JPH10306265A - Polyvinylidene fluoride-based composition adhesive to metal and electrode for battery - Google Patents

Polyvinylidene fluoride-based composition adhesive to metal and electrode for battery

Info

Publication number
JPH10306265A
JPH10306265A JP9114691A JP11469197A JPH10306265A JP H10306265 A JPH10306265 A JP H10306265A JP 9114691 A JP9114691 A JP 9114691A JP 11469197 A JP11469197 A JP 11469197A JP H10306265 A JPH10306265 A JP H10306265A
Authority
JP
Japan
Prior art keywords
vinylidene fluoride
polyvinylidene fluoride
carboxylic acid
group
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP9114691A
Other languages
Japanese (ja)
Inventor
Kazuyoshi Ohashi
和義 大橋
Yoshiyuki Miyaki
義行 宮木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema KK
Original Assignee
Elf Atochem Japan KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elf Atochem Japan KK filed Critical Elf Atochem Japan KK
Priority to JP9114691A priority Critical patent/JPH10306265A/en
Priority to PCT/EP1998/002783 priority patent/WO1998050479A1/en
Priority to AU77641/98A priority patent/AU7764198A/en
Priority to TW087106891A priority patent/TW388138B/en
Publication of JPH10306265A publication Critical patent/JPH10306265A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01M4/621—Binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09J127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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

PROBLEM TO BE SOLVED: To obtain the subject composition capable of exhibiting excellent adhesiveness to metals while retaining the properties inherent in the resin and useful for electrodes for batteries, by including a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer and introducing metal- adhesive group(s) into one or both of them. SOLUTION: This composition comprises (A) a vinylidene fluoride homopolymer and (B) a vinylidene fluoride-based copolymer [e.g. a copolymer containing trifluoro(chloro)ethylene, tetrafluoroethylene or hexafluoropropylene as a comonomer component, with a vinyl fluoride rate of 50-95 wt.%], wherein the component A and/or component B bear functional group(s) adhesive to metals [e.g. carboxylic acid (anhydride) group, epoxy or mercapto group] and the component B accounts for 0.5-50 wt.% of the composition.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、金属接着性に優れたポ
リフッ化ビニリデン系組成物、その製造方法、およびそ
の組成物を結着剤に用いた電池用電極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinylidene fluoride composition having excellent metal adhesion, a method for producing the same, and a battery electrode using the composition as a binder.

【０００２】[0002]

【従来の技術】ポリフッ化ビニリデンやフッ化ビニリデ
ン系共重合体樹脂は、耐候性や耐薬品性等の優れた溶融
成形ができるフッ素系樹脂として、塗料や電気・電子部
品、鋼管ライニング、化学プラント部品、耐候防汚フィ
ルム等に用いられている。しかし他材料との接着性が殆
どないため、他素材との複合や改質が出来にくい欠点が
あった。2. Description of the Related Art Polyvinylidene fluoride and vinylidene fluoride copolymer resins are paints, electric and electronic parts, steel pipe linings, and chemical plants that can be melt-molded with excellent weather resistance and chemical resistance. It is used for parts, weather-resistant antifouling films and the like. However, there is little adhesion to other materials, so that there is a disadvantage that it is difficult to combine or modify with other materials.

【０００３】そのため、ポリフッ化ビニリデン系樹脂に
カルボン酸基を導入して親水性の付与、接着性、染色性
分散性等の向上、架橋部位の導入等の試みが種々なされ
た。例えば、カルボン酸基の導入方法として、アクリル
酸、メタクリル酸エステルあるいはこれらのエステル類
のごとくカルボン酸基もしくはこれに変換可能な基を有
する単量体をフッ化ビニリデンモノマーと共重合せしめ
て直接導入する方法（特公平２−６０４号公報、他）が
公知である。For this reason, various attempts have been made to introduce a carboxylic acid group into a polyvinylidene fluoride resin to impart hydrophilicity, improve adhesion, dispersibility of dyeability, and introduce a crosslinked site. For example, as a method for introducing a carboxylic acid group, a monomer having a carboxylic acid group or a group that can be converted to a carboxylic acid group such as acrylic acid or methacrylic acid ester or these esters is copolymerized with a vinylidene fluoride monomer and directly introduced. (Japanese Patent Publication No. 2-604, etc.) are known.

【０００４】しかしながら、カルボン酸基含有ポリフッ
化ビニリデン系樹脂の製造に際して上記の手法を採用す
る場合には、含フッ素単量体等との共重合特性の面から
カルボン酸基含有単量体として複雑な製造工程を要する
特殊なものを使用しないと重合速度が著しく低下した
り、低分子量物しか得られなくなる場合があり、さら
に、共重合成分の導入により、重合体本来の特性が得ら
れなくなる場合があるなどの難点があった。However, when the above-mentioned method is employed in the production of a carboxylic acid group-containing polyvinylidene fluoride resin, the carboxylic acid group-containing monomer is complicated because of its copolymerization property with a fluorine-containing monomer. If a special product requiring a special manufacturing process is not used, the polymerization rate may be significantly reduced, or only a low molecular weight product may be obtained. There was a disadvantage such as there.

【０００５】さらに、特開昭５０−４１７９１号公報に
は、電離性放射線照射下にカルボン酸基含有フッ素単量
体をグラフトさせる方法が開示されていが、該方法にお
いては放射線の取り扱いという工業的な困難さに加え
て、重合体主鎖の分解あるいは架橋反応の併発というと
いう難点があった。 このように、含フッ素重合体につ
いて試みられた従来の例においては、いずれも工業的な
実施に際して困難を伴うものであった。Further, Japanese Patent Application Laid-Open No. Sho 50-41791 discloses a method of grafting a carboxylic acid group-containing fluoromonomer under irradiation with ionizing radiation. In addition to the difficulties, the polymer main chain is decomposed or a cross-linking reaction occurs simultaneously. As described above, in all of the conventional examples that have been tried for the fluoropolymer, there have been difficulties in industrial practice.

【０００６】一方、近年、携帯電話、ビデオカメラ、ノ
ート型パソコン等のポータブル機器に用いられるように
なったリチウム二次電池においては、その負極活性物質
としては、リチウムイオンをドーピング、脱ドーピング
するコークスやグラファイト等の炭素質材料が用いられ
（特開昭６２−９０８６３号公報）、正極活性物質とし
ては、マンガン酸化物、五酸化バナジウムのような遷移
金属酸化物、硫化鉄、硫化チタンのような遷移金属酸化
物、さらにこれらとリチウムとの複合化合物（例えば、
リチウムコバルト複合酸化物、リチウムコバルトニッケ
ル複合酸化物、リチウムマンガン酸化物）などが用いら
れている。これらの場合、通常、粉体状の電極活性材料
に結着剤を適当量添加した混合物に溶媒を混ぜてペース
ト状にしたものを集電体に塗布、乾燥後圧着させて電極
が得られる。On the other hand, in a lithium secondary battery which has recently been used for portable equipment such as a mobile phone, a video camera, and a notebook personal computer, a coke for doping and undoping lithium ions is used as a negative electrode active material. Carbonaceous materials such as carbon and graphite are used (Japanese Patent Application Laid-Open No. 62-90863), and as the positive electrode active substance, transition metal oxides such as manganese oxide and vanadium pentoxide, and iron sulfide and titanium sulfide are used. Transition metal oxides, and composite compounds thereof with lithium (for example,
Lithium cobalt composite oxide, lithium cobalt nickel composite oxide, lithium manganese oxide) and the like are used. In these cases, usually, a mixture of a powdery electrode active material and an appropriate amount of a binder added with an appropriate amount of a binder, mixed with a solvent to form a paste, applied to the current collector, dried and pressed to obtain an electrode.

【０００７】このような二次電池の電極に用いる結着剤
には、電解液に用いられる有機溶媒に対する耐性と電極
反応によって生じる活性種への耐性が要求され、さらに
電極を作製する工程上、特定の溶媒への溶解性も必要で
ある。これらを満足する結着剤として、多くの場合、ポ
リフッ化ビニリデン（ＰＶＤＦ）樹脂が用いられる。し
かしながら、ＰＶＤＦ樹脂は元来金属との接着性が悪
く、負極と正極いずれの場合も、活性物質を集電体に圧
着させた後、集電体と活性物質との接着力が十分でない
ために、活性物質が集電体から剥離し易く、電池のサイ
クル特性が悪くなるという問題があった。The binder used for the electrode of such a secondary battery is required to have resistance to an organic solvent used for an electrolytic solution and resistance to active species generated by an electrode reaction. Solubility in certain solvents is also required. In many cases, a polyvinylidene fluoride (PVDF) resin is used as a binder satisfying these. However, PVDF resin originally has poor adhesion to metal, and in both cases of the negative electrode and the positive electrode, after the active material is pressed against the current collector, the adhesive force between the current collector and the active material is not sufficient. Further, there has been a problem that the active substance is easily peeled off from the current collector, and the cycle characteristics of the battery are deteriorated.

