JP2006066400A - Organic solvent based binder composition, electrode, and battery - Google Patents

Organic solvent based binder composition, electrode, and battery Download PDF

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JP2006066400A
JP2006066400A JP2005246826A JP2005246826A JP2006066400A JP 2006066400 A JP2006066400 A JP 2006066400A JP 2005246826 A JP2005246826 A JP 2005246826A JP 2005246826 A JP2005246826 A JP 2005246826A JP 2006066400 A JP2006066400 A JP 2006066400A
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unsaturated carboxylic
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JP4380608B2 (en
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Koichiro Maeda
耕一郎 前田
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Zeon Corp
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    • YGENERAL 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
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    • Y02E60/10Energy storage using batteries

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder for manufacturing a battery which has a large initial capacity, hardly peels off carbonaceous active materials from an electrode even when charge and discharge are repeated and fixes a large amount of the active materials to the electrode. <P>SOLUTION: The battery is manufactured using the electrode with an active material layer formed therein. The active layer is formed by dispersing active materials into an organic solvent based binder composition consisting of latex particles and a polar organic solvent (preferably N-methyl pyrrolidone), and by applying the active material to an electrode base and drying the base. The latex particles are obtained by copolymerizing an aromatic vinyl monomer not containing elements other than carbon and hydrogen (for example, styrene) of 25-60 wt%, a conjugated diene monomer not containing elements other than carbon and hydrogen (for example, butadiene) of 15-50 wt%, ethylenic unsaturated carboxylic acid ester (for example, methyl methacrylate) of 0-40 wt%, an unsaturated carboxylic monomer (for example, itaconic acid) of 0-40 wt% with the total amount of the ethylenic unsaturated carboxylic acid ester monomer and the unsaturated carboxylic acid monomer of 15-40 wt%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、電池用バインダー組成物に関し、さらに詳しくは、活物質を多量に用いることができ、電池の初期容量を大きくでき、充放電を繰り返しても活物質が脱落し難いため、電池の容量低下が小さい電池用有機溶媒系バインダー組成物に関する。   The present invention relates to a binder composition for a battery. More specifically, the active material can be used in a large amount, the initial capacity of the battery can be increased, and the active material does not easily fall off even after repeated charge and discharge. The present invention relates to an organic solvent-based binder composition for batteries having a small decrease.

電池用バインダーは、電極に活物質を固定するのに用いられる。電池の容量は、活物質の種類、量、電解液の種類、量などの複数の要因によって決められるが、バインダーが充分量の活物質を電極に固定できないと初期容量の大きな電池が得られず、また、充放電を繰り返すことなどによって電極から活物質が脱落するに従って電池の容量は低下する。   The battery binder is used to fix the active material to the electrode. The capacity of the battery is determined by multiple factors such as the type and amount of the active material, the type and amount of the electrolyte, but if the binder cannot fix a sufficient amount of active material to the electrode, a battery with a large initial capacity cannot be obtained. In addition, the capacity of the battery decreases as the active material is removed from the electrode due to repeated charging and discharging.

電池用バインダーは、通常、バインダーを溶媒に溶解したバインダー組成物に活物質を分散させて、電極に塗布し、溶媒を揮発させ、バインダー構造中に活物質が固定された状態にすることにより、電極表面に活物質を固定する。   The binder for a battery is usually obtained by dispersing an active material in a binder composition in which the binder is dissolved in a solvent, coating the electrode, volatilizing the solvent, and fixing the active material in the binder structure. An active material is fixed on the electrode surface.

バインダー組成物には、有機溶媒系バインダー組成物と水系バインダー組成物の二種類がある。有機溶媒系バインダー組成物としては、通常、ポリビニリデンフルオライドをN−メチルピロリドンに溶解したものが用いられいる(例えば、特開平4−249860号公報など)。この有機溶媒系バインダー組成物にに活物質を分散させたスラリーを電極基体に塗布して、N−メチルピロリドンを除去して製造した電極を用いると電池の初期容量を大きくすることができるが、この電極を用いた電池で充放電を繰り返すと電極に固定された活物質が脱落しやすいという問題がある。   There are two types of binder compositions: organic solvent-based binder compositions and water-based binder compositions. As the organic solvent-based binder composition, one obtained by dissolving polyvinylidene fluoride in N-methylpyrrolidone is generally used (for example, JP-A-4-249860). When an electrode manufactured by applying a slurry in which an active material is dispersed in this organic solvent binder composition to an electrode substrate and removing N-methylpyrrolidone is used, the initial capacity of the battery can be increased. When charging / discharging is repeated in a battery using this electrode, there is a problem that the active material fixed to the electrode tends to fall off.

一方、水系バインダー組成物としては、通常、SBRラテックス(スチレン、ブタジエンを共重合したゴムのラテックス)の水分散液に増粘剤としてカルボキシルメチルセルロースなどを添加したものが用いられており(例えば、特開平5−21068号公報、特開平5−74461号公報など)、これを用いて電極に活物質を固定した電池では充放電を繰り返しても活物質が脱落しにくいが、十分量の増粘剤を使用するとそれだけ活物質の割合が減り、固定される活物質の量が経る。また、多くの電池に用いられている炭素質活物質では、水と炭素が接触するために、炭素表面に水酸基が多く結合し、その影響で初期容量が低下するという問題があった。   On the other hand, as an aqueous binder composition, usually an aqueous dispersion of SBR latex (rubber latex copolymerized with styrene and butadiene) added with carboxymethyl cellulose or the like as a thickener is used (for example, special In a battery in which an active material is fixed to an electrode using this, the active material is unlikely to fall off even after repeated charge and discharge, but a sufficient amount of thickener. When using, the proportion of the active material is reduced accordingly, and the amount of the active material to be fixed passes. In addition, carbonaceous active materials used in many batteries have a problem in that since water and carbon come into contact with each other, many hydroxyl groups are bonded to the carbon surface, and the initial capacity decreases due to the influence.

また、スチレンとブタジエンからなるSBRラテックスは、水分散系で製造されるが、水分を除去した後はゲル化してしまい、非極性有機溶媒では膨潤するが分散せず、極性有機溶媒では固体のままで分散しなかいため、有機溶媒系バインダー組成物には用いられなかった。   SBR latex composed of styrene and butadiene is produced in an aqueous dispersion, but after removing water, it gels and swells in a nonpolar organic solvent but does not disperse, and remains solid in a polar organic solvent. It was not used in the organic solvent binder composition.

