JPH04161450A - Method for forming formed body of composite material - Google Patents
Method for forming formed body of composite materialInfo
- Publication number
- JPH04161450A JPH04161450A JP28713990A JP28713990A JPH04161450A JP H04161450 A JPH04161450 A JP H04161450A JP 28713990 A JP28713990 A JP 28713990A JP 28713990 A JP28713990 A JP 28713990A JP H04161450 A JPH04161450 A JP H04161450A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- solution
- resin
- methylpyrrolidone
- composite material
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 20
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 69
- 239000004917 carbon fiber Substances 0.000 claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001879 gelation Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 36
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 description 16
- 239000000835 fiber Substances 0.000 description 13
- 239000011295 pitch Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電子・電気機器１機械部品などの素材として好
適な高強度の複合材料成形体の成形方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for molding a high-strength composite material molded body suitable as a material for mechanical parts of electronic and electrical equipment.
〔従来の技術及び発明が解決しようとする課題〕炭素繊
維は、その界面の接着性に乏しいため、これを成形する
にあたり、エポキシ樹脂など接着性に優れたマトリック
ス樹脂が用いられてきた。[Prior Art and Problems to be Solved by the Invention] Since carbon fibers have poor adhesive properties at their interfaces, matrix resins with excellent adhesive properties such as epoxy resins have been used to mold them.
このようにして得られる複合材料は、軽量で強度か大き
いため、スポーツ用品などの分野で用いられているが、
耐熱性か２００℃以下であることから、使用分野か制約
されるという問題があった。The composite materials obtained in this way are lightweight and strong, so they are used in fields such as sports equipment.
Since the heat resistance is 200° C. or less, there is a problem that the field of use is restricted.
また、この複合材料については、エポキシ樹脂は熱硬化
性であることから、欠陥部の修理かできないという問題
もあった。Another problem with this composite material is that since the epoxy resin is thermosetting, it is only possible to repair defective parts.
このような問題を解決するべく、様々な試みかなされて
いる。Various attempts have been made to solve these problems.
たとえば特開昭６０−２０９０３３号公報には、炭素繊
維と熱可塑性樹脂の繊維とをブレンドしたヤーン（コミ
ングルヤーン）を作り、これをクロス化した後に、複雑
形状物を成形する方法か示されている。For example, Japanese Patent Application Laid-Open No. 60-209033 discloses a method of making a yarn (commingle yarn) that is a blend of carbon fiber and thermoplastic resin fiber, forming it into a cloth, and then molding a complex-shaped object. ing.
しかしながら、この場合、炭素繊維と熱可塑性樹脂の繊
維という２種類の伸度や強度が異なる糸が混り合ってい
るため、ボビンからの解舒か困難であったり、あるいは
ケバか出やすかったりするなど、取扱いが容易でないほ
か、両繊維が相互に均一に分散しがたく、その結果、充
分な性能が得られないという問題かある。However, in this case, two types of yarns, carbon fiber and thermoplastic resin fiber, with different elongation and strength are mixed, so it may be difficult to unwind from the bobbin, or it may easily become fluffy. In addition to not being easy to handle, it is also difficult for both fibers to disperse uniformly, resulting in a problem in that sufficient performance cannot be obtained.
また特開昭６０−３６１５６号公報には、炭素繊維束の
繊維間隙に熱可塑性樹脂の粉末を入れ、これらを樹脂層
で被覆し、クロスに編んだ後、成形体をつくる方法か提
案されている。Furthermore, Japanese Patent Application Laid-open No. 60-36156 proposes a method in which thermoplastic resin powder is put into the fiber gaps of a carbon fiber bundle, these are covered with a resin layer, and after being knitted into a cross, a molded body is made. There is.
しかしなから、この場合にも、熱可塑性樹脂の粉末を、
炭素繊維束の繊維間隙に均一に分散させることか困難で
あり、この結果、均質で性能の高い成形体を得ることは
できないという問題を有している。However, in this case as well, thermoplastic resin powder is
It is difficult to uniformly disperse the carbon fibers in the fiber gaps of the carbon fiber bundle, and as a result, there is a problem in that it is impossible to obtain a homogeneous molded product with high performance.
本発明者は、このような従来の問題点を解消し、耐熱性
に優れた熱可塑性樹脂を炭素繊維間隙に均一に分散させ
ることによって、炭素繊維とマトリックス樹脂が緻密に
結合した高強度の複合材料成形体を提供することを目的
とするものである。The present inventor solved these conventional problems and created a high-strength composite in which carbon fibers and matrix resin are tightly bonded by uniformly dispersing a thermoplastic resin with excellent heat resistance in the gaps between carbon fibers. The object is to provide a material molded body.
