JP2002008665A - Conductive resin sheet and method for producing the same - Google Patents
Conductive resin sheet and method for producing the sameInfo
- Publication number
- JP2002008665A JP2002008665A JP2000186136A JP2000186136A JP2002008665A JP 2002008665 A JP2002008665 A JP 2002008665A JP 2000186136 A JP2000186136 A JP 2000186136A JP 2000186136 A JP2000186136 A JP 2000186136A JP 2002008665 A JP2002008665 A JP 2002008665A
- Authority
- JP
- Japan
- Prior art keywords
- conductive
- sheet
- conductive resin
- conductive layer
- resin
- 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
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 79
- 239000011347 resin Substances 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000005540 biological transmission Effects 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 238000009832 plasma treatment Methods 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 41
- 239000011342 resin composition Substances 0.000 description 15
- 239000004020 conductor Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 3
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000657326 Homo sapiens Protein TANC2 Proteins 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 102100034784 Protein TANC2 Human genes 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
(57)【要約】
【課題】ピンホール等の存在しない、耐薬品性に優れた
品質良好な導電性樹脂シートを提供すること。
【解決手段】非導電層の少なくとも片表面に導電層を有
する導電性樹脂シートであって、その非導電層の体積固
有抵抗が１０3Ω・ｃｍ以上、その電層の体積固有抵抗
が１００Ω・ｃｍ以下、水蒸気透過率が５０ｇ／（ｍ2
・day）未満である導電性樹脂シート。(57) [Problem] To provide a high-quality conductive resin sheet excellent in chemical resistance and free of pinholes and the like. A conductive resin sheet having a conductive layer on at least one surface of a non-conductive layer, wherein the non-conductive layer has a volume resistivity of 10 3 Ω · cm or more, and the volume resistivity of the electric layer is 100 Ω · cm. cm or less, and the water vapor transmission rate is 50 g / (m 2
・ A conductive resin sheet that is less than day).
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐薬品性、耐ピン
ホール性および導電性に優れた導電性樹脂シートおよび
その製造方法に関するものであり、詳しくは本発明は、
１次電池または２次電池の電極材用途に好適な優れた品
質を有する導電性樹脂シートおよびその導電性樹脂シー
トを製造する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive resin sheet excellent in chemical resistance, pinhole resistance and conductivity, and a method for producing the same.
The present invention relates to a conductive resin sheet having excellent quality suitable for use as an electrode material of a primary battery or a secondary battery, and a method for producing the conductive resin sheet.
【０００２】[0002]
【従来の技術】従来、樹脂からなる導電性シートは、金
属繊維やカーボンブラックなどの導電体を高濃度に樹脂
に配合し、スリットダイを用いた溶融押出しまたは射出
成形によって導電性樹脂シートが製造されている。ま
た、カーボンブラックを高濃度に含有させる方法が、特
開平８−２４４０５６号公報に示されている。2. Description of the Related Art Conventionally, a conductive sheet made of a resin is prepared by blending a conductive material such as metal fiber or carbon black with the resin at a high concentration, and performing melt extrusion or injection molding using a slit die. Have been. Further, a method of containing carbon black at a high concentration is disclosed in Japanese Patent Application Laid-Open No. H8-244056.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、このよ
うな従来の導電性樹脂シートでは、次のような欠点が存
在した。すなわち、金属繊維を樹脂に含有させる方法で
は、シートを溶融押し出しによって安価に製造すること
が困難であり、射出成形などによらなければシートを得
ることができなかった。また、カーボンブラックを樹脂
に含有させる方法では、カーボンブラックを高濃度に含
有させなければ十分な導電性を得ることができず、この
場合にはシートにピンホールが生成したり機械特性の低
下を免れることができなかった。さらに、これらの導電
性樹脂シートの表面では、導電体が樹脂に包まれている
ために表面抵抗値が大きくならざるを得なかった。However, such a conventional conductive resin sheet has the following disadvantages. That is, it is difficult to produce a sheet at low cost by melt extrusion by a method of incorporating metal fibers into a resin, and a sheet cannot be obtained without injection molding or the like. In addition, in the method in which carbon black is contained in a resin, sufficient conductivity cannot be obtained unless carbon black is contained in a high concentration. In this case, pinholes are generated in a sheet or mechanical properties are reduced. I could not escape. Furthermore, on the surface of these conductive resin sheets, since the conductor is wrapped in the resin, the surface resistance value has to be increased.
【０００４】一方、金属箔は導電性シートとして優れた
導電性を有しているが、金属は密度が樹脂に比較して大
きく、金属箔を電池の電極材として用いた場合、電池の
重量あたりの電気出力が小さくなっていた。[0004] On the other hand, metal foil has excellent conductivity as a conductive sheet, but metal has a higher density than resin, and when metal foil is used as an electrode material of a battery, the weight per weight of the battery is low. The electrical output of was small.
