JP2014051555A - Fiber reinforced plastic molding substrate - Google Patents
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本発明は、軽量な繊維強化プラスチックを製造するための、取り扱い性が良好で、かつ、変形性に優れ立体形状への賦型が容易である繊維強化プラスチック成形用基材に関するものである。 The present invention relates to a fiber-reinforced plastic molding base material that is easy to handle, has excellent deformability, and can be easily shaped into a three-dimensional shape for producing a lightweight fiber-reinforced plastic.
炭素繊維を強化材として使用した複合材料は、引張強度・引張弾性率が高く、線膨張係数が小さいので寸法安定性に優れることおよび、耐熱性、耐薬品性、耐疲労特性、耐摩耗性、電磁波シールド性、Ｘ線透過性にも優れることから、炭素繊維を強化材として使用した繊維強化プラスチックは、自動車、スポーツ・レジャー、航空・宇宙、一般産業用途に幅広く適用されている。 Composite materials using carbon fiber as a reinforcing material have high tensile strength / tensile modulus, low coefficient of linear expansion, so excellent dimensional stability, heat resistance, chemical resistance, fatigue resistance, wear resistance, The fiber reinforced plastic using carbon fiber as a reinforcing material has been widely applied to automobiles, sports / leisure, aviation / space, and general industrial applications because of its excellent electromagnetic shielding properties and X-ray transparency.
炭素繊維強化プラスチックを製造する方法としては、フィラメントワインディング法、プレス成型法、オートクレーブ法、射出成型法など、種々の手段が知られているが、３次元形状等の複雑な形状に適した成形方法として、ＳＭＣ（シートモールディングコンパウンド）等の不連続な強化繊維からなる基材が挙げられる。ＳＭＣとは、熱硬化性樹脂を含浸した２５ｍｍ程度の長さを持つチョップドストランドという繊維構造体を成形型内にシート状に配置した後、加熱、加圧することによりプラスチックを成形するものであり、比較的流動性が高いため、複雑な立体構造を形成することが可能であるが、一方、シート化工程において、チョップドストランドの分布ムラ、配向ムラが必然的に生じているため、機械的特性に均一なプラスチックを成形することは難しかった。 Various methods such as filament winding method, press molding method, autoclave method, injection molding method and the like are known as methods for producing carbon fiber reinforced plastic, but a molding method suitable for a complicated shape such as a three-dimensional shape. And a substrate made of discontinuous reinforcing fibers such as SMC (sheet molding compound). SMC is to mold a plastic by placing a fiber structure called chopped strand impregnated with a thermosetting resin into a sheet shape in a mold, followed by heating and pressing. Due to its relatively high fluidity, it is possible to form a complex three-dimensional structure, but on the other hand, in the sheeting process, uneven distribution of chopped strands and uneven alignment are inevitably generated, resulting in mechanical properties. It was difficult to mold a uniform plastic.
一方、リサイクル性を向上させるために熱可塑性樹脂を強化繊維にプルトリュージョン法、樹脂含浸法、フィルム積層法などを用いて賦与する方法も試みられているが、生産性、均一性、プレス時の樹脂の濡れ性などの観点から、機械特性とコストを満足するものは得られていない。 On the other hand, in order to improve recyclability, a method of applying a thermoplastic resin to reinforcing fibers by using a pultrusion method, a resin impregnation method, a film lamination method, etc. has been tried. From the viewpoint of the wettability of the resin, no material satisfying the mechanical properties and cost has been obtained.
本発明の目的は、取扱い性が良好であり、変形性に優れ、立体形状への賦型が容易であり、機械的特性に優れた繊維強化プラスチックが得られる繊維強化プラスチック成形用基布を提供することにある。 An object of the present invention is to provide a fiber reinforced plastic molding base fabric that has good handleability, excellent deformability, can be easily molded into a three-dimensional shape, and provides a fiber reinforced plastic excellent in mechanical properties. There is to do.
本発明者が、検討した結果、強化繊維および熱可塑性繊維を一定の条件で混合した基材とすることにより、機械的特性に優れたプラスチック成形物を得るための、均一で取り扱い性、立体成形性に優れたプラスチック成形用基材を提供できることを見出した。 As a result of the inventor's study, uniform and easy-to-handle, three-dimensional molding to obtain a plastic molded article having excellent mechanical properties by using a base material in which reinforcing fibers and thermoplastic fibers are mixed under certain conditions. It has been found that a plastic molding substrate having excellent properties can be provided.
かくして本発明によれば、強化繊維と熱可塑性繊維とからなり、強化繊維：熱可塑性繊維が重量比で５：９５〜７０：３０であり、任意の一方向の伸度Ｅ１とこれと直角に交わる方向の伸度Ｅ２がいずれも３０％以上、かつ、Ｅ１／Ｅ２＝０．８〜１．２であることを特徴とする繊維強化プラスチック成形用基材が提供される。また、上記の繊維強化プラスチック成形用基材を熱可塑性繊維の融点または軟化点以上の温度で加熱処理または加熱加圧処理してなる繊維強化プラスチックが提供される。 Thus, according to the present invention, the reinforcing fiber and the thermoplastic fiber are composed of the reinforcing fiber and the thermoplastic fiber, and the weight ratio of the fiber is 5:95 to 70:30, and the elongation E1 in any one direction is perpendicular to this. There is provided a fiber-reinforced plastic molding substrate characterized in that the elongation E2 in the intersecting direction is 30% or more and E1 / E2 = 0.8 to 1.2. Moreover, the fiber reinforced plastic formed by heat-processing or heat-pressurizing the said fiber reinforced plastic shaping | molding base material at the temperature more than melting | fusing point or softening point of a thermoplastic fiber is provided.
本発明の繊維強化プラスチック成形用基材は、高い機械的物性を示すことはもちろん、マトリックスである熱可塑繊維と強化繊維とが、交絡した不織布構造を有することにより、均一で取り扱い性に優れ、かつ非連続繊維を用いることによる流動性により、立体成形性に優れている。 The fiber-reinforced plastic molding substrate of the present invention not only exhibits high mechanical properties, but also has a non-woven structure in which thermoplastic fibers and reinforcing fibers as a matrix are entangled, so that it is uniform and excellent in handleability. In addition, the three-dimensional formability is excellent due to the fluidity by using discontinuous fibers.
