、2-鋰-1-[N,N-雙(三甲基矽烷基)]胺基乙烷、3-鋰-2,2-二甲基-1-[N,N-雙(三甲基矽烷基)]胺基丙烷、2,2,5,5-四甲基 -1-(3-鋰丙基)-1-氮雜-2,5-二矽雜環戊烷、2,2,5,5-四甲基-1-(3-鋰-2,2-二甲基-丙基)-1-氮雜-2,5-二矽雜環戊烷、2,2,5,5-四甲基-1-(2-鋰乙基)-1-氮雜-2,5-二矽雜環戊烷、3-鋰-1-[N-(第三丁基-二甲基矽烷基)-N-三甲基矽烷基]胺基丙烷、3-鋰-1-(N-甲基-N-三甲基矽烷基)胺基丙烷、3-鋰-1-(N-乙基-N-三甲基矽烷基)胺基丙烷、及哌啶鋰。 There are no particular limitations on the "polymerization initiator having a constituent component of the electrode active material layer or a binding group for the solid electrolyte or an adhesive group for the current collector", for example, 3-lithium-1- [N,N-Bis(trimethylsilyl)]aminopropane, 2-Lithium-1-[N,N-bis(trimethylsilyl)]aminoethane, 3-Lithium-2,2 -Dimethyl-1-[N,N-bis(trimethylsilyl)]aminopropane, 2,2,5,5-tetramethyl -1-(3-Lithiumpropyl)-1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1-(3-lithium-2,2- Dimethyl-propyl)-1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1-(2-lithiumethyl)-1-aza -2,5-Disilacyclopentane, 3-lithium-1-[N-(tert-butyl-dimethylsilyl)-N-trimethylsilyl]aminopropane, 3-lithium- 1-(N-methyl-N-trimethylsilyl)aminopropane, 3-lithium-1-(N-ethyl-N-trimethylsilyl)aminopropane, and lithium piperidine.

作為「具有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基之不飽和單體」，並無特別限制，例如可例舉：對[N,N-雙(三甲基矽烷基)胺基]苯乙烯、對[N,N-雙(三甲基矽烷基)胺基甲基]苯乙烯、對{2-[N,N-雙(三甲基矽烷基)胺基]乙基}苯乙烯、間[N,N-雙(三甲基矽烷基)胺基]苯乙烯、對(N-甲基-N-三甲基矽烷基胺基)苯乙烯、及對(N-甲基-N-三甲基矽烷基胺基甲基)苯乙烯。 There are no particular limitations on the "unsaturated monomer having a constituent of the electrode active material layer or a binding group for the solid electrolyte or an adhesive group for the current collector", for example, for [N,N- Bis(trimethylsilyl)amino]styrene, p-[N,N-bis(trimethylsilyl)aminomethyl]styrene, p-{2-[N,N-bis(trimethyl Silyl)amino]ethyl}styrene, m-[N,N-bis(trimethylsilyl)amino]styrene, p-(N-methyl-N-trimethylsilylamino)benzene Ethylene, and p-(N-methyl-N-trimethylsilylaminomethyl)styrene.

作為「形成或含有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基之改性劑」，並無特別限制，例如可例舉：四縮水甘油基甲基二甲苯二胺、四縮水甘油基-1,3-雙胺基甲基環己烷、ε-己內酯、1,3-二甲基-2-咪唑啶酮、1,3-二乙基-2-咪唑啶酮、N,N'-二甲基伸丙基脲、及N-甲基吡咯啶酮。 There are no particular limitations on the "modifying agent that forms or contains the constituent components of the electrode active material layer or the binding group of the solid electrolyte or the binding group to the current collector", for example, tetraglycidyl methyl Ditolylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl Base-2-imidazolidinone, N,N'-dimethylpropylidene, and N-methylpyrrolidone.

作為導入改性基之其他方法，例如可例舉：藉由使共軛二烯系聚合物與有機鋰化合物等有機鹼金屬化合物進行反應(金屬化反應)，而獲得加成有有機鹼金屬之聚合物，對該加成有有機鹼金屬之聚合物加成上述改性劑之方法。 As another method for introducing a modifying group, for example, a compound containing an organic alkali metal can be obtained by reacting a conjugated diene polymer with an organic alkali metal compound such as an organic lithium compound (metallation reaction). A polymer is a method of adding the above modifier to a polymer to which an organic alkali metal is added.

又，作為導入改性基之又一方法，例如可例舉：對共軛二烯系聚合物接枝加成具有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基的原子團之方法。 In addition, as another method of introducing a modifying group, for example, graft addition of a conjugated diene polymer having a constituent component of an electrode active material layer or a binding group of a solid electrolyte or an electrode collector The method of the atomic group of the bonding group.

此種方法可為對共軛二烯系聚合物直接接枝加成之方法，亦可為使導入了一次改性基之共軛二烯系聚合物與具有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基的原子團進行反應(二次改性)之方法。 This method can be a method of directly grafting and adding a conjugated diene polymer, or a conjugated diene polymer introduced with a primary modification group and a constituent component having a counter electrode active material layer or The bonding group of the solid electrolyte or the method of reacting (secondary modification) to the atomic group of the bonding group of the current collector.

作為「具有對電極活性物質層之構成成分或固體電解質之黏結性基或對集電體之接著性基的原子團」，並無特別限制，例如可例舉：包含α,β-不飽和羧酸或其衍生物之分子單元。作為α,β-不飽和羧酸或其衍生物，例如可例舉：順丁烯二酸、鹵化順丁烯二酸、伊康酸、順-4-環己烯-1,2-二羧酸、內順-雙環[2,2,1]-5-庚烯-2,3-二羧酸等、及該等二羧酸之酐、丙烯酸、甲基丙烯酸、丁烯酸等、及該等單羧酸之酯(例如丙烯酸-2-羥基乙酯、甲基丙烯酸甲酯、甲基丙烯酸縮水甘油酯、及甲基丙烯酸3-(三甲氧基矽烷基)丙酯等)、以及烷氧基矽烷化合物(例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三丙氧基矽烷、乙烯基三丁氧基矽烷、乙烯基二甲氧基甲基矽烷、乙烯基二乙氧基乙基矽烷、乙烯基二丙氧基丙基矽烷、及乙烯基二丁氧基丁基矽烷等)。該等中，較佳為丙烯酸、酐、甲基丙烯酸縮水甘油酯、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷，就進一步提高接著性之觀點而言，更佳為順丁烯二酸酐。 There are no particular limitations on the "atomic group having a constituent component of the electrode active material layer or a solid electrolyte binding group or a binding group to the current collector", for example, α,β-unsaturated carboxylic acid is included Molecular units of its derivatives. Examples of α,β-unsaturated carboxylic acids or derivatives thereof include: maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylate acid, internal cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid, etc., and the anhydrides of these dicarboxylic acids, acrylic acid, methacrylic acid, crotonic acid, etc., and the Esters of monocarboxylic acids (such as 2-hydroxyethyl acrylate, methyl methacrylate, glycidyl methacrylate, and 3-(trimethoxysilyl) propyl methacrylate, etc.), and alkoxy Silane compounds (such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyldimethoxymethylsilane, vinyldiethylsilane oxyethylsilane, vinyldipropoxypropylsilane, and vinyldibutoxybutylsilane, etc.). Among these, acrylic acid, anhydride, glycidyl methacrylate, vinyltrimethoxysilane, and vinyltriethoxysilane are preferable, and from the viewpoint of further improving adhesiveness, maleic diacetate is more preferable. anhydride.

含有α,β-不飽和羧酸或其衍生物之分子單元之加成量相對於共軛二烯系聚合物100質量份，較佳為0.1質量份以上20質量份以下，更佳為0.1質量份以上10質量份以下，進而較佳為0.1質量份以上5質量份以下。就對電極活性物質層之構成成分或固體電解質等之黏結性、或對集電體之接著性之觀點而言，上述加成量較佳為0.1質量份以上。另一方面，就提高包含共軛二烯系聚合物之全固體電池黏著劑之流動性之觀點而言，上述加成量較佳為20質量份以下。 The addition amount of molecular units containing α,β-unsaturated carboxylic acid or derivatives thereof is preferably 0.1 to 20 parts by mass, more preferably 0.1 parts by mass, based on 100 parts by mass of the conjugated diene polymer It is not less than 10 parts by mass, and more preferably not less than 0.1 parts by mass and not more than 5 parts by mass. From the viewpoint of the binding properties to the constituent components of the electrode active material layer, the solid electrolyte, etc., or the adhesiveness to the current collector, the above added amount is preferably 0.1 parts by mass or more. On the other hand, from the viewpoint of improving the fluidity of the all-solid battery adhesive containing a conjugated diene polymer, the above added amount is preferably 20 parts by mass or less.

作為接枝加成之方法，例如可例舉：於包含自由基起始劑、共軛二烯系聚合物、及含有α,β-不飽和羧酸或其衍生物基之化合物的溶液中使其等進行反應之方法；使自由基起始劑、共軛二烯系聚合物、及含有α,β-不飽和羧酸或其衍生物基之化合物於加熱熔融下或加熱未熔融下進行反應之方法；使共軛二烯系聚合物、及含有α,β-不飽和羧酸或其衍生物基之化合物於加熱熔融下或加熱未熔融下進行反應之方法；於包含與含有α,β-不飽和羧酸或其衍生物基之化合物均會反應而形成鍵之化合物、及接枝有含有α,β-不飽和羧酸或其衍生物基之化合物之共軛二烯系聚合物的溶液中使其等進行反應之方法；使與含有α,β-不飽和羧酸或其衍生物基之化合物均會反應而形成鍵之化合物、及接枝有含有α,β-不飽和羧酸或其衍生物基之化合物之共軛二烯系聚合物於加熱熔融下或加熱未熔融下進行反應之方法。於上述任一情形時，均可不含自由基起始劑而為藉由烯加成進行之接枝加成。 As a method of graft addition, for example, use in a solution containing a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid or a derivative thereof The method of carrying out the reaction; reacting the free radical initiator, the conjugated diene polymer, and the compound containing α, β-unsaturated carboxylic acid or its derivative group under heating melting or heating without melting The method; the method of reacting the conjugated diene polymer and the compound containing α, β-unsaturated carboxylic acid or its derivative group under heating and melting or heating; - Compounds of unsaturated carboxylic acids or their derivatives react to form bonds, and conjugated diene polymers grafted with compounds containing α, β-unsaturated carboxylic acids or their derivatives A method of reacting them in a solution; a compound that reacts with a compound containing an α, β-unsaturated carboxylic acid or its derivatives to form a bond, and a compound that is grafted with an α, β-unsaturated carboxylic acid A method in which a conjugated diene polymer of a derivative-based compound thereof is reacted under heating and melting or heating without melting. In any of the above cases, graft addition by ene addition may be performed without a radical initiator.

較佳為使自由基起始劑、共軛二烯系聚合物、及含有α,β-不飽和羧酸基或其衍生物基之化合物於加熱熔融下或加熱未熔融下或溶液中進行反應之方法，更佳為於加熱熔融下進行反應之方法。於上述較佳之任一情形時，均可不含自由基起始劑而為藉由烯加成進行之接枝加成。 Preferably, the free radical initiator, the conjugated diene polymer, and the compound containing an α, β-unsaturated carboxylic acid group or its derivative group are reacted under heat melting or heat unmelting or in a solution The method is more preferably the method of carrying out the reaction under heating and melting. In any of the above preferred cases, graft addition by ene addition may be performed without a radical initiator.

作為使自由基起始劑、共軛二烯系聚合物、及含有α,β-不飽和羧酸基或其衍生物基之化合物於加熱熔融下進行反應之方法，例如可例舉：使用班布里混合機、單螺桿擠出機、雙螺桿擠出機、雙向捏合機、及多螺桿擠出機之類的一般混合機對各成分進行熔融混練之方法。就成本及生產穩定性之觀點而言，較佳為使用單、雙或多螺桿擠出機之方法，更佳為使用雙螺桿擠出機之方法。 As a method of 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, for example, the use of A method of melting and kneading each component in a common mixer such as a Brie mixer, a single-screw extruder, a twin-screw extruder, a two-way kneader, and a multi-screw extruder. From the viewpoint of cost and production stability, a method using a single, twin or multi-screw extruder is preferable, and a method using a twin-screw extruder is more preferable.

自由基起始劑、共軛二烯系聚合物、及含有α,β-不飽和羧酸基或其衍生物基之化合物可進行乾摻而一起投入，可按原料不同分開進料，亦可將相同之原料分成複數次添加。 Free radical initiators, conjugated diene polymers, and compounds containing α, β-unsaturated carboxylic acid groups or their derivatives can be dry-blended and fed together. They can be fed separately according to different raw materials, or can be Divide the same raw material into multiple additions.

就使含有α,β-不飽和羧酸或其衍生物基之化合物於共軛二烯系聚合物中均勻地加成之觀點而言，螺桿之轉速較佳為50rpm以上400rpm以下，更佳為100rpm以上350rpm以下。又，就抑制剪切導致之樹脂劣化，使含有α,β-不飽和羧酸或其衍生物基之化合物於共軛二烯系聚合物中均勻地加成之觀點而言，該轉速較佳為150rpm以上300rpm以下。 From the viewpoint of uniformly adding the compound containing α,β-unsaturated carboxylic acid or its derivative group to the conjugated diene polymer, the rotation speed of the screw is preferably from 50 rpm to 400 rpm, more preferably Above 100rpm and below 350rpm. Also, from the viewpoint of suppressing resin deterioration due to shearing and uniformly adding compounds containing α,β-unsaturated carboxylic acid or derivatives thereof to the conjugated diene polymer, the rotational speed is preferable. It is not less than 150 rpm and not more than 300 rpm.

混練溫度只要是使共軛二烯系聚合物熔融之溫度且由自由基起始劑 產生自由基之溫度，則無特別限制，較佳為100℃以上350℃以下。就含有α,β-不飽和羧酸或其衍生物基之化合物之加成量之控制及抑制熱導致之樹脂劣化之觀點而言，該混練溫度更佳為120℃以上300℃以下，進而較佳為150℃以上250℃以下。 As long as the kneading temperature is the temperature at which the conjugated diene polymer melts and the free radical initiator The temperature at which free radicals are generated is not particularly limited, but is preferably not less than 100°C and not more than 350°C. From the viewpoint of controlling the addition amount of the compound containing α,β-unsaturated carboxylic acid or its derivative group and suppressing resin deterioration caused by heat, the kneading temperature is more preferably 120°C or higher and 300°C or lower. Preferably, it is not less than 150°C and not more than 250°C.

為了抑制氧導致之自由基活性種之失活，亦可於氮氣等惰性氣體氛圍下進行熔融混練。 In order to suppress the deactivation of free radical active species caused by oxygen, melt kneading can also be carried out under an inert gas atmosphere such as nitrogen.

共軛二烯系聚合物之改性基之量於接著性、黏結性、揮發性、導電助劑分散性充分之範圍內，就抑制吸濕之觀點而言，以較少為佳，相對於聚合物每100g，較佳為20mmol以下，更佳為15mmol以下，進而較佳為10mmol以下、4mmmol以下、2mmmol以下。尤其當分子量為20萬以上時，為15mmol以下，進而較佳為10mmol以下、4mmmol以下、2mmmol以下。分子量越高，則聚合物間之纏結越多，若改性基與導電助劑相互作用，則導電助劑之分散性變差，因此較佳為於滿足接著性、黏結性、揮發性之基礎上減少改性量。尤其於上述改性基中，酸酐基、羧基、胺基、環氧基、烷氧基矽烷基、羥基等與水分子具有親和性之官能基中，以改性基量較少為佳。導電助劑以含有碳者為主，於其表面存在大量COOH或OH等官能基，因此認為無論導電助劑之種類為何，均具有與共軛二烯系聚合物之相互作用。 The amount of the modified group of the conjugated diene polymer is within the sufficient range of adhesiveness, cohesiveness, volatility, and dispersion of the conductive additive. From the viewpoint of suppressing moisture absorption, it is better to be less. The amount per 100 g of the polymer is preferably 20 mmol or less, more preferably 15 mmol or less, further preferably 10 mmol or less, 4 mmmol or less, and 2 mmmol or less. Especially when the molecular weight is not less than 200,000, it is not more than 15 mmol, more preferably not more than 10 mmol, not more than 4 mmmol, and not more than 2 mmmol. The higher the molecular weight, the more entanglement between the polymers. If the modified group interacts with the conductive additive, the dispersion of the conductive additive will become worse. Reduce the amount of modification on the basis. Especially among the above-mentioned modifying groups, among functional groups having affinity with water molecules such as acid anhydride groups, carboxyl groups, amino groups, epoxy groups, alkoxysilyl groups, and hydroxyl groups, it is better to have a smaller amount of modifying groups. Conductive additives mainly contain carbon, and there are a large number of functional groups such as COOH or OH on the surface. Therefore, it is believed that no matter what the type of conductive additive is, it can interact with the conjugated diene polymer.

作為接枝加成中之自由基起始劑，並無特別限制，例如可例舉：過氧化酮、過氧縮酮、過氧化氫、二烷基過氧化物、二醯基過氧化物、過氧酯、 及過氧化二碳酸酯類。其中，較佳為1分鐘半衰期溫度處於混練溫度區域內之自由基起始劑。更佳為1分鐘半衰期溫度處於150℃以上250℃以下之自由基起始劑，作為此種自由基起始劑，例如可例舉：1,1-二(第三己基過氧基)環己烷、1,1-二(第三丁基過氧基)環己烷、2,2-二(4,4-二-(第三丁基過氧基)環己基)丙烷、過氧化單碳酸O,O-第三己基-O-異丙基酯、過氧化順丁烯二酸第三丁酯、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、過氧化單碳酸O,O-第三丁基-O-異丙基酯、過氧化單碳酸O,O-第三丁基-O-2-乙基己基酯、過氧化苯甲酸第三己酯、2,5-二甲基-2,5-二(苯甲醯基過氧基)己烷、過氧化乙酸第三丁酯、2,2-二-(第三丁基過氧基)丁烷、過氧化苯甲酸第三丁酯、4,4-二-(第三丁基過氧基)戊酸正丁酯、二(2-第三丁基過氧基異丙基)苯、二異丙苯基過氧化物、二第三己基過氧化物、2,5-二甲基-2,5-二(第三丁基過氧基)己烷、第三丁基異丙苯基過氧化物、二第三丁基過氧化物、對甲烷過氧化氫、2,5-二甲基-2,5-二(第三丁基過氧基)己炔-3、二異丙基苯過氧化氫、及1,1,3,3-四甲基丁基過氧化氫。 As the free radical initiator in the graft addition, there is no particular limitation, for example, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, Peroxyester, and peroxydicarbonates. Among them, a free radical initiator whose half-life of 1 minute is within the range of the kneading temperature is preferred. More preferably, it is a free radical initiator with a half-life temperature of 1 minute above 150°C and below 250°C. As such a free radical initiator, for example, 1,1-bis(tertiary hexylperoxy)cyclohexyl Alkanes, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(4,4-bis-(tert-butylperoxy)cyclohexyl)propane, peroxymonocarbonic acid O,O-tert-hexyl-O-isopropyl ester, tert-butyl peroxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate, peroxylauric acid Tertiary butyl ester, O, O-tert-butyl-O-isopropyl peroxymonocarbonate, O, O-tert-butyl-O-2-ethylhexyl peroxymonocarbonate, Benzene peroxide Tri-hexyl formate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tri-butyl peroxyacetate, 2,2-di-(tert-butyl Peroxy) butane, tert-butyl peroxybenzoate, 4,4-di-(tert-butylperoxy) n-butyl valerate, bis(2-tert-butylperoxyisopropyl base) benzene, dicumyl peroxide, di-tertiary hexyl peroxide, 2,5-dimethyl-2,5-di(tertiary butylperoxy) hexane, tertiary butyl Cumyl peroxide, di-tert-butyl peroxide, p-methane hydroperoxide, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexyne-3, Diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

就提昇與共軛二烯系聚合物之相容性之觀點而言，較佳為二(2-第三丁基過氧基異丙基)苯、二異丙苯基過氧化物、二第三己基過氧化物、2,5-二甲基-2,5-二(第三丁基過氧基)己烷、第三丁基異丙苯基過氧化物、二第三丁基過氧化物、及2,5-二甲基-2,5-二(第三丁基過氧基)己炔-3。其中，更佳為2,5-二甲基-2,5-二(第三丁基過氧基)己烷及2,5-二甲基-2,5-二(第三丁基過氧基)己炔-3。 From the viewpoint of improving the compatibility with the conjugated diene polymer, bis(2-tert-butylperoxyisopropyl)benzene, dicumyl peroxide, dicumyl peroxide, and dicumyl peroxide are preferred. Trihexyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butyl peroxy) hexane, tertiary butylcumyl peroxide, di-tertiary butyl peroxide substances, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3. Among them, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane are more preferred base) hexyne-3.

相對於自由基起始劑，含有α,β-不飽和羧酸或其衍生物基之化合物之 mol當量較佳為300mol當量以下，更佳為200mol當量以下，更佳為100mol當量以下。藉由使該mol當量為上述範圍內，相對於共軛二烯系聚合物100質量份，可更易於使含有α,β-不飽和羧酸或其衍生物基之化合物加成至多於0質量份且10質量份以下左右。 Compounds containing α,β-unsaturated carboxylic acids or their derivatives as opposed to free radical initiators The mol equivalent is preferably not more than 300 mol equivalent, more preferably not more than 200 mol equivalent, more preferably not more than 100 mol equivalent. By setting the molar equivalent within the above range, it becomes easier to add the compound containing α,β-unsaturated carboxylic acid or its derivative group to more than 0 mass with respect to 100 parts by mass of the conjugated diene polymer parts and about 10 parts by mass or less.