【０００５】本発明の目的は、上記した従来技術の欠点
を解消し、耐薬品性、耐ピンホール性および導電性に優
れた導電性樹脂シートおよびその製造方法を提供するこ
とにある。An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide a conductive resin sheet excellent in chemical resistance, pinhole resistance and conductivity, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上述した
問題に鑑み鋭意検討した結果、導電層と非導電層を積層
した導電性樹脂シートによって前記問題が解決できるこ
とを見出し本発明をなすに至った。Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, have found that the above problems can be solved by a conductive resin sheet in which a conductive layer and a non-conductive layer are laminated. Reached.
【０００７】すなわち、本発明の導電性樹脂シートは、
非導電層の少なくとも片表面に導電層を有する導電性樹
脂シートであり、該非導電層の体積固有抵抗が１０3Ω
・ｃｍ以上、該導電層の体積固有抵抗が１００Ω・ｃｍ
以下、シートの水蒸気透過率が５０ｇ／（ｍ2・day）未
満であることを特徴とする導電性樹脂シートである。That is, the conductive resin sheet of the present invention comprises:
A conductive resin sheet having a conductive layer on at least one surface of the non-conductive layer, wherein the non-conductive layer has a volume resistivity of 10 3 Ω.
Cm or more, the volume resistivity of the conductive layer is 100 Ωcm
Hereinafter, a conductive resin sheet characterized in that the sheet has a water vapor transmission rate of less than 50 g / (m 2 · day).
【０００８】また、本発明の導電性樹脂シートの製造方
法は、非導電性樹脂を溶融し口金から押出すことで非導
電性シートを製造する工程および導電性樹脂を溶融し口
金から溶融シートとして非導電性シート上に押出し、ラ
ミネーションする工程からなることを特徴とする導電性
樹脂シートの製造方法、または、導電性樹脂を溶融し口
金から押出すことで導電性シートを製造する工程および
非導電性樹脂を溶融し口金から溶融シートとして導電性
シート上に押出し、ラミネーションする工程からなるこ
とを特徴とする導電性樹脂シートの製造方法である。Further, the method for producing a conductive resin sheet of the present invention comprises a step of producing a non-conductive sheet by melting and extruding a non-conductive resin from a die, and a step of melting the conductive resin to form a molten sheet from the die. A method of manufacturing a conductive resin sheet, comprising a step of extruding on a non-conductive sheet and laminating, or a step of manufacturing a conductive sheet by melting and extruding a conductive resin from a die; A method for producing a conductive resin sheet, comprising a step of melting a conductive resin, extruding a molten sheet from a die as a molten sheet onto a conductive sheet, and laminating the conductive sheet.
【０００９】[0009]
【発明の実施の形態】以下、本発明の好ましい実施の形
態を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described.
【００１０】本発明における導電性樹脂シートは、体積
固有抵抗が１０3Ω・ｃｍ以上である非導電層の少なく
とも片表面に、体積固有抵抗が１００Ω・ｃｍ以下であ
る導電層を設けたものである。非導電層の体積固有抵抗
が１０3Ω・ｃｍ未満である場合、これに添加する導電
性粒子のためにピンホールが発生し、さらに引っ張り特
性などの機械特性が低下する。非導電層の体積固有抵抗
は、実用上１０14Ω・ｃｍまでで十分である。非導電性
層の体積固有抵抗を１０3Ω・ｃｍ以上とする方法であ
るが、通常の熱可塑性樹脂（例えば、ポリオレフィン）
であれば、１０ 10Ω・ｃｍ以上の体積固有抵抗を有して
いるので、該層に添加する導電性粒子の量を調整するこ
とで自在に設定することができる。また、導電層の体積
固有抵抗が１００Ω・ｃｍを超える場合、導電性が不十
分となり電池の集電体としての使用に不適である。電池
電極材としては抵抗値は低いほど好ましく、特に１０Ω
・ｃｍ未満が、さらには１Ω・ｃｍ未満が好ましい。導
電性樹脂シートとしては、水蒸気透過率が５０ｇ／（ｍ
2・day）未満であることが必要である。水蒸気透過率が
５０ｇ／（ｍ2・day）以上である場合、導電性シートに
実質的にピンホールが形成されており、電池の集電体と
して用いたときに電解液の漏れや電極活物質の漏れを招
く。The conductive resin sheet of the present invention has a volume
Specific resistance is 10ThreeLess non-conductive layer of Ω · cm or more
Both have a volume resistivity of 100 Ωcm or less on one surface.