【０００８】集電体と電極活性物質との接着性を改善す
る方法として、集電体表面を粗面化することが提案され
たが（特開平５−６７６６号公報）、これにおいても接
着性は十分とは言えず、さらなる改良が求められてい
る。また、フッ化ビニリデンとカルボン酸基を有するモ
ノマーとの共重合体（特開平６−１７２４５２号公報）
が提案されたが、通常、フッ素系モノマーとカルボン酸
基を有する他のモノマーとの共重合は容易でなく、量産
化が困難で実用的とは言えない．As a method for improving the adhesion between the current collector and the electrode active material, it has been proposed to roughen the surface of the current collector (Japanese Patent Laid-Open No. 5-6766). Is not enough, and further improvement is required. Also, a copolymer of vinylidene fluoride and a monomer having a carboxylic acid group (JP-A-6-172452).
However, copolymerization of a fluorine-based monomer with another monomer having a carboxylic acid group is usually not easy, and mass production is difficult and it cannot be said that it is practical.

【０００９】[0009]

【発明が解決しようとする課題】本発明は、ポリフッ化
ビニリデン系樹脂が本来有する耐溶剤性や機械的・熱的
性質を損なわずに、しかも、簡便な方法で金属接着性を
導入した金属接着性ポリフッ化ビニリデン系組成物およ
び製造方法を提供し、さらに該組成物を電池用電極の結
着剤に用いることにより電極活性物質と集電体との接着
性を向上させた電池用電極を提供することを目的とす
る。DISCLOSURE OF THE INVENTION The present invention relates to a metal bonding method in which a metal bonding property is introduced by a simple method without impairing the solvent resistance, mechanical and thermal properties inherent in polyvinylidene fluoride resin. The present invention provides a conductive polyvinylidene fluoride-based composition and a production method, and further provides a battery electrode having improved adhesiveness between an electrode active material and a current collector by using the composition as a binder for a battery electrode. The purpose is to do.

【００１０】[0010]

【課題を解決するための手段】本発明者らは、フッ化ビ
ニリデン単独重合体とフッ化ビニリデン系共重合体の混
合物において、それらの成分の少なくとも片方が金属接
着性を示す官能基を有する場合に優れた金属接着性が発
現することを見いだした。さらに、この組成物を電池用
電極の結着剤として用いることにより電極活性物質と集
電体との接着性を著しく改善させ得ることを見いだし本
発明に到達した。Means for Solving the Problems The present inventors have found that in a mixture of a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer, at least one of the components has a functional group exhibiting metal adhesiveness. It was found that excellent metal adhesion was exhibited. Furthermore, they have found that by using this composition as a binder for a battery electrode, the adhesiveness between the electrode active substance and the current collector can be significantly improved, and the present invention has been achieved.

【００１１】すなわち、本発明は、フッ化ビニリデン単
独重合体とフッ化ビニリデン系共重合体から構成される
組成物において、これら重合体の両方あるいは片方が金
属接着性を示す官能基を有し、フッ化ビニリデン系共重
合体の含有率が全体の０．５〜５０重量％であるポリフ
ッ化ビニリデン系金属接着性組成物に関する。That is, the present invention relates to a composition comprising a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer, wherein both or one of these polymers has a functional group exhibiting metal adhesiveness, The present invention relates to a polyvinylidene fluoride-based metal adhesive composition containing 0.5 to 50% by weight of a vinylidene fluoride-based copolymer.

【００１２】本発明で用いられるフツ化ビニリデン単独
重合体（ホモポリマー）は、フッ化ビニリデンモノマー
を懸濁重合法あるいは乳化重合法等で重合することによ
り得られ、２３０℃、２．１６ｋｇ荷重下でのメルトフ
ローレート（ＭＦＲ）が０．００５〜３００ｇ／１０分
であることが望ましく、さらに望ましくは、０．０１〜
３０ｇ／１０分である。The vinylidene fluoride homopolymer (homopolymer) used in the present invention is obtained by polymerizing a vinylidene fluoride monomer by a suspension polymerization method, an emulsion polymerization method, or the like. Is preferably 0.005 to 300 g / 10 min, and more preferably 0.01 to 300 g / 10 min.
30 g / 10 min.

【００１３】また、フッ化ビニリデン系共重合体とは、
フツ化ビニリデンモノマーとこれと共重合可能な他のモ
ノマーとの共重合体で、該共重合体中のフッ化ビニリデ
ン成分比率が５０〜９５重量％であればよく、さらに望
ましくは、７５〜９５重量％である。ここで共重合可能
な他のモノマーとしては、四フッ化エチレン、六フッ化
プロピレン、三フッ化エチレン、三フッ化塩化エチレン
等のフッ素系モノマーが望ましく、これらの１種又は２
種以上を用いることができる。この樹脂の場合も、上記
モノマーを懸濁重合あるいは乳化重合法等で重合するこ
とにより得られ、２３０℃、２．１６ｋｇ荷重下でのメ
ルトフローレート（ＭＦＲ）が０．００５〜３００ｇ／
１０分であることが望ましく、さらに望ましくは、０．
０１〜３０ｇ／１０分である。[0013] The vinylidene fluoride copolymer is
It is a copolymer of a vinylidene fluoride monomer and another monomer copolymerizable therewith, provided that the vinylidene fluoride component ratio in the copolymer is 50 to 95% by weight, more preferably 75 to 95% by weight. % By weight. The other copolymerizable monomer is desirably a fluorine-based monomer such as ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride, or ethylene trifluoride chloride.
More than one species can be used. This resin is also obtained by polymerizing the above monomer by a suspension polymerization or an emulsion polymerization method, and has a melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg of 0.005 to 300 g /
It is preferably 10 minutes, and more preferably 0.1 minute.
01 to 30 g / 10 min.

【００１４】本発明で、金属に対して接着性（結合性あ
るいは親和性）を示す官能基としては、特に限定されな
いが、カルボン酸基あるいはカルボン酸無水物基、エポ
キシ基（グリシジル基）、メルカプト基、スルフィド
基、オキサゾリン基、フェノール基、エステル基等が挙
げられる。In the present invention, the functional group exhibiting adhesiveness (binding property or affinity) to a metal is not particularly limited, but may be a carboxylic acid group or a carboxylic anhydride group, an epoxy group (glycidyl group), a mercapto group, or the like. Group, sulfide group, oxazoline group, phenol group, ester group and the like.

【００１５】本発明において、フッ化ビニリデン単独重
合体とフッ化ビニリデン系共重合体から構成される組成
物に含有されるフッ化ビニリデン系共重合体は全体の５
０重量％以下であるが、望ましくは０．５〜２０重量
％、、さらに望ましくは１〜１０重量％である。フッ化
ビニリデン系共重合体の含有率が少なすぎる場合、金属
材料とＰＶＤＦ系組成物との接着性改善の効果が不十分
となり、これらが多すぎる場合、ＰＶＤＦ系組成物の耐
薬品性が低下することにより、金属材料との接着性を損
なう結果となって現れる。特に、ＰＶＤＦ系組成物を電
池の電極の結着剤として用いる場合、電解液に用いられ
る有機溶剤（エチレンカーボネート、プロピレンカーボ
ネート、ジメチルカーボネート、ジエチルカーボネート
等）による膨潤が大きくなり、いずれの場合も、本発明
の電極や二次電池の性能に悪影響を及ぼす。特に、５０
℃以上の温度でこれらの影響が大きい。In the present invention, the vinylidene fluoride-based copolymer contained in the composition comprising the vinylidene fluoride homopolymer and the vinylidene fluoride-based copolymer is 5% in total.
The content is 0% by weight or less, preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight. When the content of the vinylidene fluoride-based copolymer is too small, the effect of improving the adhesion between the metal material and the PVDF-based composition becomes insufficient. When the content is too large, the chemical resistance of the PVDF-based composition decreases. This results in impairing the adhesiveness to the metal material. In particular, when a PVDF-based composition is used as a binder for a battery electrode, the swelling due to the organic solvent (ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, etc.) used in the electrolytic solution increases, and in any case, It adversely affects the performance of the electrode and the secondary battery of the present invention. In particular, 50
These effects are significant at temperatures above ℃.