於將導入了一次改性基之共軛二烯系聚合物進而藉由具有對電極活性物質層之構成成分或固體電解質或集電體之接著性之原子團進行二次改性之情形時，反應方法並無特別限制，可利用公知方法。例如，可例舉：於將一次共軛二烯系聚合物與改性劑進行乾摻之後，使用班布里混合機、單螺桿擠出機、雙螺桿擠出機、雙向捏合機、及多螺桿擠出機之類的一般混合機對各成分進行熔融混練之方法；以及於將各成分溶解或分散混合於溶劑中之後將該溶劑加熱去除之方法。 In the case where the conjugated diene polymer introduced with the primary modifying group is further modified by the atomic group having adhesiveness to the constituents of the electrode active material layer or the solid electrolyte or the current collector, the reaction The method is not particularly limited, and known methods can be used. For example, after dry-blending the primary conjugated diene polymer and the modifying agent, using a Banbury mixer, a single-screw extruder, a twin-screw extruder, a two-way kneader, and a multiple A method of melt-kneading each component with a general mixer such as a screw extruder; and a method of removing the solvent by heating after dissolving or dispersing and mixing each component in a solvent.

該等中，就提高生產性及良混練性之觀點而言，較佳為利用擠出機之熔融混練法。 Among these, the melt-kneading method using an extruder is preferable from the viewpoint of improving productivity and good kneading properties.

本實施方式之共軛二烯系聚合物之形狀並無特別限制，可例舉顆粒狀、片狀、股線狀、及小片狀、粉末狀、屑粒狀。又，於熔融混練後，可直接製成成形品，亦可製成小片狀、粉末狀、屑粒狀。就共軛二烯系聚合物中所含之水分去除效率之觀點而言，較佳為比表面積較大之形狀，相較於顆粒而言，較佳為屑粒或粉末。 The shape of the conjugated diene polymer of this embodiment is not particularly limited, and examples thereof include granular, flake, strand, flake, powder, and crumb. In addition, after melting and kneading, it can be directly made into molded products, and can also be made into small flakes, powders, and crumbs. From the viewpoint of removal efficiency of water contained in the conjugated diene polymer, a shape with a large specific surface area is preferable, and crumbs or powder are more preferable than granules.

作為顆粒化之方法，例如可例舉：從單軸或雙軸擠出機將共軛二烯系 聚合物呈股線狀擠出，利用設置於模頭部前面之旋轉刀，於水中進行切斷之方法(水中切割等)；從單軸或雙軸擠出機將共軛二烯系聚合物呈股線狀擠出，於水冷或氣冷後，利用股線切割機進行切斷之方法；以及利用開口滾筒或班布里混合機使共軛二烯系聚合物熔融混合後，利用滾筒將其成型為片狀，進而將該片切割成短條狀後，利用造粒機切斷成立方狀顆粒之方法。於水中進行切斷之方法中，由於聚合物表面會混入水分，故可藉由離心脫水或空氣輸送等後步驟去除水分。又，於利用股線切割機進行切斷之方法中，亦可於氣冷步驟中藉由鼓風或抽吸式脫水、空氣輸送等後步驟而去除水分。 As a method of granulation, for example, a conjugated diene-based The polymer is extruded in the form of strands, and the method of cutting in water (cutting in water, etc.) is carried out by using a rotary knife installed in front of the die head; the conjugated diene polymer is extruded from a single-screw or twin-screw extruder Extrude in the form of strands, after water cooling or air cooling, use a strand cutter to cut; and use an open drum or Banbury mixer to melt and mix the conjugated diene polymer, and use a drum to melt It is formed into a sheet, and then the sheet is cut into short strips, and then cut into cubic granules by a granulator. In the method of cutting in water, since water will be mixed on the surface of the polymer, the water can be removed by subsequent steps such as centrifugal dehydration or air transportation. In addition, in the method of cutting with a strand cutter, water may be removed by post-steps such as air blowing or suction dehydration, air transport, etc. in the air cooling step.

再者，顆粒之大小、形狀並無特別限制，就抑制顆粒彼此接著之觀點而言，相較於將股線相對於股線長軸垂直地切斷所獲得之圓柱狀顆粒，接近球狀之顆粒能將顆粒彼此之接著面抑制得更小，故較佳。作為接近球狀之顆粒之一般製造方法，例如可例舉水中切割或中心熱切割。 Furthermore, the size and shape of the particles are not particularly limited. From the viewpoint of suppressing the adhesion of the particles to each other, compared with the cylindrical particles obtained by cutting the strands perpendicular to the long axis of the strands, they are closer to spherical. It is preferable that the particles can suppress the bonding surfaces between the particles to be smaller. As a general method of producing nearly spherical pellets, for example, water cutting or central thermal cutting may be mentioned.

以抑制顆粒黏連為目的，共軛二烯系聚合物之顆粒亦可含有抗黏連劑。 The particles of the conjugated diene polymer may also contain an anti-blocking agent for the purpose of suppressing particle blocking.

共軛二烯系聚合物亦可含有磷化合物。磷化合物之含量以磷原子換算計，相對於共軛二烯系共聚物，較佳為10ppm以上，更佳為20ppm以上，進而較佳為50ppm以上。較佳之上限為250ppm以下，更佳為120ppm以下。 The conjugated diene polymer may also contain a phosphorus compound. The content of the phosphorus compound is, in terms of phosphorus atoms, preferably at least 10 ppm, more preferably at least 20 ppm, and still more preferably at least 50 ppm relative to the conjugated diene-based copolymer. A preferable upper limit is 250 ppm or less, more preferably 120 ppm or less.

作為抗黏連劑，並無特別限制，例如可例舉：高級脂肪酸金屬鹽、聚烯烴、脂肪醯胺、滑石、二氧化矽。具體而言，可例舉：硬脂酸鈣、硬脂酸鎂、硬脂酸鋅、聚乙烯、聚丙烯、伸乙基雙硬脂醯胺、滑石、及非晶形二氧化矽。就低滲出性之觀點而言，較佳為硬脂酸鈣、硬脂酸鎂、硬脂酸鋅、聚乙烯、聚丙烯、滑石、及非晶形二氧化矽，就料斗添加時之順滑性之觀點而言，更佳為硬脂酸鈣、硬脂酸鎂、硬脂酸鋅、聚乙烯、聚丙烯、及非晶形二氧化矽，就不易發生粉末飛散之觀點而言，進而較佳為聚乙烯或非晶形二氧化矽，最佳為非晶形二氧化矽。 The anti-blocking agent is not particularly limited, and examples thereof include higher fatty acid metal salts, polyolefins, fatty amide, talc, and silicon dioxide. Specifically, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylidenebisstearamide, talc, and amorphous silicon dioxide may, for example, be mentioned. From the point of view of low exudation, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, talc, and amorphous silicon dioxide are preferred, in terms of smoothness when adding from a hopper From the point of view, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, and amorphous silicon dioxide are more preferable, and from the point of view that powder scattering is less likely to occur, more preferably Polyethylene or amorphous silica, most preferably amorphous silica.

就對所獲得之電極活性物質層之構成成分或固體電解質或集電體之接著性之觀點而言，抗黏連劑較佳為硬脂酸鈣、聚乙烯、聚丙烯、及伸乙基雙硬脂醯胺。 From the viewpoint of the adhesiveness of the constituents of the obtained electrode active material layer or the solid electrolyte or the current collector, the anti-blocking agent is preferably calcium stearate, polyethylene, polypropylene, and ethylene bis Stearylamide.

作為抗黏連劑之較佳使用量，相對於共軛二烯系聚合物為500ppm以上8000ppm以下。就長期保管共軛二烯系聚合物之顆粒時抑制顆粒黏連之觀點及減少於使用共軛二烯系聚合物之顆粒時抗黏連劑飛散之觀點而言，抗黏連劑之使用量更佳為相對於共軛二烯系聚合物為1000ppm以上7000ppm以下。抗黏連劑較佳為以附著於顆粒表面之狀態調配，亦可包含於顆粒內部。 The preferred usage amount of the anti-blocking agent is not less than 500 ppm and not more than 8000 ppm relative to the conjugated diene polymer. The amount of anti-blocking agent used is from the point of view of suppressing particle sticking during long-term storage of conjugated diene-based polymer particles and reducing anti-blocking agent scattering when using conjugated diene-based polymer particles More preferably, it is 1000 ppm or more and 7000 ppm or less with respect to a conjugated diene-type polymer. The anti-blocking agent is preferably formulated in a state of being attached to the surface of the particles, and may also be contained inside the particles.

又，共軛二烯系聚合物可含有其他添加劑，並無特別限制，例如可例舉：油、填料、熱穩定劑、紫外線吸收劑、成核劑、抗氧化劑、耐候劑、光穩定劑、塑化劑、抗靜電劑、阻燃劑、滑澤劑、防霧劑、潤滑劑、顏料、染 料、分散劑、銅毒抑制劑、中和劑、氣泡防止劑、焊接強度改良劑、天然油、合成油、蠟等添加劑。又，亦可以任意比率使用其他彈性體或熱塑性樹脂作為添加劑。該等可僅使用1種，亦可併用2種以上。 In addition, the conjugated diene polymer may contain other additives without particular limitation, for example, oil, filler, heat stabilizer, ultraviolet absorber, nucleating agent, antioxidant, weather resistance agent, light stabilizer, Plasticizers, antistatic agents, flame retardants, slip agents, antifogging agents, lubricants, pigments, dyes Additives such as additives, dispersants, copper poison inhibitors, neutralizers, anti-foaming agents, weld strength improvers, natural oils, synthetic oils, waxes, etc. In addition, other elastomers or thermoplastic resins may be used as additives in arbitrary ratios. These may use only 1 type, and may use 2 or more types together.

[全固體電池] [All solid battery]

其次，記載使用上述全固體電池黏著劑之全固體電池之態樣。本實施方式之全固體電池包含：含有上述全固體電池黏著劑之正極層、含有上述全固體電池黏著劑之固體電解質層、及含有上述全固體電池黏著劑之負極層中之至少一層。 Next, the state of the all-solid battery using the above-mentioned all-solid battery adhesive is described. The all-solid battery of this embodiment includes: at least one of the positive electrode layer containing the above-mentioned all-solid battery adhesive, the solid electrolyte layer containing the above-mentioned all-solid battery adhesive, and the negative electrode layer containing the above-mentioned all-solid battery adhesive.

圖1係表示本實施方式之全固體電池之一例之概略剖視圖。該全固體電池(全固體電池)100具備：固體電解質層110、從兩側夾隔該固體電解質層110之正極層140及負極層150、進而夾隔其等之積層體之正極集電體160(配置於正極之外側)與負極集電體170(配置於負極之外側)、以及收容其等之電池外裝180。 FIG. 1 is a schematic cross-sectional view showing an example of an all-solid-state battery according to this embodiment. The 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, and a positive electrode current collector 160 sandwiching the laminated body thereof. (arranged outside the positive electrode) and negative electrode current collector 170 (arranged outside the negative electrode), and the battery case 180 for accommodating them.

本實施方式中，藉由使用上述全固體電池黏著劑，能夠生產出減少了水分量之全固體電池，藉此可實現具有作為電池之高電容之全固體電池。 In the present embodiment, by using the above-mentioned all-solid battery adhesive, it is possible to produce an all-solid battery with reduced water content, thereby realizing an all-solid battery having a high capacity as a battery.

全固體電池中所含之水分量較佳為200ppm以下，更佳為100ppm以下，進而較佳為50ppm以下，進而更佳為10ppm以下，尤佳為1ppm以下。水分可利用常壓或減壓之乾燥機進行乾燥去除，亦可保管於除濕環境下而去除。 The moisture contained in the all-solid battery is preferably 200 ppm or less, more preferably 100 ppm or less, further preferably 50 ppm or less, still more preferably 10 ppm or less, especially preferably 1 ppm or less. Moisture can be removed by drying with a normal pressure or reduced pressure dryer, or stored in a dehumidified environment.

[正極] [positive electrode]

正極具有正極集電體及形成於該正極集電體上之正極層。正極層含有正極活性物質，視需要可含有導電助劑、全固體電池黏著劑、用以提高離子傳導性之無機固體電解質、高分子凝膠電解質、高分子電解質、添加劑等。 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 positive active materials, and may contain conductive additives, all-solid battery adhesives, inorganic solid electrolytes for improving ion conductivity, polymer gel electrolytes, polymer electrolytes, additives, etc. if necessary.

作為正極活性物質，可使用用於一般之鋰離子電池之正極活性物質。例如可例舉氧化物活性物質、硫化物活性物質等。 As the positive electrode active material, a positive electrode active material used in general lithium ion batteries can be used. For example, an oxide active material, a sulfide active material, etc. are mentioned.

具體而言，可使用作為層狀岩鹽型正極材料之LiCoO2等Li-Co複合氧化物、LiNiO2等Li-Ni複合氧化物、由該等衍生之鎳系化合物LiNi(Co、Al)O2、三元系化合物LiNi1/3Mn1/3Co1/3O2、LiNi0.8Co0.15Al0.05O2、作為鎳錳系化合物之LiNi0.5Mn0.5O2、鋰過量系化合物Li2MnO3-LiMO2(M=Co、Ni、Mn)、作為尖晶石型正極材料之LiMn2O4、LiMn1.5Ni0.5O4、作為橄欖石系正極材料之LiFeO2、LiCoPO4、LiNiPO4、LiFePO4、LiMnPO4、Li2MSiO4(M為過渡金屬)、LiMPO4F(M為過渡金屬)、作為高容量系正極材料之氧化釩系、硫系正極材。正極活性物質可使用1種或組合2種以上使用。 Specifically, Li-Co composite oxides such as LiCoO 2 , Li-Ni composite oxides such as LiNiO 2 , and nickel-based compounds derived from them, LiNi(Co, Al)O 2 , which are layered rock-salt-type positive electrode materials, can be used. , ternary compound LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.5 Mn 0.5 O 2 as a nickel-manganese compound, lithium-excess compound Li 2 MnO 3 -LiMO 2 (M=Co, Ni, Mn), LiMn 2 O 4 , LiMn 1.5 Ni 0.5 O 4 as spinel cathode materials, LiFeO 2 , LiCoPO 4 , LiNiPO 4 , LiFePO as olivine cathode materials 4. LiMnPO 4 , Li 2 MSiO 4 (M is a transition metal), LiMPO 4 F (M is a transition metal), vanadium oxide-based and sulfur-based positive electrode materials as high-capacity positive electrode materials. The positive electrode active material may be used alone or in combination of two or more.

正極只要為作為鋰離子二次電池之正極發揮作用者則並無特別限制，例如可以下述方式獲得。 The positive electrode is not particularly limited as long as it functions as a positive electrode of a lithium ion secondary battery, and can be obtained, for example, as follows.

首先，將上述正極活性物質與視需要使用之其他成分(例如導電助劑、黏著劑等)一起混合而獲得正極混合劑，使該正極混合劑分散於溶劑中而製備含有正極混合劑之漿料。繼而，將該含有正極混合劑之漿料塗佈於正極集電體(基材)，加以乾燥而形成正極層，進而視需要進行加壓而調整厚度，藉此製作正極。 First, mix the above-mentioned positive electrode active material with other components (such as conductive aids, binders, etc.) as needed to obtain a positive electrode mixture, and disperse the positive electrode mixture in a solvent to prepare a slurry containing the positive electrode mixture . Next, the slurry containing the positive electrode mixture is applied to a positive electrode current collector (substrate), dried to form a positive electrode layer, and the thickness is adjusted by applying pressure as necessary to prepare a positive electrode.

上述含有正極混合劑之漿料中之固形物成分濃度並無特別限制，較佳為30~80質量%，更佳為40~70質量%。 The solid content concentration in the slurry containing the positive electrode mixture is not particularly limited, but is preferably 30-80% by mass, more preferably 40-70% by mass.

上述正極集電體例如包含鋁、不鏽鋼、金、鉑、鈦、錫、銅、鋅等金屬箔。亦可為對該等材料實施碳塗佈而得者、將該等材料加工成網狀者。 The positive electrode current collector includes, for example, metal foils such as aluminum, stainless steel, gold, platinum, titanium, tin, copper, and zinc. Those obtained by applying carbon coating to these materials, or those obtained by processing these materials into a mesh shape may also be used.

視需要可使用藉由具有鋰離子傳導性之物質填充粒子間之方法，以確保與固體電解質之鋰離子傳導性。作為具有鋰離子傳導性之物質，例如可使用非晶質之具有鋰離子傳導性之物質，作為非晶質之具有鋰離子傳導性之物質，可使用聚合物電解質、非晶質且具有鋰離子傳導性之無機化合物。 If necessary, a method of filling the particles with a substance having lithium ion conductivity may be used to ensure lithium ion conductivity with the solid electrolyte. As a material having lithium ion conductivity, for example, an amorphous material having lithium ion conductivity can be used. As an amorphous material having lithium ion conductivity, a polymer electrolyte, an amorphous material having lithium ion conductivity, and a polymer electrolyte can be used. Conductive inorganic compounds.

正極層中所含之水分量較佳為200ppm以下，更佳為100ppm以下，進而較佳為50ppm以下，進而更佳為10ppm以下，尤佳為1ppm以下。水分可利用常壓或減壓之乾燥機進行乾燥去除，亦可保管於除濕環境下而去除。 The moisture contained in the positive electrode layer is preferably 200 ppm or less, more preferably 100 ppm or less, further preferably 50 ppm or less, still more preferably 10 ppm or less, especially preferably 1 ppm or less. Moisture can be removed by drying with a normal pressure or reduced pressure dryer, or stored in a dehumidified environment.

[負極] [negative electrode]

負極具有負極集電體及形成於該負極集電體上之負極層。負極層含有負極活性物質，視需要可含有導電助劑、全固體電池黏著劑、用以提高離子傳導性之無機固體電解質、高分子凝膠電解質、高分子電解質、添加劑等。 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 negative electrode active materials, and may contain conductive additives, all-solid battery adhesives, inorganic solid electrolytes for improving ion conductivity, polymer gel electrolytes, polymer electrolytes, additives, etc. if necessary.

負極較佳為含有選自由能夠吸藏及釋放鋰離子之材料及金屬鋰所組成之群中之1種以上之材料作為負極活性物質。作為此種材料，除包含金屬鋰、能夠與鋰形成合金之元素之材料等金屬材料以外，例如可例舉：非晶形碳(硬碳)、人造石墨、天然石墨、石墨、熱分解碳、焦炭、玻璃狀碳、有機高分子化合物之煅燒體、中間相微碳球、碳纖維、活性碳、石墨、碳膠體、碳黑為代表之碳材料。 The negative electrode preferably contains one or more materials selected from the group consisting of materials capable of storing and releasing lithium ions and metal lithium as the negative electrode active material. As such a material, in addition to metal materials such as metal lithium and materials capable of forming an alloy with lithium, for example, amorphous carbon (hard carbon), artificial graphite, natural graphite, graphite, pyrolytic carbon, coke , glassy carbon, calcined body of organic polymer compound, mesophase microcarbon spheres, carbon fiber, activated carbon, graphite, carbon colloid, and carbon black are the representative carbon materials.

該等中，作為焦炭，例如可例舉瀝青焦、針狀焦、石油焦等。所謂有機高分子化合物之煅燒體係指將酚樹脂、呋喃樹脂等高分子材料於適當之溫度下進行煅燒而碳化者。 Among these, as coke, pitch coke, needle coke, petroleum coke, etc. are mentioned, for example. The so-called calcined system of organic polymer compounds refers to those polymer materials such as phenol resin and furan resin that are calcined and carbonized at an appropriate temperature.

碳材料中，除碳以外，亦可包含含有O、B、P、N、S、SiC、B4C等之異種化合物。作為異種化合物之含量，相對於負極活性物質整體，較佳為0~10質量%。 In addition to carbon, the carbon material may contain heterogeneous compounds containing O, B, P, N, S, SiC, B4C, and the like. The content of the heterogeneous compound is preferably 0 to 10% by mass relative to the entire negative electrode active material.

上述能夠與鋰形成合金之金屬材料可為金屬或半金屬之單質，可為合金，亦可為化合物，又，亦可為至少一部分具有該等之1種或2種以上之相之類的材料。或者，可使用SiOx、Li4Ti5O12等氧化物活性物質等公知之 材料。又，可使用上述負極活性物質之1種或組合2種以上使用。 The above-mentioned metal material capable of forming an alloy with lithium may be a single substance of metal or semimetal, may be an alloy, may also be a compound, and may also be a material having at least one or two or more of these phases. . Alternatively, known materials such as oxide active materials such as SiOx and Li 4 Ti 5 O 12 can be used. Moreover, one type or a combination of two or more types of the above negative electrode active materials may be used.

負極活性物質之數量平均粒徑(一次粒徑)較佳為0.1μm~100μm，更佳為1μm~10μm。 The number average particle diameter (primary particle diameter) of the negative electrode active material is preferably 0.1 μm to 100 μm, more preferably 1 μm to 10 μm.

負極例如以下述方式獲得。首先，將上述負極活性物質與視需要使用之其他成分(例如導電助劑、黏著劑等)一起混合而獲得負極混合劑，使該負極混合劑分散於溶劑中，而製備含有負極混合劑之漿料。繼而，將該含有負極混合劑之漿料塗佈於負極集電體(基材)，進行乾燥而形成負極層，進而視需要進行加壓而調整厚度，藉此製作負極。 The negative electrode is obtained, for example, as follows. First, mix the above-mentioned negative electrode active material with other components (such as conductive additives, binders, etc.) as needed to obtain a negative electrode mixture, and disperse the negative electrode mixture in a solvent to prepare a slurry containing the negative electrode mixture material. Next, the slurry containing the negative electrode mixture is applied to a negative electrode current collector (base material), dried to form a negative electrode layer, and the thickness is adjusted by applying pressure as necessary to prepare a negative electrode.

此處，含有負極混合劑之漿料中之固形物成分濃度較佳為30~80質量%，更佳為40~70質量%。負極集電體例如包含銅、鎳、不鏽鋼、金、鉑、鈦、錫、鋅等金屬箔。 Here, the solid content concentration in the slurry containing the negative electrode mixture is preferably from 30 to 80% by mass, more preferably from 40 to 70% by mass. The negative electrode current collector includes, for example, metal foils such as copper, nickel, stainless steel, gold, platinum, titanium, tin, and zinc.

