JP2014062143A - Fiber-reinforced plastic - Google Patents
Fiber-reinforced plastic Download PDFInfo
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- JP2014062143A JP2014062143A JP2012206337A JP2012206337A JP2014062143A JP 2014062143 A JP2014062143 A JP 2014062143A JP 2012206337 A JP2012206337 A JP 2012206337A JP 2012206337 A JP2012206337 A JP 2012206337A JP 2014062143 A JP2014062143 A JP 2014062143A
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- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims abstract description 69
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims abstract description 69
- 239000000835 fiber Substances 0.000 claims abstract description 120
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 38
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 31
- 239000004917 carbon fiber Substances 0.000 claims abstract description 31
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920006231 aramid fiber Polymers 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000004431 polycarbonate resin Substances 0.000 claims description 8
- 229920005668 polycarbonate resin Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims 1
- 229920000069 polyphenylene sulfide Polymers 0.000 claims 1
- 230000035515 penetration Effects 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract 2
- 229920003023 plastic Polymers 0.000 abstract 2
- 239000000463 material Substances 0.000 description 30
- 229920001169 thermoplastic Polymers 0.000 description 21
- 239000004416 thermosoftening plastic Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000004745 nonwoven fabric Substances 0.000 description 18
- 238000010137 moulding (plastic) Methods 0.000 description 15
- 238000000465 moulding Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 239000004760 aramid Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004419 Panlite Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、軽量化が可能であり、機械的特性、特に耐衝撃性能に優れた繊維強化プラスチックに優れた繊維強化プラスチックに関するものである。 The present invention relates to a fiber-reinforced plastic that can be reduced in weight and excellent in a fiber-reinforced plastic that is excellent in mechanical properties, particularly impact resistance.
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.
具体例としては、炭素繊維フィラメントと他の有機繊維を混編、混織する方法や、炭素繊維および他の繊維をフィラメント状態のまま開繊し、シート状にしたものを積層した後、マトリックス樹脂のシート材とともにプレス等の技術手段により成型する方法、あるいは、炭素繊維および他の繊維を６ｍｍ以下の長さにカッティングしたカットファイバーを熱可塑性樹脂にコンパウンドの後、射出成型する方法などが挙げられる（特許文献１及び２等）。 Specific examples include a method of knitting and knitting carbon fiber filaments and other organic fibers, or a method of laminating carbon fibers and other fibers in a filament state and laminating them into a sheet, and then matrix resin And a method of molding the sheet material by a technical means such as a press, or a method of injection molding after compounding a cut fiber obtained by cutting carbon fiber and other fibers to a length of 6 mm or less into a thermoplastic resin. (Patent Documents 1 and 2, etc.).
フィラメント繊維による成型方法の場合、強度、剛性の高いハイグレードな繊維強化プラスチックの製造が可能であるものの、成型にかかるコストが非常に高く、一部の用途にのみ展開されているのが実状である。一方、射出成型を用いる方法では、加工特性に優れ、安価な繊維強化プラスチックが製造できるものの、添加する繊維が短くなり、剛性、耐衝撃性の面で十分な性能を得ることが困難である。 In the case of the molding method using filament fibers, it is possible to produce high-grade fiber reinforced plastics with high strength and rigidity, but the cost of molding is very high, and it is actually deployed only in some applications. is there. On the other hand, in the method using injection molding, although an excellent fiber reinforced plastic can be produced with excellent processing characteristics, the added fiber becomes short and it is difficult to obtain sufficient performance in terms of rigidity and impact resistance.
本発明の目的は、軽量化が可能であり、機械的特性、特に耐衝撃性能に優れた繊維強化プラスチックに優れた繊維強化プラスチックを提供することにある。 An object of the present invention is to provide a fiber-reinforced plastic that can be reduced in weight and that is superior to a fiber-reinforced plastic that is excellent in mechanical properties, particularly impact resistance.
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を用いて成形することにより、高い機械的特性を有し、特に耐衝撃性能において優れた性能を発揮する繊維強化プラスチックが得られることを見出し、本発明に至った。 As a result of examination by the present inventor, molding is performed using a base material in which reinforcing fibers and thermoplastic fibers are mixed under certain conditions, so that it has high mechanical properties and exhibits particularly excellent performance in impact resistance. As a result, the present inventors have found that a fiber reinforced plastic can be obtained.