本発明の目的は、初期容量が大きく、充放電を繰り返しても炭素質活物質が電極から剥離しにくく、活物質を多量が電極に固定した電池を製造できるようにすることにある。   An object of the present invention is to make it possible to manufacture a battery in which a large amount of active material is fixed to an electrode because the initial capacity is large and the carbonaceous active material is difficult to peel from the electrode even after repeated charge and discharge.

本発明者らは、鋭意努力の結果、特定のSBR系ラテックスが有機溶媒に分散でき、また、バインダーとして活物質を十分強固に電極基体に固定できることを見い出し、本発明を完成させるに至った。かくして、本発明によれば、芳香族ビニル系単量体25〜60重量%、共役ジエン系単量体15〜50重量%、エチレン性不飽和カルボン酸エステル0〜40重量%、および不飽和カルボン酸系単量体0〜40重量%、かつエチレン性不飽和カルボン酸エステル系単量体と不飽和カルボン酸系単量体の合計量が15〜40重量%の単量体を共重合したラテックス粒子と極性有機溶媒からなる有機溶媒系バインダー組成物、該バインダー組成物と活物質を混合し電極基体表面に塗布し有機溶媒を除去した電極、および電極が該電極である電池が提供される。   As a result of diligent efforts, the present inventors have found that a specific SBR latex can be dispersed in an organic solvent, and that an active material can be fixed sufficiently firmly on an electrode substrate as a binder, and the present invention has been completed. Thus, according to the present invention, the aromatic vinyl-based monomer 25-60 wt%, the conjugated diene monomer 15-50 wt%, the ethylenically unsaturated carboxylic acid ester 0-40 wt%, and the unsaturated carboxylic acid Latex obtained by copolymerization of 0 to 40% by weight of an acid monomer and a monomer having a total amount of ethylenically unsaturated carboxylic acid ester monomer and unsaturated carboxylic acid monomer of 15 to 40% by weight Provided are an organic solvent-based binder composition comprising particles and a polar organic solvent, an electrode obtained by mixing the binder composition and an active material and applying the mixture to the surface of an electrode substrate to remove the organic solvent, and a battery in which the electrode is the electrode.

本発明のバインダー組成物を用いた場合、電池の初期容量を大きくでき、充放電を繰り返しても活物質が脱落し難いため、電池の容量低下が小さい電池が製造できる。   When the binder composition of the present invention is used, the initial capacity of the battery can be increased, and the active material is unlikely to fall off even after repeated charge and discharge, so that a battery with a small decrease in battery capacity can be produced.

(SBR系ラテックス)本発明に用いるSBR系ラテックスは、芳香族ビニル系単量体25〜60重量%、共役ジエン系単量体15〜50重量%、エチレン性不飽和カルボン酸エステル0〜40重量%、および不飽和カルボン酸系単量体0〜40重量%、かつエチレン性不飽和カルボン酸エステル系単量体と不飽和カルボン酸系単量体の合計量が15〜40重量%の単量体を共重合したものである。   (SBR latex) The SBR latex used in the present invention is composed of 25 to 60% by weight of an aromatic vinyl monomer, 15 to 50% by weight of a conjugated diene monomer, and 0 to 40% by weight of an ethylenically unsaturated carboxylic acid ester. %, And an unsaturated carboxylic acid monomer of 0 to 40% by weight, and a total amount of ethylenically unsaturated carboxylic acid ester monomer and unsaturated carboxylic acid monomer of 15 to 40% by weight The body is copolymerized.

本発明に用いる芳香族ビニル系単量体は、炭素、水素以外の元素を含有していないものであり、スチレン、α−メチルスチレン、β−メチルスチレンなどが例示される。炭素、水素以外の元素を含有している場合は重合が阻害されたり、電池の充放電の機能を阻害したりする。共重合させる全単量体中の割合は、25重量%以上、好ましくは30重量%以上、かつ60重量%以下、好ましくは55重量%以下である。芳香族ビニル系単量体の共重合割合が小さすぎるとSBR系ラテックスの強度が不足し、活物質が脱落しやすくなり、大きすぎるとSBR系ラテックスの柔軟性が低下するため、充放電の際の電極表面の体積変化などによって活物質が脱落しやすくなる。   The aromatic vinyl monomer used in the present invention does not contain elements other than carbon and hydrogen, and examples thereof include styrene, α-methylstyrene, β-methylstyrene and the like. When elements other than carbon and hydrogen are contained, polymerization is inhibited, or the function of charge / discharge of the battery is inhibited. The proportion of all monomers to be copolymerized is 25% by weight or more, preferably 30% by weight or more and 60% by weight or less, preferably 55% by weight or less. If the copolymerization ratio of the aromatic vinyl monomer is too small, the strength of the SBR latex will be insufficient and the active material will easily fall off. If it is too large, the flexibility of the SBR latex will be reduced. The active material easily falls off due to the volume change of the electrode surface.

本発明に用いる共役ジエン系単量体は、炭素、水素以外の元素を含有していないものであり、ブタジエン、ピペリレンなどが例示される。炭素、水素以外の元素を含有していると、通常共役しておらず、またクロロプレンのように共役している場合には電池の充放電の機能を阻害することがある。また、α位の炭素に水素が結合していないものを用いたSBR系ラテックスをバインダーとすると、電解液と反応して分解することがあり、バインダーとしての機能が低下し、また、電池としての機能も阻害することがあるので、α位の炭素に水素が結合したものを用いることが好ましい。共重合させる全単量体中の割合は、15重量%以上、好ましくは25重量%以上、かつ50重量%以下、好ましくは45重量%以下である。共役ジエン系単量体の共重合割合が小さすぎるとSBR系ラテックスの柔軟性が不足し、活物質が脱落しやすくなり、大きすぎるとSBR系ラテックスの強度が低下するため、やはり活物質が脱落しやすくなる。   The conjugated diene monomer used in the present invention does not contain elements other than carbon and hydrogen, and examples thereof include butadiene and piperylene. When elements other than carbon and hydrogen are contained, they are not usually conjugated, and when they are conjugated like chloroprene, the charge / discharge function of the battery may be hindered. In addition, when an SBR latex using hydrogen that is not bonded to α-position carbon is used as a binder, it may be decomposed by reacting with the electrolytic solution, and the function as a binder is reduced. Since the function may be hindered, it is preferable to use those in which hydrogen is bonded to the α-position carbon. The proportion of all monomers to be copolymerized is 15% by weight or more, preferably 25% by weight or more and 50% by weight or less, preferably 45% by weight or less. If the copolymerization ratio of the conjugated diene monomer is too small, the flexibility of the SBR latex is insufficient, and the active material tends to fall off. If it is too large, the strength of the SBR latex decreases, so the active material also falls off. It becomes easy to do.