In which a conductive layer is provided. Volume resistivity of non-conductive layer
Is 10ThreeIf it is less than Ω · cm, the conductivity added to this
Pinholes are generated due to conductive particles,
The mechanical properties such as properties are reduced. Volume resistivity of non-conductive layer
Is practically 1014Up to Ω · cm is sufficient. Non-conductive
The volume resistivity of the layer is 10ThreeΩ · cm or more
But ordinary thermoplastic resin (eg polyolefin)
Then 10 TenWith volume resistivity of Ω · cm or more
Therefore, adjust the amount of conductive particles added to the layer.
And can be set freely. Also, the volume of the conductive layer
If the specific resistance exceeds 100Ω · cm, the conductivity is insufficient.
This is unsuitable for use as a battery current collector. battery
As the electrode material, the lower the resistance value is, the more preferable it is.
Cm, more preferably less than 1 Ωcm. Guidance
The conductive resin sheet has a water vapor transmission rate of 50 g / (m
Two・ It is necessary to be less than day). Water vapor transmission rate
50 g / (mTwo・ Day) or more, the conductive sheet
A pinhole is formed substantially, and the current collector of the battery
Causes leakage of electrolyte and leakage of the electrode active material.
Good.
【００１１】導電性シートの水蒸気透過率を５０ｇ／
（ｍ2・day）未満とするには、シートのピンホールをな
くすこと、シート厚みを厚くすることや水蒸気透過率の
低い樹脂を使用するなどの方法で実施することができ
る。The water vapor transmission rate of the conductive sheet is 50 g /
(M 2 · day) can be achieved by a method such as eliminating pinholes in the sheet, increasing the thickness of the sheet, or using a resin having a low water vapor transmission rate.
【００１２】導電層のみの導電性樹脂シートではピンホ
ールが発生しやすく、水蒸気透過率が大きくなる。そこ
でピンホールが存在しない非導電層を積層することで上
記した水蒸気透過率を得ることが出来る。さらに、非導
電層は機械特性に劣る導電層を支持する役割もある。In a conductive resin sheet having only a conductive layer, pinholes are easily generated, and the water vapor permeability is increased. Therefore, the above-described water vapor transmission rate can be obtained by laminating a non-conductive layer having no pinhole. Further, the non-conductive layer also has a role of supporting a conductive layer having poor mechanical properties.
【００１３】本発明において、導電層は樹脂と導電性粒
子から構成されることが好ましく、導電性粒子として
は、カーボンブラック、金属、金属酸化物から選ぶこと
が好ましく、特に耐薬品性にも優れ、樹脂への分散性に
も優れたカーボンブラックが好ましく用いられる。これ
ら導電体としての導電性粒子の導電層への添加量は、１
０重量％以上であることが導電層の体積固有抵抗値を１
００Ω・ｃｍ以下とする上で好ましく、より好ましくは
３０重量％以上である。導電性粒子の添加量は多いほど
シートの導電性は向上するが、分散性などの点から６０
重量％以下が好ましい。In the present invention, the conductive layer is preferably composed of a resin and conductive particles. The conductive particles are preferably selected from carbon black, metal and metal oxide, and are particularly excellent in chemical resistance. Carbon black excellent in dispersibility in resin is preferably used. The amount of the conductive particles added to the conductive layer as the conductor is 1
0% by weight or more requires the volume resistivity of the conductive layer to be 1
The content is preferably set to not more than 00 Ω · cm, more preferably not less than 30% by weight. The larger the amount of the conductive particles, the higher the conductivity of the sheet.
% By weight or less is preferred.
【００１４】導電層および／または非導電層を構成する
樹脂は、耐薬品性に優れたポリオレフィン樹脂を用いる
ことが好ましく、特にポリエチレン、ポリプロピレン、
ポリエチレンプロピレン共重合体あるいはポリスチレン
が好ましく用いられる。As the resin constituting the conductive layer and / or the non-conductive layer, it is preferable to use a polyolefin resin having excellent chemical resistance.
Polyethylene propylene copolymer or polystyrene is preferably used.
【００１５】導電層および非導電層を構成する樹脂は同
種でも異種でもかまわないが、同種樹脂同士が層間接着
性が良好なことから好ましい。The resin constituting the conductive layer and the non-conductive layer may be the same or different, but the same resin is preferable because of good interlayer adhesion.
【００１６】本発明の導電性樹脂シートの厚みには特に
限定はないが、機械強度などの観点から２５μｍ以上で
あることが好ましく、さらには５０μｍから１ミリの範
囲であることが好ましい。各層の厚み比率も特に限定は
ないが、導電層として１５μｍ以上、さらには３０μｍ
以上であることが好ましい。非導電層の場合、１０μｍ
以上であればよい。The thickness of the conductive resin sheet of the present invention is not particularly limited, but is preferably 25 μm or more, more preferably 50 μm to 1 mm, from the viewpoint of mechanical strength and the like. The thickness ratio of each layer is not particularly limited, but is 15 μm or more as a conductive layer, and further 30 μm.