かくして本発明によれば、強化繊維と熱可塑性樹脂とからなる繊維強化プラスチックであって、該繊維強化プラスチックが、強化繊維５〜７０重量％および熱可塑性樹脂３０〜９５重量％からなり、該強化繊維が、炭素繊維４０〜１００重量％および耐熱有機繊維０〜６０重量％からなり、厚さが１０ｍｍ以下であり、先端部が直径２５ｍｍの半球であり、重さが５ｋｇである落錐治具を、３０ｍ／ｓの速度で落錐して貫通させたときの貫通孔の最も長い直径Ａと落錐治具の先端の半球の直径Ｂとの比Ａ／Ｂが６０％以下であることを特徴とする繊維強化プラスチック。提供される。 Thus, according to the present invention, a fiber reinforced plastic comprising reinforced fibers and a thermoplastic resin, the fiber reinforced plastic comprising 5 to 70% by weight of reinforced fibers and 30 to 95% by weight of a thermoplastic resin, A falling cone jig in which the fibers are composed of 40 to 100% by weight of carbon fibers and 0 to 60% by weight of heat-resistant organic fibers, the thickness is 10 mm or less, the tip is a hemisphere with a diameter of 25 mm, and the weight is 5 kg. The ratio A / B between the longest diameter A of the through hole and the diameter B of the hemisphere at the tip of the falling jig when the steel is dropped and penetrated at a speed of 30 m / s is 60% or less. Characteristic fiber reinforced plastic. Provided.
本発明の繊維強化プラスチックは、強化繊維を用いていることにより、高い機械的物性を示す。また、本発明の繊維強化プラスチックは、射出成形のように炭素繊維や耐熱有機繊維といった強化繊維が切断されて短くなったり、塊状となったりすることがなく、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。 The fiber-reinforced plastic of the present invention exhibits high mechanical properties due to the use of reinforcing fibers. In addition, the fiber reinforced plastic of the present invention can be entangled between fibers without being shortened or agglomerated by cutting reinforcing fibers such as carbon fibers and heat-resistant organic fibers as in injection molding, A sufficient strength and elastic modulus can be exhibited as a molded body.
本発明の繊維強化プラスチックは、強化繊維と熱可塑性樹脂とからなる繊維強化プラスチックであって、繊維強化プラスチックが、強化繊維５〜７０重量％および熱可塑性樹脂３０〜９５重量％からなり、該強化繊維が、炭素繊維４０〜１００重量％および耐熱有機繊維０〜６０重量％からなる。 The fiber reinforced plastic of the present invention is a fiber reinforced plastic composed of a reinforced fiber and a thermoplastic resin, and the fiber reinforced plastic is composed of 5 to 70% by weight of the reinforced fiber and 30 to 95% by weight of the thermoplastic resin. The fibers consist of 40 to 100% by weight of carbon fibers and 0 to 60% by weight of heat resistant organic fibers.
本発明における強化繊維の形態は、カットファイバー（短繊維）であり、高い剛性を保持するために、繊維長は、好ましくは２０〜１５０ｍｍであり、より好ましくは２０〜１２０ｍｍ、さらに好ましくは２０〜１００ｍｍ、よりさらに好ましくは２０〜８０ｍｍ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 reinforcing fiber in the present invention is a cut fiber (short fiber), and the fiber length is preferably 20 to 150 mm, more preferably 20 to 120 mm, still more preferably 20 to 20 in order to maintain high rigidity. It is 100 mm, more preferably 20 to 80 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.
本発明においては、強化繊維として、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。
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。
In the present invention, only carbon fibers are used as reinforcing fibers, or carbon fibers and heat-resistant organic fibers are used in combination in order to improve impact resistance.
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.
本発明に用いる耐熱有機繊維は、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。 The heat-resistant organic fiber used in the present invention is preferably a heat-resistant organic fiber having a melting point, a softening point, or a thermal decomposition starting temperature of 250 ° C. or higher. For example, aromatic polyamide (aramid), aromatic polyether amide, Paraphenylene benzobisoxazole, polybenzimidazole, polyimide, polyetheretherketone, 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.
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.
