JPH08209584A - Electro-conductive aramide paper and its production - Google Patents
Electro-conductive aramide paper and its productionInfo
- Publication number
- JPH08209584A JPH08209584A JP1176495A JP1176495A JPH08209584A JP H08209584 A JPH08209584 A JP H08209584A JP 1176495 A JP1176495 A JP 1176495A JP 1176495 A JP1176495 A JP 1176495A JP H08209584 A JPH08209584 A JP H08209584A
- Authority
- JP
- Japan
- Prior art keywords
- organic heat
- paper
- fine particles
- aramid
- resistant
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はアラミド紙に関するもの
である。更に詳細には、ｍ−アラミドフィブリッドと有
機耐熱性繊維から湿式で抄造して成り、耐熱性であると
共にある程度の導電性を有し、シールド材、電界緩和材
等として有用なｍ−アラミド紙に関するものである。FIELD OF THE INVENTION The present invention relates to aramid paper. More specifically, m-aramid paper, which is made by wet-making paper from m-aramid fibrids and organic heat resistant fibers, has heat resistance and a certain degree of conductivity, and is useful as a shield material, electric field relaxation material, etc. It is about.
【０００２】[0002]
【従来の技術】ｍ−アラミド紙と呼ばれる薄手のシート
は既に幾種類ものものが開発され、用いられてきた。こ
の主な用途には電気絶縁物と薄葉構造材料等が挙げられ
る。2. Description of the Related Art Several types of thin sheets called m-aramid paper have already been developed and used. Its main uses include electrical insulators and thin leaf structural materials.
【０００３】電気絶縁物としてのシートは、変圧器、電
動機、チョークコイル等の巻線関係の絶縁物やプリント
基板等に広く用いられており、ある程度の導電性を有す
るシートは、その導電性の程度により、発熱体等やシー
ルド材、電界緩和材等としても用いられている。Sheets as electrical insulators are widely used for winding-related insulators such as transformers, electric motors, choke coils, and printed circuit boards. A sheet having a certain degree of conductivity is a conductive material. Depending on the degree, it is also used as a heating element, a shield material, an electric field relaxation material, or the like.
【０００４】ｍ−アラミドは通常はポリメタフェニレン
イソフタルアミドあるいはその共重合物を意味し、ｍ−
アラミド紙は普通、ｍ−アラミドのフィブリッドと耐熱
性の繊維とを混合してスラリーとなし、抄造したもので
ある。ここでフィブリッドと呼んでいるものは、基本的
には抄紙性のある高分子微小片でデュポン社の造語であ
り、抄紙性の視点からはしばしばパルプ（または合成パ
ルプ）とも呼ばれている（特公昭第３５−１１８５１号
公報、特公昭第３７−５７３２号公報等を参照。） 上記の耐熱性繊維としては、ｍ−アラミド繊維が一般的
であるが、その他、ｐ−アラミド繊維、アリレート繊
維、ポリエステル繊維等の有機耐熱性繊維、ガラス繊
維、アスベスト等の無機繊維が挙げられる。ｍ−アラミ
ドフィブリッドとｍ−アラミド繊維との組み合わせより
成るｍ−アラミド絶縁紙はＨ種絶縁物として適当なもの
であり、ｍ−アラミドフィブリッドとポリエステル繊
維、特にポリエチレンテレフタレート繊維、との組み合
わせより成るｍ−アラミド絶縁紙はＥ種もしくはＦ種絶
縁物として適当なものである。M-aramid usually means polymetaphenylene isophthalamide or its copolymer, and m-aramid
Aramid paper is usually prepared by mixing m-aramid fibrids with heat resistant fibers to form a slurry. What is called fibrids here is basically a microparticulate polymer with paper-making properties, coined by DuPont, and is often called pulp (or synthetic pulp) from the viewpoint of paper-making properties (special characteristics). See Japanese Patent Publication No. 35-11851, Japanese Patent Publication No. 37-5732, etc.) As the heat resistant fiber, m-aramid fiber is generally used, but in addition, p-aramid fiber, arylate fiber, Examples thereof include organic heat resistant fibers such as polyester fibers, glass fibers, and inorganic fibers such as asbestos. An m-aramid insulating paper consisting of a combination of m-aramid fibrids and m-aramid fibers is suitable as a class H insulating material, and is a combination of m-aramid fibrids and polyester fibers, especially polyethylene terephthalate fibers. The m-aramid insulating paper is suitable as a Class E or Class F insulation.
【０００５】ｍ−アラミド紙にはこのほか、フィブリッ
ドを用いない、ｍ−アラミド繊維のみから成るものもあ
り、ｍ−アラミド不織布とも呼ばれている。この場合に
は、繊維同士の融着を図るため、未延伸、半延伸等の状
態で、繊維を構成するポリマーの結晶化度や結晶配向度
の低いものを用い、またはこれらと充分に延伸した繊維
とを併用することが多い。また、場合によっては融点が
低めの他の繊維を併用することもある。これに対し、フ
ィブリッドを有機耐熱性繊維と共に用いた紙の場合に
は、フィブリッドが接着材の役を果たし、有機耐熱性繊
維が紙の物性と抄紙性の向上のための機能を果たす。得
られた紙は高温でカレンダー（熱圧）して物性の向上を
図ることが多い。In addition to the m-aramid paper, there is a m-aramid paper which is made of only m-aramid fibers without using fibrids, and is also called an m-aramid nonwoven fabric. In this case, in order to fuse the fibers with each other, a polymer having a low degree of crystallinity or crystal orientation of the polymer constituting the fibers is used in a state of unstretched, semi-stretched or the like, or sufficiently stretched with these. Often used in combination with fiber. In some cases, other fibers having a lower melting point may be used together. On the other hand, in the case of paper using the fibrid together with the organic heat-resistant fiber, the fibrid serves as an adhesive and the organic heat-resistant fiber serves to improve the physical properties and paper-making property of the paper. The obtained paper is often calendered (hot pressed) at high temperature to improve the physical properties.