すなわち本発明は、炭素繊維成形体に、ポリシアノアリ
ールエーテル樹脂のＮ−メチルピロリドン溶液を１８０
〜２０５℃において含浸させた後、該溶液のゲル化温度
以下に冷却し、次いでＮ−メチルピロリドンを蒸発除去
した後、３４０〜３８０℃において加圧成形することを
特徴とする複合材料成形体の成形方法を提供するもので
ある。That is, in the present invention, a solution of polycyanoarylether resin in N-methylpyrrolidone is added to a carbon fiber molded article at 180%
A composite material molded article, which is impregnated at ~205°C, cooled to a temperature below the gelation temperature of the solution, and then evaporated to remove N-methylpyrrolidone, and then pressure-molded at 340-380°C. The present invention provides a molding method.
本発明の方法では炭素繊維成形体を用いる。In the method of the present invention, a carbon fiber molded body is used.
このような炭素繊維成形体の元になる炭素繊維としては
、ピッチ系またはポリアクリロニトリル（ＰＡＮ）系の
いずれの炭素繊維も用いることかできるか、特にピッチ
系炭素繊維か好適に用いられる。As the carbon fibers that form the basis of such carbon fiber molded bodies, either pitch-based or polyacrylonitrile (PAN)-based carbon fibers can be used, and pitch-based carbon fibers are particularly preferably used.
このようなピッチ系炭素繊維は、例えば紡糸用ピッチと
して、光学的異方性相であるメソ相（メソフェーズ）を
含有するメソフェーズピッチ、または光学的等方性ピッ
チを用いる。これらピッチを紡糸し、繊維状ピッチ（ピ
ッチ繊維）を空気中において、通常、１５０〜３５０℃
の範囲の温度で不融化処理した後、３５０〜ｌ、 ００
０℃て一次炭化し、次いで、ｉ、 ｏｏｏ〜１．８００
℃て二次炭化して得られるものか挙げられる。Such pitch-based carbon fibers use mesophase pitch containing a mesophase, which is an optically anisotropic phase, or optically isotropic pitch, for example, as a pitch for spinning. These pitches are spun and the fibrous pitch (pitch fiber) is placed in the air at a temperature of usually 150 to 350°C.
After infusibility treatment at a temperature in the range of 350~l, 00
Primary carbonization at 0°C, then i, ooo ~ 1.800
Examples include those obtained by secondary carbonization at ℃.
本発明の方法において用いる炭素繊維成形体の元になる
炭素繊維としては、その引張強度か２００〜５００ ｋ
ｇ ／ ｍｍ ２．引張弾性率か１０〜５０ｔ／ｍｕ＋
２の範囲にあるものか好ましい。ここで引張強度が２０
０ｋｇ ／ ｍｍ ２未満の炭素繊維を用いたものであ
ると、最終的に得られる複合材料成形体の強度か不充分
なものとなってしまうため、好ましくない。The carbon fiber that is the source of the carbon fiber molded article used in the method of the present invention has a tensile strength of 200 to 500 k.
g/mm 2. Tensile modulus: 10-50t/mu+
Preferably, it is within the range of 2. Here the tensile strength is 20
If less than 0 kg/mm 2 of carbon fiber is used, the strength of the final composite material molded product will be insufficient, which is not preferable.
また、このような炭素繊維としては、通常、繊維径か１
〜１３μｍ、好ましくは７〜１０μｍの範囲のものであ
り、またフィラメント数か５００〜１００万本、特に２
．０００〜２４．０００本の繊維束からなるものが好ま
しい。In addition, such carbon fibers usually have a fiber diameter of 1
~13 μm, preferably 7~10 μm, and the number of filaments is 5 to 1 million, especially 2
．． Preferably, the fiber bundle consists of 000 to 24,000 fiber bundles.
本発明の方法では、上記の如き原料炭素繊維の表面を、
必要により、予め酸化処理しておくことか好ましい。In the method of the present invention, the surface of the raw carbon fiber as described above is
It is preferable to carry out oxidation treatment in advance if necessary.
ここで原料炭素繊維の表面酸化処理の仕方は特に制限は
なく、電解酸化法、気相酸化法、薬液酸化法等の通常行
なわれている方法でよいか、中でも電解酸化法は処理速
度が速く、しかも給電量。Here, there are no particular restrictions on the method of surface oxidation treatment of the raw material carbon fibers, and commonly used methods such as electrolytic oxidation, gas phase oxidation, and chemical oxidation may be used. Among them, electrolytic oxidation has a fast processing speed. , and the amount of power supplied.