視需要可使用藉由具有鋰離子傳導性之物質填充粒子間之方法，以確保與固體電解質之鋰離子傳導性。作為具有鋰離子傳導性之物質，例如可使用非晶質之具有鋰離子傳導性之物質，作為非晶質之具有鋰離子傳導性之物質，可使用聚合物電解質、非晶質且具有鋰離子傳導性之無機化合物。 If necessary, a method of filling the particles with a substance having lithium ion conductivity may be used to ensure lithium ion conductivity with the solid electrolyte. As a material having lithium ion conductivity, for example, an amorphous material having lithium ion conductivity can be used. As an amorphous material having lithium ion conductivity, a polymer electrolyte, an amorphous material having lithium ion conductivity, and a polymer electrolyte can be used. Conductive inorganic compounds.

負極層中所含之水分量較佳為200ppm以下，更佳為100ppm以下，進而較佳為50ppm以下，進而更佳為10ppm以下，尤佳為1ppm以下。水分可利用常壓或減壓之乾燥機進行乾燥去除，亦可保管於除濕環境下而 去除。 The moisture contained in the negative electrode layer is preferably 200 ppm or less, more preferably 100 ppm or less, further preferably 50 ppm or less, still more preferably 10 ppm or less, especially preferably 1 ppm or less. Moisture can be removed by drying with a normal pressure or reduced pressure dryer, or it can be stored in a dehumidified environment. remove.

[漿料] [slurry]

可用作上述含有正極混合劑之漿料或上述含有負極混合劑之漿料的本實施方式之漿料含有上述全固體電池黏著劑，可視需要含有導電助劑、溶劑、及上述正極活性物質或上述負極活性物質等。 The slurry of this embodiment that can be used as the above-mentioned slurry containing the positive electrode mixture or the above-mentioned slurry containing the negative electrode mixture contains the above-mentioned all-solid battery adhesive, and optionally contains a conductive additive, a solvent, and the above-mentioned positive electrode active material or The aforementioned negative electrode active material and the like.

再者，本實施方式之漿料較佳為不含水分，漿料之水分量較佳為200ppm以下，更佳為100ppm以下，進而較佳為50ppm以下，進而更佳為10ppm以下，尤佳為1ppm以下。全固體電池黏著劑中所含之水分可利用常壓或減壓之乾燥機進行乾燥去除，亦可保管於除濕環境下而去除。 Furthermore, the slurry in this embodiment is preferably free of moisture, and the moisture content of the slurry is preferably below 200ppm, more preferably below 100ppm, further preferably below 50ppm, even more preferably below 10ppm, especially preferably below 10ppm. Below 1ppm. The moisture contained in the all-solid battery adhesive can be removed by drying it with a dryer at normal pressure or reduced pressure, or by storing it in a dehumidified environment.

(導電助劑) (conductive additive)

作為本實施方式之導電助劑，只要具有電子傳導性，則並無特別限制。例如可例舉：石墨；乙炔黑及科琴黑為代表之碳黑；氣相生長碳纖維或奈米碳管為代表之碳纖維等。其中，較佳為碳黑。用於正極之導電助劑之數量平均粒徑(一次粒徑)較佳為10nm~10μm，更佳為20nm~1μm。用於負極之導電助劑之數量平均粒徑(一次粒徑)較佳為0.1μm~100μm，更佳為1μm~10μm。該等可僅使用1種，亦可併用2種以上。藉由使用導電助劑，可確保各電極層之電子傳導路徑，可降低全固體電池之內部電阻，藉由電流量之增大，全固體電池之充放電特性提高。藉由對應於導電助劑表面之官能基來選擇全固體電池黏著劑之改性基，可藉由相互作用來控制分散性。由於碳系導電助劑之表面存在羧基或羥基等，故就基於氫鍵之相 互作用而言，較佳為羧基、羥基、胺基。 There are no particular limitations on the conduction aid in this embodiment as long as it has electron conductivity. For example, graphite; carbon black represented by acetylene black and Ketjen black; carbon fiber represented by vapor-phase grown carbon fiber or carbon nanotube, etc. may be mentioned. Among them, 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 may use only 1 type, and may use 2 or more types together. By using a conductive additive, the electron conduction path of each electrode layer can be ensured, the internal resistance of the all-solid battery can be reduced, and the charging and discharging characteristics of the all-solid battery can be improved by increasing the current. By selecting the modification group of the all-solid battery adhesive corresponding to the functional group on the surface of the conductive additive, the dispersibility can be controlled through interaction. Since there are carboxyl groups or hydroxyl groups on the surface of carbon-based conductive additives, the phase based on hydrogen bonds In terms of interaction, carboxyl, hydroxyl, and amino groups are preferred.

作為碳黑，可例舉：藉由爐法(不完全燃燒法)所製造之油爐黑、煤氣爐黑、藉由熱法(熱分解法)所製造之乙炔黑、熱碳黑。其中，就電子傳導性之觀點而言，較佳為油爐黑或乙炔黑。作為油爐黑，有科琴黑(Lion Specialty Chemicals股份有限公司製之製品)，作為乙炔黑，有Denka black(註冊商標)(Denka股份有限公司製之製品)等。 Examples of carbon black include oil furnace black and gas furnace black produced by a furnace method (incomplete combustion method), acetylene black and thermal black produced by a thermal method (pyrolysis method). Among them, oil furnace black or acetylene black is preferable from the viewpoint of electron conductivity. As the oil furnace black, there is Ketjen black (manufactured by Lion Specialty Chemicals Co., Ltd.), and as acetylene black, there is Denka black (registered trademark) (manufactured by Denka Co., Ltd.).

(黏著劑) (adhesive)

本實施方式之黏著劑為共軛二烯系聚合物。亦可併用共軛二烯系聚合物以外之高分子材料，具體而言，例如可例舉聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚丙烯酸、苯乙烯丁二烯橡膠、氟橡膠等，但並無特別限制。該等亦可藉由改性而具有官能基。黏著劑可使用1種或組合2種以上使用。 The adhesive in this embodiment is a conjugated diene polymer. Polymer materials other than conjugated diene polymers may also be used in combination. Specifically, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid, styrene butadiene rubber, etc. , fluorine rubber, etc., but not particularly limited. These may also have functional groups by modification. Adhesives can be used alone or in combination of two or more.

正極中所含之全固體電池黏著劑之含量並無特別限制，就離子傳導性及電子傳導性之觀點而言，較佳為將正極之總重量(集電體除外)設為100wt%時為其中之10wt%以下，更佳為5wt%以下，進而較佳為3wt%以下，尤佳為1wt%以下。 The content of the all-solid battery binder contained in the positive electrode is not particularly limited. From the viewpoint of ion conductivity and electronic conductivity, it is preferably Among them, 10wt% or less, more preferably 5wt% or less, further preferably 3wt% or less, especially preferably 1wt% or less.

又，負極中所含之全固體電池黏著劑之含量並無特別限制，就離子傳導性及電子傳導性之觀點而言，較佳為將負極之總重量(集電體除外)設為100wt%時為其中之10wt%以下，更佳為5wt%以下，進而較佳為3wt% 以下，尤佳為1wt%以下。 Also, the content of the all-solid battery binder contained in the negative electrode is not particularly limited. From the viewpoint of ion conductivity and electronic conductivity, it is preferable to set the total weight of the negative electrode (excluding the current collector) to 100wt%. 10wt% or less, more preferably 5wt% or less, and more preferably 3wt% less than, preferably less than 1 wt%.

又，固體電解質層中所含之全固體電池黏著劑之含量並無特別限制，就離子傳導性及電子傳導性之觀點而言，較佳為將固體電解質層之總重量設為100wt%時為其中之10wt%以下，更佳為5wt%以下，進而較佳為3wt%以下，尤佳為1wt%以下。 Also, the content of the all-solid battery adhesive contained in the solid electrolyte layer is not particularly limited, and from the viewpoint of ion conductivity and electron conductivity, when the total weight of the solid electrolyte layer is set as 100wt%, it is preferably Among them, 10wt% or less, more preferably 5wt% or less, further preferably 3wt% or less, especially preferably 1wt% or less.

全固體電池黏著劑於各層中可均勻地分佈，可不均勻地分佈，亦可具有傾斜地分佈。又，亦可視需要以將各層之界面接著為目的而使用。 The all-solid battery adhesive can be distributed uniformly, unevenly, or obliquely in each layer. Moreover, it can also be used for the purpose of bonding the interface of each layer as needed.

全固體電池中，正極層中所含之導電助劑之濃度分佈並無特別限制，就電子傳導性之觀點而言，較佳為正極集電體附近之導電助劑之濃度高於固體電解質層附近。於全固體電池之充放電過程中，正極層整體之電流集中於正極層之正極集電體附近。因此，藉由提高正極集電體附近之導電助劑之濃度，可消除正極層之電子傳導路徑之瓶頸，使電池之充放電負荷特性或循環壽命特性變得良好。 In an all-solid battery, the concentration distribution of the conductive additive contained in the positive electrode layer is not particularly limited. From the viewpoint of electronic conductivity, it is preferable that the concentration of the conductive additive near the positive electrode current collector is higher than that of the solid electrolyte layer nearby. During the charging and discharging process of the all-solid-state battery, the current of the positive electrode layer as a whole is concentrated near the positive electrode current collector of the positive electrode layer. Therefore, by increasing the concentration of the conductive additive near the positive electrode current collector, the bottleneck of the electron conduction path of the positive electrode layer can be eliminated, so that the charge and discharge load characteristics or cycle life characteristics of the battery become better.

本實施方式之全固體電池中，關於正極層所含之導電助劑之濃度，正極集電體附近之導電助劑之濃度高於固體電解質層附近，較佳為正極集電體附近之導電助劑之濃度為固體電解質層附近之導電助劑之濃度之10倍以上。於全固體電池之充放電時，在正極集電體附近，相較鋰離子傳導而言，更多地進行電子傳導。因此，提高正極集電體附近之導電助劑之濃度即可。藉此，可提高充放電時之正極層之電子傳導性，獲得良好之充放電 特性。 In the all-solid-state battery of this embodiment, regarding the concentration of the conductive additive contained in the positive electrode layer, the concentration of the conductive additive near the positive electrode current collector is higher than that near the solid electrolyte layer, preferably the conductive additive near the positive electrode current collector. The concentration of the additive is more than 10 times the concentration of the conductive additive near the solid electrolyte layer. During the charge and discharge of the all-solid-state battery, more electron conduction takes place near the positive electrode collector than lithium ion conduction. Therefore, it is sufficient to increase the concentration of the conductive additive near the positive electrode current collector. In this way, the electronic conductivity of the positive electrode layer can be improved during charge and discharge, and good charge and discharge can be obtained. characteristic.

又，本實施方式之全固體電池中，負極層所含之導電助劑之濃度分佈並無特別限制，就電子傳導性之觀點而言，較佳為負極集電體附近之導電助劑之濃度高於固體電解質層附近。於全固體電池之充放電過程中，負極層整體之電流集中於負極層之負極集電體之附近。因此，藉由提高負極集電體附近之導電助劑之濃度，可消除負極層之電子傳導路徑之瓶頸，使電池之充放電負荷特性或循環壽命特性變得良好。 In addition, in the all-solid-state battery of this embodiment, the concentration distribution of the conductive additive contained in the negative electrode layer is not particularly limited, and from the viewpoint of electronic conductivity, the concentration of the conductive additive near the negative electrode current collector is preferably above the solid electrolyte layer. During the charging and discharging process of the all-solid-state battery, the current of the entire negative electrode layer is concentrated near the negative electrode current collector of the negative electrode layer. Therefore, by increasing the concentration of the conductive additive near the negative electrode current collector, the bottleneck of the electron conduction path of the negative electrode layer can be eliminated, so that the charge and discharge load characteristics or cycle life characteristics of the battery become better.

又，與正極層同樣，於全固體電池之充放電時，在負極集電體附近，相較鋰離子傳導而言，更多地進行電子傳導。因此，本實施方式之負極層只要使負極集電體附近之導電助劑之濃度高於固體電解質層附近即可，較佳為負極集電體附近之導電助劑之濃度為固體電解質層附近之導電助劑之濃度之8倍以上。藉此，可提高充放電時之負極層之電子傳導性，獲得良好之充放電特性。 Also, similarly to the positive electrode layer, during charge and discharge of the all-solid-state battery, more electron conduction than lithium ion conduction occurs near the negative electrode current collector. Therefore, the negative electrode layer of the present embodiment only needs to make the concentration of the conductive additive near the negative electrode current collector higher than that near the solid electrolyte layer. More than 8 times the concentration of conductive additives. Thereby, the electron conductivity of the negative electrode layer during charge and discharge can be improved, and good charge and discharge characteristics can be obtained.

(溶劑) (solvent)

作為本實施方式之溶劑，只要不對固體電解質之性能造成不良影響，則無特別限制，例如可例舉作為親水性較低之溶劑之無極性溶劑。作為無極性溶劑，例如可例舉烴系溶劑之庚烷、二甲苯、甲苯、己烷等、或該等之組合。就抑制固體電解質之分解之觀點而言，較佳為使用經脫水處理而使水分含量降低之烴系有機溶劑。又，就生產性之觀點而言，較佳為常壓下之沸點為100℃以上且熔點為0℃以下之無極性溶劑，更佳為常壓下之 沸點為150℃以上且熔點為-20℃以下之無極性溶劑。 The solvent in this embodiment is not particularly limited as long as it does not adversely affect the performance of the solid electrolyte, and examples thereof include non-polar solvents that are less hydrophilic solvents. As the nonpolar solvent, for example, heptane, xylene, toluene, hexane, etc., which are hydrocarbon solvents, or combinations thereof may be mentioned. From the viewpoint of suppressing the decomposition of the solid electrolyte, it is preferable to use a hydrocarbon-based organic solvent that has been dehydrated to reduce the water content. Also, from the viewpoint of productivity, it is preferably a nonpolar solvent having a boiling point of 100° C. or higher and a melting point of 0° C. or lower under normal pressure, and more preferably a solvent under normal pressure. A non-polar solvent with a boiling point above 150°C and a melting point below -20°C.

[固體電解質層] [Solid Electrolyte Layer]

本實施方式之固體電解質層含有離子傳導性之固體電解質，視需要含有全固體電池黏著劑。作為離子傳導性之固體電解質，只要可用於全固體電池，則無特別限制，可例舉硫化物系固體電解質或氧化物系固體電解質等。 The solid electrolyte layer of the present embodiment contains an ion-conductive solid electrolyte and, if necessary, an all-solid battery adhesive. The ion-conductive solid electrolyte is not particularly limited as long as it can be used in an all-solid battery, and examples thereof include sulfide-based solid electrolytes and oxide-based solid electrolytes.

關於硫化物系固體電解質，作為硫化物系非晶質固體電解質，可例舉Li2S-SiS2、LiI-Li2S-SiS2、LiI-Li2S-P2S5、LiI-Li2SP2O5、LiI-Li3PO4-P2S5、Li2S-P2S5等，作為硫化物系玻璃陶瓷固體電解質，可例舉含有Li2S及P2S5者，作為Thio-LISICON系固體電解質，可例舉Li3.25Ge0.25P0.75S4、Li10GeP2S12等。 Regarding the sulfide-based solid electrolyte, examples of the sulfide-based amorphous solid electrolyte include Li 2 S-SiS 2 , LiI-Li 2 S-SiS 2 , LiI-Li 2 SP 2 S 5 , LiI-Li 2 SP 2 O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 2 SP 2 S 5 , etc., as the sulfide-based glass ceramic solid electrolyte, one containing Li 2 S and P 2 S 5 is exemplified, as Thio- The LISICON-based solid electrolyte may, for example, be Li 3.25 Ge 0.25 P 0.75 S 4 , Li 10 GeP 2 S 12 or the like.

關於氧化物系固體電解質，作為氧化物系結晶質固體電解質，可例舉：γ-LiPO4型氧化物、逆螢石型氧化物、NASICON型氧化物之Li1.3Al0.3Ti0.7(PO4)3、鈣鈦礦型之Li0.5La0.5TiO3、石榴石型之Li7La3Zr2O12等。又，作為氧化物系非晶質固體電解質，可例舉：LiPON、Li2O-B2O3-P2O5、Li2O-SiO2等。該等可使用1種或併用2種以上。 Regarding the oxide-based solid electrolyte, examples of the oxide-based crystalline solid electrolyte include: Li 1.3 Al 0.3 Ti 0.7 (PO 4 ) of γ-LiPO 4 type oxide, inverse fluorite type oxide, and NASICON type oxide 3. Li 0.5 La 0.5 TiO 3 of perovskite type, Li 7 La 3 Zr 2 O 12 of garnet type, etc. Moreover, examples of the oxide-based amorphous solid electrolyte include LiPON, Li 2 OB 2 O 3 -P 2 O 5 , Li 2 O-SiO 2 , and the like. These can be used 1 type or in combination of 2 or more types.

其中，就性能與製造之平衡之觀點而言，固體電解質較佳為使用硫化物系固體電解質。 Among them, it is preferable to use a sulfide-based solid electrolyte as the solid electrolyte from the viewpoint of the balance between performance and production.

固體電解質之形狀並無特別限制，為粒子形狀或薄膜形狀等，於粒子之情形時，平均粒徑較佳為100μm以下，更佳為80μm以下，進而較佳為40μm以下。隨著粒子變細，填充率提高，獲得良好之離子傳導性。又，就固體電解質層之物理強度及防止短路之觀點而言，粒徑較佳為0.1μm以上。 The shape of the solid electrolyte is not particularly limited, and it can be particle shape 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 more preferably 40 μm or less. As the particles become finer, the filling rate increases and good ion conductivity is obtained. Also, from the standpoint of physical strength of the solid electrolyte layer and prevention of short circuits, the particle size is preferably 0.1 μm or more.

固體電解質容易與水分反應而發生分解，因此固體電解質層所含之水分量較佳為200ppm以下，更佳為100ppm以下，進而較佳為50ppm以下，進而更佳為10ppm以下，尤佳為1ppm以下。水分可利用常壓或減壓之乾燥機進行乾燥去除，亦可保管於除濕環境下而去除。 The solid electrolyte is easily decomposed by reacting with moisture, so the moisture contained in the solid electrolyte layer is preferably 200ppm or less, more preferably 100ppm or less, further preferably 50ppm or less, further preferably 10ppm or less, especially preferably 1ppm or less . Moisture can be removed by drying with a normal pressure or reduced pressure dryer, or stored in a dehumidified environment.

形成固體電解質層之方法並無特別限制，例如可藉由對包含固體電解質或視需要而定之全固體電池黏著劑等其他成分之混合物進行加壓成型而獲得。或者，將含有包含固體電解質或視需要而定之全固體電池黏著劑等其他成分之混合物之漿料塗佈於基材後加以乾燥，進而視需要進行加壓而調整厚度後，從基材剝離，藉此獲得固體電解質層。 The method of forming the solid electrolyte layer is not particularly limited, for example, it can be obtained by press-molding a mixture containing a solid electrolyte or an all-solid battery adhesive as needed. Alternatively, the slurry containing a mixture of other components such as a solid electrolyte or an all-solid battery adhesive as required is coated on the substrate, dried, and then pressurized as necessary to adjust the thickness, and then peeled off from the substrate. Thereby a solid electrolyte layer is obtained.

[電池之製作] [Making of batteries]

本實施方式之全固體電池係使用上述正極、負極、及固體電解質層，藉由公知方法而製作。例如，藉由如下態樣構成電極積層體，即：製成介置有正極、負極及固體電解質層之積層體之態樣；交替地積層有該積層體之於複數個正極與負極之間介置有電子傳導體的構成為多層結構之積層體之態樣等。繼而，將該電極積層體收容於電池殼(外裝)內並進行封印，藉此 可製作本實施方式之全固體電池。 The all-solid-state battery of this embodiment is produced by a known method using the above-mentioned positive electrode, negative electrode, and solid electrolyte layer. For example, an electrode laminate is formed in such a manner that a positive electrode, a negative electrode, and a solid electrolyte layer are interposed therebetween; Embodiments of laminates having a multi-layered structure provided with electron conductors, etc. Next, the electrode laminate is housed in a battery case (exterior) and sealed to thereby The all-solid battery of this embodiment can be produced.

於電池製作時，較佳為對正極及負極之對向面加壓0.1~4000kgf/cm2之壓力，進而較佳為以0.1~100kgf/cm2之壓力加壓，最佳為以0.5~15kgf/cm2之壓力加壓。藉由將壓力設為0.1kgf/cm2以上，電極活性物質與固體電解質之接觸狀態變得良好，電池特性提高。藉由將壓力設為4000kgf/cm2以下，可防止電池內部損傷所導致之短路。電池亦可維持電池製作時之加壓狀態而作動，但只要充放電特性無問題，則亦可於無加壓之狀態下作動。 When making batteries, it is preferable to apply a pressure of 0.1~4000kgf/cm 2 to the opposing surfaces of the positive electrode and the negative electrode, further preferably 0.1~100kgf/cm 2 , and most preferably 0.5~15kgf /cm 2 pressure. By setting the pressure at 0.1 kgf/cm 2 or more, the contact state between the electrode active material and the solid electrolyte becomes favorable, and battery characteristics are improved. By setting the pressure below 4000kgf/cm 2 , it is possible to prevent short circuit caused by damage inside the battery. The battery can also be operated while maintaining the pressurized state when the battery is manufactured, but as long as there is no problem with the charge and discharge characteristics, it can also be operated without pressurization.

本實施方式之全固體電池之形狀並無特別限制，例如適宜採用圓筒形、橢圓形、角形柱型、按鈕形、硬幣形、扁平形、層壓形等。又，本實施方式之固體電解質不僅可應用於如上所述之全固體電池，亦可應用於其他電池。 The shape of the all-solid-state battery in this embodiment is not particularly limited, for example, cylindrical, oval, angular column, button, coin, flat, laminated, etc. are suitable. In addition, the solid electrolyte of this embodiment can be applied not only to the above-mentioned all-solid battery, but also to other batteries.

以上，對本發明之實施方式進行了說明，但本發明並不限制於上述實施方式。本發明能夠於不脫離其主旨之範圍內進行各種變化。 As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment. Various changes can be made in this invention in the range which does not deviate from the summary.

