JP3301773B2 - Carbon fiber reinforced phenolic resin composite for railway vehicles - Google Patents
Carbon fiber reinforced phenolic resin composite for railway vehiclesInfo
- Publication number
- JP3301773B2 JP3301773B2 JP03411492A JP3411492A JP3301773B2 JP 3301773 B2 JP3301773 B2 JP 3301773B2 JP 03411492 A JP03411492 A JP 03411492A JP 3411492 A JP3411492 A JP 3411492A JP 3301773 B2 JP3301773 B2 JP 3301773B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyvinyl butyral
- parts
- production example
- 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.)
- Expired - Fee Related
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- Reinforced Plastic Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は運輸省法の燃焼試験で
「不燃性」であり、且つ機械強度及びその弾性率がほぼ
エポキシ樹脂並の高い値を持つカーボン繊維強化ポリビ
ニルブチラール変性フェノール樹脂からなる鉄道車両用
複合成形物に関するものである。The present invention relates to a carbon fiber reinforced polyvinyl butyral-modified phenol resin which is "nonflammable" in a combustion test according to the Ministry of Transportation and has a mechanical strength and an elastic modulus as high as an epoxy resin. The present invention relates to a composite molded article for railway vehicles.
【０００２】[0002]
【従来の技術】従来、カーボン繊維系複合材料はエポキ
シ樹脂をマトリックスにしたものが一般的に広く使用さ
れている。軽量で強度・剛性に優れている為、航空分
野、人工衛星分野、スポーツ分野及び最近では車両、建
築などの分野における構造材料に使用されるようになっ
て来た。2. Description of the Related Art Heretofore, carbon fiber composite materials using an epoxy resin as a matrix have been widely used. Due to its light weight and excellent strength and rigidity, it has been used as a structural material in the fields of aeronautics, satellites, sports, and recently vehicles, construction, and the like.
【０００３】近年になり、火災発生時の安全性の確保か
ら難燃性及び燃焼時の低発煙性、低発熱性、低有毒ガス
性といった特長を有するフェノール樹脂の適用気運が増
大してきており、エポキシ樹脂の代替となりうるフェノ
ール樹脂の開発が強く望まれているがフェノール樹脂を
使用すると引張り、曲げ等の強度がかなり低下する欠点
があった。In recent years, the application of phenolic resins, which have the characteristics of flame retardancy, low smoke emission, low heat generation, and low toxic gas, has been increasing in order to ensure safety in the event of fire. The development of a phenol resin which can be used as an alternative to an epoxy resin is strongly desired, but the use of a phenol resin has a drawback that the strength such as tension and bending is considerably reduced.
【０００４】[0004]
【発明が解決しようとする課題】本発明はフェノール樹
脂をポリビニルブチラール樹脂で変性した後カーボン繊
維に含浸・乾燥した後、圧縮成形やオートクレーブ成形
等の方法で加熱・加圧して得られた複合成形物が運輸省
法の「不燃性」で、かつエポキシ樹脂と同等の強度を有
する複合成形物を提供するにある。SUMMARY OF THE INVENTION The present invention relates to a composite molding obtained by modifying a phenolic resin with a polyvinyl butyral resin, impregnating and drying carbon fibers, and then heating and applying pressure by a method such as compression molding or autoclave molding. An object of the present invention is to provide a composite molded article which is "nonflammable" according to the Ministry of Transportation Law and has the same strength as epoxy resin.
【０００５】[0005]
【課題を解決するための手段】本発明は、触媒として２
価金属水酸化物とアンモニアを併用して合成された含窒
素結合を持つ特定のレゾール型フェノール樹脂の固形分
に対しポリビニルブチラール樹脂の変性率が５〜１５重
量％であるポリビニルブチラール変性フェノール樹脂と
カーボン繊維とからなる複合材料を、圧縮成形、オート
クレーブ成形、引抜成形等の成形方法にて加熱・加圧す
ることを特徴とする複合成形物に関するものである。SUMMARY OF THE INVENTION The present invention provides a catalyst comprising 2
A polyvinyl butyral-modified phenol resin having a polyvinyl butyral resin modification rate of 5 to 15% by weight with respect to a solid content of a specific resol-type phenol resin having a nitrogen-containing bond synthesized by using a combination of a valent metal hydroxide and ammonia; The present invention relates to a composite molded product characterized in that a composite material composed of carbon fibers is heated and pressed by a molding method such as compression molding, autoclave molding, or pultrusion molding.