したがって、上記基材は、プルトリュージョン法などにより製造されたチョップドストランドを金型内にセットする方法や、強化繊維に樹脂を含浸する方法に比べて極めて取り扱いやすく、均一性に優れる。また、強化繊維基材にフィルムを積層しプレスする方法などに比べて、格段に柔軟性に富んだ基材を提供することができる。 Therefore, the substrate is extremely easy to handle and excellent in uniformity compared to a method of setting chopped strands manufactured by a pultrusion method or the like in a mold or a method of impregnating reinforcing fibers with a resin. In addition, it is possible to provide a substrate that is significantly more flexible than a method of laminating and pressing a film on a reinforcing fiber substrate.
また、本発明の基材では、射出成形のように炭素繊維が切断されて短くなるといったことがなく、繊維間の交絡を成形できるため、成形体として十分な強度や弾性率を発揮することができる。また、熱可塑性樹脂が繊維の形状で他の繊維間に存在し、かつ交絡しているため、従来のプルトリュージョン法、樹脂含浸法、フィルム積層法に比べて、シート状物の取り扱い性（持ち運び性など）に優れ、熱プレス等の工程において、これら熱可塑繊維が溶融して十分に強化繊維の隙間に浸透し、かつ流動性に優れることから、複雑な形状を賦形する立体成形性を有し、強度、弾性率、特に耐衝撃性を優れた繊維強化プラスチックを容易に得ることができる。 Further, in the base material of the present invention, the carbon fiber is not cut and shortened as in the case of injection molding, and the entanglement between the fibers can be molded, so that sufficient strength and elastic modulus can be exhibited as a molded body. it can. In addition, since the thermoplastic resin exists in the form of fibers and is entangled with other fibers, it is easier to handle the sheet-like material than the conventional pultrusion method, resin impregnation method, and film lamination method ( Excellent portability, etc. In the process of hot pressing, etc., these thermoplastic fibers melt and sufficiently penetrate into the gaps of reinforcing fibers, and have excellent fluidity, so that three-dimensional formability that shapes complex shapes It is possible to easily obtain a fiber-reinforced plastic having excellent strength and elastic modulus, particularly impact resistance.
本発明の繊維強化プラスチック成形用基材（以下、単に基材と称することがある）は、これを加熱処理、または加熱加圧処理することによって、熱可塑性繊維を溶融し、繊維強化プラスチックを成形することができる基材である。 The fiber-reinforced plastic molding substrate of the present invention (hereinafter sometimes simply referred to as a substrate) is heat-treated or heat-pressed to melt thermoplastic fibers and form fiber-reinforced plastic. It is a substrate that can be made.
本発明の基材は強化繊維と熱可塑性繊維とからなり、強化繊維：熱可塑性繊維が重量比で５：９５〜７０：３０であり、好ましくは２０：８０〜６０：４０である。強化繊維の重量比が５重量％未満では、十分な力学的特性、すなわち曲げ強度や、曲げ弾性率を得ることができず、一方、熱可塑性樹脂の重量比が３０重量％未満では、熱可塑性繊維を溶融し十分に繊維間に含浸させて繊維強化プラスチックを成形するのが難しくなる。 The base material of this invention consists of a reinforced fiber and a thermoplastic fiber, and a reinforced fiber: thermoplastic fiber is 5: 95-70: 30 by weight ratio, Preferably it is 20: 80-60: 40. If the weight ratio of the reinforcing fibers is less than 5% by weight, sufficient mechanical properties, that is, bending strength and flexural modulus cannot be obtained. On the other hand, if the weight ratio of the thermoplastic resin is less than 30% by weight, thermoplasticity is not obtained. It becomes difficult to mold the fiber reinforced plastic by melting and sufficiently impregnating the fibers between the fibers.
本発明に用いる強化繊維は、炭素繊維、および／または、融点、軟化点、または熱分解開始温度が２５０℃以上の耐熱性有機繊維であることが好ましい。特に、炭素繊維のみを用いるか、耐衝撃性を高めるため、炭素繊維と耐熱性有機繊維とを併用することが望ましい。この際、炭素繊維：耐熱性有機繊維は重量比で、好ましくは１００：０〜４０：６０、より好ましくは９０：１０〜４０：６０、さらに好ましくは７０：３０〜４０：６０である。炭素繊維の割合が少ないと曲げ強度や曲げ弾性率といった優れた機械的特性が得られ難くなる傾向にある。一方で、耐熱性有機繊維を上記割合で含有させることにより耐衝撃性を向上させる上で有利である。 The reinforcing fibers used in the present invention are preferably carbon fibers and / or heat-resistant organic fibers having a melting point, a softening point, or a thermal decomposition starting temperature of 250 ° C. or higher. In particular, it is desirable to use only carbon fibers or to use carbon fibers and heat-resistant organic fibers in combination in order to improve impact resistance. Under the present circumstances, carbon fiber: heat-resistant organic fiber is a weight ratio, Preferably it is 100: 0-40: 60, More preferably, it is 90: 10-40: 60, More preferably, it is 70: 30-40: 60. When the proportion of carbon fiber is small, excellent mechanical properties such as bending strength and flexural modulus tend to be difficult to obtain. On the other hand, it is advantageous to improve impact resistance by containing the heat-resistant organic fiber in the above ratio.
