JPS6112918A - Production of porous carbon plate - Google Patents

Abstract

PURPOSE:Organic fibers for making carbon fibers and wood pulp are made into sheets of paper, impregnated with a solution of an organic high molecular weight substance and carbonized with heat in an inert atmosphere to give an inexpensive and high-quality porous carbon plate. CONSTITUTION:(A) 65-90pts.wt. of organic fiber for making carbon fibers such as rayon or pitch fibers and (B) 5-40pts.wt. of pulp such as cellulose pulp are made into sheets and impregnated with a solution of an organic high-molecular substance such as a phenolic or epoxy resin. Then, the impregnated sheets are carbonized by heating them in an inert gas atmosphere at a temperature over 800 deg.C to give the objective carbon plates.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、多孔質炭素板の新規な製造方法に関するもの
である。更に詳しく述べると、抄紙法によシ得られたシ
ートを樹脂金没後、焼成することによル、耐薬品性、電
気伝導性、強度の優れた、嵩高な厚手の多孔質炭素板を
製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel method for manufacturing porous carbon plates. More specifically, a bulky, thick porous carbon plate with excellent chemical resistance, electrical conductivity, and strength is produced by casting the sheet obtained by the papermaking method into a resin and then firing it. It is about the method.

先行技術 従来炭素繊維シートを得る方法としては、あらかじめ焼
成された炭素繊紅をノぞルゾ、ノ々インダーと共に抄紙
し次炭素繊維混抄紙が知られている。Prior Art Conventionally, as a method for obtaining a carbon fiber sheet, there has been known a method of making carbon fiber mixed paper by making paper from pre-fired carbon fibers together with a nozoruzo and a nonoinder.

しかしながらこのような混抄紙は、電気抵抗値が比較的
高く、耐薬品性に欠け、燃料電池用電極基材等の用途に
は不適当であった。これらの性能の嵯善方法として、上
記混抄紙を熱硬化性樹脂の溶液に含浸させ、再度、不活
性雰囲気中で加熱炭化する方法が知られている。この方
法ではパルプ等の有機物が加熱処理によシ炭化される次
め、電気抵抗値が低く、耐薬品性も改善された繊維紙が
得られる。しかしながら炭素繊維自身が高弾性率を有す
るため繊維の接触部が十分に結合されず、そのため、十
分な低電気抵抗の炭素繊維紙は得られにくかった。However, such mixed paper has a relatively high electrical resistance value and lacks chemical resistance, making it unsuitable for applications such as electrode base materials for fuel cells. As a method for improving these properties, a method is known in which the above-mentioned mixed paper is impregnated with a thermosetting resin solution and heated and carbonized again in an inert atmosphere. In this method, organic materials such as pulp are carbonized by heat treatment, and then fiber paper with low electrical resistance and improved chemical resistance is obtained. However, since the carbon fiber itself has a high modulus of elasticity, the contact portions of the fibers are not sufficiently bonded, making it difficult to obtain carbon fiber paper with sufficiently low electrical resistance.

また炭素繊維は比重が高いため、嵩高な多孔質板が得ら
れに＜＜、各種用途に適合した嵩密度および孔径にコン
トロールするのがむずかしい。しかも、２回の焼成工程
が必要なため、非常に高価格なものになる欠点を有して
おシ、安価な製造法の開発が望まれていた。Furthermore, since carbon fiber has a high specific gravity, bulky porous plates cannot be obtained, and it is difficult to control the bulk density and pore diameter to suit various uses. Furthermore, since two firing steps are required, the product has the drawback of being extremely expensive, and there has been a desire to develop an inexpensive manufacturing method.

また上記の方法では、均一な厚みの厚手シートを抄紙す
るのはむつかしく、炭素繊維は親水性がなく、高弾性の
危め、パルプとの接着が悪く、シート強度が弱い欠点が
あった。その為ノξルプ以外の／々イングー繊維の配合
が必要であつ＊Ｃ％公昭５３−１８６０３）。Furthermore, with the above method, it is difficult to make a thick sheet of uniform thickness, and carbon fibers have the disadvantages of not having hydrophilic properties, risk of high elasticity, poor adhesion to pulp, and weak sheet strength. Therefore, it is necessary to mix in/ingu fibers other than Norupu (*C% Kosho 53-18603).

本発明者らは先に、抄紙法による方法を出願（特願昭５
７−２２６４９４号）したが、上記方法ζ１０」体バイ
ンダー繊維を使用するため、多孔質のシートが得られに
くい欠点があった。また、この方法では、バインダー繊
維等が抄紙時にドライヤーやカンバスに付着し、定常的
操業を困難にするという欠点がおった。The present inventors previously filed an application for a paper-making method (patent application filed in 1973).
No. 7-226494), but since the above method uses ζ10'' binder fibers, it has the disadvantage that it is difficult to obtain a porous sheet. Furthermore, this method has the disadvantage that binder fibers and the like adhere to the dryer and canvas during paper making, making regular operation difficult.