本発明に用いるエチレン性不飽和カルボン酸エステル系単量体としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、クロトン酸エチル、イソクロトン酸エチル、ヒドロキシエチルアクリレート、ヒドロキシエチルメタアクリレートなどが例示され、共重合させる全単量体中の割合は、0重量%以上、40重量%以下、好ましくは30重量%以下である。エチレン性不飽和カルボン酸エステル系単量体の共重合割合が大きすぎるとSBR系ラテックスの柔軟性が低下するため、活物質が脱落しやすくなる。   Examples of the ethylenically unsaturated carboxylic acid ester monomer used in the present invention include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl crotonate, ethyl isocrotonate, Hydroxyethyl acrylate, hydroxyethyl methacrylate and the like are exemplified, and the proportion in the total monomers to be copolymerized is 0% by weight or more and 40% by weight or less, preferably 30% by weight or less. If the copolymerization ratio of the ethylenically unsaturated carboxylic acid ester monomer is too large, the flexibility of the SBR latex is lowered, so that the active material is easily removed.

本発明に使用する不飽和カルボン酸系単量体としては、マレイン酸、フマル酸、シトラコン酸、メサコン酸、グルタコン酸、イタコン酸などの不飽和ジカルボン酸系単量体; アクリル酸、メタクリル酸などの不飽和カルボン酸系単量体;などが例示され、SBR系ラテックスの強度、柔軟性の点から不飽和ジカルボン酸系単量体が好ましい。共重合させる全単量体中の割合は、0重量%以上、かつ40重量%以下、好ましくは35重量%以下である。やはり、不飽和カルボン酸も共重合割合が小さすぎるとSBR系ラテックスの柔軟性が不足し、活物質が脱落しやすくなる。   Examples of the unsaturated carboxylic acid monomer used in the present invention include unsaturated dicarboxylic acid monomers such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, itaconic acid; acrylic acid, methacrylic acid, etc. And unsaturated dicarboxylic acid monomers are preferred from the viewpoint of the strength and flexibility of the SBR latex. The proportion of all monomers to be copolymerized is 0% by weight or more and 40% by weight or less, preferably 35% by weight or less. Again, if the copolymerization ratio of the unsaturated carboxylic acid is too small, the flexibility of the SBR latex is insufficient and the active material tends to fall off.

また、アクリロニトリルなどのニトリル基を有するものを全単量体中好ましくは5重量%以上、より好ましくは10重量%以上用いると、後述のように最も広く使用されている極性有機溶媒であるN−メチルピロリドンにSBR系ラテックスが分散させやすくなる。なお、アクリロニトリルは好ましくは30重量%以下用いる。アクリロニトリルが多すぎるとSBR系ラテックスの柔軟性が低下するため、活物質が脱落しやすくなる場合がある。   In addition, when a monomer having a nitrile group such as acrylonitrile is preferably used in an amount of not less than 5% by weight, more preferably not less than 10% by weight, N— which is the most widely used polar organic solvent as described later. SBR latex is easily dispersed in methylpyrrolidone. Acrylonitrile is preferably used in an amount of 30% by weight or less. If there is too much acrylonitrile, the flexibility of the SBR latex decreases, and the active material may easily fall off.

また、エチレン性不飽和カルボン酸エステル系単量体と不飽和カルボン酸系単量体の合計量、アクリロニトリルを用いる場合は、エチレン性不飽和カルボン酸エステル系単量体、不飽和カルボン酸系単量体及びアクリロニトリルの合計量が15重量%以上、好ましくは20重量%以上、40重量%以下、好ましくは35重量%以下である。この合計量が大きすぎるとSBR系ラテックスの柔軟性が不足し、活物質が脱落しやすくなり、小さすぎるとSBR系ラテックスが有機溶媒中に分散しにくく、電極基体に塗布し難く、活物質も脱落しやすく、使用に適さない。   In addition, the total amount of the ethylenically unsaturated carboxylic acid ester monomer and the unsaturated carboxylic acid monomer, and when acrylonitrile is used, the ethylenically unsaturated carboxylic acid ester monomer, the unsaturated carboxylic acid monomer The total amount of the monomer and acrylonitrile is 15% by weight or more, preferably 20% by weight or more and 40% by weight or less, preferably 35% by weight or less. If this total amount is too large, the flexibility of the SBR latex will be insufficient, and the active material will easily fall off. If it is too small, the SBR latex will be difficult to disperse in the organic solvent and difficult to apply to the electrode substrate. It is easy to fall off and is not suitable for use.

本発明においてはSBR系ラテックスの合成方法は特に限定されず、通常は乳化重合法により重合され、その粒径も特に限定されず、平均で、好ましくは0.01μm以上、かつ好ましくは0.5μm以下、より好ましくは0.3μm以下である。小さすぎるとバインダーとして性能が低下し、大きすぎると活物質層の表面に不活性な部分が多くなり電池の性能が低下する。   In the present invention, the method for synthesizing the SBR latex is not particularly limited, and is usually polymerized by an emulsion polymerization method, and the particle size thereof is not particularly limited, and is preferably 0.01 μm or more and preferably 0.5 μm on average. Below, more preferably 0.3 μm or less. If it is too small, the performance as a binder is lowered, and if it is too large, there are many inactive portions on the surface of the active material layer, and the performance of the battery is lowered.

また、SBR系ラテックスは、ゲル含量が好ましくは75重量%以上、より好ましくは80重量%以上、かつ100重量%以下のものである。ここでゲル含量はトルエンに対する不溶分をいう。ゲル含量が少なすぎると電極基体に固定しにくくなり、電解液に膨潤しやすくなる。   The SBR latex has a gel content of preferably 75% by weight or more, more preferably 80% by weight or more and 100% by weight or less. Here, the gel content refers to an insoluble content in toluene. When the gel content is too small, it is difficult to fix the gel content to the electrode substrate, and the gel solution easily swells.

