JPH04209712A - Production of molded article of glassy carbon - Google Patents
Production of molded article of glassy carbonInfo
- Publication number
- JPH04209712A JPH04209712A JP2338782A JP33878290A JPH04209712A JP H04209712 A JPH04209712 A JP H04209712A JP 2338782 A JP2338782 A JP 2338782A JP 33878290 A JP33878290 A JP 33878290A JP H04209712 A JPH04209712 A JP H04209712A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- molded article
- molded body
- glassy carbon
- polycarbodiimide
- 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
- 229910021397 glassy carbon Inorganic materials 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 238000000071 blow moulding Methods 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000007666 vacuum forming Methods 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 13
- 239000002243 precursor Substances 0.000 abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 125000002723 alicyclic group Chemical group 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 238000010304 firing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ガラス状炭素成形体の製造方法に関するもの
であり、更に詳しくは、短い成形時間のうちに、歩留り
よく、良好な成形体を製造することのできるガラス状成
形体の製造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 method for producing a glassy carbon molded body, and more specifically, a method for producing a good molded body with a high yield and in a short molding time. The present invention relates to a method for manufacturing a glass-like molded body that can be manufactured.
（従来の技術）
ガラス状炭素成形体は、気孔率や気体透過性が小さく、
しかも、硬度、曲げ強度や耐熱性が大きいという性質を
有しているので、様々な分野での利用が期待されている
素材である。(Conventional technology) Glassy carbon molded bodies have low porosity and gas permeability.
Moreover, it has properties such as high hardness, bending strength, and heat resistance, so it is a material that is expected to be used in various fields.
このように広い応用範囲が期待されているガラス状炭素
成形体については、従来より、ガラス状炭素成形体を製
造するために焼成工程に供する成形体、即ち、樹脂成形
体プレカーサーを得る方法が数多く研究されている。こ
れは、ガラス状炭素成形体の容易にしかも安価に得るた
めには、成形体プレカーサーをいかに容易且つ安価に製
造することができるかにかかっているからである。Regarding glassy carbon molded bodies, which are expected to have a wide range of applications, there have been many methods to obtain molded bodies, that is, resin molded body precursors, which are subjected to the firing process to produce glassy carbon molded bodies. being researched. This is because in order to easily and inexpensively obtain a glassy carbon molded body, it depends on how easily and inexpensively a molded body precursor can be manufactured.
この樹脂成形体プレカーサーを得る方法としては、例え
ば、フェノール樹脂やフラン樹脂を、所定の硬化剤など
の併用の下、任意形状の型に付着させて固化させたり、
或いは、前記樹脂を任意形状の型中に注入して硬化させ
る方法等が提案されている。Methods for obtaining this resin molded precursor include, for example, attaching phenol resin or furan resin to a mold of an arbitrary shape and solidifying it in combination with a predetermined hardening agent, etc.
Alternatively, a method has been proposed in which the resin is injected into a mold of an arbitrary shape and cured.
（発明が解決しようとする問題点）
しかし、上記従来方法のうち、樹脂を型に付着固化させ
る方法は、複雑であり、工業化に適さない、又、樹脂を
型中に注入して硬化させる方法には、所望の形状のプレ
カーサーを得るのが非常に難しいという問題がある。(Problems to be Solved by the Invention) However, among the above conventional methods, the method of adhering and solidifying the resin to the mold is complicated and unsuitable for industrialization, and the method of injecting the resin into the mold and hardening it. However, there is a problem in that it is very difficult to obtain a precursor with a desired shape.
一方、熱可塑性樹脂について一般に広く用いられている
成形方法に、ブロー成型法及び真空成形法があるので、
これらの成型方法を利用することも理論上は考えられる
。On the other hand, the commonly used molding methods for thermoplastic resins include blow molding and vacuum molding.
It is theoretically possible to use these molding methods.