また炭素板の強度を高くするπめ、原シートをフェノー
ル樹脂溶液等で含浸処理して補強することが通常行われ
るが、厚手シートでは含浸が不均一になり易く、また含
浸−乾燥能力の制約から生産性が上がらない欠点がおっ
た。Additionally, in order to increase the strength of the carbon plate, the original sheet is usually reinforced by impregnating it with a phenolic resin solution, but thick sheets tend to have uneven impregnation, and impregnation-drying performance is limited. The problem was that productivity did not increase.

発明の目的 不発明は上記の欠点を改良すると共に、安価で高品質の
多孔質炭素板の製造方法を提供することを目的とする。OBJECTS OF THE INVENTION It is an object of the invention to improve the above-mentioned drawbacks and to provide a method for manufacturing an inexpensive and high-quality porous carbon plate.

発明の構成 ここに提案する発明は、 （１）炭素繊維製造用重機繊維６５〜９０重量部、パル
プ１０〜３５重量部を抄紙して得られたシートに有機高
分子物質の溶液を含浸して含浸シー）ｔ−得、咳含浸シ
ートヲ乾燥後、不活性ガス゛雰囲気中で８００℃以上の
温度で加熱炭化させることを特徴とする多孔質炭素板の
製造方法。Structure of the Invention The invention proposed herein is as follows: (1) A sheet obtained by making paper from 65 to 90 parts by weight of heavy machinery fiber for carbon fiber production and 10 to 35 parts by weight of pulp is impregnated with a solution of an organic polymer substance. A method for producing a porous carbon plate, which comprises drying the obtained cough-impregnated sheet and then heating and carbonizing it at a temperature of 800° C. or higher in an inert gas atmosphere.

および （２）炭素繊維製造用有機繊維６５〜９０重量部、ノξ
ルプ１０〜３５重量部を抄紙して得られたシートに有機
高分子物質の溶液を含浸して含浸シート′Ｉｋ４、該含
浸シートｌ乾燥後、加熱プレスして成形および硬化を行
い・不活性ガス雰囲気中で８００℃以上の温度で加熱炭
化されることを特徴とする多孔質炭素板の製造方法。and (2) 65 to 90 parts by weight of organic fiber for carbon fiber production, ξ
The impregnated sheet 'Ik4' is obtained by impregnating a sheet obtained by paper-making 10 to 35 parts by weight of organic polymer material with a solution of an organic polymer substance. A method for producing a porous carbon plate, characterized in that the porous carbon plate is heated and carbonized at a temperature of 800° C. or higher in an atmosphere.

に関する。Regarding.

上記方法において、含浸シートは、乾燥稜、単独又は複
数枚積層し加熱プレスして成形および硬化処理を併せて
行ってもよい。In the above method, the impregnated sheet may be formed on a dry edge, singly or in a plurality of layers, and heated and pressed to perform molding and curing treatment.

本発明の構成要素について以下に詳説する。Components of the present invention will be explained in detail below.

本発明に用いる有機繊維としては、レーヨン。The organic fiber used in the present invention is rayon.

ピッチ繊維、リグニン繊維、フェノール樹脂繊維、アク
リル繊維等、炭素繊維を製造する場合に普通に使用され
る有機繊維の何れもが使用可能である。Any of the organic fibers commonly used in producing carbon fibers, such as pitch fibers, lignin fibers, phenolic resin fibers, and acrylic fibers, can be used.

有機繊維は、０．５〜１５デニール、長さ１−１５皿、
好ましくは抄紙性等の点から０．５〜８デニール、長さ
１．５〜１０ｍｍのものを目的に応じて選択し、単独で
あるいは２種以上を配合して使用する。Organic fibers are 0.5-15 denier, 1-15 plates long,
Preferably, those having a denier of 0.5 to 8 denier and a length of 1.5 to 10 mm are selected depending on the purpose from the viewpoint of paper-making properties, etc., and used alone or in combination of two or more.

上記の有機繊維は親水性が弱いため単独では抄紙ができ
ない。そのため抄紙性向上のためのつなぎとして、パル
プを配合する。The above-mentioned organic fibers cannot be used alone to make paper because of their weak hydrophilicity. Therefore, pulp is added as a binder to improve paper-making properties.

この発明に用いられるパルプとしては、セルロースノぐ
ルゾのはか、合成樹脂製の各種合成パルプが適している
。Suitable pulps for use in this invention include cellulose pulp and various synthetic pulps made from synthetic resins.

本発明は、有機繊維とパルプから抄紙するために、嵩高
なシートが得られるが、強度が必要な場合は、通常、抄
紙に使用される紙力増強剤を少量添加してもよい。紙力
増強剤としては、水溶性のものが望ましく、例えばカチ
オン化殿粉、カチオン又はアニオン化ポリアクリルアマ
イド、メラミン樹脂、尿素樹脂、エポキシ化ポリアミド
樹脂、カルゼキシ変性ポリビニルアルコール等、通常抄
紙の際使用される樹脂が使える。In the present invention, a bulky sheet can be obtained because paper is made from organic fibers and pulp, but if strength is required, a small amount of a paper strength enhancer that is normally used in paper making may be added. The paper strength enhancer is preferably water-soluble, such as cationized starch, cationic or anionized polyacrylamide, melamine resin, urea resin, epoxidized polyamide resin, calzoxy-modified polyvinyl alcohol, etc., which are commonly used in paper making. Resin that can be used can be used.

