JPH09111011A - Hot-pressed article of laminated prepreg having high heat resistance - Google Patents
Hot-pressed article of laminated prepreg having high heat resistanceInfo
- Publication number
- JPH09111011A JPH09111011A JP8148629A JP14862996A JPH09111011A JP H09111011 A JPH09111011 A JP H09111011A JP 8148629 A JP8148629 A JP 8148629A JP 14862996 A JP14862996 A JP 14862996A JP H09111011 A JPH09111011 A JP H09111011A
- Authority
- JP
- Japan
- Prior art keywords
- hot
- resin
- heat resistance
- prepreg
- high heat
- 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
Landscapes
- Laminated Bodies (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はポリカルボジイミド
系熱硬化性樹脂含有炭素繊維複合材に関し、更に詳しく
は必須成分として分子中に２個以上のカルボジイミド基
を有するポリカルボジイミド樹脂を含む耐熱性の高いプ
リプレグ積層体の熱圧成型品に関するものである。TECHNICAL FIELD The present invention relates to a carbon fiber composite material containing a polycarbodiimide-based thermosetting resin, and more specifically, it has a high heat resistance containing a polycarbodiimide resin having two or more carbodiimide groups in the molecule as an essential component. The present invention relates to a thermocompression molded product of a prepreg laminate.
【０００２】[0002]
【従来の技術】近年炭素繊維複合材は、そのすぐれた強
度，高い弾性率，軽量さによって各種構造部材に用いら
れている。2. Description of the Related Art In recent years, carbon fiber composite materials have been used for various structural members due to their excellent strength, high elastic modulus and light weight.
【０００３】例えば、航空機用部品，ゴルフクラブ，テ
ニスラケット等が代表的なものである。さらに高度な応
用としてロケットや人工衛星の部材にも適用されてい
る。[0003] For example, aircraft parts, golf clubs, tennis rackets and the like are typical. As a more advanced application, it is also applied to components of rockets and satellites.
【０００４】而して、その製造方法は、一般に熱硬化性
樹脂をマトリックスとしたシ−ト状の中間体を作り、そ
れを積層し熱硬化して成型品を得るものである。[0004] Thus, the manufacturing method is generally to prepare a sheet-like intermediate body using a thermosetting resin as a matrix, stack the sheet-like intermediate bodies, and thermoset them to obtain a molded product.
【０００５】従来、最も一般的に用いられている炭素繊
維用のマトリックス樹脂としては、エポキシ樹脂が知ら
れている。Heretofore, epoxy resins have been known as the most commonly used matrix resin for carbon fibers.
【０００６】[0006]
【発明が解決しようとする課題】このエポキシ樹脂は接
着力が高く、層間剪断強度が７kg/mm2以上あり、高性能
の複合材を得られるのであるが、一般に120〜170℃で60
分以上という長時間の硬化条件を要する欠点があり、ま
た、このエポキシ樹脂を用いた炭素繊維複合材は耐熱性
の面においても充分満足すべきものとは言えず、厳しい
高温状態にさらされる宇宙航空分野等においては、更に
耐熱性を向上させた炭素繊維複合材の出現が望まれてい
る。This epoxy resin has a high adhesive strength, an interlaminar shear strength of 7 kg / mm 2 or more, and a high-performance composite material can be obtained.
The carbon fiber composite material using this epoxy resin is not sufficiently satisfactory in terms of heat resistance because it has the drawback of requiring a long curing time of more than a minute, and aerospace exposed to severe high temperature conditions In fields and the like, the advent of carbon fiber composite materials having further improved heat resistance is desired.
【０００７】一般に炭素繊維複合材の耐熱性は主として
マトリックスを形成する樹脂の耐熱性に依存するところ
が大きい。これは炭素繊維自身は通常問題となる程度の
高温（250℃以下）では殆ど影響はみられないからであ
る。Generally, the heat resistance of the carbon fiber composite material largely depends on the heat resistance of the resin forming the matrix. This is because the carbon fiber itself has almost no effect at a high temperature (250 ° C or lower), which is usually a problem.
【０００８】従って、上記の要望を満足させる炭素繊維
複合材を得るためには、エポキシ樹脂より速硬化性で且
つ適正な耐熱性を有するマトリックス樹脂が用いられな
ければならない。Therefore, in order to obtain a carbon fiber composite material that satisfies the above-mentioned demand, a matrix resin having a faster curing property and an appropriate heat resistance than an epoxy resin must be used.