【００１６】本発明において、フッ化ビニリデン単独重
合体とフッ化ビニリデン系共重合体の両方あるいはいず
れか片方に金属接着性を示す官能基を導入する方法とし
て、（ａ）金属接着性を示す官能基を有する有機過酸化
物を加熱下作用させる方法、（ｂ）金属接着性を示す官
能基を有する不飽和有機化合物と過酸化物の存在下で加
熱処理する方法、（ｃ）金属接着性を示す官能基を有す
る不飽和あるいは飽和有機化合物を放射線を用いてグラ
フトさせる方法、（ｄ）金属接着性を示す官能基を有す
る不飽和有機化合物を共重合成分として用いてフッ化ビ
ニリデンモノマーやフッ素系モノマー重合する方法、
（ｅ）金属接着性を示す官能基を有する有機過酸化物を
開始剤として用いてフッ化ビニリデンモノマーやフッ素
系モノマーを重合する方法、（ｆ）金属接着性を示す官
能基を有する不飽和あるいは飽和有機化合物をフッ化ビ
ニリデンモノマーやフッ素系モノマーの重合の連鎖移動
剤として用いる方法などが挙げられる。In the present invention, a method of introducing a metal-adhesive functional group into both or any one of vinylidene fluoride homopolymer and vinylidene fluoride-based copolymer includes the following methods: A method of causing an organic peroxide having a group to act under heating, (b) a method of performing a heat treatment in the presence of an unsaturated organic compound having a functional group exhibiting metal adhesion and a peroxide, and (c) a method of performing metal adhesion. A method of grafting an unsaturated or saturated organic compound having a functional group having a functional group shown by radiation, (d) a vinylidene fluoride monomer or a fluorine-based compound using a unsaturated organic compound having a functional group having a metal adhesive property as a copolymerization component; A method of monomer polymerization,
(E) a method of polymerizing a vinylidene fluoride monomer or a fluorine-based monomer using an organic peroxide having a functional group exhibiting metal adhesiveness as an initiator; A method in which a saturated organic compound is used as a chain transfer agent in the polymerization of vinylidene fluoride monomer or fluorine-based monomer, may be used.

【００１７】上記（ａ）の方法においては、カルボン酸
基、カルボン酸無水物基およびカルボン酸エステル基か
ら選ばれる少なくとも１つの官能基を有する有機過酸化
物を、加熱下、ポリフッ化ビニリデン系樹脂に作用させ
ることにより、容易にカルボン酸基、カルボン酸無水物
基あるいはカルボン酸エステル基が導入される。In the above method (a), an organic peroxide having at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group and a carboxylic acid ester group is added to a polyvinylidene fluoride resin under heating. , A carboxylic acid group, a carboxylic acid anhydride group or a carboxylic acid ester group is easily introduced.

【００１８】ここで用いられるカルボン酸基、カルボン
酸無水物基あるいはカルボン酸エステル基から選ばれる
少なくとも１つの官能基を有する過酸化物の例として
は、ジコハク酸パーオキサイド、ｔ−ブチルパーオキシ
マレイン酸等がある。ＰＶＤＦ系樹脂を、これら有機過
酸化物の存在下で、加熱処理することにより、反応のメ
カニズムは必ずしも明らかではないが、当該樹脂にカル
ボン酸基、カルボン酸無水物基あるいはカルボン酸エス
テル基が導入される。Examples of the peroxide having at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group and a carboxylic acid ester group include disuccinic acid peroxide and t-butyl peroxymalein. Acids and the like. By subjecting a PVDF-based resin to heat treatment in the presence of these organic peroxides, the mechanism of the reaction is not always clear, but a carboxylic acid group, a carboxylic anhydride group or a carboxylic ester group is introduced into the resin. Is done.

【００１９】この場合の反応の条件としては、ポリフッ
化ビニリデン系樹脂１００重量部に対して、カルボン酸
基、カルボン酸無水物およびカルボン酸エステル基から
選ばれる少なくとも１つの官能基を有する有機過酸化物
を０．５〜１００重量部、好ましくは１〜２０重量部を
作用させる。The reaction conditions in this case are as follows: 100 parts by weight of a polyvinylidene fluoride resin is an organic peroxide having at least one functional group selected from carboxylic acid groups, carboxylic anhydrides and carboxylic ester groups. The product is applied in an amount of 0.5 to 100 parts by weight, preferably 1 to 20 parts by weight.

【００２０】上記（ｂ）の方法では、ポリフッ化ビニリ
デン系樹脂を、過酸化物とカルボン酸基とカルボン酸無
水物基から選ばれる少なくとも１つの官能基を有する不
飽和有機化合物の存在下加熱処理することにより、ポリ
フッ化ビニリデン系樹脂にカルボン酸基あるいはカルボ
ン酸無水物基がグラフト的に導入される。In the above method (b), the polyvinylidene fluoride resin is heat-treated in the presence of an unsaturated organic compound having at least one functional group selected from a peroxide, a carboxylic acid group and a carboxylic anhydride group. By doing so, a carboxylic acid group or a carboxylic anhydride group is grafted into the polyvinylidene fluoride resin.

【００２１】この場合、用いられるカルボン酸基あるい
はカルボン酸無水物基を有する不飽和有機化合物の例と
しては、アクリル酸、メタクリル酸、クロトン酸、マレ
イン酸、フマル酸、アルケニルコハク酸、アクリルアミ
ドグリコール酸、１，２−シクロヘキサンジカルボン酸
モノアリル等の不飽和カルボン酸、および無水マレイン
酸、無水アルケニルコハク酸などの不飽和カルボン酸無
水物、さらにこれらの誘導体がある。In this case, examples of the unsaturated organic compound having a carboxylic acid group or a carboxylic anhydride group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, alkenyl succinic acid, and acrylamidoglycolic acid. And unsaturated carboxylic anhydrides such as maleic anhydride and alkenyl succinic anhydride, and derivatives thereof.

【００２２】また、（ｂ）の方法で用いられる過酸化物
は特に限定されない。例として、パーオキシケタール
類、アルキルハイドロパーオキサイド類、ジアルキルパ
ーオキサイド類、アルキルパーオキシエステル類、ジア
シルパーオキサイド類、パーオキシジカーボネート類、
パーオキシエステル類等があるThe peroxide used in the method (b) is not particularly limited. Examples include peroxy ketals, alkyl hydroperoxides, dialkyl peroxides, alkyl peroxy esters, diacyl peroxides, peroxy dicarbonates,
Peroxyesters, etc.

【００２３】（ａ）および（ｂ）の方法において、過酸
化物存在下でのＰＶＤＦ系樹脂の加熱処理は、溶融状態
で行う場合と溶媒中で行う方法があり、いずれの場合も
適用可能である。溶媒中で行う場合、例えば、ＰＶＤＦ
系樹脂、過酸化物を溶媒に溶解あるいは分散させた状態
で反応が行われる。これらいずれの状態での反応におい
ても、過酸化物が十分分解する条件で加熱処理を行えば
よい。ここで、過酸化物が十分分解する条件とは、過酸
化物の１０時間半減期温度以上の温度で、反応時間が１
分間〜１０時間であり、望ましくは１０分間〜５時間で
ある。In the methods (a) and (b), the heat treatment of the PVDF-based resin in the presence of a peroxide includes a method in which the heat treatment is performed in a molten state and a method in which the heat treatment is performed in a solvent. is there. When performed in a solvent, for example, PVDF
The reaction is carried out in a state where the system resin and the peroxide are dissolved or dispersed in a solvent. In any of these reactions, the heat treatment may be performed under the condition that the peroxide is sufficiently decomposed. Here, the condition under which the peroxide is sufficiently decomposed is that the reaction is performed at a temperature equal to or higher than the 10-hour half-life temperature of the peroxide and the reaction time is 1 hour.
Minutes to 10 hours, preferably 10 minutes to 5 hours.

