JPH08294918A - Raw material for manufacturing frtp product and manufacture thereof - Google Patents
Raw material for manufacturing frtp product and manufacture thereofInfo
- Publication number
- JPH08294918A JPH08294918A JP7104126A JP10412695A JPH08294918A JP H08294918 A JPH08294918 A JP H08294918A JP 7104126 A JP7104126 A JP 7104126A JP 10412695 A JP10412695 A JP 10412695A JP H08294918 A JPH08294918 A JP H08294918A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- fiber bundle
- thermoplastic resin
- producing
- frtp
- 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
Landscapes
- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、ＦＲＴＰ（Fiber Re
inforced Thermoplastics ）品、特に薄肉のＦＲＴＰ
品、たとえば、パーソナルコンピュータ、ワードプロセ
ッサ等のＯＡ機器や、ＣＤプレーヤー、ヘッドホンステ
レオ等のＡＶ機器や、携帯電話やトランシーバー等の通
信機器といった電子・電気機器の筐体、内装部品を製造
するのに好適な素材およびその製造方法に関する。ま
た、この発明は、上述したようなＦＲＴＰ品を製造する
ための中間素材を製造する方法に関する。さらに、この
発明は、そのような素材や中間素材を用いてＦＲＴＰ品
を製造する方法に関する。BACKGROUND OF THE INVENTION The present invention relates to FRTP (Fiber Re
inforced Thermoplastics), especially thin-walled FRTP
Suitable for manufacturing products such as OA devices such as personal computers and word processors, AV devices such as CD players and headphone stereos, and casings and interior parts of electronic and electric devices such as communication devices such as mobile phones and transceivers. Material and its manufacturing method. The present invention also relates to a method for producing an intermediate material for producing the FRTP product as described above. Furthermore, the present invention relates to a method for manufacturing FRTP products using such materials and intermediate materials.
【０００２】[0002]
【従来の技術】ＦＲＴＰ品を製造する方法の一つに、射
出成形法がある。この方法は、素材として強化繊維と熱
可塑性樹脂とを複合してなるペレットを用い、そのペレ
ットを溶融、混練し、所望の製品形状のキャビティを有
する型内に射出して成形するもので、長い強化繊維を用
いたペレットとしては、たとえば特公昭６３−３７６９
４号公報や特公平３−２５３４０号公報に記載されてい
るように、単糸が一方向に延在している強化繊維束に熱
可塑性樹脂を含浸、複合してなる、長さ２〜１００mm程
度の比較的長いものが用いられている。ところが、この
ようなペレットの使用によって、強度や剛性等の力学的
諸特性に優れた薄肉ＦＲＴＰ品を得ることは、以下にお
いて説明するようになかなか難しい。2. Description of the Related Art One of the methods for manufacturing FRTP products is injection molding. This method uses pellets composed of reinforced fibers and a thermoplastic resin as a raw material, melts and kneads the pellets, and injects them into a mold having a cavity of a desired product shape to form a long product. Pellets using reinforcing fibers include, for example, Japanese Examined Patent Publication Sho 63-3769.
As described in Japanese Patent Publication No. 4 and Japanese Patent Publication No. 3-25340, a reinforcing fiber bundle in which a single yarn extends in one direction is impregnated with a thermoplastic resin and is composited, and the length is 2 to 100 mm. A relatively long one is used. However, it is quite difficult to obtain a thin-walled FRTP product excellent in mechanical properties such as strength and rigidity by using such pellets as described below.
【０００３】すなわち、ＦＲＴＰに限らず、一般に繊維
強化樹脂複合材料は、その強度や剛性といった力学的特
性が強化繊維の長さに大きく左右されるが、上述したよ
うなペレットを射出成形に供すると、混練や射出等の各
過程で、強化繊維が、０．１〜１mmほどに短く、しか
も、不規則な長さに折損してしまい、補強効果が大きく
低下してしまう。これは、強化繊維を含むために粘ちょ
うで流動性が低くなっている熱可塑性樹脂が強化繊維束
を構成している単糸の滑り、移動を阻害し、単糸間に絡
みといえるような状態が現われて単糸にそれを屈曲させ
ようとする大きな力が作用するからである。単糸間の摩
擦力が大きいのである。単糸を屈曲させようとする力
は、強化繊維のアスペクト比が大きいほど大きくなる
が、それによる折損は、混練に低圧縮型のスクリューを
用いたり、射出圧力や射出速度を低くしたりすることで
ある程度低減できる。しかしながら、そうすると、こん
どは混練が不十分になったり、強化繊維や熱可塑性樹脂
が型の隅々に行き渡らなくなったりして、得られるＦＲ
ＴＰ品は強化繊維の分布のむらが大きくなったり、表面
品位が低下したりするようになる。そのため、従来は、
製品の厚みを厚くして上述した折損に伴う力学的特性の
低下を補わざるを得なかった。That is, not only FRTP but generally fiber-reinforced resin composite materials have mechanical properties such as strength and rigidity which are greatly influenced by the length of the reinforcing fiber. However, when the above pellets are subjected to injection molding. In each process such as kneading and injection, the reinforcing fiber is broken to an irregular length as short as 0.1 to 1 mm, and the reinforcing effect is greatly reduced. This is because the thermoplastic resin, which is viscous and has low fluidity because it contains reinforcing fibers, hinders the slipping and movement of the single yarns that make up the reinforcing fiber bundle, and can be said to be entangled between the single yarns. This is because a state appears and a large force acts on the single yarn to bend it. The frictional force between the single yarns is large. The force to bend the single yarn increases as the aspect ratio of the reinforcing fiber increases, but the resulting breakage is to use a low compression type screw for kneading or to lower the injection pressure or injection speed. Can be reduced to some extent. However, if you do so, the kneading will become insufficient, and the reinforcing fibers and thermoplastic resin will not spread all over the mold, resulting in FR.