本発明においては、炭素繊維：耐熱有機繊維は重量比で、１００：０〜４０：６０、好ましくは９０：１０〜４０：６０、より好ましくは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。 In the present invention, the weight ratio of carbon fiber: heat-resistant organic fiber is 100: 0 to 40:60, preferably 90:10 to 40:60, more preferably 70:30 to 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.
本発明に用いる熱可塑性樹脂としては、ポリプロプピレン樹脂、ポリエチレン樹脂、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。
上記熱可塑性樹脂は、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、熱可塑性樹脂が、強化繊維間に十分に含浸し、さらに得られる繊維強化プラスチックの剛性や、耐衝撃性の向上が容易となる。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、上記効果がより顕著に表れることがわかった。また、後述する繊維強化プラスチックの部材の粘りの点でも有利である。
As the thermoplastic resin used in the present invention, polypropylene resin, polyethylene resin, polyester resin, polyamide resin, polycarbonate resin, and ABS resin are preferably used.
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, it is preferably 16 to 30 cm 3/10 minutes. By having the above-mentioned melting characteristics, the thermoplastic resin is sufficiently impregnated between the reinforcing fibers, and the rigidity and impact resistance of the resulting fiber-reinforced plastic can be easily improved. In particular, when a polycarbonate resin is used as the thermoplastic resin, it has been found that the above-described effect appears more remarkably by using a resin having the melt volume flow rate. Moreover, it is advantageous also in the point of the stickiness of the member of the fiber reinforced plastic mentioned later.
本発明においては、強化繊維：熱可塑性樹脂が重量比で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、強化繊維を十分に結合して繊維強化プラスチックを形成するのが難しくなる。 In the present invention, the weight ratio of reinforcing fiber: thermoplastic resin is 5:95 to 70:30, preferably 20:80 to 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, the reinforcing fibers It becomes difficult to form a fiber-reinforced plastic by sufficiently bonding the two.
本発明の繊維強化プラスチックは、厚さが１０ｍｍ以下であり、先端部が直径２５ｍｍの半球であり重さが５ｋｇである落錐治具を、３０ｍ／ｓの速度で落錐して貫通させたときの貫通孔の最も長い直径Ａと落錐治具の先端の半球の直径Ｂとの比Ａ／Ｂが６０％以下であることが肝要である。 The fiber reinforced plastic of the present invention has a falling cone having a thickness of 10 mm or less, a tip of a hemisphere having a diameter of 25 mm, and a weight of 5 kg, dropped and penetrated at a speed of 30 m / s. It is important that the ratio A / B between the longest diameter A of the through hole and the diameter B of the hemisphere at the tip of the falling jig is 60% or less.
繊維強化プラスチックは衝撃吸収性が低いと、落錐治具貫通の際に落錐治具先端部の半球と形状・大きさに殆ど近い孔が試験片の繊維強化プラスチックに空くことになり、この場合、上記の比Ａ／Ｂはほぼ１００％となる。これに対し、本発明の繊維強化プラスチックでは、Ａ／Ｂが６０％以下という極めて特異な性能を呈し、これにより十分な耐衝撃性能が得られることがわかった。すなわち、優れた衝撃吸収性能を有し、部材に粘りが出てくると、直径Ｂの落錐治具の球状の錐（落錐）が貫通の際に部材破壊を受ける周囲の部材が貫通する方向に巻き込まれながら通過し、貫通の直後から巻き込まれた貫通方向に引っ張られた部材は元の方向に戻り貫通孔は小さくなって落ち着き、耐衝撃吸収性能が高い程この傾向が強くなると考えられる。本発明では、さらに検討を行い上記のようにＡ／Ｂを６０％以下まで小さくした場合、繊維強化プラスチックとして従来にない極めて優れた耐衝撃性能が得られることを見出したものである。 If the fiber reinforced plastic has low impact absorption, a hole almost close to the shape and size of the hemisphere at the tip of the drop pit jig and the shape and size will be vacated when penetrating the drop pit jig. In this case, the ratio A / B is almost 100%. On the other hand, it was found that the fiber reinforced plastic of the present invention exhibited extremely unique performance of A / B of 60% or less, and thereby sufficient impact resistance performance was obtained. In other words, it has excellent shock absorbing performance, and when the member becomes sticky, the surrounding members that are subjected to member destruction penetrate when the spherical cone (falling cone) of the falling cone jig of diameter B penetrates. It is thought that the member that passed while being wound in the direction and pulled in the penetration direction immediately after the penetration returned to the original direction and the through hole became smaller and settled, and this tendency is considered to be stronger as the shock absorption capacity is higher. . In the present invention, the inventors have further studied and found that when the A / B is reduced to 60% or less as described above, extremely excellent impact resistance performance as a fiber reinforced plastic can be obtained.