【００２４】（ａ）および（ｂ）の方法において使用さ
れる溶剤は、パーオキサイドに対して安定な有機溶剤あ
るいは水から選ばれ、特に限定されない。ただし、反応
を均一に且つ効率よく行うためには、結着剤樹脂が溶解
した状態でパーオキサイドとの反応を行うことが望まし
い。ここで使用されるＰＶＤＦ系樹脂の溶剤の例とし
て、Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルホルムア
ミド、ジメチルアセトアミド、ジメチルスルホキシド、
テトラメチル尿素、アセトン、メチルエチルケトンなど
がある。反応後、必要に応じて、沈澱としてポリマーを
回収し、アルコール等の溶剤で洗浄を行い、最後に乾燥
して目的のカルボン酸基を有する結着剤樹脂が得られ
る。The solvent used in the methods (a) and (b) is selected from peroxide-stable organic solvents or water, and is not particularly limited. However, in order to carry out the reaction uniformly and efficiently, it is desirable to carry out the reaction with peroxide in a state where the binder resin is dissolved. Examples of the solvent for the PVDF resin used here include N-methylpyrrolidone, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide,
Examples include tetramethyl urea, acetone, and methyl ethyl ketone. After the reaction, if necessary, the polymer is recovered as a precipitate, washed with a solvent such as alcohol, and finally dried to obtain a desired binder resin having a carboxylic acid group.

【００２５】上記の方法で導入される官能基は、溶液か
らの再沈殿や有機溶剤によるソックスレー抽出等の精製
操作後も、ＰＶＤＦ樹脂中にある一定量以上は残存す
る。このことより、何らかの化学結合によってＰＶＤＦ
系樹脂に固定されていると考えられる。このように本発
明の方法でポリフッ化ビニリデン系樹脂に固定される
（精製操作によって除去されない）カルボン酸基、カル
ボン酸無水物基、あるいはカルボン酸エステル基の量
は、乾燥樹脂１ｇあたり、０．００２〜２ミリ等量、さ
らに望ましくは０．０１〜１ミリ等量である。The functional group introduced by the above-mentioned method remains in the PVDF resin in a certain amount or more even after reprecipitation from a solution or Soxhlet extraction with an organic solvent. From this, PVDF can be produced by some kind of chemical bonding.
It is considered to be fixed to the system resin. As described above, the amount of the carboxylic acid group, carboxylic acid anhydride group, or carboxylic acid ester group fixed (not removed by the purification operation) to the polyvinylidene fluoride-based resin in the method of the present invention is 0.1 g / g of the dry resin. It is 002 to 2 milliequivalents, more preferably 0.01 to 1 milliequivalent.

【００２６】[0026]

【作用】本発明のポリフッ化ビニリデン系金属接着性組
成物は、集電体の表面に少なくとも電極活性物質と結着
剤からなる電極構成物質層が形成されている電池用電極
において、結着剤として用いることができ、これにより
電極活性物質と集電体との接着性が改善され、電池の製
造の途中での電極活性物質の集電体からの脱落を防止で
きるばかりでなく、最終的にサイクル特性が改善された
電池用電極が得られる。According to the present invention, there is provided a polyvinylidene fluoride-based metal adhesive composition, which is used in a battery electrode having at least an electrode active material and a binder formed on the surface of a current collector. As a result, the adhesiveness between the electrode active material and the current collector is improved, and not only can the electrode active material be prevented from falling off from the current collector during the production of the battery, but also finally A battery electrode with improved cycle characteristics is obtained.

【００２７】電極の集電体としては、金属箔、金属メッ
シュ、三次元多孔体等があるが、この集電体に用いる金
属としては、リチウムと合金ができ難い金属が望まし
く、特に、鉄、ニッケル、コバルト、銅、アルミニウ
ム、チタン、バナジウム、クロム、マンガンが単独、あ
るいはこれらの合金で用いられる。The current collector of the electrode may be a metal foil, a metal mesh, a three-dimensional porous body, or the like. The metal used for the current collector is preferably a metal which cannot easily form an alloy with lithium. Nickel, cobalt, copper, aluminum, titanium, vanadium, chromium, and manganese are used alone or in an alloy thereof.

【００２８】電極活性物質のうち負極活性物質として
は、リチウムイオンをドーピング、脱ドーピングし得る
材料であればよい。このような材料として、石油系コー
クスや炭素系コークスなどのコークス材料、アセチレン
ブラックなどのカーボンブラック類、グラファイト、ガ
ラス状炭素、活性炭、炭素繊維、有機高分子を非酸化性
雰囲気中で焼成して得られる有機高分子焼成体等の炭素
質材料がある。また、酸化銅を添加する場合もある。As the negative electrode active material among the electrode active materials, any material capable of doping and undoping lithium ions may be used. As such materials, coke materials such as petroleum coke and carbon coke, carbon blacks such as acetylene black, graphite, glassy carbon, activated carbon, carbon fiber, and organic polymers are fired in a non-oxidizing atmosphere. There is a carbonaceous material such as a fired organic polymer obtained. In some cases, copper oxide is added.

【００２９】また、正極活性物質としては、上述の一般
に使用されるものであり、特に限定されない。さらに、
これに導電体を添加してもよい。The positive electrode active material is the one generally used as described above, and is not particularly limited. further,
A conductor may be added to this.

【００３０】カルボン酸基あるいはカルボン酸無水物基
等の金属接着性官能基を有する上記のポリマーとこれら
の官能基を持たないポリマーとを混合して結着剤として
用いてもよい。この場合、前者の含有率は当該結着剤の
５重量％以上であることが望ましく、さらに望ましくは
１０重量％以上である。The above polymer having a metal adhesive functional group such as a carboxylic acid group or a carboxylic acid anhydride group and a polymer having no such functional group may be mixed and used as a binder. In this case, the former content is preferably at least 5% by weight of the binder, more preferably at least 10% by weight.

【００３１】電極を作製するプロセス例として、所定量
の電極活性物質、および結着剤として本発明のポリフッ
化ビニリデン系金属接着性組成物を溶媒の存在下で混練
して得られたスラリーを電極集電体に塗布した後、乾燥
後、必要に応じてプレスして電極が得られる。この場
合、スラリーを塗布後、必要に応じて、６０〜２５０
℃、さらに望ましくは８０〜２００℃で、１分間〜１０
時間、加熱処理することが望ましい。こうして得られる
帯状電極を、帯状セパレータとともにロール状（渦巻
状）に巻回し、巻回電極体としてもよい。As an example of a process for manufacturing an electrode, a slurry obtained by kneading a predetermined amount of an electrode active substance and a polyvinylidene fluoride-based metal adhesive composition of the present invention as a binder in the presence of a solvent is used. After being applied to the current collector, dried, and then pressed as necessary to obtain an electrode. In this case, after applying the slurry, if necessary, 60 to 250
C., more preferably 80 to 200 C., for 1 minute to 10 minutes.
It is desirable to perform heat treatment for a time. The strip-shaped electrode obtained in this way may be wound in a roll (or spiral) together with the strip-shaped separator to form a wound electrode body.

【００３２】ここで、電極集電体に塗布するスラリーを
得るために用いられる溶媒としては、Ｎ−メチルピロリ
ドン、Ｎ，Ｎ−ジメチルホルムアミド、テトラヒドロフ
ラン、ジメチルアセトアミド、ジメチルスルホキシド、
ヘキサメチルスルホルアミド、テトラメチル尿素、アセ
トン、メチルエチルケトン等の有機溶媒や水であればよ
く、これらを単独で用いても、混合して用いてもよい。
これらのうち、Ｎ−メチルピロリドンが特に好んで用い
られる。また、必要に応じて分散剤を添加してもよい。
この場合、ノニオン系の分散剤が好んで用いられる。Here, as a solvent used for obtaining a slurry to be applied to the electrode current collector, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, dimethylacetamide, dimethylsulfoxide,
Organic solvents such as hexamethylsulfformamide, tetramethylurea, acetone, and methyl ethyl ketone and water may be used, and these may be used alone or in combination.
Of these, N-methylpyrrolidone is particularly preferably used. Moreover, you may add a dispersing agent as needed.
In this case, a nonionic dispersant is preferably used.

【００３３】また、電極活性物質に添加する結着剤の量
は、電極活性物質１００重量部に対して、１〜３０重量
部であることが望ましく、さらに望ましくは３〜１５重
量部である。この添加量が多すぎても少なすぎても高性
能な電池を得ることができない。さらに、電極構成物質
層には、必要に応じて、導電性付与剤やその他添加剤
（酸化銅等）等を添加してもよい。The amount of the binder added to the electrode active substance is preferably 1 to 30 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the electrode active substance. If the amount is too large or too small, a high-performance battery cannot be obtained. Further, a conductivity-imparting agent or other additives (such as copper oxide) may be added to the electrode constituent material layer as needed.