【０００６】ｍ−アラミド紙に導電性を付与し、シール
ド材、電界緩和材等として使用できるようにするために
は、上記のフィブリッド／耐熱性繊維の組合わせにおい
て、耐熱性繊維として導電性の繊維を用いたり、ｍ−ア
ラミドフィブリッドを導電性としたものがある。例えば
耐熱性繊維として炭素繊維、金属繊維等を使用するもの
としては特開昭第５１−４７１０３号公報、特開昭第５
７−１１５７０２号公報、特開平第４−６５２２６号公
報、特開平第４−１５３３９９号公報等に記載のもの
が、炭素粉末等の導電性微粒子を含んだｍ−アラミドフ
ィブリッドを使用するものとしては特開昭第５１−５５
４０１号公報、特公昭第５７−２７２０４号公報等に記
載のものが知られている。In order to impart conductivity to the m-aramid paper so that it can be used as a shield material, an electric field relaxation material, etc., in the above-mentioned fibrid / heat resistant fiber combination, the heat resistant fiber is a conductive material. Some of them use fibers or make m-aramid fibrid conductive. For example, as a heat-resistant fiber using carbon fiber, metal fiber, etc., JP-A-51-47103 and JP-A-5-47103.
Nos. 7-115702, JP-A-4-65226, JP-A-4-153399 and the like use m-aramid fibrids containing conductive fine particles such as carbon powder. Is JP-A-51-55
Those described in JP-A-401, JP-B-57-27204, etc. are known.
【０００７】[0007]
【発明が解決しようとする課題】上述の如く、ｍ−アラ
ミド紙に導電性を付与する場合、耐熱性繊維として炭素
繊維、金属繊維等を使用する方法とフィブリツドに炭素
粉末等の導電性微粒子を加える方法が公知であるが、こ
れらの方法はなお問題を残している。すなわち、このよ
うな導電性繊維の比重（密度）はｍ−アラミドよりかな
り大きく、長網抄紙機等でウエブ化するに際して繊維が
偏在し易く、均一な積層が困難であり、また、導電性の
繊維が紙層を貫くように存在したり、導電性繊維より成
る毛羽がある紙が出来易くなり、これらを電気絶縁材料
として用いる場合には絶縁破壊につながり易いという問
題が生じる。炭素繊維等の毛羽を実質的に抑える方法と
しては、例えば炭素繊維等を含まない層（絶縁層）と抄
き合わせをする方法も提案されているが（特開平第４−
８００２５号公報参照）、この方法を実行してみてもな
お、剛性の大きい上記の導電繊維は絶縁層を破壊するこ
とが多い。更に、これらの導電繊維では個々の導電繊維
の電気抵抗が低すぎるため、シート全体の導電性を所定
の範囲にしようとする場合に、導電繊維の使用量が少な
ければ導電繊維が均一に分散した製品を作り難く、充分
な導電性を有しない部分を含むシートとなり、多けれ
ば、所定の導電性の範囲を逸脱した高い導電性のシート
となってしまい、絶縁破壊も起こりやすくなる等、品質
の管理が困難である。As described above, when imparting conductivity to m-aramid paper, a method of using carbon fiber, metal fiber or the like as the heat resistant fiber and conductive fine particles such as carbon powder in the fibrid are used. Addition methods are known, but these methods still have problems. That is, the specific gravity (density) of such an electrically conductive fiber is considerably larger than that of m-aramid, the fibers are apt to be unevenly distributed when being made into a web by a Fourdrinier paper machine, etc., and uniform lamination is difficult. There is a problem that fibers are present so as to penetrate through the paper layer or paper having fluffs made of conductive fibers is easily produced, and when these are used as an electric insulating material, dielectric breakdown is likely to occur. As a method of substantially suppressing fluff such as carbon fibers, a method of combining with a layer (insulating layer) containing no carbon fibers or the like has been proposed (JP-A-4-
(See Japanese Patent No. 80025), the conductive fibers having high rigidity often destroy the insulating layer even when this method is executed. Furthermore, since the electric resistance of each conductive fiber is too low with these conductive fibers, when the amount of the conductive fibers used is small, the conductive fibers are uniformly dispersed when the conductivity of the entire sheet is set within a predetermined range. It becomes a sheet that is difficult to make a product and contains a part that does not have sufficient conductivity, and if there are many, it becomes a highly conductive sheet that deviates from the predetermined conductivity range, and dielectric breakdown easily occurs. It is difficult to manage.
【０００８】製造面から言えば、このような剛性の大き
い導電性繊維を含有する材料は抄紙やその後の工程で支
障を来すことが多い。例えば、抄紙工程においては、抄
造から乾燥に至る間で脱水のために搾水するが、この際
のロールプレス等で繊維が折れて紙の表面に残ったり、
ローラー表面を傷つけたりする問題や、炭素繊維等の剛
性の大きい繊維が抄紙ワイヤに突き刺さり、紙がワイヤ
面から離れ難くなる等の問題がある。また、このような
導電性を有するアラミド紙はシールド、電界緩和材等に
用いられるので表面強度や薄さを求められることが多
く、従って熱圧紙とされることが多いが、これらの繊維
を加えた紙を熱圧すると繊維が折れたり、熱圧設備の表
面に傷を付けたりして、良好な製品が得られないのみな
らず、設備を壊す場合も多い。From a manufacturing standpoint, such a material containing a conductive fiber having high rigidity often causes troubles in papermaking and the subsequent steps. For example, in the papermaking process, water is squeezed for dehydration between papermaking and drying, but the fibers are broken by a roll press or the like on the surface of the paper,
There are problems that the roller surface may be damaged, fibers having high rigidity such as carbon fibers may stick into the papermaking wire, and the paper may be difficult to separate from the wire surface. In addition, since aramid paper having such conductivity is used as a shield, an electric field relaxation material, etc., it is often required to have surface strength and thinness. Therefore, it is often used as a hot-pressed paper. When hot-pressing hot paper, the fibers may be broken or the surface of the hot-pressing equipment may be damaged, resulting in not only a good product but also the equipment being destroyed in many cases.
【０００９】フィブリッドのみに炭素粉末等の導電性粉
末を加える方法の場合には、通常、フィブリッドが厚さ
０．１μｍ程度の微細フィルムであるために、必要量の
導電性粉末を加えると、得られた合成紙を取り扱う際
に、加えられた導電性微粒子が徐々にフィブリッドから
（すなわち合成紙から）離脱してしまう場合が多い。In the case of the method of adding the conductive powder such as carbon powder only to the fibrids, since the fibrid is usually a fine film having a thickness of about 0.1 μm, it is possible to obtain it by adding the necessary amount of the conductive powder. When handling the prepared synthetic paper, it is often the case that the added conductive fine particles gradually separate from the fibrids (that is, from the synthetic paper).