また、従来のカットファイバー（短繊維）からなる繊維強化プラスチックでは、射出成型によるものが一般的であり、かかる方法では、添加する繊維の繊維長が短くなるか、繊維が塊状になり十分な耐衝撃性を得ることができない。
これに対して、本発明者らは、例えば、以下に説明する繊維強化プラスチック成形用基材（以下、単に基布と称することがある）を加熱処理、または加熱加圧処理し、熱可塑性繊維を溶融することにより得られる繊維強化プラスチックが、本発明の要件Ａ／Ｂを満たし、かつ曲げ強度や曲げ弾性率にも優れていることを見出し、本発明に到達したものである。
In addition, conventional fiber reinforced plastics made of cut fibers (short fibers) are generally produced by injection molding. With such a method, the fiber length of the added fibers is shortened or the fibers are agglomerated to provide sufficient resistance. Impossibility cannot be obtained.
On the other hand, the present inventors, for example, heat-treat or heat-pressurize a fiber-reinforced plastic molding base material (hereinafter sometimes referred to simply as a base fabric) described below, thereby producing a thermoplastic fiber. It has been found that the fiber reinforced plastic obtained by melting is satisfying the requirement A / B of the present invention and is excellent in bending strength and bending elastic modulus.
本発明で用いる基材は、前記の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 used in the present invention is composed of the above-mentioned reinforcing fiber and thermoplastic fiber, and the reinforcing fiber: thermoplastic fiber is in a weight ratio of 5:95 to 70:30, preferably 20:80 to 60:40. is there. 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.
本発明で用いる熱可塑性繊維は、前記の熱可塑性樹脂を溶融紡糸等により繊維状に成形したものを好ましく提示でき、前記のように該熱可塑性樹脂は、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。 The thermoplastic fiber used in the present invention can preferably present the above-mentioned thermoplastic resin formed into a fiber shape by melt spinning or the like. As described above, the thermoplastic resin has a load of 300 ° C. according to ISO 1133. was measured at 1.2 kg, melt volume flow rate is preferably 12~60cm 3/10 min, more preferably 16~40cm 3/10 min, more preferably 16~30cm 3/10 min.
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であり、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.
本発明においては、基材の柔軟性を確保するために繊維の伸度を高くすることが有用である。一般に、強化繊維は高モジュラスであり、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、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６０％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 the present invention, it is useful to increase the elongation of the fiber in order to ensure the flexibility of the substrate. In general, the reinforcing fiber has a high modulus, and it is desirable to design the thermoplastic fiber with a high elongation. 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 60% or more. 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.
本発明で用いる基材は、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とを容易に密着することができる。 The base material used in the present invention is a mixture of reinforcing fibers and thermoplastic fibers. 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 to each other.
本発明で用いる基布としては、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 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. However, in products that particularly require rigidity and impact resistance, the fiber length is Since it is beneficial to have a long length, it is more preferable to prepare by a dry nonwoven fabric method. Further, the fibers are arranged in one direction by a process such as a spreader or a card, thereby further improving 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、基布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 base fabric 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し、前記のＡ／Ｂの要件を満足させることが容易となる。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. This makes it easier to satisfy the above A / B requirements by exhibiting high rigidity and impact resistance as compared with fiber reinforced plastic that is contained in thermoplastic resin without entanglement of reinforcing fibers. . 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.
基材をニードルパンチ不織布とする場合は、打ち込み密度を、好ましくは２００〜８００本／ｃｍ２、好ましくは３００〜７００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に変動し易くなる。一方、打ち込み密度が２００本／ｃｍ２超えると、基材が硬くなり易く好ましくない。 When the substrate is a needle punched nonwoven fabric, the driving density is preferably 200 to 800 pieces / cm 2 , preferably 300 to 700 pieces / cm 2 . If the driving density is less than 200 / 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 200 / cm 2 , the substrate tends to be hard, which is not preferable.