It is preferable that it is above. 10 μm for non-conductive layer
All that is required is the above.
【００１７】導電層を構成する樹脂組成物は、カーボン
ブラックなどの導電体をポリエチレンなどの樹脂に溶融
混練することで得ることができる。もちろん必要に応じ
てその他の添加物、例えば、ブロッキング防止剤、増量
剤、安定剤、酸化防止剤、減粘・増粘剤およびその他樹
脂を添加する事が出来る。溶融混練は、２軸混練機など
の従来から公知の装置を用いることができる。また、非
導電層においても導電層と同様に、必要に応じて各種の
添加剤を添加することが出来る。The resin composition constituting the conductive layer can be obtained by melting and kneading a conductor such as carbon black with a resin such as polyethylene. Of course, other additives such as an antiblocking agent, a bulking agent, a stabilizer, an antioxidant, a viscosity reducing / thickening agent, and other resins can be added as needed. For the melt kneading, a conventionally known device such as a twin-screw kneader can be used. In addition, various additives can be added to the non-conductive layer as needed, similarly to the conductive layer.
【００１８】本発明の導電性樹脂シートの製造方法は、
上記した導電体を含有する樹脂組成物を溶融押出機に供
給して溶融し、口金から押し出すことでシート化する工
程、さらに該シート上に非導電性樹脂組成物を押出機に
供給して溶融し、口金から押し出すことでラミネーショ
ンする工程からなる。さらに、導電性の樹脂組成物と非
導電性の樹脂組成物を入れ替えた工程、すなわち、非導
電性の樹脂組成物を溶融押出機に供給して溶融し、口金
から押し出すことでシート化する工程、さらに該シート
上に導電体を含有する樹脂組成物を押出機に供給して溶
融し、口金から押し出すことでラミネーションする工程
からなる。樹脂組成物の溶融押し出しは、従来から公知
の押出機を用いることができ、Ｔダイ口金などから溶融
シートとして押し出す。溶融シートは、冷却体上に密着
させることで冷却され、固化したシートとなる。冷却さ
れ固化したシート（冷却体）は、例えば、回転金属ドラ
ムなどを用いることができ、該冷却体にエアーナイフな
どの密着手段によって密着・冷却固化させる。さらに、
導電層または非導電層となる樹脂組成物を第２の押出機
で溶融押し出しし、溶融シートを第一の工程で得られた
シート上に吐出することでラミネーションするのであ
る。このような工程により、導電層／非導電層からなる
導電性樹脂シートを得ることが出来る。なお、必要に応
じて第３の押出機を使用すれば、シートの両表面を導電
層としたシートを得ることが出来る。The method for producing a conductive resin sheet according to the present invention comprises:
A step of supplying the resin composition containing the above-described conductor to a melt extruder to melt and extrude it from a die into a sheet, and further supplying a non-conductive resin composition to the extruder to melt the sheet on the sheet; And lamination by extruding from a base. Furthermore, the step of exchanging the conductive resin composition and the non-conductive resin composition, that is, the step of supplying the non-conductive resin composition to a melt extruder to melt and extrude from a die to form a sheet. And laminating the resin composition containing a conductor on the sheet by supplying the resin composition to an extruder and extruding the resin composition from a die. For extruding the resin composition, a conventionally known extruder can be used, and the resin composition is extruded as a molten sheet from a T-die die or the like. The molten sheet is cooled by bringing it into close contact with the cooling body, and becomes a solidified sheet. As the cooled and solidified sheet (cooling body), for example, a rotating metal drum or the like can be used, and the cooling body is brought into close contact with the cooling body by cooling means such as an air knife and solidified by cooling. further,
Lamination is performed by extruding a resin composition to be a conductive layer or a non-conductive layer with a second extruder and discharging the molten sheet onto the sheet obtained in the first step. Through such steps, a conductive resin sheet including a conductive layer / a non-conductive layer can be obtained. If a third extruder is used as required, a sheet having both surfaces of the sheet as conductive layers can be obtained.