【００３４】本発明のポリフッ化ビニリデン系金属接着
性組成物においては、リチウム電池に通常用いられるカ
ーボネート系溶媒に対する膨潤性は、未変成のフッ化ビ
ニリデン単独重合体と同程度である。また、ＤＳＣによ
る観測において、未変成のフッ化ビニリデン単独重合体
に対する融点である１７０℃付近にピークが観測され、
耐熱性の劣化は認められない。このように、本発明の金
属接着性組成物は、集電体への接着性のみならず非水系
のリチウム電池の電極の結着剤に要求される性能を全て
備えている。In the polyvinylidene fluoride-based metal adhesive composition of the present invention, the swelling property with respect to a carbonate-based solvent generally used for a lithium battery is almost the same as that of an unmodified vinylidene fluoride homopolymer. Further, in the observation by DSC, a peak was observed at around 170 ° C., which is the melting point of the unmodified vinylidene fluoride homopolymer,
No deterioration in heat resistance is observed. As described above, the metal adhesive composition of the present invention has not only the adhesiveness to the current collector but also all the properties required for a binder for an electrode of a non-aqueous lithium battery.

【００３５】以下、実施例により本発明を説明するが、
本発明は実施例により何ら限定されるものではない。Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited at all by the examples.

【００３６】[0036]

【実施例】【Example】

【実施例１】ポリフッ化ビニリデン（エルフ・アトケム
社製、カイナー３０１Ｆ、２３０℃、２．１６ｋｇ荷重
下でのＭＦＲが０．０３ｇ／１０分）１００重量部およ
びジコハク酸パーオキサイド２重量部をＮ−メチルピロ
リドン１０００重量部に溶解してなる溶液を１２０℃で
３０分間加熱処理を行った後、反応液をメタノール中に
注ぎ、ポリマーを沈澱させた。このポリマーをメタノー
ルにて還流下２４時間ソックスレー抽出を行い、ポリマ
ー中に残留している未反応パーオキサイドおよびパーオ
キサイドの分解物を除去した。このポリマーから作製し
たフィルムを用いて測定したＩＲスペクトルの１７００
〜１８００ｃｍ-1付近のカルボニル基による吸収と８８
１ｃｍ-1のＰＶＤＦに由来する吸収の大きさから、別途
ポリフッ化ビニリデンとジコハク酸パーオキサイドとの
混合体を用いて作製した検量線をもとに算出したカルボ
ニル基含有量は０．０８５ミリ等量／ｇであった。Example 1 100 parts by weight of polyvinylidene fluoride (manufactured by Elf Atochem Co., Ltd., Kynar 301F, MFR under a load of 2.16 kg at 0.03 g / 10 min. At 0.03 g / 10 minutes) and 2 parts by weight of disuccinic acid peroxide were added to N. A solution prepared by dissolving in 1000 parts by weight of methylpyrrolidone was heated at 120 ° C. for 30 minutes, and then the reaction solution was poured into methanol to precipitate a polymer. The polymer was subjected to Soxhlet extraction with methanol for 24 hours under reflux to remove unreacted peroxide and decomposition products of peroxide remaining in the polymer. 1700 of the IR spectrum measured using a film made from this polymer
The absorption due to the carbonyl group around 1800 cm -1 and 88
The carbonyl group content calculated from the magnitude of absorption derived from PVDF of 1 cm -1 based on a calibration curve separately prepared using a mixture of polyvinylidene fluoride and disuccinic acid peroxide was 0.085 mm Amount / g.

【００３７】得られたポリマー１ｇおよびフッ化ビニリ
デンと六フッ化プロピレンとの共重合体（六フッ化プロ
ピレン含量１０重量％、エルフ・アトケム社製、カイナ
ー２８０１、２３０℃、２．１６ｋｇ荷重下でのＭＦＲ
が０．２ｇ／１０分）０．１重量部を、Ｎ−メチルピロ
リドン１０ｇに溶解してなる溶液を、厚さ１ｍｍのアル
ミニウム板および銅板に塗布し、１２０℃で１時間放置
した後、減圧乾燥を行なった。1 g of the obtained polymer and a copolymer of vinylidene fluoride and propylene hexafluoride (propylene hexafluoride content: 10% by weight, manufactured by Elf Atochem Co., Ltd., Kynar 2801, 230 ° C., under a load of 2.16 kg) MFR
Is 0.2 g / 10 min.) A solution prepared by dissolving 0.1 part by weight of N-methylpyrrolidone in 10 g is applied to an aluminum plate and a copper plate having a thickness of 1 mm. Drying was performed.

【００３８】得られたポリマー塗布面を１ｍｍ間隔でカ
ットし、碁盤目試験（ＪＩＳ Ｋ５４００ ６・１５に
準ずる）を行ったところ、ＰＶＤＦ塗布層の付着残留率
は、アルミニウムおよび銅板とも１００％、さらにテー
プ剥離試験を行ったところ、付着残留率は、アルミニウ
ム板では９５％、銅板上では１００％であった。含カル
ボン酸基ポリフッ化ビニリデンと金属板との接着性が良
好であることが確認された。また、ポリマー層を金属板
から剥がし、エチレンカーボネート中、６０℃で７２時
間浸漬後の溶媒膨潤度は２７％であり、未変成のカイナ
ー３０１Ｆに比べやや増加したが、大きな変化は見られ
なかった。The obtained polymer-coated surface was cut at 1 mm intervals and subjected to a grid test (according to JIS K5400 6.15). As a result, the adhesion residual ratio of the PVDF coating layer was 100% for both aluminum and copper plates, and further, When a tape peeling test was performed, the residual adhesion ratio was 95% on the aluminum plate and 100% on the copper plate. It was confirmed that the adhesion between the carboxylic acid-containing polyvinylidene fluoride and the metal plate was good. The polymer layer was peeled off from the metal plate, and the solvent swelling after immersion in ethylene carbonate at 60 ° C. for 72 hours was 27%, which was slightly increased as compared with the unmodified Kainer 301F, but no significant change was observed. .

【００３９】[0039]

【実施例２】ポリフッ化ビニリデン（カイナー３０１
Ｆ）９０重量部、カイナー２８０１を１０重量部、およ
びジコハク酸パーオキサイド２重量部をＮ−メチルピロ
リドン１０００重量部に溶解してなる溶液を１２０℃で
３０分間加熱処理を行った後、反応液をメタノール中に
注ぎ、ポリマーを沈澱させた。このポリマーをメタノー
ルにて還流下２４時間ソックスレー抽出を行い、ポリマ
ーの精製を行った。このポリマーから作製したフィルム
を用いて、ＩＲスペクトルから実施例１と同様に算出し
たカルボニル基含有量は０．１５ミリ等量／ｇであっ
た。Example 2 Polyvinylidene fluoride (Kyner 301)
F) A solution prepared by dissolving 90 parts by weight, 10 parts by weight of Kynar 2801 and 2 parts by weight of disuccinic acid peroxide in 1000 parts by weight of N-methylpyrrolidone was subjected to a heat treatment at 120 ° C. for 30 minutes, and then the reaction solution Was poured into methanol to precipitate the polymer. This polymer was subjected to Soxhlet extraction with methanol for 24 hours under reflux to purify the polymer. Using a film produced from this polymer, the carbonyl group content calculated from the IR spectrum in the same manner as in Example 1 was 0.15 meq / g.

【００４０】こうして得られた樹脂組成物１ｇを、Ｎ−
メチルピロリドン１０ｇに溶解してなる溶液を、厚さ１
ｍｍのアルミニウム板および銅板に塗布し、１２０℃で
１時間放置した後、減圧乾燥を行なった。実施例１と同
様にして、接着性試験として碁盤目試験を行ったとこ
ろ、ＰＶＤＦ塗布層の付着残留率は、アルミニウムおよ
び銅板とも１００％、さらにテープ剥離試験を行ったと
ころ、付着残留率は、アルミニウム板では９０％、銅板
上では９８％であった。含カルボン酸基ポリフッ化ビニ
リデンと金属板との接着性が良好であることが確認され
た。また、金属板から剥がした樹脂を用い実施例１と同
様の方法で測定したエチレンカーボネートでの膨潤度は
２６％であった。1 g of the resin composition thus obtained was mixed with N-
A solution prepared by dissolving 10 g of methylpyrrolidone in a thickness of 1
It was applied to an aluminum plate and a copper plate having a thickness of 1 mm, left at 120 ° C. for 1 hour, and dried under reduced pressure. A cross-cut test was performed as an adhesiveness test in the same manner as in Example 1. The adhesion residual ratio of the PVDF coating layer was 100% for both the aluminum and copper plates, and a tape peeling test was performed. It was 90% on an aluminum plate and 98% on a copper plate. It was confirmed that the adhesion between the carboxylic acid-containing polyvinylidene fluoride and the metal plate was good. The degree of swelling in ethylene carbonate measured by the same method as in Example 1 using the resin peeled from the metal plate was 26%.

