JPH0244325B2 - - Google Patents
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- Publication number
- JPH0244325B2 JPH0244325B2 JP58122408A JP12240883A JPH0244325B2 JP H0244325 B2 JPH0244325 B2 JP H0244325B2 JP 58122408 A JP58122408 A JP 58122408A JP 12240883 A JP12240883 A JP 12240883A JP H0244325 B2 JPH0244325 B2 JP H0244325B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- prepreg
- impact
- type epoxy
- composite materials
- 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 - Lifetime
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- Reinforced Plastic Materials (AREA)
Description
【発明の詳細な説明】
本発明は、耐熱性良好で且つ耐衝撃性に優れた
複合材料製造用一方向又は織物プリプレグに関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a unidirectional or woven prepreg for producing composite materials that has good heat resistance and excellent impact resistance.
近年、炭素繊維、芳香族ポリアミド繊維等を強
化繊維として用いた複合材料は、高い比強度、比
剛性を利用して航空機等の構造材として多く用い
られている。これらの航空機用複合材料が上記特
性の外に、更に耐熱性と耐衝撃性を具備したもの
であれば、複合材料の応用範囲は第二次構造材に
限定されず、第一次構造材にも適用可能となり、
航空機の軽量化は飛躍的に進み省エネルギーの面
から大きな利点がある。従来、複合材料特にエポ
キシ樹脂を用いた炭素繊維強化熱硬化性樹脂
（CFRP）は、衝撃強度の低いことが最大の欠点
であり、このため、航空機第一次構造材の如き重
要な用途への適用には限界があつた。 In recent years, composite materials using carbon fibers, aromatic polyamide fibers, and the like as reinforcing fibers have been widely used as structural materials for aircraft and the like due to their high specific strength and specific rigidity. If these composite materials for aircraft have heat resistance and impact resistance in addition to the above properties, the range of application of composite materials is not limited to secondary structural materials, but can also be used as primary structural materials. is also applicable,
The weight of aircraft has been reduced dramatically, which has great advantages in terms of energy conservation. Traditionally, the biggest drawback of composite materials, especially carbon fiber reinforced thermosetting resins (CFRP) made using epoxy resins, is their low impact strength, which makes them difficult to use for important applications such as primary structural materials for aircraft. There were limits to its application.
本発明者らは、耐熱性と耐衝撃性を具備した耐
衝撃性複合材料製造用プリプレグについて鋭意検
討した結果、本発明に到達した。 The present inventors have arrived at the present invention as a result of intensive studies on prepregs for producing impact-resistant composite materials that have heat resistance and impact resistance.
本発明は下記のとおりである。 The present invention is as follows.
伸度1.5％以上の炭素繊維からなる一方向配向
物又は織物に、〔Ａ〕多官能性マレイミド類、
〔Ｂ〕多官能性シアン酸エステル類及び〔Ｃ〕エ
ポキシ樹脂を含有する樹脂組成物を含浸させた耐
衝撃性複合材料用一方向又は織物プリプレグ。 [A] polyfunctional maleimide,
[B] A unidirectional or woven prepreg for impact-resistant composite materials impregnated with a resin composition containing a polyfunctional cyanate ester and [C] an epoxy resin.
本発明のプリプレグを用いることにより、航空
機用に多く用いられている従来の350゜F硬化タイ
プ炭素繊維強化エポキシ樹脂プリプレグを用いる
場合に比較し、格段に優れた耐衝撃性を有する複
合材料を製造することができる。 By using the prepreg of the present invention, a composite material with significantly superior impact resistance can be produced compared to the case of using the conventional 350°F hardening type carbon fiber reinforced epoxy resin prepreg that is often used for aircraft. can do.
本発明における〔Ａ〕成分の多官能性マレイミ
ド類とは、分子中に２個以上のマレイミド基を有
する次の一般式(1)で表わされるポリマレイミド化
合物及びこのポリマレイミド化合物から誘導され
るプレポリマーを意味する。 In the present invention, the polyfunctional maleimide of component [A] refers to a polymaleimide compound represented by the following general formula (1) having two or more maleimide groups in the molecule, and preforms derived from this polymaleimide compound. means polymer.