【０００６】本発明を構成するフェノール樹脂とは、フ
ェノール類としてフェノール及び／又はクレゾールを使
用し、アルデヒド類としてはホルムアルデヒド、パラホ
ルムアルデヒド、アセトアルデヒドのいずれかを使用
し、フェノール類に対するアルデヒド類のモル比１．３
〜１．５で反応させて得られるものである。このモル比
が１．３より小さいと樹脂が柔らかく熱時の剛性が劣る
ようになり、１．５より大きいと成形時ガスの発生が多
く、欠陥を生じやすく好ましくない。The phenolic resin constituting the present invention uses phenol and / or cresol as the phenol, and uses any of formaldehyde, paraformaldehyde and acetaldehyde as the aldehyde, and a molar ratio of the aldehyde to the phenol. 1.3
To 1.5. If the molar ratio is less than 1.3, the resin is soft and the rigidity at the time of heating is inferior. If the molar ratio is more than 1.5, a large amount of gas is generated at the time of molding, and defects are liable to occur.
【０００７】反応触媒として２価金属水酸化物とアンモ
ニアを併用することが必要である。触媒に、 ２価金属水
酸化物を使用することにより、樹脂硬化物の耐熱性が向
上し、樹脂中に窒素原子を有することにより、複合成形
物を構成するカーボン繊維に対する密着性に優れ、強度
を向上させることができる。It is necessary to use a divalent metal hydroxide and ammonia in combination as a reaction catalyst. By using a divalent metal hydroxide as the catalyst, the heat resistance of the cured resin is improved, and by having a nitrogen atom in the resin, the adhesion to the carbon fibers constituting the composite molded article is excellent, and the strength is high. Can be improved.
【０００８】２価金属水酸化物としては、水酸化カルシ
ウム、水酸化バリウム等を使用すことができるが、耐熱
性及び耐燃性向上のためには、フェノール樹脂の合成
時、フェノール類１００重量部に対して、２価金属水酸
化物を０．５〜１．０重量部使用することが望ましい。
０．５重量部より少ないと前記効果が小さく、１．０重
量部より多くてもこれ以上効果の向上は小さく、フェノ
ール樹脂への反応が速すぎコントロールが困難となる傾
向がある。As the divalent metal hydroxide, calcium hydroxide, barium hydroxide and the like can be used. However, in order to improve heat resistance and flame resistance, 100 parts by weight of phenol is used when synthesizing a phenol resin. On the other hand, it is desirable to use 0.5 to 1.0 parts by weight of the divalent metal hydroxide.
When the amount is less than 0.5 part by weight, the effect is small, and when the amount is more than 1.0 part by weight, the effect is not further improved, and the reaction with the phenol resin tends to be too fast to control.
【０００９】窒素原子（主にアンモニアに由来する）の
含有量はフェノール樹脂中に０．４〜０．９重量％とす
ることが、密着性や強度の点で望ましい。０．４重量％
より少ないと密着性が低下し、０．９重量％より多いと
耐熱性が低下する傾向がある。The content of nitrogen atoms (derived mainly from ammonia) in the phenol resin is preferably 0.4 to 0.9% by weight in view of adhesion and strength. 0.4% by weight
If the amount is less than the above, the adhesiveness tends to decrease, and if it is more than 0.9% by weight, the heat resistance tends to decrease.
【００１０】複合成形物の「不燃性」は、触媒種に２価
金属水酸化物を使用することにより向上し、又成形時に
未反応物を出来るだけ無くし、反応により発生する副産
物（縮合水など）をできるだけ外部へ除去することによ
り更に向上する。[0010] The "nonflammability" of the composite molded article is improved by using a divalent metal hydroxide as a catalyst species. In addition, unreacted substances are eliminated as much as possible during molding, and by-products generated by the reaction (such as condensed water) Is further improved by removing as much as possible to the outside.