【００４１】[0041]

【実施例３】ポリフッ化ビニリデン（エルフ・アトケム
社製、カイナー３０１Ｆ）を９５重量部、カイナー２８
０１を５重量部、無水マレイン酸を１０重量部、および
ラウロイルパーオキサイドを１０重量部をＮ−メチルピ
ロリドンに溶解してなる溶液を１００℃で３０分間加熱
処理を行った後、反応液をメタノール中に注ぎ、ポリマ
ーを沈澱させた。このポリマーをメタノールにて還流下
２４時間ソックスレー抽出を行い、ポリマーの精製を行
った。このポリマーから作製したフィルムを用いて、Ｉ
Ｒスペクトルから実施例１と同様に算出したカルボニル
基含有量は０．０５５ミリ等量／ｇであった。Example 3 95 parts by weight of polyvinylidene fluoride (Kyner 301F, manufactured by Elf Atchem Co., Ltd.), Kyner 28
01, 10 parts by weight of maleic anhydride, and 10 parts by weight of lauroyl peroxide in N-methylpyrrolidone were subjected to a heat treatment at 100 ° C. for 30 minutes. And the polymer was precipitated. This polymer was subjected to Soxhlet extraction with methanol for 24 hours under reflux to purify the polymer. Using a film made from this polymer, I
The carbonyl group content calculated from the R spectrum in the same manner as in Example 1 was 0.055 meq / g.

【００４２】こうして得られた樹脂組成物１ｇを、Ｎ−
メチルピロリドン１０ｇに溶解してなる溶液を、厚さ１
ｍｍのアルミニウム板および銅板に塗布し、１２０℃で
１時間放置した後、減圧乾燥を行なった。実施例１と同
様にして、接着性試験として碁盤目試験を行ったとこ
ろ、ＰＶＤＦ塗布層の付着残留率は、アルミニウムおよ
び銅板とも１００％、さらにテープ剥離試験を行ったと
ころ、付着残留率は、アルミニウム板では９０％、銅板
上では９５％であった。含カルボン酸基ポリフッ化ビニ
リデンと金属板との接着性が良好であることが確認され
た。また、金属板から剥がした樹脂を用い実施例１と同
様の方法で測定したエチレンカーボネートでの膨潤度は
２４％であった。1 g of the resin composition thus obtained was mixed with N-
A solution prepared by dissolving 10 g of methylpyrrolidone in a thickness of 1
It was applied to an aluminum plate and a copper plate having a thickness of 1 mm, left at 120 ° C. for 1 hour, and dried under reduced pressure. A cross-cut test was performed as an adhesiveness test in the same manner as in Example 1. The adhesion residual ratio of the PVDF coating layer was 100% for both the aluminum and copper plates, and a tape peeling test was performed. It was 90% on an aluminum plate and 95% on a copper plate. It was confirmed that the adhesion between the carboxylic acid-containing polyvinylidene fluoride and the metal plate was good. The degree of swelling in ethylene carbonate measured by the same method as in Example 1 using the resin peeled from the metal plate was 24%.

【００４３】[0043]

【実施例４】実施例２においてカイナー３０１Ｆの代わ
りにより高ＭＦＲのポリフッ化ビニリデン（エルフ・ア
トケム社製、カイナー７４１、２３０℃、２．１６ｋｇ
荷重下でのＭＦＲが０．３ｇ／１０分）を用いた他は、
実施例２と同様に金属接着性樹脂組成物を作製した。得
られた樹脂組成物のカルボニル基含有量は０．０４ミリ
等量／ｇであり、実施例２と同様に優れた金属接着性を
示した。また、該樹脂組成物を用い、実施例１と同様の
方法で測定したエチレンカーボネートによる膨潤度は２
５％であった。Example 4 In Example 2, polyvinylidene fluoride having a high MFR (Kyner 741, manufactured by Elf Atochem Co., Ltd., 230 ° C., 2.16 kg) was used instead of Kynar 301F.
Except that the MFR under load is 0.3 g / 10 min)
A metal adhesive resin composition was produced in the same manner as in Example 2. The carbonyl group content of the obtained resin composition was 0.04 meq / g, and showed excellent metal adhesion as in Example 2. The degree of swelling due to ethylene carbonate measured using the resin composition in the same manner as in Example 1 was 2
5%.

【００４４】[0044]

【実施例４】負極活性物質担持体として石炭ピッチコー
クスをボールミルで粉砕したもの１００重量部および結
着剤として実施例２で得られたカルボン酸基を有するポ
リフッ化ビニリデン樹脂組成物１０重量部を混合し、こ
れをＮ−メチルピロリドン中に分散させてスラリー（ペ
ースト）状にした。このスラリーを、集電体としての厚
さ２０μｍのアルミニウム箔の片面に塗布し、１２０℃
で２０分間乾燥し、厚さ１１０μｍ、幅２０ｍｍの負極
を作製した。Example 4 100 parts by weight of a coal pitch coke pulverized by a ball mill as a negative electrode active material carrier and 10 parts by weight of a carboxylic acid group-containing polyvinylidene fluoride resin composition obtained in Example 2 as a binder were used. This was mixed and dispersed in N-methylpyrrolidone to form a slurry (paste). This slurry was applied to one side of a 20 μm-thick aluminum foil as a current collector,
For 20 minutes to produce a negative electrode having a thickness of 110 μm and a width of 20 mm.

【００４５】この電極表面の電極活性層に粘着テープを
接着し、引っ張り試験機により集電体と電極活性層との
接着強度を測定したところ２２０ｇ／ｃｍであった。ま
た、剥がした後、集電体上にかなりの電極活性物質の付
着残留物が認められた、電極活性物質と集電体との接着
性が良好であることが確認された。さらに、直径１ｍｍ
のシリンダーにロール状に巻き付けて行う接着性試験に
おいて、電極活性層の剥離は全く認められず、この後、
電極をエチレンカーボネート中に浸漬し、６０℃で３日
間放置しても電極活性層の剥離は全く認められなかっ
た。An adhesive tape was adhered to the electrode active layer on the surface of the electrode, and the adhesion strength between the current collector and the electrode active layer was measured by a tensile tester to be 220 g / cm. Also, after peeling, considerable residue of the electrode active substance was observed on the current collector, and it was confirmed that the adhesion between the electrode active substance and the current collector was good. Furthermore, diameter 1mm
In an adhesion test performed by winding the film into a roll around the cylinder, no peeling of the electrode active layer was observed at all.
When the electrode was immersed in ethylene carbonate and left at 60 ° C. for 3 days, no peeling of the electrode active layer was observed.

【００４６】[0046]

【実施例４】正極活性物質としてのＬｉＣｏＯ2９４重
量部、導電剤としてのグラファイト６重量部、および結
着剤として実施例３で得られたカルボン酸基を有するＰ
ＶＤＦ樹脂組成物１０重量部を混合し、これをＮ−メチ
ルピロリドン中に分散させてスラリー（ペースト）状に
した。このスラリーを、集電体としての厚さ２０μｍの
銅箔の片面に塗布し、１２０℃で２０分間乾燥し、厚さ
１１０μｍ、幅２０ｍｍの正極を作製した。Example 4 94 parts by weight of LiCoO 2 as a positive electrode active material, 6 parts by weight of graphite as a conductive agent, and the carboxylic acid-containing P obtained in Example 3 as a binder
10 parts by weight of the VDF resin composition were mixed, and this was dispersed in N-methylpyrrolidone to form a slurry (paste). This slurry was applied to one surface of a copper foil having a thickness of 20 μm as a current collector, and dried at 120 ° C. for 20 minutes to produce a positive electrode having a thickness of 110 μm and a width of 20 mm.

【００４７】この電極表面の電極活性層に粘着テープを
接着し、引っ張り試験機により集電体と電極活性層との
接着強度を測定したところ１９０ｇ／ｃｍであった。ま
た、剥がした後、集電体上にかなりの電極活性物質の付
着残留物が認められた、電極活性物質と集電体との接着
性が良好であることが確認された。さらに、直径１ｍｍ
のシリンダーにロール状に巻き付けて行う接着性試験に
おいて、電極活性層の剥離は全く認められず、この後、
電極をエチレンカーボネート中に浸漬し、６０℃で３日
間放置しても電極活性層の剥離は全く認められなかっ
た。An adhesive tape was adhered to the electrode active layer on the electrode surface, and the adhesion strength between the current collector and the electrode active layer was measured by a tensile tester to be 190 g / cm. Also, after peeling, considerable residue of the electrode active substance was observed on the current collector, and it was confirmed that the adhesion between the electrode active substance and the current collector was good. Furthermore, diameter 1mm
In an adhesion test performed by winding the film into a roll around the cylinder, no peeling of the electrode active layer was observed at all.
When the electrode was immersed in ethylene carbonate and left at 60 ° C. for 3 days, no peeling of the electrode active layer was observed.

