JPH08259650A - Phenolic resin and carbonaceous material - Google Patents
Phenolic resin and carbonaceous materialInfo
- Publication number
- JPH08259650A JPH08259650A JP7062546A JP6254695A JPH08259650A JP H08259650 A JPH08259650 A JP H08259650A JP 7062546 A JP7062546 A JP 7062546A JP 6254695 A JP6254695 A JP 6254695A JP H08259650 A JPH08259650 A JP H08259650A
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- firing
- benzene rings
- polycyclic
- carbon material
- 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.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、炭素材料に適したフェ
ノール系樹脂及びこのフェノール系樹脂を原料とする炭
素材料に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic resin suitable for a carbon material and a carbon material using the phenolic resin as a raw material.
【０００２】[0002]
【従来の技術】炭素材料、なかでもガラス状炭素材料
は、耐熱性、耐薬品性、導電性等に優れると共に自己潤
滑性を有し、燃料電池セパレータや垂直磁気ヘッド等に
応用されている。そしてこのような炭素材料はフェノー
ル樹脂やフラン樹脂などの熱硬化性樹脂の成形物を焼成
炭化（以下焼成という）することによって作製されてい
るが、クラックが入らないように３〜６ヵ月という非常
に長時間をかけて焼成をおこなう必要があり、エネルギ
ー多消費となって高コストになることが避けられないと
いう問題があり、しかも厚みが厚くなるとクラックが避
けられないために３ｍｍ以上の厚みのものを得ることが
難しいという問題もあった。2. Description of the Related Art Carbon materials, especially glassy carbon materials, are excellent in heat resistance, chemical resistance, conductivity, etc. and have self-lubricating properties, and are applied to fuel cell separators, perpendicular magnetic heads and the like. And such a carbon material is produced by firing and carbonizing a molded product of a thermosetting resin such as a phenol resin or a furan resin (hereinafter referred to as firing). It is necessary to perform firing for a long time, and there is a problem that energy consumption and high cost are unavoidable, and cracks are unavoidable when the thickness becomes thicker. There was also the problem that it was difficult to get things.
【０００３】そこで焼成時間が従来より短く、厚みの大
きな炭素材料を得ることができる樹脂が要望されてお
り、この目的のために例えばナフタレンとベンゼンジメ
タノールで架橋させて得られるような芳香族系縮合多環
多核樹脂（炭素材料学会発行「炭素」Ｎｏ１２７（１９
６６年）第１６２頁〜第１７０頁に所載）が開発されて
いる。この芳香族系縮合多環多核樹脂は１週間程度の焼
成によって炭素材料を得ることができるが、１０００℃
までの加熱で残炭率が３０〜４０重量％と大きく低下し
（現在実用化されているフェノール樹脂やフラン樹脂の
場合、残炭率は５０〜６０重量％）、また炭化後はクラ
ックやボイドが多く発生し、さらに寸法収縮も２０〜２
５％程度発生し、実用化には多くの問題を抱えているも
のであった。Therefore, there is a demand for a resin which can obtain a carbon material having a shorter firing time and a larger thickness, and for this purpose, for example, an aromatic system obtained by crosslinking with naphthalene and benzenedimethanol. Condensed polycyclic polynuclear resin (Carbon Society of Japan "Carbon" No 127 (19
66), pp. 162-170) has been developed. A carbon material can be obtained from this aromatic condensed polycyclic polynuclear resin by firing for about one week.
The residual coal rate is greatly reduced to 30-40% by weight when heated up to 50% by weight (in the case of phenol resin and furan resin which are currently in practical use, the residual coal rate is 50-60% by weight), and cracks and voids after carbonization Occurs, and dimensional shrinkage is 20 to 2
About 5% occurred, and there were many problems in practical application.
【０００４】[0004]
【発明が解決しようとする課題】上記のように現状は、
焼成時間を短縮し、肉厚の厚い炭素材料を得ることの他
に、炭素材料の残炭率を向上させると共にクラックやボ
イドの発生を防止することが課題となっているものであ
り、従って本発明は、この課題を解決することを目的と
するものである。As described above, the present situation is as follows:
In addition to shortening the firing time and obtaining a thick carbon material, improving the residual carbon rate of the carbon material and preventing the occurrence of cracks and voids are important issues. The invention aims to solve this problem.