本発明で用いる炭素繊維としては、引張強度３０００ＭＰａ以上、弾性率２００ＧＰａ以上の炭素繊維が好ましい。前記炭素繊維の原料としては特に限定するものではないが、ポリアクリロニトリル（ＰＡＮ）系炭素繊維、ピッチ系炭素繊維、レーヨン系炭素繊維等が例示できる。これらの炭素繊維のうち、取扱性能、製造工程通過性能に適したＰＡＮ系炭素繊維が特に好ましい。 The carbon fiber used in the present invention is preferably a carbon fiber having a tensile strength of 3000 MPa or more and an elastic modulus of 200 GPa or more. Although it does not specifically limit as a raw material of the said carbon fiber, A polyacrylonitrile (PAN) type | system | group carbon fiber, a pitch type | system | group carbon fiber, a rayon type | system | group carbon fiber etc. can be illustrated. Of these carbon fibers, PAN-based carbon fibers suitable for handling performance and production process passing performance are particularly preferred.
本発明における炭素繊維の形態は、加工性の観点から、カットファイバー（短繊維）であることが好ましく、なかでも高い剛性を保持するために、繊維長は好ましくは１０〜１５０ｍｍ、より好ましくは２０〜１００ｍｍであり、さらに好ましくは２０〜８０ｍｍ、さらにより好ましくは２０〜６０ｍｍである。また、同様の観点から、繊維径は好ましくは５〜１００μｍ、より好ましくは５〜８０μｍ、さらに好ましくは５〜６０μｍである。 The form of the carbon fiber in the present invention is preferably a cut fiber (short fiber) from the viewpoint of processability, and the fiber length is preferably 10 to 150 mm, more preferably 20 in order to maintain high rigidity. It is -100 mm, More preferably, it is 20-80 mm, More preferably, it is 20-60 mm. From the same viewpoint, the fiber diameter is preferably 5 to 100 μm, more preferably 5 to 80 μm, and still more preferably 5 to 60 μm.
本発明で耐熱有機繊維とは、特に限定されるものではなく、例えば、芳香族ポリアミド（アラミド）、芳香族ポリエーテルアミド、ポリパラフェニレンベンゾビスオキサゾール、ポリベンズイミダゾール、ポリイミド、ポリエーテルエーテルケトン、ポリエーテルイミドなどが好ましく使用できる。なかでも耐衝撃性、生産性、価格などからアラミド繊維が好ましく使用できる。また、炭素繊維と同時に加工する際の加工性の観点から、カットファイバー（短繊維）であることが好ましく、なかでも高い耐衝撃性を保持するために、繊維長は好ましくは２０〜１２０ｍｍ、より好ましくは３５〜８０ｍｍ、さらに好ましくは３５〜６０ｍｍである。 In the present invention, the heat-resistant organic fiber is not particularly limited. For example, aromatic polyamide (aramid), aromatic polyether amide, polyparaphenylene benzobisoxazole, polybenzimidazole, polyimide, polyether ether ketone, Polyetherimide and the like can be preferably used. Among these, aramid fibers can be preferably used from the viewpoint of impact resistance, productivity, and price. Further, from the viewpoint of workability when processing simultaneously with carbon fibers, cut fibers (short fibers) are preferable, and in order to maintain high impact resistance, the fiber length is preferably 20 to 120 mm. Preferably it is 35-80 mm, More preferably, it is 35-60 mm.
本発明におけるアラミド繊維とは、芳香族ジカルボン酸成分と芳香族ジアミン成分、もしくは芳香族アミノカルボン酸成分から構成される芳香族ポリアミド、又はこれらの芳香族共重合ポリアミドからなるポリマーであり、例えばポリパラフェニレンテレフタルアミド、コポリパラフェニレン・３，４’−オキシジフェニレンテレフタルアミド、ポリメタフェニレンイソフタルアミドなどが例示できる。特にコポリパラフェニレン・３，４’−オキシジフェニレンテレフタルアミドが、耐衝撃性の点から好ましい。 The aramid fiber in the present invention is an aromatic polyamide composed of an aromatic dicarboxylic acid component and an aromatic diamine component, or an aromatic aminocarboxylic acid component, or a polymer composed of these aromatic copolyamides. Examples thereof include paraphenylene terephthalamide, copolyparaphenylene 3,4'-oxydiphenylene terephthalamide, and polymetaphenylene isophthalamide. In particular, copolyparaphenylene 3,4'-oxydiphenylene terephthalamide is preferable from the viewpoint of impact resistance.
本発明に用いる熱可塑性繊維は、熱可塑性樹脂を原料とし、一般的な溶融紡糸法により紡糸される繊維状物であって、原料となる熱可塑性樹脂としては、ポリプロプピレン樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリカーボネート樹脂、ＡＢＳ樹脂が好ましく使用される。 The thermoplastic fiber used in the present invention is a fibrous material spun from a thermoplastic resin as a raw material and is spun by a general melt spinning method. The thermoplastic resin used as a raw material is a polypropylene resin or a polyester resin. Polyamide resins, polycarbonate resins and ABS resins are preferably used.
上記の熱可塑性樹脂は、ＩＳＯ １１３３に準拠して３００℃、荷重１．２ｋｇにて測定した、メルトボリュームフローレイトが、好ましくは１２〜６０ｃｍ３／１０分、より好ましくは１６〜４０ｃｍ３／１０分、さらに好ましくは１６〜３０ｃｍ３／１０分であることが好ましい。上記の溶融特性を有することにより、熱可塑繊維を溶融した際、強化繊維の繊維間に該樹脂が十分に含浸し、さらに得られる繊維強化プラスチックの剛性、耐衝撃性が容易となる。特に、熱可塑性樹脂としてポリカーボネート樹脂を用いる場合、上記メルトボリュームフローレイトを有する樹脂を用いることで、より顕著な効果得られることがわかった。 The thermoplastic resin, 300 ° C. in compliance with ISO 1133, measured at a load 1.2 kg, melt volume flow rate is preferably 12~60cm 3/10 min, more preferably 16~40cm 3/10 Min, more preferably 16 to 30 cm 3/10 min. By having the above melting characteristics, when the thermoplastic fiber is melted, the resin is sufficiently impregnated between the fibers of the reinforcing fiber, and the rigidity and impact resistance of the resulting fiber reinforced plastic are facilitated. In particular, it has been found that when a polycarbonate resin is used as the thermoplastic resin, a more remarkable effect can be obtained by using the resin having the melt volume flow rate.
