JPH01118625A - Production of porous carbon plate - Google Patents
Production of porous carbon plateInfo
- Publication number
- JPH01118625A JPH01118625A JP26400488A JP26400488A JPH01118625A JP H01118625 A JPH01118625 A JP H01118625A JP 26400488 A JP26400488 A JP 26400488A JP 26400488 A JP26400488 A JP 26400488A JP H01118625 A JPH01118625 A JP H01118625A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- pulp
- parts
- sheet
- weight
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000835 fiber Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 8
- 239000004917 carbon fiber Substances 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 8
- 229920000620 organic polymer Polymers 0.000 claims abstract description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007380 fibre production Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000005011 phenolic resin Substances 0.000 abstract description 6
- 229920000297 Rayon Polymers 0.000 abstract description 5
- 239000002964 rayon Substances 0.000 abstract description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001568 phenolic resin Polymers 0.000 abstract description 4
- 229920002678 cellulose Polymers 0.000 abstract description 2
- 239000001913 cellulose Substances 0.000 abstract description 2
- 239000000123 paper Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229940035053 monobasic magnesium phosphate Drugs 0.000 description 1
- 229940111688 monobasic potassium phosphate Drugs 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
- Paper (AREA)
Abstract
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、抄紙法により得られた樹
脂混抄シートを焼成することにより、耐薬品性、電気伝
導性、強度の優れた、嵩高な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, the present invention relates to a method for producing a bulky porous carbon plate with excellent chemical resistance, electrical conductivity, and strength by firing a resin-mixed sheet obtained by a papermaking method.
従来炭素ＭＡ維レシート得る方法としては、あらかじめ
焼成された炭素繊維をパルプ、バインダーと共に抄紙し
た炭素ｔａＩＪｔｉ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（特公昭５３−１８６０３号公報）。The conventional method for obtaining carbon MA fiber receipts is to impregnate carbon taIJti mixed paper, which is made from pre-fired carbon fibers together with pulp and binder, in a solution of thermosetting resin, and heat and carbonize it again in an inert atmosphere. It is known (Japanese Patent Publication No. 18603/1983).
しかしながら上記方法は、抄紙性、シート強度補強のた
めバインダー繊維の配合が必要であった。そのため抄紙
シートの密度が高くなり、多孔質のシートが得られにく
いという問題点を有している。また、抄紙シートは炭化
後の炭素板の強度及び電気伝導性を向上させるため、フ
ェノール樹脂溶液等で含浸処理が必要である。溶液が有
機溶媒の場合には、特殊な防爆型含浸装置が必要であり
、水溶液の場合には、シート強度が低下し切断し易いの
でシート強度の向上が特に必要であるという問題点があ
る。However, the above method requires the addition of binder fibers to enhance paper-making properties and sheet strength. Therefore, there is a problem that the density of the paper sheet becomes high and it is difficult to obtain a porous sheet. Furthermore, the paper sheet needs to be impregnated with a phenol resin solution or the like in order to improve the strength and electrical conductivity of the carbonized carbon plate. When the solution is an organic solvent, a special explosion-proof impregnation device is required, and when the solution is an aqueous solution, the sheet strength decreases and is easily cut, so it is particularly necessary to improve the sheet strength.
本発明は上記の欠点を改良すると共に、工程が１ｌｆｉ
略化され、安価で高、２￥１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。The present invention improves the above-mentioned drawbacks and the process is 1lfi.
The object of the present invention is to provide a method for manufacturing a porous carbon plate that is simplified, inexpensive, and costs only 2 yen.
炭素繊維製造用有機繊維６５〜９０重量部、パルプ５〜
４０重量部、及び、有機高分子物質のエマルジョンを有
効固形分として３０〜２００重量部（有機繊維及びバル
ブ１００重４１部に対し）からなる抄紙シートを加熱処
理後、必要に応じ安定化処理を行なった後、不活性ガス
雰囲気中で８００℃以ｌ二の温度で加熱炭化させる多孔
質炭素板の製造方法である。65-90 parts by weight of organic fiber for carbon fiber production, 5-90 parts of pulp
After heating a paper sheet consisting of 40 parts by weight and 30 to 200 parts by weight (based on 100 parts by weight of organic fibers and bulbs) of an emulsion of an organic polymer substance as an effective solid content, stabilization treatment is performed as necessary. After this process, the porous carbon plate is heated and carbonized at a temperature of 800° C. or higher in an inert gas atmosphere.