【０００５】[0005]
【課題を解決するための手段】本発明に係るフェノール
系樹脂は、ベンゼン環を２つ以上有する多環のフェニル
フェノール類を、アルデヒド基を有する５員環以上の環
状化合物のアルデヒド類で架橋して得ることができるも
のである。また本発明に係る炭素材料は、このフェノー
ル系樹脂の成形物を焼成することによって得ることがで
きるものである。The phenolic resin according to the present invention is obtained by crosslinking polycyclic phenylphenols having two or more benzene rings with aldehydes of a 5-membered or more cyclic compound having an aldehyde group. It is something that can be obtained. The carbon material according to the present invention can be obtained by firing the molded product of the phenolic resin.
【０００６】以下、本発明を詳細に説明する。本発明に
おいてフェノール類としては、ベンゼン環を２つ以上有
する多環のフェニルフェノール類を用いる。ベンゼン環
を２つ以上有するものであれば、ベンゼン環同士が一重
結合で直接結合されているものであって、ベンゼン環が
炭素原子や硫黄原子等の原子を介して結合されているも
のであっても、特に制限されることなく使用することが
できる。The present invention will be described in detail below. In the present invention, as the phenols, polycyclic phenylphenols having two or more benzene rings are used. If it has two or more benzene rings, it means that the benzene rings are directly bonded by a single bond, and the benzene rings are bonded through an atom such as a carbon atom or a sulfur atom. However, it can be used without particular limitation.
【０００７】このような多環のフェニルフェノール類と
しては、式１に示すｏ−，ｍ−，ｐ−のフェニルフェノ
ール（式１にはｐ−フェニルフェノールを示す）、式２
に示すｏ−，ｍ−，ｐ−のビフェノール（式２にはｐ−
ビフェノールを示す）、式３〜式４に示す３環のフェニ
ルフェノール類、さらに式５〜式１１に示すビスフェノ
ール、式１２のビスフェノールフルオレン、式１３のビ
スクレゾールフルオレン、式１４のビスエチルフェノー
ルフルオレン、式１５のビスキシレノールフルオレン、
式１６のビスフェノールフルオレン−４−カルボン酸な
どを例示することができる。これらの中でも、式１〜４
のベンゼン環同士が一重結合で結合されている多環フェ
ニルフェノール類が好ましい。Examples of such polycyclic phenylphenols include o-, m-, and p-phenylphenols represented by Formula 1 (formula 1 represents p-phenylphenol) and Formula 2
O-, m-, and p-biphenol shown in (in formula 2, p-
Biphenol), tricyclic phenylphenols represented by formulas 3 to 4, bisphenols represented by formulas 5 to 11, bisphenol fluorene represented by formula 12, biscresol fluorene represented by formula 13, bisethylphenol fluorene represented by formula 14, Bis-xylenol fluorene of formula 15,
The bisphenol fluorene-4-carboxylic acid of Formula 16 can be exemplified. Among these, formulas 1 to 4
The polycyclic phenylphenols in which the benzene rings are bonded by a single bond are preferred.
【０００８】[0008]
【化１】 Embedded image
【０００９】[0009]
【化２】 Embedded image
【００１０】[0010]
【化３】 Embedded image
【００１１】また本発明においてアルデヒド類として
は、５員環以上の環状化合物にアルデヒド基が官能基と
して付加しているアルデヒド化合物を用いるものであ
り、環状化合物としては５員環あるいは６員環のものが
好ましい。５員環のアルデヒド類としては、式１７のフ
ランアルデヒドや式１８のチオフェンアルデヒドなどを
例示することができる。In the present invention, as the aldehyde, an aldehyde compound in which an aldehyde group is added as a functional group to a cyclic compound having a 5-membered ring or more is used, and the cyclic compound has a 5-membered ring or a 6-membered ring. Those are preferable. Examples of 5-membered ring aldehydes include furanaldehyde of formula 17 and thiophene aldehyde of formula 18.
【００１２】[0012]
【化４】 [Chemical 4]
【００１３】６員環としてはベンゼン環であることが好
ましく、６員環のアルデヒド類としては、式１９のベン
ズアルデヒド、式２０のテレフタルアルデヒド、式２１
のビフェニルジアルデヒドなどを例示することができ
る。本発明ではアルデヒド類として、これらのベンゼン
環にアルデヒド基を有するアルデヒド類が特に好まし
い。The 6-membered ring is preferably a benzene ring, and the 6-membered aldehydes include benzaldehyde of the formula 19, terephthalaldehyde of the formula 20, and formula 21.