本発明における熱可塑性繊維の形態は、また、炭素繊維や耐熱有機繊維と同時に加工する際の加工性の観点から、カットファイバー（短繊維）であることが好ましく、繊維長は好ましくは２０〜１５０ｍｍ、より好ましくは３０〜１００ｍｍ、さらに好ましくは３５〜８０ｍｍ、よりさらに好ましくは３５〜６５ｍｍである。また、同様の観点から、繊維径は、好ましくは５〜１５０μｍ、より好ましくは５〜１００μｍ、さらに好ましくは５〜６０μｍである。 The form of the thermoplastic fiber in the present invention is preferably a cut fiber (short fiber), and the fiber length is preferably 20 to 150 mm from the viewpoint of processability when processing simultaneously with carbon fiber and heat-resistant organic fiber. More preferably, it is 30-100 mm, More preferably, it is 35-80 mm, More preferably, it is 35-65 mm. From the same viewpoint, the fiber diameter is preferably 5 to 150 μm, more preferably 5 to 100 μm, and still more preferably 5 to 60 μm.
本発明は、繊維強化プラスチック成形用の基材として用いることのできる強化繊維と熱可塑性繊維を混合したものである。強化繊維を予めマトリックス樹脂となる熱可塑性繊維と混合することにより、均一な基材を作成可能であり、例えばポリカーボネート樹脂のように溶融時の粘度が高い樹脂であっても、強化繊維近傍にマトリックス樹脂を存在させることが可能となるため、強化繊維とマトリックス樹脂を容易に密着させることができる。 The present invention is a mixture of reinforced fibers and thermoplastic fibers that can be used as a substrate for molding fiber reinforced plastics. It is possible to create a uniform base material by mixing the reinforcing fibers with the thermoplastic fibers that become the matrix resin in advance. Even if the resin has a high viscosity at the time of melting, such as a polycarbonate resin, the matrix is located near the reinforcing fibers. Since the resin can be present, the reinforcing fibers and the matrix resin can be easily adhered.
本発明で用いるシート状の基布としては、不織布の形態であることが好ましく、乾式不織布、湿式不織布のいずれもが使用可能であるが、剛性、耐衝撃性を特に要求される製品においては、繊維長の長いことが有益であるため、乾式不織布法にて作成することがより好ましい。また、繊維は開繊機、カードなどの工程により繊維を開繊、混合することができるが、この際、一方向に引き揃えられることが剛性、耐衝撃性をより向上させる。 The sheet-like base fabric used in the present invention is preferably in the form of a nonwoven fabric, and any of a dry nonwoven fabric and a wet nonwoven fabric can be used, but in products that particularly require rigidity and impact resistance, Since it is beneficial to have a long fiber length, it is more preferable to prepare by a dry nonwoven fabric method. In addition, the fibers can be opened and mixed by a process such as a spreader or a card. In this case, the fibers can be aligned in one direction to further improve rigidity and impact resistance.
一方、湿式不織布法においては、完成した繊維強化プラスチックの剛性面では劣るものの、黒鉛、セラミックなどに代表されるフィーラーを同時に添加することにより、耐熱性、導電性、蓄熱性、伝熱性、電磁波遮蔽性などの新たな機能を追加した繊維強化プラスチックの作成が可能であり、非常に有用である。 On the other hand, in the wet nonwoven fabric method, although the finished fiber reinforced plastic is inferior in rigidity, heat resistance, conductivity, heat storage, heat transfer, electromagnetic shielding are added by simultaneously adding a feeler represented by graphite, ceramic, etc. It is possible to create a fiber reinforced plastic with new functions such as properties, which is very useful.
本発明において、強化繊維と熱可塑性繊維とが、少なくとも一部で交絡していることが好ましい。かかる交絡としては、厚さ方向に切断した基材の切断面を、走査型電子顕微鏡（倍率：１２倍）にて観察し、基材の厚さの半分以上の長さにわたって、厚さ方向（厚さ方向に対し、±４５°以内の方向を含む）に配列している５本以上の短繊維が絡み合って集束した繊維束が、基材表面を観察し１ｃｍ２当たり１ケ以上あることが好ましい。かかる交絡の存在により、基材の取扱いが容易になり、かつ、立体成形性においても有利な構造となる。よって、あまり上記交絡が多すぎても、基材が硬くなる傾向にあり、強化繊維と熱可塑性繊維とが両方で５本以上絡み合った繊維束の数（交絡数）は、基材表面において、好ましくは１〜５０ケ／ｃｍ２であり、より好ましくは１〜２０ケ／ｃｍ２である。なお、この交絡は、ニードルパンチ不織布の場合は針の打ち込み密度により、ウォーターニードルの場合は水柱の密度により、湿式不織布の場合は繊維の水中への分散、撹拌の条件の調整により上記範囲とすることができる。 In the present invention, it is preferable that the reinforcing fiber and the thermoplastic fiber are entangled at least partially. As such entanglement, the cut surface of the base material cut in the thickness direction is observed with a scanning electron microscope (magnification: 12 times), and the thickness direction (over the length of more than half the thickness of the base material ( The fiber bundle in which five or more short fibers arranged in a direction (including a direction within ± 45 ° with respect to the thickness direction) are entangled and focused is observed at least one piece per 1 cm 2 by observing the substrate surface. preferable. The presence of such entanglement facilitates the handling of the base material and provides an advantageous structure in terms of three-dimensional formability. Therefore, even if there is too much entanglement, the substrate tends to be hard, and the number of fiber bundles (entanglement number) in which five or more reinforcing fibers and thermoplastic fibers are entangled with each other is Preferably it is 1-50 / cm < 2 >, More preferably, it is 1-20 / cm < 2 >. This entanglement is within the above range by adjusting the needle driving density in the case of a needle punched nonwoven fabric, by the density of the water column in the case of a water needle, and by adjusting the conditions of dispersion and stirring of fibers in the case of a wet nonwoven fabric. be able to.
