JP2012057277A5

JP2012057277A5 -

Info

Publication number: JP2012057277A5
Application number: JP2010202955A
Authority: JP
Filing date: 2010-09-10
Publication date: 2013-07-18
Anticipated expiration: 2030-09-10

Description

本発明者らは、鋭意検討した結果、上記課題を解決することができる、次の複合強化繊維束の製造方法を発明するに至った。すなわち、強化繊維束（Ａ）５０〜８７質量％に、条件（１）、（２）を満たし、１０℃／分昇温（空気中）の３００℃における加熱減量が５％以下であるエポキシ樹脂（Ｂ）１３〜５０質量％を含浸させてなる強化繊維束の製造方法であって、成分（Ａ）に成分（Ｂ）を供給し、成分（Ｂ）を１００〜３００℃の溶融状態で成分（Ａ）と接触させる工程（Ｉ）と、成分（Ｂ）と接触している成分（Ａ）を加熱して成分（Ｂ）の供給量の８０〜１００質量％を成分（Ａ）に含浸させる工程（II）を有する複合強化繊維束の製造方法である。
条件（１）：成分（Ｂ）１００質量部のうちグリシジルエーテル型エポキシ樹脂が５０〜１００質量部、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、脂環式エポキシ樹脂から選ばれる少なくとも１種のエポキシ樹脂が０〜５０質量部である。
条件（２）：２００℃における溶融粘度は０．００１〜１０Ｐａ・ｓであり、かつ、２００℃にて２時間加熱後の溶融粘度変化率が２以下である。 As a result of intensive studies, the present inventors have invented the following method for producing a composite reinforcing fiber bundle that can solve the above problems. That is, the reinforcing fiber bundle (A) 50-87 wt%, Condition (1), (2) meets, heat loss at 300 ° C. for 10 ° C. / min heating (in air) is not more than 5% epoxy A method for producing a reinforcing fiber bundle impregnated with 13 to 50% by mass of resin (B), wherein component (B) is supplied to component (A), and component (B) is melted at 100 to 300 ° C. The step (I) for contacting with the component (A) and the component (A) in contact with the component (B) are heated to impregnate the component (A) with 80 to 100% by mass of the supply amount of the component (B). It is a manufacturing method of the composite reinforcing fiber bundle which has the process (II) to make.
Condition (1): At least one selected from glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, and alicyclic epoxy resin among 100 parts by mass of component (B). The epoxy resin is 0 to 50 parts by mass.
Condition (2): The melt viscosity at 200 ° C. is 0.001 to 10 Pa · s, and the rate of change in melt viscosity after heating at 200 ° C. for 2 hours is 2 or less.

炭素繊維の表面酸素濃度比は、Ｘ線光電子分光法により、次の手順にしたがって求めるものである。まず、溶剤で炭素繊維表面に付着しているサイジング剤などを除去した炭素繊維束を２０ｍｍにカットして、銅製の試料支持台に拡げて並べた後、Ｘ線源としてＡ１Ｋα１、２を用い、試料チャンバー中を１×１０^−８Ｔｏｒｒに保つ。測定時の帯電に伴うピークの補正値としてＣ_１ｓの主ピークの運動エネルギー値（Ｋ．Ｅ．）を１２０２ｅＶに合わせる。Ｃ_１ｓピーク面積をＫ．Ｅ．として１１９１〜１２０５ｅＶの範囲で直線のベースラインを引くことにより求める。Ｏ_１ｓピーク面積をＫ．Ｅ．として９４７〜９５９ｅＶの範囲で直線のベースラインを引くことにより求める。 The surface oxygen concentration ratio of the carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, after cutting the carbon fiber bundle from which the sizing agent and the like adhering to the carbon fiber surface with a solvent was cut to 20 mm and spreading and arranging on a copper sample support base, using A1Kα1,2 as the X-ray source, The sample chamber is kept at 1 × 10 ⁻⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. Is obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area E. Is obtained by drawing a straight base line in the range of 947 to 959 eV.

ここで、表面酸素濃度比は、表面酸化処理を行ったあとの炭素繊維を用いて、Ｘ線光電子分光法により、次の手順にしたがって求めた。まず、炭素繊維束を２０ｍｍにカットして、銅製の試料支持台に拡げて並べた後、Ｘ線源としてＡ１Ｋα１、２を用い、試料チャンバー中を１×１０^−８Ｔｏｒｒに保った。測定時の帯電に伴うピークの補正値としてＣ_１ｓの主ピークの運動エネルギー値（Ｋ．Ｅ．）を１２０２ｅＶに合わせた。Ｃ_１ｓピーク面積をＫ．Ｅ．として１１９１〜１２０５ｅＶの範囲で直線のベースラインを引くことにより求めた。Ｏ_１ｓピーク面積をＫ．Ｅ．として９４７〜９５９ｅＶの範囲で直線のベースラインを引くことにより求めた。Ｏ_１ｓピーク面積とＣ_１ｓピーク面積の比から装置固有の感度補正値を用いて原子数比として算出した。Ｘ線光電子分光法装置として、国際電気社製モデルＥＳ−２００を用い、感度補正値を１．７４とした。 Here, the surface oxygen concentration ratio was determined according to the following procedure by X-ray photoelectron spectroscopy using the carbon fiber after the surface oxidation treatment. First, the carbon fiber bundle was cut to 20 mm, spread and arranged on a copper sample support, and then A1Kα1 and 2 were used as X-ray sources, and the inside of the sample chamber was kept at 1 × 10 ⁻⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s was adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. As a linear base line in the range of 1191 to 1205 eV. O _1s peak area E. As a linear base line in the range of 947 to 959 eV. The atomic ratio was calculated from the ratio of the O _1s peak area to the C _1s peak area using the sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, Kokusai Denki Co., Ltd. model ES-200 was used, and the sensitivity correction value was set to 1.74.