Biphenyldialdehyde and the like can be exemplified. In the present invention, as the aldehydes, aldehydes having an aldehyde group on these benzene rings are particularly preferable.
【００１４】[0014]
【化５】 Embedded image
【００１５】そして、上記のベンゼン環を２つ以上有す
る多環のフェニルフェノール類と、アルデヒド基を有す
る５員環以上の環状化合物のアルデヒド類とを酸触媒の
存在下、トルエン等の有機溶媒中で共沸脱水して反応さ
せることによって、フェノール類をアルデヒド類で反応
させ、本発明に係るフェノール系樹脂を得ることができ
る。フェノール類とアルデヒド類との反応割合は、フェ
ノール類１モルに対してアルデヒド類０．６５〜２．０
モルの範囲が好ましい。また酸触媒としては、パラトル
エンスルホン酸、フェノールスルホン酸、キシレンスル
ホン酸等のスルホン酸やその他の有機酸、あるいは硫酸
や硝酸のような無機酸を用いることができ、酸触媒の添
加量はフェノール類とアルデヒド類の合計量に対して
０．５〜５．０重量％の範囲が好ましい。Then, the polycyclic phenylphenols having two or more benzene rings and the aldehydes of a 5-membered or more cyclic compound having an aldehyde group are added to an organic solvent such as toluene in the presence of an acid catalyst. The phenolic resin according to the present invention can be obtained by reacting phenols with aldehydes by azeotropically dehydrating and reacting with. The reaction ratio of phenols and aldehydes is 0.65 to 2.0 for 1 mol of phenols.
A molar range is preferred. As the acid catalyst, sulfonic acids such as paratoluene sulfonic acid, phenol sulfonic acid, xylene sulfonic acid and other organic acids, or inorganic acids such as sulfuric acid and nitric acid can be used. The range of 0.5 to 5.0% by weight is preferable with respect to the total amount of compounds and aldehydes.
【００１６】このように本発明に係るフェノール系樹脂
を合成するにあたって、上記の範囲内でフェノール類に
対するアルデヒド類の反応量を変えることによって、フ
ェノール系樹脂に任意の流動性を持たせることができ
る。そして、このように調製したフェノール系樹脂を必
要に応じて１５０℃で１０分〜６０分程度加熱してＢス
テージ化した後、プレスして成形することによって、耐
熱性に優れた成形品を得ることができる。成形は１６０
〜２５０℃、５０〜８００ｋｇ／ｃｍ2 、１０〜３０分
の条件でおこなうことことができる。また本発明に係る
フェノール系樹脂を有機溶媒に溶かして炭素繊維に含浸
させることによって、耐熱性や強度に優れたＣＦＲＰ
（炭素繊維強化プラスチック）を成形することができ
る。Thus, in synthesizing the phenolic resin according to the present invention, the phenolic resin can be made to have an arbitrary fluidity by changing the reaction amount of the aldehydes with respect to the phenols within the above range. . Then, if necessary, the phenolic resin thus prepared is heated at 150 ° C. for about 10 to 60 minutes to be B-staged, and then pressed to obtain a molded article having excellent heat resistance. be able to. Molding is 160
It can be carried out under conditions of ˜250 ° C., 50 to 800 kg / cm 2 , and 10 to 30 minutes. Further, CFRP excellent in heat resistance and strength is obtained by dissolving the phenolic resin according to the present invention in an organic solvent and impregnating the carbon fiber.
(Carbon fiber reinforced plastic) can be molded.
【００１７】そしてこれらの成形品は、このまま使用す
ることも可能であるが、本発明では、このように成形し
た成形物を不活性ガス雰囲気下で焼成することによっ
て、ガラス状等の炭素材料を得ることができる。焼成は
フェノール系樹脂の成形物を５００℃〜２０００℃程度
にまで加熱することによっておこなうことができるが、
成形物の厚みが３ｍｍ以下であれば２４時間以下の焼成
で炭素材料を得ることができ、成形物の厚みが３〜４ｍ
ｍであれば４８時間以下の焼成で炭素材料を得ることが
でき、また成形物の厚みが４ｍｍを超える場合には、そ
の厚みが厚くなるに従って焼成時間も長くなるが、例え
ば厚み５ｍｍの場合には７２時間以下の焼成で炭素材料
を得ることができる。Although these molded products can be used as they are, in the present invention, a carbon material such as glass is obtained by firing the molded product thus molded in an inert gas atmosphere. Obtainable. Firing can be performed by heating the molded product of the phenolic resin to about 500 ° C. to 2000 ° C.,
If the thickness of the molded product is 3 mm or less, the carbon material can be obtained by firing for 24 hours or less, and the thickness of the molded product is 3 to 4 m.