電解液、濃度等を変えることで種々の表面状態か得られ
るため工業的に有利である。It is industrially advantageous because various surface states can be obtained by changing the electrolyte, concentration, etc.
このようにして必要に応じて、炭素繊維の表面を酸化処
理するか、炭素繊維表面の酸素原子／炭素原子（０／Ｃ
）の値が０．１〜０．５、特に０．１５〜０．２５の範
囲になるように炭素繊維の表面を酸化処理することが好
ましい。ここで酸素原子／炭素原子（０／Ｃ）の値が０
．１未満であると樹脂との接着性か悪く、一方、０．５
を超えると炭素繊維の強度か低下するため、いずれも好
ましくない。In this way, if necessary, the surface of the carbon fiber may be oxidized or the oxygen atom/carbon atom (0/C
) is preferably in the range of 0.1 to 0.5, particularly 0.15 to 0.25, on the surface of the carbon fiber. Here, the value of oxygen atom/carbon atom (0/C) is 0
．． When it is less than 1, the adhesion with the resin is poor; on the other hand, when it is 0.5
Exceeding this is not preferable because the strength of the carbon fiber decreases.
また同様に、炭素繊維表面の窒素原子／炭素原子（Ｎ／
Ｃ）の値か０．０１未満となるように、炭素繊維の表面
を酸化処理することが好ましい。これは電解液によって
はＨＮＯ，のように窒素原子を含むものかあり、充分に
洗浄しないと窒素原子が残ってしまい、樹脂に悪影響を
及ぼすからである。Similarly, nitrogen atoms/carbon atoms (N/
It is preferable to oxidize the surface of the carbon fiber so that the value of C) is less than 0.01. This is because some electrolytes, such as HNO, contain nitrogen atoms, and if they are not thoroughly cleaned, the nitrogen atoms will remain and have an adverse effect on the resin.
さらに本発明の方法においては、炭素繊維成形体の原料
として、比表面積か０．０５〜０．８０ｒｄ／ ｇの範
囲にある炭素繊維を用いることか好ましい。Further, in the method of the present invention, it is preferable to use carbon fibers having a specific surface area of 0.05 to 0.80 rd/g as the raw material for the carbon fiber molded article.
ここで炭素繊維の比表面積か０．０５ ｄ１ｇ未満であ
ると樹脂との接着性か悪く、一方、０．８０ｆＩｆ／ｇ
を超えると炭素繊維の強度か低下する。Here, if the specific surface area of carbon fiber is less than 0.05 d1g, the adhesion with the resin is poor, while on the other hand, it is 0.80 fIf/g.
If it exceeds this, the strength of the carbon fiber will decrease.
本発明の方法で用いる炭素繊維成形体は、上記炭素繊維
を用いて、炭素繊維クロス、炭素繊維ペーパー、炭素繊
維ヤーン、炭素繊維編物などに成形したものである。こ
こで炭素繊維クロスとしては平織、綾織り、朱子織りな
どが好適である。The carbon fiber molded article used in the method of the present invention is one molded into carbon fiber cloth, carbon fiber paper, carbon fiber yarn, carbon fiber knitted fabric, etc. using the above-mentioned carbon fibers. Here, plain weave, twill weave, satin weave, etc. are suitable as the carbon fiber cloth.
また、炭素繊維成形体としてはポリシアノアリールエー
テル樹脂を被覆した炭素繊維ヤーンを用いてもよい。こ
の炭素繊維ヤーンは１８０〜２０５℃の範囲のＮ−メチ
ルピロリドン溶液中にポリシアノアリールエーテル樹脂
を溶解させた溶液中に、炭素繊維を連続的に浸漬し、そ
の後、Ｎ−メチルピロリドンを除去することで得られる
。このようなポリシアノアリールエーテル樹脂のＮ−メ
チルピロリドン溶液は後述するものと同様のものである
。なお、炭素繊維へのポリシアノアリールエーテル樹脂
の被覆量は、炭素繊維束の含浸速度２時間、引取テンシ
ョンと溶液の濃度、温度、含浸回数等により変化するの
で、目的に応じて最適の条件を選択すればよい。Further, as the carbon fiber molded article, a carbon fiber yarn coated with a polycyanoaryl ether resin may be used. The carbon fiber yarn is prepared by continuously dipping the carbon fibers in a solution of polycyanoarylether resin dissolved in N-methylpyrrolidone solution at a temperature ranging from 180 to 205°C, and then removing the N-methylpyrrolidone. You can get it by doing that. Such a solution of polycyanoarylether resin in N-methylpyrrolidone is similar to that described below. The amount of polycyanoaryl ether resin coated on the carbon fibers varies depending on the impregnation speed of the carbon fiber bundle (2 hours), take-up tension, concentration of the solution, temperature, number of impregnations, etc., so select the optimal conditions depending on the purpose. Just choose.