有機繊維、ノクルプは、それぞれ６５〜９０重量部、１
０〜３５重量部（固形分として〕の割合で混合して常法
によシ抄紙する。Organic fiber and Nokulup are 65 to 90 parts by weight and 1 part by weight, respectively.
The mixture is mixed in a proportion of 0 to 35 parts by weight (as solid content) and paper is made by a conventional method.

有機繊維が６５重量部以下になると、孔径、気孔率等の
コン）　Ｌｌ−ルがむずかしくなシ、気孔率の高い多孔
質シートが得られなくなシ、一方９０重量部以上では抄
紙の際に良好なシート形成がむずかしい。ノぐルゾは１
０重置部以下では抄紙性が悪く々シ、シート形成が困難
になし、３５重量部以上では嵩高なシートが得られない
。好ましい範囲としては、有機繊維が７５〜９０重量部
、パルプがｉｏ〜２５重景部で置部。If the amount of organic fiber is less than 65 parts by weight, it will be difficult to control the pore diameter, porosity, etc., and it will be difficult to obtain a porous sheet with high porosity. It is difficult to form a good sheet. Noguruzo is 1
If the amount is less than 0 parts by weight, paper-making properties are poor and sheet formation becomes difficult, and if it is more than 35 parts by weight, a bulky sheet cannot be obtained. Preferred ranges include 75 to 90 parts by weight of organic fibers and io to 25 parts by weight of pulp.

抄紙シートの含浸に用いる有機高分子物質としては、例
えばフェノール樹脂、エポキシ樹脂：不飽和ポリエステ
ル樹脂、ポリジビニルベンゼンの如き熱硬化性樹脂、塩
化ビニル樹脂、塩化ビニリデン樹脂、フッ化ビニル樹脂
、フッ化ビニリデン樹脂、アクリル樹脂等の熱可塑性樹
脂、さらにはリグニン、ピッチ又はタールの如きものも
使用される。Examples of organic polymer substances used for impregnating paper sheets include phenol resins, epoxy resins: unsaturated polyester resins, thermosetting resins such as polydivinylbenzene, vinyl chloride resins, vinylidene chloride resins, vinyl fluoride resins, and fluoride resins. Thermoplastic resins such as vinylidene resins, acrylic resins, and even lignin, pitch, or tar are also used.

これらの高分子化合物の好ましい性質としては、何等か
の溶剤に溶解するか又は熱処理時の高温で融解すること
および炭素含有量が３０重量％以上あシ炭化後、炭素質
／々インダーとして炭素繊維内の結合に役立つものであ
り、熱硬化性樹脂が好ましい。The preferable properties of these polymer compounds are that they are soluble in some kind of solvent or melted at high temperatures during heat treatment, and that they have a carbon content of 30% or more by weight.After carbonization, they can be made into carbon fibers as an inder. A thermosetting resin is preferable.

前記の有機高分子物質の溶液−！たけ分散液によシ混抄
紙を含浸処理する。混抄紙に耐着する含浸量が少なすぎ
ると、ノ々イングー効果、及び炭化の際の炭化収率が劣
シ、あまシ過剰になると目づまシの穴め気孔率の調整が
むつかしく、又もろくなる。好ましい含浸付着量として
は、混抄紙の重量の２０〜２００％、更に好ましくは３
０〜１２０チである。Solution of the organic polymer substance mentioned above! The mixed paper is impregnated with the bamboo dispersion. If the amount of impregnated paper that is resistant to adhesion to the mixed paper is too small, the carbonization effect and the carbonization yield during carbonization will be poor. Become. The preferred amount of impregnation is 20 to 200% of the weight of the mixed paper, more preferably 3
It is 0 to 120 inches.

有機繊維として再生セルロース、例えばレーヨンを使用
する場合には、上記有機高分子液の含浸処理とは別に、
耐熱性向上剤の含浸処理を併用すると、炭化収率、強度
等の点によい効果をも友らす。耐熱性向上剤としては、
レーヨン炭素繊維を製造する場合に一般に使用されるも
のなら何れでも使用可能である。例えば、リン酸金属塩
として、第一リン酸マグネシウム、第一リン酸カルシウ
ム、第一リン酸ナトリウム、第一リン酸カリウムなど、
マタ各種酸のアンモニウム塩として、塩化アンモニウム
、硫酸アンモニウム、硫酸水素アンモニウム、リン酸ア
ンモニウム、リン酸水素アンモニウム、リン酸二水素ア
ンモニウム、ポリリン酸のアンモニウム塩、ホウ酸アン
モニウム等が好適に使用できる。When using regenerated cellulose, such as rayon, as the organic fiber, apart from the impregnation treatment with the organic polymer liquid,
If impregnation treatment with a heat resistance improver is used in combination, good effects will be obtained in terms of carbonization yield, strength, etc. As a heat resistance improver,
Any material commonly used in producing rayon carbon fibers can be used. For example, as metal phosphates, monobasic magnesium phosphate, monobasic calcium phosphate, monobasic sodium phosphate, monobasic potassium phosphate, etc.
As ammonium salts of various acids, ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium salts of polyphosphoric acid, ammonium borate, etc. can be suitably used.