In the TP product, the uneven distribution of the reinforcing fiber becomes large, and the surface quality is deteriorated. Therefore, conventionally,
There was no choice but to increase the thickness of the product to compensate for the above-mentioned deterioration in mechanical properties due to breakage.
【０００４】[0004]
【発明が解決しようとする課題】この発明の目的は、従
来の素材の上述した問題点を解決し、いわゆるベアリン
グ効果をもっていて流動性に優れ、成形の各過程におけ
る強化繊維の折損を防止することができて、たとえ薄く
ても力学的特性に優れたＦＲＴＰ品を得ることができる
ＦＲＴＰ品製造用素材およびその製造方法を提供するに
ある。SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the conventional materials, to have a so-called bearing effect and to have excellent fluidity, and to prevent breakage of the reinforcing fiber in each process of molding. The object is to provide a material for producing an FRTP product and a method for producing the FRTP product, which enables to obtain an FRTP product excellent in mechanical properties even if it is thin.
【０００５】また、この発明の他の目的は、ＦＲＴＰ品
を製造するための中間素材を製造する方法を提供するに
ある。Another object of the present invention is to provide a method for producing an intermediate material for producing FRTP products.
【０００６】この発明のさらに他の目的は、上述した素
材や中間素材を用いた、薄くても強度や剛性等の力学的
特性に優れたＦＲＴＰ品を製造する方法を提供するにあ
る。Still another object of the present invention is to provide a method for producing an FRTP product using the above-mentioned material or intermediate material, which is thin but has excellent mechanical properties such as strength and rigidity.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、この発明は、単糸が一方向に延在している強化繊維
束に、粉体を含む熱可塑性樹脂が含浸、複合されている
ＦＲＴＰ品製造用素材（以下、第１の素材という。）、
単糸が一方向に延在している強化繊維束に、熱可塑性樹
脂が含浸、複合され、かつ、複合体の表面に粉体が担持
されているＦＲＴＰ品製造用素材（以下、第２の素材と
いう。）、単糸が一方向に延在している強化繊維束に、
粉体を含む熱可塑性樹脂の外被層が設けられているＦＲ
ＴＰ品製造用素材（以下、第３の素材という。）、単糸
が一方向に延在している強化繊維束に、熱可塑性樹脂の
外被層が設けられ、かつ、その外被層の表面に粉体が担
持されているＦＲＴＰ品製造用素材（以下、第４の素材
という。）、表面に粉体が担持されている、単糸が一方
向に延在している強化繊維束に、熱可塑性樹脂の外被層
が設けられているＦＲＴＰ品製造用素材（以下、第５の
素材という。）、および、単糸間に粉体が担持されてい
る、単糸が一方向に延在している強化繊維束に、熱可塑
性樹脂の外被層が設けられているＦＲＴＰ品製造用素材
（以下、第６の素材という。）を提供する。第３〜第５
の素材において、強化繊維束の単糸間に粉体がさらに担
持されていてもよい。また、第２、第４または第５の素
材において、熱可塑性樹脂が粉体を含んでいてもよい。
これらの素材は、円形や楕円形、矩形等の横断面形状を
もち、連続した線状やテープ状のものであってもよく、
一定長さを有するペレットであってもよい。ペレットの
場合、その長さは、上述した力学的特性の向上効果とＦ
ＲＴＰ品製造時の成形性とのバランスを考えると、３〜
５０mm程度であるのが好ましい。さらに好ましい長さ
は、５〜３０mmである。In order to achieve the above object, the present invention is a composite of a reinforcing fiber bundle in which a single yarn extends in one direction impregnated with a thermoplastic resin containing a powder to form a composite. Material for manufacturing FRTP products (hereinafter referred to as the first material),
A material for manufacturing FRTP products in which a reinforcing fiber bundle in which single yarns extend in one direction is impregnated with a thermoplastic resin to be composite, and a powder is carried on the surface of the composite (hereinafter referred to as the second It is called a material.), A bundle of reinforcing fibers in which a single yarn extends in one direction,
FR provided with a thermoplastic resin coating layer containing powder
A material for producing a TP product (hereinafter referred to as a third material), a reinforcing fiber bundle in which single yarns extend in one direction, is provided with an outer coating layer of a thermoplastic resin, and the outer coating layer of the thermoplastic resin is provided. A material for manufacturing FRTP products in which powder is carried on the surface (hereinafter referred to as a fourth material), and a reinforcing fiber bundle in which powder is carried on the surface and single yarns extend in one direction. , A material for manufacturing FRTP products provided with a thermoplastic resin outer layer (hereinafter referred to as a fifth material), and a powder carried between the single yarns, the single yarns extending in one direction Provided is a material for producing a FRTP product (hereinafter, referred to as a sixth material), in which an existing coating layer of a thermoplastic resin is provided on an existing reinforcing fiber bundle. Third to fifth
In the above material, powder may be further supported between the single yarns of the reinforcing fiber bundle. Further, in the second, fourth or fifth material, the thermoplastic resin may contain powder.