【００１１】複合成形物の強度は、含窒素結合の導入の
ための触媒種を選択しポリビニルブチラール樹脂を適当
量使用することにより向上させることができる。ポリビ
ニルブチラール樹脂の変性率としては、 フェノール樹脂
の固形分の５〜１５重量％、好ましくは８〜１３重量％
である。即ち、ポリビニルブチラール樹脂が１５重量％
より多いと可塑剤として作用したり、「不燃性」を低下
させたりする。一方、５重量％より少ないと強度向上の
効果が小さいのでフェノール樹脂に対するポリビニルブ
チラール樹脂の変性量のバランスをとることが重要であ
り、前記の範囲が採用される。The strength of the composite molded article can be improved by selecting a catalyst type for introducing a nitrogen-containing bond and using an appropriate amount of a polyvinyl butyral resin. As the modification rate of the polyvinyl butyral resin, 5 to 15% by weight of solid content of the phenol resin, preferably 8 to 13% by weight
It is. That is, the polyvinyl butyral resin is 15% by weight.
If it is larger, it acts as a plasticizer or reduces “nonflammability”. On the other hand, if the content is less than 5% by weight, the effect of improving the strength is small, so it is important to balance the amount of modification of the polyvinyl butyral resin with respect to the phenol resin, and the above range is adopted.
【００１２】更にポリビニルブチラール樹脂の分子量が
小さい（溶液粘度が低い）場合も可塑剤として作用して
しまうので、高分子量の樹脂を選択するのがよい。本発
明で使用するポリビニルブチラール樹脂は、樹脂１０ｇ
をトルエン／エタノール＝１／１（重量比）の混合溶剤
１５０mlで溶解した時２０℃での溶液粘度が１５０cst
以上であることが好ましい。Further, when the molecular weight of the polyvinyl butyral resin is small (solution viscosity is low), it also acts as a plasticizer, so it is preferable to select a high molecular weight resin. The polyvinyl butyral resin used in the present invention has a resin content of 10 g.
Was dissolved in 150 ml of a mixed solvent of toluene / ethanol = 1/1 (weight ratio) and the solution viscosity at 20 ° C. was 150 cst.
It is preferable that it is above.
【００１３】本発明に用いるカーボン繊維としては高強
度（引張強度３５００ＭＰa 以上)、高弾性率（２３０
ＧＰa 以上）のものであればＰＡＮ系、ピッチ系どちら
でもよいが、ＰＡＮ系が引っ張り強度が高いので望まし
い。また、繊維の形体としては平織り、朱子織り等の織
布、あるいは一方向性のものを得る場合には糸（ロービ
ング又はヤーン）を用いる。The carbon fiber used in the present invention has a high strength (tensile strength of 3500 MPa or more) and a high elastic modulus (230
(GPa or more) may be PAN-based or pitch-based, but PAN-based is preferable because of its high tensile strength. Further, as a form of the fiber, a woven fabric such as a plain weave or a satin weave, or a yarn (a roving or a yarn) is used when a unidirectional fabric is obtained.
【００１４】上記の樹脂と繊維から得られた複合材料を
用い加熱加圧成形を行う。成形方法としては圧縮成形、
オートクレーブ成形あるいは引抜成形が通常採用される
が、これには限定されない。Heat and pressure molding is performed using the composite material obtained from the above resin and fiber. As the molding method, compression molding,
Autoclave molding or pultrusion molding is usually employed, but is not limited thereto.
【００１５】圧縮成形の場合は成形時にガス抜きを行う
ことが好ましい。オートクレーブ成形では通常一般に行
われている方法により、ツールにレイアップし、減圧
下、適正条件で加熱・加圧すればよい。引抜成形法で
は、糸又は糸と織布を組合せた繊維に樹脂を含浸させた
後、成形品断面と同じ形状の型に引込んで加熱硬化さ
せ、引取機により型から引抜く一般的な方法でよい。In the case of compression molding, it is preferable to perform degassing during molding. In the autoclave molding, a lay-up on a tool is usually performed by a generally used method, and heating and pressurization may be performed under reduced pressure and under appropriate conditions. In the pultrusion molding method, a resin is impregnated with yarn or a fiber combining yarn and woven fabric, then drawn into a mold having the same shape as the cross section of the molded product, heat-cured, and pulled out from the mold by a take-off machine. Good.
【００１６】その他、カーボン繊維束を含浸させ、フィ
ラメントワインディング（ＦＷ）方式によりマンドレル
に巻き付けた後オーブン中に導入し加熱硬化させて、円
筒状の複合成形物も得ることが可能である。In addition, it is also possible to impregnate a carbon fiber bundle, wind it around a mandrel by a filament winding (FW) method, introduce it into an oven, and heat and cure it to obtain a cylindrical composite molded product.