【００１９】このようにして得られた導電性樹脂シート
には優れた導電性が発現するが、シート表面では、導電
性粒子が樹脂によって包まれているために表面抵抗が大
きくなる。そこで、表面に存在する樹脂を除去し、導電
性粒子を露出させることが好ましい。シート表面の樹脂
を除去し、導電性粒子を露出させる方法として、火炎処
理やプラズマ処理を施すことが好ましい。火炎処理と
は、可燃性気体をノズルから噴射して火炎を発生させ、
この火炎によってシート表面の樹脂の一部を燃焼・酸化
せせる処理をいう。また、プラズマ処理は、希ガスまた
は大気中に高電圧を印可し、プラズマ化した気体によっ
てシート表面の樹脂を処理する方法を指す。火炎処理、
プラズマ処理のいずれも従来から公知の装置によって行
なうことができる。さらに、機械的な研磨処理によって
も同様な効果を得ることができ、例えば、研磨剤を含有
した回転ロールによってシート表面を研磨する方法を好
ましく挙げることが出来る。Although the conductive resin sheet thus obtained exhibits excellent conductivity, the surface of the sheet has a large surface resistance because the conductive particles are wrapped in the resin. Therefore, it is preferable to remove the resin present on the surface to expose the conductive particles. As a method of removing the resin on the sheet surface and exposing the conductive particles, it is preferable to perform a flame treatment or a plasma treatment. Flame treatment means that a combustible gas is injected from a nozzle to generate a flame,
The process of burning and oxidizing a part of the resin on the sheet surface by the flame. In addition, the plasma treatment refers to a method in which a high voltage is applied to a rare gas or the atmosphere, and the resin on the sheet surface is treated with the plasma gas. Flame treatment,
Any of the plasma treatments can be performed by a conventionally known apparatus. Further, the same effect can be obtained by a mechanical polishing treatment. For example, a method of polishing the sheet surface by a rotating roll containing an abrasive can be preferably mentioned.
【００２０】このようにして得られた導電性樹脂シート
は、優れた導電性、耐薬品性および耐ピンホール性を有
しており、電池の集電体として好ましく用いることが出
来る。例えば、鉛蓄電池の場合、従来は正極・負極とも
に集電体として鉛または鉛合金が使用されているが、こ
れらの金属は密度が大きく、電池重量を増す原因の一つ
となっており、重量あたりのエネルギー密度を低下させ
ていた。そこで、鉛蓄電池では負極集電体として本発明
の導電性樹脂シートを用いることにより、電池の重量エ
ネルギー密度を向上させることができるのである。本発
明の導電性樹脂シートは、熱を加えることで熱接着を行
なうことも可能であり、本シートと正極集電体をスペー
サーを介して接着させ、間に電解液を満たすことで電池
セルを構成することもできる。The conductive resin sheet thus obtained has excellent conductivity, chemical resistance and pinhole resistance, and can be preferably used as a current collector of a battery. For example, in the case of a lead-acid battery, lead or a lead alloy is conventionally used as a current collector for both the positive electrode and the negative electrode. Energy density was reduced. Thus, in the lead storage battery, the weight energy density of the battery can be improved by using the conductive resin sheet of the present invention as the negative electrode current collector. The conductive resin sheet of the present invention can also be thermally bonded by applying heat, and the present sheet and the positive electrode current collector are bonded via a spacer, and the battery cell is filled with an electrolytic solution therebetween. It can also be configured.
【００２１】［物性の測定法］次に、本発明で使用した
測定法について述べる。[Measurement Method of Physical Properties] Next, the measurement method used in the present invention will be described.
【００２２】１．シートの体積固有抵抗 ＪＩＳ−Ｋ７１９４法に則り、４探針法によって測定し
た。1. Volume resistivity of sheet Measured by a four-probe method in accordance with JIS-K7194.
【００２３】２．水蒸気透過率 ＪＩＳ−Ｋ７１２９法に則り、Ｍｏｄｅｒｎ Ｃｏｎｔ
ｒｏｌｓ Ｉｎｃ製ＰＥＲＭＡＴＲＡＮ−Ｗ３／３０に
より、２５±０．５℃、相対湿度９０±２％ＲＨの条件
で測定した。2. Water vapor permeability According to JIS-K7129 method, Modern Cont
The measurement was performed with PERMATRAN-W3 / 30 manufactured by rols Inc. under the conditions of 25 ± 0.5 ° C. and 90 ± 2% RH.
【００２４】[0024]
【実施例】実施例により、本発明をさらに詳細に説明す
る。The present invention will be described in more detail by way of examples.