These materials have a cross-sectional shape such as a circle, an ellipse, and a rectangle, and may be continuous linear or tape-like,
It may be a pellet having a certain length. In the case of pellets, the length of the pellets is
Considering the balance with the moldability at the time of manufacturing RTP products,
It is preferably about 50 mm. A more preferable length is 5 to 30 mm.
【０００８】強化繊維束は、炭素繊維、ガラス繊維、ポ
リアラミド繊維、アルミナ繊維、炭化ケイ素繊維、ボロ
ン繊維等の高強度、高弾性率繊維からなる。単糸は一方
向に延在している。なかでも、炭素繊維、ガラス繊維ま
たはポリアラミド繊維、とりわけ力学的特性の向上効果
に優れ、また、導電性を有するために得られるＦＲＴＰ
品に電磁波シールド効果をもたせることができる炭素繊
維からなるものであるのが好ましい。そのような炭素繊
維からなる強化繊維束は、単糸径が１〜５０μｍの範囲
にあり、単糸数が５００〜５００，０００本、好ましく
は１，０００〜１００，０００本の範囲にあるものがよ
い。素材製造時の問題として、あまり細いと糸切れが起
こりやすくなり、一方、あまり太いと熱可塑性樹脂等の
含浸性、その他が悪くなる。また、あまり太いと素材の
ハンドリング性も悪くなる。The reinforcing fiber bundle is composed of high-strength and high-modulus fibers such as carbon fiber, glass fiber, polyaramid fiber, alumina fiber, silicon carbide fiber and boron fiber. The single yarn extends in one direction. Among them, carbon fiber, glass fiber or polyaramid fiber, especially FRTP obtained because of its excellent effect of improving mechanical properties and having conductivity
It is preferable that the product is made of carbon fiber that can have an electromagnetic wave shielding effect. The reinforcing fiber bundle composed of such carbon fibers has a single yarn diameter in the range of 1 to 50 μm, and a single yarn number in the range of 500 to 500,000, preferably 1,000 to 100,000. Good. As a problem during material production, if the fiber is too thin, yarn breakage is likely to occur, while if it is too thick, impregnation with a thermoplastic resin and the like deteriorate. If it is too thick, the handling of the material will be poor.
【０００９】素材中における強化繊維の量は、少なすぎ
ると補強効果が低くなり、多すぎると強化繊維と熱可塑
性樹脂との複合が難しくなるので、５〜７０体積％、好
ましくは１０〜４０体積％の範囲にあるのがよい。If the amount of the reinforcing fibers in the material is too small, the reinforcing effect will be low, and if the amount is too large, it will be difficult to combine the reinforcing fibers and the thermoplastic resin. Therefore, the amount is 5 to 70% by volume, preferably 10 to 40% by volume. It should be in the range of%.
【００１０】熱可塑性樹脂は、ポリアミド（ナイロン
６、ナイロン６６、ナイロン１１、ナイロン６１０、ナ
イロン６１２等）、ポリエステル（ポリエチレンテレフ
タレート、ポリブチレンテレフタレート等）、ポリスチ
レン、ＡＢＳ、ポリオレフィン（ポリエチレン、ポリプ
ロピレン等）、ポリカーボネート、ポリアミドイミド、
ポリフェニレンスルフィド、ポリフェニレンオキシド、
ポリスルホン、ポリエーテルスルホン、ポリエーテルエ
ーテルケトン、ポリエーテルイミド、ポリアセタール、
ポリイミド、ポリアミドエラストマー、ポリエステルエ
ラストマーのようなものである。これらの熱可塑性樹脂
は、ナイロン６とナイロン６６との共重合ナイロン等、
共重合したものであってもよい。特に、電子・電気機器
の筐体や内装部品を製造するときには、燃えにくいポリ
フェニレンスルフィドや、難燃剤の添加によって容易に
難燃化しやすいＡＢＳや、ＡＢＳとポリカーボネートと
のポリマーアロイが適している。また、特に薄肉のＦＲ
ＴＰ品を製造するときには、流動性に優れるポリアミド
やポリフェニレンスルフィドが適している。これらの熱
可塑性樹脂には、得たいＦＲＴＰ品の用途等に応じて、
トリフェニルホスフェート、トリクレジルホスフェー
ト、三酸化アンチモン、四酸化アンチモン、臭素化エポ
キシ樹脂、臭素化フェノール樹脂等の難燃性改良剤や、
タルク、雲母等の耐熱性改良剤や、サリチル酸フェニル
等の耐候性改良剤や、その他、酸化防止剤、熱安定化
剤、紫外線吸収剤、可塑剤、着色剤等を添加しておくこ
とができる。粉体は、シリカ、アルミナ、チタニア、ガ
ラスビーズ、ガラスバルーン等のセラミックスや、炭素
や、銅、ニッケル、銀、パラジウム等の金属からなる無
機質粉体のようなものである。また、シリコーン樹脂、
フッ素樹脂、アクリル樹脂、フェノール樹脂、ポリアミ
ド、ポリエチレン、ポリエーテルエーテルケトン、ポリ
エーテルスルホン等からなる有機質粉体で、かつ、上述
した熱可塑性樹脂よりも融点の高いものを用いることが
できる。これら粉体は、素材溶融時において強化繊維束
を構成している単糸の滑り、移動をよくし、単糸間の上
述した絡みを防いで、単糸に作用する、単糸を屈曲させ
ようとする力を低減させ、混練や射出等の各過程で強化
繊維が短く、しかも、不規則な長さに折損してしまうの
を抑制するように作用する。ベアリング効果である。こ
のベアリング効果を有効に発現させるためには、粉体は
できるだけ真球に近いほうがよい。また、平均粒子径
は、あまり小さいと、凝集して扱いにくくなったり、熱
可塑性樹脂中等における分散性が低下したりし、一方、
あまり大きいと、ベアリング効果が低くなったり、強化
繊維束を構成する単糸間に入りにくくなったりするの