【００４８】[0048]

【比較例１】ポリフッ化ビニリデン（エルフ・アトケム
社製、カイナー３０１Ｆ）１ｇをＮ−メチルピロリドン
１０ｇに溶解してなる溶液を９０℃で６時間加熱した
後、室温まで冷却し、厚さ１ｍｍのアルミニウム板およ
び銅板に塗布し、１２０℃で１時間放置し、さらに減圧
乾燥を行なった。このポリマー塗布層に対する接着性試
験として、実施例１と同様に碁盤目試験を行ったとこ
ろ、ＰＶＤＦ塗布層の付着残留率は、アルミニウムおよ
び銅板とも２０％以下であった。さらにテープ剥離試験
を行ったところ、ＰＶＤＦ層は全て剥がれた。また、金
属板から剥がした樹脂を用い実施例１と同様の方法で測
定したエチレンカーボネートでの膨潤度は２３％であっ
た。Comparative Example 1 A solution prepared by dissolving 1 g of polyvinylidene fluoride (Kyner 301F, manufactured by Elf Atochem Co., Ltd.) in 10 g of N-methylpyrrolidone was heated at 90 ° C. for 6 hours, and then cooled to room temperature. It was applied to an aluminum plate and a copper plate, left at 120 ° C. for 1 hour, and further dried under reduced pressure. As a test for adhesion to the polymer coating layer, a grid test was performed in the same manner as in Example 1. As a result, the adhesion residual ratio of the PVDF coating layer was 20% or less for both the aluminum and copper plates. Further, when a tape peeling test was performed, the entire PVDF layer was peeled off. The degree of swelling in ethylene carbonate measured by the same method as in Example 1 using the resin peeled from the metal plate was 23%.

【００４９】[0049]

【比較例２】実施例１で得られたカルボン酸基を有する
ポリフッ化ビニリデン樹脂樹脂１ｇを、カイナー２８０
１を添加することなく、Ｎ−メチルピロリドン１０ｇに
溶解してなる溶液を、厚さ１ｍｍのアルミニウム板およ
び銅板に塗布し、１２０℃で１時間放置した後、減圧乾
燥を行なった。COMPARATIVE EXAMPLE 2 1 g of the carboxylic acid group-containing polyvinylidene fluoride resin obtained in Example 1 was applied to a Kynar 280 resin.
Without adding 1, a solution obtained by dissolving in 10 g of N-methylpyrrolidone was applied to an aluminum plate and a copper plate having a thickness of 1 mm, left at 120 ° C. for 1 hour, and dried under reduced pressure.

【００５０】ポリマー塗布層に対する接着性試験とし
て、実施例１同様に碁盤目試験を行ったところ、ＰＶＤ
Ｆ塗布層の付着残留率は、アルミニウムおよび銅板とも
１００％、さらにテープ剥離試験を行ったところ、付着
残留率は、アルミニウム板では５０％、銅板上では８０
％以上であった。ＰＶＤＦ層と金属箔との接着性は実施
例１に比べて劣ることが確認された。As a test for adhesion to the polymer coating layer, a grid test was carried out in the same manner as in Example 1.
The adhesion residual ratio of the F coating layer was 100% for both aluminum and copper plates, and a tape peeling test was performed. The adhesion residual ratio was 50% for aluminum plates and 80% for copper plates.
% Or more. It was confirmed that the adhesiveness between the PVDF layer and the metal foil was inferior to Example 1.

【００５１】[0051]

【比較例３】負極活性物質担持体として石炭ピッチコー
クスをボールミルで粉砕したもの１００重量部および結
着剤としてポリフッ化ビニリデン樹脂（エルフ・アトケ
ム社製、カイナー３０１Ｆ）１０重量部を混合し、これ
をＮ−メチルピロリドン中に分散させてスラリー（ペー
スト）状にした。このスラリーを、集電体としての厚さ
２０μｍのアルミニウム箔の片面に塗布し、１２０℃で
２０分間乾燥し、厚さ１２０μｍ、幅２０ｍｍの負極を
作製した。Comparative Example 3 100 parts by weight of coal pitch coke pulverized by a ball mill as a negative electrode active material carrier and 10 parts by weight of a polyvinylidene fluoride resin (Kyner 301F, manufactured by Elf Atochem) as a binder were mixed. Was dispersed in N-methylpyrrolidone to form a slurry (paste). This slurry was applied to one side of a 20 μm-thick aluminum foil as a current collector, and dried at 120 ° C. for 20 minutes to produce a negative electrode having a thickness of 120 μm and a width of 20 mm.

【００５２】この電極表面の電極活性層に粘着テープを
接着し、引っ張り試験機により集電体と電極活性層との
接着強度を測定したところ４０ｇ／ｃｍと低く、剥がし
た後、集電体上には電極活性物質の付着残留物は見られ
なかった。さらに、直径１ｍｍのシリンダーにロール状
に巻き付けたところ、電極活性層の約２０％が剥離し
た。A pressure-sensitive adhesive tape was adhered to the electrode active layer on the electrode surface, and the adhesion strength between the current collector and the electrode active layer was measured as low as 40 g / cm using a tensile tester. No residue of the electrode active substance was observed. Furthermore, when wound in a roll shape around a cylinder having a diameter of 1 mm, about 20% of the electrode active layer was peeled off.

【００５３】[0053]

【比較例４】負極活性物質担持体として石炭ピッチコー
クスをボールミルで粉砕したもの１００重量部および結
着剤として実施例１で得られたカルボン酸基を有するポ
リフッ化ビニリデン樹脂１０重量部を混合し、これをＮ
−メチルピロリドン中に分散させてスラリー（ペース
ト）状にした。このスラリーを、集電体としての厚さ２
０μｍのアルミニウム箔の片面に塗布し、１２０℃で２
０分間乾燥し、厚さ１２０μｍ、幅２０ｍｍの負極を作
製した。Comparative Example 4 100 parts by weight of a coal pitch coke ground by a ball mill as a negative electrode active material carrier and 10 parts by weight of a carboxylic acid group-containing polyvinylidene fluoride resin obtained in Example 1 as a binder were mixed. , This is N
-Dispersed in methylpyrrolidone to form a slurry (paste). This slurry was used as a current collector to a thickness of 2
Apply to one side of 0 μm aluminum foil,
After drying for 0 minutes, a negative electrode having a thickness of 120 μm and a width of 20 mm was prepared.

【００５４】この電極表面の電極活性層に粘着テープを
接着し、引っ張り試験機により集電体と電極活性層との
接着強度を測定したところ８０ｇ／ｃｍとやや改善され
たが、剥がした後、集電体上には電極活性物質の付着残
留物は見られず、さらに、直径１ｍｍのシリンダーにロ
ール状に巻き付けたところ、電極活性層の一部に剥離が
生じた。An adhesive tape was adhered to the electrode active layer on the electrode surface, and the adhesion strength between the current collector and the electrode active layer was measured by a tensile tester. The adhesion was slightly improved to 80 g / cm. No residue of the electrode active substance was observed on the current collector. Further, when the electrode active material was wound in a roll around a cylinder having a diameter of 1 mm, a part of the electrode active layer was peeled off.

【００５５】[0055]

【発明の効果】本発明により、ＰＶＤＦ系樹脂が本来有
する耐溶剤性や機械的・熱的性質を損なわずに、しか
も、簡便な方法で金属接着性ＰＶＤＦ系樹脂組成物を得
ることが可能となる。本発明の金属接着性ＰＶＤＦ系樹
脂組成物を電池の電極の結着剤に使用すれば、電極活性
物質と集電体との接着強度が強い電極の作製が可能とな
る。これを二次電池に適用すれば、電池製造時における
電極活性物質と集電体との剥離を防止できるばかりでな
く、充放電の繰り返しにより放電容量が劣化しない二次
電池が得られる。本発明は、特に、リチウム二次電池な
ど非水系の二次電池に有用である。Industrial Applicability According to the present invention, it is possible to obtain a metal-adhesive PVDF resin composition by a simple method without impairing the solvent resistance and mechanical and thermal properties inherent in the PVDF resin. Become. When the metal-adhesive PVDF-based resin composition of the present invention is used as a binder for a battery electrode, an electrode having a high adhesive strength between the electrode active material and the current collector can be produced. If this is applied to a secondary battery, it is possible not only to prevent separation of the electrode active material and the current collector during battery manufacture, but also to obtain a secondary battery in which the discharge capacity is not deteriorated by repeated charging and discharging. The present invention is particularly useful for non-aqueous secondary batteries such as lithium secondary batteries.