[實施例] [Example]

以下，例舉具體之實施例及比較例，詳細地說明本實施方式，但本實施方式並不受以下實施例及比較例任何限定。 Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples and comparative examples.

以下表示實施例及比較例中之共軛二烯系聚合物之結構、共軛二烯系 聚合物黏著劑之物性之測定方法及評價方法。 The following shows the structures of the conjugated diene polymers in Examples and Comparative Examples, and the conjugated diene polymers Determination and evaluation methods of physical properties of polymer adhesives.

[共軛二烯系聚合物之結構及共軛二烯系聚合物黏著劑之物性之測定及評價] [Structure of Conjugated Diene Polymer and Measurement and Evaluation of Physical Properties of Conjugated Diene Polymer Adhesive] (1)共軛二烯系聚合物中之各聚合物嵌段之含量 (1) The content of each polymer block in the conjugated diene polymer

使用下述式，計算氫化前之共軛二烯系聚合物中之各聚合物嵌段之含量，算出共軛二烯系聚合物中之各聚合物嵌段之含量。 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.

氫化前之共軛二烯系聚合物中之各嵌段之含量=[(於各步驟中進料之單體合計量)/(總單體量)]×100(質量%) Content of each block in the conjugated diene polymer before hydrogenation=[(total amount of monomers fed in each step)/(total monomer amount)]×100(mass%)

其中，以如下方式，於共軛二烯系聚合物之各聚合過程之每一步驟中，確認丁二烯單體及苯乙烯單體之聚合率為100%。 Here, in each step of each polymerization process of the conjugated diene polymer, it was confirmed that the polymerization rate of the butadiene monomer and the styrene monomer was 100% as follows.

將聚合過程之每一步驟中取樣之聚合物溶液約20mL注入至封入有用作內部標準之正丙基苯0.50mL及約20mL之甲苯之100mL瓶中，製作樣品。使用安裝了擔載有阿匹鬆密封臘之填充管柱的氣相層析儀(島津製作所製：GC-14B(製品名))測定各樣品，由預先獲得之丁二烯單體及苯乙烯單體之校準曲線求出聚合物溶液中之殘留單體量，確認不存在殘留單體。 About 20 mL of the polymer solution sampled in each step of the polymerization process was poured into a 100 mL bottle sealed with 0.50 mL of n-propylbenzene used as an internal standard and about 20 mL of toluene to prepare a sample. Each sample was measured using a gas chromatograph (manufactured by Shimadzu Corporation: GC-14B (product name)) equipped with a packed column loaded with apixon wax, and the butadiene monomer and styrene obtained in advance Calibration curve of monomer Calculate the amount of residual monomer in the polymer solution, and confirm that there is no residual monomer.

再者，作為氣相層析測定中之溫度條件，丁二烯之聚合率設為固定之90℃，苯乙烯之聚合率設為從90℃(保持10分鐘)升溫(10℃/分鐘)至150℃之條件。 In addition, as the temperature conditions in the gas chromatography measurement, the polymerization rate of butadiene was fixed at 90°C, and the polymerization rate of styrene was raised from 90°C (holding for 10 minutes) (10°C/min) to 150°C condition.

(2)共軛二烯系聚合物之氫化前之乙烯基鍵量 (2) Vinyl bond amount of conjugated diene polymer before hydrogenation

共軛二烯系聚合物之氫化前之乙烯基鍵量係使用共軛二烯系聚合物之聚合過程之每一步驟中取樣之聚合物溶液，藉由質子核磁共振(1H-NMR)法進行測定。 The amount of vinyl bonds before hydrogenation of the conjugated diene polymer is determined by the proton nuclear magnetic resonance ( 1 H-NMR) method using the polymer solution sampled in each step of the polymerization process of the conjugated diene polymer To measure.

使用ECS400(JEOL製造)作為測定機器，使用氘代氯仿作為溶劑，樣品濃度設為50mg/mL，於以下條件下進行測定。乙烯基鍵量係於求出共軛二烯單體單元中之歸屬於1,4-鍵及1,2-鍵之訊號之累計值後，根據1,4-鍵與1,2-鍵之訊號比率而算出。 ECS400 (manufactured by JEOL) was used as a measuring device, deuterated chloroform was used as a solvent, and the sample concentration was set to 50 mg/mL, and the measurement was performed under the following conditions. The amount of vinyl bonds is based on the cumulative value of the signals attributable to 1,4-bonds and 1,2-bonds in the conjugated diene monomer unit, based on the relationship between 1,4-bonds and 1,2-bonds Calculated from the signal ratio.

(測定條件) (measurement conditions)

觀測頻率：400MHz Observation frequency: 400MHz

化學位移基準：四甲基矽烷 Chemical shift basis: Tetramethylsilane

脈衝延遲：2.904秒 Pulse delay: 2.904 seconds

掃描次數：64次 Number of scans: 64 times

脈衝寬度：45° Pulse width: 45°

測定溫度：26℃ Measuring temperature: 26°C

(3)共軛二烯系聚合物之氫化率 (3) Hydrogenation rate of conjugated diene polymer

共軛二烯系聚合物之基於共軛二烯單體單元之不飽和鍵之氫化率係使用氫化前後之共軛二烯系聚合物，藉由質子核磁共振(1H-NMR)進行測定。測定條件及測定資料之處理方法與上述(2)相同。 The hydrogenation rate of the conjugated diene polymer based on the unsaturated bond of the conjugated diene monomer unit was measured by proton nuclear magnetic resonance ( 1 H-NMR) using the conjugated diene polymer before and after hydrogenation. The measurement conditions and the processing method of the measurement data are the same as those in (2) above.

再者，氫化率係求出源自4.5~5.5ppm之雙鍵之訊號及源自經氫化 之共軛二烯之訊號之累計值，根據其訊號比率而算出。 Furthermore, the hydrogenation rate is calculated from the signal of the double bond at 4.5~5.5ppm and the signal from the hydrogenated The cumulative value of the signal of the conjugated diene was calculated according to the signal ratio.

(4)共軛二烯系聚合物之丁烯量及丙烯量之合計 (4) The total amount of butene and propylene in the conjugated diene polymer

共軛二烯系聚合物中，相對於共軛二烯單體單元之合計100mol%的丁烯量及丙烯量之合計係使用氫化後之共軛二烯系聚合物，藉由質子核磁共振(1H-NMR)進行測定。測定條件及測定資料之處理方法與上述(2)及(3)相同。 In the conjugated diene polymer, the total amount of butene and propylene relative to the total of 100 mol% of the conjugated diene monomer units is obtained by proton nuclear magnetic resonance ( 1 H-NMR) for measurement. The measurement conditions and the processing method of the measurement data are the same as the above (2) and (3).

再者，丁烯量係求出源自氫化後之共軛二烯系聚合物中之所有共軛二烯單體單元的訊號、及源自光譜之0~2.0ppm之丁烯部(經氫化之1,2-鍵)之訊號之累計值，根據其訊號比率而算出。 Furthermore, the amount of butene is derived from the signal of all conjugated diene monomer units in the conjugated diene polymer after hydrogenation, and the butene portion of 0-2.0 ppm from the spectrum (hydrogenated The cumulative value of the signal of 1,2-key) is calculated according to the signal ratio.

(5)共軛二烯系聚合物之苯乙烯含量 (5) Styrene content of conjugated diene polymer

使用氫化前之共聚物，使用紫外分光光度計(島津製作所製造，UV-2450)，根據262nm之吸收強度而算出。於氫化前後，所有乙烯基芳香族化合物單體單元之含量並未大幅地變化，因此將關於氫化前之共聚物所獲得之所有乙烯基芳香族化合物單體單元(苯乙烯單體單元)之含量視為氫化共聚物之所有乙烯基芳香族化合物單體單元之含量(總苯乙烯含量)。 Using the copolymer before hydrogenation, it calculated from the absorption intensity at 262 nm using the ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450). Before and after hydrogenation, the content of all vinyl aromatic compound monomer units does not change significantly, so the content of all vinyl aromatic compound monomer units (styrene monomer units) obtained with respect to the copolymer before hydrogenation The content of all vinyl aromatic monomer units considered as hydrogenated copolymers (total styrene content).

(6)共軛二烯系聚合物之以苯乙烯單元作為主體之聚合物嵌段之含量(Os值) (6) The content of the polymer block mainly composed of styrene units in the conjugated diene polymer (Os value)

使用氫化前之未改性之共軛二烯系聚合物，藉由I.M.KOLTHOFF,et al.,J.Polym.Soi.1,429(1946)所記載之四氧化鋨分解法測定共軛二烯系 聚合物中之以苯乙烯單元作為主體之聚合物嵌段之含量(以下，亦稱為「Os值」)。 Using the unmodified conjugated diene polymer before hydrogenation, the conjugated diene system was determined by the osmium tetroxide decomposition method described by I.M.KOLTHOFF, et al., J.Polym.Soi.1, 429 (1946) The content of the polymer block mainly composed of styrene units in the polymer (hereinafter also referred to as "Os value").

氫化前之未改性之共軛二烯系聚合物之分解係使用鋨酸之0.1g/125mL三級丁醇溶液。 The decomposition of the unmodified conjugated diene polymer before hydrogenation uses 0.1g/125mL tertiary butanol solution of osmic acid.

(7)共軛二烯系聚合物及共軛二烯系聚合物之重量平均分子量及分子量分佈 (7) Weight average molecular weight and molecular weight distribution of conjugated diene polymers and conjugated diene polymers

對於共軛二烯系聚合物及共軛二烯系聚合物之重量平均分子量及分子量分佈，使用GPC[GPC裝置：HLC8220(Tosoh製，製品名)、管柱：4.6mm×30cm之TSKgelSUPER-HZM-N(Sigma-Aldrich公司製，製品名)]進行測定。溶劑係使用四氫呋喃。 For the weight average molecular weight and molecular weight distribution of the conjugated diene polymer and the conjugated diene polymer, use GPC [GPC device: HLC8220 (manufactured by Tosoh, product name), column: TSKgelSUPER-HZM of 4.6mm×30cm -N (manufactured by Sigma-Aldrich, product name)] was measured. As the solvent, tetrahydrofuran was used.

重量平均分子量係根據層析圖之峰，基於使用市售之標準聚苯乙烯獲得之校準曲線而求出。再者，層析圖中存在複數個峰之情形時之分子量係根據各峰之分子量與各峰之組成比(藉由層析圖各自之峰之面積比而求出)而求出重量平均分子量。共軛二烯系聚合物存在因改性基與管柱之相互作用而吸附於管柱之情形，於此情形時，測定非吸附部分之分子量或改性前之共聚物。 The weight-average molecular weight was determined from the peaks in the chromatogram based on a calibration curve obtained using commercially available standard polystyrene. In addition, the molecular weight when there are several peaks in a chromatogram is obtained from the weight average molecular weight from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in a chromatogram). The conjugated diene polymer may be adsorbed on the column due to the interaction between the modified group and the column. In this case, the molecular weight of the non-adsorbed part or the copolymer before modification is measured.

分子量分佈係由所獲得之重量平均分子量(Mw)與數量平均分子量(Mn)之比(Mw/Mn)算出。共軛二烯系聚合物存在因改性基與管柱之相互作用而吸附於管柱之情形，於此情形時測定非吸附部分之分子量。 The molecular weight distribution was calculated from the ratio (Mw/Mn) of the obtained weight average molecular weight (Mw) to the number average molecular weight (Mn). The conjugated diene polymer may be adsorbed on the column due to the interaction between the modified group and the column, and the molecular weight of the non-adsorbed part is measured in this case.

(8)共軛二烯系聚合物之酸酐加成量 (8) Acid anhydride addition amount of conjugated diene polymer

將藉由酸酐改性後之共軛二烯系聚合物溶解於甲苯中，利用係數為1±0.05之鈉甲氧化物之甲醇溶液進行滴定，藉此算出共軛二烯系聚合物中之酸酐加成量。 Dissolve the conjugated diene polymer modified by acid anhydride in toluene, and titrate it with a methanol solution of sodium methoxide with a coefficient of 1±0.05, thereby calculating the acid anhydride in the conjugated diene polymer Addition amount.

(9)胺末端共軛二烯系聚合物之改性率 (9) Modification rate of amine-terminated conjugated diene polymer

應用改性後之成分會吸附於以二氧化矽凝膠作為填充材之GPC管柱之特性，關於包含共軛二烯系聚合物及低分子量內部標準聚苯乙烯之試樣溶液，比較上述(6)中測定之層析圖中之相對於標準聚苯乙烯之共軛二烯系聚合物之比率、與藉由二氧化矽系管柱GPC[裝置：LC-10(島津製作所製造)，管柱：Zorbax(杜邦公司製造)]所測定之層析圖中之相對於標準聚苯乙烯之共軛二烯系聚合物之比率，根據其等之差量，測定對二氧化矽系管柱之吸附量，將該比率設為改性率。藉由下述式而算出。 The modified components will be adsorbed on the characteristics of the GPC column with silica gel as the packing material. Regarding the sample solution containing the conjugated diene polymer and the low molecular weight internal standard polystyrene, compare the above ( The ratio of the conjugated diene-based polymer to the standard polystyrene in the chromatogram measured in 6) and GPC with a silica-based column [device: LC-10 (manufactured by Shimadzu Corporation), tube Column: Zorbax (manufactured by DuPont)] The ratio of the conjugated diene polymer relative to the standard polystyrene in the chromatogram measured, according to the difference between them, was determined for the silica column. Adsorption amount, and this ratio was defined as the modification rate. Calculated by the following formula.

Figure 110148596-A0305-02-0068-1
Figure 110148596-A0305-02-0068-1

a：藉由聚苯乙烯系凝膠(PLgel)測定之全部聚合物之面積(%) a: The area (%) of the total polymer measured by polystyrene-based gel (PLgel)

b：藉由聚苯乙烯系凝膠(PLgel)測定之低分子量內部標準PS之面積(%) b: Area (%) of low molecular weight internal standard PS measured by polystyrene-based gel (PLgel)

c：藉由二氧化矽系管柱(Zorbax)測定之全部聚合物之面積(%) c: The area of the total polymer measured by a silica column (Zorbax) (%)

d：藉由二氧化矽系管柱(Zorbax)測定之低分子量內部標準PS之面積 (%) d: Area of low molecular weight internal standard PS measured by silica-based column (Zorbax) (%)

(10)甲苯不溶分 (10) Toluene insoluble matter

將共軛二烯系聚合物1g投入至利用200目金屬絲網製作之試驗管形狀之容器，將該容器浸漬於甲苯100mL中，利用振盪機振盪24小時以上，充分溶解後，取出容器，從容器外側以甲苯洗淨容器，利用真空乾燥機以60℃乾燥12小時。使用所獲得之容器之重量W1與試驗前之容器之重量W0、共軛二烯系聚合物之稱量值P，根據下述式，算出甲苯不溶分。 Put 1 g of conjugated diene polymer into a test tube-shaped container made of 200-mesh wire mesh, immerse the container in 100 mL of toluene, and shake it with a shaker for more than 24 hours. After fully dissolving, take out the container and remove it from the The outside of the container was washed with toluene, and dried at 60° C. for 12 hours with a vacuum dryer. Using the weight W1 of the obtained container, the weight W0 of the container before the test, and the weighing value P of the conjugated diene polymer, the toluene insoluble content was calculated according to the following formula.

不溶分率(%)=(W1-W0)/P×100 Insoluble fraction (%)=(W1-W0)/P×100

(11)鬆裝比重及壓縮度 (11) Loose specific gravity and compression

藉由Powder Tester PT-X型(Hosokawa Micron股份有限公司製造)進行評價。於100cm3之鬆密度測定容器中，以超出上表面之量投入共軛二烯系聚合物，去除超出之部分，根據此時之重量及筒之容量求出鬆裝比重。又，反覆進行180次以超出上表面之量投入共軛二烯系聚合物及振實，求出振實比重。根據以下式評價壓縮度。 Evaluation was performed by a Powder Tester PT-X type (manufactured by Hosokawa Micron Co., Ltd.). Into a 100cm3 bulk density measuring container, put the conjugated diene polymer in an amount exceeding the upper surface, remove the excess part, and calculate the bulk specific gravity based on the weight at this time and the capacity of the cylinder. Further, the injection and tapping of the conjugated diene polymer in an amount exceeding the upper surface were repeated 180 times to obtain the tapped specific gravity. The degree of compression was evaluated according to the following formula.

壓縮度=(振實比重-鬆裝比重)/振實比重×100 Compression degree = (tapped specific gravity - loose specific gravity) / tapped specific gravity × 100

(12)使用攪拌機時之溶劑溶解性 (12) Solvent solubility when using a mixer

將共軛二烯系聚合物10g及甲苯100mL投入至內容積200mL之玻璃製螺旋口瓶中，對利用磁力攪拌器攪拌5分鐘後之溶解性進行評價。 10 g of the conjugated diene-based polymer and 100 mL of toluene were put into a glass screw bottle with an internal volume of 200 mL, and the solubility after stirring for 5 minutes with a magnetic stirrer was evaluated.

(評價基準) (evaluation criteria)

○：無溶解殘留 ○: No dissolved residue

△：0%~未達20%之溶解殘留 △: 0%~less than 20% dissolved residue

×：20%以上之溶解殘留 ×: more than 20% dissolved residue

(13)熱穩定性 (13) thermal stability

根據將聚合物以100℃乾燥48小時之加熱前後之GPC圖之微分分子量分佈中峰高度之減少量，對熱穩定性進行評價。 Thermal stability was evaluated based on the decrease in peak height in the differential molecular weight distribution of the GPC chart before and after drying the polymer at 100° C. for 48 hours and heating.

(評價基準) (evaluation criteria)

○：未達0.1% ○: Less than 0.1%

△：0.1%以上~未達0.3% △: More than 0.1% to less than 0.3%

×：0.3%以上 ×: 0.3% or more

(14)進料穩定性 (14) Feed stability

假定材料供給，對以單螺桿進料機排出全固體電池黏著劑時相對於設定值之誤差範圍進行評價。從進料機，以設定值5kg/h用5分鐘排出全固體電池黏著劑，將每3秒記錄之與設定值之誤差之絕對值之總和以記錄數進行平均，評價相對於設定值之誤差之比率。 Assuming material supply, evaluate the error range relative to the set value when discharging the all-solid battery adhesive with a single-screw feeder. From the feeder, discharge the all-solid battery adhesive at a set value of 5kg/h for 5 minutes, and average the sum of the absolute values of the errors recorded every 3 seconds from the set value with the number of records to evaluate the error relative to the set value ratio.

(評價基準) (evaluation criteria)

○：未達0.5% ○: Less than 0.5%

△：0.5%以上~未達1.0% △: More than 0.5% to less than 1.0%

×：1.0%以上 ×: 1.0% or more

(15)共軛二烯系聚合物與鋁片之界面剝離強度(接著性) (15) Interfacial peel strength (adhesion) between conjugated diene polymer and aluminum sheet

共軛二烯系聚合物與鋁片之界面剝離強度係使用在鋁片熱熔接共軛 二烯系聚合物所獲得之多層體，藉由180度剝離試驗進行測定。具體而言，將1mm厚之鋁片及2mm厚之共軛二烯系聚合物片於2mm厚之模具內重疊並固定，於200℃下在不施加壓力之情況下預熱5分鐘，其後於200℃下以10MPa加熱加壓2分鐘，其後於20℃下以10MPa冷卻加壓3分鐘，藉此，製作包含1mm厚之鋁片及1mm厚之共軛二烯系聚合物之多層體。於所獲得之多層體之共軛二烯系聚合物側之面切入10mm寬之切口，將包含共軛二烯系聚合物之層之端部剝離數cm。將包含共軛二烯系聚合物之層之剝離部分、及鋁片分別各自固定於拉伸試驗機[MinebeaMitsumi股份有限公司製造，TGE-500N(製品名)]之夾頭。將包含共軛二烯系聚合物之層之剝離部分及鋁片沿180℃方向以300mm/min進行拉伸，藉此將2個層剝離。將剝離時施加之拉伸力設為共軛二烯系聚合物與鋁片之多層體之界面剝離強度(N/cm)，根據下述評價基準進行評價。 The interface peel strength between conjugated diene polymer and aluminum sheet is used in the thermal welding of aluminum sheet The multilayer body obtained from the diene polymer was measured by a 180-degree peel test. Specifically, a 1mm-thick aluminum sheet and a 2mm-thick conjugated diene polymer sheet were stacked and fixed in a 2mm-thick mold, preheated at 200°C for 5 minutes without applying pressure, and then Heat and press at 10MPa at 200°C for 2 minutes, then cool and press at 10MPa at 20°C for 3 minutes to produce a multilayer body consisting of a 1mm-thick aluminum sheet and a 1mm-thick conjugated diene polymer . A 10 mm wide incision was made on the conjugated diene polymer side surface of the obtained multilayer body, and the end of the layer containing the conjugated diene polymer was peeled off for several cm. The peeled part of the layer containing the conjugated diene-based polymer and the aluminum sheet were respectively fixed to chucks of a tensile tester [manufactured by Minebea Mitsumi Co., Ltd., TGE-500N (product name)]. The peeled portion of the layer containing the conjugated diene polymer and the aluminum sheet were stretched at 300 mm/min in the direction of 180° C., thereby peeling off the two layers. The tensile force applied at the time of peeling was defined 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 evaluation criteria.

(評價基準) (evaluation criteria)

○：10N/cm以上 ○: 10N/cm or more

△：3N/cm以上且未達10N/cm △: More than 3N/cm and less than 10N/cm

×：未達3N/cm ×: Less than 3N/cm

(16)單位改性基量之接著力 (16) Adhesion per unit amount of modified base

由下述式算出。 Calculated from the following formula.