【０００９】[0009]
【課題を解決するための手段】本発明は上述のような従
来技術の問題点を解決し、エポキシ樹脂より速硬化性で
且つ耐熱性の高いマトリックス樹脂を用いた耐熱性の高
いプリプレグ積層体の熱圧成型品を提供することを目的
としてなされたもので、その構成は、分子内に少なくと
も２個以上のカルボジイミド基を含むポリカルボジイミ
ドの粉末状樹脂の溶融物もしくは前記ポリカルボジイミ
ドの液状反応混合物を炭素繊維に含浸させて形成したプ
リプレグの積層体を、熱圧成型して成ることを特徴とす
るものである。The present invention solves the problems of the prior art as described above, and provides a highly heat-resistant prepreg laminate using a matrix resin that is faster curable and has higher heat resistance than an epoxy resin. The purpose of the present invention is to provide a hot-pressed product, the composition of which is a melt of powdered resin of polycarbodiimide containing at least two or more carbodiimide groups in the molecule or a liquid reaction mixture of the polycarbodiimide. A laminate of prepregs formed by impregnating carbon fibers is formed by thermocompression molding.
【００１０】即ち、本発明者は、炭素繊維に対して速硬
化性でエポキシ樹脂並みの接着力を有し、且つ、それ以
上の耐熱性を有するマトリックス樹脂と炭素繊維の組み
合せを見出すべく鋭意研究の結果、前記マトリックス樹
脂としてポリカルボジイミド樹脂を用いればよいことを
知得し、本発明を完成したのであって、本発明の熱硬化
性樹脂を含有した熱圧成型品は、エポキシ樹脂を用いた
ものより硬化が早い上に、耐熱性も良好で、優れた機械
特性を示す。That is, the present inventor diligently researched to find a combination of a matrix resin and a carbon fiber, which has a fast curing property with respect to the carbon fiber, has an adhesive strength comparable to that of an epoxy resin, and has heat resistance higher than that. As a result, they learned that a polycarbodiimide resin may be used as the matrix resin, and completed the present invention. The thermocompression-molded article containing the thermosetting resin of the present invention used an epoxy resin. It cures faster than other materials and has good heat resistance and excellent mechanical properties.
【００１１】[0011]
【発明の実施の形態】次に本発明について詳細に説明す
る。本発明に使用されるカルボジイミド樹脂としては、
イソシアネ−トのカルボジイミド化を促進する触媒の一
種以上を使用する等して一種以上の有機ポリイソシアネ
−トと一種以上の有機モノイソシアネ−トとから、分子
量を規制しつつ、実質的に生ぜしめたポリカルボジイミ
ド樹脂が最も好ましい。Next, the present invention will be described in detail. As the carbodiimide resin used in the present invention,
From one or more organic polyisocyanate and one or more organic monoisocyanate, for example, by using at least one catalyst that promotes carbodiimidization of isocyanate, while controlling the molecular weight, a poly- Carbodiimide resins are most preferred.
【００１２】この有機モノイソシアネ−トを用いて重縮
合を停止させる方法でポリカルボジイミドの平均分子量
を規制することは公知である（I.M.AlberinoらJAPS,21,
1999−2008 1977)が、これを炭素繊維などと複合して耐
熱性を向上させたプリプレグを製造しこの方法により製
造したプリプレグを熱圧成型して所定の炭素繊維複合材
を製造する試みはなされていなかった。It is known to control the average molecular weight of polycarbodiimide by a method of stopping polycondensation using this organic monoisocyanate (IMAlberino et al. JAPS, 21,
1999-2008 1977 ), a prepreg having improved heat resistance is manufactured by compounding it with carbon fiber or the like, and an attempt is made to manufacture a predetermined carbon fiber composite material by thermocompression molding the prepreg manufactured by this method. Didn't.
【００１３】本発明は、このような背景技術を考慮した
上で、フェニル基により末端を封止したポリカルボジイ
ミドの粉末状樹脂の溶融物もしくはポリカルボジイミド
の液状反応混合物を炭素繊維に含浸させることにより、
まず、プリプレグを作製する。この方法により製造した
プリプレグは熱硬化性を有しているので、熱圧成型する
ことが可能である。従って、このプリプレグを積層し、
目的にあった形状に熱圧成型法により成型すれば、所定
の熱圧成型品を得ることができるわけである。In view of the background art described above, the present invention provides a method of impregnating carbon fibers with a melt of a powdered resin of polycarbodiimide end-capped with a phenyl group or a liquid reaction mixture of polycarbodiimide. ,
First, a prepreg is manufactured. Since the prepreg manufactured by this method has thermosetting properties, it can be hot-press molded. Therefore, stacking this prepreg,
A predetermined hot-pressed product can be obtained by molding the product into a shape suitable for the purpose by the hot-pressing method.