【００１０】本発明の目的は、このような製造上の問題
が少なく、適度の導電性を有し、そのばらつきが少な
く、品質の安定した合成紙を提供することにある。An object of the present invention is to provide a synthetic paper which has few such problems in production, has appropriate conductivity, has little variation, and has stable quality.
【００１１】[0011]
【問題を解決するための手段】本発明者等は各種検討の
結果、有機耐熱性繊維側に導電性微粒子を加えることに
よりこの問題を解決できることを見いだした。すなわ
ち、本発明は以下の（１）〜（９）に示すものである。As a result of various investigations, the present inventors have found that this problem can be solved by adding conductive fine particles to the organic heat resistant fiber side. That is, the present invention is shown in the following (1) to (9).
【００１２】（１）導電性微粒子を包含した有機耐熱性
繊維とｍ−アラミドフィブリッドとから実質的に成る合
成紙。 （２）導電性微粒子を包含した有機耐熱性繊維とｍ−ア
ラミドフィブリッドとから実質的に成り、体積抵抗率が
１０2〜１０8Ωｃｍ、表面抵抗が１０2〜１０1 0Ωであ
る合成紙。 （３）導電性微粒子を包含した有機耐熱性繊維と導電性
微粒子を包含したｍ−アラミドフィブリッドとから実質
的に成る合成紙。 （４）導電性微粒子を包含した有機耐熱性繊維と導電性
微粒子を包含したｍ−アラミドフィブリッドとから実質
的に成り、体積抵抗率が１０2〜１０8Ωｃｍ、表面抵抗
が１０2〜１０10Ωである合成紙。 （５）導電性微粒子が炭素粒子であることを特徴とす
る、上記（１）、（２）、（３）または（４）の項に記
載の合成紙。 （６）有機耐熱性繊維がｍ−アラミド繊維であるとを特
徴とする、上記（１）、（２）、（３）、（４）または
（５）の項に記載の合成紙。 （７）有機耐熱性繊維がポリエステル繊維であることを
特徴とする、上記（１）、（２）、（３）、（４）また
は（５）の項に記載の合成紙。 （８）上記（１）、（２）、（３）、（４）、（５）、
（６）または（７）の項に記載の合成紙の製造方法であ
って、溶融した有機耐熱性高分子若しくは有機耐熱性高
分子溶液中に導電性微粒子を分散させ、該溶融高分子若
しくは該高分子溶液から有機耐熱性繊維を紡糸し、切断
し、ｍ−アラミドフィブリッドと混合してスラリーと
し、抄紙し、脱水乾燥させることを特徴とする方法。 （９）上記（１）、（２）、（３）、（４）、（５）、
（６）の項に記載の合成紙の製造方法であって、溶融し
た有機耐熱性高分子若しくは有機耐熱性高分子溶液中に
導電性粒子を分散させ、該溶融高分子若しくは該高分子
溶液から有機耐熱性繊維を紡糸し、切断し、ｍ−アラミ
ドフィブリッドと混合してスラリーとし、抄紙し、脱水
乾燥させた後、更に熱圧することを特徴とする方法。(1) A synthetic paper consisting essentially of organic heat-resistant fibers containing conductive fine particles and m-aramid fibrids. (2) become essentially of conductive fine particles and organic heat resistant fibers include a m- aramid fibrids, combined volume resistivity of 10 2 to 10 8 [Omega] cm, a surface resistance of 10 2 to 10 1 0 Omega paper. (3) A synthetic paper consisting essentially of organic heat-resistant fibers containing conductive fine particles and m-aramid fibrids containing conductive fine particles. (4) Substantially consisting of organic heat resistant fibers containing conductive fine particles and m-aramid fibrids containing conductive fine particles, having a volume resistivity of 10 2 to 10 8 Ωcm and a surface resistance of 10 2 to 10 10. Synthetic paper that is 10 Ω. (5) The synthetic paper according to item (1), (2), (3) or (4), wherein the conductive fine particles are carbon particles. (6) The synthetic paper according to item (1), (2), (3), (4) or (5), wherein the organic heat resistant fiber is m-aramid fiber. (7) The synthetic paper as described in the above item (1), (2), (3), (4) or (5), wherein the organic heat resistant fiber is a polyester fiber. (8) The above (1), (2), (3), (4), (5),
The method for producing a synthetic paper according to item (6) or (7), wherein conductive fine particles are dispersed in a melted organic heat-resistant polymer or an organic heat-resistant polymer solution, A method characterized in that organic heat resistant fibers are spun from a polymer solution, cut, mixed with m-aramid fibrids to form a slurry, paper-made, and dehydrated and dried. (9) The above (1), (2), (3), (4), (5),
The method for producing a synthetic paper according to the item (6), wherein conductive particles are dispersed in a molten organic heat-resistant polymer or an organic heat-resistant polymer solution, and the molten polymer or the polymer solution is used. A method characterized in that the organic heat-resistant fiber is spun, cut, mixed with m-aramid fibrid to form a slurry, paper-made, dehydrated and dried, and then hot pressed.
【００１３】有機繊維に導電性微粒子を加えることによ
り当該有機繊維に導電性を与えられることは公知であ
る。しかしながら、通常の使用においては、導電性微粒
子の含有量が少ないと導電性が不十分になり、また逆
に、導電性微粒子の含有量が、有機繊維に導電性を付与
できるほど多いと繊維自体の強度が不足し、結局、現実
の使用に耐えないものがほとんとであり、当該発明に係
る用途への応用は全く研究されていなかった。しかしな
がら、本発明者等はこの可能性について着目し、鋭意検
討した結果、有機耐熱性繊維とｍ−アラミドフィブリッ
ドとを組み合わせた組成であること、有機耐熱性繊維と
ｍ−アラミドフィブリッドとの混抄による紙であるこ
と、当該有機耐熱性繊維に導電性微粒子を包含させるこ
と等を組み合わせれば導電性付与の課題が達成でき、紙
としての強度は充分であり、しかも、この導電性のばら
つきは少なく、合成紙製造時の作業性が向上し、ローラ
ー面を傷つける等の問題も減少することを見いだしたも
のである。有機耐熱性繊維がｍ−アラミドである場合
は、耐熱特性、強度特性、導電性に特に優れた合成紙が
得られる。It is known that the organic fibers can be made conductive by adding conductive fine particles to the organic fibers. However, in normal use, if the content of the conductive fine particles is small, the conductivity becomes insufficient, and conversely, if the content of the conductive fine particles is large enough to impart conductivity to the organic fibers, the fibers themselves. Insufficient strength was found, and in the end, most of them could not withstand actual use, and application to the use according to the invention has not been studied at all. However, the present inventors have paid attention to this possibility, and as a result of diligent studies, as a result, it is a composition that combines an organic heat-resistant fiber and m-aramid fibrid, and an organic heat-resistant fiber and m-aramid fibrid. If the paper is a mixed paper, and the organic heat-resistant fibers are combined with conductive fine particles, the problem of imparting conductivity can be achieved, the strength of the paper is sufficient, and the dispersion of the conductivity It was found that the workability during the production of synthetic paper is improved and the problems such as scratching the roller surface are reduced. When the organic heat resistant fiber is m-aramid, a synthetic paper having particularly excellent heat resistance, strength characteristics and conductivity can be obtained.