（式中、R1は２価〜５価の芳香族又は脂肪族
性有機基であり、X1，X2は水素、ハロゲン、ア
ルキル基であり、ｍは２〜５の整数である。）
更に、ポリマレイミド化合物にアミン類を付加
して得られる変性プレポリマーも〔Ａ〕成分に包
含される。これらは単独で用いられても混合して
用いられてもよい。上記プレポリマーは、ポリマ
レイミド化合物を触媒の存在下又は不存在下に、
所望により、更に分子中に１個以上のアミノ基を
有する化合物とともにゲル化に至らないように加
熱させて得られる生成物である。 (In the formula, R 1 is a divalent to pentavalent aromatic or aliphatic organic group, X 1 and X 2 are hydrogen, halogen, or an alkyl group, and m is an integer of 2 to 5.) Furthermore, modified prepolymers obtained by adding amines to polymaleimide compounds are also included in component [A]. These may be used alone or in combination. The above prepolymer is prepared by adding a polymaleimide compound in the presence or absence of a catalyst,
If desired, the product is obtained by heating with a compound having one or more amino groups in the molecule so as not to cause gelation.
本発明における〔Ｂ〕成分の多官能性シアン酸
エステル類とは、分子中に２個以上のシアン酸エ
ステル基を有する次の一般式(2)で表わされるポリ
シアン酸エステル化合物及びこのポリシアン酸エ
ステル化合物から誘導されるプレポリマーを意味
する。 The polyfunctional cyanate esters of component [B] in the present invention refer to polycyanate ester compounds represented by the following general formula (2) having two or more cyanate ester groups in the molecule, and the polycyanate esters. means a prepolymer derived from a compound.
R2−（−Ｃ≡Ｎ）ｎ ……(2)
（式中、R2は多価の芳香族性有機基であり、
シアン酸エステル基はR2の芳香環に直接結合し
ており、ｎは２〜10の整数である。）
本発明における〔Ｃ〕成分のエポキシ樹脂は、
特に制限がなく、ビスフエノールＡ型エポキシ樹
脂、ビスフエノールＦ型エポキシ樹脂、ビスフエ
ノールＳ型エポキシ樹脂、ノボラツク型エポキシ
樹脂、グリシジルアミン型エポキシ樹脂、環式脂
肪族エポキシ樹脂、グリセリングリシジルエーテ
ル型エポキシ樹脂、ポリグリコールジグリシジル
エーテル型エポキシ樹脂、ハロゲン化ビスフエノ
ールＡ型エポキシ樹脂等の１種又は２種以上であ
る。 R 2 -(-C≡N)n...(2) (wherein, R 2 is a polyvalent aromatic organic group,
The cyanate ester group is directly bonded to the aromatic ring of R2 , and n is an integer from 2 to 10. ) The epoxy resin of the [C] component in the present invention is
There are no particular restrictions, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolak type epoxy resin, glycidylamine type epoxy resin, cycloaliphatic epoxy resin, glycerin glycidyl ether type epoxy resin. , polyglycol diglycidyl ether type epoxy resin, and halogenated bisphenol A type epoxy resin.
上記〔Ａ〕〜〔Ｃ〕成分を含有する樹脂組成物
は、他に、硬化促進剤としてイミダゾール化合
物、オクチル酸亜鉛、ジクミルパーオキサイド等
の過酸化物を含有してもよい。 The resin composition containing the above components [A] to [C] may also contain a peroxide such as an imidazole compound, zinc octylate, or dicumyl peroxide as a curing accelerator.
本発明において伸度1.5％以上の炭素繊維から
なる一方向配向物又は織物は、ストランドを一方
向に配列させた一方向配向物の形態又は織物の形
態のものである。これらは樹脂組成物により含浸
され、それぞれ一方向プリプレグ又は織物プリプ
レグが作られる。含浸方法は、溶剤を用いないホ
ツトメルト法又は溶剤法のいずれでもよい。 In the present invention, the unidirectionally oriented product or woven fabric made of carbon fibers having an elongation of 1.5% or more is in the form of a unidirectionally oriented product or a woven fabric in which strands are arranged in one direction. These are impregnated with a resin composition to produce unidirectional prepregs or woven prepregs, respectively. The impregnation method may be either a hot melt method that does not use a solvent or a solvent method.