【００１７】[0017]
【実施例】以下に、本発明を実施例により説明する。以
下における「部」及び「％」は、すべて「重量部」及び
「重量％」を示すものである。EXAMPLES The present invention will be described below with reference to examples. In the following, "parts" and "%" all indicate "parts by weight" and "% by weight".
【００１８】（１）フェノール樹脂の製造 製造例１ 撹拌機付き反応釜にフェノール１０００部、３７％ホル
マリン１２０８部（ホルムアルデヒド（Ｆ）／フェノー
ル（Ｐ）モル比１．４）を仕込み、 次いで２８％アンモ
ニア水２０部、水酸化バリウム８部を添加後徐々に昇温
し、還流させた状態で４５分間反応させた。反応終了
後、７５％乳酸１０部で中和し、水を加えて洗浄し、分
離した水を除去後、真空下で脱水を行い、７０mmHgで８
０℃に達した時点でエタノール５６０部を添加して、レ
ゾール型フェノール樹脂の溶液１６００部を得た。(1) Production of Phenol Resin Production Example 1 A reaction vessel equipped with a stirrer was charged with 1000 parts of phenol and 1208 parts of 37% formalin (formaldehyde (F) / phenol (P) molar ratio of 1.4), and then 28% After adding 20 parts of ammonia water and 8 parts of barium hydroxide, the temperature was gradually raised, and the mixture was reacted for 45 minutes under reflux. After completion of the reaction, the mixture was neutralized with 10 parts of 75% lactic acid, washed by adding water, and after removing separated water, dehydration was performed under vacuum.
When the temperature reached 0 ° C., 560 parts of ethanol was added to obtain 1600 parts of a resol-type phenol resin solution.
【００１９】この溶液に、あらかじめメチルエチルケト
ンで２０％に溶解しておいたポリビニルブチラール樹脂
溶液３７０部を投入し、 約２時間反応混合して目的とす
るポリビニルブチラール変性フェノール樹脂１９７０部
（変性率８％）を得た。この変性樹脂を１３５℃で１時
間乾燥させたところ残存固形分は５５％であり、窒素含
有量は固形分に対して０．５％であった。To this solution, 370 parts of a polyvinyl butyral resin solution previously dissolved to 20% with methyl ethyl ketone is added, and the mixture is reacted and mixed for about 2 hours, and 1970 parts of the objective polyvinyl butyral-modified phenol resin (denaturation rate: 8% ) Got. When this modified resin was dried at 135 ° C. for 1 hour, the residual solid content was 55%, and the nitrogen content was 0.5% based on the solid content.
【００２０】製造例２ 製造例１において、３７％ホルマリン１２９３部（Ｆ／
Ｐモル比１．５）、２８％アンモニア水２４部（変性樹
脂中の窒素含有量０．６％）とした以外は製造例１と同
様にしてポリビニルブチラール変性フェノール樹脂２０
００部（残存固形分５５％）を得た。Production Example 2 In Production Example 1, 1293 parts of 37% formalin (F /
Polyvinyl butyral-modified phenolic resin 20 in the same manner as in Production Example 1 except that the P molar ratio was 1.5) and 24 parts of 28% aqueous ammonia (nitrogen content in the modified resin was 0.6%).
00 parts (residual solid content 55%) were obtained.
【００２１】製造例３ 製造例１において、ポリビニルブチラール樹脂溶液５０
５部（変性率１２％）とした以外は製造例１と同様にし
てポリビニルブチラール変性フェノール樹脂２１００部
（残存固形分５３％）を得た。Production Example 3 In Production Example 1, the polyvinyl butyral resin solution 50 was used.
2100 parts of polyvinyl butyral-modified phenol resin (residual solid content: 53%) were obtained in the same manner as in Production Example 1 except that the amount was changed to 5 parts (modification ratio: 12%).
【００２２】製造例４ 製造例１において、３７％ホルマリン８６２部（Ｆ／Ｐ
モル比１．０）とした以外は製造例１と同様にしてポリ
ビニルブチラール変性フェノール樹脂１８３０部（残存
固形分５５％）を得た。Production Example 4 In Production Example 1, 862 parts of 37% formalin (F / P
1830 parts of polyvinyl butyral-modified phenol resin (residual solid content: 55%) was obtained in the same manner as in Production Example 1 except that the molar ratio was changed to 1.0.