If the thickness is m, the carbon material can be obtained by firing for 48 hours or less, and if the thickness of the molded product exceeds 4 mm, the firing time becomes longer as the thickness becomes thicker. The carbon material can be obtained by firing for 72 hours or less.
【００１８】このように、ベンゼン環を２つ以上有する
多環のフェニルフェノール類をアルデヒド基を有する５
員環以上の環状化合物のアルデヒド類で架橋して得たフ
ェノール系樹脂の成形物を焼成するにあたって、フェノ
ール系樹脂は三次元架橋距離が大きくなり、焼成時の炭
化過程における脱水や脱水素が容易になって、クラック
やボイドが発生することを低減できるものである。また
フェノール系樹脂は分子内にベンゼン環や環状化合物が
多く含まれることによって、焼成の際の残炭率を高く得
ることができるものであり、この結果、焼成時間の短縮
化、厚肉化及び緻密化が可能になるものである。As described above, polycyclic phenylphenols having two or more benzene rings have aldehyde groups.
When a molded product of a phenolic resin obtained by crosslinking with an aldehyde of a cyclic compound having a member ring or more is fired, the phenolic resin has a large three-dimensional cross-linking distance, which facilitates dehydration and dehydrogenation during the carbonization process during firing. Therefore, the occurrence of cracks and voids can be reduced. Further, the phenolic resin can obtain a high residual carbon ratio during firing by containing many benzene rings and cyclic compounds in the molecule, and as a result, shortening the firing time, increasing the thickness and It is possible to make it more compact.
【００１９】[0019]
【実施例】次に、本発明を実施例によって例証する。 （実施例１）ｐ−フェニルフェノール１７．０ｇ（０．
１モル）にテレフタルアルデヒド２０．１ｇ（０．１５
モル）及びパラトルエンスルホン酸１．１１ｇをフラス
コ中に入れ、トルエン溶媒中１１５℃で６時間、共沸脱
水反応させ、この後トルエンを留去してバット上に払い
出した。得られたフェノール系樹脂は軟化点が１１０℃
であった。このようにして得られたＢステージ化した樹
脂を粉砕し、２００℃、４００ｋｇｆ／ｃｍ2 、１５分
の条件でプレス成形することによって、成形物を得た。The invention will now be illustrated by the examples. (Example 1) 17.0 g of p-phenylphenol (0.
20.1 g (0.15) of terephthalaldehyde per 1 mol)
Mol) and 1.11 g of paratoluenesulfonic acid were placed in a flask and subjected to an azeotropic dehydration reaction in a toluene solvent at 115 ° C. for 6 hours, after which the toluene was distilled off and discharged onto a vat. The obtained phenolic resin has a softening point of 110 ° C.
Met. The B-staged resin thus obtained was crushed and press-molded under the conditions of 200 ° C., 400 kgf / cm 2 and 15 minutes to obtain a molded product.
【００２０】この成形物から２０ｍｍ×２０ｍｍ×厚み
３．０ｍｍの試料を作製し、これを窒素ガス雰囲気下に
おいて０．２℃／分の等速昇温速度で４８時間（２日）
かけて６００℃まで昇温させると共に６００℃の温度を
３時間保持させる条件で焼成して炭化させ、炭素材料を
得た。 （実施例２）実施例１と同様にしてフェノール系樹脂を
調製し、実施例１と同様に成形して２０ｍｍ×２０ｍｍ
×厚み３．０ｍｍの試料を作製し、これを窒素ガス雰囲
気下において０．０７５℃／分の等速昇温速度で１７７
時間（７．４日）かけて８００℃まで昇温させると共に
８００℃の温度を６時間保持させる条件で焼成して炭化
させ、炭素材料を得た。A sample having a size of 20 mm × 20 mm × thickness 3.0 mm was prepared from this molded product, and this was heated in a nitrogen gas atmosphere at a constant heating rate of 0.2 ° C./min for 48 hours (2 days).
