JPH0645444B2 - Method for manufacturing glassy carbon sheet - Google Patents
Method for manufacturing glassy carbon sheetInfo
- Publication number
- JPH0645444B2 JPH0645444B2 JP1149984A JP14998489A JPH0645444B2 JP H0645444 B2 JPH0645444 B2 JP H0645444B2 JP 1149984 A JP1149984 A JP 1149984A JP 14998489 A JP14998489 A JP 14998489A JP H0645444 B2 JPH0645444 B2 JP H0645444B2
- Authority
- JP
- Japan
- Prior art keywords
- glassy carbon
- carbon sheet
- sheet
- film
- carbonaceous
- 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.)
- Expired - Lifetime
Links
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- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ガラス状カーボンシートの製造方法に係り、
とくに良好な表面平滑性と均質組識を備える厚さ20μｍ
〜２mmの薄膜シート性ガラス状カーボンを製造するため
の方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a glassy carbon sheet,
20 μm thickness with particularly good surface smoothness and homogeneous texture
A method for producing a thin sheet glassy carbon of ~ 2 mm.
ガラス状カーボンは、カーボン材料の中でも取分け気体
不透過性、耐薬品性などの特性に優れているため電子、
化学をはじめ多くの工業分野で使用されている。Among the carbon materials, glassy carbon is particularly excellent in gas impermeability, chemical resistance, etc.
It is used in many industrial fields including chemistry.
通常、ガラス状カーボンはフラン系樹脂またはフェノー
ル系樹脂のような炭化残留率の高い熱硬化性樹脂を原料
とし、これを所望の形状に成形したのち非酸化性雰囲気
炉で焼成炭化する方法によって製造されている。しか
し、この種の樹脂原料系を用いて薄いシートに成形する
ことは能率的、得率的および品質的に極めて困難であ
る。Usually, glassy carbon is produced by a method in which a thermosetting resin having a high carbonization residual ratio such as a furan-based resin or a phenol-based resin is used as a raw material, and this is molded into a desired shape and then fired and carbonized in a non-oxidizing atmosphere furnace. Has been done. However, it is extremely difficult in terms of efficiency, efficiency and quality to mold a thin sheet using this type of resin raw material system.
このため、上記の樹脂をセルロース繊維に含浸してから
シートに成形し、これを炭素化する方法（特開昭60−42
213号公報）が提案されている。このほかにも、各種の
有機質フィルムを炭化してシート状カーボンを得る方法
（特開昭54−26292号公報）が知られている。For this reason, a method of impregnating the above-mentioned resin into a cellulose fiber, forming into a sheet, and carbonizing the sheet (JP-A-60-42)
No. 213) has been proposed. In addition, a method of carbonizing various organic films to obtain sheet-like carbon (Japanese Patent Laid-Open No. 54-26292) is known.
ところが、上記の従来技術ではシートあるいはフィルム
を焼成炭化する過程で起こる収縮現象により得られるカ
ーボンシート皺、うねり、反り等が発生し、特に面積の
大きいものについて精度のよい平滑面を形成することが
難しい問題点がある。硬質のカーボン材は極めて脆弱で
あるため、このような形状不良があると使用時に材料破
損を多発する結果を招く。However, in the above-mentioned conventional techniques, wrinkles, waviness, warpage, and the like of the carbon sheet obtained by the contraction phenomenon that occurs in the process of firing and carbonizing a sheet or film occur, and it is possible to form an accurate smooth surface particularly for a large area. There are difficult problems. Since a hard carbon material is extremely fragile, such a defective shape results in frequent material damage during use.
本発明の目的は、従来技術の問題点を解消し、焼成炭化
過程で皺、うねり、反り等の発生を伴うことなく常に優
れた表面平滑性と均質組識を有するガラス状カーボンシ
ートの製造方法を提供するところにある。The object of the present invention is to solve the problems of the prior art, and a method for producing a glassy carbon sheet having always excellent surface smoothness and homogeneous texture without the occurrence of wrinkles, waviness, warpage, etc. in the firing carbonization process. Is in the place of providing.