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、７０〜３００ｇ／ｃｍ２とすることが好ましい。目付が５０ｇ／ｃｍ２未満では取扱い性が悪くなる傾向があり、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 base material is preferably 50 to 500 g / cm 2 , more preferably 70 to 400 g / cm 2 , and 70 to 300 g / cm 2 . When the basis weight is less than 50 g / cm 2 , the handleability tends to be poor, and when it exceeds 500 g / cm 2 , the substrate becomes hard and the three-dimensional moldability tends to be lowered.
上記基材を用いて本発明の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 the fiber reinforced plastic of the present invention is molded using the above-mentioned base material, one or more base materials 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.
不織布の作成方法としては、一般的な乾式不織布、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。 As a method for producing the nonwoven fabric, both general dry nonwoven fabrics and wet nonwoven fabrics can be used, but in products that particularly require rigidity and impact resistance, it is beneficial to have a long fiber length. It is more preferable to prepare by a dry nonwoven fabric method. Further, the fibers are arranged in one direction by a process such as a spreader or a card, thereby further improving rigidity and impact resistance.
本発明の繊維強化プラスチックの基材となる不織布は、開繊機、カードなどの工程を通過することで、その機械方向に異方性を持った基材となる。また、一般的なクロスレイヤー工程での方向転換や、ニードルパンチ工程での機械方向の張力負荷により、異方性の程度を制御することが可能である。また、不織布基材を積層してプレス成形する方法も取られる手段であり、積層方向を変化させることでも異方性の制御は可能である。 The nonwoven fabric used as the base material of the fiber reinforced plastic of the present invention becomes a base material having anisotropy in the machine direction by passing through a process such as a fiber opening machine and a card. In addition, the degree of anisotropy can be controlled by changing the direction in a general cross-layer process or by applying a tensile load in the machine direction in a needle punch process. In addition, a method in which a nonwoven fabric base material is laminated and press-molded is also a means, and anisotropy can be controlled by changing the lamination direction.
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、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, the fiber reinforced plastic can be molded by heating or heating and pressing at a temperature equal to or higher than the melting point or softening point of the thermoplastic fiber.
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。
（１）繊維長、繊度
ＪＩＳ Ｌ １０１５に準拠して測定した。
（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。
（３）繊維の引張強度、伸度、弾性率
ＡＳＴＭ Ｄ８８５に準拠して測定した。
（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。
（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。
（６）繊維の交絡
厚さ方向に切断した不織布の切断面を、走査型電子顕微鏡（倍率：１２倍）にて観察し、不織布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、不織布表面１ｃｍ２あたり何個あるかを数え、ケ／ｃｍ２で表わした。
（７）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。
（８）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。
（９）繊維強化プラスチックの耐衝撃性
ＮＩＪ規格１１５．００の落錐試験装置を用い、錐（落錐）を圧縮空気で加速発射できるように改造した。落錐の先端部を鉄製にて直径２５ｍｍの半球状とし、この先端部を含めた落下する落錐治具の総重量を５ｋｇとする。繊維強化プラスチックからタテ、ヨコとも２５０ｍｍの試験片を切り出す。試験片を設置する台は、タテ、ヨコ３００ｍｍ、高さ１００ｍｍの鉄製の直方体とし、その上面の中央部に直径１００ｍｍ深さ１００ｍｍの穴を設ける。この穴の開いた上面部中央に試験片を載せ、その中央に、落錐の先端部の半球の中央が落下接触するようにする。落下接触時の落錐の速度が３０ｍ／ｓとなるように、錐（落錐）を圧縮空気を用いて鉛直落下開始させる。落錐試験終了後の試験片の貫通孔の最も長い直径Ａを測定し、落錐治具の先端部の半球の直径Ａ（２５ｍｍ）との比Ａ／Ｂを算出した。この値が６０％以下のものは、耐衝撃性が良好である。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.
(1) Fiber length and fineness Measured according to JIS L 1015.
(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) Tensile strength, elongation, and elastic modulus of fiber Measured according to ASTM D885.