【００２３】製造例５ 製造例１において、２８％アンモニア水８部(変性樹脂
中の窒素含有量０．２％）とした以外は製造例１と同様
にしてポリビニルブチラール変性フェノール樹脂１９５
０部（残存固形分５５％）を得た。Production Example 5 Polyvinyl butyral-modified phenolic resin 195 was prepared in the same manner as in Production Example 1 except that 8 parts of 28% aqueous ammonia was used (the nitrogen content in the modified resin was 0.2%).
0 parts (residual solid content 55%) were obtained.
【００２４】製造例６ 製造例１において、ポリビニルブチラール樹脂溶液１４
０部（変性率３％）とした以外は製造例１と同様にして
ポリビニルブチラール変性フェノール樹脂１７４０部
（残存固形分６０％）を得た。Production Example 6 In Production Example 1, the polyvinyl butyral resin solution 14
1740 parts (residual solid content: 60%) of a polyvinyl butyral-modified phenol resin was obtained in the same manner as in Production Example 1 except that the amount was changed to 0 part (modification ratio: 3%).
【００２５】製造例７ 製造例１において、ポリビニルブチラール樹脂溶液９２
５部（変性率２０％）とした以外は製造例１と同様にし
てポリビニルブチラール変性フェノール樹脂２５２５部
（残存固形分４８％）を得た。Production Example 7 In Production Example 1, the polyvinyl butyral resin solution 92 was used.
2525 parts of polyvinyl butyral-modified phenolic resin (residual solid content: 48%) was obtained in the same manner as in Production Example 1 except that the amount was changed to 5 parts (modification ratio: 20%).
【００２６】（２）複合成形物の製造 以下の実施例及び比較例において、複合成形物の繊維含
有率が７０％になるようプリプレグの樹脂分を３０〜３
５％に調整した。(2) Production of Composite Molded Product In the following Examples and Comparative Examples, the resin content of the prepreg was adjusted to 30 to 3 so that the fiber content of the composite molded product became 70%.
Adjusted to 5%.
【００２７】実施例１ 製造例１のポリビニルブチラール変性フェノール樹脂を
メチルエチルケトン（ＭＥＫ）で希釈後、目付量２００
g ／m2、かつ平織りのカーボン繊維織布に含浸し、乾燥
して樹脂分３２％のプリプレグを得た。このプリプレグ
を７枚重ね、１６０℃、９．８ＭＰa で加熱・加圧（途
中で２回ガス抜きを行う）して繊維含有率７０％の複合
成形物を得た。Example 1 The polyvinyl butyral-modified phenolic resin of Production Example 1 was diluted with methyl ethyl ketone (MEK) and the basis weight was 200.
A carbon fiber woven fabric of g / m 2 and plain weave was impregnated and dried to obtain a prepreg having a resin content of 32%. Seven prepregs were stacked and heated and pressed at 160 ° C. and 9.8 MPa (gas removal was performed twice) to obtain a composite molded product having a fiber content of 70%.
【００２８】実施例２ 実施例１で得たプリプレグをオートクレーブで成形用プ
レート（ステンレス板）上に７枚重ね、離型フィルム、
プリーダー、プレッシャープレート、ブリーダークロ
ス、バキュームバッグを使用してレイアップ後、１６０
℃、０．８ＭＰaで加熱・加圧（真空度７５５mmHg以
下）して繊維含有率７０％の複合成形物を得た。Example 2 Seven layers of the prepreg obtained in Example 1 were stacked on a molding plate (stainless steel plate) by an autoclave, and a release film was prepared.
After laying up using a breeder, pressure plate, bleeder cloth, and vacuum bag,
Heating and pressurizing (vacuum degree: 755 mmHg or less) at 0.8 ° C. and 0.8 ° C. yielded a composite molded article having a fiber content of 70%.