また、本発明においては、強化繊維同士、強化繊維が炭素繊維と耐熱有機繊維からなる場合、それらが少なくとも一部で交絡していることが好ましい。これによって、熱可塑性樹脂中に強化繊維が交絡せずに含有される繊維強化プラスチックと対比し、高い剛性や耐衝撃性を発揮することができる。かかる観点から、上記交絡の状態としては、強化繊維と熱可塑性繊維、または、強化繊維同士が不織布形状として互いの繊維が交絡していることが好ましい。 Moreover, in this invention, when reinforcing fiber consists of carbon fiber and a heat resistant organic fiber, it is preferable that they are entangled at least partially. As a result, it is possible to exhibit high rigidity and impact resistance as compared with the fiber-reinforced plastic that is contained in the thermoplastic resin without entanglement of the reinforcing fiber. From this point of view, the entangled state is preferably that the reinforcing fibers and the thermoplastic fibers, or the reinforcing fibers are in a nonwoven fabric shape, and the fibers are entangled with each other.
また、本発明においては、強化繊維同士、強化繊維が炭素繊維と耐熱有機繊維からなる場合、それらが少なくとも一部で交絡していることが好ましい。これによって、熱可塑性樹脂中に強化繊維が交絡せずに含有される繊維強化プラスチックと対比し、高い剛性や耐衝撃性を発揮することができる。かかる観点から、上記交絡の状態としては、強化繊維と熱可塑性繊維、または、強化繊維同士が不織布形状として互いの繊維が交絡していることが好ましい。 Moreover, in this invention, when reinforcing fiber consists of carbon fiber and a heat resistant organic fiber, it is preferable that they are entangled at least partially. As a result, it is possible to exhibit high rigidity and impact resistance as compared with the fiber-reinforced plastic that is contained in the thermoplastic resin without entanglement of the reinforcing fiber. From this point of view, the entangled state is preferably that the reinforcing fibers and the thermoplastic fibers, or the reinforcing fibers are in a nonwoven fabric shape, and the fibers are entangled with each other.
本発明においては、基材の任意の一方向の伸度Ｅ１とこれと直角に交わる方向の伸度Ｅ２がいずれも３０％以上、好ましくは４０％以上、かつ、Ｅ１／Ｅ２＝０．８〜１．２、好ましくは０．８５〜１．１５であることが肝要である。上記伸度が３０％未満であると、基材が金型の壁に沿わず、十分な立体成形性を得にくくなる。一方、あまり基材の伸度があまり大きすぎても取扱い性が悪くなるため、該伸度は好ましくは９０％以下、より好ましくは８０％以下、さらに好ましくは７０％以下であることが望ましい。また、Ｅ１／Ｅ２が０．８〜１．２の範囲から外れる場合は、立体成形後に適正な厚みを得るのが難しくなることがわかった。 In the present invention, the elongation E1 in any one direction of the base material and the elongation E2 in the direction perpendicular to this are both 30% or more, preferably 40% or more, and E1 / E2 = 0.8 to It is important that the ratio is 1.2, preferably 0.85 to 1.15. When the elongation is less than 30%, the base material does not follow the mold wall, and it becomes difficult to obtain sufficient three-dimensional moldability. On the other hand, if the elongation of the base material is too large, the handleability deteriorates. Therefore, the elongation is preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less. Moreover, when E1 / E2 deviated from the range of 0.8-1.2, it turned out that it becomes difficult to obtain appropriate thickness after three-dimensional shaping.
一般に、強化繊維は高モジュラスであり、基材の伸度を３０％以上とするためには、熱可塑性繊維の伸度を高く設計することが望ましい。特に融点や軟化点が高く、溶融粘度が高い熱可塑ポリマーからなる熱可塑性繊維を用いた場合、該繊維の伸度を高くすることにより、基材の柔軟性を高めることができる。よって、熱可塑性繊維の伸度は、最大強度伸度として、好ましくは３０％以上、より好ましくは４５％以上、さらに好ましくは５５％以上である。一方、伸度があまり大きすぎても、ニードルパンチ等で繊維が伸び成形性が悪くなるため、好ましくは１５０％以下、より好ましくは１２０％以下、さらに好ましくは１００％以下とするのが望ましい。特に、熱可塑性繊維としてポリカーボネート繊維を用いる場合は、上記伸度とすることが好ましい。 In general, the reinforcing fiber has a high modulus, and it is desirable to design the thermoplastic fiber with a high elongation in order to make the elongation of the base material 30% or more. In particular, when a thermoplastic fiber made of a thermoplastic polymer having a high melting point and softening point and a high melt viscosity is used, the flexibility of the substrate can be increased by increasing the elongation of the fiber. Therefore, the elongation of the thermoplastic fiber is preferably 30% or more, more preferably 45% or more, and further preferably 55% or more as the maximum strength elongation. On the other hand, even if the elongation is too large, the fiber is stretched by needle punch or the like and the formability is deteriorated. Therefore, it is preferably 150% or less, more preferably 120% or less, and still more preferably 100% or less. In particular, when polycarbonate fiber is used as the thermoplastic fiber, the above elongation is preferable.
また、基材をニードルパンチ不織布とする場合は、針の打ち込み密度を、好ましくは２００〜８００本／ｃｍ２、好ましくは３００〜６００本／ｃｍ２とすることが望ましい。打ち込み密度が２００本／ｃｍ２未満では、十分に繊維同士を交絡させることができず、基材の形態維持性が低下し、繊維強化プラスチックに立体成型する際に目付が変動し易くなる。一方、打ち込み密度が７００本／ｃｍ２を超えると、基材の伸度が低下し易くなり好ましくない。 Moreover, when making a base material into a needle punched nonwoven fabric, it is desirable that the driving density of the needle is preferably 200 to 800 / cm 2 , and preferably 300 to 600 / cm 2 . If the driving density is less than 200 fibers / cm 2 , the fibers cannot be sufficiently entangled, the form maintainability of the base material is lowered, and the basis weight tends to fluctuate when three-dimensionally molded into fiber reinforced plastic. On the other hand, if the driving density exceeds 700 / cm 2 , the elongation of the base material tends to decrease, which is not preferable.