含浸シートは、次いで必要に応じプレス処理を行う。プ
レス処理の前に含浸シートを予備硬化処理してもよい。The impregnated sheet is then subjected to pressing treatment if necessary. The impregnated sheet may be precured before pressing.

予備硬化を行うと、シート内の有機高分子物質が流動し
なくｚ、４ｙ、卜均−なプレス処理が行える。予備硬ｆ
。ヒの処理条件としては完全硬化しない条件で１０５℃
〜１８０℃、１分〜３０分程度が好適である。When precuring is performed, the organic polymeric substance within the sheet does not flow, and uniform press processing in z, 4y, and unilateral directions can be performed. Preliminary hardness f
. The processing conditions for H are 105℃ without complete curing.
~180°C and about 1 minute to 30 minutes are suitable.

プレス成型は最終炭素板に必要な厚さ、形状、気孔率、
孔径を付与するために行い、その際、加熱処理を併用す
ることによシ含浸シート中の樹脂を硬化させる。この硬
化処理によシシートの厚みを一定に保持すると同時に平
坦なシートを得ることが可能になった。またプレス圧力
ｔ−調整することにより炭素板の気孔率、孔径を任意に
変えることができる。Press molding determines the thickness, shape, porosity, etc. required for the final carbon plate.
This is carried out in order to give the pore size, and at this time, the resin in the impregnated sheet is cured by also using heat treatment. This curing treatment made it possible to maintain a constant thickness of the sheet and at the same time obtain a flat sheet. Further, by adjusting the press pressure t-, the porosity and pore diameter of the carbon plate can be changed arbitrarily.

上記プレス処理の際、薄手の含浸シートを必要枚数、好
ましくは３枚以上重ね合せ、同様にプレス処理を行うと
、容易に厚手の炭素板が得られる。During the above press treatment, a thick carbon plate can be easily obtained by stacking a required number of thin impregnated sheets, preferably three or more sheets, and performing the press treatment in the same manner.

通常では剥離を生じ易く、製造が困難な多孔質シートの
積層が、本発明のプレス積層、硬化法で可能になった。The press lamination and curing method of the present invention has made it possible to laminate porous sheets, which are normally prone to peeling and are difficult to manufacture.

含浸シートを重ね合せる際、シートの縦方向と横方向を
交互に積層するとシートの方向性が無くなシ、加熱炭化
の際の歪が生じにくくなシカール、ヒビ割れのない厚み
の均−力炭素板が得られる。プレス加熱条件としては、
１５０〜２２０℃、１〜６０分間が適当である。When stacking impregnated sheets, stacking the sheets alternately in the vertical and horizontal directions will eliminate the orientation of the sheets, create a seal that is less prone to distortion during heating and carbonization, and create a uniform carbon thickness with no cracks. A board is obtained. The press heating conditions are as follows:
A temperature of 150 to 220°C for 1 to 60 minutes is appropriate.

含浸シートあるいは上記プレス処理を行ったシートは必
要に応じて安定化処理を行った後、焼成されて本発明の
多孔質炭素板が得られる。The impregnated sheet or the sheet subjected to the above-mentioned press treatment is subjected to stabilization treatment if necessary, and then fired to obtain the porous carbon plate of the present invention.

安定化処理は、加熱炭化工程後の有機繊維の炭化収率′
を向上させるために行う。有機繊維がアクリル繊維、ピ
ッチ繊維の場合特に有効である。The stabilization treatment reduces the carbonization yield of organic fibers after the heating carbonization process.
Do this to improve your performance. This is particularly effective when the organic fiber is acrylic fiber or pitch fiber.

安定化の処理条件は、特に特定しないが、好ましくは１
５０〜３５０℃、数１０分〜１０数時間の範囲で、使用
する有機繊維の種類で異なるが、空気中で処理する。The stabilization treatment conditions are not particularly specified, but are preferably 1
The treatment is carried out in the air at 50 to 350°C for several tens of minutes to several tens of hours, depending on the type of organic fiber used.

上記の安定化されたシートは、次いで不活性ガス雰囲気
中で、８００℃以上の温度下で加熱焼成することによシ
、本発明の多孔質炭素板ｆ：得る。The above-mentioned stabilized sheet is then heated and fired at a temperature of 800° C. or higher in an inert gas atmosphere to obtain the porous carbon plate f of the present invention.