〔課題を解決するための手段〕 上記の目的を達成するために開発された本発明によるガ
ラス状カーボンシートの製造方法は、芳香族ポリイミド
のフィルムを表面粗さ６５μｍＲMAX以下の炭素質押え
板で挟み付け、押え圧力を掛けた状態で非酸化性雰囲気
中800〜2100℃の温度で焼成することを構成上の特徴と
する。[Means for Solving the Problems] A method for producing a glassy carbon sheet according to the present invention developed to achieve the above object is to use an aromatic polyimide film as a carbonaceous pressing plate having a surface roughness of 65 μmR MAX or less. It is characterized in that it is baked at a temperature of 800 to 2100 ° C. in a non-oxidizing atmosphere while being sandwiched and pressed with pressure.
原料として芳香族ポリイミドを用いる理由は、この樹脂
がフラン系あるいはフェノール系の熱硬化性樹脂に比べ
てシート成形性に優れており、均質な薄膜状のシート材
料として容易に形成することができるからである。本発
明の目的には、下記の分子構造を有する芳香族ポリイミ
ドで、厚さ25μｍから2.5mmのフィルムが有効に適用さ
れる。The reason for using aromatic polyimide as a raw material is that this resin is superior in sheet formability to a furan-based or phenol-based thermosetting resin and can be easily formed as a homogeneous thin film sheet material. Is. For the purpose of the present invention, a film having an aromatic polyimide having the following molecular structure and having a thickness of 25 μm to 2.5 mm is effectively applied.
芳香族ポリイミドのフィルムを挟み付けるための押え板
は、表面粗さ６５μｍＲMAX以下に研磨処理した炭素質
材料で構成することが重要で、表面粗さが６５μｍＲ
MAXを越えると炭化過程での円滑なフィルム収縮が阻害
されて亀裂や破損を生じたり、表面に凹凸が発生する原
因となる。最も好ましい炭素質押え板は、原料として最
大粒子径が100μｍ以下の微細組識をもつかさ密度1.75g
/cm3以上の黒鉛材で形成したものであり、この性状の黒
鉛材は表面平滑化が容易で滑りも良い。 It is important that the holding plate for sandwiching the aromatic polyimide film is made of a carbonaceous material that has been polished to a surface roughness of 65 μmR MAX or less.
If it exceeds MAX , smooth film shrinkage during the carbonization process is hindered, which may cause cracks or breakage, or unevenness on the surface. The most preferred carbonaceous press plate has a fine structure with a maximum particle size of 100 μm or less as a raw material, and has a bulk density of 1.75 g.
It is formed of a graphite material of / cm 3 or more, and the graphite material of this property has a smooth surface and is easy to slip.
芳香族ポリイミドのフィルムは炭素質押え板を介し押え
圧力を掛けた状態で焼成されるが、この際少なくとも２
０gf/cm2の押え圧力を付加することが望ましく、これを
下廻る圧力では得られるガラス状カーボンシートの表面
に凹凸が発生する場合がある。The aromatic polyimide film is fired with a holding pressure applied through a carbonaceous holding plate, and at this time, at least 2
It is desirable to apply a pressing pressure of 0 gf / cm 2 , and if the pressure is less than this, unevenness may occur on the surface of the glassy carbon sheet obtained.
焼成処理は、窒素、アルゴンなどの非酸化性雰囲気に保
持された炉を用い、800〜2100℃の温度域で加熱するこ
とによっておこなわれる。The firing treatment is performed by heating in a temperature range of 800 to 2100 ° C. using a furnace maintained in a non-oxidizing atmosphere such as nitrogen and argon.
本発明によれば、成形性のよい芳香族ポリイミドのフィ
ルムを表面平滑性の炭素質押え板で加圧下に挟み付けた
状態で焼成炭化されるから、この段階で起きるフィルム
の収縮は平滑な押え板の面に沿って抵抗を受けることな
く円滑に進行するとともに押え圧力の作用により凹凸、
皺、うねり、反り等の現象を巧みに回避する。したがっ
て、比較的大きな面積のフィルムであっても常に平面精
度の良好なガラス状カーボンシートに転化させることが
可能となる。According to the present invention, a film of aromatic polyimide having good moldability is calcined and carbonized in a state of being sandwiched between carbonaceous pressing plates having a surface smoothness under pressure, so that the shrinkage of the film occurring at this stage is a smooth pressing. It moves smoothly along the surface of the plate without receiving resistance and it is uneven due to the action of the pressing pressure.