【００１４】なお、得られた熱圧成型品を、更に不活性
ガス中で1000℃程度で焼成することにより、高収率でＣ
／Ｃコンポジットを得ることができる。更には、このＣ
／Ｃコンポジットにワニス状のカルボジイミド樹脂を含
浸焼成することにより、更に高収率，高効率で密度の高
いＣ／Ｃコンボジットを得ることもできる。The obtained hot-pressed product is further baked in an inert gas at about 1000 ° C. to give a high yield of C.
/ C composite can be obtained. Furthermore, this C
By impregnating and burning a varnish-like carbodiimide resin in a / C composite, it is possible to obtain a C / C convoyit with higher yield, higher efficiency and higher density.
【００１５】[0015]
【実施例】以下に本発明の実施例と応用例を示す。 実施例 １ メチレンジフェニルジイソシアネート250g，フェニルイ
ソシアネ−ト23gの組成で、テトラクロロエチレン中、1
20℃で3-メチル-1-フェニルフォスフォレン-1-オキサイ
ドを触媒として加えカルボジイミド化し、粉末状の樹脂
を得た。その粉末状樹脂を120〜140℃で溶融し、炭素繊
維に含浸させてドラム上に巻き取った。含浸後の炭素繊
維を２本のロ−ラではさみ、その間隙を制御することに
より、樹脂含有率を40重量％に調整し、プリプレグを得
た。得られたプリプレグを一方向に積層し、200℃で10
分プレスして成型品を得た。この成型品の物性は次の通
りであった。 密 度 1.38 曲げ強度 40kg／mm2 熱変形温度 210℃EXAMPLES Examples and applications of the present invention will be shown below. Example 1 A composition of 250 g of methylene diphenyl diisocyanate and 23 g of phenyl isocyanate in 1 g of tetrachloroethylene was used.
At 20 ° C., 3-methyl-1-phenylphosphoren-1-oxide was added as a catalyst to form a carbodiimide, and a powdery resin was obtained. The powdery resin was melted at 120 to 140 ° C., impregnated in carbon fiber and wound on a drum. The impregnated carbon fiber was sandwiched by two rollers and the gap was controlled to adjust the resin content to 40% by weight to obtain a prepreg. Laminate the obtained prepregs in one direction and
Minute pressing was performed to obtain a molded product. The physical properties of this molded product were as follows. Density 1.38 Bending strength 40kg / mm 2 Heat distortion temperature 210 ℃
【００１６】実施例 ２ 実施例１と同様にプリプレグを作製し、得られたプリプ
レグを一方向に積層し、350℃で10分プレスして成型品
を得た。この成型品の物性は次の通りであった。 密 度 1.38 曲げ強度 35kg／mm2 熱変形温度 300℃以上Example 2 A prepreg was prepared in the same manner as in Example 1, and the obtained prepreg was laminated in one direction and pressed at 350 ° C. for 10 minutes to obtain a molded product. The physical properties of this molded product were as follows. Density 1.38 Bending strength 35kg / mm 2 Heat distortion temperature 300 ℃ or more
【００１７】実施例 ３ 実施例１と同様に樹脂を合成し、該樹脂を120〜140℃で
溶融し、炭素繊維から成るクロスに含浸させて、プリプ
レグを作製した。このプリプレグを積層し、350℃でプ
レスして成型品を得た。この成型品の物性は次の通りで
あった。 密 度 1.35 曲げ強度 20kg／mm2 熱変形温度 300℃以上Example 3 A resin was synthesized in the same manner as in Example 1, and the resin was melted at 120 to 140 ° C. and impregnated with a cloth made of carbon fiber to prepare a prepreg. This prepreg was laminated and pressed at 350 ° C. to obtain a molded product. The physical properties of this molded product were as follows. Density 1.35 Bending strength 20kg / mm 2 Heat distortion temperature 300 ℃ or more
【００１８】実施例 ４ トリレンジイソシアネート200g，フェニルイソシアネ−
ト５gの組成でテトラクロロエチレン中、120℃で3-メチ
ル1-フェノ−ル-2-ホスフォレン-1-オキシドを触媒とし
て加え、カルボジイミド化して、樹脂ワニスを得た。こ
のワニスを炭素繊維から成るクロスに含浸させて70℃で
乾燥させプリプレグを得た。その成型品の物性は次の通
りであった。 密 度 1.35 曲げ強度 20kg／mm2 熱変形温度 300℃以上Example 4 Tolylene diisocyanate 200 g, phenyl isocyanate
The resin varnish was obtained by carbodiimidizing 3-methyl 1-phenol-2-phosphoren-1-oxide as a catalyst in tetrachloroethylene at 120 ° C. with a composition of 5 g. A cloth made of carbon fiber was impregnated with this varnish and dried at 70 ° C. to obtain a prepreg. The physical properties of the molded product were as follows. Density 1.35 Bending strength 20kg / mm 2 Heat distortion temperature 300 ℃ or more
【００１９】応用例 １ 実施例２と同様にして成型品を得た後、該成型品を真空
下、1000℃で１時間焼成しＣ／Ｃコンポジットを製造し