さらに、このような炭素繊維ヤーンを平織り、朱子織り
なとしたクロスや、このクロスを多層に積層したもの、
あるいはこの炭素繊維ヤーンやクロスを種々の形状に編
んだ編物なとの炭素繊維成形体も好適に用いることがて
きる。ここて編物の形状としては、例えば帽子状（パラ
ボラアンテナ状）や３次元状のものなどが挙げられる。Furthermore, there are cloths made of carbon fiber yarns such as plain weave and satin weave, and cloths made by laminating these cloths in multiple layers.
Alternatively, a carbon fiber molded article such as a knitted fabric made of carbon fiber yarn or cloth knitted into various shapes can also be suitably used. Examples of the shape of the knitted fabric include a hat shape (parabolic antenna shape) and a three-dimensional shape.
本発明の方法では、上記の如き炭素繊維成形体に、ポリ
シアノアリールエーテル樹脂のＮ−メチルピロリドン溶
液を含浸させる。In the method of the present invention, a carbon fiber molded article as described above is impregnated with a solution of polycyanoarylether resin in N-methylpyrrolidone.
ここで用いるポリシアノアリールエーテル樹脂としては
ｐ−タロルフェノールを溶媒とする６０℃における極限
粘度〔η〕が０．２ｄｌ／ ｇ以上、好ましくは０．３
〜２．Ｏｄｌ／ｇのものである。ここで極限粘度〔η〕
が０．２ｄｌ／ ｇ未満のものであると、炭素繊維成形
体表面への付着量か少なく、付着ムラを生じやすく、又
炭素繊維成形体の強度や耐熱性に劣ったものとなる。一
方、極限粘度〔η〕か２、０ｄｌ／ ｇを超えると溶融
流動性か低下し、プリプレグとしたときの成形性が低下
するようになる。The polycyanoarylether resin used here has an intrinsic viscosity [η] of 0.2 dl/g or more, preferably 0.3 at 60°C using p-thalolphenol as a solvent.
~2. Odl/g. Here, the limiting viscosity [η]
If it is less than 0.2 dl/g, the amount of adhesion to the surface of the carbon fiber molded article will be small, uneven adhesion will likely occur, and the strength and heat resistance of the carbon fiber molded article will be poor. On the other hand, if the intrinsic viscosity [η] exceeds 2.0 dl/g, the melt fluidity decreases and the moldability when made into a prepreg decreases.
このようなポリシアノアリールエーテル樹脂は、好まし
くは、融点か３４０℃程度、ガラス転移点か１４５℃程
度、熱変形温度か１６５℃程度（繊維強化系では３３０
℃程度）の超耐熱性の熱可塑性樹脂である。Such a polycyanoaryl ether resin preferably has a melting point of about 340°C, a glass transition point of about 145°C, and a heat distortion temperature of about 165°C (for fiber-reinforced systems, it has a melting point of about 340°C).
It is a thermoplastic resin that is extremely heat resistant (around 30°F (°C)).
このようなポリシアノアリールエーテル樹脂として具体
的には例えば、式
などの繰り返し単位を有するホモポリマーまたは任意の
組合せのコポリマーなとを挙げることかてきる。Specific examples of such polycyanoaryl ether resins include homopolymers having repeating units of the formula and copolymers in any combination.
これらの重合体は、種々の方法により製造することかで
きるか、例えば次のような方法で製造することができる
。These polymers can be manufactured by various methods, for example, as follows.
本発明では、上記の如きポリシアノアリールエーテル樹
脂のＮ−メチルピロリドン溶液を用いる。In the present invention, a solution of the polycyanoarylether resin as described above in N-methylpyrrolidone is used.
二の溶液は、例えば次のようにして作製すればよい。The second solution may be prepared, for example, as follows.
すなわち、ポリシアノアリールエーテル樹脂としては、
パウダー状のものを用いる。ここでポリシアノアリール
エーテル樹脂としては、パウダー粒径か通常、１〜１０
０μｍ、好ましくは３０〜５０μｍのものを用いる。That is, as a polycyanoaryl ether resin,
Use powder form. Here, the powder particle size of the polycyanoaryl ether resin is usually 1 to 10
0 μm, preferably 30 to 50 μm.