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】フッ化ビニリデン単独重合体とフッ化ビニ
リデン系共重合体から構成される組成物において、これ
ら重合体の両方あるいは片方が金属接着性を示す官能基
を有し、フッ化ビニリデン系共重合体の含有率が全体の
０．５〜５０重量％であるポリフッ化ビニリデン系金属
接着性組成物。1. A composition comprising a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer, wherein both or one of these polymers has a functional group exhibiting metal adhesion, A polyvinylidene fluoride-based metal adhesive composition having a copolymer content of 0.5 to 50% by weight of the whole. 【請求項２】フッ化ビニリデン系共重合体が、四フッ化
エチレン、六フッ化プロピレン、三フッ化エチレン、お
よび三フッ化塩化エチレンから選ばれる少なくとも１種
類のモノマーとフッ化ビニリデンとの共重合体であり、
該共重合体中のフッ化ビニリデン成分の比率が５０重量
％以上である請求項１記載のポリフッ化ビニリデン系金
属接着性組成物。2. A vinylidene fluoride copolymer comprising at least one monomer selected from ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride and ethylene trifluoride chloride and vinylidene fluoride. A polymer,
2. The polyvinylidene fluoride-based metal adhesive composition according to claim 1, wherein the ratio of the vinylidene fluoride component in the copolymer is 50% by weight or more. 【請求項３】フッ化ビニリデン単独重合体とフッ化ビニ
リデン系共重合体の両方あるいはいずれか片方に、
（ａ）金属接着性を示す官能基を有する有機過酸化物を
加熱下作用させる方法あるいは（ｂ）金属接着性を示す
官能基を有する不飽和有機化合物と過酸化物の存在下で
加熱処理する方法のいずれかにより、金属接着性を示す
官能基が導入された請求項１および２記載のポリフッ化
ビニリデン系金属接着性組成物。3. A method according to claim 1, wherein the vinylidene fluoride homopolymer and / or the vinylidene fluoride-based copolymer are
(A) a method in which an organic peroxide having a functional group having metal adhesiveness is caused to act under heating or (b) a heat treatment in the presence of a peroxide and an unsaturated organic compound having a functional group having metal adhesiveness. 3. The polyvinylidene fluoride-based metal adhesive composition according to claim 1, wherein a functional group exhibiting metal adhesiveness is introduced by any of the methods. 【請求項４】金属接着性を示す官能基が、カルボキシル
基、カルボン酸無水物基およびカルボン酸エステル基か
ら選ばれる少なくとも１つの官能基である請求項１〜３
記載のポリフッ化ビニリデン系金属接着性組成物。4. The functional group exhibiting metal adhesiveness is at least one functional group selected from a carboxyl group, a carboxylic anhydride group and a carboxylic ester group.
The polyvinylidene fluoride-based metal adhesive composition according to the above. 【請求項５】ポリフッ化ビニリデン系樹脂に化学結合に
より固定されるカルボン酸基、カルボン酸無水物基およ
びカルボン酸エステル基から選ばれる少なくとも１つの
官能基の量が当該組成物の０．００２〜２ミリ等量／ｇ
である請求項１〜４記載のポリフッ化ビニリデン系金属
接着性組成物。5. The amount of at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group and a carboxylic acid ester group, which is fixed to the polyvinylidene fluoride resin by a chemical bond, is 0.002 to 0.002%. 2 milliequivalents / g
The polyvinylidene fluoride-based metal adhesive composition according to claim 1, wherein 【請求項６】フッ化ビニリデン単独重合体とフッ化ビニ
リデン系共重合体からなり、フッ化ビニリデン系共重合
体の含有率が全体の０．５〜５０重量％である混合物
に、カルボキシル基、カルボン酸無水物基およびカルボ
ン酸エステル基から選ばれる少なくとも１つの官能基を
有する有機過酸化物を、溶液中あるいは溶融状態で、加
熱下、作用させることによるポリフッ化ビニリデン系金
属接着性組成物の製造方法。6. A mixture comprising a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer, wherein the content of the vinylidene fluoride copolymer is 0.5 to 50% by weight of the mixture, An organic peroxide having at least one functional group selected from a carboxylic acid anhydride group and a carboxylic acid ester group, in a solution or in a molten state, being heated and allowed to act on a polyvinylidene fluoride-based metal adhesive composition. Production method. 【請求項７】カルボキシル基、カルボン酸無水物基およ
びカルボン酸エステル基から選ばれる少なくとも１つの
官能基を有する有機過酸化物を、溶液中あるいは溶融状
態で、加熱下、作用させることにより変性されたフッ化
ビニリデン単独重合体１００重量部およびフッ化ビニリ
デン系共重合体０．５〜１００重量部を混合させること
によるポリフッ化ビニリデン系金属接着性組成物の製造
方法7. An organic peroxide having at least one functional group selected from a carboxyl group, a carboxylic anhydride group and a carboxylic ester group, which is modified by allowing it to act in a solution or in a molten state under heating. For producing a polyvinylidene fluoride-based metal adhesive composition by mixing 100 parts by weight of a vinylidene fluoride homopolymer and 0.5 to 100 parts by weight of a vinylidene fluoride-based copolymer 【請求項８】フッ化ビニリデン系共重合体が、四フッ化
エチレン、六フッ化プロピレン、三フッ化エチレン、お
よび三フッ化塩化エチレンから選ばれる少なくとも１種
類のモノマーとフッ化ビニリデンとの共重合体であり、
該共重合体中のフッ化ビニリデン成分の比率が５０重量
％以上である請求項６あるいは７記載のポリフッ化ビニ
リデン系金属接着性組成物の製造方法。8. A copolymer of vinylidene fluoride with at least one monomer selected from ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride and ethylene trifluoride chloride. A polymer,
8. The method for producing a polyvinylidene fluoride-based metal adhesive composition according to claim 6, wherein the ratio of the vinylidene fluoride component in the copolymer is 50% by weight or more. 【請求項９】ポリフッ化ビニリデン系樹脂１００重量部
に対して、カルボン酸基、カルボン酸無水物基およびカ
ルボン酸エステル基から選ばれる少なくとも１つの官能
基を有する有機過酸化物０．５〜１００重量部を作用さ
せることを特徴とする請求項６〜８記載のポリフッ化ビ
ニリデン系金属接着性組成物の製造方法。9. An organic peroxide having at least one functional group selected from carboxylic acid groups, carboxylic acid anhydride groups and carboxylic acid ester groups, based on 100 parts by weight of polyvinylidene fluoride resin. 9. The method for producing a polyvinylidene fluoride-based metal adhesive composition according to claim 6, wherein a part by weight is applied. 【請求項１０】集電体の表面に少なくとも電極活性物質
と結着剤からなる電極構成物質層が形成されている電池
用電極において、結着剤が請求項１記載のポリフッ化ビ
ニリデン系金属接着性組成物であることを特徴とする電
極。10. A polyvinylidene fluoride-based metal bond according to claim 1, wherein the binder is used in a battery electrode in which an electrode constituent material layer comprising at least an electrode active material and a binder is formed on the surface of a current collector. An electrode, which is a conductive composition.
JP9114691A 1997-05-02 1997-05-02 Polyvinylidene fluoride-based composition adhesive to metal and electrode for battery Pending JPH10306265A (en)

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JP9114691A JPH10306265A (en) 1997-05-02 1997-05-02 Polyvinylidene fluoride-based composition adhesive to metal and electrode for battery
PCT/EP1998/002783 WO1998050479A1 (en) 1997-05-02 1998-04-29 A polyvinylidene fluoride metal-adhesive composition and an electrode for a battery
AU77641/98A AU7764198A (en) 1997-05-02 1998-04-29 A polyvinylidene fluoride metal-adhesive composition and an electrode for a battery
TW087106891A TW388138B (en) 1997-05-02 1998-05-05 A polyvinylidene fluoride metal-adhesive composition and an electrode for a battery

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AU (1) AU7764198A (en)
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Also Published As

Publication number Publication date
AU7764198A (en) 1998-11-27
WO1998050479A1 (en) 1998-11-12
TW388138B (en) 2000-04-21

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