しかし、フェノール樹脂や、フラン樹脂等の熱硬化性樹
脂は、フィルムになりに＜＜、又、フィルム化できても
非常に割れやすいため、ブロー成形や真空成形の適用が
難しく、たとえ適用が可能になったとしても、工業化す
ることは困難である。However, thermosetting resins such as phenolic resins and furan resins cannot be made into films, and even if they can be made into films, they are extremely fragile, making it difficult to apply blow molding or vacuum forming. Even if it were, it would be difficult to industrialize it.
（問題を解決するための手段）
本発明は、上述した従来技術の難点を解決することを目
的としてなされたもので、その主たる構成は、ポリカル
ボジイミド樹脂フィルムを、ブロー成形及び／又は真空
成形することにより樹脂成形体を作成した後、不活性雰
囲気中で焼成することを特徴とするものである。(Means for Solving the Problems) The present invention has been made for the purpose of solving the above-mentioned difficulties of the prior art, and its main structure is to blow mold and/or vacuum mold a polycarbodiimide resin film. This method is characterized in that after a resin molded body is created, it is fired in an inert atmosphere.
即ち、本発明の発明者らは、フィルム化が容易で、柔軟
性を持つため、ブロー成形及び／又は真空成形により、
容易に樹脂成形体プレカーサーとすることができ、しか
も熱処理を行なうことにより硬化する樹脂について検討
をおこなった結果、ポリカルポジミド樹脂に注目し、本
発明を完成するに致っな。That is, the inventors of the present invention believe that the film can be easily formed into a film and has flexibility, so by blow molding and/or vacuum forming,
As a result of studying resins that can be easily made into resin molded body precursors and that harden by heat treatment, we focused on polycarposimide resin and completed the present invention.
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
本発明において使用される上記ポリカルボジイミド樹脂
は、焼成炭化後の炭素含有量が高く、且つ、収率も高い
樹脂であり、それ自体は周知のものか、或いは、周知の
ものと同様にして製造することができるものであって（
米国特許第２，９４１．９５６号明細書；特公昭４７−
３３２７９号公報； Ｊ、Ｏｒｇ、Ｃｈｅｍ、、２８．
２０６９〜２０７５（１９６３）Ｃｈｅｍｉｃａｌ
Ｒｅｖｉｅｗ １９８１．ｖｏｌ、８１．Ｎｏ、４，
６１９〜６２１等参照）、例えば有機ジイソシアネート
の脱二酸化炭素を伴う縮合反応により容易に製造するこ
とができる。ポリカルボジイミド樹脂の製造に使用され
る有機ジイソシアネートは、脂肪族系、指環式系、芳香
族系、芳香−脂肪族系等のいずれのタイプのものであっ
てもよく、これらは単独で用いても、或いは、２種以上
を組み合わせて共重合体として用いてもよい。The polycarbodiimide resin used in the present invention has a high carbon content and high yield after firing and carbonization, and is either a well-known resin or can be produced in the same manner as a well-known resin. It is something that can be done (
U.S. Patent No. 2,941.956; Japanese Patent Publication No. 1973-
Publication No. 33279; J, Org, Chem, 28.
2069-2075 (1963) Chemical
Review 1981. vol, 81. No, 4,
619-621, etc.), for example, can be easily produced by a condensation reaction of an organic diisocyanate accompanied by removal of carbon dioxide. The organic diisocyanate used in the production of polycarbodiimide resins may be of any type, such as aliphatic, cyclic, aromatic, or aromatic-aliphatic, and these may be used alone. Alternatively, two or more types may be used in combination as a copolymer.
而して、本発明において使用されるポリカルボジイミド
樹脂には、下記式
％式％
（但し、式中のＲは有機ジイソシアネート残基を表す）
で示される少なくとも１種の繰り返し単位からなる単独
重合体または共重合体が包含される。Therefore, the polycarbodiimide resin used in the present invention has the following formula % formula % (However, R in the formula represents an organic diisocyanate residue)
Homopolymers or copolymers consisting of at least one type of repeating unit represented by are included.