発明の効果 本発明は、再生セルロース繊維、ピッチ繊維、アクリル
繊維等、通常炭素縁＃を製造する際の原料となる繊維か
ら抄紙法によシ得たシートを、含浸処理後、好ましくは
積層してプレスで、加熱成型処理を行い厚手の多孔性炭
素板を得る方法である。　・ 本発明の第一の特色は、原シートが有機繊維とパルプか
ら抄紙するため、シート密度の低いものが得られ、又炭
素繊維を使用しないため、８００℃以上で加熱焼成の際
、約牛分はガスとして消失するため、非常に気孔率の高
い多孔質炭素板が容易に得られるようになった。Effects of the Invention The present invention preferably involves laminating sheets obtained by a papermaking method from fibers such as regenerated cellulose fibers, pitch fibers, acrylic fibers, etc., which are normally used as raw materials for manufacturing carbon edge #s, after an impregnation treatment. In this method, a thick porous carbon plate is obtained by heat-forming using a press. - The first feature of the present invention is that the raw sheet is made from organic fibers and pulp, so a sheet with low density can be obtained, and since carbon fiber is not used, it can be heated and fired at 800°C or higher. Since the carbon atoms disappear as gas, porous carbon plates with extremely high porosity can now be easily obtained.

例えば従来炭素繊維の抄紙から得られた炭素板では気孔
率は７０％が限度であったが本発明の方法では８０〜８
５％の気孔率の炭素板を容易に得ることができる。For example, in conventional carbon plates obtained from carbon fiber papermaking, the porosity was limited to 70%, but with the method of the present invention, the porosity was 80-80%.
A carbon plate with a porosity of 5% can be easily obtained.

第二の特色は、原シートは通常の湿式抄紙機で抄紙が可
能なため、生産性が向上し、安価なシートを得ることが
できるようになった。The second feature is that the original sheet can be made using a normal wet paper machine, which improves productivity and makes it possible to obtain sheets at low cost.

また本発明の原料配合は炭素繊維に比べ抄紙性が良好な
ため均一で平坦なシートが容易に得られ、更にはシート
坪量も任意のものが得られる利点がある。更には、薄手
のシートを積層し本発明のプレス処理を行うことにより
任意の厚みの多孔質炭素板の製造も可能になった。Furthermore, since the raw material composition of the present invention has better paper-making properties than carbon fibers, it is easy to obtain uniform and flat sheets, and furthermore, there is an advantage that sheet basis weights can be obtained as desired. Furthermore, by laminating thin sheets and performing the pressing process of the present invention, it has become possible to manufacture a porous carbon plate of any thickness.

また、原料繊維の太さの選択、配合及びプレス処理の調
整によシ、燃料電池用の電極基材として使用する場合に
特に問題になる板の孔径や気孔率を自由にかつ容易にコ
ントロールすることが可能になった。In addition, by selecting the thickness of the raw fibers, adjusting the blending and press processing, it is possible to freely and easily control the pore size and porosity of the plate, which is a particular problem when used as an electrode base material for fuel cells. It became possible.

実施例 本発明をいっそう理解しやすくするために、以下に実施
例を示すが、下記の実施例は本発明を制限するものでは
ない。EXAMPLES In order to make the present invention easier to understand, examples are shown below, but the following examples do not limit the present invention.

なお、実施例中、部および−とあるのはそれぞれ重量部
および重ｆｔ％である。In the examples, parts and - are parts by weight and ft% by weight, respectively.

実施例１〜３ 太さ８デニール及ヒ１．５テニールのレーヨン短繊維、
カナディアンフリーネス５００　ｍｌ　のパルプ（Ｎ、
ＵＫＰ　）、を第１表の割合で水を加えてスラリーを得
、丸網式抄紙機で常法によシ坪量２００２／ｍ２　のシ
ートを抄造した。このシートをリン酸二水素す）　ＩＪ
ウム３０チ水溶液で含浸を行い（リン酸二水素ナトリウ
ム付着量４０％／混抄紙）、更にフェノール樹脂（体皮
デュレズ製ＰＲ，−５１４０４）２０％水溶液に含浸し
くフェノール樹脂付着量４０チ／シート）、ｉｏｏ℃の
温度で乾燥後、更に１８０℃で３０分間空気中で加熱し
安定化処理を行った。Examples 1 to 3 Short rayon fibers with a thickness of 8 denier and 1.5 tenier,
Canadian Freeness 500 ml pulp (N,
UKP) was added with water at the proportions shown in Table 1 to obtain a slurry, and a sheet having a basis weight of 2002/m2 was produced using a circular mesh paper machine in a conventional manner. This sheet is dihydrogen phosphate (IJ)
The paper was impregnated with a 30% aqueous solution of sodium dihydrogen phosphate (sodium dihydrogen phosphate coating amount 40%/mixed paper), and further impregnated with a 20% aqueous solution of phenolic resin (Durez PR, -51404).The phenol resin coating amount was 40%/sheet. ), ioo°C, and was further heated in air at 180°C for 30 minutes for stabilization treatment.