聚合物1g中所含之單位改性基量之接著力(N‧cm-1/g)=界面剝離強度(N‧cm-1)/(1g×改性基之質量%/100) Adhesion force per unit of modified group contained in 1g of polymer (N‧cm -1 /g)=interfacial peel strength (N‧cm -1 )/(1g×mass% of modified group/100)

(17)共軛二烯系聚合物黏著劑之黏結性 (17) Adhesiveness of conjugated diene polymer adhesive

利用攪拌器將共軛二烯系聚合物0.15g及乙炔黑0.35g與甲苯4.5g以2000rpm攪拌2分鐘，進而追加適量甲苯以進行黏度調整，獲得漿料。利用敷料器將該漿料塗佈於鋁箔上，於加熱板上靜置，於50℃下乾燥5分鐘，進而於70℃下乾燥10小時，獲得電極層與集電體成為一體之電極。 0.15 g of the 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 an appropriate amount of toluene was added to adjust the viscosity to obtain a slurry. The slurry was coated on an aluminum foil with an applicator, left to stand on a heating plate, dried at 50° C. for 5 minutes, and then dried at 70° C. for 10 hours to obtain an electrode in which the electrode layer and the current collector were integrated.

將電極捲繞於直徑10mm之SUS棒，目視觀察彎曲之電極層之情況，評價黏著劑之黏結性。 Wrap the electrode around a SUS rod with a diameter of 10 mm, visually observe the state of the bent electrode layer, and evaluate the adhesiveness of the adhesive.

(評價基準) (evaluation criteria)

○：電極層無裂紋，顯示出較強之密接性 ○: There is no crack in the electrode layer, showing strong adhesion

△：電極層之一部分產生裂紋，顯示出中等程度之密接性 △: Part of the electrode layer has cracks, showing a moderate degree of adhesion

×：電極層整體產生裂紋，顯示出較弱之密接性 ×: The entire electrode layer has cracks, showing weak adhesion

(18)塗膜之平滑性 (18) Smoothness of coating film

藉由目視確認將黏結性評價用漿料塗佈於鋁箔上時之表面凹凸並進行評價。 The surface unevenness|corrugation when the slurry for adhesiveness evaluation was apply|coated to the aluminum foil was visually confirmed and evaluated.

(評價基準) (evaluation criteria)

○：無凹凸 ○: No unevenness

△：一部分存在凹凸 △: Concave-convex partly exists

×：整體存在凹凸 ×: There is unevenness as a whole

(19)共軛二烯系聚合物黏著劑溶液之揮發性 (19) Volatility of conjugated diene polymer adhesive solution

將共軛二烯系聚合物0.3g及甲苯10mL投入至內容積30mL之玻璃製螺旋口瓶，利用振盪機進行振盪，藉此獲得均勻之溶液。於外部大氣24 ℃之條件下，將卸除了蓋之裝有溶液之小瓶靜置於通風室內，測定經過10小時後之溶劑之揮發重量，評價黏著劑溶液之儲存性。 0.3 g of the conjugated diene-based polymer and 10 mL of toluene were put into a glass screw bottle with an internal volume of 30 mL, and shaken by a shaker to obtain a uniform solution. in the external atmosphere 24 Under the condition of ℃, the vial with the solution removed was placed in a ventilated room, and the volatile weight of the solvent after 10 hours was measured to evaluate the storage property of the adhesive solution.

(評價基準) (evaluation criteria)

◎：未達3g，製成黏著劑溶液或漿料儲存時，組成變化較小 ◎: Less than 3g, when it is made into an adhesive solution or slurry for storage, the composition changes little

○：3g以上且未達5g，製成黏著劑溶液或漿料儲存時，組成變化為中等程度 ○: More than 3g and less than 5g, when it is stored as an adhesive solution or slurry, the composition changes to a moderate degree

△：5g以上且未達7g，製成黏著劑溶液或漿料儲存時，組成變化較大 △: More than 5g and less than 7g, when it is made into adhesive solution or slurry for storage, the composition changes greatly

×：7g以上，製成黏著劑溶液或漿料儲存時，組成變化較大 ×: more than 7g, when it is made into adhesive solution or slurry for storage, the composition changes greatly

(20)導電助劑分散性 (20) Dispersion of conductive additives

將共軛二烯系聚合物0.2g、乙炔黑0.4g及甲苯19.4g投入至內容積30mL之玻璃製螺旋口瓶，利用振盪機振盪1小時後，立即於靜置狀態下目視觀察，評價乙炔黑之分散狀態。 Put 0.2 g of conjugated diene polymer, 0.4 g of acetylene black, and 19.4 g of toluene into a glass screw-necked bottle with an inner volume of 30 mL, shake it with a shaker for 1 hour, and immediately observe visually in a static state to evaluate acetylene The scattered state of black.

(評價基準) (evaluation criteria)

○：分散有乙炔黑 ○: Acetylene black is dispersed

△：確認到乙炔黑之凝聚，佔據較液面更上方之小瓶壁面之未達20% △: Condensation of acetylene black was confirmed, occupying less than 20% of the vial wall above the liquid level

×：確認到乙炔黑之凝聚，佔據較液面更上方之小瓶壁面之20%以上 ×: Condensation of acetylene black was confirmed, occupying more than 20% of the vial wall above the liquid level

(21)共軛二烯系聚合物黏著劑之儲存穩定性 (21) Storage stability of conjugated diene polymer adhesive

將共軛二烯系聚合物於23℃/濕度50%之環境下保管1天，評價保管前後之IR Store the conjugated diene polymer at 23°C/humidity 50% for 1 day, and evaluate the IR before and after storage

(評價基準) (evaluation criteria)

有：源於官能基之IR有變化。 Yes: IR changes due to functional groups.

無：源於官能基之IR無變化。 None: No change in IR due to functional groups.

(22)包含共軛二烯系聚合物黏著劑之電極層之電化學穩定性 (22) Electrochemical stability of electrode layer containing conjugated diene polymer binder

利用攪拌器將共軛二烯系聚合物0.15g及乙炔黑0.35g與甲苯4.5g以2000rpm攪拌2分鐘，進而追加適量甲苯以進行黏度調整，以2000rpm攪拌2分鐘，獲得漿料。利用敷料器將該漿料塗佈於鉑箔上，於加熱板上靜置，於50℃下乾燥5分鐘，進而於70℃下乾燥10小時，獲得電極層與集電體成為一體之氧化側評價用電極。 0.15 g of the 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 an appropriate amount of toluene was added to adjust the viscosity, and stirred at 2000 rpm for 2 minutes to obtain a slurry. Use an applicator to coat the slurry on a platinum foil, let it stand on a heating plate, and dry it at 50°C for 5 minutes, and then dry it at 70°C for 10 hours to obtain an oxidized side where the electrode layer and the current collector are integrated. Electrodes for evaluation.

又，利用攪拌器將共軛二烯系聚合物0.5g及甲苯4.5g以2000rpm攪拌2分鐘，獲得漿料。利用敷料器將該漿料塗佈於鉑箔上，於加熱板上靜置，於50℃下乾燥5分鐘，進而於70℃下乾燥10小時，獲得電極層與集電體成為一體之還原側評價用電極。 Moreover, 0.5 g of the conjugated diene polymer and 4.5 g of toluene were stirred at 2000 rpm for 2 minutes with a stirrer to obtain a slurry. Use an applicator to coat the slurry on platinum foil, let it stand on a heating plate, and dry it at 50°C for 5 minutes, and then dry it at 70°C for 10 hours to obtain the reduction side where the electrode layer and the current collector are integrated. Electrodes for evaluation.

於露點被控制為-60℃以下之氬氣氛圍下之手套箱內，於包含共軛二烯系聚合物黏著劑之電極層與集電體成為一體之氧化側評價用電極或還原側評價用電極(各14mm×20mm見方)連接用以擷取電流之鉑製引線片，將所得者作為工作電極，於鋰金屬片連接用以擷取電流之鎳製引線片，將所得者作為相對電極，於鋰金屬片連接用以擷取電流之鎳製引線片，將所得者作為參考電極，將微孔膜隔片與玻璃不織布之積層片作為各電極間之隔片，將該等收容於鋁層壓片外裝體內，以1M LiPF6/(碳酸乙二酯/碳酸甲乙酯(=30wt%/70wt%))作為電解液注入至外裝體內，其後對外裝體進 行密封，藉此製作測定用層壓單元。使用該單元於下述條件下進行測定。 In a glove box under an argon atmosphere whose dew point is controlled below -60°C, in an electrode for oxidation side evaluation or reduction side evaluation electrode that integrates an electrode layer and a current collector including a conjugated diene polymer binder The electrodes (each 14mm×20mm square) are connected to platinum lead sheets for extracting current, and the resultant is used as the working electrode, and the nickel lead sheet for extracting current is connected to the lithium metal sheet, and the resultant is used as the counter electrode, Connect the nickel lead sheet for extracting current to the lithium metal sheet, use the resultant as a reference electrode, use the laminated sheet of microporous membrane separator and glass non-woven fabric as the separator between each electrode, and house them in the aluminum layer Press the outer body of the tablet, inject 1M LiPF 6 /(ethylene carbonate/ethyl methyl carbonate (=30wt%/70wt%)) as the electrolyte into the outer body, and then seal the outer body to make Lamination unit for measurement. Using this unit, measurement was performed under the following conditions.

(條件) (condition)

測定方法：線性掃描伏安法 Determination method: linear sweep voltammetry

掃描速度：2mV/sec Scan speed: 2mV/sec

電壓範圍：(氧化側)3.0V(初始電壓)-5.4V(最終電壓)vs.Li/Li+/V Voltage range: (oxidation side) 3.0V (initial voltage)-5.4V (final voltage) vs. Li/Li + /V

(還原側)3.0V(初期電壓)-0.0V(最終電壓)vs.Li/Li+/V (Reduction side) 3.0V (initial voltage)-0.0V (final voltage) vs. Li/Li + /V

電極面積：2.8cm2(14mm×20mm) Electrode area: 2.8cm 2 (14mm×20mm)

溫度：25℃ Temperature: 25°C

關於包含共軛二烯系聚合物黏著劑之電極層之電化學穩定性，若氧化側於3.0V(vs.Li/Li+/V)以上之條件下電流值成為0.0005A/mg以上時之電壓為4.6V(vs.Li/Li+/V)以上，則記為合格(○)，若還原側於未達3.0V(vs.Li/Li+/V)之條件下電流值成為-0.00005A/mg以下時之電壓未達0.1V(vs.Li/Li+/V)，則記為合格(○)。 Regarding the electrochemical stability of the electrode layer containing the conjugated diene-based polymer binder, if the current value becomes 0.0005A/mg or more under the condition that the oxidation side is 3.0V ( vs. Li/Li + /V) If the voltage is above 4.6V ( vs. Li/Li + /V), it will be marked as qualified (○), and if the reduction side is less than 3.0V ( vs. Li/Li + /V), the current value becomes -0.00005 When the voltage is below A/mg and the voltage does not reach 0.1V ( vs. Li/Li + /V), it is rated as pass (○).

(23)共軛二烯系聚合物之水分量 (23) Moisture content of conjugated diene polymer

使用卡氏水分計，於樣品重量1.50g、氣化裝置溫度200℃、載氣(氮氣)250mL/min之條件下進行測定，若水分量為200ppm以下，則記為合格(○)。 Use a Karl Fischer moisture meter to measure under the conditions of sample weight 1.50g, gasification device temperature 200°C, and carrier gas (nitrogen) 250mL/min. If the moisture content is below 200ppm, it is marked as qualified (○).

(氫化觸媒之製備) (Preparation of hydrogenation catalyst)

共軛二烯系聚合物之氫化反應中使用之氫化觸媒係藉由下述方法來製備。 The hydrogenation catalyst used in the hydrogenation reaction of the conjugated diene polymer was prepared by the following method.

於經氮氣置換之反應容器中，投入乾燥及純化之環己烷1L，添加雙(η5-環戊二烯基)二氯化鈦100mmol，一面充分攪拌一面添加包含三甲基鋁200mmol之正己烷溶液後，於室溫下反應約3天，獲得氫化觸媒。 Put 1 L of dry and purified cyclohexane into a reaction vessel replaced with nitrogen, add 100 mmol of bis(η5-cyclopentadienyl) titanium dichloride, and add 200 mmol of n-hexane containing trimethylaluminum while fully stirring After solution, react at room temperature for about 3 days to obtain a hydrogenation catalyst.

[共軛二烯系嵌段共聚物之製造] [Manufacture of Conjugated Diene Block Copolymer] [製造例1] [manufacturing example 1] (共軛二烯系嵌段共聚物(a-1)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-1)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中投入1L環己烷，以相對於全部單體100質量份成為0.13質量份之方式添加正丁基鋰，進而相對於正丁基鋰1mol，添加N,N,N',N'-四甲基乙二胺(TMEDA)0.3mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. Put 1 L of cyclohexane into the reactor, add n-butyllithium to 0.13 parts by mass with respect to 100 parts by mass of all monomers, and add N,N,N',N' to 1 mol of n-butyllithium - Tetramethylethylenediamine (TMEDA) 0.3 mol.

其次，將包含苯乙烯16質量份(相對於全部單體100質量份，以下於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)投入至反應器中，於70℃下進行45分鐘聚合。其次，加入包含丁二烯68質量份之環己烷溶液(丁二烯濃度：20質量%)，於70℃下進行1.5小時聚合。最後，投入包含苯乙烯16質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。反應結束後，添加甲醇，作為步驟1，獲得共軛二烯系嵌段共聚物。 Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (relative to 100 parts by mass of all monomers, the same applies to this paragraph below) was put into the reactor, and heated at 70° C. Polymerization was carried out for 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 68 parts by mass of butadiene was added, and polymerization was performed at 70° C. for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene was charged, and polymerization was performed at 70° C. for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene block copolymer as step 1.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為32質量%，聚苯乙烯嵌段含量為32質量%，丁二烯部之乙烯基鍵量為36mol%。 The obtained 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 butadiene portion of 36 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於共軛二烯系嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained conjugated diene block copolymer, the above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm relative to the conjugated diene block copolymer. under hydrogenation reaction.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-1)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為6.9萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-1) had a styrene content of 32% by mass, a butene content of 36mol%, a weight average molecular weight of 69,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例2] [Manufacturing example 2] (共軛二烯系嵌段共聚物(a-2)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-2)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L環己烷，以相對於全部單體100質量份成為0.12質量份之方式添加正丁基鋰，進而相對於正丁基鋰1mol，添加N,N,N',N'-四甲基乙二胺(TMEDA)0.3mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. Add 1 L of cyclohexane to the reactor, add n-butyllithium so that it becomes 0.12 parts by mass with respect to 100 parts by mass of all monomers, and then add N,N,N',N' with respect to 1 mol of n-butyllithium - Tetramethylethylenediamine (TMEDA) 0.3 mol.

其次，將包含苯乙烯9.5質量份(相對於全部單體100質量份，以下， 於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)投入至反應器中，於70℃下進行45分鐘聚合。其次，加入包含丁二烯81質量份之環己烷溶液(丁二烯濃度：20質量%)，於70℃下進行1.5小時聚合。最後，投入包含苯乙烯9.5質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。於反應結束後添加甲醇，作為步驟1，獲得共軛二烯系嵌段共聚物。 Next, 9.5 parts by mass of styrene (with respect to 100 parts by mass of all monomers, the following, A cyclohexane solution (styrene concentration: 20% by mass) in this paragraph) was charged into the reactor, and polymerization was performed 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 polymerization was performed 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 charged, and polymerization was performed at 70° C. for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer as step 1.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為19質量%，聚苯乙烯嵌段含量為19質量%，丁二烯部之乙烯基鍵量為36mol%。 The obtained 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 butadiene portion of 36 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於共軛二烯系嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained conjugated diene block copolymer, the above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm relative to the conjugated diene block copolymer. under hydrogenation reaction.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-2)，苯乙烯含量為19質量%，丁烯量為36mol%，重量平均分子量為8.5萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-2) had a styrene content of 19% by mass, a butene content of 36mol%, a weight average molecular weight of 85,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例3] [Manufacturing example 3] (共軛二烯系嵌段共聚物(a-3)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-3)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中投入1L環己烷，以相對於全部單體100質量份成為0.08質量份之方式添加正丁基鋰，進而相對於正丁基鋰1mol，添加TMEDA(四甲基乙二胺)0.5mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was put into the reactor, n-butyllithium was added so as to be 0.08 parts by mass with respect to 100 parts by mass of all monomers, and TMEDA (tetramethylethylenediamine) was added to 1 mol of n-butyllithium 0.5mol.

其次，將包含苯乙烯6.5質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)投入至反應器中，於70℃下進行45分鐘聚合。其次，加入包含丁二烯87質量份之環己烷溶液(丁二烯濃度：20質量%)，於50℃下進行80分鐘聚合。其次，投入包含苯乙烯6.5質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。於反應結束後添加甲醇，獲得共軛二烯系嵌段共聚物。 Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene (relative to 100 parts by mass of all monomers, hereinafter, the same in this paragraph) was put into the reactor, and at 70 Polymerization was carried out at 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 87 parts by mass of butadiene was added, and polymerization was performed at 50° C. for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene was charged, and polymerization was performed at 70° C. for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為13質量%，聚苯乙烯嵌段含量為13質量%，丁二烯部之乙烯基鍵量為45mol%。 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 butadiene portion of 45 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於共軛二烯系嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained conjugated diene block copolymer, the above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm relative to the conjugated diene block copolymer. under hydrogenation reaction.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-3)，苯乙烯含量為13質量%，丁烯量為45mol%，重量平均分子量為8.0萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-3) had a styrene content of 13% by mass, a butene content of 45mol%, a weight average molecular weight of 80,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例4] [Manufacturing example 4] (共軛二烯系嵌段共聚物(a-4)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-4)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L之環己烷，以相對於全部單體100質量份成為0.11質量份之方式添加正丁基鋰，進而相對於正丁基鋰1mol，添加TMEDA(四甲基乙二胺)1.5mol，且相對於正丁基鋰1mol，添加第三戊氧化鈉0.05mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was added to the reactor, n-butyllithium was added in such a manner that it became 0.11 parts by mass with respect to 100 parts by mass of all monomers, and TMEDA (tetramethylethylenediamine ) 1.5 mol, and 0.05 mol of sodium pentoxide was added to 1 mol of n-butyllithium.

其次，加入包含丁二烯5質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(丁二烯濃度：20質量%)，於70℃下進行20分鐘聚合。其次，投入包含苯乙烯9質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。其次，加入包含丁二烯77質量份之環己烷溶液(丁二烯濃度：20質量%)，於50℃下進行80分鐘聚合。其次，投入包含苯乙烯9質量份之環己烷溶液(苯乙烯濃度：20質量%)， 於70℃下進行45分鐘聚合。於反應結束後添加甲醇，獲得共軛二烯系嵌段共聚物。 Next, add a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (with respect to 100 parts by mass of all monomers, hereinafter, the same applies in this paragraph), and carry out at 70° C. 20 minutes to polymerize. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 9 parts by mass of styrene was charged, and polymerization was performed 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 performed at 50° C. for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 9 parts by mass of styrene was thrown in, Polymerization was carried out at 70°C for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為18質量%，聚苯乙烯嵌段含量為18質量%，丁二烯部之乙烯基鍵量為73mol%。 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 butadiene portion of 73 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於共軛二烯系嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained conjugated diene block copolymer, the above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm relative to the conjugated diene block copolymer. under hydrogenation reaction.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造未改性且經氫化之共軛二烯系嵌段共聚物(a-4)。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce unmodified hydrogenated conjugated diene block copolymer (a-4).

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-4)，苯乙烯含量為18質量%，丁烯量為73mol%，重量平均分子量為10.7萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-4) had a styrene content of 18% by mass, a butene content of 73mol%, a weight average molecular weight of 107,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例5] [Manufacturing example 5] (共軛二烯系嵌段共聚物(a-5)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-5)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L環己烷，以相對於全部單體100質量份成為0.07質量 份之方式添加正丁基鋰，進而相對於正丁基鋰1mol，添加TMEDA(四甲基乙二胺)1.8mol，且相對於正丁基鋰1mol，添加第三戊氧化鈉0.05mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. Add 1L of cyclohexane to the reactor so that it becomes 0.07 mass parts with respect to 100 mass parts of all monomers N-butyllithium was added in portions, and 1.8 mol of TMEDA (tetramethylethylenediamine) was added to 1 mol of n-butyllithium, and 0.05 mol of sodium pentoxide was added to 1 mol of n-butyllithium.

其次，加入包含丁二烯5質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(丁二烯濃度：20質量%)，於70℃下進行20分鐘聚合。其次，投入包含苯乙烯7質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。其次，加入包含丁二烯82質量份之環己烷溶液(丁二烯濃度：20質量%)，於50℃下進行80分鐘聚合。其次，投入包含苯乙烯6質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。於反應結束後添加甲醇，獲得共軛二烯系嵌段共聚物。 Next, add a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (with respect to 100 parts by mass of all monomers, hereinafter, the same applies in this paragraph), and carry out at 70° C. 20 minutes to polymerize. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 7 parts by mass of styrene was charged, and polymerization was performed 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 performed at 50° C. for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6 parts by mass of styrene was charged, and polymerization was performed at 70° C. for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為13質量%，聚苯乙烯嵌段含量為13質量%，丁二烯部之乙烯基鍵量為78mol%。 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 butadiene portion of 78 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 The hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the concentration in terms of titanium would be 100 ppm based on the block copolymer, and hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物(a-5)。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer (a-5).

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-5)，苯乙烯含量為13質量%，丁烯量為78mol%，重量平均分子量為16.0萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-5) had a styrene content of 13% by mass, a butene content of 78mol%, a weight average molecular weight of 160,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例6] [Manufacturing example 6] (共軛二烯系嵌段共聚物(a-6)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-6)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L之環己烷，以相對於全部單體100質量份成為0.07質量份之方式添加正丁基鋰，進而，相對於正丁基鋰1mol，添加TMEDA(四甲基乙二胺)1.8mol，且相對於正丁基鋰1mol添加第三戊氧化鈉0.05mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was added to the reactor, n-butyllithium was added in such a manner that it became 0.07 parts by mass with respect to 100 parts by mass of all the monomers, and TMEDA (tetramethylethylenedioxide) was added to 1 mol of n-butyllithium. amine) 1.8 mol, and 0.05 mol of sodium pentapentoxide was added to 1 mol of n-butyllithium.

