JPH05202201A - Molded composite object of carbon-fiber-reinforced phenolic resin for railway vehicle - Google Patents
Molded composite object of carbon-fiber-reinforced phenolic resin for railway vehicleInfo
- Publication number
- JPH05202201A JPH05202201A JP4034114A JP3411492A JPH05202201A JP H05202201 A JPH05202201 A JP H05202201A JP 4034114 A JP4034114 A JP 4034114A JP 3411492 A JP3411492 A JP 3411492A JP H05202201 A JPH05202201 A JP H05202201A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl butyral
- resin
- railway vehicle
- phenolic resin
- composite molded
- 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
- Reinforced Plastic Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
(57)【要約】
【構成】 フェノール類に対するアルデヒド類のモル比
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プリプレグを
加熱・加圧してなることを特徴とする鉄道車両用複合成
形物。
【効果】 厚み１mmのものでも、運輸省法燃焼試験にお
いて「不燃性」に合格する。工業的製造上も問題なく、
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。(57) [Summary] [Structure] Resol-type phenol resin having a nitrogen-containing bond in which the molar ratio of aldehydes to phenols is 1.3 to 1.5 and a divalent metal hydroxide and ammonia are used together as a catalyst. A composite molded article for a railway vehicle, comprising heating and pressurizing a prepreg composed of a polyvinyl butyral-modified phenolic resin having a modification rate of polyvinyl butyral of 5 to 15% by weight with respect to the solid content and a carbon fiber. [Effect] Even with a thickness of 1 mm, it passes "non-combustibility" in the flammability test of the Ministry of Transport. There is no problem in industrial manufacturing,
As a substitute for metal, it can be sufficiently used as a structural member such as a bogie of a railway vehicle, a side structure of a car body, a roof structure, a gable structure, and an underframe, and requires flame retardancy, low smoke generation, and heat resistance. It can be expected to be applied to various fields.
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 phenolic resin which is "noncombustible" in a combustion test of the Ministry of Transport and has a mechanical strength and its 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-based composite materials having an epoxy resin as a matrix have generally been widely used. Due to its light weight and excellent strength and rigidity, it has come to be used as a structural material in the fields of aeronautics, artificial satellites, sports, and recently vehicles and construction.
【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, in order to ensure safety in the event of a fire, the application momentum of phenolic resins, which have the features of flame retardancy, low smoke generation at combustion, low heat generation, and low toxic gas properties, has been increasing. There is a strong demand for the development of a phenolic resin that can replace the epoxy resin, but the use of a phenolic resin has the 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。DISCLOSURE OF THE INVENTION The present invention is a composite molding obtained by modifying a phenol resin with a polyvinyl butyral resin, impregnating and drying carbon fiber, and then applying heat and pressure by a method such as compression molding or autoclave molding. The object is to provide a composite molded article that is "non-flammable" according to the Ministry of Transport and has strength equivalent to that of 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。The present invention provides a catalyst as a catalyst.
A polyvinyl butyral modified phenolic resin having a modification rate of 5 to 15% by weight based on the solid content of a specific resol type phenolic resin having a nitrogen-containing bond, which is synthesized by using a valent metal hydroxide and ammonia in combination; The present invention relates to a composite molded article which is 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 means phenol and / or cresol as the phenols, formaldehyde, paraformaldehyde or acetaldehyde as the aldehydes, and the molar ratio of the aldehydes to the phenols. 1.3
It is obtained by reacting at ~ 1.5. When this molar ratio is less than 1.3, the resin becomes soft and the rigidity during heating becomes poor, and when it is more than 1.5, gas is often generated during molding and defects are likely to occur, which is not preferable.
【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 together as a reaction catalyst. By using a divalent metal hydroxide for the catalyst, the heat resistance of the resin cured product is improved, and the nitrogen atom in the resin makes it excellent in adhesion to the carbon fibers that make up the composite molded product, and has good strength. 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。Calcium hydroxide, barium hydroxide and the like can be used as the divalent metal hydroxide, but in order to improve heat resistance and flame resistance, 100 parts by weight of phenols are used at the time of synthesizing the phenol resin. On the other hand, it is desirable to use 0.5 to 1.0 part by weight of the divalent metal hydroxide.
If the amount is less than 0.5 part by weight, the above effect is small, and if the amount is more than 1.0 part by weight, the improvement of the effect is small, and the reaction to the phenol resin is too fast, and control tends to be difficult.