このようなポリシアノアリールエーテル樹脂のパウダー
を、Ｎ−メチルピロリドン（ＮＭＰ）溶媒中に１〜２５
重量％、好ましくは１０〜２５重量％の割合て入れ、１
８０〜２０５℃１好ましくは１９０〜２０５℃の温度に
昇温する。その際、ミキサーで溶液を攪拌すると、溶液
が効率良く得られる。A powder of such a polycyanoaryl ether resin is dissolved in an N-methylpyrrolidone (NMP) solvent at a concentration of 1 to 25%.
% by weight, preferably 10-25% by weight, 1
The temperature is raised to 80-205°C, preferably 190-205°C. At this time, if the solution is stirred with a mixer, the solution can be obtained efficiently.
なお、溶液の濃度が２０〜２５重量％の範囲では攪拌の
為のミキサーだけでなくホモジナイザーも使用した方か
よい。また、昇温したときの温度か１８０℃未満ではポ
リシアノアリールエーテル樹脂ｄ脂か溶けにくいため好
ましくない。一方、２０５℃を超えるとＮＭＰの蒸発が
著しいため、好ましくない。Note that when the concentration of the solution is in the range of 20 to 25% by weight, it is better to use not only a mixer for stirring but also a homogenizer. Furthermore, if the temperature is lower than 180°C, the polycyanoaryl ether resin will be difficult to melt, which is not preferable. On the other hand, if the temperature exceeds 205°C, NMP evaporates significantly, which is not preferable.
本発明の方法においては、このようにして得られたポリ
シアノアリールエーテル樹脂か均一に溶解しているＮ−
メチルピロリドン溶液中に、前記した如き炭素繊維成形
体を含浸する。In the method of the present invention, the polycyanoarylether resin thus obtained is uniformly dissolved in N-
A carbon fiber molded article as described above is impregnated in a methylpyrrolidone solution.
ここで炭素繊維成形体への樹脂の含浸は、炭素繊維成形
体をステンレス製の枠等の治具で固定した後に行なうこ
とが好ましく、ポリシアノアリールエーテル樹脂のＮ−
メチルピロリドン溶液に含浸してもよいし、あるいは炭
素繊維成形体を予め容器中に入れておき、この溶液を注
入して含浸してもよい。Here, it is preferable to impregnate the carbon fiber molded body with the resin after fixing the carbon fiber molded body with a jig such as a stainless steel frame.
The carbon fiber molded article may be impregnated with a methylpyrrolidone solution, or the carbon fiber molded article may be placed in a container in advance and this solution may be poured into the container to impregnate it.
次に、この含浸成形体をポリシアノアリールエーテル樹
脂のＮ−メチルピロリドン溶液のゲル化温度以下に冷却
する。Next, this impregnated molded body is cooled to a temperature below the gelation temperature of the N-methylpyrrolidone solution of the polycyanoaryl ether resin.
ここで冷却方法としては、そのまま室温中で放置する方
法は簡便で低コストであるが、冷却速度を制御できる容
器を用いて冷却するのが、特に好ましい。Here, as a cooling method, a method of leaving it as it is at room temperature is simple and low cost, but it is particularly preferable to cool it using a container in which the cooling rate can be controlled.
この冷却は、通常、０℃からＮ−メチルピロリドン溶液
のゲル化温度以下の範囲となるように行なう。なお、ゲ
ル化温度は溶液濃度か高いほと高くなる。This cooling is usually carried out in a range from 0° C. to a temperature below the gelation temperature of the N-methylpyrrolidone solution. Note that the gelation temperature increases as the solution concentration increases.
含浸成形体か充分に冷却されたならば、この成形体を固
定治具ごと取出し、成形体のまわりに余分に付着してい
るゼリー状あるいはローソク状の固形物を取り除く。Once the impregnated molded body has been sufficiently cooled, the molded body is taken out together with the fixing jig, and excess jelly-like or candle-like solid matter adhering around the molded body is removed.
次いで、溶剤であるＮ−メチルピロリドンを蒸発除去す
る。Next, the solvent N-methylpyrrolidone is removed by evaporation.
Ｎ−メチルピロリドンを蒸発除去するには、例えばオー
ブン、ホットプレート、真空乾燥機、遠赤外乾燥機、熱
風循環乾燥機等を使用することかできる。例えば、真空
乾燥機を用いる場合には、２００℃，３ｔｏｒｒ未満の
圧力で１時間程度処理することが好ましい。To remove N-methylpyrrolidone by evaporation, an oven, hot plate, vacuum dryer, far-infrared dryer, hot air circulation dryer, etc. can be used, for example. For example, when using a vacuum dryer, it is preferable to perform the treatment at 200° C. and a pressure of less than 3 torr for about 1 hour.
最後に、成形体中のボイド等を除き、より一層緻密な組
織とする為、熱プレスやオートクレーブを用いて、加熱
、加圧を行なう。Finally, in order to remove voids and the like in the compact and create a more dense structure, heat and pressure are applied using a hot press or an autoclave.