上記方法において、シートは加熱処理後、予備硬化処理
して、加熱プレス成形を行なうか、予備硬化なしで、加
熱プレスして成形および硬化処理を併せて行なってもよ
い。In the above method, the sheet may be heat-treated, then pre-cured, and then hot-press molded, or the sheet may be heat-pressed and molded and hardened simultaneously without pre-curing.
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.
本発明ば用いる有ａ繊維としては、レーヨン、ピッチｍ
維、リグニン繊維、フェノール樹脂繊維、アクリル繊＃
Ｉ等、炭素ｍ雑を製造する場合に杼道に使用される有機
繊維の何れもが使用可能である６有機繊維は、０．５〜
１５デニール、長さ１〜１５ ｍ ｍ、好ましくは抄紙
性等の点から０．５〜８デニール、長さ１．５〜１０ｍ
ｍ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。The a-containing fibers used in the present invention include rayon, pitch m
fiber, lignin fiber, phenolic resin fiber, acrylic fiber#
Any of the organic fibers used for the shed when manufacturing carbon m miscellaneous materials such as I can be used.
15 denier, length 1 to 15 mm, preferably 0.5 to 8 denier, length 1.5 to 10 m from the viewpoint of paper-making properties, etc.
m is selected depending on the purpose and used alone or in combination of two or more.
」；記の有機繊維は親木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。Because the organic fibers mentioned above have weak wood-philicity, they cannot be used alone to make paper.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、セルロースパル
プのほか、合成樹脂製の各種合成パルプが適しており、
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。As the pulp used in this invention, in addition to cellulose pulp, various synthetic pulps made of synthetic resin are suitable.
In the present invention, since paper is made from organic fibers and pulp, a bulky sheet can be obtained.
強度が必要な場合は、各種バインダーの他通常の抄紙に
使用される紙力増強剤を少量添加してもよい１紙力増強
剤としては、カチオン化澱粉、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、カルボ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の他、合成樹脂
エマルジョンが使える。If strength is required, a small amount of paper strength enhancers used in ordinary paper making may be added in addition to various binders. Examples of paper strength enhancers include cationized starch, cationic or anionized polyacrylamide, and melamine. In addition to resins normally used in papermaking, such as resins, urea resins, epoxidized polyamide resins, and carboxy-modified polyvinyl alcohols, synthetic resin emulsions can be used.
抄紙用バインダーとしては、例えばポリビニルアルコー
ル繊維、抄紙用レーヨン等の冷水中に溶゛解しないが熱
水に溶解する１ｍ維で、抄紙用バインダーとして一般に
市販されているものを本発明の目的を阻害しない範囲で
使用することができる。Examples of binders for paper making include polyvinyl alcohol fibers, rayon for paper making, and other 1m fibers that do not dissolve in cold water but dissolve in hot water, and are generally commercially available as binders for paper making, but do not interfere with the purpose of the present invention. It can be used within the range.
有機繊維、パルプは、それぞれ６５〜９０重量部、５〜
４０重量部（固形分として）の割合で混合して常法によ
り抄紙する。Organic fiber and pulp are 65 to 90 parts by weight and 5 to 90 parts by weight, respectively.
They are mixed in a proportion of 40 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
コントロールがむずかしくなり、気孔率の高い多孔質シ
ートが得られなくなり、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、パルプは５重量部
以下では抄紙性が悪くなり、シート形成が困難になり、
４０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重縫部である。If the amount of organic fiber is less than 65 parts by weight, it becomes difficult to control the pore diameter, porosity, etc., and a porous sheet with high porosity cannot be obtained, while if it is more than 90 parts by weight, it is difficult to form a good sheet during paper making. If the pulp is less than 5 parts by weight, papermaking properties will be poor and sheet formation will be difficult.
If the amount is 40 parts by weight or more, a bulky sheet cannot be obtained.The preferable range is 75 to 90 parts by weight of the organic fiber and io to 25 parts by weight of the pulp.