Then, the temperature was raised to 600 ° C. and the temperature was kept at 600 ° C. for 3 hours for firing and carbonization to obtain a carbon material. (Example 2) A phenolic resin was prepared in the same manner as in Example 1 and was molded in the same manner as in Example 1 to obtain 20 mm x 20 mm.
× A sample having a thickness of 3.0 mm was prepared, and this was 177 at a constant rate of temperature increase of 0.075 ° C./min in a nitrogen gas atmosphere.
The temperature was raised to 800 ° C. over a period of time (7.4 days), and the temperature was kept at 800 ° C. for 6 hours for firing and carbonization to obtain a carbon material.
【００２１】（実施例３）実施例１と同様にしてフェノ
ール系樹脂を調製し、実施例１と同様に成形して２０ｍ
ｍ×２０ｍｍ×厚み４．０ｍｍの試料を作製し、これを
窒素ガス雰囲気下において０．７２℃／分の等速昇温速
度で２３時間かけて１０００℃まで昇温させると共に１
０００℃の温度を１時間保持させる条件で焼成して炭化
させ、炭素材料を得た。Example 3 A phenolic resin was prepared in the same manner as in Example 1 and molded in the same manner as in Example 1 to obtain 20 m.
A sample of m × 20 mm × thickness 4.0 mm was prepared and heated to 1000 ° C. in a nitrogen gas atmosphere at a constant heating rate of 0.72 ° C./min for 23 hours and 1
A carbon material was obtained by firing and carbonizing under the condition that the temperature of 000 ° C. was maintained for 1 hour.
【００２２】（実施例４）ビスフェノールＡ２２．８ｇ
（０．１モル）にテレフタルアルデヒド２０．１ｇ
（０．１５モル）及びパラトルエンスルホン酸１．１１
ｇをフラスコ中に入れ、トルエン溶媒中１１５℃で６時
間、共沸脱水反応させ、この後トルエンを留去してバッ
ト上に払い出した。得られたフェノール系樹脂は軟化点
が１０６℃であった。(Example 4) 22.8 g of bisphenol A
20.1 g of terephthalaldehyde in (0.1 mol)
(0.15 mol) and paratoluenesulfonic acid 1.11
g was put in a flask and subjected to an azeotropic dehydration reaction in a toluene solvent at 115 ° C. for 6 hours, after which toluene was distilled off and discharged onto a vat. The obtained phenolic resin had a softening point of 106 ° C.
【００２３】後はこのフェノール系樹脂を用いて実施例
１と同様に成形して２０ｍｍ×２０ｍｍ×厚み３．０ｍ
ｍの試料を作製し、これを窒素ガス雰囲気下において
０．２℃／分の等速昇温速度で４８時間（２日）かけて
６００℃まで昇温させると共に６００℃の温度を３時間
保持させる条件で焼成して炭化させ、炭素材料を得た。 （比較例１）軟化点１００℃のノボラック樹脂にヘキサ
メチレンテトラミン１２．５ｐｈｒを良く混合し、これ
を１２０℃で３０分間予備硬化した後に粉砕することに
よって、フェノール樹脂成形材料を調製した。このフェ
ノール樹脂成形材料を用い、１６０℃、１５０ｋｇｆ／
ｃｍ2 、１０分の条件でプレス成形して２０ｍｍ×２０
ｍｍ×厚み３．０ｍｍの試料を作製した。そしてこれを
窒素ガス雰囲気下において０．２℃／分の等速昇温速度
で４８時間（２日）かけて６００℃まで昇温させると共
に６００℃の温度を３時間保持させる条件で焼成して炭
化させ、炭素材料を得た。Thereafter, this phenol resin was used for molding in the same manner as in Example 1 to obtain 20 mm × 20 mm × thickness of 3.0 m.
m sample was prepared and heated to 600 ° C. in a nitrogen gas atmosphere at a constant heating rate of 0.2 ° C./min for 48 hours (2 days) and the temperature of 600 ° C. was maintained for 3 hours. A carbon material was obtained by firing and carbonizing under the conditions. Comparative Example 1 A phenol resin molding material was prepared by thoroughly mixing 12.5 phr of hexamethylenetetramine with a novolak resin having a softening point of 100 ° C., pre-curing the mixture at 120 ° C. for 30 minutes, and then pulverizing the mixture. Using this phenol resin molding material, 160 ℃, 150kgf /
by press molding under the conditions of cm 2, 10 minutes 20mm × 20
A sample of mm × thickness 3.0 mm was prepared. Then, this is fired under a nitrogen gas atmosphere at a constant rate of temperature increase of 0.2 ° C./min to 600 ° C. over 48 hours (2 days) and the temperature of 600 ° C. is maintained for 3 hours. Carbonized to obtain a carbon material.