其次，投入包含苯乙烯6.5質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。其次，加入包含丁二烯87質量份之環己烷溶液(丁二烯濃度：20質量%)，於50℃下進行80分鐘聚合。其次，投入包含苯乙烯6.5質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。於反應結束後添加甲醇，獲得共軛二烯系嵌段共聚物。 Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene (with respect to 100 parts by mass of all monomers, the same applies to the following paragraphs) was charged, and the reaction was carried out at 70° C. for 45 minutes. polymerization. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 87 parts by mass of butadiene was added, and polymerization was performed at 50° C. for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 6.5 parts by mass of styrene was charged, and polymerization was performed at 70° C. for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為13質量%，聚苯乙烯嵌段含量為13質量%，丁二烯部之乙烯基鍵量為78mol%。 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 butadiene portion of 78 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 The hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the concentration in terms of titanium would be 100 ppm based on the block copolymer, and hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物(a-6)。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer (a-6).

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-6)，苯乙烯含量為13質量%，丁烯量為78mol%，重量平均分子量為16.0萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-6) had a styrene content of 13% by mass, a butene content of 78mol%, a weight average molecular weight of 160,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例7] [Manufacturing example 7] (共軛二烯系嵌段共聚物(a-7)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-7)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L之環己烷，以相對於全部單體100質量份成為0.05質量份之方式添加正丁基鋰，進而，相對於正丁基鋰1mol，添加TMEDA(四甲基乙二胺)0.05mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was added to the reactor, n-butyllithium was added in such a manner that it became 0.05 parts by mass with respect to 100 parts by mass of all the monomers, and TMEDA (tetramethylethylene diethylene glycol) was added to 1 mol of n-butyllithium. amine) 0.05mol.

其次，加入包含丁二烯10質量份(相對於全部單體100質量份，以下， 於該段落中同樣如此)之環己烷溶液(丁二烯濃度：20質量%)，於65℃下進行20分鐘聚合。其次，相對於正丁基鋰1mol，添加TMEDA 1.50mol，且相對於正丁基鋰1mol，添加第三戊氧化鈉0.05mol後，加入包含丁二烯85質量份之環己烷溶液(丁二烯濃度：20質量%)，於60℃下進行70分鐘聚合。其次，投入包含苯乙烯5質量份之環己烷溶液(苯乙烯濃度：20質量%)，於65℃下進行15分鐘聚合。於反應結束後添加甲醇，獲得共軛二烯系嵌段共聚物。 Next, add 10 parts by mass of butadiene (with respect to 100 parts by mass of all monomers, the following, The same applies in this paragraph) to a cyclohexane solution (butadiene concentration: 20% by mass), and polymerization was performed at 65° C. for 20 minutes. Next, 1.50 mol of TMEDA was added to 1 mol of n-butyllithium, and 0.05 mol of sodium pentoxide was added to 1 mol of n-butyllithium, and then a cyclohexane solution containing 85 parts by mass of butadiene (butadiene ene concentration: 20% by mass), polymerization was performed at 60° C. for 70 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 5 parts by mass of styrene was injected, and polymerization was performed at 65° C. for 15 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為5質量%，聚苯乙烯嵌段含量為5質量%，以共軛二烯單體單元作為主體之聚合物嵌段(以下，亦稱為「丁二烯部」)之乙烯基鍵量為78mol%。 The obtained conjugated diene block copolymer had a styrene content of 5% by mass, a polystyrene block content of 5% by mass, and a polymer block mainly composed of a conjugated diene monomer unit (hereinafter , also known as "butadiene part") has a vinyl bond content of 78 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 The hydrogenation catalyst was added to the obtained conjugated diene block copolymer so that the concentration in terms of titanium would be 100 ppm based on the block copolymer, and hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物(a-7)。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer (a-7).

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-7)，苯乙烯含量為5質量%，丁烯量為78mol%，重量平均分子量為24.9萬，分子量分佈為 1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-7) had a styrene content of 5% by mass, a butene content of 78mol%, a weight average molecular weight of 249,000, and a molecular weight distribution of 1.2, the hydrogenation rate is 99mol%.

[製造例8] [Manufacturing example 8] (共軛二烯系嵌段共聚物(a-8)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-8)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L之環己烷，以相對於全部單體100質量份成為0.10質量份之方式添加正丁基鋰，進而，相對於正丁基鋰1mol，添加TMEDA(四甲基乙二胺)1.8mol，且相對於正丁基鋰1mol，添加第三戊氧化鈉0.05mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was added to the reactor, n-butyllithium was added in such a manner that it became 0.10 parts by mass with respect to 100 parts by mass of all the monomers, and TMEDA (tetramethylethylene diethylene glycol) was added to 1 mol of n-butyllithium amine) 1.8 mol, and 0.05 mol of sodium pentoxide was added to 1 mol of n-butyllithium.

其次，加入包含丁二烯5質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(丁二烯濃度：20質量%)，於70℃下進行20分鐘聚合。其次，投入包含苯乙烯21.5質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。其次，加入包含丁二烯52質量份之環己烷溶液(丁二烯濃度：20質量%)，於50℃下進行80分鐘聚合。其次，投入包含苯乙烯21.5質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。於反應結束後添加甲醇，獲得共軛二烯系嵌段共聚物。 Next, add a cyclohexane solution (butadiene concentration: 20% by mass) containing 5 parts by mass of butadiene (with respect to 100 parts by mass of all monomers, hereinafter, the same applies in this paragraph), and carry out at 70° C. 20 minutes to polymerize. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 21.5 parts by mass of styrene was charged, and polymerization was performed 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 performed at 50° C. for 80 minutes. Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 21.5 parts by mass of styrene was charged, and polymerization was performed at 70° C. for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為43質量%，聚苯乙烯嵌段含量為43質量%，丁二烯部之乙烯基鍵量為78mol%。 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 butadiene portion of 78 mol%.

<步驟2> <Step 2>

於所獲得之嵌段共聚物中，以相對於嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained block copolymer, the hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm with respect to the block copolymer, and hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物(a-8)。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer (a-8).

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-8)，苯乙烯含量為43質量%，丁烯量為78mol%，重量平均分子量為10.3萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-8) had a styrene content of 43% by mass, a butene content of 78mol%, a weight average molecular weight of 103,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例9] [Manufacturing example 9] (共軛二烯系嵌段共聚物(a-9-1~a-9-13)之製造) (Manufacture of Conjugated Diene Block Copolymers (a-9-1~a-9-13)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L環己烷，以相對於全部單體100質量份成為0.04質量份之方式添加正丁基鋰，進而，相對於正丁基鋰1mol，添加N,N,N',N'-四甲基乙二胺(TMEDA)0.3mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was added to the reactor, n-butyllithium was added so as to be 0.04 parts by mass with respect to 100 parts by mass of all monomers, and N,N,N',N '-Tetramethylethylenediamine (TMEDA) 0.3 mol.

其次，將包含苯乙烯16質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)投入至反應器 中，於70℃下進行45分鐘聚合。其次，加入包含丁二烯68質量份之環己烷溶液(丁二烯濃度：20質量%)，於70℃下進行1.5小時聚合。最後，投入包含苯乙烯16質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。於反應結束後添加甲醇，作為步驟1，獲得共軛二烯系嵌段共聚物。 Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (with respect to 100 parts by mass of all monomers, hereinafter, the same in this paragraph) was put into the reactor , polymerization was carried out 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 polymerization was performed at 70° C. for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene was charged, and polymerization was performed at 70° C. for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer as step 1.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為32質量%，聚苯乙烯嵌段含量為32質量%，丁二烯部之乙烯基鍵量為36mol%。 The obtained 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 butadiene portion of 36 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於共軛二烯系嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained conjugated diene block copolymer, the above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm relative to the conjugated diene block copolymer. under hydrogenation reaction.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-9-1)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為28.5萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-9-1) had a styrene content of 32% by mass, a butene content of 36mol%, a weight average molecular weight of 285,000, and a molecular weight distribution of 1.2 , The hydrogenation rate is 99mol%.

於(a-9-1)中添加三(2,4-二第三丁基苯氧基)膦，使得以磷原子換算計 成為10ppm、50ppm、及100ppm，分別獲得(a-9-2)、(a-9-3)、及(a-9-4)。 Add tris(2,4-di-tert-butylphenoxy)phosphine to (a-9-1), so that in conversion of phosphorus atom At 10 ppm, 50 ppm, and 100 ppm, (a-9-2), (a-9-3), and (a-9-4) were obtained, respectively.

藉由對所獲得之氫化嵌段共聚物之溶液進行以下所示之去灰操作，實現源於起始劑及氫化觸媒之金屬量之降低。即，氫化結束後，相對於氫化嵌段共聚物100質量份，添加30質量份之水/硫酸之混合溶液。再者，硫酸之添加量係以後步驟中藉由傾析器去除之水之pH值成為7.0之方式進行調整。藉由傾析器將該溶液之大部分水去除，直至水量成為3質量份，相對於起始劑之金屬1mol，添加、混合二氧化碳0.4mol。其後，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份。藉由日本專利特公平05-54845號公報所記載之蒸汽汽提法(於90~98℃之水中去除溶劑之大部分之後，將屑粒濃度約5重量%之水分散漿料投入至雙軸擠出機，藉此脫溶劑之方法)對該溶液實施脫溶劑，獲得氫化嵌段共聚物(a-9-5)及(a-9-6)。 By performing the deashing operation shown below on the obtained solution of the hydrogenated block copolymer, the amount of metals derived from the initiator and the hydrogenation catalyst can be reduced. That is, after completion of hydrogenation, 30 parts by mass of a mixed solution of water/sulfuric acid was added to 100 parts by mass of the hydrogenated block copolymer. In addition, the addition amount of sulfuric acid was adjusted so that the pH value of the water removed by the decanter in the next step might become 7.0. Most of the water in this solution was removed by a decanter until the amount of water became 3 parts by mass, and 0.4 mol of carbon dioxide was added and mixed with respect to 1 mol of the metal of the initiator. Thereafter, 0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer. By means of the steam stripping method described in Japanese Patent Publication No. 05-54845 (after removing most of the solvent in water at 90-98°C, put the water dispersion slurry with a particle concentration of about 5% by weight into the biaxial Extruder, by the method of desolventizing) this solution was desolventized, and hydrogenated block copolymers (a-9-5) and (a-9-6) were obtained.

將所獲得之經氫化之共軛二烯系嵌段共聚物(a-9-1)進行冷凍粉碎，分別獲得鬆裝比重及分散度成為表所記載之值之(a-9-7)~(a-9-11)。 The obtained hydrogenated conjugated diene-based block copolymer (a-9-1) was frozen and pulverized to obtain bulk specific gravity and dispersity (a-9-7)~ (a-9-11).

將所獲得之經氫化之共軛二烯系嵌段共聚物(a-9-1)進行冷凍粉碎，分別獲得於鬆裝比重及分散度為表所記載之值之共軛二烯系嵌段共聚物中添加有1000ppm之非晶形二氧化矽及硬脂酸鈣的(a-9-12)及(a-9-13)。 The obtained hydrogenated conjugated diene block copolymer (a-9-1) was frozen and pulverized to obtain the conjugated diene block whose bulk specific gravity and dispersity were the values recorded in the table (a-9-12) and (a-9-13) in which 1000 ppm of amorphous silicon dioxide and calcium stearate were added to the copolymer.

[製造例10] [Manufacturing example 10] (胺共軛二烯系聚合物之製造) (Manufacture of amine-conjugated diene polymers) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L之環己烷，以相對於全部單體100質量份成為0.13質量份之方式添加正丁基鋰，進而，相對於正丁基鋰1mol，添加N,N,N',N'-四甲基乙二胺(TMEDA)0.3mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was put into the reactor, n-butyllithium was added so as to be 0.13 parts by mass with respect to 100 parts by mass of all monomers, and N,N,N', N'-tetramethylethylenediamine (TMEDA) 0.3 mol.

其次，將包含苯乙烯16質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)投入至反應器中，於70℃下進行45分鐘聚合。其次，加入包含丁二烯68質量份之環己烷溶液(丁二烯濃度：20質量%)，於70℃下進行1.5小時聚合。最後，投入包含苯乙烯16質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。其次，相對於正丁基鋰1mol，添加等莫耳之1,3-二甲基-2-咪唑啶酮(以下，亦簡稱為「DMI」)，於70℃下進行10分鐘反應。於反應結束後，添加甲醇，作為步驟1，獲得改性共軛二烯系嵌段共聚物。關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為32質量%，聚苯乙烯嵌段含量為32質量%，丁二烯部之乙烯基鍵量為36mol%。 Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (relative to 100 parts by mass of all monomers, hereinafter, the same in this paragraph) was put into the reactor, and at 70 Polymerization was carried out at 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 68 parts by mass of butadiene was added, and polymerization was performed at 70° C. for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene was charged, and polymerization was performed at 70° C. for 45 minutes. Next, equimolar 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added to 1 mol of n-butyllithium, and the reaction was carried out at 70° C. for 10 minutes. After the reaction, methanol was added to obtain a modified conjugated diene block copolymer as step 1. The obtained 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 butadiene portion of 36 mol%.

<步驟2> <Step 2>

於所獲得之改性共軛二烯系嵌段共聚物中，以相對於改性共軛二烯系嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained modified conjugated diene block copolymer, the above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm relative to the modified conjugated diene block copolymer. , The hydrogenation reaction was carried out at a temperature of 70°C.

於氫化反應結束後，繼而相對於改性共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之改性共軛二烯系嵌段共聚物。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid is added as a stabilizer to 100 parts by mass of the modified conjugated diene block copolymer 0.3 parts by mass of stearyl ester to produce a hydrogenated modified conjugated diene block copolymer.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-10)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為7.5萬，分子量分佈為1.2，氫化率為72mol%，改性率為65%(每一聚合鏈之改性基之數量為0.65個)。 The obtained hydrogenated conjugated diene block copolymer (a-10) had a styrene content of 32% by mass, a butene content of 36mol%, a weight average molecular weight of 75,000, and a molecular weight distribution of 1.2. The rate was 72 mol%, and the modification rate was 65% (the number of modifying groups per polymer chain was 0.65).

[改性共軛二烯系嵌段共聚物之製造] [Manufacture of modified conjugated diene block copolymer]

使用以下材料製造共軛二烯系聚合物。 A conjugated diene polymer was produced using the following materials.

順丁烯二酸酐(扶桑化學工業股份有限公司製造) Maleic anhydride (manufactured by Fuso Chemical Industry Co., Ltd.)

自由基起始劑：Perhexa 25B(日油股份有限公司製造) Free radical initiator: Perhexa 25B (manufactured by NOF Corporation)

[製造例11] [Manufacturing example 11] (改性共軛二烯系嵌段共聚物(aa-1)之製造) (Manufacture of modified conjugated diene block copolymer (aa-1)) <步驟3> <Step 3>

將製成顆粒狀之經氫化之共軛二烯系聚合物(a-1)100質量份、順丁烯二酸酐2.1質量份、Perhexa 25B 0.12質量份進行乾摻。對於該等摻合物，藉由雙軸擠出機TEX30(日本製鋼所股份有限公司製造)，以料筒設定溫度210℃、螺桿轉速253rpm、噴出量5kg/小時進行熔融混練，製造順丁烯二酸酐共軛二烯系聚合物(aa-1)。 100 parts by mass of 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. For these blends, by twin-screw extruder TEX30 (manufactured by Japan Steel Works Co., Ltd.), melting and kneading is carried out at a barrel setting temperature of 210 ° C, a screw speed of 253 rpm, and a discharge rate of 5 kg/hour to produce maleic butene Diic anhydride conjugated diene polymer (aa-1).

[製造例12] [Manufacturing example 12] (改性共軛二烯系嵌段共聚物(aa-2a)之製造) (Manufacture of modified conjugated diene block copolymer (aa-2a)) <步驟3> <Step 3>

除使用製成顆粒狀之經氫化之共軛二烯系聚合物(a-2)100質量份、順丁烯二酸酐2.1質量份、及Perhexa 25B 0.12質量份進行乾摻以外，以與製造例11相同之方式製造共軛二烯系聚合物(aa-2a)。 In addition to dry blending 100 parts by mass of the hydrogenated conjugated diene polymer (a-2) made into pellets, 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B, the same method as in the production example 11. Prepare the conjugated diene polymer (aa-2a) in the same manner.

[製造例13] [Manufacturing example 13] (改性共軛二烯系嵌段共聚物(aa-2b)之製造) (Manufacture of modified conjugated diene block copolymer (aa-2b)) <步驟3> <Step 3>

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-2)100質量份、順丁烯二酸酐4.2質量份、及Perhexa 25B 0.48質量份以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-2b)。 Except changing the ingredients in dry blending to 100 parts by mass of hydrogenated conjugated diene polymer (a-2) in pellet form, 4.2 parts by mass of maleic anhydride, and 0.48 parts by mass of Perhexa 25B , A maleic anhydride conjugated diene polymer (aa-2b) was produced in the same manner as in Production Example 11.

[製造例14] [Manufacturing example 14] (改性共軛二烯系嵌段共聚物(aa-3)之製造) (Manufacture of modified conjugated diene block copolymer (aa-3)) <步驟3> <Step 3>

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-3)100質量份、順丁烯二酸酐2.1質量份、及Perhexa 25B 0.12質量份以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-3)。 Except changing the ingredients in dry blending to 100 parts by mass of the hydrogenated conjugated diene polymer (a-3) in pellet form, 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B , A maleic anhydride conjugated diene polymer (aa-3) was produced in the same manner as in Production Example 11.

[製造例15] [Manufacturing example 15] (改性共軛二烯系嵌段共聚物(aa-4)之製造) (Manufacture of modified conjugated diene block copolymer (aa-4)) <步驟3> <Step 3>

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-4)100質量份、順丁烯二酸酐1.4質量份、及Perhexa 25B 0.08質量份以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-4)。 Except that the ingredients in dry blending were changed to 100 parts by mass of hydrogenated conjugated diene polymer (a-4) in pellet form, 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B , A maleic anhydride conjugated diene polymer (aa-4) was produced in the same manner as in Production Example 11.

[製造例16] [Manufacturing example 16] (改性共軛二烯系嵌段共聚物(aa-5)之製造) (Manufacture of modified conjugated diene block copolymer (aa-5)) <步驟3> <Step 3>

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-5)100質量份、順丁烯二酸酐1.4質量份、及Perhexa 25B 0.08質量份以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-5)。 Except that the ingredients in dry blending were changed to 100 parts by mass of the hydrogenated conjugated diene polymer (a-5) in pellet form, 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B , A maleic anhydride conjugated diene polymer (aa-5) was produced in the same manner as in Production Example 11.

[製造例17] [Manufacturing example 17] (改性共軛二烯系嵌段共聚物(aa-6)之製造) (Manufacture of modified conjugated diene block copolymer (aa-6)) <步驟3> <Step 3>

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-6)100質量份、順丁烯二酸酐1.4質量份、及Perhexa 25B 0.08質量份以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-6)。 Except that the ingredients in dry blending were changed to 100 parts by mass of the hydrogenated conjugated diene polymer (a-6) in pellet form, 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B , A maleic anhydride conjugated diene polymer (aa-6) was produced in the same manner as in Production Example 11.

[製造例18] [Manufacturing example 18] (改性共軛二烯系嵌段共聚物(aa-7)之製造) (Manufacture of modified conjugated diene block copolymer (aa-7)) <步驟3> <Step 3>

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-7)100質量份、順丁烯二酸酐1.4質量份、及Perhexa 25B 0.08質量份以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-7)。 In addition to changing the ingredients during dry blending to 100 parts by mass of hydrogenated conjugated diene polymer (a-7) in pellet form, 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B , A maleic anhydride conjugated diene polymer (aa-7) was produced in the same manner as in Production Example 11.

[製造例19] [Manufacturing example 19] (改性共軛二烯系嵌段共聚物(aa-8)之製造) (Manufacture of modified conjugated diene block copolymer (aa-8)) <步驟3> <Step 3>

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-8)100質量份、順丁烯二酸酐2.1質量份、及Perhexa 25B 0.12質量份以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-8)。 In addition to changing the components during dry blending to 100 parts by mass of hydrogenated conjugated diene polymer (a-8) in pellet form, 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B , A maleic anhydride conjugated diene polymer (aa-8) was produced in the same manner as in Production Example 11.

[製造例20] [Manufacturing example 20] (改性共軛二烯系嵌段共聚物(aa-9)之製造) (Manufacture of modified conjugated diene block copolymer (aa-9)) <步驟3> <Step 3>

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-9)100質量份、順丁烯二酸酐2.1質量份、及Perhexa 25B 0.12質量份，將料筒設定溫度變更為240℃以外，以與製造例11相同之方式製造順 丁烯二酸酐共軛二烯系聚合物(aa-9)。 In addition to changing the components during dry blending to 100 parts by mass of the hydrogenated conjugated diene polymer (a-9) made into pellets, 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B, Except changing the set temperature of the cylinder to 240°C, the same method as in Manufacturing Example 11 was used to manufacture Butenedioic anhydride conjugated diene polymer (aa-9).

[製造例21] [Manufacturing example 21] (共軛二烯系嵌段共聚物(a-11)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-11)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L環己烷，以相對於全部單體100質量份成為0.04質量份之方式添加正丁基鋰，進而，相對於正丁基鋰1mol，添加N,N,N',N'-四甲基乙二胺(TMEDA)0.3mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was added to the reactor, n-butyllithium was added so as to be 0.04 parts by mass with respect to 100 parts by mass of all monomers, and N,N,N',N '-Tetramethylethylenediamine (TMEDA) 0.3 mol.