上記式における有機ジイソシアネート残基Ｒとしては、
なかでも芳香族ジイソシアネート残基が好適である（こ
こで、有機ジイソシアネート残基とは、有機ジイソシア
ネート分子から２つのインシアネート基（ＮＧＯ）を除
いた残りの部分である）、このようなポリカルボジイミ
ド樹脂の具体例としては、以下のものを挙げることがで
きる。As the organic diisocyanate residue R in the above formula,
Among these, aromatic diisocyanate residues are preferred (here, the organic diisocyanate residue is the remaining portion after removing two incyanate groups (NGO) from the organic diisocyanate molecule), such polycarbodiimide resins. Specific examples include the following.
上記各式中において、ｎは１０〜１０．０００の範囲内
、好ましくは５０〜５，０００の範囲内である。In each of the above formulas, n is within the range of 10 to 10,000, preferably within the range of 50 to 5,000.
ここで、ポリカルボジイミド樹脂の末端はモノイソシア
ネート等を用いて封止されていてもよい。Here, the ends of the polycarbodiimide resin may be sealed using monoisocyanate or the like.
上記ポリカルボジイミド樹脂は、溶液のまま或いは溶液
から沈殿させた粉末として得ることができる。The polycarbodiimide resin can be obtained as a solution or as a powder precipitated from a solution.
このようにして得られたポリカルボジイミド樹脂を、シ
ート或いはフィルムにする。この工程は、通常のポリマ
ーをシート或いはフィルム化する場合と同様である。The polycarbodiimide resin thus obtained is made into a sheet or film. This process is the same as in the case of forming a sheet or film from ordinary polymers.
次に、樹脂成形体プレカーサーを作成する。この工程は
、通常の熱可塑性樹脂の成形に用いられるプロー成形又
は真空成形により行なう、尚、ブロー成形及び真空成形
の両方を組み合わせてもよい。Next, a resin molded body precursor is created. This step is carried out by blow molding or vacuum molding, which are commonly used for molding thermoplastic resins, and both blow molding and vacuum molding may be combined.
このようにして得られた成形体を、例えば３５０乃至３
５００℃で焼成することにより、最終的に目的とするガ
ラス状炭素成形が得られるのである。The molded body thus obtained is, for example, 350 to 3
By firing at 500°C, the desired glass-like carbon molding can be finally obtained.
（実施例） 以下、実施例により本発明を更に詳細に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
２．４−トリレンジイソシアネート／２，６−トリレン
ジイソシアネートあ混合物（８０： ２０）［ＴＤＩ］
５４ｇを、テトラクロロエチレン５００ｍ１中で、カル
ボジイミド化触媒（１−フェニル−３−メチルホスフオ
レンオキサイド）０゜１２ｇと共に、１２０℃で４時間
反応させ、ポリカルボジイミド溶液を得た。Example 1 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture (80:20) [TDI]
54 g was reacted with 0.12 g of a carbodiimidation catalyst (1-phenyl-3-methylphosphorene oxide) in 500 ml of tetrachloroethylene at 120° C. for 4 hours to obtain a polycarbodiimide solution.
このポリカルボジイミド樹脂溶液を用いて、乾式法によ
り厚さ２ｍｍ （ａ） 、８００μｍ （ｂ）、１００
μｍ（ｃ）及び５０μｍ（ｄ）のポリカルボジイミドフ
ィルムを得た。Using this polycarbodiimide resin solution, the thickness of 2 mm (a), 800 μm (b), 100 μm was obtained by dry method.
Polycarbodiimide films of μm (c) and 50 μm (d) were obtained.
次に、上記工程で得られたフィルムを用い、プロー成形
機により、半球形（半径３０ｍｍ）の樹脂成形プレカー
サーを作成した（熱風温度＝１８０℃）。Next, using the film obtained in the above step, a hemispherical (radius 30 mm) resin molded precursor was created using a blow molding machine (hot air temperature = 180° C.).