上記有機繊維、パルプに混抄され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 the organic polymer substances to be mixed with the above-mentioned organic fibers and pulp include phenol resin, epoxy resin, unsaturated polyester resin, thermosetting resin such as polydivinylbenzene, vinyl chloride resin, vinylidene chloride resin, and vinyl fluoride. Thermoplastic resins such as resins, vinylidene fluoride 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、熱処理
時の高温で融解することおよび炭素含有ｒ逢が３０重量
％以上あり炭化後、炭素質パインターとして炭素ｍ＃ｌ
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 melt at high temperatures during heat treatment, and that they contain 30% or more of carbon by weight, so that after carbonization, carbon m#l is formed as a carbonaceous pinter.
A thermosetting resin is preferable.
前記の有機高分子物質は粒径が０．５ｇ〜５０ル好まし
くは１〜１ＯＩＬのエマルジョン分散液の形で混抄され
る。必要なら、通常抄紙の際使用される、歩留向上剤を
添加してもよい、高分子物質のｆａｔが少なすぎると、
炭素板のバインダー効果、及び炭化の際の炭化収率が劣
り、あまり過剰になると１１づまりのため気孔率の調整
がむづかしく、又もろくなる。好ましい配合量としては
、有機繊維及びパルプの重量の２０〜２００％、更に好
ましくは３０〜１２０％である。The above-mentioned organic polymeric substances are mixed in the form of an emulsion dispersion having a particle size of 0.5 g to 50 L, preferably 1 to 1 OIL. If necessary, a retention aid that is normally used in paper making may be added.If the fat content of the polymeric material is too low,
The binder effect of the carbon plate and the carbonization yield during carbonization are poor, and if too much is used, it is difficult to adjust the porosity due to 11 clogging, and the plate becomes brittle. The preferred blending amount is 20 to 200%, more preferably 30 to 120% of the weight of the organic fibers and pulp.
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、耐熱性向上剤を含浸処理させると、炭化
収率、強度等の点によい効果をもたらす。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０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、また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 regenerated cellulose, such as rayon, is used as the organic fiber, impregnating it with a heat resistance improver brings about good effects in terms of carbonization yield, strength, etc. As the heat resistance improver, any of those commonly used in producing rayon carbon fibers can be used. For example, as metal phosphates, monobasic magnesium phosphate, monobasic calcium phosphate, monobasic phosphate Sodium, monobasic potassium phosphate, etc., and ammonium salts of various acids such as ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium salts of polyphosphoric acid, and boric acid. Ammonium and the like can be suitably used.
有機繊維、パルプおよび有機高分子物質のエマルジョン
は、水に分散され通常の長網、円網抄紙機等で抄紙され
る。抄紙シートは次いで加熱処理を行なう、加熱処理は
シート中の有機高分子物質を溶融させ、有機繊維、パル
プ同志を接着させる効果を有する。加熱条件は、使用す
る樹脂によって異なるが、溶融、接着する温度範囲で適
当に選択すればよい、加熱処理は、抄紙の際の乾煙工程
で行なってもよく、抄紙後の別工程で行なってもよい。The emulsion of organic fibers, pulp, and organic polymeric substances is dispersed in water and made into paper using a conventional fourdrinier, cylinder paper machine, or the like. The papermaking sheet is then subjected to heat treatment. The heat treatment has the effect of melting the organic polymer substance in the sheet and adhering the organic fibers and pulp together. Heating conditions vary depending on the resin used, but should be selected appropriately within the temperature range for melting and adhesion.Heating treatment may be performed in the dry smoke process during papermaking, or it may be performed in a separate process after papermaking. Good too.
加熱処理シートは、次いで必要に応じプレス処理を行な
う。プレス処理の前に抄紙シートを予備硬化処理しても
よい、予備硬化を行なうと、シート内の有機高分子物質
が流動しなくなる為、均一なプレス処理が行える。予備
硬化の処理条件としては完全硬化しない条件でｉ４０℃
〜１８０℃、１分〜３０分程度が好適である。The heat-treated sheet is then subjected to a press treatment, if necessary. The paper sheet may be subjected to pre-curing treatment before the press treatment. If pre-cure is performed, the organic polymeric substance in the sheet will not flow, so that a uniform press treatment can be performed. Pre-curing processing conditions are i40℃ 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。Press molding produces the thickness and shape required for the final carbon plate.