【００２５】［実施例１］低密度ポリエチレンとして、
住友化学工業（株）製スミカセンＬ４３０を６０重量
部、旭カーボン（株）製カーボンブラック旭＃８０を４
０重量部混合し、２軸混練機によって溶融混練し、導電
性の樹脂組成物Ａを得た。また、カーボンブラックを添
加しないスミカセンＬ４３０をそのまま非導電性の樹脂
Ｂとして用いた。非導電性の樹脂Ｂをシリンダー径９０
ミリの押し出し機に供給し、２８０℃で溶融押し出し、
幅４００ミリのＴダイから溶融シートとして金属ドラム
上に押し出した。金属ドラムは、直径５００ミリ、表面
温度が２０℃であり、溶融シートはエアーナイフによっ
て金属ドラムに密着させた。次に、シリンダー径が４０
ミリである第２の押し出し機に導電性の樹脂組成物Ａを
供給し、３２０℃で溶融押し出し、幅４００ミリのコー
ティング用Ｔダイから先に得た非道電性の樹脂Ｂからな
るシート上に溶融シートを押し出した。溶融シートはチ
ルロールによって冷却し、導電層が１５μｍ、非導電層
が４０μｍである２層積層導電性樹脂シートを得た。得
られた導電性樹脂シートの特性を表１に示す。水蒸気透
過率が低いことがピンホールが存在しないことを示して
いる。Example 1 As a low-density polyethylene,
60 parts by weight of Sumikasen L430 manufactured by Sumitomo Chemical Co., Ltd. and 4 carbon black Asahi # 80 manufactured by Asahi Carbon Co., Ltd.
0 parts by weight were mixed and melt-kneaded by a biaxial kneader to obtain a conductive resin composition A. In addition, Sumikasen L430 without addition of carbon black was used as the non-conductive resin B as it was. Non-conducting resin B with cylinder diameter 90
Milled extruder, melt extruded at 280 ° C,
It was extruded on a metal drum as a molten sheet from a 400 mm wide T-die. The metal drum had a diameter of 500 mm and a surface temperature of 20 ° C. The molten sheet was brought into close contact with the metal drum with an air knife. Next, when the cylinder diameter is 40
The conductive resin composition A is supplied to a second extruder, which is a millimeter, melt-extruded at 320 ° C., and is placed on a sheet made of the non-conductive resin B obtained earlier from a 400 mm wide coating T-die. The molten sheet was extruded. The molten sheet was cooled by a chill roll to obtain a two-layer laminated conductive resin sheet having a conductive layer of 15 μm and a non-conductive layer of 40 μm. Table 1 shows the properties of the obtained conductive resin sheet. A low water vapor transmission rate indicates the absence of pinholes.
【００２６】［比較例１］導電性の樹脂組成物Ａをシリ
ンダー径９０ミリの押し出し機に供給し、実施例１と同
様にシートを得た。このようにして導電層のみからなる
導電性樹脂シートを得た。特性を表１に示す。Comparative Example 1 A conductive resin composition A was supplied to an extruder having a cylinder diameter of 90 mm, and a sheet was obtained in the same manner as in Example 1. Thus, a conductive resin sheet consisting of only the conductive layer was obtained. Table 1 shows the characteristics.
【００２７】［実施例２］カーボンブラック粒子を二酸
化錫に変更した以外は、実施例１と同様にして導電性樹
脂シートを得た。特性を表１に示す。Example 2 A conductive resin sheet was obtained in the same manner as in Example 1 except that the carbon black particles were changed to tin dioxide. Table 1 shows the characteristics.
【００２８】［実施例３］カーボンブラック粒子を金属
銅粒子に変更した以外は、実施例１と同様にして導電性
樹脂シートを得た。特性を表１に示す。Example 3 A conductive resin sheet was obtained in the same manner as in Example 1, except that the carbon black particles were changed to metal copper particles. Table 1 shows the characteristics.
【００２９】［実施例４］樹脂として（株）グランドポ
リマー製ポリプロピレン樹脂Ｆ７６９を用い、第２の押
出機から押し出す温度を実施例１の３２０℃から３００
℃へ変更した以外は、実施例１と同様にしてシートを得
た。特性を表１に示す。Example 4 A polypropylene resin F769 made by Grand Polymer Co., Ltd. was used as the resin, and the temperature at which the resin was extruded from the second extruder was changed from 320 ° C. of Example 1 to 300 ° C.
A sheet was obtained in the same manner as in Example 1 except that the temperature was changed to ° C. Table 1 shows the characteristics.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明によれば、導電層および非導電層
からなる導電性樹脂シートとすることで、ピンホール等
の存在しない品質の良い導電性樹脂シートが得られる。
このような導電性樹脂シートは電池の集電体として好ま
しく用いることができ、電池の重量エネルギー密度を向
上させることが出来る。According to the present invention, by forming a conductive resin sheet comprising a conductive layer and a non-conductive layer, a high quality conductive resin sheet free of pinholes and the like can be obtained.