で、０．１〜５０μｍの範囲にあるのが好ましい。より
好ましい平均粒子径の範囲は、０．１〜２０μｍであ
る。さらに、素材中に占める粉体の量は、極端に少ない
とベアリング効果が期待できなくなり、一方、あまり多
いと素材溶融時の粘度が高くなりすぎるようになるの
で、熱可塑性樹脂に対して０．１〜３０体積％程度の範
囲になるようにするのが好ましい。より好ましい範囲
は、０．５〜１０体積％である。Thermoplastic resins include polyamide (nylon 6, nylon 66, nylon 11, nylon 610, nylon 612, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polystyrene, ABS, polyolefin (polyethylene, polypropylene, etc.), Polycarbonate, polyamide imide,
Polyphenylene sulfide, polyphenylene oxide,
Polysulfone, polyether sulfone, polyether ether ketone, polyether imide, polyacetal,
Such as polyimide, polyamide elastomer, polyester elastomer. These thermoplastic resins are copolymer nylon such as nylon 6 and nylon 66,
It may be a copolymer. In particular, when manufacturing casings and interior parts for electronic / electrical devices, polyphenylene sulfide, which is difficult to burn, ABS which easily becomes flame-retardant by the addition of a flame retardant, and polymer alloys of ABS and polycarbonate are suitable. Also, especially thin FR
When manufacturing TP products, polyamide and polyphenylene sulfide, which have excellent fluidity, are suitable. Depending on the intended use of the FRTP product, etc.
Flame retardant improvers such as triphenyl phosphate, tricresyl phosphate, antimony trioxide, antimony tetroxide, brominated epoxy resin, brominated phenol resin, etc.,
It is possible to add heat resistance improvers such as talc and mica, weather resistance improvers such as phenyl salicylate, and other antioxidants, heat stabilizers, UV absorbers, plasticizers, colorants, etc. . The powder is such as ceramics such as silica, alumina, titania, glass beads, and glass balloons, inorganic powder made of carbon, and metals such as copper, nickel, silver, and palladium. Also, silicone resin,
It is possible to use an organic powder made of a fluororesin, an acrylic resin, a phenol resin, a polyamide, a polyethylene, a polyether ether ketone, a polyether sulfone or the like and having a higher melting point than that of the above-mentioned thermoplastic resin. These powders improve the sliding and movement of the single yarns constituting the reinforcing fiber bundle when the material is melted, prevent the above-mentioned entanglement between the single yarns, and act on the single yarns. It acts to reduce the force to be used and to prevent the reinforcing fiber from being broken into irregular lengths in each process such as kneading and injection. It is a bearing effect. In order to effectively develop this bearing effect, the powder should be as close to a true sphere as possible. If the average particle size is too small, the particles may aggregate and become difficult to handle, or the dispersibility in the thermoplastic resin may decrease.
If it is too large, the bearing effect will be low, and it will be difficult for it to enter between the single yarns constituting the reinforcing fiber bundle, so it is preferably in the range of 0.1 to 50 μm. A more preferable range of the average particle diameter is 0.1 to 20 μm. Furthermore, if the amount of powder in the raw material is extremely small, the bearing effect cannot be expected, while if it is too large, the viscosity when the raw material melts becomes too high. It is preferable to set it in the range of about 1 to 30% by volume. A more preferable range is 0.5 to 10% by volume.