参考例２
被含浸剤として、成分（Ｂ）である（Ｂ）−２（三菱化学（株）製フェノールノボラック型エポキシ樹脂、ｊＥＲ（登録商標）１５４）を用い、成分（Ｃ）として、ＰＰＳ（東レ（株）製、ポリフェニレンスルフィド樹脂、Ｍ２５８８）を用い、シリンダー温度：３２０℃、金型温度：１５０℃に変更した以外は実施例１と同様にして、複合体、成形材料、成形品を得た。特性評価結果はまとめて表１に記載した。 Reference example 2
(B) -2 (Mitsubishi Chemical Co., Ltd. phenol novolac type epoxy resin, jER (registered trademark) 154) is used as the impregnating agent, and PPS (Toray Industries, Inc.) is used as the component (C). ), Polyphenylene sulfide resin, M2588), a composite, a molding material, and a molded product were obtained in the same manner as in Example 1 except that the cylinder temperature was changed to 320 ° C. and the mold temperature was changed to 150 ° C. The characteristic evaluation results are collectively shown in Table 1.

参考例１４
被含浸剤として、成分（Ｂ）である（Ｂ）−１１（三菱化学（株）製ビスフェノールＡ型エポキシ樹脂の混合物、ｊＥＲ（登録商標）８２８／ｊＥＲ（登録商標）１００１＝９０／１０）を用いた以外は実施例１と同様にして、複合体、成形材料、成形品を得た。特性評価結果はまとめて表２に記載した。 Reference Example 14
As an impregnating agent, component (B) -11 (B) -11 (mixture of bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) 828 / jER (registered trademark) 1001 = 90/10) Except having used, it carried out similarly to Example 1, and obtained the composite_body | complex, the molding material, and the molded article. The characteristic evaluation results are collectively shown in Table 2.

以上のように、実施例１、３〜１３においては、本発明における複合強化繊維束の製造方法により、含浸性が良好であり、かつボイドの少ない複合強化繊維束が得られる。また、得られた複合強化繊維束を用いた成形材料は、成形時に揮発分が少なく、強化繊維の成形品中への分散が良好である成形材料を得ることができた。 As described above, in Examples 1 and 3 to 13 , a composite reinforcing fiber bundle with good impregnation and few voids can be obtained by the method for manufacturing a composite reinforcing fiber bundle in the present invention. Moreover, the molding material using the obtained composite reinforcing fiber bundle had a low volatile content at the time of molding, and a molding material having good dispersion of the reinforcing fibers in the molded product could be obtained.

Claims

The reinforcing fiber bundle (A) 50 to 87 wt%, Condition (1), (2) meets, 10 ° C. / min heating epoxy resin heat loss at 300 ° C. of (in air) is not more than 5% ( B) A method for producing a composite reinforcing fiber bundle impregnated with 13 to 50% by mass, wherein component (B) is supplied to component (A), and component (B) is melted at 100 to 300 ° C. The step (I) for contacting with the component (A) and the component (A) in contact with the component (B) are heated to impregnate the component (A) with 80 to 100% by mass of the supply amount of the component (B). The manufacturing method of the composite reinforcing fiber bundle which has the process (II) to make.
Condition (1): At least one selected from glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, and alicyclic epoxy resin among 100 parts by mass of component (B). The epoxy resin is 0 to 50 parts by mass.
Condition (2): The melt viscosity at 200 ° C. is 0.001 to 10 Pa · s, and the rate of change in melt viscosity after heating at 200 ° C. for 2 hours is 2 or less.

The method for producing a composite reinforcing fiber bundle according to claim 1, wherein the component (A) is provided with a sizing agent, and the mass ratio of the sizing agent and the component (B) is 0.001 to 0.5 / 1. .

The method for producing a composite reinforcing fiber bundle according to claim 2, wherein the sizing agent is a trifunctional or higher polyfunctional aliphatic epoxy.

The method for producing a composite reinforcing fiber bundle according to any one of claims 1 to 3, wherein the component (B) has an epoxy equivalent of 100 to 2500 g / eq.

The number average molecular weight of the component (B) is 500 to 3000. The method for producing a composite reinforcing fiber bundle according to any one of claims 1 to 4.

In the condition (1), the glycidyl ether type epoxy resin is a method for producing a composite reinforcing fiber bundle according to any one of claims 1 to 5, wherein the novolac type epoxy resin accounts for 50 to 100% by mass.

In the condition (1), the glycidyl ether type epoxy resin is 80 to 99 parts by mass and the glycidyl amine type epoxy resin is 1 to 20 parts by mass in 100 parts by mass of the component (B). A method for producing a composite reinforcing fiber bundle.

The method for producing a composite reinforcing fiber bundle according to any one of claims 1 to 7, wherein the reinforcing fiber bundle is a carbon fiber.

The method for producing a composite reinforcing fiber bundle according to claim 8, wherein the number of filaments of the carbon fiber bundle is 20,000 to 100,000.

The method for producing a composite reinforcing fiber bundle according to any one of claims 1 to 9, wherein in step (II), the maximum temperature of the component (B) is 150 to 400 ° C.

The molding material by which the thermoplastic resin (C) is adhere | attached on the composite reinforcing fiber bundle manufactured by the method in any one of Claims 1-10.

The molding material according to claim 11, wherein the composite reinforcing fiber bundle has a core structure and a core-sheath structure in which the component (C) is covered.

The molding material according to claim 11 or 12, which is cut into a length of 1 to 50 mm.