Skillfully avoid phenomena such as wrinkles, undulations, and warpage. Therefore, even a film having a relatively large area can be always converted into a glassy carbon sheet having good planar accuracy.
また、焼成時に発生する樹脂原料からの分解ガスは、炭
素質押え板の有する微小な気孔を介して排出もしくは吸
蔵される。このため、製造されるガラス状カーボンシー
トには発泡組織がなく、完全なガス不透過性を備える高
度な均質緻密組織が付与される。Further, the decomposition gas generated from the resin raw material during firing is discharged or stored through the minute pores of the carbonaceous pressing plate. Therefore, the glassy carbon sheet produced does not have a foamed structure and is imparted with a highly homogeneous and dense structure having complete gas impermeability.
以下、本発明の実施例を比較例と対比して説明する。 Hereinafter, examples of the present invention will be described in comparison with comparative examples.
実施例１ 上記(1)の分子構造式からなる厚さ0.125mm、縦横200mm
のポリイミドフィルム〔東レデュポン（株）製“カプト
ン”〕を、表面粗さ２０μｍＲMAXに研磨した最大粒子
径100μｍ、かさ密度1.83g/cm3の黒鉛板〔東海カーボン
（株）製、“Ｇ347”厚さ10mm〕からなる押え板に挟み
付けた。これに60gf/cm2の押え圧力を掛けた状態で窒素
ガス雰囲気炉に入れ、1500℃の温度で焼成してガラス状
カーボンシートを得た。Example 1 Thickness of 0.125 mm and length and width of 200 mm, which is based on the molecular structural formula of (1) above
Graphite plate with a maximum particle size of 100 μm and a bulk density of 1.83 g / cm 3 obtained by polishing a polyimide film (“Kapton” manufactured by Toray DuPont Co., Ltd.) to a surface roughness of 20 μm R MAX (“G347” manufactured by Tokai Carbon Co., Ltd.) It was clamped by a holding plate made of 10 mm thick. A glass-like carbon sheet was obtained by placing this in a nitrogen gas atmosphere furnace while applying a pressing pressure of 60 gf / cm 2 and firing it at a temperature of 1500 ° C.
実施例２ 上記(2)の分子構造式からなる厚さ1.0mm、縦横200mmの
ポリイミドフィルム〔宇部興産（株）製、“ユーピレッ
クス”〕を原料とし、実施例１と同一の条件により焼成
してガラス状カーボンシートを得た。Example 2 A polyimide film having a thickness of 1.0 mm and a length of 200 mm (“Upilex” manufactured by Ube Industries, Ltd.) having the molecular structural formula of (2) above was used as a raw material and fired under the same conditions as in Example 1. A glassy carbon sheet was obtained.
実施例３ 実施例１において、表面粗さを６５μｍＲMAXになるよ
うに研磨した黒鉛押え板を用いたほかは同一の条件でガ
ラス状カーボンシートを製造した。Example 3 A glassy carbon sheet was manufactured under the same conditions as in Example 1, except that a graphite pressing plate polished to have a surface roughness of 65 μm R MAX was used.
実施例４ 実施例１において、押え圧力を10gf/cm2としたほかは同
一の条件によりガラス状カーボンシートを製造した。Example 4 A glassy carbon sheet was produced under the same conditions as in Example 1 except that the pressing pressure was 10 gf / cm 2 .
比較例１ 実施例１と同一のポリイミドフィルムを、表面粗さ７５
μｍＲMAXに研磨した最大粒子径1.0mm、かさ密度1.60g/
cm3の黒鉛板〔東海カーボン（株）製、“G140”、厚さ1
0mm〕に挟み付け、あとは実施例１と同様にしてガラス
状カーボンシートを製造した。Comparative Example 1 The same polyimide film as in Example 1 was used, and the surface roughness was 75
maximum particle size 1.0mm polished to μmR MAX, bulk density 1.60 g /
cm 3 graphite plate [Tokai Carbon Co., Ltd., “G140”, thickness 1
0 mm], and then a glassy carbon sheet was manufactured in the same manner as in Example 1.