【００１１】さて、この発明は、上記目的を達成するた
めに、熱可塑性樹脂と粉体との混合物を溶融してダイに
供給するとともに、ダイを通して、単糸が一方向に延在
している強化繊維束を引き抜いてその強化繊維束に上記
混合物を含浸、複合する、ＦＲＴＰ品製造用素材の製造
方法を提供する。In the present invention, in order to achieve the above object, a mixture of a thermoplastic resin and powder is melted and supplied to a die, and a single yarn extends in one direction through the die. Provided is a method for producing a material for producing an FRTP product, which comprises extracting a reinforcing fiber bundle, impregnating the reinforcing fiber bundle with the mixture, and forming a composite.
【００１２】すなわち、まず、上述した熱可塑性樹脂と
粉体との混合物を調製する。この調製は、粉粒状の熱可
塑性樹脂と粉体とを混合することによることができる。
それをさらに溶融してダイから線状に押し出し、一定長
に切断してペレットとしてもよい。次に、上記混合物を
溶融してダイに供給するとともに、ダイを通して、単糸
が一方向に延在している強化繊維束を引き抜き、強化繊
維束に混合物を含浸、複合する。このとき、強化繊維束
に圧力空気や超音波、振動等を作用させたり、太鼓状の
ローラに接触させたりして開繊しながらダイに導入する
と、混合物の含浸、複合がより均一に行われるようにな
るし、ダイ中で強化繊維束をしごくのもよい。以下に説
明する方法においても、同様である。かくして、単糸が
一方向に延在している強化繊維束に、粉体を含む熱可塑
性樹脂が含浸、複合されている第１の素材が得られる。
素材は長い線状のままでも使用でき、それを一定長に切
断して得たペレットの形態でも使用できる。That is, first, a mixture of the above-mentioned thermoplastic resin and powder is prepared. This preparation can be carried out by mixing the powdery granular thermoplastic resin and the powder.
It may be further melted, extruded linearly from a die, and cut into a certain length to obtain pellets. Next, the mixture is melted and supplied to the die, and the reinforcing fiber bundle in which the single yarn extends in one direction is pulled out through the die, and the reinforcing fiber bundle is impregnated with the mixture to form a composite. At this time, when the reinforcing fiber bundle is introduced into the die while opening the fiber by applying pressure air, ultrasonic waves, vibration, or the like, or by contacting with a drum-shaped roller, impregnation and compounding of the mixture are performed more uniformly. It is also good to squeeze the reinforcing fiber bundle in the die. The same applies to the method described below. Thus, the first raw material is obtained in which the reinforcing fiber bundle in which the single yarns extend in one direction is impregnated with the thermoplastic resin containing the powder and is composited.
The raw material can be used in a long linear form, or in the form of pellets obtained by cutting it into a certain length.
【００１３】また、この発明は、熱可塑性樹脂を溶融し
てダイに供給するとともに、ダイを通して、単糸が一方
向に延在している強化繊維束を引き抜いてその強化繊維
束に上記熱可塑性樹脂を含浸、複合した後、粉体と接触
させて複合体の表面に粉体を付着させる、ＦＲＴＰ品製
造用素材の製造方法を提供する。Further, according to the present invention, the thermoplastic resin is melted and supplied to the die, the reinforcing fiber bundle in which the single yarn extends in one direction is pulled out through the die, and the thermoplastic fiber is incorporated into the thermoplastic fiber bundle. Provided is a method for producing a material for producing an FRTP product, which comprises impregnating a resin, making a composite, and then bringing the powder into contact with the powder to adhere the powder to the surface of the composite.
【００１４】すなわち、まず、熱可塑性樹脂を溶融して
ダイに供給するとともに、ダイを通して、単糸が一方向
に延在している強化繊維束を引き抜き、強化繊維束に混
合物を含浸、複合する。しかる後、複合体を、熱可塑性
樹脂が未だ完全には固化しないうちに粉体に接触させ、
その表面に粉体を付着させる。この接触は、たとえば、
複合体を粉体中に通すことで行うことができる。する
と、単糸が一方向に延在している強化繊維束に、熱可塑
性樹脂が含浸、複合され、かつ、複合体の表面に粉体が
担持されている第２の素材が得られる。粉体にエポキシ
系、ポリエステル系、ポリビニルアルコール系等のバイ
ンダを添加、混合しておいてもよい。この場合は、強化
繊維束に含浸された熱可塑性樹脂が完全に固化していて
もよい。That is, first, the thermoplastic resin is melted and supplied to the die, and the reinforcing fiber bundle in which the single yarn extends in one direction is pulled out through the die, and the reinforcing fiber bundle is impregnated with the mixture to form a composite. . After that, the composite is contacted with the powder before the thermoplastic resin is completely solidified,
The powder is attached to the surface. This contact is, for example,
It can be carried out by passing the composite through a powder. Then, a second material is obtained in which the reinforcing fiber bundle in which the single yarns extend in one direction is impregnated with the thermoplastic resin to form a composite, and the powder is carried on the surface of the composite. An epoxy-based, polyester-based, polyvinyl alcohol-based binder or the like may be added to and mixed with the powder. In this case, the thermoplastic resin impregnated in the reinforcing fiber bundle may be completely solidified.