【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 (mainly derived from ammonia) in the phenol resin is preferably 0.4 to 0.9% by weight in terms of adhesion and strength. 0.4% by weight
If it is less, the adhesion tends to decrease, and if it exceeds 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。The "non-combustibility" of the composite molded article is improved by using a divalent metal hydroxide as a catalyst species, and unreacted materials are eliminated as much as possible during molding, so that by-products (condensed water etc.) generated by the reaction are generated. ) Is removed to the outside as much as possible to further improve.
【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 species for introducing a nitrogen-containing bond and using an appropriate amount of polyvinyl butyral resin. The modification ratio of the polyvinyl butyral resin is 5 to 15% by weight, preferably 8 to 13% by weight of the solid content of the phenol resin.
Is. That is, the polyvinyl butyral resin is 15% by weight.
If the amount is larger, it acts as a plasticizer and reduces "nonflammability". On the other hand, if the amount is less than 5% by weight, the effect of improving the strength is small, so it is important to balance the modification amount 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, even if the molecular weight of the polyvinyl butyral resin is small (the solution viscosity is low), it will act as a plasticizer, so it is preferable to select a high molecular weight resin. The polyvinyl butyral resin used in the present invention is 10 g of resin.
When dissolved in 150 ml of a mixed solvent of toluene / ethanol = 1/1 (weight ratio), the solution viscosity at 20 ° C is 150 cst
The above is preferable.
【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 high strength (tensile strength of 3500 MPa or more) and high elastic modulus (230
If it is GPa or more), either PAN type or pitch type may be used, but PAN type is preferable because it has high tensile strength. In addition, as the form of the fiber, a woven fabric such as a plain weave and a satin weave, or a yarn (roving or 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 fibers. As a molding method, compression molding,
Autoclave molding or pultrusion molding is usually employed, but is not limited to this.
【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 degas during molding. In autoclave molding, it is sufficient to lay up the tool and heat / pressurize it under appropriate conditions under reduced pressure by a method generally used in general. In the pultrusion molding method, a resin is impregnated into a yarn or a fiber in which a yarn and a woven fabric are combined, and then it is 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 obtain a cylindrical composite molded article by impregnating a carbon fiber bundle, winding it around a mandrel by a filament winding (FW) method, and then introducing it into an oven and curing it by heating.
【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. "Parts" and "%" in the following all mean "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 kettle 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), followed by 28%. After adding 20 parts of ammonia water and 8 parts of barium hydroxide, the temperature was gradually raised and the reaction was carried out for 45 minutes under reflux. After completion of the reaction, neutralize with 10 parts of 75% lactic acid, wash by adding water, remove the separated water, and dehydrate under vacuum to 8 at 70 mmHg.
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 in 20% with methyl ethyl ketone was added, and the mixture was reacted and mixed for about 2 hours to obtain the desired polyvinyl butyral modified phenolic resin 1970 parts (modification 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 P mole ratio was 1.5) and 28% ammonia water was 24 parts (nitrogen content in modified resin was 0.6%).
00 parts (remaining 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, polyvinyl butyral resin solution 50
2100 parts (residual solid content: 53%) of polyvinyl butyral modified phenol resin was obtained in the same manner as in Production Example 1 except that the amount was 5 parts (modification rate: 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 phenolic resin (remaining solid content 55%) was obtained in the same manner as in Production Example 1 except that the molar ratio was 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% ammonia water (nitrogen content in the modified resin was 0.2%) was used.
0 part (remaining solid content 55%) was 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 Polyvinyl butyral resin solution 14 in Production Example 1
1740 parts of polyvinyl butyral modified phenol resin (residual solid content 60%) were obtained in the same manner as in Production Example 1 except that 0 part (modification rate 3%) was used.
【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, polyvinyl butyral resin solution 92
2525 parts of polyvinyl butyral modified phenolic resin (residual solid content 48%) were obtained in the same manner as in Production Example 1 except that 5 parts (modification rate 20%) was used.
【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) Manufacture of Composite Molded Products In the following Examples and Comparative Examples, the resin content of the prepreg was 30 to 3 so that the fiber content of the composite molded products was 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 phenol resin of Production Example 1 was diluted with methyl ethyl ketone (MEK), and then a basis weight of 200 was applied.