【００２４】（比較例２）パラトルエンスルホン酸３重
量％の存在下、ナフタレン１．５モルを１，４−ベンゼ
ンジメタノール１．５モルで反応させて得られる芳香族
系縮合多環多核樹脂を用い、これを実施例１と同様に成
形して２０ｍｍ×２０ｍｍ×厚み３．０ｍｍの試料を作
製した。そしてこれを窒素ガス雰囲気下において０．０
７５℃／分の等速昇温速度で１７７時間（７．４日）か
けて８００℃まで昇温させると共に８００℃の温度を６
時間保持させる条件で焼成して炭化させ、炭素材料を得
た。(Comparative Example 2) Aromatic condensed polycyclic polynuclear resin obtained by reacting 1.5 mol of naphthalene with 1.5 mol of 1,4-benzenedimethanol in the presence of 3% by weight of paratoluenesulfonic acid. Was molded in the same manner as in Example 1 to prepare a sample of 20 mm × 20 mm × thickness 3.0 mm. Then, in a nitrogen gas atmosphere, this is 0.0
At a constant heating rate of 75 ° C / min, the temperature was raised to 800 ° C over 177 hours (7.4 days) and the temperature of 800 ° C was increased to 6
A carbon material was obtained by firing and carbonizing under the condition of holding for a time.
【００２５】（比較例３）比較例１で作製した試料を、
窒素ガス雰囲気下で１７７時間（７．４日）かけて８０
０℃まで昇温させると共に８００℃の温度を６時間保持
させる条件で焼成して炭化させ、炭素材料を得た。上記
のようにして得た実施例１乃至４及び比較例１乃至３の
炭素材料について、残炭率、最大減量速度、炭化前密
度、炭化後密度、収縮率、クラック・ボイドの発生の有
無、炭化後の厚みを測定した。尚、最大減量速度の測定
は、熱天秤で昇温速度１０℃／ｍｉｎ、窒素ガス２００
ｍｌ／ｍｉｎの雰囲気でおこなった。これらの結果を表
１に示す。Comparative Example 3 The sample prepared in Comparative Example 1 was
80 in 177 hours (7.4 days) under nitrogen gas atmosphere
A carbon material was obtained by firing under the condition that the temperature was raised to 0 ° C. and the temperature was kept at 800 ° C. for 6 hours to be carbonized. For the carbon materials of Examples 1 to 4 and Comparative Examples 1 to 3 obtained as described above, the residual carbon rate, the maximum weight reduction rate, the density before carbonization, the density after carbonization, the shrinkage ratio, the presence or absence of cracks and voids, The thickness after carbonization was measured. The maximum weight loss rate was measured with a thermobalance at a heating rate of 10 ° C./min and nitrogen gas of 200.
It was performed in an atmosphere of ml / min. Table 1 shows the results.
【００２６】尚、比較例１及び比較例２については、焼
成炭化の際に試料が割れて形状を保たなかったので、炭
化後密度、収縮率、炭化後の厚みは測定できなかった。In Comparative Example 1 and Comparative Example 2, since the sample was broken during firing and carbonization and did not maintain its shape, the density after carbonization, the shrinkage ratio, and the thickness after carbonization could not be measured.
【００２７】[0027]
【表１】 [Table 1]
【００２８】表１にみられるように、各実施例のもの
は、残炭率が高く、収縮が小さく、またクラックやボイ
ドの発生がないことが確認される。しかも各実施例のも
のは短時間の焼成で炭化材料を得ることができ、実施例
３のように厚みが３ｍｍ以上の炭素材料を得ることもで
きるものであった。As can be seen from Table 1, it is confirmed that each of the examples has a high residual carbon rate, a small shrinkage, and no cracks or voids. Moreover, in each of the examples, a carbonized material can be obtained by firing for a short time, and as in example 3, a carbon material having a thickness of 3 mm or more can be obtained.