Such a conductive resin sheet can be preferably used as a current collector of a battery, and can improve the weight energy density of the battery.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｊ 7/00 ３０１ Ｃ０８Ｊ 7/00 ３０１ ５Ｇ３０７ ３０６ ３０６ ５Ｇ３２３ Ｃ０８Ｋ 3/04 Ｃ０８Ｋ 3/04 ５Ｈ０１７ 3/08 3/08 3/22 3/22 Ｃ０８Ｌ 23/04 Ｃ０８Ｌ 23/04 23/10 23/10 23/16 23/16 25/04 25/04 Ｈ０１Ｂ 5/14 Ｈ０１Ｂ 5/14 Ｚ 13/00 ５０３ 13/00 ５０３Ｚ // Ｂ２９Ｋ 23:00 Ｂ２９Ｋ 23:00 105:16 105:16 105:22 105:22 105:34 105:34 Ｂ２９Ｌ 7:00 Ｂ２９Ｌ 7:00 9:00 9:00 31:00 31:00 Ｆターム(参考） 4F071 AA15 AA15X AA18 AA20 AA20X AA76X AB03 AB06 AB18 AD02 AE15 AF02 AF37 AH15 BA01 BB06 BC01 4F073 AA04 AA21 BA07 BA08 BA19 BA49 BB01 BB09 CA01 GA03 4F100 AA37A AA37H AB00A AB00H AB17A AB17H AK01A AK04A AK04B AK06 AK07A AK07B AK12A AK12B AK64A AK64B BA02 CA23A CA23H EH23 EJ27 EJ52 EJ64 GB41 JD04B JG01 JG01A JG04 JG04B YY00A YY00B 4F207 AA03E AA04 AA11 AA13 AB13 AB16 AB18 AD05 AD08 AE03 AG01 AG03 AH33 AR20 KA01 KA17 KB13 KB26 KF01 KJ05 KL84 KW26 KW50 4J002 BB031 BB121 BB151 BC031 DA036 DA066 DE046 FA086 GQ02 5G307 GA02 GC02 5G323 AA01 5H017 BB01 BB03 BB06 BB11 CC01 DD06 EE01 EE06 EE07 HH00 HH01 HH10 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C08J 7/00 301 C08J 7/00 301 5G307 306 306 5G323 C08K 3/04 C08K 3/04 5H017 3/08 3 / 08 3/22 3/22 C08L 23/04 C08L 23/04 23/10 23/10 23/16 23/16 25/04 25/04 H01B 5/14 H01B 5/14 Z 13/00 503 13/00 503Z // B29K 23:00 B29K 23:00 105: 16 105: 16 105: 22 105: 22 105: 34 105: 34 B29L 7:00 B29L 7:00 9:00 9:00 31:00 31:00 F Terms (reference) 4F071 AA15 AA15X AA18 AA20 AA20X AA76X AB03 AB06 AB18 AD02 AE15 AF02 AF37 AH15 BA01 BB06 BC01 4F073 AA04 AA21 BA07 BA08 BA19 BA49 BB01 BB09 CA01 GA03 4F100 AA37A AA37HABA ABB AB AB01 AK13A BA02 CA23A CA23H EH23 EJ27 EJ52 EJ64 GB41 JD04B JG01 JG01A JG04 JG04B YY00A YY00B 4F207 AA03E AA04 AA11 AA13 AB13 AB16 AB18 AD05 AD08 DA03 AE03 AG01 AG03 AH33 AR20 KA01 K03 K01 K01 K13 K01 K01 K01 K01 K01 K01 K01 K01 KB13 K01 GA02 GC02 5G323 AA01 5H017 BB01 BB03 BB06 BB11 CC01 DD06 EE01 EE06 EE07 HH00 HH01 HH10
Claims (8)
有する導電性樹脂シートであって、該非導電層の体積固
有抵抗が１０3Ω・ｃｍ以上、該導電層の体積固有抵抗
が１００Ω・ｃｍ以下、水蒸気透過率が５０ｇ／（ｍ2
・day）未満であることを特徴とする導電性樹脂シー
ト。1. A conductive resin sheet having a conductive layer on at least one surface of a non-conductive layer, wherein the non-conductive layer has a volume resistivity of 10 3 Ω · cm or more, and the conductive layer has a volume resistivity of 100 Ω · cm. cm or less, and the water vapor transmission rate is 50 g / (m 2
・ A conductive resin sheet characterized by being less than day).
金属酸化物のなかから選択された導電性粒子を１０重量
％以上含有することを特徴とする請求項１記載の導電性
樹脂シート。2. The conductive resin sheet according to claim 1, wherein the conductive layer contains at least 10% by weight of conductive particles selected from carbon black, metal and metal oxide.
る樹脂が、ポリエチレン、ポリプロピレン、ポリエチレ
ンプロピレン共重合体およびポリスチレンのなかから選
択された樹脂であることを特徴とする請求項１または２
記載の導電性樹脂シート。3. The resin constituting the conductive layer and / or the non-conductive layer is a resin selected from polyethylene, polypropylene, polyethylene propylene copolymer and polystyrene.