さらに、上記ニードルパンチ不織布を成形する際、例えば、ランダムウェーバー機を用いるか、針の打ち込み数が不織布の長さ方向と幅方向が同程度となるよう配列したカード機を用いることで、Ｅ１／Ｅ２を上記範囲とすることができる。 Further, when forming the needle punched nonwoven fabric, for example, by using a random weber machine, or by using a card machine in which the number of needles is arranged so that the length direction and the width direction of the nonwoven fabric are approximately the same, E1 / E2 can be within the above range.
また、基材の１枚の目付は、好ましくは５０〜５００ｇ／ｃｍ２、より好ましくは７０〜４００ｇ／ｃｍ２、さらに好ましくは７０〜３００ｇ／ｃｍ２である。目付が５０ｇ／ｃｍ２未満では取扱い性が悪くなる傾向があり、一方、目付が５００ｇ／ｃｍ２を超えると基材が硬くなり立体成形性が低下する傾向にある。 The basis weight of one substrate is preferably 50 to 500 g / cm 2 , more preferably 70 to 400 g / cm 2 , and still more preferably 70 to 300 g / cm 2 . When the basis weight is less than 50 g / cm 2 , the handleability tends to be poor. On the other hand, when the basis weight exceeds 500 g / cm 2 , the substrate becomes hard and the three-dimensional formability tends to be lowered.
本発明の基材を用いて繊維強化プラスチックを成形する際は、基材を１枚または複数積層して用いることができる。本発明においては、１枚の基布の目付を上記範囲とすることにより、積層数を増やしても、基材が複雑な金型にも柔軟に適応して、立体成形を容易に行うことができる。 When molding a fiber reinforced plastic using the substrate of the present invention, one or more substrates can be laminated and used. In the present invention, by setting the basis weight of one base fabric within the above range, even if the number of layers is increased, the base material can be flexibly adapted to a mold having a complicated base material, and three-dimensional molding can be easily performed. it can.
繊維強化プラスチックの成型方法としては、プレス成型、スタンパブル成型などが好適例として示されるが、一般的な熱圧成型法は全て適用可能である。この際、熱可塑性繊維の融点または軟化点以上の温度で加熱または加熱加圧を行うことで、好ましくは熱可塑性繊維の繊維形状がなくなり樹脂状となるまで溶融し、繊維強化プラスチックを成形することができる。 As a method for molding the fiber reinforced plastic, press molding, stampable molding, and the like are shown as suitable examples, but all general hot-pressure molding methods are applicable. At this time, by heating or heating and pressurizing at a temperature equal to or higher than the melting point or softening point of the thermoplastic fiber, it is preferably melted until the fiber shape of the thermoplastic fiber disappears and becomes a resinous shape to form a fiber reinforced plastic. Can do.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.
（１）繊維長、繊度
ＪＩＳ Ｌ １０１５に準拠して測定した。
(1) Fiber length and fineness Measured according to JIS L 1015.
（２）繊径
キーエンス社製光学顕微鏡ＤＥＧＩＴＡＬ ＭＩＣＲＯＳＣＯＰＥ ＶＨＸ−１０００を用い１０００倍で繊維断面の直径を１０本測定し、その平均値とした。
(2) Fine Diameter Ten diameters of fiber cross-sections were measured at 1000 times using a Keyence optical microscope, DEGITAL MICROSCOPE VHX-1000, and the average value was obtained.
（３）繊維の引張強度、伸度、弾性率
ＡＳＴＭ Ｄ８８５に準拠して測定した。
(3) Tensile strength, elongation, and elastic modulus of fiber Measured according to ASTM D885.
（４）ポリカーボネート樹脂のメルトボリュームフローレイト
ＩＳＯ １１３３に準拠して３００℃、荷重１．２ｋｇにて測定した。
(4) Melt volume flow rate of polycarbonate resin Measured at 300 ° C. and a load of 1.2 kg in accordance with ISO 1133.
（５）各繊維の融点、軟化点、熱分解開始温度
株式会社リガク社製示差熱分析装置ＴＡＳ２００にて窒素雰囲気下、昇温速度１０℃／分にて測定し算出した。
(5) Melting point, softening point, and thermal decomposition start temperature of each fiber Measurement and calculation were carried out at a heating rate of 10 ° C./min in a nitrogen atmosphere using a differential thermal analyzer TAS200 manufactured by Rigaku Corporation.
（６）繊維強化プラスチックの曲げ強度、弾性率
ＪＩＳ Ｋ ７１７１に準拠し、厚さ２ｍｍ、長さ１００ｍｍ、幅１０ｍｍの試験片を用いて、支点間距離８０ｍｍでの３点曲げにて測定した。
(6) Flexural strength and elastic modulus of fiber reinforced plastics Measured by three-point bending at a fulcrum distance of 80 mm using a test piece having a thickness of 2 mm, a length of 100 mm, and a width of 10 mm in accordance with JIS K 7171.
（７）繊維強化プラスチックの衝撃強度
ＪＩＳ Ｋ ７１１１に準拠し、厚さ２ｍｍ、長さ１００ｍｍ、幅１０ｍｍの試験片を用いて測定した。
(7) Impact strength of fiber reinforced plastics Measured using a test piece having a thickness of 2 mm, a length of 100 mm, and a width of 10 mm in accordance with JIS K7111.
（８）交絡数
厚さ方向に切断した基材（不織布）の切断面を、走査型電子顕微鏡（倍率：１２倍）にて観察し、基材の厚さの半分以上の長さにわたって、厚さ方向（厚さ方向に対し、±４５°以内の方向を含む）に配列している５本以上の短繊維が集束した繊維束が、基材表面１ｃｍ２あたり何個あるかを数え、ケ／ｃｍ２で表わした。
(8) Number of entanglements The cut surface of the base material (nonwoven fabric) cut in the thickness direction is observed with a scanning electron microscope (magnification: 12 times), and the thickness is more than half the thickness of the base material. Count how many bundles of fiber bundles of five or more short fibers arranged in the vertical direction (including directions within ± 45 ° with respect to the thickness direction) per 1 cm 2 of the substrate surface. / Cm 2 .