(極性有機溶媒)本発明に用いる極性有機溶媒は、炭素、水素以外の元素を含有する有機溶媒であって、活物質の機能を低下させにくいことから、活性水素を有していないものが好ましく、具体的には、アセトニトリル、N−メチルピロリドン、アセチルピリジン、シクロペンタノン、ジメチルフォルムアミド、ジメチルスルフォキシド、メチルフォルムアミド、メチルエチルケトン、フルフラール、エチレンジアミンなどが例示される。これらの中でも、バインダー組成物用の溶媒として、SBR系ラテックスの分散性、取扱いやすさ、安全性、合成の容易さなどのバランスから、N−メチルピロリドンが最も好ましい。   (Polar organic solvent) The polar organic solvent used in the present invention is an organic solvent containing an element other than carbon and hydrogen, and since it is difficult to lower the function of the active material, it preferably has no active hydrogen. Specifically, acetonitrile, N-methylpyrrolidone, acetylpyridine, cyclopentanone, dimethylformamide, dimethylsulfoxide, methylformamide, methyl ethyl ketone, furfural, ethylenediamine and the like are exemplified. Among these, as a solvent for the binder composition, N-methylpyrrolidone is most preferable from the balance of the dispersibility of SBR latex, ease of handling, safety, ease of synthesis, and the like.

(バインダー組成物)本発明のバインダー組成物は、SBR系ラテックスを極性有機溶媒に分散させたものであって、SBR系ラテックスの濃度が10重量%以上、好ましくは20重量%以上、かつ60重量%以下、好ましくは50重量%以下のものである。SBR系ラテックス濃度が小さすぎると塗布しやすい濃度に調整しにくく、大きすぎると粘度が高くなりすぎ、SBR系ラテックスが凝集しやすくなる。   (Binder composition) The binder composition of the present invention is obtained by dispersing SBR latex in a polar organic solvent, and the concentration of SBR latex is 10 wt% or more, preferably 20 wt% or more, and 60 wt%. % Or less, preferably 50% by weight or less. If the SBR latex concentration is too small, it is difficult to adjust the concentration to be easy to apply, and if it is too large, the viscosity becomes too high and the SBR latex tends to aggregate.

なお、SBR系ラテックスは、通常水系溶媒中で製造する。そのため、水系溶媒を除去する必要がある。用いる極性有機溶媒の沸点が水よりも高いものであれば、極性有機溶媒を加えてエバポレーターなどを用いて水を蒸発させて除去すればよい。用いる極性有機溶媒の沸点が水より低い場合は、例えば、極性有機溶媒を加えて水と共沸させてエバポレーターなどによりある程度水の量を減らした後にモレキュラーシーブなど吸水剤を用いたり、逆浸透膜を用いて水分を除去すればよい。   The SBR latex is usually produced in an aqueous solvent. Therefore, it is necessary to remove the aqueous solvent. If the polar organic solvent to be used has a boiling point higher than that of water, the polar organic solvent may be added and water removed by evaporation using an evaporator or the like. When the boiling point of the polar organic solvent used is lower than that of water, for example, after adding a polar organic solvent to azeotrope with water and reducing the amount of water to some extent with an evaporator, a water absorbent such as molecular sieve is used, or a reverse osmosis membrane The water may be removed using

(電極)本発明の電極は、本発明のバインダー組成物に活物質を配合してスラリーを調製し、電極基体に塗布し、溶媒を除去して、電極基体表面に形成された活物質層のマトリックス中に活物質を固定したものである。   (Electrode) The electrode of the present invention is an active material layer formed on the surface of the electrode substrate by preparing a slurry by blending the active material with the binder composition of the present invention, applying the slurry to the electrode substrate, removing the solvent. An active material is fixed in a matrix.

本発明で用いる活物質は、活物質として機能する限り特に限定されず、通常は、負極活物質として炭素を用い、正極活物質としてモリブデン、バナジウム、チタン、ニオブなどの酸化物、硫化物、セリン化物などのほか、リチウムマンガン酸化物、リチウムコバルト酸化物、リチウムニッケル酸化物、リチウム鉄酸化物などのリチウム含有複合酸化物などが用いられる。   The active material used in the present invention is not particularly limited as long as it functions as an active material. Usually, carbon is used as a negative electrode active material, and oxides such as molybdenum, vanadium, titanium, niobium, sulfide, serine are used as a positive electrode active material. In addition to chemical compounds, lithium-containing composite oxides such as lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, and lithium iron oxide are used.

本発明に用いるスラリーの活物質量も特に限定されないが、SBR系ラテックス量に対して、重量基準で好ましくは10倍以上、より好ましくは15倍以上、かつ1000倍以下、より好ましくは100倍以下になるようバインダー組成物に活物質を配合したものである。活物質量が少なすぎると活物質層表面に不活性な部分が多くなり、電極としての機能が不十分となることがあり、活物質量が多すぎると活物質が電極基体に十分に固定されずに脱落しやすくなる。なお、スラリーは、溶媒を追加して、塗布しやすい濃度にして使用する。   The amount of the active material of the slurry used in the present invention is not particularly limited, but is preferably 10 times or more, more preferably 15 times or more and 1000 times or less, more preferably 100 times or less, based on the weight of the SBR latex amount. An active material is blended in the binder composition. If the amount of the active material is too small, there are many inactive parts on the surface of the active material layer, and the function as an electrode may be insufficient. If the amount of the active material is too large, the active material is sufficiently fixed to the electrode substrate. It will be easy to drop off. In addition, the slurry is used by adding a solvent to a concentration that facilitates coating.

本発明に用いる電極基体は導電性材料からなるものであれば特に限定されないが、一般には鉄、銅、アルミニウムなどの金属製のものを用いる。形状も特に限定されないが、電極表面積が大きいものが好ましいことから、通常、厚さ0.05〜0.5mm程度のシートを用いる。   The electrode substrate used in the present invention is not particularly limited as long as it is made of a conductive material, but generally a metal substrate such as iron, copper or aluminum is used. Although the shape is not particularly limited, a sheet having a thickness of about 0.05 to 0.5 mm is usually used because a large electrode surface area is preferable.