以下、本発明を実施例により説明するとともに
比較例を示す。 Hereinafter, the present invention will be explained with reference to examples, and comparative examples will be shown.
実施例 １
２・２−ビス（４−シアナトフエニル）プロパ
ンとビス（４−マレイミドフエニル）メタンの予
備反応物であり、70℃における粘度が20ポイズで
あるビスマレイミド樹脂（三菱ガス化学社製、
BTレジン）500ｇとフエノールノボラツク型エ
ポキシ樹脂（エポキシ当量178）80ｇ、硬化剤と
して２−エチル４−メチルイミダゾール２ｇを
Ｎ・Ｎ−ジメチルホルムアミドに溶解させた。Example 1 Bismaleimide resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.;
500 g of BT resin), 80 g of a phenol novolac type epoxy resin (epoxy equivalent: 178), and 2 g of 2-ethyl 4-methylimidazole as a hardening agent were dissolved in N.N-dimethylformamide.
得られた樹脂組成物を伸度（ストランド引張破
断伸度）1.84％の炭素繊維〔東邦レーヨン(株)社
製、ベスフアイト
ST−6000〕に含浸させた。
次いで、加熱乾燥して炭素繊維重量145ｇ／m2、
樹脂含有率40重量％の一方向プリプレグを得た。 The obtained resin composition was impregnated into carbon fiber (Besphite ST-6000, manufactured by Toho Rayon Co., Ltd.) having an elongation (strand tensile elongation at break) of 1.84%.
Next, the carbon fiber weight is 145g/m 2 by heating and drying.
A unidirectional prepreg with a resin content of 40% by weight was obtained.
このプリプレグを一方向に20枚積層し、180℃、
４Kg／cm2で２時間オートクレーブ成形して、一方
向CFRPを得た。このものの層間剪断強度
（ILSS）は次のとおりであつた。 20 sheets of this prepreg were laminated in one direction and heated at 180℃.
A unidirectional CFRP was obtained by autoclave molding at 4 kg/cm 2 for 2 hours. The interlaminar shear strength (ILSS) of this product was as follows.
23℃ 13.1Kg／mm2
150℃ 7.8Kg／mm2
このプリプレグを（±45／０／90／０／90）2／
±45／０／90／±45／±45／90／０／±45／
（90／０／90／０／±45／2の如く36枚積層し、同
じ条件で成形して成形板を得た。この積層板に衝
撃速度4ft／sec、衝撃エネルギー25ft−bsの衝
撃を加え積層板を貫通するに要する力、すなわち
貫通衝撃強度を測定したところ、835bsであつ
た。 23℃ 13.1Kg/mm 2 150℃ 7.8Kg/mm 2 This prepreg (±45/0/90/0/90) 2 /
±45/0/90/±45/±45/90/0/±45/
(36 sheets were laminated like 90/0/90/0/±45/ 2 and molded under the same conditions to obtain a molded plate.This laminated plate was subjected to an impact with an impact speed of 4 ft/sec and an impact energy of 25 ft-bs. In addition, the force required to penetrate the laminate, ie, the penetration impact strength, was measured and found to be 835bs.
実施例 ２
実施例１において、フエノールノボラツク型エ
ポキシ樹脂の代りにクレゾールノボラツク型エポ
キシ樹脂を同量用いて、実施例１と全く同様にし
てプリプレグを作つた。Example 2 A prepreg was prepared in exactly the same manner as in Example 1 except that the same amount of cresol novolac type epoxy resin was used in place of the phenol novolac type epoxy resin.
このものから成形板を作つてILSSと衝撃強度
を測定したところ、次の結果を得た。 When a molded plate was made from this material and its ILSS and impact strength were measured, the following results were obtained.