(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) 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) Fiber entanglement The cut surface of the nonwoven fabric cut in the thickness direction is observed with a scanning electron microscope (magnification: 12 times), and the thickness direction (thickness) over the length of more than half the thickness of the nonwoven fabric. Count how many bundles of fiber bundles of 5 or more short fibers arranged in a direction of ± 45 ° (including the direction within ± 45 ° with respect to the vertical direction) per 1 cm 2 of the surface of the nonwoven fabric, and express it in ke / cm 2 . It was.
(7) 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.
(8) 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.
(9) Impact resistance of fiber reinforced plastic Using an NIJ standard 115.00 falling cone test apparatus, the cone (falling cone) was remodeled so that it could be accelerated with compressed air. The tip of the falling cone is made of iron and is hemispherical with a diameter of 25 mm, and the total weight of the falling falling jig including this tip is 5 kg. Cut out 250 mm test pieces from fiber reinforced plastic. The stage on which the test piece is installed is an iron rectangular parallelepiped having a length of 300 mm and a height of 100 mm, and a hole having a diameter of 100 mm and a depth of 100 mm is provided at the center of the upper surface. A test piece is placed at the center of the upper surface where the hole is opened, and the center of the hemisphere at the tip of the falling cone is brought into contact with the center of the test piece. The vertical fall of the cone (falling cone) is started using compressed air so that the falling velocity at the time of drop contact is 30 m / s. The longest diameter A of the through-hole of the test piece after the drop-fall test was measured, and the ratio A / B with the diameter A (25 mm) of the hemisphere at the tip of the drop-fall jig was calculated. When this value is 60% or less, the impact resistance is good.
［実施例１］
強化繊維として繊維径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、耐熱有機繊維であるアラミド繊維（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にカットした繊維とを重量比９０：１０（３６：４）で開繊機にて混合し、強化繊維混合物を得た。一方、熱可塑性繊維として、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、直径３０μｍ、伸度６２％のフィラメントを得、これを５１ｍｍにカットしたポリカーボネート繊維と用いた。
上記の強化繊維混合物と該ポリカーボネート繊維とを、重量比で４０：６０に混合し、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、目付け４０３ｇ／ｍ２のプラスチック成形用基材を得た。上記基材を６枚積層して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、圧力５ＭＰａ、温度３００℃にてプレス成型し、厚さ２ｍｍの繊維強化プラスチックを成形した。
[Example 1]
As a reinforcing fiber, a carbon fiber having a fiber diameter of 7 μm (manufactured by Toho Tenax Co., Ltd., tensile strength 4200 MPa) cut to 35 mm and an aramid fiber (copolyparaphenylene 3,4′-oxydiphenylene terephthalamide fiber) which is a heat-resistant organic fiber Fibers cut to 51 mm (Technola (trademark) manufactured by Teijin Techno Products, Ltd., tensile strength: 3400 MPa) were mixed at a weight ratio of 90:10 (36: 4) with a fiber spreader to obtain a reinforced fiber mixture. On the other hand, as the thermoplastic fibers, resulting polycarbonate resin (Teijin Chemicals Ltd., Panlite L-1225L melt volume flow rate 18cm 3/10 minutes) was melt-extruded at 290 ° C., diameter 30 [mu] m, elongation 62% of the filaments, this Used with polycarbonate fiber cut to 51 mm.
The above-mentioned reinforcing fiber mixture and the polycarbonate fiber are mixed at a weight ratio of 40:60, mixed by a fiber spreader, and then passed through a card process, whereby a base material for plastic molding having a basis weight of 403 g / m 2 is obtained. Obtained. After laminating 6 sheets of the above-mentioned base material and 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, a pressure of 5 MPa, Press molding was performed at a temperature of 300 ° C. to fabricate a fiber reinforced plastic having a thickness of 2 mm.
［実施例２］
炭素繊維とアラミド繊維の混合比率を４０：６０（１６：２４）にした以外は実施例１と同様にして、目付け４０４ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例１と同様にして繊維強化プラスチックを成形した。
[Example 2]
A base material for plastic molding having a basis weight of 404 g / m 2 was prepared in the same manner as in Example 1 except that the mixing ratio of carbon fiber and aramid fiber was 40:60 (16:24). Further, a fiber reinforced plastic was molded in the same manner as in Example 1.