其次，將包含苯乙烯16質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)投入至反應器中，於70℃下進行45分鐘聚合。其次，加入包含丁二烯68質量份之環己烷溶液(丁二烯濃度：20質量%)，於70℃下進行1.5小時聚合。最後，投入包含苯乙烯16質量份之環己烷溶液(苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。於反應結束後添加甲醇，作為步驟1，獲得共軛二烯系嵌段共聚物。 Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene (relative to 100 parts by mass of all monomers, hereinafter, the same in this paragraph) was put into the reactor, and at 70 Polymerization was carried out at 45 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 68 parts by mass of butadiene was added, and polymerization was performed at 70° C. for 1.5 hours. Finally, a cyclohexane solution (styrene concentration: 20% by mass) containing 16 parts by mass of styrene was charged, and polymerization was performed at 70° C. for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer as step 1.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為32質量%，聚苯乙烯嵌段含量為32質量%，丁二烯部之乙烯基鍵量為36mol%。 The obtained 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 butadiene portion of 36 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於共軛二烯系嵌段共聚 物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 In the obtained conjugated diene block copolymer, relative to the conjugated diene block copolymer The above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm, and hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-11)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為28.7萬，分子量分佈為1.2，氫化率為75mol%。 The obtained hydrogenated conjugated diene block copolymer (a-11) had a styrene content of 32% by mass, a butene content of 36mol%, a weight average molecular weight of 287,000, and a molecular weight distribution of 1.2. The rate is 75mol%.

[製造例22~25] [Manufacturing example 22~25] (共軛二烯系嵌段共聚物(a-12~15)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-12~15))

除調整正丁基鋰量、TMEDA量以外，以與製造例9相同之方式製造。 It produced in the same manner as Production Example 9 except adjusting the amount of n-butyllithium and the amount of TMEDA.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-12)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為19.0萬，分子量分佈為1.2，氫化率為99mol%。關於(a-13-1)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為35.1萬，分子量分佈為1.2，氫化率為99mol%。關於(a-14)，苯乙烯含量為32質量%，丁烯量為58mol%，重量平均分子量為35.1萬，分子量分佈為1.2，氫化率為99mol%。關於(a-15-1)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為45.1萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-12) had a styrene content of 32% by mass, a butene content of 36mol%, a weight average molecular weight of 190,000, and a molecular weight distribution of 1.2. The rate is 99mol%. Regarding (a-13-1), the styrene content was 32% by mass, the amount of butene was 36mol%, the weight average molecular weight was 351,000, the molecular weight distribution was 1.2, and the hydrogenation rate was 99mol%. Regarding (a-14), the styrene content was 32% by mass, the amount of butene was 58mol%, the weight average molecular weight was 351,000, the molecular weight distribution was 1.2, and the hydrogenation rate was 99mol%. Regarding (a-15-1), the styrene content was 32% by mass, the amount of butene was 36mol%, the weight average molecular weight was 451,000, the molecular weight distribution was 1.2, and the hydrogenation rate was 99mol%.

於(a-13-1)中添加三(2,4-二第三丁基苯氧基)膦，使得以磷原子換算計成為10ppm、50ppm、及100ppm，分別獲得(a-13-2)、(a-13-3)、及(a-13-4)。 Tris(2,4-di-tert-butylphenoxy)phosphine was added to (a-13-1) so that it became 10 ppm, 50 ppm, and 100 ppm in terms of phosphorus atoms, respectively, to obtain (a-13-2) , (a-13-3), and (a-13-4).

藉由對所獲得之氫化嵌段共聚物之溶液進行以下所示之去灰操作，實現源於起始劑及氫化觸媒之金屬量之降低。即，氫化結束後，相對於氫化嵌段共聚物100質量份，添加30質量份之水/硫酸之混合溶液。再者，硫酸之添加量係以後步驟中藉由傾析器去除之水之pH值成為7.0之方式進行調整。藉由傾析器將該溶液之大部分水去除，直至水量成為3質量份，相對於起始劑之金屬1mol，添加、混合二氧化碳0.4mol。其後，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份。藉由日本專利特公平05-54845號公報所記載之蒸汽汽提法(於90~98℃之水中去除溶劑之大部分後，將屑粒濃度約5重量%之水分散漿料投入至雙軸擠出機，藉此進行脫溶劑之方法)對該溶液實施脫溶劑，獲得氫化嵌段共聚物(a-13-5)及(a-13-6)。 By performing the deashing operation shown below on the obtained solution of the hydrogenated block copolymer, the amount of metals derived from the initiator and the hydrogenation catalyst can be reduced. That is, after completion of hydrogenation, 30 parts by mass of a mixed solution of water/sulfuric acid was added to 100 parts by mass of the hydrogenated block copolymer. In addition, the addition amount of sulfuric acid was adjusted so that the pH value of the water removed by the decanter in the next step might become 7.0. Most of the water in this solution was removed by a decanter until the amount of water became 3 parts by mass, and 0.4 mol of carbon dioxide was added and mixed with respect to 1 mol of the metal of the initiator. Thereafter, 0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer. By means of the steam stripping method described in Japanese Patent Publication No. 05-54845 (after removing most of the solvent in water at 90-98°C, put the water dispersion slurry with a particle concentration of about 5% by weight into the biaxial Extruder, the method of performing desolventization by this) desolventizes this solution, and obtains hydrogenated block copolymer (a-13-5) and (a-13-6).

將所獲得之經氫化之共軛二烯系嵌段共聚物(a-13-1)進行冷凍粉碎，分別獲得鬆裝比重及分散度成為表所記載之值之(a-13-7)~(a-13-11)。 The obtained hydrogenated conjugated diene block copolymer (a-13-1) was frozen and pulverized to obtain bulk specific gravity and dispersity (a-13-7)~ (a-13-11).

將所獲得之經氫化之共軛二烯系嵌段共聚物(a-13-1)進行冷凍粉碎，分別獲得於鬆裝比重及分散度為表所記載之值之共軛二烯系嵌段共聚物中添加有1000ppm之非晶形二氧化矽及硬脂酸鈣之(a-13-12)及(a-13-13)。 The obtained hydrogenated conjugated diene block copolymer (a-13-1) was frozen and pulverized to obtain the conjugated diene block whose bulk specific gravity and dispersity were the values recorded in the table (a-13-12) and (a-13-13) with 1000ppm of amorphous silicon dioxide and calcium stearate added to the copolymer.

於(a-15-1)中添加三(2,4-二第三丁基苯氧基)膦，使得以磷原子換算計成為10ppm、50ppm、及100ppm，分別獲得(a-15-2)、(a-15-3)、及(a-15-4)。 Tris(2,4-di-tert-butylphenoxy)phosphine was added to (a-15-1) so that it became 10ppm, 50ppm, and 100ppm in terms of phosphorus atoms, respectively, to obtain (a-15-2) , (a-15-3), and (a-15-4).

藉由對所獲得之氫化嵌段共聚物之溶液進行以下所示之去灰操作，實現源於起始劑及氫化觸媒之金屬量之降低。即，氫化結束後，相對於氫化嵌段共聚物100質量份，添加30質量份之水/硫酸之混合溶液。再者，硫酸之添加量係以後步驟中藉由傾析器去除之水之pH值成為7.0之方式進行調整。藉由傾析器去除該溶液之大部分水，直至水量成為3質量份，相對於起始劑之金屬1mol，添加、混合二氧化碳0.4mol。其後，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份。藉由日本專利特公平05-54845號公報所記載之蒸汽汽提法(於90~98℃之水中去除溶劑之大部分後，將屑粒濃度約5重量%之水分散漿料投入至雙軸擠出機，藉此進行脫溶劑之方法)對該溶液實施脫溶劑，獲得氫化嵌段共聚物(a-15-5)及(a-15-6)。 By performing the deashing operation shown below on the obtained solution of the hydrogenated block copolymer, the amount of metals derived from the initiator and the hydrogenation catalyst can be reduced. That is, after completion of hydrogenation, 30 parts by mass of a mixed solution of water/sulfuric acid was added to 100 parts by mass of the hydrogenated block copolymer. In addition, the addition amount of sulfuric acid was adjusted so that the pH value of the water removed by the decanter in the next step might become 7.0. Most of the water in this solution was removed by a decanter until the amount of water became 3 parts by mass, and 0.4 mol of carbon dioxide was added and mixed with respect to 1 mol of the metal of the initiator. Thereafter, 0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer. By means of the steam stripping method described in Japanese Patent Publication No. 05-54845 (after removing most of the solvent in water at 90-98°C, put the water dispersion slurry with a particle concentration of about 5% by weight into the biaxial Extruder, the method of performing desolventization by this) desolventizes this solution, and obtains hydrogenated block copolymer (a-15-5) and (a-15-6).

將所獲得之經氫化之共軛二烯系嵌段共聚物(a-15-1)進行冷凍粉碎，分別獲得鬆裝比重及分散度成為表所記載之值之(a-15-7)~(a-15-11)。 The obtained hydrogenated conjugated diene block copolymer (a-15-1) was frozen and pulverized to obtain bulk specific gravity and dispersity (a-15-7)~ (a-15-11).

將所獲得之經氫化之共軛二烯系嵌段共聚物(a-15-1)進行冷凍粉碎，分別獲得於鬆裝比重及分散度為表所記載之值之共軛二烯系嵌段共聚物中添加有1000ppm之非晶形二氧化矽及硬脂酸鈣之(a-15-12)及(a-15-13)。 The obtained hydrogenated conjugated diene block copolymer (a-15-1) was frozen and pulverized to obtain the conjugated diene block whose bulk specific gravity and dispersity were the values recorded in the table (a-15-12) and (a-15-13) with 1000ppm of amorphous silicon dioxide and calcium stearate added to the copolymer.

[製造例26] [Manufacturing example 26] (共軛二烯系嵌段共聚物(a-16)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-16))

除變更正丁基鋰量，且變更為每次導入苯乙烯9.5質量份以外，以與製造例9相同之方式製造。 It was produced in the same manner as in Production Example 9, except that the amount of n-butyllithium was changed, and 9.5 parts by mass of styrene was introduced every time.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-16)，苯乙烯含量為19質量%，丁烯量為36mol%，重量平均分子量為35.2萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-16) had a styrene content of 19% by mass, a butene content of 36mol%, a weight average molecular weight of 352,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例27] [Manufacturing example 27] (共軛二烯系嵌段共聚物(a-17)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-17)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。於反應器中加入1L環己烷，以相對於全部單體100質量份成為0.04質量份之方式添加正丁基鋰，進而，相對於正丁基鋰1mol，添加N,N,N',N'-四甲基乙二胺(TMEDA)0.3mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was added to the reactor, n-butyllithium was added so as to be 0.04 parts by mass with respect to 100 parts by mass of all monomers, and N,N,N',N '-Tetramethylethylenediamine (TMEDA) 0.3 mol.

其次，將包含苯乙烯15質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)投入至反應器中，於70℃下進行45分鐘聚合。其次，加入包含丁二烯35質量份/異戊二烯35質量份之環己烷溶液(丁二烯及異戊二烯整體之濃度：20質量%)，於70℃下進行1.5小時聚合。最後，投入包含苯乙烯15質量份之環己烷溶液 (苯乙烯濃度：20質量%)，於70℃下進行45分鐘聚合。於反應結束後添加甲醇，作為步驟1，獲得共軛二烯系嵌段共聚物。 Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 15 parts by mass of styrene (relative to 100 parts by mass of all monomers, hereinafter, the same in this paragraph) was put into the reactor, and at 70 Polymerization was carried out at 45 minutes. Next, a cyclohexane solution containing 35 parts by mass of butadiene/35 parts by mass of isoprene (total concentration of butadiene and isoprene: 20 mass %) was added, and polymerization was performed at 70° C. for 1.5 hours. Finally, drop into the cyclohexane solution that contains 15 parts by mass of styrene (Styrene concentration: 20% by mass), polymerization was performed at 70° C. for 45 minutes. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer as step 1.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為30質量%，聚苯乙烯嵌段含量為30質量%，丁二烯/異戊二烯部之乙烯基鍵量為36mol%。 The obtained 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 butadiene/isoprene portion of 36 mol%. .

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於共軛二烯系嵌段共聚物，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained conjugated diene block copolymer, the above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm relative to the conjugated diene block copolymer. under hydrogenation reaction.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-17)，苯乙烯含量為30質量%，丁烯量為36mol%，重量平均分子量為45.0萬，分子量分佈為1.2，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-17) had a styrene content of 30% by mass, a butene content of 36mol%, a weight average molecular weight of 450,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

[製造例28] [Manufacturing example 28] (共軛二烯系嵌段共聚物(a-18)之製造) (Manufacture of Conjugated Diene Block Copolymer (a-18)) <步驟1> <step 1>

使用內容積為10L之附攪拌裝置及套管之槽型反應器進行批次聚合。 於反應器中加入1L環己烷，以相對於全部單體100質量份成為0.056質量份之方式添加正丁基鋰，進而，相對於正丁基鋰1mol，添加N,N,N',N'-四甲基乙二胺(TMEDA)1.2mol。 Batch polymerization was carried out using a tank reactor with an inner volume of 10 L with a stirring device and a jacket. 1 L of cyclohexane was added to the reactor, n-butyllithium was added so as to become 0.056 parts by mass with respect to 100 parts by mass of all monomers, and N,N,N',N '-Tetramethylethylenediamine (TMEDA) 1.2 mol.

其次，將包含苯乙烯20質量份(相對於全部單體100質量份，以下，於該段落中同樣如此)之環己烷溶液(苯乙烯濃度：20質量%)投入至反應器中，於45℃下進行30分鐘聚合。其次，加入包含丁二烯80質量份之環己烷溶液(丁二烯濃度：20質量%)，於80℃下進行1.0小時聚合。最後，相對於正丁基鋰1mol，添加四甲氧基矽烷0.27mol，進行偶合反應。於反應結束後添加甲醇，作為步驟1，獲得共軛二烯系嵌段共聚物。 Next, a cyclohexane solution (styrene concentration: 20% by mass) containing 20 parts by mass of styrene (relative to 100 parts by mass of all monomers, hereinafter, the same in this paragraph) was put into the reactor, and at 45 Polymerization was carried out at °C for 30 minutes. Next, a cyclohexane solution (butadiene concentration: 20% by mass) containing 80 parts by mass of butadiene was added, and polymerization was performed at 80° C. for 1.0 hour. Finally, 0.27 mol of tetramethoxysilane was added to 1 mol of n-butyllithium, and a coupling reaction was performed. Methanol was added after completion of the reaction to obtain a conjugated diene block copolymer as step 1.

關於所獲得之共軛二烯系嵌段共聚物，苯乙烯含量為20質量%，聚苯乙烯嵌段含量為20質量%，丁二烯部之乙烯基鍵量為63mol%。 The obtained 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 the butadiene portion of 63 mol%.

<步驟2> <Step 2>

於所獲得之共軛二烯系嵌段共聚物中，以相對於共軛二烯系嵌段共聚物100質量份，鈦換算濃度成為100ppm之方式添加上述氫化觸媒，於氫壓0.7MPa、溫度70℃下進行氫化反應。 To the obtained conjugated diene block copolymer, the above-mentioned hydrogenation catalyst was added so that the concentration in terms of titanium would be 100 ppm with respect to 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation catalyst was added at a hydrogen pressure of 0.7 MPa, The hydrogenation reaction was carried out at a temperature of 70°C.

於氫化反應結束後，繼而相對於共軛二烯系嵌段共聚物100質量份，添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯0.3質量份，製造經氫化之共軛二烯系嵌段共聚物。 After the hydrogenation reaction is completed, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanoate is added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer 0.3 parts by mass of alkyl ester to produce a hydrogenated conjugated diene block copolymer.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-18)，苯乙烯含量為20質量%，丁烯量為62mol%，重量平均分子量為43.4萬，分子量分佈為2.3，氫化率為99mol%。 The obtained hydrogenated conjugated diene block copolymer (a-18) had a styrene content of 20% by mass, a butene content of 62mol%, a weight average molecular weight of 434,000, and a molecular weight distribution of 2.3. The rate is 99mol%.

[製造例29~35] [Manufacturing example 29~35] (胺共軛二烯系聚合物(a-19~25)之製造) (Manufacture of amine-conjugated diene polymers (a-19~25))

除變更正丁基鋰量、TMEDA量、DMI量以外，以與製造例10相同之方式製造。 It manufactured in the same manner as the manufacture example 10 except having changed the amount of n-butyllithium, the amount of TMEDA, and the amount of DMI.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-19)，苯乙烯含量為32質量%，丁烯量為30mol%，重量平均分子量為18.0萬，分子量分佈為1.1，氫化率為87mol%，改性率為71%(每一聚合鏈之改性基之數量為0.71個)。 The obtained hydrogenated conjugated diene block copolymer (a-19) had a styrene content of 32% by mass, a butene content of 30mol%, a weight average molecular weight of 180,000, and a molecular weight distribution of 1.1. Hydrogenated The rate was 87 mol%, and the modification rate was 71% (the number of modifying groups per polymer chain was 0.71).

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-20)，苯乙烯含量為32質量%，丁烯量為21mol%，重量平均分子量為20.3萬，分子量分佈為1.1，氫化率為87mol%，改性率為71%(每一聚合鏈之改性基之數量為0.71個)。關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-21)，苯乙烯含量為32質量%，丁烯量為30mol%，重量平均分子量為20.3萬，分子量分佈為1.1，氫化率為87mol%，改性率為70%(每一聚合鏈之改性基之數量為0.70個)。關於(a-22)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為25.2萬，分子量分佈為1.1，氫化率為84mol%，改性率為71%(每一聚合鏈之改性基之數量為0.71個)。關於(a-23)，苯乙烯含量為32質量 %，丁烯量為36mol%，重量平均分子量為25.1萬，分子量分佈為1.1，氫化率為84mol%，改性率為25%(每一聚合鏈之改性基之數量為0.25個)。關於(a-24)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為35.1萬，分子量分佈為1.1，氫化率為84mol%，改性率為71%(每一聚合鏈之改性基之數量為0.71個)。關於(a-25)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為45萬，分子量分佈為1.1，氫化率為84mol%，改性率為71%(每一聚合鏈之改性基之數量為0.71個)。 The obtained hydrogenated conjugated diene block copolymer (a-20) had a styrene content of 32% by mass, a butene content of 21mol%, a weight average molecular weight of 203,000, and a molecular weight distribution of 1.1. Hydrogenated The rate was 87 mol%, and the modification rate was 71% (the number of modifying groups per polymer chain was 0.71). The obtained hydrogenated conjugated diene block copolymer (a-21) had a styrene content of 32% by mass, a butene content of 30mol%, a weight average molecular weight of 203,000, and a molecular weight distribution of 1.1. Hydrogenated The rate was 87 mol%, and the modification rate was 70% (the number of modifying groups per polymer chain was 0.70). Regarding (a-22), the styrene content is 32% by mass, the amount of butene is 36mol%, the weight average molecular weight is 252,000, the molecular weight distribution is 1.1, the hydrogenation rate is 84mol%, and the modification rate is 71% (per polymerization The number of modifying groups in the chain is 0.71). Regarding (a-23), the styrene content is 32 mass %, the amount of butene is 36mol%, the weight average molecular weight is 251,000, the molecular weight distribution is 1.1, the hydrogenation rate is 84mol%, and the modification rate is 25% (the number of modified groups per polymer chain is 0.25). Regarding (a-24), the styrene content is 32% by mass, the amount of butene is 36mol%, the weight average molecular weight is 351,000, the molecular weight distribution is 1.1, the hydrogenation rate is 84mol%, and the modification rate is 71% (per polymerization The number of modifying groups in the chain is 0.71). Regarding (a-25), the styrene content is 32% by mass, the amount of butene is 36mol%, the weight average molecular weight is 450,000, the molecular weight distribution is 1.1, the hydrogenation rate is 84mol%, and the modification rate is 71% (per polymerization The number of modifying groups in the chain is 0.71).

[製造例36] [Manufacturing example 36] (胺共軛二烯系聚合物(a-26)之製造) (Manufacture of amine-conjugated diene polymer (a-26))

除變更正丁基鋰量，且每次導入苯乙烯19.0質量份以外，以與製造例10相同之方式製造。 It was produced in the same manner as in Production Example 10, except that the amount of n-butyllithium was changed and 19.0 parts by mass of styrene was introduced each time.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-26)，苯乙烯含量為38質量%，丁烯量為36mol%，重量平均分子量為25.2萬，分子量分佈為1.1，氫化率為83mol%，改性率為70%(每一聚合鏈之改性基之數量為0.70個)。 The obtained hydrogenated conjugated diene block copolymer (a-26) had a styrene content of 38% by mass, a butene content of 36mol%, a weight average molecular weight of 252,000, and a molecular weight distribution of 1.1. Hydrogenated The rate is 83 mol%, and the modification rate is 70% (the number of modifying groups per polymer chain is 0.70).

[製造例37] [Manufacturing example 37] (胺共軛二烯系聚合物(a-27)之製造) (Manufacture of amine-conjugated diene polymer (a-27))

除變更正丁基鋰量，且變更為每次導入苯乙烯21質量份以外，以與製造例10相同之方式製造。 It was produced in the same manner as in Production Example 10, except that the amount of n-butyllithium was changed, and 21 parts by mass of styrene was introduced at a time.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-27)，苯乙烯含量為42質量%，丁烯量為36mol%，重量平均分子量為25.2萬，分子量分佈為1.1，氫化率為84mol%，改性率為75%(每一聚合鏈之改性基之數量為0.75個)。 The obtained hydrogenated conjugated diene block copolymer (a-27) had a styrene content of 42% by mass, a butene content of 36mol%, a weight average molecular weight of 252,000, and a molecular weight distribution of 1.1. The rate was 84 mol%, and the modification rate was 75% (the number of modifying groups per polymer chain was 0.75).

[製造例38] [Manufacturing example 38] (胺共軛二烯系聚合物(a-28)之製造) (Manufacture of amine-conjugated diene polymer (a-28))

除變更正丁基鋰量，且變更為每次導入苯乙烯6.5質量份以外，以與製造例10相同之方式製造。 It was produced in the same manner as in Production Example 10, except that the amount of n-butyllithium was changed, and 6.5 parts by mass of styrene was introduced every time.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-28)，苯乙烯含量為13質量%，丁烯量為36mol%，重量平均分子量為25.0萬，分子量分佈為1.1，氫化率為83mol%，改性率為75%(每一聚合鏈之改性基之數量為0.75個)。 The obtained hydrogenated conjugated diene block copolymer (a-28) had a styrene content of 13% by mass, a butene content of 36mol%, a weight average molecular weight of 250,000, and a molecular weight distribution of 1.1. Hydrogenated The rate is 83 mol%, and the modification rate is 75% (the number of modifying groups per polymer chain is 0.75).