【００１４】本用途に使用される有機耐熱性繊維は通常
数１０μｍφ以下であり、フィブリッドの普通の厚さで
ある０．１μｍ程度では包含しがたい大粒の導電性微粒
子まで包含できる。また、導電性微粒子は有機耐熱性繊
維中に容易に均一に分散できるため、個々の有機耐熱性
繊維は適度の導電性を有しており、そのばらつきも小さ
く、安定した品質の製品を得ることが可能となった。ま
た、導電性微粒子を包含する耐熱性繊維が有機高分子で
出来ているため適度の柔軟性を持ち、抄造物を搾水する
場合やカレンダーによる熱圧等での破損も少なく、この
作業に於いてカレンダーロール等を傷つけることが大幅
に少なくなった。又、導電性微粒子を包含した有機導電
性繊維は、これら粒子が当該繊維中で相互に連結してい
るのではないにも関わらず、当該繊維中の包含量に対応
した導電性を示すことが見いだされた。The organic heat-resistant fiber used for this purpose is usually several tens μmφ or less, and large conductive fine particles, which are hard to be included in the ordinary thickness of about 0.1 μm, can be included. In addition, since the conductive fine particles can be easily and uniformly dispersed in the organic heat-resistant fiber, each organic heat-resistant fiber has an appropriate conductivity and its variation is small, and a product of stable quality can be obtained. Became possible. In addition, since the heat-resistant fiber containing the conductive fine particles is made of an organic polymer, it has appropriate flexibility and is less likely to be damaged when the papermaking product is squeezed by water or due to heat pressure due to a calendar. It significantly reduced the damage to the calendar rolls. Further, an organic conductive fiber containing conductive fine particles may show conductivity corresponding to the amount of inclusion in the fiber, even though these particles are not connected to each other in the fiber. Was found.
【００１５】導電性微粒子を包含した有機耐熱繊維は導
電性微粒子を溶融耐熱性高分子若しくは耐熱性高分子溶
液中に分散させ、該溶融高分子若しくは該高分子溶液か
らこの有機耐熱性繊維を紡糸して得られるが、導電性微
粒子が極めて小さい場合には、予め作った繊維の表面
に、導電性微粒子を溶融耐熱性高分子若しくは耐熱性高
分子溶液中に分散させたものを、塗布して乾燥若しくは
固化して得た繊維でもよい。The organic heat-resistant fiber containing conductive fine particles is prepared by dispersing conductive fine particles in a molten heat-resistant polymer or a heat-resistant polymer solution, and spinning the organic heat-resistant fiber from the molten polymer or the polymer solution. However, when the conductive fine particles are extremely small, the surface of the prefabricated fiber is coated with the conductive fine particles dispersed in a molten heat resistant polymer or a heat resistant polymer solution. Fibers obtained by drying or solidifying may be used.
【００１６】本発明に係る合成紙に含まれる導電性微粒
子は、紙の全体に汎ってできるだけ均一に、かつ、所定
の導電性が得られる限りできるだけ低濃度にあることが
電気絶縁材料としては好ましいので、繊維と共にフィブ
リッドにも導電粒子を分散させたものであることが好ま
しい場合がある。この場合、両者に導電性微粒子を分散
させるため、フィブリッドのみに導電性微粒子を分散さ
せた場合よりフィブリッド中の導電性微粒子量を低くで
き、したがってフィブリッドからの導電性微粒子の離脱
を抑制する効果が得られる。The electrically conductive fine particles contained in the synthetic paper according to the present invention should be as uniform as possible throughout the paper and at a concentration as low as possible as long as a predetermined conductivity can be obtained. Since it is preferable, it may be preferable that the conductive particles are dispersed in the fibrids together with the fibers. In this case, since the conductive fine particles are dispersed in both of them, the amount of the conductive fine particles in the fibrid can be made lower than in the case where the conductive fine particles are dispersed only in the fibrids, and therefore, the effect of suppressing the separation of the conductive fine particles from the fibrids is obtained. can get.
【００１７】本発明に使用されるｍ−アラミドは、ポリ
メタフェニレンイソフタルアミドまたはその共重合物を
意味し、ｍ−アラミドフィブリッドはｍ−アラミドのフ
ィブリッドを意味する。ｍ−アラミド紙とは、ｍ−アラ
ミドのフィブリッドと耐熱性の有機繊維とを混合してス
ラリーとなし、抄造したものである。なお、本来の物性
を大幅には損なわない限り他の成分を含む共重合体、例
えばテレフタル酸やパラフェニレンジアミン、ヘキサメ
チレンジアミン、シクロヘキシルジアミン等を含む共重
合体、や他の高分子との混合物も本発明に言うｍ−アラ
ミドに含まれる。メタフェニレンイソフタルアミド成分
は本発明でいうｍ−アラミドの全体量の内５０重量％を
越えるものが望ましく、８０重量％を越えるものが更に
望ましい。The m-aramid used in the present invention means polymetaphenylene isophthalamide or a copolymer thereof, and the m-aramid fibrids means the fibrids of m-aramid. The m-aramid paper is prepared by mixing m-aramid fibrids with heat-resistant organic fibers to form a slurry, and papermaking. Incidentally, a copolymer containing other components, for example, a copolymer containing terephthalic acid, paraphenylenediamine, hexamethylenediamine, cyclohexyldiamine, or the like, or a mixture with another polymer unless the original physical properties are significantly impaired. Is also included in m-aramid referred to in the present invention. The metaphenylene isophthalamide component is preferably 50% by weight or more, more preferably 80% by weight or more of the total amount of m-aramid in the present invention.