た。このものの物性は次の通りであった。 嵩 密 度 1.20 曲げ強度 9kg／mm2 Application Example 1 After obtaining a molded product in the same manner as in Example 2, the molded product was fired at 1000 ° C. for 1 hour under vacuum to produce a C / C composite. Its physical properties were as follows. Bulk density 1.20 Bending strength 9kg / mm 2
【００２０】応用例 ２ 応用例１で得られたＣ／Ｃコンポジットにカルボジイミ
ド樹脂のテトラクロロエチレン溶液を含浸させて乾燥し
た後、真空下、1000℃で１時間焼成した。このものの物
性は次の通りであった。 嵩 密 度 1.40 曲げ強度 18kg／mm2 Application Example 2 The C / C composite obtained in Application Example 1 was impregnated with a tetrachloroethylene solution of a carbodiimide resin, dried, and then baked under vacuum at 1000 ° C. for 1 hour. Its physical properties were as follows. Bulk density 1.40 Bending strength 18kg / mm 2
【００２１】[0021]
【発明の効果】本発明の熱圧成型品は以上の通りであっ
て、エポキン樹脂より速硬化性で且つ耐熱性の高いマト
リックス樹脂を用いたため、航空採用部品等として好適
に用いることができ、優れた機械特性を示す。EFFECTS OF THE INVENTION The thermocompression molded product of the present invention is as described above, and since it uses a matrix resin that is faster curable and has higher heat resistance than Epokin resin, it can be suitably used as an aviation adopted component, It exhibits excellent mechanical properties.
Claims (1)
イミド基を含むポリカルボジイミドの粉末状樹脂の溶融
物もしくは前記ポリカルボジイミドの液状反応混合物を
炭素繊維に含浸させて形成したプリプレグの積層体を、
熱圧成型して成ることを特徴とする耐熱性の高いプリプ
レグ積層体の熱圧成型品。1. A laminate of prepregs formed by impregnating carbon fibers with a melt of a powdered resin of polycarbodiimide containing at least two or more carbodiimide groups in the molecule or a liquid reaction mixture of the polycarbodiimide.
A heat-pressed product of a prepreg laminate having high heat resistance, which is formed by hot-pressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8148629A JPH09111011A (en) | 1996-05-20 | 1996-05-20 | Hot-pressed article of laminated prepreg having high heat resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8148629A JPH09111011A (en) | 1996-05-20 | 1996-05-20 | Hot-pressed article of laminated prepreg having high heat resistance |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61307784A Division JPH0745582B2 (en) | 1986-12-25 | 1986-12-25 | Method for manufacturing prepreg with high heat resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09111011A true JPH09111011A (en) | 1997-04-28 |
Family
ID=15457069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8148629A Pending JPH09111011A (en) | 1996-05-20 | 1996-05-20 | Hot-pressed article of laminated prepreg having high heat resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09111011A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9221073B2 (en) | 2011-08-30 | 2015-12-29 | Basf Se | High molecular weight polycarbodiimide and method of producing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5015877A (en) * | 1973-05-11 | 1975-02-19 | ||
| JPS5161599A (en) * | 1974-10-02 | 1976-05-28 | Upjohn Co | |
| JPS6116934A (en) * | 1984-07-04 | 1986-01-24 | Toray Ind Inc | Heat-resistant prepreg |
-
1996
- 1996-05-20 JP JP8148629A patent/JPH09111011A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5015877A (en) * | 1973-05-11 | 1975-02-19 | ||
| JPS5161599A (en) * | 1974-10-02 | 1976-05-28 | Upjohn Co | |
| JPS6116934A (en) * | 1984-07-04 | 1986-01-24 | Toray Ind Inc | Heat-resistant prepreg |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9221073B2 (en) | 2011-08-30 | 2015-12-29 | Basf Se | High molecular weight polycarbodiimide and method of producing same |
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