［実施例３］
強化繊維混合物とポリカーボネート繊維の比率を３０：７０にした以外は実施例２と同様にして、目付け４０２ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例２と同様にして、繊維強化プラスチックを成形した。
[Example 3]
A base material for plastic molding having a basis weight of 402 g / m 2 was prepared in the same manner as in Example 2 except that the ratio of the reinforcing fiber mixture and the polycarbonate fiber was 30:70. Further, a fiber reinforced plastic was molded in the same manner as in Example 2.
［実施例４］
強化繊維混合物とポリカーボネート繊維の比率を６０：４０にした以外は実施例２と同様にして、目付け４０１ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例２と同様にして、繊維強化プラスチックを成形した。
[Example 4]
A plastic molding substrate having a basis weight of 401 g / m 2 was prepared in the same manner as in Example 2 except that the ratio of the reinforcing fiber mixture and the polycarbonate fiber was 60:40. Further, a fiber reinforced plastic was molded in the same manner as in Example 2.
［実施例５］
強化繊維混合物とポリカーボネート繊維の比率を７０：３０にした以外は実施例２と同様にして、目付け４０３ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例２と同様にして、繊維強化プラスチックを成形した。
[Example 5]
A base material for plastic molding having a basis weight of 403 g / m 2 was prepared in the same manner as in Example 2 except that the ratio of the reinforcing fiber mixture and the polycarbonate fiber was 70:30. Further, a fiber reinforced plastic was molded in the same manner as in Example 2.
［実施例６］
熱可塑性繊維を直径１２μｍのポリエステル繊維とした以外は実施例４と同様にして、目付け４０４ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例４と同様にして、繊維強化プラスチックを成形した。
[Example 6]
A base material for plastic molding having a basis weight of 404 g / m 2 was prepared in the same manner as in Example 4 except that the thermoplastic fiber was a polyester fiber having a diameter of 12 μm. Further, a fiber reinforced plastic was molded in the same manner as in Example 4.
［実施例７］
熱可塑性繊維を直径１８μｍのポリプロピレン繊維とし、プレス成型の温度を２２０℃とした以外は実施例４と同様にして、目付け４０２ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例４と同様にして、繊維強化プラスチックを成形した。
[Example 7]
A base material for plastic molding having a basis weight of 402 g / m 2 was prepared in the same manner as in Example 4 except that the thermoplastic fiber was a polypropylene fiber having a diameter of 18 μm and the temperature of press molding was 220 ° C. Further, a fiber reinforced plastic was molded in the same manner as in Example 4.
［実施例８］
熱可塑性繊維を直径１４μｍのポリアミド繊維（Ｎｙ６６繊維）とし、プレス成型の温度を２８０℃とした以外は実施例４と同様にして、目付け４０５ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例４と同様にして、繊維強化プラスチックを成形した。
[Example 8]
A base material for plastic molding having a basis weight of 405 g / m 2 was prepared in the same manner as in Example 4 except that the thermoplastic fiber was polyamide fiber (Ny66 fiber) having a diameter of 14 μm and the temperature of press molding was 280 ° C. Further, a fiber reinforced plastic was molded in the same manner as in Example 4.
［実施例９］
アラミド繊維を直径１４μｍのポリパラフェニレンベンゾビスオキサゾール繊維（ＰＢＯ繊維 引張強度５８００ＭＰａ）とした以外は実施例４と同様にして、目付け４０３ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例４と同様にして、繊維強化プラスチックを成形した。
[Example 9]
A base material for plastic molding having a basis weight of 403 g / m 2 was prepared in the same manner as in Example 4 except that the aramid fiber was a polyparaphenylene benzobisoxazole fiber (PBO fiber, tensile strength: 5800 MPa) having a diameter of 14 μm. Further, a fiber reinforced plastic was molded in the same manner as in Example 4.
［実施例１０］
アラミド繊維を直径１４μｍのポリエーテルイミド繊維とした以外は実施例４と同様にして、目付け４０３ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例４と同様にして、繊維強化プラスチックを成形した。
[Example 10]
A base material for plastic molding having a basis weight of 403 g / m 2 was prepared in the same manner as in Example 4 except that the aramid fiber was a polyetherimide fiber having a diameter of 14 μm. Further, a fiber reinforced plastic was molded in the same manner as in Example 4.