【００１８】本発明に使用されるｍ−アラミド紙に使用
される有機耐熱性繊維は、上記と同様なｍ−アラミドが
一般的であるが、その他の有機耐熱性繊維でもよく、具
体的には、例えばｐ−アラミド繊維、耐熱性ポリエステ
ル繊維、ポリアリレート繊維、ＰＰＳ繊維、耐熱性ナイ
ロン等、またはこれらの混合物が用いられる。The organic heat-resistant fiber used in the m-aramid paper used in the present invention is generally the same m-aramid as described above, but other organic heat-resistant fibers may be used. For example, p-aramid fiber, heat resistant polyester fiber, polyarylate fiber, PPS fiber, heat resistant nylon, etc., or a mixture thereof is used.
【００１９】また、本発明に使用される有機耐熱性繊維
に含まれる導電性粒子は炭素が普通であるが、ニッケ
ル、クロム、金、銀、銅等の金属の微粒子、ヨウ化銅等
の導電性の金属化合物の微粒子でもよい。微粒子のサイ
ズは数１０μｍφ以下、好ましくは１０μｍφ以下であ
る。粒子が大きすぎれば有機耐熱性繊維（フィブリッド
にも包含させる場合には、フィブリッドも含めて）への
包含が不良となり、且つ、高分子溶液または溶融高分子
中に分散させて繊維化する際に、紡糸口金の穴が詰まっ
たり、押し出し（吐出）圧力が異常に高くなる等の不都
合が生じ、逆に小さすぎれば、分散に際して凝集する等
の実用上の問題がある。検討の結果、本発明の目的を達
成するには、０．０１〜１０μｍであることが好まし
く、０．０１〜１μｍであることが更に好ましいことが
判明した。The conductive particles contained in the organic heat resistant fiber used in the present invention are usually carbon, but fine particles of metal such as nickel, chromium, gold, silver and copper, and conductive material such as copper iodide. Fine particles of a metallic compound having a volatile property may be used. The size of the fine particles is several tens μmφ or less, preferably 10 μmφ or less. If the particles are too large, the inclusion in the organic heat resistant fiber (including the fibrid when included in the fibrid) becomes poor, and when dispersed in a polymer solution or a molten polymer to form a fiber. However, problems such as clogging of holes in the spinneret and abnormally high extrusion (discharging) pressure occur. On the contrary, when the spinneret is too small, there is a problem in practical use such as aggregation during dispersion. As a result of investigation, it was found that the thickness is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm in order to achieve the object of the present invention.
【００２０】また、紙の基本物性を大幅には損なわない
限り、ｍ−アラミドフィブリッドと共に他のフィブリッ
ド、例えば、特公昭第５９−１６００２号公報に記載さ
れたポリエーテルアミドのフィブリッド、を含むものも
本発明の範囲に含まれるが、ｍ−アラミドフィブリッド
がフィブリッド全体量の内５０重量％を越えるものが好
ましく、８０重量％を越えるものが更に好ましい。シー
ト全体に対してはｍ−アラミドフィブリッドが１５重量
％以上、９５重量％未満のものが好ましい。In addition to the m-aramid fibrids, other fibrids, for example, the polyetheramide fibrids described in Japanese Patent Publication No. 59-16002, are included unless the basic physical properties of the paper are significantly impaired. Although it is also included in the scope of the present invention, it is preferable that the m-aramid fibrid exceeds 50% by weight of the total amount of the fibrids, and more preferably 80% by weight. The amount of m-aramid fibrids is preferably 15% by weight or more and less than 95% by weight based on the entire sheet.
【００２１】なお、全ての繊維が導電性である必要はな
く、混入される繊維の一部のみが導電性であってもよ
い。It is not necessary that all the fibers be conductive, and only a part of the mixed fibers may be conductive.
【００２２】各種の検討の結果、シールド材として好ま
しいのは１０2〜１０8Ωｃｍ程度の体積抵抗率、１０2
〜１０10Ω程度の表面抵抗率を有するｍ−アラミド紙で
あることが判明した。As a result of various investigations, the volume resistivity of about 10 2 to 10 8 Ωcm is preferable as the shield material, 10 2
It was found to be m-aramid paper having a surface resistivity of about 10 10 Ω.
【００２３】[0023]
【実施例】次に例をあげて本発明を詳細に説明する。但
し、これらは本発明の例示を行うものであり、本発明を
制約するものではない。The present invention will be described in detail below with reference to examples. However, these are merely examples of the present invention and do not limit the present invention.
【００２４】［実施例１］フィブリッドと繊維の準備 特公昭第４７−１０８６３号公報の記載に基づいて界面
重合法でポリメタフェニレンイソフタルアミドのポリマ
ーを準備した。このポリマーをＮ−メチル−２−ピロリ
ドンに溶解して測定した固有粘度（Ｉ．Ｖ．）は１．３
５であり、実質的に無機塩類を含まないものであった。[Example 1] Preparation of fibrids and fibers A polymer of polymetaphenylene isophthalamide was prepared by an interfacial polymerization method based on the description in Japanese Patent Publication No. 47-10863. The intrinsic viscosity (IV) measured by dissolving this polymer in N-methyl-2-pyrrolidone is 1.3.
5, which was substantially free of inorganic salts.
【００２５】このポリマーを特公昭４８−１７５５１号
公報に記載の方法に基づいて繊維とした。得られた繊維
の太さは２ｄｅで、引張強度は３．５５ｇ／ｄｅ、伸度
は１８％であった。これを長さ６ｍｍに切断した。This polymer was made into fibers based on the method described in JP-B-48-17551. The obtained fiber had a thickness of 2 de, a tensile strength of 3.55 g / de, and an elongation of 18%. This was cut into a length of 6 mm.
【００２６】また、同じ方法により、但し紡糸に際し
て、導電性微粒子として、公称０．１μｍφのカーボン
ブラック（炭素粉末）を１３０ｇ／ｋｇ（対ポリマー）
加えて紡糸した。紡糸された繊維の電気抵抗（体積抵抗
率）は１０4Ωｃｍであった。これも長さ６ｍｍに切断
した。Also, by the same method, but at the time of spinning, 130 g / kg (against polymer) of carbon black (carbon powder) of nominally 0.1 μmφ was used as conductive fine particles.
In addition, it was spun. The electrical resistance (volume resistivity) of the spun fiber was 10 4 Ωcm. This was also cut to a length of 6 mm.
【００２７】また、上記のポリマーを特公昭５２−１５
１６２１号公報に記載の沈澱装置（直径１５０ｍｍ）を
用いてフィブリッドとした。濾水度はカナダ標準濾水度
で９０ｍｌであった。Further, the above-mentioned polymer is used in Japanese Patent Publication No. 52-15.