塗布する方法は特に限定されない。例えば、浸漬、ハケ塗りなどによって塗布される。塗布する量は、有機溶媒を除去した後に形成される活物質層の厚さが好ましくは0.1mm以上、より好ましくは0.5mm以上、好ましくは5mm以下、より好ましくは2mm以下になるようにする。有機溶媒を除去する方法も特に限定されないが、通常は、応力集中が起こって活物質層に亀裂がはいったり、電極基体から剥離したりしない程度の速度範囲で、できるだけ早く有機溶媒が揮発するように、減圧の程度、加熱の程度を調整して有機溶媒を除去する。   The method for applying is not particularly limited. For example, it is applied by dipping or brushing. The amount to be applied is such that the thickness of the active material layer formed after removing the organic solvent is preferably 0.1 mm or more, more preferably 0.5 mm or more, preferably 5 mm or less, more preferably 2 mm or less. To do. The method for removing the organic solvent is not particularly limited, but usually the organic solvent volatilizes as quickly as possible within a speed range that does not cause stress concentration and cracks in the active material layer or peeling from the electrode substrate. In addition, the organic solvent is removed by adjusting the degree of decompression and the degree of heating.

(電池)本発明の電池は電極として本発明の電極を用いたものである。大型の電池の場合には、電極をテープ状のものとし、負電極と正電極の間にセパレーター・シートを挟みこんで巻回し、電解液に満たしたケース中に浸漬するなどの方法で、また小型電池の場合には、電極を円状のシートにして電解液を満たしたコイン型ケース中に浸漬するなどの方法で電池として使用しやすく、かつ大きな容量のものが得られるようにすることができる。   (Battery) The battery of the present invention uses the electrode of the present invention as an electrode. In the case of a large battery, the electrode is tape-shaped, the separator sheet is sandwiched between the negative electrode and the positive electrode, wound, and immersed in a case filled with the electrolytic solution. In the case of a small battery, it is easy to use it as a battery by immersing it in a coin-shaped case filled with an electrolyte solution by making the electrode into a circular sheet, and to obtain a battery with a large capacity. it can.

電解液も特に限定されず、負極活物質、正極活物質の種類に応じて、電池としての機能を発揮するものを選択すればよい。例えば、電解質として、LiClO、LiBF、CFSOLi、LiI、LiAlCl、LiPF、NaClO、NaBF、NaI、(n−Bu)NClOなどが例示され、溶媒として、エーテル類、ケトン類、ラクトン類、ニトリル類、アミン類、アミド類、硫黄化合物類、塩素化炭化水素類、エステル類、カーボネート類、ニトロ化合物類、リン酸エステル系化合物類、スルホラン系化合物類などが例示され、一般には、エチレンカーボネートやジエチルカーボネートなどが広く使用されている。 There is no particular limitation on the electrolytic solution, and a material that functions as a battery may be selected according to the types of the negative electrode active material and the positive electrode active material. Examples of the electrolyte include LiClO 4 , LiBF 4 , CF 3 SO 3 Li, LiI, LiAlCl 4 , LiPF 6 , NaClO 4 , NaBF 4 , NaI, (n-Bu) 4 NClO 4, and the like as the solvent. , Ketones, lactones, nitriles, amines, amides, sulfur compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, phosphate ester compounds, sulfolane compounds, etc. In general, ethylene carbonate and diethyl carbonate are widely used.