（９）基材の伸度
ＪＩＳ Ｌ １９１３に準拠して測定した。
(9) Base material elongation Measured according to JIS L 1913.
（１０）立体成形性
巾１０ｃｍ、奥行１０ｃｍ、立ち上がり角度７０度、高さ３ｃｍの斜面をもつ金型を用い、基材をプレス加工した際の、立体加工性を目し判定した。なお、プレス加工温度は、熱可塑性繊維が、ポリカーボネート繊維の場合は３００℃、ポリプロピレン繊維の場合は２２０℃とした。また、判定基準は以下の通りとした。
○：繊維が７０度斜度面に均一に広がっており、樹脂の含浸ムラが無いもの。
△：繊維が７０度斜度面に均一に広がっているが、樹脂の未含浸が見られるもの。
×：繊維が７０度斜度面に均一に広がらず、偏りが見られるもの。
(10) Three-dimensional formability Using a mold having an inclined surface with a width of 10 cm, a depth of 10 cm, a rising angle of 70 degrees, and a height of 3 cm, the three-dimensional workability when the substrate was pressed was determined. The pressing temperature was 300 ° C. when the thermoplastic fiber was polycarbonate fiber, and 220 ° C. when the thermoplastic fiber was polypropylene fiber. Moreover, the judgment criteria were as follows.
○: Fibers spread evenly on a 70-degree oblique surface, and there is no resin impregnation unevenness.
(Triangle | delta): Although the fiber has spread uniformly on the 70 degree | times inclination surface, what is not impregnated with resin is seen.
X: The fiber does not spread evenly on the 70-degree oblique surface, and unevenness is observed.
［実施例１］
繊維径７μｍの炭素繊維（東邦テナックス製、引張強度４２００ＭＰａ）を３５ｍｍにカットした繊維と、ポリカーボネート樹脂（帝人化成製 パンライトＬ−１２２５Ｌ メルトボリュームフローレイト １８ｃｍ３／１０分間）を２９０℃にて溶融押し出しし、直径３０μｍ、伸度６５％のフィラメントとし、これを５１ｍｍにカットしたものとを重量比４０：６０とし開繊機にて混合し、ランダムウェーバー機を通過させることにより、ウェブを作成した。このようにして得られたウェブをニードルパンチ機により３８番針にて針深度１０ｍｍ、打ち込み密度５００本／ｃｍ２として、目付２００ｇ／ｍ２のプラスチック成形用基材を得た。上記基材を１２枚積層したものを予め離型処理を施したステンレス板で挟み、ホットプレス熱盤上にセットした後、同じく予め離型処理を施した鋼製スペーサーを使用して、成型圧力５ＭＰａ、成型温度が３００℃にて約２ｍｍ厚の繊維強化プラスチックを作成した。
[Example 1]
Carbon fiber (Toho Tenax Co., Ltd., tensile strength 4200 MPa) of fiber diameter 7μm and fibers were cut to 35 mm, the polycarbonate resin (Teijin Chemicals Ltd., Panlite L-1225L melt volume flow rate 18cm 3/10 minutes) at 290 ° C. melt Extruded to obtain a filament having a diameter of 30 μm and an elongation of 65%, which was cut into 51 mm, mixed in a spreader at a weight ratio of 40:60, and passed through a random weber machine to prepare a web. The web thus obtained was obtained by a needle punching machine using a 38th needle with a needle depth of 10 mm and a driving density of 500 pieces / cm 2 to obtain a plastic molding substrate having a basis weight of 200 g / m 2 . A laminate of 12 sheets of the above-mentioned base material is sandwiched between pre-released stainless steel plates, set on a hot press hot platen, and then subjected to a molding pressure using a steel spacer that has also been pre-released. A fiber reinforced plastic having a thickness of about 2 mm was prepared at 5 MPa and a molding temperature of 300 ° C.
［実施例２］
炭素繊維の代わりに繊維径１２μｍのアラミド繊維（コポリパラフェニレン・３，４’−オキシジフェニレンテレフタルアミド繊維）（帝人テクノプロダクツ製 テクノーラ（商標）、引張強度３４００ＭＰａ）を５１ｍｍにカットした繊維を用いた以外は実施例１と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 2]
Instead of carbon fiber, a fiber with a fiber diameter of 12 μm (copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber) (Teijin Techno Products Technora (trademark), tensile strength 3400 MPa) cut to 51 mm is used. A substrate for molding a fiber reinforced plastic was prepared in the same manner as in Example 1 except that a fiber reinforced plastic was further prepared.
［実施例３］
炭素繊維の代わりに炭素繊維とアラミド繊維を５０：５０で予め混綿した繊維を用いた以外は実施例１の場合と同様の処理をして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 3]
A fiber reinforced plastic molding base material was prepared by performing the same treatment as in Example 1 except that a fiber in which carbon fiber and aramid fiber were mixed in advance at 50:50 was used instead of carbon fiber, and a fiber-reinforced plastic molding substrate was formed. Made reinforced plastic.
［実施例４］
炭素繊維と熱可塑性繊維の比率を５：９５に変更した以外は実施例１と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 4]
A substrate for molding fiber reinforced plastic was prepared in the same manner as in Example 1 except that the ratio of carbon fiber to thermoplastic fiber was changed to 5:95, and further a fiber reinforced plastic was prepared.
［実施例５］
炭素繊維と熱可塑性繊維の重量比を７０：３０に変更した以外は実施例１と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 5]
A substrate for molding fiber reinforced plastic was prepared in the same manner as in Example 1 except that the weight ratio of carbon fiber to thermoplastic fiber was changed to 70:30, and further a fiber reinforced plastic was prepared.
［実施例６］
炭素繊維とアラミド繊維の重量比を９０：１０に変更した以外は実施例３と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 6]
A substrate for molding fiber reinforced plastic was prepared in the same manner as in Example 3 except that the weight ratio of carbon fiber to aramid fiber was changed to 90:10, and further a fiber reinforced plastic was prepared.