【００１５】さらに、この発明は、熱可塑性樹脂と粉体
との混合物を溶融し、走行している、単糸が一方向に延
在している強化繊維束に接触させてその強化繊維束に上
記混合物の外被層を形成する、ＦＲＴＰ品製造用素材の
製造方法を提供する。Further, according to the present invention, the mixture of the thermoplastic resin and the powder is melted and brought into contact with the running reinforcing fiber bundle in which the single yarns extend in one direction to form the reinforcing fiber bundle. Provided is a method for producing a material for producing FRTP products, which forms an outer coat layer of the above mixture.
【００１６】すなわち、まず、熱可塑性樹脂と粉体との
混合物を溶融し、これを、走行している、単糸が一方向
に延在している強化繊維束に接触させてその強化繊維束
に上記混合物の外被層を形成する。強化繊維束と混合物
との接触による外被層の形成は、たとえば、押出機のヘ
ッドに装着したワイヤーコーティングダイを用いて容易
に行うことができる。すると、単糸が一方向に延在して
いる強化繊維束に、粉体を含む熱可塑性樹脂の外被層が
設けられている第３の素材が得られる。That is, first, a mixture of a thermoplastic resin and powder is melted, and this is brought into contact with a running reinforcing fiber bundle in which single yarns extend in one direction, and the reinforcing fiber bundle is then contacted. A coating layer of the above mixture is formed on. The formation of the envelope layer by contacting the reinforcing fiber bundle with the mixture can be easily performed using, for example, a wire coating die attached to the head of an extruder. Then, a third material is obtained in which the reinforcing fiber bundle in which the single yarns extend in one direction is provided with the coating layer of the thermoplastic resin containing the powder.
【００１７】また、この発明は、熱可塑性樹脂を溶融
し、走行している、単糸が一方向に延在している強化繊
維束に接触させてその強化繊維束に上記熱可塑性樹脂の
外被層を形成した後、粉体と接触させて上記外被層の表
面に粉体を付着させる、ＦＲＴＰ品製造用素材の製造方
法を提供する。Further, according to the present invention, the thermoplastic resin is melted and brought into contact with the running reinforcing fiber bundle in which the single yarns extend in one direction, and the reinforcing fiber bundle is applied to the outside of the thermoplastic resin. Provided is a method for producing a material for producing an FRTP product, which comprises forming a coating layer and then bringing the powder into contact with the powder to deposit the powder on the surface of the outer coating layer.
【００１８】すなわち、まず、熱可塑性樹脂を溶融し、
その溶融熱可塑性樹脂を、走行している、単糸が一方向
に延在している強化繊維束に接触させてその強化繊維束
に上記熱可塑性樹脂の外被層を形成する。この外被層の
形成もまた、上記ワイヤーコーティングダイによること
ができる。外被層を形成した後は、第２の発明の素材を
製造するときと同様にして、外被層の表面に粉体を付着
させる。すると、単糸が一方向に延在している強化繊維
束に、熱可塑性樹脂の外被層が設けられ、かつ、その外
被層の表面に粉体が担持されている第４の素材が得られ
る。That is, first, the thermoplastic resin is melted,
The molten thermoplastic resin is brought into contact with the running reinforcing fiber bundle in which the single yarns extend in one direction to form an outer coat layer of the thermoplastic resin on the reinforcing fiber bundle. The formation of this overcoat layer can also be by the wire coating die described above. After forming the outer coat layer, the powder is attached to the surface of the outer coat layer in the same manner as in the case of manufacturing the material of the second invention. Then, a fourth material in which a reinforcing fiber bundle in which single yarns extend in one direction is provided with an outer coat layer of a thermoplastic resin, and a powder is carried on the surface of the outer coat layer is obtained. can get.
【００１９】さらに、この発明は、走行している、単糸
が一方向に延在している強化繊維束を粉体に接触させて
その強化繊維束の表面に粉体を付着させた後、溶融して
いる熱可塑性樹脂に接触させ、粉体が付着している強化
繊維束に上記熱可塑性樹脂の外被層を形成する、ＦＲＴ
Ｐ品製造用素材の製造方法を提供する。Further, according to the present invention, a running reinforcing fiber bundle in which a single yarn extends in one direction is brought into contact with the powder to deposit the powder on the surface of the reinforcing fiber bundle. Forming an outer coat layer of the thermoplastic resin on the reinforced fiber bundle to which the powder adheres by contacting with a molten thermoplastic resin, FRT
Provided is a method for manufacturing a material for manufacturing a P product.
【００２０】すなわち、まず、走行している、単糸が一
方向に延在している強化繊維束を、粉体に接触させて、
たとえば粉体中に通して、その強化繊維束の表面に粉体
を付着させる。粉体に、上述したバインダを添加してお
くのもよい。しかる後、溶融している熱可塑性樹脂に接
触させ、粉体が付着している強化繊維束に上記熱可塑性
樹脂の外被層を形成する。すると、表面に粉体が担持さ
れている、単糸が一方向に延在している強化繊維束に、
熱可塑性樹脂の外被層を設けてなる第５の素材が得られ
る。That is, first, the running reinforcing fiber bundle in which the single yarn extends in one direction is brought into contact with the powder,
For example, the powder is passed through the powder to adhere the powder to the surface of the reinforcing fiber bundle. The above-mentioned binder may be added to the powder. After that, the molten thermoplastic resin is brought into contact with the reinforcing fiber bundle to which the powder adheres to form an outer coat layer of the thermoplastic resin. Then, in the reinforcing fiber bundle in which the single yarn extends in one direction, the powder is carried on the surface,
A fifth material is obtained which is provided with a thermoplastic resin jacket layer.