Fibrid was prepared using the precipitation apparatus (diameter 150 mm) described in Japanese Patent No. 1621. The freeness was 90 ml as Canadian standard freeness.
【００２８】抄 紙 上記のフィブリッドを家庭用のミキサーで水に分散させ
た。また、上記の２種類の繊維を５０／５０（重量比）
の割合で混合して、同様に家庭用のミキサーで水に分散
させ、これを上記のフィブリッドのスラリーと混合し、
繊維／フィブリッド＝６０／４０（重量比）とした。[0028] A papermaking above fibrids are dispersed in water in a mixer for home use. In addition, 50/50 (weight ratio) of the above two types of fibers
In the same manner, disperse in water with a household mixer in the same manner, and mix it with the slurry of the above fibrids,
Fiber / fibrid = 60/40 (weight ratio).
【００２９】このスラリーを実験用のタッピー抄紙機で
抄紙し、抄き上げてローラーで脱水後に写真用の乾燥機
で乾燥して、４０ｇ／ｍ2のｍ−アラミド紙を得た。乾
燥後得られた紙の密度は０．３０１ｇ／ｃｍ3、強度は
１．２ｋｇ／ｍｍ2、体積抵抗率は平均３×１０7Ωｃ
ｍ、表面抵抗率は平均３×１０8Ωであった。This slurry was paper-made by a tappy paper machine for experiments, made up and dehydrated by rollers, and then dried by a dryer for photography to obtain 40 g / m 2 of m-aramid paper. The density of the paper obtained after drying was 0.301 g / cm 3 , the strength was 1.2 kg / mm 2 , and the volume resistivity was 3 × 10 7 Ωc on average.
m, and the surface resistivity was 3 × 10 8 Ω on average.
【００３０】紙の熱圧 上記で得られた導電性アラミド紙を熱圧した。すなわ
ち、得られたｍ−アラミド紙を充分に乾燥してカレンダ
ーで２８０℃、１００ｋｇ／ｃｍ、６ｍ／ｍｉｎの速度
でプレスし、更に２５０℃、１００ｋｇ／ｃｍ、６ｍ／
ｍｉｎの速度で熱圧した。得られたシートの密度は０．
８０２ｇ／ｃｍ3、強度は６．４ｋｇ／ｍｍ2、体積抵抗
率は平均４×１０7Ωｃｍ、表面抵抗率は平均２×１０8
Ωであった。[0030] The conductive aramid paper obtained by the paper hot pressure above was heat-pressed. That is, the obtained m-aramid paper was sufficiently dried, pressed with a calendar at 280 ° C., 100 kg / cm, 6 m / min, and further 250 ° C., 100 kg / cm, 6 m / min.
It was hot pressed at a speed of min. The density of the obtained sheet was 0.
802 g / cm 3 , strength 6.4 kg / mm 2 , volume resistivity average 4 × 10 7 Ωcm, surface resistivity average 2 × 10 8
Ω.
【００３１】［比較例１］抄紙に際して、カーボンブラ
ック（炭素粉末）を混入した繊維の代わりに、炭素繊維
を混合した以外は実施例１とまったく同様にして抄造物
を得た（特開昭第５１−４７１０３号公報参照）。この
紙を実施例１と同様の条件で熱圧し、電気抵抗を測定し
たところ、体積抵抗率の値、表面抵抗率の値は、共に、
０．０（実質的に短絡）から無限大（実質的に絶縁）迄
のばらつきを示した。また、プレスに際して炭素繊維が
折れ、その一部が露出した。[Comparative Example 1] A paper product was obtained in exactly the same manner as in Example 1 except that carbon fibers were mixed in place of the fibers mixed with carbon black (carbon powder) at the time of papermaking (Japanese Patent Laid-Open No. Sho-06-1999). 51-47103). When this paper was hot pressed under the same conditions as in Example 1 and the electrical resistance was measured, both the volume resistivity value and the surface resistivity value were
It showed a variation from 0.0 (substantially short circuit) to infinity (substantially insulation). Further, the carbon fiber was broken during the pressing, and a part thereof was exposed.
【００３２】［実施例２］フィブリッドと繊維の準備 実施例１で用いたフィブリッド、繊維を準備した。[Example 2] Preparation of fibrids and fibers The fibrids and fibers used in Example 1 were prepared.
【００３３】抄 紙 上記のフィブリッドを工業用のパルパーで水に分散さ
せ、さらにディスクリファイナーと高速離解機で処理し
た。また、上記の２種類の繊維を５０／５０（重量比）
の割合で混合して、専用の工業用パルパーで水に分散さ
せ、上記のフィブリッドのスラリーと混合し、繊維／フ
ィブリッド＝６０／４０（重量比）とした。[0033] The papermaking above fibrids are dispersed in water in pulper industrial and further with a disk refiner and fast disintegrator machine. In addition, 50/50 (weight ratio) of the above two types of fibers
The mixture was mixed at a ratio of 1), dispersed in water with a dedicated industrial pulper, and mixed with the above-mentioned slurry of fibrid to obtain fiber / fibrid = 60/40 (weight ratio).
【００３４】このスラリーを長網抄紙機で抄紙し、抄き
上がり脱水後に乾燥して４０ｇ／ｍ 2のｍ−アラミド紙
を得た。乾燥後得られた紙の密度は０．３０１ｇ／ｃｍ
3、強度はＭＤ（縦）方向が１．６ｋｇ／ｍｍ2、ＣＤ
（横）方向が１．１ｋｇ／ｍｍ2であった。This slurry is made into paper with a Fourdrinier paper machine and
40g / m after drying after dehydration 2M-aramid paper
Got The density of the paper obtained after drying is 0.301 g / cm
3, Strength is 1.6kg / mm in MD (longitudinal) direction2, CD
1.1 kg / mm in the (lateral) direction2Met.