A plain weave carbon fiber woven fabric of g / m 2 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 (degassing twice during the process) 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 prepregs obtained in Example 1 were superposed on a molding plate (stainless steel plate) by an autoclave, a release film,
After laying up with a breeder, pressure plate, breeder cloth, and vacuum bag, 160
By heating and pressurizing at 0.8 ° C. and 0.8 MPa (vacuum degree of 755 mmHg or less), a composite molded product having a fiber content of 70% was obtained.
【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 phenol resin obtained in Production Example 1 was diluted with MEK and then impregnated into a carbon fiber narrow fabric (width 200 mm) having a basis weight of 200 g / m 2 to obtain a width 200 mm and a thickness of about 1 It was drawn into a flat plate-shaped die (die) of 0.2 mm, heated and pressed at 160 ° C., and pulled out from the die by a take-up machine to obtain a continuous flat plate-shaped composite molded product 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 article 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 Using the polyvinyl butyral modified phenolic resin obtained in Production Example 1, a composite molded article was obtained in the same manner as in Example 2.
【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 shell chemical Epicoat 210 and a curing agent BF 3 -MEA was melted with MEK and then 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 ℃,
A double molded product having a fiber content of 70% was obtained by heating at 5.9 MPa.
【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 article was obtained in the same manner as in Example 1.
【００３４】比較例３ 製造例５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 3 Using the polyvinyl butyral modified phenolic resin obtained in Production Example 5, a composite molded article was obtained in the same manner as in Example 2.
【００３５】比較例４ 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 4 A composite molded article was obtained in the same manner as in Example 1, except that the polyvinyl butyral-modified phenol resin obtained in Production Example 6 was used.
【００３６】比較例５ 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 5 Using the polyvinyl butyral modified phenolic resin obtained in Production Example 7, a composite molded article 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 resins in the above Examples and Comparative Examples and the properties of the obtained composite molded articles.
【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。EFFECTS OF THE INVENTION According to the present invention, as can be seen from the evaluation results of the examples and comparative examples in Tables 1 and 2, for railway vehicles comprising polyvinyl butyral-modified phenolic resin and carbon fiber within the scope of claims. It is understood that the composite molded product passes "nonflammability" even if it has a thickness of 1 mm, in the flammability test by the Ministry of Transport. This has not been obtained in the conventional case using an epoxy resin. The composite molded article 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 railroad vehicle, a side structure of a car body, a roof structure, a gable structure, an underframe as a substitute for metal. Therefore, it can be expected to be applied to fields requiring flame retardancy, low smoke generation, and heat resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 康文 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 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 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasufumi Suzuki 2-8, Hikarimachi, Kokubunji 38 Tokyo Metropolitan Railway Research Institute (72) Inventor Kiyoshi Sato 38-8, Hikarimachi, Kokubunji, Tokyo Incorporated Railway Research Institute (72) Inventor Yoshishiro Tate 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Masaaki Tatara 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Yasushi Arita 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Sumitomo Durez Co., Ltd.
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. A solid content of a resol type phenol resin having a nitrogen-containing bond in which a molar ratio of aldehydes to phenols is 1.3 to 1.5 and a divalent metal hydroxide and ammonia are used together as a catalyst. On the other hand, a composite molded article for a railway vehicle comprising a polyvinyl butyral modified phenolic resin having a modification rate of polyvinyl butyral resin of 5 to 15% by weight and carbon fiber.
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 true JPH05202201A (en) | 1993-08-10 |
| JP3301773B2 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0889077A4 (en) * | 1996-03-22 | 2000-06-21 | Toho Rayon Kk | Carbon fiber prepreg for wood reinforcement, wooden sheet laminated therewith, wood reinforcing composite comprising carbon fibers and the wooden sheet, and carbon fiber reinforced wood |
| 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 |
| JP2020097124A (en) * | 2018-12-17 | 2020-06-25 | 株式会社イノアックコーポレーション | Carbon fiber reinforced molded body and method for producing the same |
-
1992
- 1992-01-23 JP JP03411492A patent/JP3301773B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0889077A4 (en) * | 1996-03-22 | 2000-06-21 | Toho Rayon Kk | Carbon fiber prepreg for wood reinforcement, wooden sheet laminated therewith, wood reinforcing composite comprising carbon fibers and the wooden sheet, and carbon fiber reinforced wood |
| JP2020097124A (en) * | 2018-12-17 | 2020-06-25 | 株式会社イノアックコーポレーション | Carbon fiber reinforced molded body and method for producing 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3301773B2 (en) | 2002-07-15 |
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