加熱条件は通常、３４０〜３８０℃であり、また加圧成
形は通常のプレス成形機を用いて行なえばよい。さらに
、マツチドダイ方式で加熱、加圧を行なうこともできる
。The heating conditions are usually 340 to 380°C, and the pressure molding may be performed using a normal press molding machine. Furthermore, heating and pressurization can also be performed using a mated die method.
このようにして複合材料成形体を得ることができる。In this way, a composite material molded body can be obtained.
次に本発明を実施例により詳しく説明する。 Next, the present invention will be explained in detail with reference to examples.
実施例１
炭素繊維として、繊維径か１０μｍ、引張強度２３０
ｋｇ／ｍｍ２．弾性率２０ｔ／ｒｎｎ’の石油ピッチ系
炭素繊維を用いた。Example 1 As carbon fiber, fiber diameter is 10 μm, tensile strength is 230
kg/mm2. Petroleum pitch carbon fiber with an elastic modulus of 20t/rnn' was used.
また、ポリシアノアリールエーテル樹脂としては、２，
６−シクロロペンゾニトリルとレゾルシンとを炭酸カリ
ウムの存在下に反応させて得られた、下記の繰り返し単
位を有し、極限粘度〔η〕が１．２ｄｌ／ｇであり、ガ
ラス転移温度１４５℃、融点３４０℃であるものを用い
た。In addition, as polycyanoaryl ether resin, 2,
It is obtained by reacting 6-cyclopenzonitrile and resorcinol in the presence of potassium carbonate, has the following repeating unit, has an intrinsic viscosity [η] of 1.2 dl/g, and has a glass transition temperature of 145 ℃, and the melting point was 340℃.
上記の炭素繊維３０００本のヤーンを平織りして作成し
た織物（クロス）を、ステンレス製の枠に挟んで容器に
入れ、次いで、このクロス上に、２００℃に加熱した上
記ポリシアノアリールエーテル樹脂のＮ−メチル−２−
ピロリドンを溶媒とする濃度１０重量％の溶液を注入し
た。A fabric (cloth) made by plain-weaving 3000 carbon fiber yarns was placed in a container between stainless steel frames, and then the polycyanoarylether resin heated to 200°C was placed on top of the cloth. N-methyl-2-
A 10% by weight solution containing pyrrolidone as a solvent was injected.
次に、これを２５℃まて徐冷した。この間、クロスに含
浸した溶液は、約１５０℃においてゲル化した。Next, this was slowly cooled to 25°C. During this time, the solution impregnated into the cloth gelled at about 150°C.
次いで、この含浸クロスを減圧乾燥器に入れ、２００℃
，１ｔｏｒｒの条件下で１時間乾燥することにより、Ｎ
−メチル−２−ピロリドンを蒸発除去した。Next, this impregnated cloth was placed in a vacuum dryer and heated to 200°C.
, 1 torr for 1 hour.
-Methyl-2-pyrrolidone was removed by evaporation.
引続き、得られた含浸クロスをホットプレスにより、３
７０℃，４０ｋｇ／ｃｄで５分間加圧成形することによ
り、炭素繊維−ポリシアノアリールエーテル樹脂複合材
を得た。Subsequently, the obtained impregnated cloth was hot pressed for 3
A carbon fiber-polycyanoaryl ether resin composite material was obtained by pressure molding at 70° C. and 40 kg/cd for 5 minutes.
このようにして得た肉厚０．２０ｍｍの複合材を、１０
枚重ねにして、ホットプレスにより、３７０’Ｃ，４０
ｋｇ／ｃｄの条件下に１０分間加圧成形して、厚さ２ｍ
ｍの積層体を得た。The thus obtained composite material with a wall thickness of 0.20 mm was
Stacked and hot pressed at 370'C, 40
Pressure molded for 10 minutes under kg/cd conditions to a thickness of 2m.
A laminate of m was obtained.
この積層体より、たて５ｍｍ、 よこ５０世の試験片を
切り取り、これを用いてＡＳＴＭ Ｄ−２３４４に準拠
して層間剪断強度を測定した結果、１．１３０ ｋｇ／
ｃｎｆであった。A test piece of 5 mm in length and 50 in width was cut from this laminate, and the interlaminar shear strength was measured using this in accordance with ASTM D-2344, and the result was 1.130 kg/
It was cnf.