The conductive resin sheet according to the above.
とで非導電性シートを製造する工程、および導電性樹脂
を溶融し口金から溶融シートとして該非導電性シート上
に押出し、ラミネーションする工程からなることを特徴
とする導電性樹脂シートの製造方法。4. A step of producing a non-conductive sheet by melting a non-conductive resin and extruding the same from a die, and a step of melting the conductive resin and extruding the molten sheet from the die as a molten sheet onto the non-conductive sheet, followed by lamination. A method for producing a conductive resin sheet, comprising:
で導電性シートを製造する工程および非導電性樹脂を溶
融し口金から溶融シートとして該導電性シート上に押出
し、ラミネーションする工程からなることを特徴とする
導電性樹脂シートの製造方法。5. A process for producing a conductive sheet by melting and extruding a conductive resin from a die, and a process for melting a non-conductive resin, extruding the molten sheet from the die as a molten sheet onto the conductive sheet, and laminating. A method for producing a conductive resin sheet, comprising:
理することを特徴とする請求項４または５記載の導電性
樹脂シートの製造方法。6. The method for producing a conductive resin sheet according to claim 4, wherein the surface of the conductive layer is subjected to a flame treatment or a plasma treatment.
ることを特徴とする請求項４または５記載の導電性樹脂
シートの製造方法。7. The method for producing a conductive resin sheet according to claim 4, wherein the surface of the conductive layer is polished by a polishing roll.
する請求項１〜３のいずれかに記載の導電性樹脂シー
ト。8. The conductive resin sheet according to claim 1, which is used as an electrode material of a battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000186136A JP2002008665A (en) | 2000-06-21 | 2000-06-21 | Conductive resin sheet and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000186136A JP2002008665A (en) | 2000-06-21 | 2000-06-21 | Conductive resin sheet and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002008665A true JP2002008665A (en) | 2002-01-11 |
Family
ID=18686354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000186136A Pending JP2002008665A (en) | 2000-06-21 | 2000-06-21 | Conductive resin sheet and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002008665A (en) |
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| WO2005090452A1 (en) * | 2004-03-24 | 2005-09-29 | Mitsubishi Plastics, Inc. | Conductive thermoplastic resin film and layered conductive thermoplastic resin film |
| JP2005272591A (en) * | 2004-03-24 | 2005-10-06 | Mitsubishi Plastics Ind Ltd | Conductive thermoplastic resin film |
| JP2005281403A (en) * | 2004-03-29 | 2005-10-13 | Mitsubishi Plastics Ind Ltd | Conductive thermoplastic resin film |
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|---|---|---|---|---|
| JP2004091564A (en) * | 2002-08-30 | 2004-03-25 | Lonseal Corp | Olefin resin composition and sheet |
| WO2005090452A1 (en) * | 2004-03-24 | 2005-09-29 | Mitsubishi Plastics, Inc. | Conductive thermoplastic resin film and layered conductive thermoplastic resin film |
| JP2005272591A (en) * | 2004-03-24 | 2005-10-06 | Mitsubishi Plastics Ind Ltd | Conductive thermoplastic resin film |
| JP2005281403A (en) * | 2004-03-29 | 2005-10-13 | Mitsubishi Plastics Ind Ltd | Conductive thermoplastic resin film |
| JP2010090192A (en) * | 2008-10-03 | 2010-04-22 | Nhk Spring Co Ltd | Anisotropically electroconductive resin film and method for manufacturing the same |
| JP2010257628A (en) * | 2009-04-22 | 2010-11-11 | Nissan Motor Co Ltd | Current collector for bipolar battery |
| JP2011060560A (en) * | 2009-09-09 | 2011-03-24 | Nissan Motor Co Ltd | Collector for lithium ion secondary battery |
| JP2012111141A (en) * | 2010-11-25 | 2012-06-14 | Oike Ind Co Ltd | Transparent conductive film, and liquid crystal display element, organic el element and organic thin film solar cell using the same |
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| US12015140B2 (en) | 2018-10-22 | 2024-06-18 | Sanyo Chemical Industries, Ltd. | Method for producing resin collector for negative electrodes, method for producing negative electrode for lithium ion batteries, and method for producing lithium ion battery |
| WO2023130611A1 (en) * | 2022-01-10 | 2023-07-13 | 上海恩捷新材料科技有限公司 | Flexible current collector core layer, current collector, electrode sheet, battery, and preparation methods for flexible current collector core layer and current collector |
| WO2024124892A1 (en) * | 2022-12-12 | 2024-06-20 | 安徽元琛环保科技股份有限公司 | Composite conductive film used as current collector, preparation method therefor and use thereof |
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