【００２１】さらにまた、この発明は、走行している、
単糸が一方向に延在している強化繊維束を解繊しながら
粉体に接触させてその粉体を強化繊維束の単糸間に取り
込んだ後、溶融している熱可塑性樹脂に接触させ、単糸
間に粉体が取り込まれている強化繊維束に上記熱可塑性
樹脂の外被層を形成する、ＦＲＴＰ品製造用素材の製造
方法を提供する。Furthermore, the present invention is traveling,
While defibrating the reinforced fiber bundles in which the single yarns extend in one direction, contact the powders, capture the powders between the single yarns of the reinforced fiber bundles, and then contact the molten thermoplastic resin. A method for producing a material for producing an FRTP product, which comprises forming an outer coat layer of the thermoplastic resin on a reinforcing fiber bundle in which powder is incorporated between single yarns.
【００２２】すなわち、まず、走行している、単糸が一
方向に延在している強化繊維束を粉体に接触させてその
粉体を強化繊維束の単糸間に取り込む。この取り込みを
容易にするために、強化繊維束を上述した方法によって
開繊しておく。また、開繊しながら粉体の流動床中に通
すのもよい。流動床に代えて、粉体を分散させた液中に
強化繊維束を通した後、オーブン等で加熱して液成分を
取り除くようにしてもよい。しかる後、単糸間に粉体が
取り込まれている強化繊維束を溶融している熱可塑性樹
脂に接触させ、その周りに上記熱可塑性樹脂の外被層を
形成する。すると、単糸間に粉体を担持している、単糸
が一方向に延在している強化繊維束に、熱可塑性樹脂の
外被層を設けてなる第６の素材が得られる。That is, first, the running single yarn in which the single yarn extends in one direction is brought into contact with the powder, and the powder is taken in between the single yarns of the reinforcing fiber bundle. In order to facilitate this intake, the reinforcing fiber bundle is opened by the method described above. Further, it may be passed through a fluidized bed of powder while opening. Instead of the fluidized bed, the reinforcing fiber bundle may be passed through a liquid in which the powder is dispersed and then heated in an oven or the like to remove the liquid component. After that, the reinforcing fiber bundle in which the powder is taken in between the single yarns is brought into contact with the molten thermoplastic resin, and the outer covering layer of the thermoplastic resin is formed around it. As a result, a sixth raw material is obtained in which the reinforcing fiber bundle in which the single yarns extend in one direction, which carries the powder between the single yarns, is provided with the outer cover layer of the thermoplastic resin.
【００２３】以上説明した第３〜第５の素材の製造に際
し、強化繊維束として、単糸間に粉体を担持しているも
のを用いてもよい。また、第２、第４または第５の素材
の製造に際し、熱可塑性樹脂に代えて、熱可塑性樹脂と
粉体との混合物を用いることもできる。In manufacturing the third to fifth materials described above, a reinforcing fiber bundle may be used in which powder is carried between single yarns. Further, in the production of the second, fourth or fifth material, it is possible to use a mixture of a thermoplastic resin and powder in place of the thermoplastic resin.
【００２４】以上説明した方法において、強化繊維束を
熱可塑性樹脂、粉体等と接触させる際には、強化繊維束
を一定の速度で走行させるのが好ましい。そのときの速
度は、あまり低いと生産性が悪く、また、あまり高い
と、強化繊維が擦れて損傷したり、破断したり、熱可塑
性樹脂や粉体等の含浸、外被層の形成等に支障がでてく
るようになるので、０．２〜２０ｍ／分程度にするのが
よい。特に、強化繊維束の開繊等が必要な場合には、ロ
ーラとの接触等による強化繊維の損傷が大きいので、
０．２〜１０ｍ／分程度とするのがよい。In the above-described method, when the reinforcing fiber bundle is brought into contact with the thermoplastic resin, powder, etc., it is preferable to run the reinforcing fiber bundle at a constant speed. If the speed at that time is too low, the productivity will be poor, and if it is too high, the reinforcing fibers will be rubbed and damaged, or broken, impregnated with a thermoplastic resin or powder, or the formation of an outer coat layer, etc. Since it will cause trouble, it is preferable to set it at about 0.2 to 20 m / min. In particular, when it is necessary to open the reinforcing fiber bundle, etc., the damage of the reinforcing fiber due to contact with the roller is large,
It is preferable to set it to about 0.2 to 10 m / min.
【００２５】また、熱可塑性樹脂等をダイ等に供給する
ときの温度は、結晶性の熱可塑性樹脂の場合には、その
融点よりも１０〜３０℃ほど高めに設定するのが好まし
い。融点にあまりに近い温度では粘度が高すぎ、また、
融点よりもあまりに高い温度では熱可塑性樹脂の熱分解
が進むからである。The temperature at which the thermoplastic resin or the like is supplied to the die or the like is preferably set higher than the melting point by about 10 to 30 ° C. in the case of the crystalline thermoplastic resin. At a temperature too close to the melting point, the viscosity is too high, and
This is because the thermal decomposition of the thermoplastic resin proceeds at a temperature much higher than the melting point.