(態様)本発明の態様としては、(1)芳香族ビニル系単量体25〜60重量%、共役ジエン系単量体15〜50重量%、エチレン性不飽和カルボン酸エステル0〜40重量%、および不飽和カルボン酸系単量体0〜40重量%、かつエチレン性不飽和カルボン酸エステル系単量体と不飽和カルボン酸系単量体の合計量が15〜40重量%の単量体を共重合したラテックス粒子と極性有機溶媒からなる有機溶媒系バインダー組成物、(2)芳香族ビニル系単量体が、炭素、水素以外の元素を含有していないものである(1)記載の組成物、(3)共役ジエン系単量体が、炭素、水素以外の元素を含有していないものである(1)〜(2)記載の組成物、(4)共役ジエン系単量体が、α位の炭素に水素が結合したものである(1)〜(3)記載の組成物、(5)エチレン性不飽和カルボン酸エステル系単量体量が全単量体中5〜40重量%共重合させ、その内のニトリル基を有するもの全単量体に対して5〜40重量%である(1)〜(4)記載の組成物、(6)不飽和カルボン酸系単量体が不飽和ジカルボン酸系単量体である(1)〜(5)記載の組成物、(7)芳香族ビニル系単量体25〜60重量%、共役ジエン系単量体15〜50重量%、エチレン性不飽和カルボン酸エステル0〜40重量%、不飽和カルボン酸系単量体0〜40重量%、およびアクリロニトリル5〜30重量%、かつエチレン性不飽和カルボン酸エステル系単量体、不飽和カルボン酸系単量体、アクリロニトリルの合計量が15〜40重量%の単量体を共重合したラテックス粒子と極性有機溶媒からなる有機溶媒系バインダー組成物、さらに、アクリロニトリルを5〜30重量%共重合し、(8)SBR系ラテックスが平均粒径0.01〜0.5μmのものである(1)〜(7)記載の組成物、(9)SBR系ラテックスがゲル含量が75〜100重量%のものである(1)〜(8)記載の組成物、(10)極性有機溶媒が炭素、水素以外の元素を含有する有機溶媒である(1)〜(9)記載の組成物、(11)極性有機溶媒が活性水素を有していないものである(1)〜(10)記載の組成物、(12)極性有機溶媒がアセトニトリル、N−メチルピロリドン、アセチルピリジン、シクロペンタノン、ジメチルフォルムアミド、ジメチルスルフォキシド、メチルフォルムアミド、メチルエチルケトン、フルフラール、およびエチレンジアミンから選ばれたものである(1)〜(11)記載の組成物、(13)極性有機溶媒がN−メチルピロリドンである(1)〜(12)記載の組成物、(14)(1)〜(13)記載の組成物に、該組成物中のSBR系ラテックス量に対して、重量基準で10〜1000倍活物質を添加したスラリー、(15)さらに極性有機溶媒を追加した(14)記載のスラリー、(16)(14)〜(15)記載のスラリーを、電極基体表面に塗布し、極性有機溶媒を除去して活物質層を形成した電極、(17)電極基体が金属製のものである(16)記載の電極、(18)電極基体が厚さ0.05〜0.5mmのシートである(17)記載に電極、(19)活物質層が厚さ0.05〜2mmのものである(18)記載の電極、(20)電極が(16)〜(19)記載のものである電池、などが挙げられる。   (Aspect) As an aspect of the present invention, (1) 25 to 60% by weight of aromatic vinyl monomer, 15 to 50% by weight of conjugated diene monomer, 0 to 40% by weight of ethylenically unsaturated carboxylic acid ester , And an unsaturated carboxylic acid monomer of 0 to 40% by weight, and a total amount of ethylenically unsaturated carboxylic acid ester monomer and unsaturated carboxylic acid monomer of 15 to 40% by weight (1) The organic solvent-based binder composition comprising latex particles copolymerized with a polar organic solvent, and (2) the aromatic vinyl-based monomer does not contain elements other than carbon and hydrogen. (3) The composition according to (1) to (2), wherein the conjugated diene monomer does not contain elements other than carbon and hydrogen, and (4) the conjugated diene monomer. (1) to (3), wherein hydrogen is bonded to the α-position carbon. (5) The amount of the ethylenically unsaturated carboxylic acid ester-based monomer is 5 to 40% by weight of the total monomer, and the nitrile group is 5% based on the total monomer. The composition according to (1) to (4), which is -40% by weight, and the composition according to (1) to (5), wherein the unsaturated carboxylic acid monomer is an unsaturated dicarboxylic acid monomer. (7) 25 to 60% by weight of aromatic vinyl monomer, 15 to 50% by weight of conjugated diene monomer, 0 to 40% by weight of ethylenically unsaturated carboxylic acid ester, unsaturated carboxylic acid monomer A single amount of 0 to 40% by weight of the product, 5 to 30% by weight of acrylonitrile, and 15 to 40% by weight in total of the ethylenically unsaturated carboxylic acid ester monomer, unsaturated carboxylic acid monomer and acrylonitrile Consisting of latex particles copolymerized with a polar organic solvent (1) to (7), wherein the solvent-based binder composition is further copolymerized with acrylonitrile in an amount of 5 to 30% by weight, and (8) the SBR latex has an average particle size of 0.01 to 0.5 μm. (9) The composition according to (1) to (8), wherein the SBR latex has a gel content of 75 to 100% by weight, and (10) the polar organic solvent contains an element other than carbon and hydrogen. Compositions according to (1) to (9), which are organic solvents, (11) Compositions according to (1) to (10), wherein the polar organic solvent does not have active hydrogen, (12) Polar organics Whether the solvent is acetonitrile, N-methylpyrrolidone, acetylpyridine, cyclopentanone, dimethylformamide, dimethylsulfoxide, methylformamide, methyl ethyl ketone, furfural, and ethylenediamine The composition according to (1) to (11), which is selected, (13) the composition according to (1) to (12), wherein the polar organic solvent is N-methylpyrrolidone, (14) (1) to (13) A slurry obtained by adding 10 to 1000 times the active material on a weight basis with respect to the amount of SBR latex in the composition, (15) A polar organic solvent is further added to the composition described in (13) (16) An electrode in which the slurry described in (14) to (15) is applied to the surface of the electrode substrate, and the polar organic solvent is removed to form an active material layer. (17) The electrode substrate is made of metal. The electrode according to (16), (18) the electrode according to (17), wherein the electrode substrate is a sheet having a thickness of 0.05 to 0.5 mm, and (19) the active material layer having a thickness of 0.05 to 2 mm The electrode according to (18), (20) the electrode is (16) to (19) Examples of the battery are those described above.

以下に実施例、および比較例を挙げて、本発明を具体的に説明する。   The present invention will be specifically described below with reference to examples and comparative examples.

実施例1
攪拌機付きの3リットルのオートクレーブに、水1リットル、スチレン800g、ブタジエン600g、メタクリル酸メチル400g、アクリロニトリル100g、ラウリル硫酸アンモニウム4g、重炭酸ナトリウム10gを入れてモノマーエマルジョンを調製した。
Example 1
A monomer emulsion was prepared by adding 1 liter of water, 800 g of styrene, 600 g of butadiene, 400 g of methyl methacrylate, 100 g of acrylonitrile, 4 g of ammonium lauryl sulfate, and 10 g of sodium bicarbonate in a 3 liter autoclave equipped with a stirrer.

攪拌機付きの10リットルのオートクレーブに、水3.4リットル、エチレンジアミン四酢酸10g、ラウリル硫酸アンモニウム10g、過硫酸カリウム20gを入れ、モノマーエマルジョンの10容量%を加え、80℃に加熱し、攪拌しながら1時間反応させた。ついで、過硫酸カリウム80gをミス200mlと共に加え、80℃を維持し、攪拌したまま、残りのモノマーエマルジョン全量を4時間に渡って連続的に加えた。モノマーエマルジョンを全て加えた後、80℃を維持し、攪拌したまま、さらに4時間反応させた。なお、収率は99%で、得られたSBR系ラテックス粒子の平均粒径は0.14μmあった。   In a 10 liter autoclave with a stirrer, 3.4 liters of water, 10 g of ethylenediaminetetraacetic acid, 10 g of ammonium lauryl sulfate, and 20 g of potassium persulfate are added, 10% by volume of the monomer emulsion is added, heated to 80 ° C., and stirred for 1 Reacted for hours. Subsequently, 80 g of potassium persulfate was added together with 200 ml of mistake, and the remaining monomer emulsion was continuously added over 4 hours while maintaining the temperature at 80 ° C. and stirring. After all the monomer emulsion was added, the temperature was maintained at 80 ° C., and the mixture was further reacted for 4 hours with stirring. The yield was 99%, and the average particle size of the obtained SBR latex particles was 0.14 μm.

残留モノマーを水蒸気蒸留によって除去し、水酸化リチウムでpHを7に調整し、得られたラテックスの重量の3倍の量のN−メチルピロリドンを加え、エバポレーターで水分を蒸発させ、固形分濃度37重量%の本発明のバインダー組成物を得た。   Residual monomer was removed by steam distillation, the pH was adjusted to 7 with lithium hydroxide, N-methylpyrrolidone in an amount three times the weight of the obtained latex was added, water was evaporated with an evaporator, and the solid content was 37 A binder composition of the present invention in weight% was obtained.