次いで９００℃のチッ素ガス雰囲気炉で１時間、グラフ
ァイト板にはさんで（３ｆ／　ｃｍ　　の加圧下）加熱
焼成を行い炭素繊維シートを得た。このシートの物性を
第１表に示す。Next, the carbon fiber sheet was heated and fired in a nitrogen gas atmosphere furnace at 900° C. for 1 hour between graphite plates (under pressure of 3 f/cm 2 ). The physical properties of this sheet are shown in Table 1.

第　　１　　表 １）　孔径、気孔率は、水銀圧入法によシ測定した。Table 1 1) Pore diameter and porosity were measured by mercury intrusion method.

抄紙シートを直接坑底する本発明の方法によれは、優れ
た電気抵抗を有する炭素繊維シートが得られ、しかも原
料繊維の配合をかえることによシ、孔径、気孔率を自由
にコントロールできることがヨン短繊維、カナディアン
フリーネス５００　ｍｌｌのパルプ（ＮＵＫＰ）、を第
２表の割合で水を加えてスラリーを得、丸網式抄紙機で
常法によ＃）１坪量６５０ｒ／ｍ２　の混抄紙を抄造し
た。この混抄紙をフェノール樹脂（体皮デュレズ製ＰＩ
（、−５１４０４）２０％水溶液に含浸しくフェノール
樹脂付着量６０チ／混抄紙）、１００℃の温度で乾燥後
、更に１８０℃で１５分間加熱し予備硬化処理を行った
。By the method of the present invention, in which paper sheets are directly produced at the bottom of a mine, a carbon fiber sheet with excellent electrical resistance can be obtained, and the pore size and porosity can be freely controlled by changing the composition of raw material fibers. A slurry was obtained by adding water to 500 ml of Canadian freeness pulp (NUKP) in the proportions shown in Table 2, and using a circular wire paper machine in the usual manner to make mixed paper with a basis weight of 650 r/m2. was made into paper. This mixed paper is coated with phenol resin (PI made by Tahida Durez).
(,-51404) was impregnated with a 20% aqueous solution (phenol resin adhesion amount: 60 cm/mixed paper), dried at a temperature of 100°C, and further heated at 180°C for 15 minutes to perform a preliminary curing treatment.

このようにして得られたシートを、次いで第１図に示す
金型の雄型（１）と雌型（３）との間に挿入し、１８０
℃、１０分間１３　ｋｆ／ｃｍ２　　で加熱硬化および
加圧底形を行い、２２０℃で５時間空気中で加熱し安定
化処理を行って後、１ｉｏｏ°Ｃのテラ素ガス雰囲気炉
で３０分間加熱焼印を行い炭素繊維シートを得た。この
シートの物性を第２表に示す。The sheet thus obtained was then inserted between the male mold (1) and female mold (3) of the mold shown in FIG.
℃ for 10 minutes at 13 kf/cm2 and pressure bottom molding, heated in air at 220℃ for 5 hours for stabilization treatment, and then heated in a terra element gas atmosphere furnace at 1ioo℃ for 30 minutes. A carbon fiber sheet was obtained by branding. The physical properties of this sheet are shown in Table 2.

抄紙シートを型付収形後直接焼収する本発明の方法によ
れば、優れた電気抵抗、強度を有する炭素繊維成形シー
トが得られ、しかも原料繊維の配合をかえることによシ
、孔径、気孔率を自由にコントロールできることが第２
表かられかる。According to the method of the present invention, in which a paper sheet is directly burned after molding, a carbon fiber molded sheet with excellent electrical resistance and strength can be obtained, and by changing the composition of raw material fibers, the pore size, The second thing is that you can freely control the porosity.
It's coming from the front.

第　　２　　表 １）孔径、気孔率は、水銀圧入法によ力測定した。Table 2 1) Pore diameter and porosity were measured using mercury intrusion method.

２）抵抗はホイートストンブリッジ法によ力測定した。2) Resistance was measured using the Wheatstone bridge method.

実施例６〜９ 太さ３デニール、長さ５ｍｍ、アクリル繊維、ピッチ繊
維、カナディアンフリーネス４００　ｍｌのパルプＣＮ
ＵＫＰ）、を第３表の割合で水を加えてスラリーを得、
丸網式抄紙機で常法により坪量で６００ｔ／ｍ２のシー
トを抄造した。このシートをフェノール樹脂（体皮デュ
レズｉＰＲ，−５１４０４）４０チ水溶液に含浸しくフ
ェノール樹脂付着量８０％／シー））、１０５℃の温度
で乾燥した。Examples 6-9 Pulp CN with thickness 3 denier, length 5 mm, acrylic fiber, pitch fiber, Canadian freeness 400 ml
UKP), water is added in the proportions shown in Table 3 to obtain a slurry,
A sheet having a basis weight of 600 t/m2 was made using a circular wire paper machine using a conventional method. This sheet was impregnated with a 40% aqueous solution of phenol resin (Durez iPR, -51404), phenol resin adhesion amount was 80%/sheet), and dried at a temperature of 105°C.