【００３５】紙の熱圧 上記で得られた導電性アラミド紙を熱圧した。すなわ
ち、得られたｍ−アラミド紙を充分に乾燥して２８０℃
の予熱装置で加熱後、第一段ロールで２５０℃、２００
ｋｇ／ｃｍ、６ｍ／ｍｉｎの速度で熱圧し、３２０℃の
予熱炉で昇温後、第二ロールで２５０℃、２００ｋｇ／
ｃｍ、６ｍ／ｍｉｎの速度で熱圧した。得られたシート
の密度は０．８０２ｇ／ｃｍ3、強度はＭＤ（縦）方向
が６．４ｋｇ／ｍｍ2、ＣＤ（横）方向が３．９ｋｇ／
ｍｍ2、体積抵抗率は平均３×１０7Ωｃｍ、表面抵抗率
は平均１×１０8Ωであった。[0035] The conductive aramid paper obtained by the paper hot pressure above was heat-pressed. That is, the obtained m-aramid paper was thoroughly dried to 280 ° C.
After being heated by the preheating device of
It is hot pressed at a speed of 6 kg / cm, 6 m / min, heated in a preheating furnace at 320 ° C, and then heated at 250 ° C, 200 kg /
It was hot pressed at a speed of 6 cm / min. The density of the obtained sheet was 0.802 g / cm 3 , the strength was 6.4 kg / mm 2 in the MD (longitudinal) direction, and 3.9 kg / in the CD (transverse) direction.
mm 2 , volume resistivity was 3 × 10 7 Ωcm on average, and surface resistivity was 1 × 10 8 Ω on average.
【００３６】［実施例３］フィブリッドと繊維の準備 実施例１と同様にして界面重合法でポリメタフェニレン
イソフタルアミドのポリマーを準備した。このポリマー
をＮ−メチル−２−ピロリドンに溶解して測定した固有
粘度１．３であった。[Example 3] Preparation of fibrids and fibers A polymer of polymetaphenylene isophthalamide was prepared by the interfacial polymerization method in the same manner as in Example 1. The polymer had an intrinsic viscosity of 1.3 measured by dissolving it in N-methyl-2-pyrrolidone.
【００３７】このポリマーを特公昭第４８−１７５５１
号公報に記載の方法に基づいて繊維とした。但し、紡糸
に際して、導電性微粒子として、公称０．１μｍφのカ
ーボンブラック（炭素粉末）を１３０ｇ／ｋｇ（対ポリ
マー）加えて紡糸した。これを長さ６ｍｍに切断した。This polymer was used as Japanese Patent Publication No. 48-17551.
It was made into a fiber based on the method described in the publication. However, at the time of spinning, 130 g / kg (with respect to polymer) of carbon black (carbon powder) having a nominal diameter of 0.1 μm was added as conductive fine particles and spinning was performed. This was cut into a length of 6 mm.
【００３８】同様に上記のポリマーに公称０．１μｍφ
のカーボンブラック（炭素粉末）を１０重量％加え、特
公昭第５２−１５１６２１号公報記載の沈澱装置（直径
１５０ｍｍ）を用いて 特公昭第５７−２７２０８号公
報記載に基づくフィブリッドとした。濾水度はカナダ標
準濾水度で１２０ｍｌであった。Similarly, the above polymer is nominally 0.1 μmφ
10% by weight of carbon black (carbon powder) was added, and a fibrid based on the description of JP-B-57-27208 was prepared using a precipitation device (diameter 150 mm) described in JP-B-52-151621. The freeness was 120 ml according to Canadian standard freeness.
【００３９】抄 紙 このフィブリッドを家庭用のミキサーで水に分散させ
た。また、上記の繊維を、同様に家庭用のミキサーで水
に分散させ、これを上記のフィブリッドのスラリーと混
合し、繊維／フィブリッド＝６０／４０（重量比）とし
た。[0039] A papermaking this fibrids were dispersed in water in a mixer for home use. Further, the above fibers were similarly dispersed in water with a household mixer, and this was mixed with the slurry of the above fibrid to obtain fibers / fibrid = 60/40 (weight ratio).
【００４０】このスラリーを実験用のタッピー抄紙機で
抄紙し、抄き上げてローラーで脱水後に写真用の乾燥機
で乾燥して、４０ｇ／ｍ2のｍ−アラミド紙を得た。乾
燥後得られた紙の密度は０．３２３ｇ／ｃｍ3、強度は
１．０ｋｇ／ｍｍ2、体積抵抗率は平均３×１０6Ωｃ
ｍ、表面抵抗率は平均３×１０5Ωであった。This slurry was paper-made by a tappy paper machine for experiments, made up, dehydrated by rollers, and then dried by a dryer for photography to obtain 40 g / m 2 of m-aramid paper. The density of the paper obtained after drying was 0.323 g / cm 3 , the strength was 1.0 kg / mm 2 , and the volume resistivity was 3 × 10 6 Ωc on average.
m, and the surface resistivity was 3 × 10 5 Ω on average.
【００４１】紙の熱圧 得られた導電性アラミド紙を熱圧した。すなわち、得ら
れたｍ−アラミド紙を充分に乾燥してカレンダーで２８
０℃、１００ｋｇ／ｃｍ、６ｍ／ｍｉｎの速度でプレス
し、更に２５０℃、１００ｋｇ／ｃｍ、６ｍ／ｍｉｎの
速度で熱圧した。得られたシートの密度は０．８０２ｇ
／ｃｍ3、強度は６．４ｋｇ／ｍｍ2、体積抵抗率は平均
２×１０6Ωｃｍ、表面抵抗率は平均２×１０5Ωであっ
た。[0041] The hot pressing resulting conductive aramid paper of the paper was heat-pressed. That is, the m-aramid paper obtained was thoroughly dried and calendered to 28
Pressing was performed at 0 ° C., 100 kg / cm, 6 m / min, and further hot pressing was performed at 250 ° C., 100 kg / cm, 6 m / min. The density of the obtained sheet is 0.802 g.
/ Cm 3 , the strength was 6.4 kg / mm 2 , the volume resistivity was 2 × 10 6 Ωcm on average, and the surface resistivity was 2 × 10 5 Ω on average.
【００４２】[0042]
【発明の効果】本発明により、ばらつきの少ない適度の
導電性を持ち、耐久性と均一性に優れ、シールド材、電
界緩和材等の用途に有用なｍ−アラミド紙が得られる。
また、ローラーを傷つける等の製造上の問題も大幅に減
少する。According to the present invention, it is possible to obtain m-aramid paper which has suitable conductivity with little variation, is excellent in durability and uniformity, and is useful for applications such as shield materials and electric field relaxation materials.
Also, manufacturing problems such as scratching the rollers are greatly reduced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｂ 1/20 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location H01B 1/20
Claims (9)
とｍ−アラミドフィブリッドとから実質的に成る合成
紙。1. A synthetic paper consisting essentially of organic heat resistant fibers containing conductive fine particles and m-aramid fibrids.