【００２９】実施例３ 製造例１で得たポリビニルブチラール変性フェノール樹
脂をＭＥＫで希釈後、目付量２００g ／m2のカーボン繊
維細幅織物（幅２００mm）に含浸し、幅２００mm、厚さ
約１．２mmの平板状金型（ダイ）に引込んで１６０℃で
加熱・加圧し、引取機によってダイから引抜き、繊維含
有率７０％の連続平板状複合成形物を得た。Example 3 The polyvinyl butyral-modified phenolic resin obtained in Production Example 1 was diluted with MEK, and impregnated into a carbon fiber narrow fabric (200 mm in width) having a basis weight of 200 g / m 2 , and a width of 200 mm and a thickness of about 1 mm. It was drawn into a 0.2 mm flat mold (die), heated and pressed at 160 ° C., and pulled out from the die by a take-off machine to obtain a continuous flat composite molded article having a fiber content of 70%.
【００３０】実施例４ 製造例２で得たポリビニルブチラール変性フェノール樹
脂を用い、実施例１と同様にして複合成形物を得た。Example 4 Using the polyvinyl butyral-modified phenol resin obtained in Production Example 2, a composite molded product was obtained in the same manner as in Example 1.
【００３１】実施例５ 製造例１で得たポリビニルブチラール変性フェノール樹
脂を用い、実施例２と同様にして複合成形物を得た。Example 5 A composite molded article was obtained in the same manner as in Example 2 except that the polyvinyl butyral-modified phenol resin obtained in Production Example 1 was used.
【００３２】比較例１ エポキシ樹脂シェル・ケミカル製エピコート２１０と硬
化剤ＢＦ3 - ＭＥＡとからなる混合物をＭＥＫで溶解
後、実施例１と同じカーボン織布（平織り、目付量２０
０g ／m2）に含浸し、乾燥して樹脂分約３５％のプリプ
レグを得た。このプリプレグを７枚重ね、１６０℃、
５．９ＭＰa で加熱して繊維含有率７０％の複成形物を
得た。COMPARATIVE EXAMPLE 1 A mixture of an epoxy resin made by Epoxy Shell Chemical Co., Ltd. and a curing agent BF 3 -MEA was dissolved in MEK, and the same carbon woven fabric as in Example 1 (plain weave, basis weight 20
0 g / m 2 ) and dried to obtain a prepreg having a resin content of about 35%. 7 layers of this prepreg, 160 ° C,
By heating at 5.9 MPa, a double molded product having a fiber content of 70% was obtained.
【００３３】比較例２ 製造例４で得たポリビニルブチラール変性フェノール樹
脂を用い、実施例１と同様にして複合成形物を得た。Comparative Example 2 Using the polyvinyl butyral-modified phenol resin obtained in Production Example 4, a composite molded product was obtained in the same manner as in Example 1.
【００３４】[0034]
【００３５】比較例３ 製造例６で得たポリビニルブチラール変性フェノール樹
脂を用い、実施例１と同様にして複合成形物を得た。Comparative Example 3 Using the polyvinyl butyral-modified phenol resin obtained in Production Example 6, a composite molded product was obtained in the same manner as in Example 1.
【００３６】比較例４ 製造例７で得たポリビニルブチラール変性フェノール樹
脂を用い、実施例２と同様にして複合成形物を得た。Comparative Example 4 Using the polyvinyl butyral-modified phenolic resin obtained in Production Example 7, a composite molded product was obtained in the same manner as in Example 2.