負極活物質(ロンザ製、KS−23、カーボン)をこのバインダー組成物に重量基準でバインダー組成物中のSBR系ラテックス量の20倍加え、さらにN−メチルピロリドンを加え、25℃の粘度が約3000cpsのスラリーを調製した。このスラリーを厚さ0.1mmの銅箔の片面に塗布し、120℃で3時間放置して乾燥し、厚さ0.4mmの活物質層を形成した。   A negative electrode active material (Lonza, KS-23, carbon) was added to this binder composition 20 times the amount of SBR latex in the binder composition, and N-methylpyrrolidone was further added. A 3000 cps slurry was prepared. This slurry was applied to one side of a 0.1 mm thick copper foil and left to dry at 120 ° C. for 3 hours to form an active material layer having a thickness of 0.4 mm.

また、正極活物質LiCoO90重量部とアセチレンブラック10重量部の混合物を、重量基準でバインダー組成物中のSBR系ラテックス量の20倍をバインダー組成物に加えて、さらにN−メチルピロリドンを加え、25℃での粘度が約2000cpsのスラリーを調製した。このスラリーを厚さ0.2mmのアルミ箔の片面に塗布し、120で3時間放置して乾燥し、厚さ0.4mmの活物質層を形成した。 Further, a mixture of 90 parts by weight of the positive electrode active material LiCoO 2 and 10 parts by weight of acetylene black was added to the binder composition 20 times the amount of SBR latex in the binder composition on a weight basis, and N-methylpyrrolidone was further added. A slurry having a viscosity at 25 ° C. of about 2000 cps was prepared. This slurry was applied to one side of an aluminum foil having a thickness of 0.2 mm, and left to stand for 3 hours at 120 to dry, thereby forming an active material layer having a thickness of 0.4 mm.

活物質層を形成した銅箔とアルミ箔を直径15mmの円形に切り抜き、直径16mm、厚さ50μm(0.5mm)の円形のポリプロピレン製微多孔膜(繊維不織布)からなるセパレーターを介在させて、互いに活物質層を対向させて、ポリプロピレン製パッキンを配置したステンレス鋼製の外装容器中(直径20mm、高さ1.8mm、ステンレス鋼厚さ0.2mm)に収納した。容器中に、エチレンカーボネートとジエチルカーボネートを容積比で1:1に混合した溶媒に電解質を1mol/リットルの濃度に溶解した電解液を空気が残らないように注入して、厚さ0.2mmのステンレス鋼のキャップをかぶせて、プリプロピレン製パッキンを介して外装容器とキャップを固定し、それぞれキャップに銅箔が、容器低面にアルミ箔が接触するように内容物を封止して、直径20mm、厚さ2.0mmのコイン型電池を製造した。   The copper foil and the aluminum foil in which the active material layer is formed are cut into a circle having a diameter of 15 mm, and a separator made of a polypropylene microporous film (fiber nonwoven fabric) having a diameter of 16 mm and a thickness of 50 μm (0.5 mm) is interposed. The active material layers were opposed to each other, and stored in a stainless steel outer container (diameter 20 mm, height 1.8 mm, stainless steel thickness 0.2 mm) in which polypropylene packing was arranged. Into a container, an electrolyte solution in which an electrolyte is dissolved at a concentration of 1 mol / liter is poured into a solvent in which ethylene carbonate and diethyl carbonate are mixed at a volume ratio of 1: 1 so that no air remains. Cover the outer container and cap with a stainless steel cap and seal the contents so that the copper foil is in contact with the cap and the aluminum foil is in contact with the lower surface of the container. A coin type battery having a thickness of 20 mm and a thickness of 2.0 mm was manufactured.

この電池に、定電流法(電流密度:0.1mA/cm)で4.2Vに充電し、3.2Vまで放電する充放電を行い、容量の変化を測定した。1回目の充電での容量は19.6mAh(100%)であり、50回目の充電では17.8mAh(約91%に低下)、200回目の充電では17.5mAh(約89%に低下)であった。 The battery was charged and discharged to 4.2 V by a constant current method (current density: 0.1 mA / cm 2 ) and discharged to 3.2 V, and the change in capacity was measured. The capacity at the first charge is 19.6 mAh (100%), the charge at the first charge is 17.8 mAh (decrease to about 91%), the charge at the first charge is 17.5 mAh (decrease to about 89%) there were.

実施例2
スチレンを1000g、ブタジエンを500g、メタクリル酸メチルを300g、アクリロニトリルを100gに変え、イタコン酸を加えない以外は実施例1と同様にして、収率99%で、平均粒径15μmのSBR系ラテックス粒子を得、さらに同様にして固形分濃度40重量%の本発明のバインダー組成物を得た。
Example 2
SBR latex particles with a yield of 99% and an average particle size of 15 μm, as in Example 1, except that 1000 g of styrene, 500 g of butadiene, 300 g of methyl methacrylate, 100 g of acrylonitrile, and no itaconic acid were added. In the same manner, the binder composition of the present invention having a solid concentration of 40% by weight was obtained.

このバインダー組成物を用いる以外は実施例1と同様に電池を製造し、充放電を行ったところ、1回目の充電での容量は19.0mAhであり、50回目の充電では17.2mAh(約91%に低下)、200回目の充電では16.8mAh(約88%に低下)であった。   A battery was produced in the same manner as in Example 1 except that this binder composition was used, and the battery was charged and discharged. As a result, the capacity at the first charge was 19.0 mAh, and the charge at the 50th charge was 17.2 mAh (approximately It was 16.8 mAh (decreased to about 88%) at the 200th charge.

実施例3
スチレンを700g、ブタジエンを400g、メタクリル酸メチルを400g、アクリロニトリルを200g、イタコン酸を200gに変え、さらにフマル酸を10g加える以外は実施例1と同様にして、収率99%で、平均粒径14μmのSBR系ラテックス粒子を得、さらに同様にして固形分濃度42重量%の本発明のバインダー組成物を得た。
Example 3
700% styrene, 400 g butadiene, 400 g methyl methacrylate, 200 g acrylonitrile, 200 g itaconic acid, and 10 g fumaric acid were added in the same manner as in Example 1 except that the average particle size was 99%. 14 μm SBR latex particles were obtained, and the binder composition of the present invention having a solid content of 42% by weight was obtained in the same manner.

このバインダー組成物を用いる以外は実施例1と同様に電池を製造し、充放電を行ったところ、1回目の充電での容量は18.6mAhであり、50回目の充電では17.4mAh(約94%に低下)、200回目の充電では17.0mAh(約91%に低下)であった。   A battery was produced in the same manner as in Example 1 except that this binder composition was used, and charging and discharging were performed. As a result, the capacity in the first charge was 18.6 mAh, and in the 50th charge, 17.4 mAh (about It was 17.0 mAh (decreased to about 91%) at the 200th charge.