ILSS 23℃ 12.9Kg／mm2
同上 150℃ 8.0Kg／mm2
貫通衝撃強度 790bs
比較例１（〔Ａ〕成分及び〔Ｂ〕成分を欠く例）
現在エポキシ樹脂のうちで最も耐熱性の高い硬
化物を与えるとされるテトラグリシジルメチレン
アニリンに属するアラルダイトMY720（チバガイ
キー社製）と、硬化剤ジアミノジフエニルスルホ
ンとを500ｇのアセトンに溶かし、実施例１と同
様の伸度を有する炭素繊維を用いて、実施例１と
全く同様にしてプリプレグを作つた。得られたプ
リプレグを実施例１と全く同様にして成形して成
形板を作つた。 ILSS 23℃ 12.9Kg/mm 2 Same as above 150℃ 8.0Kg/mm 2 Penetration impact strength 790bs Comparative example 1 (example lacking component [A] and component [B]) Currently the most heat-resistant cured product among epoxy resins Araldite MY720 (manufactured by Ciba Gaiki Co., Ltd.), which belongs to tetraglycidylmethyleneaniline which is said to give A prepreg was made in exactly the same manner as in Example 1. The obtained prepreg was molded in exactly the same manner as in Example 1 to produce a molded plate.
ILSSと衝撃強度を測定した結果を次に示す。 The results of measuring ILSS and impact strength are shown below.
ILSS 23℃ 13.2Kg／mm2
同上 150℃ 6.9Kg／mm2
貫通衝撃強度 337bs
比較例 ２（伸度が本発明範囲外の例）
伸度（ストランド引張破断伸度）1.31％の炭素
繊維〔東邦レーヨン(株)社製、ベスフアイト
HTA7−6000〕に実施例１と全く同様の樹脂組
成物を含浸させて、同様のプリプレグを作つた。
このプリプレグを用いて実施例１と同様にして得
た成形物についてILSSと衝撃強度を測定したと
ころ、次の結果を得た。 ILSS 23℃ 13.2Kg/mm 2 Same as above 150℃ 6.9Kg/mm 2 Penetration impact strength 337bs Comparative example 2 (example with elongation outside the range of the present invention) Carbon fiber with elongation (strand tensile elongation at break) of 1.31% [Toho Manufactured by Rayon Co., Ltd., Besuphite
HTA7-6000] was impregnated with the same resin composition as in Example 1 to prepare a similar prepreg.
When the ILSS and impact strength of a molded product obtained using this prepreg in the same manner as in Example 1 were measured, the following results were obtained.
ILSS 23℃ 12.8Kg／mm2 同上 150℃ 7.5Kg／mm2 貫通衝撃強度 443bs ILSS 23℃ 12.8Kg/mm 2 Same as above 150℃ 7.5Kg/mm 2 Penetration impact strength 443bs
Claims (1)
向物又は織物に、〔Ａ〕多官能性マレイミド類、
〔Ｂ〕多官能性シアン酸エステル類及び〔Ｃ〕エ
ポキシ樹脂を含有する樹脂組成物を含浸させた耐
衝撃性複合材料用一方向又は織物プリプレグ。[Claims] 1. A unidirectionally oriented material or fabric made of carbon fibers having an elongation of 1.5% or more, [A] a polyfunctional maleimide,
[B] A unidirectional or woven prepreg for impact-resistant composite materials impregnated with a resin composition containing a polyfunctional cyanate ester and [C] an epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12240883A JPS6015439A (en) | 1983-07-07 | 1983-07-07 | Prepreg for impact-resistant composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12240883A JPS6015439A (en) | 1983-07-07 | 1983-07-07 | Prepreg for impact-resistant composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6015439A JPS6015439A (en) | 1985-01-26 |
| JPH0244325B2 true JPH0244325B2 (en) | 1990-10-03 |
Family
ID=14835059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12240883A Granted JPS6015439A (en) | 1983-07-07 | 1983-07-07 | Prepreg for impact-resistant composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6015439A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63205328A (en) * | 1987-02-19 | 1988-08-24 | Toray Ind Inc | Prepreg for composite material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5356264U (en) * | 1976-10-15 | 1978-05-13 | ||
| JPS5538823A (en) * | 1978-09-11 | 1980-03-18 | Mitsubishi Gas Chem Co Inc | Production of heat-resistant laminate |
| JPS6227373Y2 (en) * | 1981-01-12 | 1987-07-14 | ||
| JPS58160323A (en) * | 1982-03-18 | 1983-09-22 | Mitsubishi Gas Chem Co Inc | Production of fiber-reinforced molding material |
-
1983
- 1983-07-07 JP JP12240883A patent/JPS6015439A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6015439A (en) | 1985-01-26 |
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