【００３７】前記の実施例及び比較例における変性樹脂
の特徴と得られた複合成形物の特性を表１及び表２に示
す。Tables 1 and 2 show the characteristics of the modified resin and the characteristics of the obtained composite molded article in the above Examples and Comparative Examples.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【表２】 [Table 2]
【００４０】[0040]
【発明の効果】本発明によれば、表１及び表２の実施
例、比較例の評価結果からも判るように特許請求の範囲
にあるポリビニルブチラール変性フェノール樹脂とカー
ボン繊維とからなる鉄道車両用複合成形物は、運輸省法
燃焼試験において、厚み１mmのものでも「不燃性」に合
格することが理解される。これはエポキシ樹脂を使用し
た従来の場合では得られなかったものである。本発明の
複合成形物は工業的製造上に問題なく、金属の代替物と
して鉄道車両の台車、車体の側構体、屋根構体、妻構
体、台枠等の構造部材として充分使用することが可能で
あり、難燃性、低発煙性、耐熱性を必要とする方面にも
適用が大いに期待できる。According to the present invention, as can be seen from the evaluation results of Examples and Comparative Examples in Tables 1 and 2, for a railway vehicle comprising a polyvinyl butyral-modified phenolic resin and carbon fiber according to the claims. It is understood that the composite molded product, even in a thickness of 1 mm, passes the "nonflammability" in the combustion test of the Ministry of Transport. This cannot be obtained in the conventional case using an epoxy resin. The composite molded product of the present invention has no problem in industrial production and can be sufficiently used as a structural member such as a bogie of a railway vehicle, a side structure of a vehicle body, a roof structure, a wive structure, an underframe, etc. as a substitute for metal. Yes, it can be expected to be applied to applications that require flame retardancy, low smoke emission, and heat resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 潔 東京都国分寺市光町二丁目８番地38 財 団法人鉄道総合技術研究所内 (72)発明者 舘 芳士郎 東京都千代田区内幸町１丁目２番２号 住友ベークライト株式会社内 (72)発明者 多々良 正明 東京都千代田区内幸町１丁目２番２号 住友ベークライト株式会社内 (72)発明者 有田 靖 東京都千代田区内幸町１丁目２番２号 住友デュレズ株式会社内 (56)参考文献 特開 平５−17602（ＪＰ，Ａ) 特開 平３−231956（ＪＰ，Ａ) 特開 平３−81340（ＪＰ，Ａ) 特開 昭59−20327（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 5/04 C08G 8/38 C08L 61/32 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kiyoshi Sato 2-8-8 Hikaricho, Kokubunji-shi, Tokyo Inside the Railway Technical Research Institute (72) Inventor Yoshiro Tachi 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo 2 Sumitomo Bakelite Co., Ltd. (72) Inventor Masaaki Tatara 1-2-2, Uchisaiwaicho, Chiyoda-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Yasushi Yasushi 1-2-2, Uchisaiwaicho, Chiyoda-ku, Tokyo Sumitomo Durez (56) References JP-A-5-17602 (JP, A) JP-A-3-231956 (JP, A) JP-A-3-81340 (JP, A) JP-A-59-20327 (JP, A) A) (58) Field surveyed (Int. Cl. 7 , DB name) C08J 5/04 C08G 8/38 C08L 61/32
Claims (1)
ル比が１．３〜１．５であり、触媒として２価金属水酸
化物とアンモニアを併用した含窒素結合を持つレゾール
型フェノール樹脂の固形分に対しポリビニルブチラール
樹脂の変性率が５〜１５重量％であるポリビニルブチラ
ール変性フェノール樹脂とカーボン繊維とからなること
を特徴とする鉄道車両用複合成形物。1. The solid content of a resol type phenol resin having a nitrogen-containing bond in which a molar ratio of an aldehyde to a phenol is 1.3 to 1.5 and a divalent metal hydroxide and ammonia are used in combination as a catalyst. A composite molded article for railway vehicles, comprising a polyvinyl butyral-modified phenolic resin having a modification ratio of polyvinyl butyral resin of 5 to 15% by weight and carbon fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03411492A JP3301773B2 (en) | 1992-01-23 | 1992-01-23 | Carbon fiber reinforced phenolic resin composite for railway vehicles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03411492A JP3301773B2 (en) | 1992-01-23 | 1992-01-23 | Carbon fiber reinforced phenolic resin composite for railway vehicles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05202201A JPH05202201A (en) | 1993-08-10 |
| JP3301773B2 true JP3301773B2 (en) | 2002-07-15 |
Family
ID=12405239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03411492A Expired - Fee Related JP3301773B2 (en) | 1992-01-23 | 1992-01-23 | Carbon fiber reinforced phenolic resin composite for railway vehicles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3301773B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6287677B1 (en) * | 1996-03-22 | 2001-09-11 | Toho Rayon Co., Ltd. | Carbon fiber prepeg for wood reinforcement, wooden sheet laminated therewith, wood reinforcing composite comprising carbon fibers and the wooden sheet, and carbon fiber reinforced wood |
| JP7178251B2 (en) * | 2018-12-17 | 2022-11-25 | 株式会社イノアックコーポレーション | CARBON FIBER REINFORCED MOLDED PRODUCT AND METHOD FOR MANUFACTURING THE SAME |
| CN110016202A (en) * | 2019-04-04 | 2019-07-16 | 北京卫星制造厂有限公司 | A kind of heat insulation material and its preparation method and application with ceramic coating |
-
1992
- 1992-01-23 JP JP03411492A patent/JP3301773B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05202201A (en) | 1993-08-10 |
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