とｍ−アラミドフィブリッドとから実質的に成り、体積
抵抗率が１０2〜１０8Ωｃｍ、表面抵抗が１０2〜１０
10Ωである合成紙。2. The organic heat-resistant fiber containing conductive fine particles and m-aramid fibrids, which substantially have a volume resistivity of 10 2 to 10 8 Ωcm and a surface resistance of 10 2 to 10.
Synthetic paper that is 10 Ω.
と導電性微粒子を包含したｍ−アラミドフィブリッドと
から実質的に成る合成紙。3. A synthetic paper consisting essentially of organic heat resistant fibers containing conductive fine particles and m-aramid fibrids containing conductive fine particles.
と導電性微粒子を包含したｍ−アラミドフィブリッドと
から実質的に成り、体積抵抗率が１０2〜１０8Ωｃｍ、
表面抵抗が１０2〜１０10Ωである合成紙。4. An organic heat-resistant fiber containing conductive fine particles and m-aramid fibrid containing conductive fine particles, and having a volume resistivity of 10 2 to 10 8 Ωcm,
Synthetic paper with a surface resistance of 10 2 to 10 10 Ω.
徴とする請求項１、２、３または４記載の合成紙。5. The synthetic paper according to claim 1, 2, 3 or 4, wherein the conductive fine particles are carbon particles.
るとを特徴とする請求項１、２、３、４または５記載の
合成紙。6. The synthetic paper according to claim 1, 2, 3, 4 or 5, wherein the organic heat resistant fiber is m-aramid fiber.
ることを特徴とする請求項１、２、３、４または５記載
の合成紙。7. The synthetic paper according to claim 1, 2, 3, 4, or 5, wherein the organic heat resistant fiber is a polyester fiber.
記載の合成紙の製造方法であって、溶融した有機耐熱性
高分子若しくは有機耐熱性高分子溶液中に導電性微粒子
を分散させ、該溶融高分子若しくは該高分子溶液から有
機耐熱性繊維を紡糸し、切断し、ｍ−アラミドフィブリ
ッドと混合してスラリーとし、抄紙し、脱水乾燥させる
ことを特徴とする方法。8. The method of claim 1, 2, 3, 4, 5, 6, or 7.
A method for producing a synthetic paper according to claim 1, wherein conductive fine particles are dispersed in a molten organic heat-resistant polymer or an organic heat-resistant polymer solution, and an organic heat-resistant fiber is spun from the molten polymer or the polymer solution. And then cutting, mixing with m-aramid fibrid to form a slurry, papermaking, and dehydration drying.
記載の合成紙の製造方法であって、溶融した有機耐熱性
高分子若しくは有機耐熱性高分子溶液中に導電性粒子を
分散させ、該溶融高分子若しくは該高分子溶液から有機
耐熱性繊維を紡糸し、切断し、ｍ−アラミドフィブリッ
ドと混合してスラリーとし、抄紙し、脱水乾燥させた
後、更に熱圧することを特徴とする方法。9. A method according to claim 1, 2, 3, 4, 5, 6 or 7.
A method for producing a synthetic paper according to claim 1, wherein conductive particles are dispersed in a molten organic heat-resistant polymer or an organic heat-resistant polymer solution, and an organic heat-resistant fiber is spun from the molten polymer or the polymer solution. Then, the mixture is cut, cut, mixed with m-aramid fibrid to form a slurry, paper-made, dehydrated and dried, and then hot pressed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1176495A JPH08209584A (en) | 1995-01-27 | 1995-01-27 | Electro-conductive aramide paper and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1176495A JPH08209584A (en) | 1995-01-27 | 1995-01-27 | Electro-conductive aramide paper and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08209584A true JPH08209584A (en) | 1996-08-13 |
Family
ID=11787051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1176495A Pending JPH08209584A (en) | 1995-01-27 | 1995-01-27 | Electro-conductive aramide paper and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08209584A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999010598A1 (en) * | 1997-08-26 | 1999-03-04 | Toyo Tanso Kabushiki Kaisya | Expanded graphite sheet for electromagnetic wave shielding and process for producing the same |
| WO2002070796A1 (en) * | 2001-03-05 | 2002-09-12 | E. I. Du Pont De Nemours And Company | Electrically-conductive para-aramid pulp |
| JP2007023429A (en) * | 2005-07-19 | 2007-02-01 | Teijin Techno Products Ltd | Heat-resistant conductive paper and method for producing the same |
| JP2016216866A (en) * | 2015-05-26 | 2016-12-22 | Ｋｂセーレン株式会社 | Conducive synthetic paper |
| KR20190041487A (en) * | 2016-09-01 | 2019-04-22 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Carbon-containing fiber blends comprising aramid and mode acrylic fibers |
| CN112681010A (en) * | 2020-12-25 | 2021-04-20 | 烟台民士达特种纸业股份有限公司 | High-conductivity aramid fiber insulating paper-based material for large oil-immersed transformer and preparation method thereof |
-
1995
- 1995-01-27 JP JP1176495A patent/JPH08209584A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999010598A1 (en) * | 1997-08-26 | 1999-03-04 | Toyo Tanso Kabushiki Kaisya | Expanded graphite sheet for electromagnetic wave shielding and process for producing the same |
| WO2002070796A1 (en) * | 2001-03-05 | 2002-09-12 | E. I. Du Pont De Nemours And Company | Electrically-conductive para-aramid pulp |
| KR100761208B1 (en) * | 2001-03-05 | 2007-10-04 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Electrically-Conductive Para-Aramid Pulp |
| JP2007023429A (en) * | 2005-07-19 | 2007-02-01 | Teijin Techno Products Ltd | Heat-resistant conductive paper and method for producing the same |
| JP4694909B2 (en) * | 2005-07-19 | 2011-06-08 | 帝人テクノプロダクツ株式会社 | Heat-resistant conductive paper and method for producing the same |
| JP2016216866A (en) * | 2015-05-26 | 2016-12-22 | Ｋｂセーレン株式会社 | Conducive synthetic paper |
| KR20190041487A (en) * | 2016-09-01 | 2019-04-22 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Carbon-containing fiber blends comprising aramid and mode acrylic fibers |
| CN112681010A (en) * | 2020-12-25 | 2021-04-20 | 烟台民士达特种纸业股份有限公司 | High-conductivity aramid fiber insulating paper-based material for large oil-immersed transformer and preparation method thereof |
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