［実施例１１］
炭素繊維とアラミド繊維の混合比率を９５：５にした以外は実施例１と同様にして、目付け４０３ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例１と同様にして、繊維強化プラスチックを成形した。
[Example 11]
A base material for plastic molding having a basis weight of 403 g / m 2 was prepared in the same manner as in Example 1 except that the mixing ratio of carbon fiber and aramid fiber was 95: 5. Further, a fiber reinforced plastic was molded in the same manner as in Example 1.
［実施例１２］
強化繊維を炭素繊維のみとした以外は実施例１と同様にして、目付け４０２ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例１と同様にして、繊維強化プラスチックを成形した。
[Example 12]
A base material for plastic molding having a basis weight of 402 g / m 2 was prepared in the same manner as in Example 1 except that the reinforcing fiber was only carbon fiber. Further, a fiber reinforced plastic was molded in the same manner as in Example 1.
［比較例１］
強化繊維として、繊維長６ｍｍの炭素繊維（東邦テナックス製、引張強度４２００ＭＰａ）および繊維長６ｍｍ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５０：５０の重量比で混合したものを用い、これを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）ペレットに、強化繊維：ポリカーボネート樹脂が重量比で４０：６０となるように混合し、成型温度３００℃、射出圧力１００ＭＰａ、金型温度１００℃にて射出成型し、厚さ２ｍｍの繊維強化プラスチックを作成した。
[Comparative Example 1]
As reinforcing fibers, carbon fibers with a fiber length of 6 mm (manufactured by Toho Tenax, tensile strength 4200 MPa) and aramid fibers with a fiber length of 6 mm (copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber) (Technora made by Teijin Techno Products) R), tensile strength 3400 MPa) was used a mixture in a weight ratio of 50:50, which polycarbonate resin (Teijin Chemicals Ltd., Panlite L-1225L melt volume flow rate 18cm 3/10 minutes) to pellet the reinforcing fibers: A polycarbonate resin was mixed at a weight ratio of 40:60, and injection molded at a molding temperature of 300 ° C., an injection pressure of 100 MPa, and a mold temperature of 100 ° C. to prepare a fiber reinforced plastic having a thickness of 2 mm.
［比較例２］
強化繊維混合物とポリカーボネート繊維の比率を３：９７にした以外は実施例２と同様にして、目付け４０３ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例２と同様にして、繊維強化プラスチックを成形した。
[Comparative Example 2]
A plastic molding substrate having a basis weight of 403 g / m 2 was prepared in the same manner as in Example 2 except that the ratio of the reinforcing fiber mixture and the polycarbonate fiber was 3:97. Further, a fiber reinforced plastic was molded in the same manner as in Example 2.
［比較例３］
強化繊維混合物とポリカーボネート繊維の比率を７５：２５にした以外は実施例２と同様にして、目付け４０２ｇ／ｍ２のプラスチック成形用基材を作成した。さらに実施例２と同様にして、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]
A plastic molding substrate having a basis weight of 402 g / m 2 was prepared in the same manner as in Example 2 except that the ratio of the reinforcing fiber mixture and the polycarbonate fiber was 75:25. Further, a fiber reinforced plastic was prepared in the same manner as in Example 2.
The results are shown in Table 1.
本発明は、優れた耐衝撃性を有する軽量な繊維強化プラスチックを提供するものであり、本発明により製造さ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 present invention provides a lightweight fiber-reinforced plastic having excellent impact resistance, and the fiber-reinforced plastic produced according to the present invention is used for industrial parts such as reinforcement, friction / sliding, automobiles and ships. It can be suitably used for electrical / electronic equipment, AV equipment, OA equipment, building parts / members, building materials, joinery, packings or seals.
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| WO2017073483A1 (en) | 2015-10-30 | 2017-05-04 | 東レ株式会社 | Fibre-reinforced thermoplastic resin moulded article, and fibre-reinforced thermoplastic resin moulding material |
| WO2017073482A1 (en) | 2015-10-30 | 2017-05-04 | 東レ株式会社 | Fibre-reinforced thermoplastic resin moulded article, and fibre-reinforced thermoplastic resin moulding material |
| US11015047B1 (en) | 2017-09-05 | 2021-05-25 | Toray Industries, Inc. | Moldings of fiber-reinforced thermoplastic resin |
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