【００２９】[0029]
【発明の効果】上記のように本発明は、ベンゼン環を２
つ以上有する多環のフェニルフェノール類をアルデヒド
基を有する５員環以上の環状化合物のアルデヒド類で架
橋して得たフェノール系樹脂の成形物を焼成して炭素材
料を得るようにしたので、フェノール系樹脂の分子構造
は三次元架橋距離が大きくなり、焼成時の炭化過程にお
ける脱水や脱水素が容易になって、クラックやボイドが
発生することを低減できるものであり、またフェノール
系樹脂の分子構造にベンゼン環や環状化合物が多く含ま
れることによって、焼成の際の残炭率を高く得ることが
できると共に、焼成時間の短縮化及び厚肉化が可能にな
るものである。As described above, the present invention has two benzene rings.
Since a molded product of a phenolic resin obtained by cross-linking one or more polycyclic phenylphenols with an aldehyde of a 5-membered or more cyclic compound having an aldehyde group is used to obtain a carbon material by firing, The molecular structure of the resin is that the three-dimensional cross-linking distance is large, dehydration and dehydrogenation in the carbonization process during firing are easy, and the occurrence of cracks and voids can be reduced. By including a large amount of benzene rings and cyclic compounds in the structure, it is possible to obtain a high residual carbon ratio during firing, and to shorten the firing time and increase the wall thickness.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浅尾 勝哉 兵庫県西宮市津門呉羽町10−５ (72)発明者 薦田 俊策 大阪府大阪狭山市大野台３−22−２ (72)発明者 四谷 任 大阪府堺市赤坂台５−９−６ (72)発明者 樋口 尚登 大阪府堺市山本町５−101−８ ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Katsuya Asao 10-5 Tsumon Kureha-cho, Nishinomiya-shi, Hyogo Prefecture (72) Inventor Shunsaku Koda Osaka 3-22-2 Onodai, Sayama-shi, Osaka (72) Inventor Yotsuya Osaka 5-9-6 Akasakadai, Sakai-shi (72) Inventor Naoto Higuchi 5-101-8 Yamamotocho, Sakai City, Osaka Prefecture
Claims (2)
ニルフェノール類が、アルデヒド基を有する５員環以上
の環状化合物のアルデヒド類で架橋されて成ることを特
徴とするフェノール系樹脂。1. A phenolic resin comprising a polycyclic phenylphenol having two or more benzene rings crosslinked with an aldehyde of a 5-membered or more cyclic compound having an aldehyde group.
焼成炭化されて成ることを特徴とする炭素材料。2. A carbon material obtained by calcining and carbonizing the molded product of the phenolic resin according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06254695A JP3575709B2 (en) | 1995-03-22 | 1995-03-22 | Carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06254695A JP3575709B2 (en) | 1995-03-22 | 1995-03-22 | Carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08259650A true JPH08259650A (en) | 1996-10-08 |
| JP3575709B2 JP3575709B2 (en) | 2004-10-13 |
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ID=13203353
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06254695A Expired - Fee Related JP3575709B2 (en) | 1995-03-22 | 1995-03-22 | Carbon material |
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| Country | Link |
|---|---|
| JP (1) | JP3575709B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246594A (en) * | 2006-03-14 | 2007-09-27 | Dainippon Ink & Chem Inc | Resin composition having naphthalene skeleton |
| JP2008047456A (en) * | 2006-08-18 | 2008-02-28 | Sumitomo Bakelite Co Ltd | Carbon material and its manufacturing method, negative electrode material for secondary battery, and nonaqueous electrolyte secondary battery |
| JP2013051213A (en) * | 2012-11-27 | 2013-03-14 | Sumitomo Bakelite Co Ltd | Carbon material and method for producing the same, negative electrode material for secondary battery, and nonaqueous electrolyte secondary battery |
-
1995
- 1995-03-22 JP JP06254695A patent/JP3575709B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246594A (en) * | 2006-03-14 | 2007-09-27 | Dainippon Ink & Chem Inc | Resin composition having naphthalene skeleton |
| JP2008047456A (en) * | 2006-08-18 | 2008-02-28 | Sumitomo Bakelite Co Ltd | Carbon material and its manufacturing method, negative electrode material for secondary battery, and nonaqueous electrolyte secondary battery |
| JP2013051213A (en) * | 2012-11-27 | 2013-03-14 | Sumitomo Bakelite Co Ltd | Carbon material and method for producing the same, negative electrode material for secondary battery, and nonaqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3575709B2 (en) | 2004-10-13 |
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