[製造例39] [Manufacturing example 39] (胺共軛二烯系聚合物(a-29)之製造) (Manufacture of amine-conjugated diene polymer (a-29))

除調整正丁基鋰量、TMEDA量以外，以與製造例10相同之方式製造。 It produced in the same manner as in Production Example 10 except for adjusting the amount of n-butyllithium and the amount of TMEDA.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-29)，苯乙烯含量為32質量%，丁烯量為59mol%，重量平均分子量為25.0萬，分子量分佈為1.1，氫化率為83mol%，改性率為75%(每一聚合鏈之改性基之數量為0.75 個)。 The obtained hydrogenated conjugated diene block copolymer (a-29) had a styrene content of 32% by mass, a butene content of 59mol%, a weight average molecular weight of 250,000, and a molecular weight distribution of 1.1. The rate is 83mol%, and the modification rate is 75% (the number of modified groups per polymer chain is 0.75 indivual).

[製造例40] [Manufacturing example 40] (胺共軛二烯系聚合物(a-30)之製造) (Manufacture of amine-conjugated diene polymer (a-30))

除使用N,N-雙(三甲基矽烷基)胺基丙基甲基二乙氧基矽烷代替DMI以外，以與(a-24)相同之方式製造氫化物，其後藉由脫矽烷基保護基製造改性共軛二烯系嵌段共聚物(a-30)。 The hydride was produced in the same manner as (a-24), except that N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane was used instead of DMI, followed by desilylation Protecting group Modified conjugated diene block copolymer (a-30) was produced.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-30)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為35.1萬，分子量分佈為1.1，氫化率為90mol%，改性率為90%(每一聚合鏈之改性基之數量為0.9個)。 The obtained hydrogenated conjugated diene block copolymer (a-30) had a styrene content of 32% by mass, a butene content of 36mol%, a weight average molecular weight of 351,000, and a molecular weight distribution of 1.1. The rate is 90 mol%, and the modification rate is 90% (the number of modifying groups per polymer chain is 0.9).

[製造例41] [Manufacturing example 41] (胺共軛二烯系聚合物(a-31)之製造) (Manufacture of amine-conjugated diene polymer (a-31))

除使用1-(4-二甲基胺基苯基)-1-苯乙烯代替DMI以外，以與(a-24)相同之方式製造氫化物，製造改性共軛二烯系嵌段共聚物(a-31)。 Except for using 1-(4-dimethylaminophenyl)-1-styrene instead of DMI, a hydride was produced in the same manner as (a-24), and a modified conjugated diene block copolymer was produced (a-31).

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-31)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為35.1萬，分子量分佈為1.1，氫化率為90mol%，改性率為90%(每一聚合鏈之改性基之數量為0.9個)。 The obtained hydrogenated conjugated diene block copolymer (a-31) had a styrene content of 32% by mass, a butene content of 36mol%, a weight average molecular weight of 351,000, and a molecular weight distribution of 1.1. The rate is 90 mol%, and the modification rate is 90% (the number of modifying groups per polymer chain is 0.9).

[製造例42] [Manufacturing example 42] (胺共軛二烯系聚合物(a-32)之製造) (Manufacture of amine-conjugated diene polymer (a-32))

除變更正丁基鋰量、TMEDA量，且變更為每次導入苯乙烯6.5質量份以外，以與製造例10相同之方式製造。 It was produced in the same manner as in Production Example 10, except that the amount of n-butyllithium and TMEDA were changed, and 6.5 parts by mass of styrene was introduced every time.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-32)，苯乙烯含量為13質量%，丁烯量為36mol%，重量平均分子量為15.1萬，分子量分佈為1.2，氫化率為87mol%，改性率為80%(每一聚合鏈之改性基之數量為0.80個)。 The obtained hydrogenated conjugated diene block copolymer (a-32) had a styrene content of 13% by mass, a butene content of 36mol%, a weight average molecular weight of 151,000, and a molecular weight distribution of 1.2. The rate was 87 mol%, and the modification rate was 80% (the number of modifying groups per polymer chain was 0.80).

[製造例43] [Manufacturing example 43] (胺共軛二烯系聚合物(a-33)之製造) (Manufacture of amine-conjugated diene polymer (a-33))

除變更正丁基鋰量以外，以與製造例10相同之方式製造。 It was produced in the same manner as in Production Example 10 except that the amount of n-butyllithium was changed.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-33)，苯乙烯含量為32質量%，丁烯量為38mol%，重量平均分子量為6.0萬，分子量分佈為1.2，氫化率為87mol%，改性率為72%(每一聚合鏈之改性基之數量為0.72個)。 The obtained hydrogenated conjugated diene block copolymer (a-33) had a styrene content of 32% by mass, a butene content of 38mol%, a weight average molecular weight of 60,000, and a molecular weight distribution of 1.2. The rate was 87 mol%, and the modification rate was 72% (the number of modifying groups per polymer chain was 0.72).

[製造例44] [Manufacturing example 44] (胺共軛二烯系聚合物(a-34)之製造) (Manufacture of amine-conjugated diene polymer (a-34))

除變更正丁基鋰量、TMEDA量，且變更為每次導入苯乙烯12.5質量份以外，以與製造例10相同之方式製造。 It was manufactured in the same manner as in Production Example 10, except that the amount of n-butyllithium and TMEDA were changed, and 12.5 parts by mass of styrene was introduced every time.

關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-34)，苯乙烯含量為25質量%，丁烯量為54mol%，重量平均分子量為9.0萬，分子量分佈為1.2，氫化率為98mol%，改性率為90%(每一聚合鏈之改性基之數量為0.9個)。 The obtained hydrogenated conjugated diene block copolymer (a-34) had a styrene content of 25% by mass, a butene content of 54mol%, a weight average molecular weight of 90,000, and a molecular weight distribution of 1.2. The rate is 98 mol%, and the modification rate is 90% (the number of modifying groups per polymer chain is 0.9).

[製造例45] [Manufacturing example 45] (改性共軛二烯系嵌段共聚物(aa-10)之製造) (Manufacture of modified conjugated diene block copolymer (aa-10))

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-13)100質量份、順丁烯二酸酐1.5質量份、及Perhexa 25B 0.10質量份，將料筒設定溫度變更為240℃以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-10)。 In addition to changing the components during dry blending to 100 parts by mass of the hydrogenated conjugated diene polymer (a-13) made into pellets, 1.5 parts by mass of maleic anhydride, and 0.10 parts by mass of Perhexa 25B, A maleic anhydride conjugated diene polymer (aa-10) was produced in the same manner as in Production Example 11, except that the cylinder set temperature was changed to 240°C.

[製造例46] [Manufacturing example 46] (改性共軛二烯系嵌段共聚物(aa-11)之製造) (Manufacture of modified conjugated diene block copolymer (aa-11))

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合物(a-13)100質量份、順丁烯二酸酐2.1質量份、及Perhexa 25B 0.14質量份，將料筒設定溫度變更為240℃以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-11)。 In addition to changing the components during dry blending to 100 parts by mass of the hydrogenated conjugated diene polymer (a-13) made into pellets, 2.1 parts by mass of maleic anhydride, and 0.14 parts by mass of Perhexa 25B, A maleic anhydride conjugated diene polymer (aa-11) was produced in the same manner as in Production Example 11, except that the cylinder set temperature was changed to 240°C.

[製造例47] [Manufacturing example 47] (改性共軛二烯系嵌段共聚物(aa-12)之製造) (Manufacture of modified conjugated diene block copolymer (aa-12))

除將乾摻時之各成分變更為製成顆粒狀之經氫化之共軛二烯系聚合 物(a-13)100質量份、順丁烯二酸酐2.1質量份、及Perhexa 25B 0.12質量份，將料筒設定溫度變更為250℃以外，以與製造例11相同之方式製造順丁烯二酸酐共軛二烯系聚合物(aa-12)。 In addition to changing the ingredients during dry blending into pelletized hydrogenated conjugated diene polymers 100 parts by mass of substance (a-13), 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B, except that the preset temperature of the barrel was changed to 250° C., and maleic acid was produced in the same manner as in Production Example 11. Acid anhydride conjugated diene polymer (aa-12).

[製造例48] [Manufacturing example 48] (共軛二烯系聚合物(a-35)之製造) (Manufacture of conjugated diene polymer (a-35))

除變更正丁基鋰量以外，以與製造例1相同之方式製造。關於所獲得之經氫化之共軛二烯系嵌段共聚物(a-35)，苯乙烯含量為32質量%，丁烯量為36mol%，重量平均分子量為3.9萬，分子量分佈為1.2，氫化率為99mol%。 It produced in the same manner as Production Example 1 except changing the amount of n-butyllithium. The obtained hydrogenated conjugated diene block copolymer (a-35) had a styrene content of 32% by mass, a butene content of 36mol%, a weight average molecular weight of 39,000, and a molecular weight distribution of 1.2. The rate is 99mol%.

(聚偏二氟乙烯(a-36)) (polyvinylidene fluoride (a-36))

使用PVDF(聚偏二氟乙烯，KUREHA股份有限公司製造，KF-1100)作為黏著劑(a-36)。 PVDF (polyvinylidene fluoride, manufactured by Kureha Co., Ltd., KF-1100) was used as the adhesive (a-36).

實施例1~實施例85及比較例1~2係依照上述組成製作電極，並進行評價。 Examples 1 to 85 and Comparative Examples 1 to 2 prepared electrodes according to the above composition and evaluated them.

Figure 110148596-A0305-02-0109-2
Figure 110148596-A0305-02-0109-2

Figure 110148596-A0305-02-0109-3
Figure 110148596-A0305-02-0109-3

Figure 110148596-A0305-02-0109-4
Figure 110148596-A0305-02-0109-4

Figure 110148596-A0305-02-0110-5
Figure 110148596-A0305-02-0110-5

Figure 110148596-A0305-02-0110-6
Figure 110148596-A0305-02-0110-6

Figure 110148596-A0305-02-0111-7
Figure 110148596-A0305-02-0111-7

Figure 110148596-A0305-02-0112-8
Figure 110148596-A0305-02-0112-8

Figure 110148596-A0305-02-0113-9
Figure 110148596-A0305-02-0113-9

Figure 110148596-A0305-02-0114-11
Figure 110148596-A0305-02-0114-11

Figure 110148596-A0305-02-0115-12
Figure 110148596-A0305-02-0115-12

Figure 110148596-A0305-02-0116-13
Figure 110148596-A0305-02-0116-13

根據表1之結果可知，實施例1~85係接著性優異且電化學穩定性亦優異之共軛二烯系聚合物，又，含有水分量亦較少，適宜作為全固體電池黏著劑。可知，其中具有改性基之分子量較高之黏著劑之接著性、黏結性、揮發性之平衡優異，即便是如實施例65~80所示般改性基當量較少之分子量較高之黏著劑，亦顯示出較高之黏結性。又，可知，即便改性基較少之黏著劑高分子化，導電助劑之分散性亦優異。又，由實施例21-23、36-38、50-52可知，包含磷化合物之黏著劑之熱穩定性優異。又，由實施例24-25、39-40、53-54可知，金屬殘渣較少之黏著劑之熱穩定性優異。熱穩定性成為使用前之預乾燥時之熱劣化、或電池性能降低之指標。又，由實施例26-30、41-45、55-59可知，壓縮度較低之黏著劑之進料穩定性優異。 又，由實施例31-32、46-47、60-61可知，添加了外潤劑之黏著劑之進料穩定性優異。 According to the results in Table 1, it can be seen that Examples 1-85 are conjugated diene polymers with excellent adhesion and electrochemical stability, and contain less water, and are suitable as all-solid battery adhesives. It can be seen that among them, adhesives with higher molecular weights having modified groups have an excellent balance of adhesiveness, cohesiveness, and volatility. agent, also showed a higher cohesiveness. In addition, it can be seen that the dispersibility of the conductive auxiliary agent is excellent even when the binder having fewer modifying groups is polymerized. Moreover, it can be seen from Examples 21-23, 36-38, and 50-52 that the thermal stability of the adhesive containing the phosphorus compound is excellent. Also, from Examples 24-25, 39-40, and 53-54, it can be seen that the thermal stability of the adhesive with less metal residue is excellent. Thermal stability becomes an indicator of thermal deterioration during pre-drying before use, or degradation of battery performance. Also, from Examples 26-30, 41-45, and 55-59, it can be known that the feed stability of adhesives with lower compressibility is excellent. Also, from Examples 31-32, 46-47, and 60-61, it can be seen that the feed stability of the adhesive added with the wetting agent is excellent.

[產業上之可利用性] [Industrial availability]

本發明之改性共軛二烯系嵌段共聚物具有作為以全固體電池為代表之電池之黏著劑的產業上之可利用性。 The modified conjugated diene block copolymer of the present invention has industrial applicability as an adhesive for batteries represented by all-solid batteries.

Claims (24)

一種全固體電池黏著劑，其含有共軛二烯系聚合物，上述共軛二烯系聚合物具有以乙烯基芳香族單體單元作為主體之聚合物嵌段，且重量平均分子量為4~200萬，上述共軛二烯系聚合物之甲苯不溶分量為10wt%以下。 An all-solid battery adhesive, which contains a conjugated diene polymer, the conjugated diene polymer has a polymer block mainly composed of vinyl aromatic monomer units, and has a weight average molecular weight of 4-200 In one embodiment, the toluene-insoluble content of the conjugated diene polymer is 10% by weight or less. 如請求項1之全固體電池黏著劑，其中上述共軛二烯系聚合物具有改性基，上述改性基為選自由酸酐基、羥基、羰基、羧基、胺基、環氧基、烷氧基矽烷基、醯胺基、胺基甲酸酯基、脲基、異氰酸基、及離子性基所組成之群中之一種以上。 Such as the all-solid battery adhesive of claim 1, wherein the above-mentioned conjugated diene polymer has a modification group, and the above-mentioned modification group is selected from an acid anhydride group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxy One or more of the group consisting of silyl group, amido group, urethane group, urea group, isocyanate group, and ionic group. 如請求項1或2之全固體電池黏著劑，其中上述共軛二烯系聚合物之重量平均分子量為20~80萬。 The all-solid battery adhesive according to claim 1 or 2, wherein the weight average molecular weight of the above-mentioned conjugated diene polymer is 200,000 to 800,000. 如請求項1或2之全固體電池黏著劑，其中上述聚合物嵌段之含量相對於上述共軛二烯系聚合物之總量為40重量%以下。 The all-solid battery adhesive according to claim 1 or 2, wherein the content of the above-mentioned polymer block is 40% by weight or less relative to the total amount of the above-mentioned conjugated diene-based polymer. 如請求項1或2之全固體電池黏著劑，其中共軛二烯單體單元之氫化前之乙烯基鍵量相對於共軛二烯單體單元之合計100mol%為20mol%~60mol%。 The all-solid battery adhesive according to claim 1 or 2, wherein the vinyl bond amount of the conjugated diene monomer unit before hydrogenation is 20mol% to 60mol% relative to the total 100mol% of the conjugated diene monomer unit. 如請求項2之全固體電池黏著劑，其中上述改性基於上述共軛二烯系 聚合物100g中為0.10mmol以上0.50mmol以下。 Such as the all-solid battery adhesive of claim 2, wherein the above-mentioned modification is based on the above-mentioned conjugated diene system It is 0.10 mmol or more and 0.50 mmol or less in 100 g of polymers. 如請求項2之全固體電池黏著劑，其中上述改性基為一級胺基或二級胺基。 The all-solid battery adhesive according to claim 2, wherein the above-mentioned modifying group is a primary amino group or a secondary amino group. 如請求項2之全固體電池黏著劑，其中上述共軛二烯系聚合物之末端或偶合部具有改性基。 The all-solid battery adhesive according to claim 2, wherein the terminal or coupling part of the above-mentioned conjugated diene polymer has a modifying group. 如請求項1或2之全固體電池黏著劑，其中上述共軛二烯系聚合物具有以上述共軛二烯單體單元作為主體之聚合物嵌段。 The all-solid battery adhesive according to claim 1 or 2, wherein the above-mentioned conjugated diene polymer has a polymer block mainly composed of the above-mentioned conjugated diene monomer unit. 如請求項1或2之全固體電池黏著劑，其中上述共軛二烯系聚合物為經氫化者。 The all-solid battery adhesive according to claim 1 or 2, wherein the above-mentioned conjugated diene polymer is hydrogenated. 如請求項1或2之全固體電池黏著劑，其中上述共軛二烯單體單元之丁烯量及/或丙烯量相對於共軛二烯單體單元之合計100mol%為20mol%~60mol%，上述共軛二烯系聚合物具有以共軛二烯單體單元作為主體之聚合物嵌段。 The all-solid battery adhesive according to claim 1 or 2, wherein the amount of butene and/or propylene in the above-mentioned conjugated diene monomer units is 20mol%~60mol% relative to the total 100mol% of the conjugated diene monomer units , the conjugated diene polymer has a polymer block mainly composed of conjugated diene monomer units. 如請求項1或2之全固體電池黏著劑，其中上述共軛二烯系聚合物之鬆裝比重為0.15g/cm3以上，壓縮度未達30，且為粉末、或屑粒形狀。 The all-solid battery adhesive according to claim 1 or 2, wherein the above-mentioned conjugated diene polymer has a bulk specific gravity of 0.15 g/cm 3 or more, a degree of compression of less than 30, and is in the shape of powder or crumbs. 如請求項1或2之全固體電池黏著劑，其中上述共軛二烯系聚合物中之過渡金屬元素與Al、Li、Fe、Zn、及Mg之合計含量以原子換算計，相對於共軛二烯系聚合物為200ppm以下。 The all-solid battery adhesive of claim 1 or 2, wherein the total content of the transition metal element and Al, Li, Fe, Zn, and Mg in the above-mentioned conjugated diene polymer is calculated in atomic conversion, relative to the conjugated diene polymer. The diene-based polymer is 200 ppm or less. 如請求項1或2之全固體電池黏著劑，其包含上述共軛二烯系聚合物及磷化合物，且磷化合物之含量以磷原子換算計，相對於共軛二烯系聚合物為10ppm以上。 The all-solid battery adhesive according to claim 1 or 2, which includes the above-mentioned conjugated diene polymer and a phosphorus compound, and the content of the phosphorus compound is calculated in terms of phosphorus atoms, relative to the conjugated diene polymer is 10ppm or more . 如請求項1或2之全固體電池黏著劑，其包含上述共軛二烯系聚合物、二氧化矽及/或高級脂肪酸金屬鹽及/或聚烯烴及/或脂肪醯胺。 The all-solid battery adhesive according to claim 1 or 2, which includes the above-mentioned conjugated diene polymer, silicon dioxide and/or higher fatty acid metal salt and/or polyolefin and/or fatty amide. 如請求項1或2之全固體電池黏著劑，其中上述共軛二烯系聚合物具有異戊二烯作為共軛二烯系聚合物單元。 The all-solid battery adhesive according to claim 1 or 2, wherein the conjugated diene polymer has isoprene as a unit of the conjugated diene polymer. 如請求項1或2之全固體電池黏著劑，其中水分量為200ppm以下。 The all-solid battery adhesive of claim 1 or 2, wherein the moisture content is below 200ppm. 一種漿料，其包含如請求項1至17中任一項之全固體電池黏著劑，且水分量為200ppm以下。 A slurry comprising the all-solid battery adhesive according to any one of claims 1 to 17, and the moisture content is below 200ppm. 一種正極層，其包含：如請求項1至17中任一項之全固體電池黏著劑、及正極活性物質，且水分量為200ppm以下。 A positive electrode layer, which includes: the all-solid battery adhesive according to any one of claims 1 to 17, and a positive electrode active material, and the moisture content is less than 200ppm. 一種固體電解質層，其包含：如請求項1至17中任一項之全固體電池黏著劑、及離子傳導性之固體電解質，且水分量為200ppm以下。 A solid electrolyte layer, comprising: the all-solid battery adhesive according to any one of claims 1 to 17, and an ion-conductive solid electrolyte, and the moisture content is 200ppm or less. 一種負極層，其包含：如請求項1至17中任一項之全固體電池黏著劑、及負極活性物質，且水分量為200ppm以下。 A negative electrode layer, comprising: the all-solid battery adhesive according to any one of claims 1 to 17, and a negative electrode active material, and the moisture content is below 200ppm. 一種全固體電池，其包含：如請求項19之正極層、如請求項20之固體電解質層、及如請求項21之負極層中之至少一層。 An all-solid battery, comprising: at least one of the positive electrode layer according to claim 19, the solid electrolyte layer according to claim 20, and the negative electrode layer according to claim 21. 如請求項22之全固體電池，其中水分量為200ppm以下。 The all-solid battery as claimed in claim 22, wherein the moisture content is below 200ppm. 一種製造包含全固體電池黏著劑之正極層、固體電解質層及負極層中之至少一層之方法，上述全固體電池黏著劑之水分量為200ppm以下，上述製造方法具有如下步驟：製備包含共軛二烯系聚合物及溶劑之漿料，該共軛二烯系聚合物具有共軛二烯單體單元、以乙烯基芳香族單體單元作為主體之聚合物嵌段、及改性基，且水分量為1wt%以下；以及 將上述漿料塗佈於基材並加以乾燥；上述共軛二烯系聚合物之甲苯不溶分量為10wt%以下。 A method for manufacturing at least one of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer comprising an all-solid battery adhesive. The moisture content of the above-mentioned all-solid battery adhesive is below 200ppm. A slurry of an ethylenic polymer and a solvent, the conjugated diene polymer has a conjugated diene monomer unit, a polymer block mainly composed of a vinyl aromatic monomer unit, and a modification group, and moisture An amount of 1 wt% or less; and The above slurry is coated on the substrate and dried; the toluene insoluble content of the above conjugated diene polymer is 10wt% or less.
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