その後、真空中、室温から１５００℃まで、昇温湿度５
℃／分で焼成を行ない、ガラス状炭素成形体を得た０次
の表に、成形時間、歩留り及び状実施例２
実施例１で作成したポリカルボジイミドフィルム（ａ）
〜（ｄ）を用い、真空成形を行なった。After that, the temperature and humidity were increased from room temperature to 1500℃ in a vacuum at 5%.
The following table shows the molding time, yield, and condition of the glass-like carbon molded product obtained by firing at a temperature of 0°C/min.
Vacuum forming was performed using ~(d).
真空成形の形は、実施例１と同様に半径３０ｍｍの半球
形のものとしな、得られた樹脂成形体プレカーサーを、
実施例１と同様の条件で焼成し、ガラス状炭素成形体を
得た０次の表に、成形時間、歩留り及び状態等を示す（
尚、歩留りは１００個比較例
住友ベークライト製フェノールフェス（スミライトレジ
ン）を用いて、１ｍｍ（Ａ）、１００μｍ（Ｂ）のフェ
ノールフィルムを作成した。このフィルムについて、実
施例１と同様にブロー成形を行った。その結果、全ての
ものにクラックが入り、割れてしまったため、ガラス状
炭素成形体は得られなかった。The shape of the vacuum forming was a hemispherical one with a radius of 30 mm as in Example 1, and the obtained resin molded precursor was
The glassy carbon molded product was obtained by firing under the same conditions as in Example 1. The following table shows the molding time, yield, condition, etc.
Incidentally, the yield was 100 pieces Comparative Example Phenol films of 1 mm (A) and 100 μm (B) were created using a phenol face (Sumilite resin) manufactured by Sumitomo Bakelite. This film was blow molded in the same manner as in Example 1. As a result, all of the products were cracked and broken, so a glassy carbon molded product could not be obtained.
（発明の効果）
このように本発明によれば歩留りも良く、成形時間も短
く良好なガラス状炭素を製造することができる。(Effects of the Invention) As described above, according to the present invention, good glassy carbon can be produced with good yield and short molding time.
Claims (1)
び／又は真空成形することにより樹脂成形体を作成した
後、該樹脂成形体を不活性雰囲気中で焼成することを特
徴とするガラス状炭素成形体の製造方法。 ２ ポリカルボジイミド樹脂は、式 −Ｒ−Ｎ＝Ｃ＝Ｎ− （ただし、式中のＲは有機ジイリソシアネート残基を表
す） で示される少なくとも１種の繰り返し単位からなる単独
重合体又は共重合体であることを特徴とする請求項１に
記載のガラス状炭素成形体の製造方法。 ３ 樹脂成形体の焼成は、３５０乃至３５００℃で行な
うことを特徴とする請求項１に記載のガラス状炭素成形
体の製造方法。[Scope of Claims] 1. A glass-like product characterized in that a resin molded body is created by blow molding and/or vacuum forming a polycarbodiimide resin film, and then the resin molded body is fired in an inert atmosphere. A method for producing a carbon molded body. 2 Polycarbodiimide resin is a homopolymer or copolymer consisting of at least one type of repeating unit represented by the formula -R-N=C=N- (wherein R represents an organic diirisocyanate residue). The method for producing a glass-like carbon molded body according to claim 1, characterized in that the glass-like carbon molded body is produced by coalescence. 3. The method for producing a glassy carbon molded body according to claim 1, wherein the resin molded body is fired at a temperature of 350 to 3500°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2338782A JPH04209712A (en) | 1990-11-30 | 1990-11-30 | Production of molded article of glassy carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2338782A JPH04209712A (en) | 1990-11-30 | 1990-11-30 | Production of molded article of glassy carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04209712A true JPH04209712A (en) | 1992-07-31 |
Family
ID=18321417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2338782A Pending JPH04209712A (en) | 1990-11-30 | 1990-11-30 | Production of molded article of glassy carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04209712A (en) |
-
1990
- 1990-11-30 JP JP2338782A patent/JPH04209712A/en active Pending
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