気孔率、孔径を付与するために行ない、その際、加熱処
理を併用することによりシート中の樹脂を硬化させる。This is performed to impart porosity and pore size, and at this time, heat treatment is also used to harden the resin in the sheet.
この硬化処理によりシー［・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
レス圧力を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。This curing treatment made it possible to maintain a constant thickness of the sheet and at the same time obtain a flat sheet. Furthermore, by adjusting the press pressure, the porosity and pore diameter of the carbon plate can be changed arbitrarily.
ト記プレス処理の際、薄手の抄紙シートを必要枚数、好
ましくは３枚以上重ね合せ、同様にプレス処理を行なう
と、容易に厚手の炭素板が得られる０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。抄紙シートを重
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り、加熱炭化の際の歪が生じ
にくくなりカール、ヒビ割れのない厚みの均一な炭素板
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。During the press treatment, a thick carbon plate can be easily obtained by stacking the required number of thin paper sheets, preferably three or more sheets, and performing the same press treatment. The difficult lamination of porous sheets has become possible with the press lamination and curing method of the present invention.When stacking paper sheets, if the sheets are laminated alternately in the vertical and horizontal directions, the sheets lose their orientation. , distortion during heating carbonization is less likely to occur, and a carbon plate with a uniform thickness without curls or cracks can be obtained.The press heating conditions are 150-220
°C for 1 to 60 minutes is appropriate.
加熱処理シートあるいは上記プレス処理を行なったシー
トは必要に応じ安定化処理を行なった後、焼成されて本
発明の多孔質炭素板が得られる。安定化の処理条件は、
特に特定しないが、好ましくは１５０〜３５０℃、数１
０分〜ｌＯ数時間の範囲で、使用する有機Ｉｊ＆雑の種
類で異なるが、空気中で処理する。この安定化処理によ
り炭素化収率が５〜１０％向上し、かつ強度も向上する
。The heat-treated 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. The stabilization treatment conditions are:
Although not particularly specified, preferably 150 to 350°C, several 1
The treatment time ranges from 0 minutes to 10 hours, depending on the type of organic Ij and miscellaneous materials used, but the treatment is carried out in air. This stabilization treatment improves the carbonization yield by 5 to 10% and also improves the strength.
上記め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り
、本発明の多孔質炭素板を得る。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 of the present invention.
本発明は、再生セルロース繊維、ピッチｍ維、アクリル
＃ａ維等、通常炭素繊維を製造する際の原料となる繊維
と有機高分子物質とから抄紙法により得たシートを、加
熱処理後、好ましくは積層してプレスで、加熱成型処理
を行ない厚手の多孔性炭素板を得る方法である。In the present invention, a sheet obtained by a papermaking method from fibers that are usually raw materials for manufacturing carbon fibers, such as regenerated cellulose fibers, pitch M fibers, acrylic #A fibers, and an organic polymer substance, is preferably heated. This is a method in which a thick porous carbon plate is obtained by laminating, pressing, and heat-forming.
未発１１によれば、有機繊維およびパルプの抄紙と同時
に有機高分子物質をシート化するため、従来のように樹
脂溶液を別工程で含浸する必要がなくなり、大幅なコス
トダウンが可能になった。According to Mishappen 11, since the organic polymer material is made into a sheet at the same time as the organic fiber and pulp are made, there is no need to impregnate the paper with a resin solution in a separate process as in the past, making it possible to significantly reduce costs. .
又、従来の含浸処理を行なう場合には含浸液中での断紙
を防ぐため湿潤強度を大さくする必要があったが、本９
．明方法では、その必要性が小さく、更には、高分子物
質の添加により、焼成後の加工適性に優れた十分な強度
を有する多孔性炭素板が得られる。In addition, when performing conventional impregnation treatment, it was necessary to increase the wet strength to prevent paper breakage in the impregnating solution, but this
．． In the method, there is little need for this, and furthermore, by adding a polymeric substance, a porous carbon plate having sufficient strength and excellent processing suitability after firing can be obtained.