比較例１
実施例１で用いた炭素繊維（前者）に対し、実施例１と
同じポリシアノアリールエーテル樹脂を紡糸して得た糸
径２０μｍの繊維（後者）を、その混合割合か前者＝後
者か容量比で６０：４０となるように混合して、コミン
グルヤーンを得た。Comparative Example 1 A fiber with a thread diameter of 20 μm obtained by spinning the same polycyanoaryl ether resin as in Example 1 (latter) was added to the carbon fiber used in Example 1 (former) at a mixing ratio of the former = latter. The mixture was mixed in a volume ratio of 60:40 to obtain commingle yarn.
次いで、これを平織りして得た織物を、３７０”Ｃ，４
０ｋｇ／Ｃｉの条件下に加圧成形したのち、これを１０
枚重ねにして、同一条件下で加圧成形して積層体を得た
。ここで得られた積層体について実施例１と同様にして
測定した層間剪断強度は、８５３ｋｇ／ｃａｒてあった
。Next, the fabric obtained by plain weaving this was 370"C, 4
After pressure molding under the condition of 0 kg/Ci, this was
The sheets were stacked and pressure-molded under the same conditions to obtain a laminate. The interlaminar shear strength of the laminate thus obtained was measured in the same manner as in Example 1, and was 853 kg/car.
比較例２
実施例１て用いた炭素繊維の束を開繊しながら、これに
実施例１と同じポリシアノアリールエーテル樹脂の粉末
を付着させ、次いで、これを一方向にひき揃えてシート
状にした後、３７０℃９４０ｋｇ／ｃｄの条件下にホッ
トプレスして、肉厚０．１２５閣のシートを得た。この
シートを１６枚積層し、３７０℃，４０ｋｇ／ｃｏｒで
加圧成形して積層体を得た。ここで得られた積層体につ
いて、実施例１と同様にして測定した層間剪断強度は７
７１ ｋｇ／ｃｎｒであった。Comparative Example 2 While opening the carbon fiber bundle used in Example 1, powder of the same polycyanoaryl ether resin as in Example 1 was attached to it, and then it was pulled in one direction to form a sheet. After that, hot pressing was performed at 370° C. and 940 kg/cd to obtain a sheet with a wall thickness of 0.125 mm. Sixteen of these sheets were laminated and pressure molded at 370° C. and 40 kg/cor to obtain a laminate. Regarding the laminate obtained here, the interlaminar shear strength measured in the same manner as in Example 1 was 7.
It was 71 kg/cnr.
実施例２
炭素繊維として、繊維径カ月０μｍであり、引張強度３
７０ ｋｇ／ｍｍ”、弾性率２５ｔ／ｍｍ２であるもの
を用いたほかは、実施例１と同様にして、積層体を得た
。ここで得られた積層体について、実施例１と同様にし
て測定した層間剪断強度は１．２１５ｋｇ／ａ！であっ
た。Example 2 As carbon fiber, the fiber diameter is 0 μm and the tensile strength is 3
A laminate was obtained in the same manner as in Example 1, except that a material having a thickness of 70 kg/mm" and an elastic modulus of 25 t/mm2 was used. The laminate obtained here was treated in the same manner as in Example 1. The measured interlaminar shear strength was 1.215 kg/a!
実施例３
炭素繊維として、繊維径が７μｍであり、引張強度３６
０ ｋｇ／ｃｍ２．弾性率２４ｔ／ｍｍ２であるＰＡＮ
系炭素炭素繊維０００本の束を綾織りした織物を用い、
かつポリシアノアリールエーテル樹脂のＮ−メチル−２
−ピロリドン溶液の濃度が１２重量％のものを用いたほ
かは、実施例１と同様にして、積層体を得た。ここで得
られた積層体について、実施例１と同様にして測定した
層間剪断強度は９８０ ｋｇ／ｃｎｆてあった。Example 3 As carbon fiber, the fiber diameter is 7 μm and the tensile strength is 36
0 kg/cm2. PAN with elastic modulus of 24t/mm2
Using a fabric made by twill weaving 000 bundles of carbon-based carbon fibers,
and N-methyl-2 of polycyanoaryl ether resin
-A laminate was obtained in the same manner as in Example 1, except that a pyrrolidone solution having a concentration of 12% by weight was used. Regarding the laminate obtained here, the interlaminar shear strength measured in the same manner as in Example 1 was 980 kg/cnf.