次いでプレスで厚さ２．５　ｍｍになるように加圧し、
同時に１８０℃、１５分間加熱硬化処理を行った。次い
で２２０℃で、４時間、空気中で加熱安定化処理を行っ
た後、１０００℃のチッ素ガス雰囲気炉で１時間、グラ
ファイト板にはさんで加熱炭化を行った。均一で、平坦
性の良好な、高気孔率の多孔質炭素板が得られた。結果
を第３表に示す。Next, it was pressed to a thickness of 2.5 mm using a press.
At the same time, heat curing treatment was performed at 180° C. for 15 minutes. Next, after performing heat stabilization treatment in air at 220°C for 4 hours, heating carbonization was performed by sandwiching between graphite plates in a nitrogen gas atmosphere furnace at 1000°C for 1 hour. A porous carbon plate that was uniform, had good flatness, and had a high porosity was obtained. The results are shown in Table 3.

第　　３　　表 １）　　孔径、気孔率は、水銀圧入法により測定した。Table 3 1) Pore diameter and porosity were measured by mercury intrusion method.

実施例１０〜１１ 太さ５デニール、長さ３ｍｍ、アクリル繊維８５重量％
、カナディアンフリーネス５００　ｍｌのノ々ルゾ（Ｎ
ＵＫＰ）　１５重量部に、　水を加えてスラリーを得、
丸網式抄紙機で常法により坪量で１８０９７ｍ２のシー
トを抄造した。このシートをフェノール樹脂（体皮デュ
レズ製ＰＲ，−５１４０４）４０％水溶液に含浸しくフ
ェノール樹脂付着量１００％／シー））、１０５℃の温
度で乾燥した。Examples 10-11 Thickness 5 denier, length 3 mm, acrylic fiber 85% by weight
, Canadian Freeness 500ml Nono Ruso (N
UKP) Add water to 15 parts by weight to obtain a slurry,
A sheet having a basis weight of 18,097 m2 was made using a circular wire paper machine using a conventional method. This sheet was impregnated with a 40% aqueous solution of phenol resin (PR, -51404 manufactured by Durez Co., Ltd.), phenol resin adhesion amount was 100%/sea), and dried at a temperature of 105°C.

次いで第４表に示し九枚数を縦、横交互に積層し、プレ
スで厚さ２．５ｍｍになるように加圧し、同時に１８０
℃、１５分間加熱硬化処理を行った。Next, the nine sheets shown in Table 4 were laminated vertically and horizontally alternately, pressed with a press to a thickness of 2.5 mm, and at the same time
A heat curing treatment was performed at ℃ for 15 minutes.

次いで２２０℃で、４時間、空気中で加熱安定化処理を
行った彼、１ｏｏｏ℃のチッ素ガス雰囲気炉で１時間、
グラファイト板にはさんで加熱炭化を行った。均一で、
層間剥離のない平坦性の良好な、多孔質炭素板が得られ
た。結果を第４表に示す。Next, heat stabilization treatment was performed in air at 220°C for 4 hours, and then in a nitrogen gas atmosphere furnace at 100°C for 1 hour.
It was heated and carbonized by sandwiching it between graphite plates. uniform,
A porous carbon plate with good flatness and no delamination was obtained. The results are shown in Table 4.