比較例1
N−メチルピロリドンを加えず、エバポレータで水分を蒸発させない以外は実施例1と同様にして固形分濃度45重量%の水系バインダー組成物を得た。
Comparative Example 1
An aqueous binder composition having a solid content concentration of 45% by weight was obtained in the same manner as in Example 1 except that N-methylpyrrolidone was not added and water was not evaporated with an evaporator.

負極活物質(ロンザ製、KS−23)をこのバインダー組成物に重量基準でバインダー組成物中のSBR系ラテックス量の20倍加え、粘度が約800cpsのスラリーを調製した。このスラリーを厚さ0.1mmの銅箔の片面に塗布し、110℃で3時間放置して乾燥し、厚さ0.4mmの活物質層を形成した。   A negative electrode active material (manufactured by Lonza, KS-23) was added to this binder composition 20 times the amount of SBR latex in the binder composition on a weight basis to prepare a slurry having a viscosity of about 800 cps. This slurry was applied to one side of a 0.1 mm thick copper foil, left to stand at 110 ° C. for 3 hours and dried to form an active material layer having a thickness of 0.4 mm.

また、正極活物質LiCoO90重量部とアセチレンブラック10重量部の混合物を、実施例1のバインダー組成物に重量基準でバインダー組成物中のSBR系ラテックス量の20倍加え、さらに水を加え、粘度が約400cpsのスラリーを調製した。このスラリーを厚さ0.2μmのアルミ箔の片面に塗布し、110℃で3時間放置して乾燥し、厚さ0.4μmの活物質層を形成した。 Further, a mixture of 90 parts by weight of the positive electrode active material LiCoO 2 and 10 parts by weight of acetylene black was added to the binder composition of Example 1 20 times the amount of SBR latex in the binder composition on a weight basis, and water was further added. A slurry with a viscosity of about 400 cps was prepared. This slurry was applied to one side of an aluminum foil having a thickness of 0.2 μm, and allowed to stand at 110 ° C. for 3 hours to dry, thereby forming an active material layer having a thickness of 0.4 μm.

このスラリーを用いる以外は実施例1と同様に電池を製造し、充放電を行ったところ、1回目の充電での容量は17.4mAhであり、50回目の充電では15.9mAh(約91%に低下)、200回目の充電では14.8mAh(約85%に低下)であった。   A battery was produced in the same manner as in Example 1 except that this slurry was used, and charging and discharging were performed. As a result, the capacity at the first charge was 17.4 mAh, and at the 50th charge was 15.9 mAh (about 91% ) And 14.8 mAh (decreased to about 85%) in the 200th charge.

比較例2
スチレンを200g、ブタジエンを200g、メタクリル酸メチルを600g、アクリロニトリルを150gに変え、イタコン酸を加えない以外は実施例1と同様にして、収率99%で、平均粒径0.18μmのSBR系ラテックス粒子を得、さらに同様にして固形分濃度52重量%の本発明のバインダー組成物を得た。
Comparative Example 2
SBR system having a yield of 99% and an average particle size of 0.18 μm in the same manner as in Example 1 except that 200 g of styrene, 200 g of butadiene, 600 g of methyl methacrylate, 150 g of acrylonitrile, and no itaconic acid were added. Latex particles were obtained, and the binder composition of the present invention having a solid content concentration of 52% by weight was obtained in the same manner.

このバインダー組成物を用いる以外は実施例1と同様に、25℃での粘度が約2000cpsのスラリーを調製して電池を製造し、充放電を行ったところ、1回目の充電での容量は17.6mAhであったが、50回目の充電では3.2mAh(約18%に低下)であった。   A battery having a viscosity of about 2000 cps at 25 ° C. was prepared and charged / discharged in the same manner as in Example 1 except that this binder composition was used. The capacity at the first charge was 17 Although it was .6 mAh, it was 3.2 mAh (decreased to about 18%) at the 50th charge.

比較例3
スチレンを800g、ブタジエンを600g、メタクリル酸メチルを20gに変え、アクリロニトリル、イタコン酸を加えない以外は、実施例1と同様にして、収率99%で、平均粒径0.12μmのSBR系ラテックス粒子を得、残留モノモーを水蒸気蒸留によって除去し、水酸化リチウムでpHを7に調整し、得られたラテックスの重量の3倍の量のN−メチルピロリドンを加え、エバポレーターで水分を蒸発させたところ凝集した。
Comparative Example 3
SBR latex having a yield of 99% and an average particle size of 0.12 μm in the same manner as in Example 1 except that 800 g of styrene, 600 g of butadiene and 20 g of methyl methacrylate were added and acrylonitrile and itaconic acid were not added. Particles were obtained, the residual monomer was removed by steam distillation, the pH was adjusted to 7 with lithium hydroxide, N-methylpyrrolidone in an amount three times the weight of the obtained latex was added, and the water was evaporated with an evaporator. It was agglomerated.

Claims (3)

芳香族ビニル系単量体25〜60重量%、共役ジエン系単量体15〜50重量%、エチレン性不飽和カルボン酸エステル0〜40重量%、および不飽和カルボン酸系単量体0〜40重量%、かつエチレン性不飽和カルボン酸エステル系単量体と不飽和カルボン酸系単量体の合計量が15〜40重量%の単量体を共重合したラテックス粒子と極性有機溶媒からなる有機溶媒系バインダー組成物。   25 to 60% by weight of aromatic vinyl monomer, 15 to 50% by weight of conjugated diene monomer, 0 to 40% by weight of ethylenically unsaturated carboxylic acid ester, and 0 to 40 of unsaturated carboxylic acid monomer Organic consisting of latex particles copolymerized with 15% by weight of a monomer having a total weight of 15% to 40% by weight of ethylenically unsaturated carboxylic acid ester monomer and unsaturated carboxylic acid monomer, and a polar organic solvent Solvent-based binder composition. 請求項1記載のバインダー組成物と活物質を混合し、電極基体表面に塗布し、極性有機溶媒を除去した電極。   The electrode which mixed the binder composition and active material of Claim 1, and apply | coated to the electrode base-material surface, and removed the polar organic solvent. 電極が請求項2記載のものである電池。   A battery having an electrode according to claim 2.
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