比較例２ 比較例１の押え圧力（60gf/cm2）を20gf/cm2に変更した
ほかは、比較例１と同一の条件でガラス状カーボンシー
トを得た。Comparative Example 2 A glassy carbon sheet was obtained under the same conditions as in Comparative Example 1 except that the holding pressure (60 gf / cm 2 ) in Comparative Example 1 was changed to 20 gf / cm 2 .
上記の実施例および比較例で製造した各ガラス状カーボ
ンシートの性状について測定し、その結果を対比して下
表に示した。なお、測定は各試料10個についておこなっ
た。The properties of the glassy carbon sheets produced in the above Examples and Comparative Examples were measured, and the results are compared and shown in the table below. The measurement was carried out for 10 samples each.
上表の結果から、比較例１、２では表面状態に皺、凹凸
等が認められたが、実施例ではいずれも良好な表面状態
と均質組織を有することが確認された。なお、実施例３
および４の条件では、若干の表面凹凸が観察された。 From the results in the above table, wrinkles, irregularities, etc. were observed in the surface state in Comparative Examples 1 and 2, but it was confirmed that all of the Examples had a good surface state and a homogeneous structure. In addition, Example 3
Under the conditions of 4 and 4, some surface irregularities were observed.
以上のとおり、本発明に従えば良精度の表面平滑性と均
質緻密組織を有する厚さ20μｍ〜２mmの薄膜ガラス状カ
ーボンシートを工業的に製造することができる。したが
って、電気二重層キャパシタの集電体、燃料電池用セパ
レーターをはじめ薄くて大面積の緻密質炭素材が要求さ
れる用途分野に広く利用することができる。As described above, according to the present invention, it is possible to industrially manufacture a thin film glassy carbon sheet having a thickness of 20 μm to 2 mm, which has a highly accurate surface smoothness and a homogeneous and dense structure. Accordingly, the present invention can be widely used in current collectors of electric double layer capacitors, separators for fuel cells, and other fields of application that require a thin and large-area dense carbon material.
Claims (2)
５μｍＲMAX以下の炭素質押え板で挟み付け、押え圧力
を掛けた状態で非酸化性雰囲気中800〜2100℃の温度で
焼成することを特徴とするガラス状カーボンシートの製
造方法。1. A surface roughness of an aromatic polyimide film of 6
A method for producing a glassy carbon sheet, which is characterized in that it is sandwiched between carbonaceous pressing plates having a size of 5 μm R MAX or less, and is fired at a temperature of 800 to 2100 ° C. in a non-oxidizing atmosphere while a pressing pressure is applied.
状態で焼成する請求項１記載のガラス状カーボンシート
の製造方法。 2. The method for producing a glassy carbon sheet according to claim 1, wherein the glassy carbon sheet is fired under a pressing pressure of at least 20 gf / cm 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1149984A JPH0645444B2 (en) | 1989-06-13 | 1989-06-13 | Method for manufacturing glassy carbon sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1149984A JPH0645444B2 (en) | 1989-06-13 | 1989-06-13 | Method for manufacturing glassy carbon sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0316907A JPH0316907A (en) | 1991-01-24 |
| JPH0645444B2 true JPH0645444B2 (en) | 1994-06-15 |
Family
ID=15486928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1149984A Expired - Lifetime JPH0645444B2 (en) | 1989-06-13 | 1989-06-13 | Method for manufacturing glassy carbon sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0645444B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4936608B2 (en) * | 2001-06-28 | 2012-05-23 | イビデン株式会社 | Glassy carbon-coated ion implanter components |
| TWI478868B (en) * | 2012-09-19 | 2015-04-01 | 鐘化股份有限公司 | Method for producing carbonaceous film, and method for producing graphite film |
| JP6368509B2 (en) * | 2014-03-18 | 2018-08-01 | 株式会社カネカ | Method for producing carbonaceous film and method for producing graphite film |
-
1989
- 1989-06-13 JP JP1149984A patent/JPH0645444B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0316907A (en) | 1991-01-24 |
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