第４表 １）　孔径、気孔率は、水銀圧入法により測定した。Table 4 1) Pore diameter and porosity were measured by mercury intrusion method.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は、底形用金型の部分断面図である。図中の符号
は、それぞれ次のものを表わす。 ｌ・・・雄型 ２・・・雄型の突起部 ３・・・雌型 ４・・・雌型の溝 出　願　人　　　王子製紙株式会社 代理人　弁理士　　井　坂　實　夫 第１− 手　　続　　補　　正　　書 昭和５９年７月１１日 特許庁長官　志　賀　　学　　殿 昭和５９年６月２５日提出の特許出願 ２発明の名称 多孔質炭素板の製造方法 ３、補正をする者 事件との関係　　特許出願人 名　称　王子製紙株式会社 ４、代理人 住　所　東京都港区西新橋１丁目２１番１１号小野ビル
内 （２）明細書の発明の詳細な説明の欄　　−８、補正の
内容 （１）　　明細書の特許請求の範囲の欄を別紙のとおり
補正する。 （２）　　明細書第４頁の下から第４行目の「１０〜３
５」を「５〜４．ＯＪと補正する。 （３）同書第５頁第４行目の「１０〜３５」を「５〜４
０」と補正する。 （４）同書第６頁の下から第３行目の「１０〜３５」を
「５〜４０」と補正する。 （５）同書第７頁第４行目の「１０」を「５」と補正す
る。 （６）同書同頁第５行目の「３５」を「４０」と補正す
る。 補正する。 特許請求の範囲 （１）　　炭素繊維製造用有機繊維６５〜９０菖量部。 パルプ５〜４０重量部を抄紙して得られたシーｆ−ＫＮ
機高分子物質の＃！ｇｔ−含浸して含浸シートを得、該
含浸シートを乾燥後、不活性ガス雰囲気中で８００℃以
上の温度で加熱炭化させることを特徴とする多孔質炭素
板の製造方法。 （２）　　炭素繊維製造用有機繊維６５〜９０！量部。 パルプ５〜４０重量部を抄紙して得られたシートに有機
高分子物質の溶液を含浸して含浸シートを得、該含浸シ
ートを乾燥後、加熱プレスして成形および硬化を行い不
活性ガス雰囲気中で８００℃以上の温度で加熱炭化させ
ることを特徴とする多孔質炭素板の製造方法。 （３）　　含浸シートを積層して加熱プレス処理を行う
ことを特徴とする特許請求の範囲第２項に記載の多孔質
炭素板の製造方法。 第　　　　１　　　　表 第　　２　　表 第３表FIG. 1 is a partial sectional view of a bottom mold. The symbols in the figure represent the following, respectively. l...Male type 2...Male type protrusion 3...Female type 4...Female type groove Applicant: Oji Paper Co., Ltd. Agent Patent attorney Minoru Isaka No. 1 - Supplementary procedure Author: July 11, 1980 Manabu Shiga, Commissioner of the Patent Office Patent application filed on June 25, 1980 2 Name of the invention Method for manufacturing porous carbon plates 3 Relationship with the amended person's case Patent application Name: Oji Paper Co., Ltd. 4, Agent Address: Ono Building, 1-21-11 Nishi-Shinbashi, Minato-ku, Tokyo (2) Detailed explanation of the invention in the specification -8, Contents of the amendment (1) Details The claims section of the book shall be amended as shown in the attached sheet. (2) "10-3" in the fourth line from the bottom of page 4 of the specification
5" is corrected to "5-4.OJ."
0”. (4) "10-35" in the third line from the bottom of page 6 of the same book is corrected to "5-40". (5) "10" in the fourth line of page 7 of the same book is corrected to "5". (6) "35" in the 5th line of the same page of the same book is corrected to "40". to correct. Claims (1) 65 to 90 parts of organic fiber for carbon fiber production. Sea f-KN obtained by making paper from 5 to 40 parts by weight of pulp
# of machine polymer materials! A method for producing a porous carbon plate, comprising: obtaining an impregnated sheet by gt-impregnation, drying the impregnated sheet, and then carbonizing it by heating at a temperature of 800° C. or higher in an inert gas atmosphere. (2) Organic fiber for carbon fiber production 65-90! Quantity part. A sheet obtained by papermaking from 5 to 40 parts by weight of pulp is impregnated with a solution of an organic polymer substance to obtain an impregnated sheet, and after drying, the impregnated sheet is heated and pressed to form and harden in an inert gas atmosphere. A method for producing a porous carbon plate, which comprises heating and carbonizing the plate at a temperature of 800°C or higher. (3) The method for producing a porous carbon plate according to claim 2, characterized in that impregnated sheets are laminated and heated press treated. Table 1 Table 2 Table 3

Claims (3)

【特許請求の範囲】[Claims] （１）炭素繊維製造用有機繊維６５〜９０重量部、パル
プ１０〜３５重量部を抄紙して得られたシートに有機高
分子物質の溶液を含浸して含浸シートを得、該含浸シー
トを乾燥後、不活性ガス雰囲気中で８００℃以上の温度
で加熱炭化させることを特徴とする多孔質炭素板の製造
方法。(1) A sheet obtained by making paper from 65 to 90 parts by weight of organic fibers and 10 to 35 parts by weight of pulp for manufacturing carbon fibers is impregnated with a solution of an organic polymer substance to obtain an impregnated sheet, and the impregnated sheet is dried. A method for producing a porous carbon plate, which is then heated and carbonized at a temperature of 800° C. or higher in an inert gas atmosphere. （２）炭素繊維製造用有機繊維６５〜９０重量部、パル
プ１０〜３５重量部を抄紙して得られたシートに有機高
分子物質の溶液を含浸して含浸シートを得、該含浸シー
トを乾燥後、加熱プレスして成形および硬化を行い不活
性ガス雰囲気中で８００℃以上の温度で加熱炭化させる
ことを特徴とする多孔質炭素板の製造方法。(2) A sheet obtained by making paper from 65 to 90 parts by weight of organic fiber for carbon fiber production and 10 to 35 parts by weight of pulp is impregnated with a solution of an organic polymer substance to obtain an impregnated sheet, and the impregnated sheet is dried. A method for producing a porous carbon plate, which is then hot-pressed to form and harden, and heated and carbonized at a temperature of 800° C. or higher in an inert gas atmosphere. （３）含浸シートを積層して加熱プレス処理を行うこと
を特徴とする特許請求の範囲第２項に記載の多孔質炭素
板の製造方法。(3) The method for producing a porous carbon plate according to claim 2, wherein the impregnated sheets are laminated and subjected to a hot press treatment.