［実施例７］
炭素繊維とアラミド繊維の重量比を７０：３０に変更した以外は実施例３と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 7]
A substrate for molding fiber reinforced plastic was prepared in the same manner as in Example 3 except that the weight ratio of carbon fiber to aramid fiber was changed to 70:30, and further a fiber reinforced plastic was prepared.
［実施例８］
熱可塑性繊維を直径１８μｍ、伸度５６％のポリプロピレン繊維に変更し、プレス成型の温度を２２０℃とした以外は実施例１と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 8]
A fiber reinforced plastic molding substrate was prepared in the same manner as in Example 1 except that the thermoplastic fiber was changed to a polypropylene fiber having a diameter of 18 μm and an elongation of 56%, and the press molding temperature was 220 ° C. Made reinforced plastic.
［実施例９］
熱可塑性繊維を直径１８μｍ、伸度５６％のポリプロピレン繊維に変更し、プレス成型の温度を２２０℃とした以外は実施例２と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 9]
A fiber reinforced plastic molding substrate was prepared in the same manner as in Example 2 except that the thermoplastic fiber was changed to polypropylene fiber having a diameter of 18 μm and an elongation of 56%, and the press molding temperature was 220 ° C. Made reinforced plastic.
［実施例１０］
熱可塑性繊維を直径１８μｍ、伸度５６％のポリプロピレン繊維に変更し、プレス成型の温度を２２０℃とした以外は実施例３と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Example 10]
A fiber reinforced plastic molding substrate was prepared in the same manner as in Example 3 except that the thermoplastic fiber was changed to polypropylene fiber having a diameter of 18 μm and an elongation of 56%, and the press molding temperature was 220 ° C. Made reinforced plastic.
［比較例１］
実施例２で使用したアラミド繊維を使用し、開繊機にて混合した後、カード工程を通過させることにより、繊維の引き揃え性を向上させたウェブを作成した。このようにして得られた繊維ウェブをニードルパンチ機により３８番針にて針深度１０ｍｍ、５００本／ｃｍ２の密度で打ち込みをして目付８０ｇ／ｍ２の不織布を得た。上記不織布にポリカーボネート製フィルム（帝人化成製パンライトシート １００μｍ厚み、比重１．２）を１枚積層させ、２４０℃×０．１ＭＰａにて２０秒間圧着することにより基材間を接着させ、繊維強化プラスチック用基材２００ｇ／ｍ２を作成した。上記の基材を１２枚を積層し、予め離型処理を施したステンレス板で挟み、ホットプレス熱盤上にセットした後、同じく予め離型処理を施した鋼製スペーサーを使用して、成型圧力５ＭＰａ、成型温度が３００℃にて約２ｍｍ厚の繊維強化プラスチックを作成、同様に評価した。
[Comparative Example 1]
The aramid fibers used in Example 2 were used, mixed with a fiber spreader, and then passed through a card process to create a web with improved fiber alignment. The fiber web thus obtained was driven by a needle punch machine with a 38th needle at a needle depth of 10 mm and a density of 500 pieces / cm 2 to obtain a nonwoven fabric having a basis weight of 80 g / m 2 . One layer of polycarbonate film (Teijin Kasei Panlite sheet 100 μm thickness, specific gravity 1.2) is laminated on the nonwoven fabric, and the substrates are bonded together at 240 ° C. × 0.1 MPa for 20 seconds to strengthen the fiber. A plastic substrate 200 g / m 2 was prepared. After laminating 12 sheets of the above-mentioned base material, sandwiching them in advance with a stainless steel plate that has been subjected to a release treatment, and setting it on a hot press hot platen, using a steel spacer that has also been subjected to a release treatment in advance, molding A fiber reinforced plastic having a thickness of about 2 mm was prepared at a pressure of 5 MPa and a molding temperature of 300 ° C., and similarly evaluated.
［比較例２］
ポリカーボネート製フィルムをポリプロピレン製フィルム（１２５μｍ厚み、比重０．８）に変更し、プレス成型の温度を２２０℃とした以外は比較例１と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
[Comparative Example 2]
A substrate made of fiber-reinforced plastic was prepared in the same manner as in Comparative Example 1 except that the polycarbonate film was changed to a polypropylene film (125 μm thickness, specific gravity 0.8), and the press molding temperature was 220 ° C. Furthermore, a fiber reinforced plastic was created.
［比較例３］
アラミド不織布をアラミド織物（帝人テクノプロダクツ製テクノーラ織物 目付８０ｇ／ｍ２）に変更した以外は、比較例１と同様にして、繊維強化プラスチック成形用基材を作成し、さらに繊維強化プラスチックを作成した。
以上の結果を表１に示す。
[Comparative Example 3]
Except that the aramid non-woven fabric was changed to aramid fabric (Teijin Techno Products, Ltd. Technora fabric weight per unit area 80 g / m 2) is in the same manner as in Comparative Example 1, to create a fiber-reinforced plastic molded base material, further create a fiber-reinforced plastic .
The results are shown in Table 1.
本発明の繊維強化プラスチック成形用基材は、立体成形性に優れ、該基材からは機械的特性、耐衝撃性に優れた繊維強化プラスチックを製造することができる。また、本発明の基材から得られた繊維強化プラスチックは、補強用、摩擦・摺動用、自動車、船舶などの産業用部品、電気・電子機器、ＡＶ機器、ＯＡ機器、建築用の部品・部材、建材、建具、パッキン類又はシール類などに好適に用いることができる。 The fiber-reinforced plastic molding substrate of the present invention is excellent in three-dimensional moldability, and a fiber-reinforced plastic excellent in mechanical properties and impact resistance can be produced from the substrate. Further, the fiber reinforced plastic obtained from the base material of the present invention is used for reinforcement, friction / sliding, automobile, ship and other industrial parts, electrical / electronic equipment, AV equipment, OA equipment, architectural parts / members. It can be suitably used for building materials, joinery, packings or seals.
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