更には、繊維の接着が樹脂粒子の溶融により行われるた
め、溶液含浸の場合に比べ点接着に近い、そのため、空
間が多くなり多孔室の炭素板が得られ易くなった。Furthermore, since fiber adhesion is performed by melting resin particles, it is closer to point adhesion than in the case of solution impregnation, and therefore, the space is increased, making it easier to obtain a carbon plate with porous chambers.
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 are not intended to 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
および重量％である。In addition, parts and % in the examples are parts by weight and % by weight, respectively.
実施例１〜３
太さ７デニール３ ｍ ｍのアクリル繊維、カナデイア
ンフリーネス４００ｍＭのパルプ（ＮＢＫＰ）を第１表
の割合で水を加えてスラリーを得、さらにフェノール樹
脂エマルジョン（住人ベークライトＰＲ５１４６４）を
加え十分に混合し、抄紙直前に歩留向上剤（ポリアクリ
ルアマイドカチオン変成品）を加え、丸網式抄紙機で常
法により坪量２００ｇ／ｒｎ’のシートを抄造した。こ
れを適当な大きさに断裁後これを５枚重ね合せ１５０℃
２０分間の熟プレスにより、フェノール樹脂を融解させ
、熱硬化を行った。さらに、２２０℃４時間の安定化処
理を行った。Examples 1 to 3 Acrylic fibers with a thickness of 7 denier and 3 mm and Canadian freeness 400 mM pulp (NBKP) were added with water at the ratio shown in Table 1 to obtain a slurry, and a phenolic resin emulsion (Jin Bakelite PR51464) was further added. The mixture was added and thoroughly mixed, and a retention improver (a cationic polyacrylamide modified product) was added immediately before paper making, and a sheet with a basis weight of 200 g/rn' was made using a conventional method using a circular wire paper machine. After cutting this into an appropriate size, stack 5 sheets together and heat at 150℃.
The phenolic resin was melted and thermally cured by pressing for 20 minutes. Furthermore, stabilization treatment was performed at 220° C. for 4 hours.
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、加熱焼成を行い炭素繊維板を得た。Next, the carbon fiber board was heated and fired by sandwiching it between graphite plates for 1 hour in a nitrogen gas atmosphere furnace at 900°C.
この）Ｒ素繊維板の物性を第１表に示す。Table 1 shows the physical properties of this R-fiber board.
抄紙シートを直接焼成する未発Ｉｊｌの方法によれば、
優れた電気伝導性および多孔性を有する炭素ｍｉ板が得
られる。According to the undeveloped Ijl method of directly firing the paper sheet,
A carbon mi plate with excellent electrical conductivity and porosity is obtained.
Claims (1)
４０重量部、及び、有機高分子物質のエマルジョンを有
効固形分として３０〜２００重量部（有機繊維及ぶパル
プ１００重量部に対し）からなる抄紙シートを加熱処理
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。65-90 parts by weight of organic fiber for carbon fiber production, 5-90 parts of pulp
After heat-treating a paper sheet consisting of 40 parts by weight and 30 to 200 parts by weight (based on 100 parts by weight of organic fibers and pulp) of an emulsion of an organic polymer substance as an effective solid content, it was heated to 800°C in an inert gas atmosphere. A method for producing a porous carbon plate, characterized by heating and carbonizing it at a temperature above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26400488A JPH01118625A (en) | 1988-10-21 | 1988-10-21 | Production of porous carbon plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26400488A JPH01118625A (en) | 1988-10-21 | 1988-10-21 | Production of porous carbon plate |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59140701A Division JPS6119820A (en) | 1984-07-09 | 1984-07-09 | Production of porous carbon plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01118625A true JPH01118625A (en) | 1989-05-11 |
Family
ID=17397213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26400488A Pending JPH01118625A (en) | 1988-10-21 | 1988-10-21 | Production of porous carbon plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01118625A (en) |
-
1988
- 1988-10-21 JP JP26400488A patent/JPH01118625A/en active Pending
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