実施例４
ポリシアノアリールエーテルとして、２．６−シクロロ
ペンゾニトリルとハイドロキノンと炭酸カリウムの存在
下に反応させて得られた、下記の繰り返し単位からなり
、かつ極限粘度〔η〕か１．５ｄｉ／ｇであるものを用
いたほかは、実施例１と同様にして、積層体を得た。こ
こで得られた積層体について、実施例１と同様にして測
定した層間剪断強度は１，００５ｋｇ／ｃｏ？であった
。Example 4 A polycyanoaryl ether was obtained by reacting 2,6-cyclopenzonitrile with hydroquinone in the presence of potassium carbonate, and consisted of the following repeating units, and had an intrinsic viscosity of [η] or 1. A laminate was obtained in the same manner as in Example 1, except that a material having a density of 5 di/g was used. Regarding the laminate obtained here, the interlaminar shear strength measured in the same manner as in Example 1 was 1,005 kg/co? Met.
実施例５
実施例１て用いた炭素繊維の織物を用いて、直径１０ａ
ｎの半球状成形体を作製した。Example 5 Using the carbon fiber fabric used in Example 1, a diameter of 10 a.
A hemispherical molded body of n was produced.
次に、この成形体を、実施例１と同じポリシアノアリー
ルエーテル樹脂の濃度１５重量％のＮ−メチル−２−ピ
ロリドン溶液に、２００℃において浸漬した後、２５℃
まで冷却した。この溶液は約１８０℃においてゲル化し
た。Next, this molded body was immersed at 200°C in an N-methyl-2-pyrrolidone solution containing the same polycyanoarylether resin as in Example 1 at a concentration of 15% by weight.
Cooled to . This solution gelled at about 180°C.
次に、この成形体を実施例１と同様に減圧乾燥して、Ｎ
−メチル−２−一ピロリドンを除去し、半球状の真ちゅ
う製金型に入れ、マツチドダイ方式により、３７０℃に
おいて４０ｋｇ／ｃｍで加圧成形した。この結果、極め
て緻密な組織を有する半球状成形体か得られた。Next, this molded body was dried under reduced pressure in the same manner as in Example 1, and N
-Methyl-2-1 pyrrolidone was removed, placed in a hemispherical brass mold, and press-molded at 40 kg/cm at 370° C. using a matte die method. As a result, a hemispherical molded body having an extremely dense structure was obtained.
本発明の成形方法によれば、炭素繊維とマトリックス樹
脂であるポリシアノアリールエーテル樹脂とか均一分散
し、両者が緻密に結合した成形体を容易に得ることかで
きる。According to the molding method of the present invention, it is possible to easily obtain a molded article in which the carbon fibers and the polycyanoaryl ether resin as the matrix resin are uniformly dispersed and the two are tightly bonded.
しかも、このようにして得られる成形体は、耐熱性２機
械的強度に極めて優れたものである。Moreover, the molded product thus obtained has extremely excellent heat resistance and mechanical strength.
したかって、本発明は電子、電気機器２機械分野などに
おいて有効に利用することができる。Therefore, the present invention can be effectively utilized in the fields of electronics, electrical equipment, and machinery.
、点さ二÷, dots two ÷
Claims (1)
樹脂のＮ−メチルピロリドン溶液を１８０〜２０５℃に
おいて含浸させた後、該溶液のゲル化温度以下に冷却し
、次いでＮ−メチルピロリドンを蒸発除去した後、３４
０〜３８０℃において加圧成形することを特徴とする複
合材料成形体の成形方法。(1) A carbon fiber molded body is impregnated with a solution of polycyanoarylether resin in N-methylpyrrolidone at 180 to 205°C, then cooled to below the gelation temperature of the solution, and then N-methylpyrrolidone is removed by evaporation. After that, 34
A method for molding a composite material molded article, the method comprising pressure molding at 0 to 380°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28713990A JPH04161450A (en) | 1990-10-26 | 1990-10-26 | Method for forming formed body of composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28713990A JPH04161450A (en) | 1990-10-26 | 1990-10-26 | Method for forming formed body of composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04161450A true JPH04161450A (en) | 1992-06-04 |
Family
ID=17713576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28713990A Pending JPH04161450A (en) | 1990-10-26 | 1990-10-26 | Method for forming formed body of composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04161450A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002037895A (en) * | 2000-07-21 | 2002-02-06 | Hitachi Chem Co Ltd | Method of manufacturing resin impregnated cloth for laminate board |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61163942A (en) * | 1985-01-11 | 1986-07-24 | バスフ アクチェン ゲゼルシャフト | Fiber reinforced composite material and production of moldedbody therefrom |
-
1990
- 1990-10-26 JP JP28713990A patent/JPH04161450A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61163942A (en) * | 1985-01-11 | 1986-07-24 | バスフ アクチェン ゲゼルシャフト | Fiber reinforced composite material and production of moldedbody therefrom |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002037895A (en) * | 2000-07-21 | 2002-02-06 | Hitachi Chem Co Ltd | Method of manufacturing resin impregnated cloth for laminate board |
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