【００２６】上述した方法によって得られた素材は、そ
れを溶融しながらダイから押し出すことによって、ＦＲ
ＴＰ品製造用中間素材に加工することができる。素材
は、ダイの形状によって、線状にもできるし、シート状
にもできる。そして、得られる中間素材は、所望の製品
形状のキャビティを有する型に供給し、加圧、加熱成形
したり、スタンピンク成形することによってＦＲＴＰ品
とすることができる。中間素材の製造は、図１に示すよ
うな押出機を用いることによってもできる。The material obtained by the above-mentioned method is extruded from the die while melting it, and the FR
It can be processed into an intermediate material for manufacturing TP products. The material can be linear or sheet depending on the shape of the die. Then, the obtained intermediate material is supplied to a mold having a cavity having a desired product shape, and pressed, heat-molded, or stamp-pink molded to obtain a FRTP product. The production of the intermediate material can also be performed by using an extruder as shown in FIG.
【００２７】すなわち、この発明は、所望の温度に加熱
された、すり鉢状の空間を有するバレルと、このバレル
の空間内に設けたスクリューと、このスクリューの先端
に設けたノズルとを有する押出機を用い、バレルの空間
に請求項１〜１７のいずれかの製造用素材を供給してス
クリューで溶融、混練した後、混練された素材をノズル
から押し出す、ＦＲＴＰ品製造用中間素材の製造方法、
および、所望の温度に加熱された、すり鉢状の空間を有
するバレルと、このバレルの空間内に設けた、回転中心
に上記空間に連通可能なストロークシリンダおよびプラ
ンジャを備えたスクリューと、このスクリューの先端に
設けたノズルとを有する押出機を用い、バレルの空間に
請求項１〜１７のいずれかの製造用素材を供給してスク
リューで溶融、混練した後、混練された素材をストロー
クシリンダに取り込み、プランジャでノズルから押し出
す、ＦＲＴＰ品製造用中間素材の製造方法を提供する。That is, the present invention is an extruder having a barrel having a mortar-shaped space heated to a desired temperature, a screw provided in the space of the barrel, and a nozzle provided at the tip of the screw. A method for producing an intermediate material for producing a FRTP product, which comprises supplying the production material according to any one of claims 1 to 17 into a space of a barrel, melting and kneading with a screw, and then extruding the kneaded material from a nozzle,
And, a barrel having a mortar-shaped space heated to a desired temperature, a screw provided in the space of the barrel and having a stroke cylinder and a plunger capable of communicating with the space at the center of rotation, and a screw of this screw. Using an extruder having a nozzle provided at the tip, supply the manufacturing material according to any one of claims 1 to 17 into a space of a barrel, melt and knead with a screw, and then take the kneaded material into a stroke cylinder. Provided is a method of manufacturing an intermediate material for manufacturing FRTP products, which is extruded from a nozzle by a plunger.
【００２８】これをさらに詳細に説明するに、図１にお
いて、所望の温度に加熱された、素材投入口１を有する
とともにすり鉢状の空間を有するバレル５と、このバレ
ル５のすり鉢状の空間内に設けた、回転中心に上記空間
に連通するストロークシリンダ３およびプランジャ４を
備え、表面に溝７を有するスクリュー２と、このスクリ
ュー２の延長上に設けたノズル６とを有する押出機を用
い、ストロークシリンダ３をその先端が上記バレル５の
空間壁に当接しないように上昇させた状態で、スクリュ
ー２を回転させながら素材投入口１から素材を供給して
溶融させ、プランジャ４を徐々に上昇させながらストロ
ークシリンダ３内に所望量の溶融素材を取り込んで蓄積
し、一定量の蓄積の後、ストロークシリンダ３を下降さ
せてその先端を上記空間壁に当接させ、シリンダ４を押
し下げ、溶融素材をノズル６から押し出して中間素材を
得る。このような押出機の使用は、前に述べた射出成形
とは異なり、強化繊維の折損がほとんどない。そして、
ノズル６のノズル孔形状を選択することで、線状の中間
素材を得ることもできるし、シート状の中間素材を得る
こともでき、上述した方法によるものと同様、加熱、加
圧成形やスタンピング成形に供することができる。ま
た、ノズル６から、溶融素材を、直接に、所望の製品形
状のキャビティを有する型に注入し、ＦＲＴＰ品とする
こともできる。この押出機を用いる場合、ストロークシ
リンダ３とプランジャ４を取り外し、スクリュー２のみ
を用いて素材を溶融、混練し、ノズル６から押し出すよ
うにしてもよい。To explain this in more detail, in FIG. 1, a barrel 5 having a material inlet 1 and having a mortar-shaped space heated to a desired temperature, and a mortar-shaped space of the barrel 5 are shown. An extruder having a screw cylinder 2 having a groove 7 on the surface thereof and a nozzle 6 provided on an extension of the screw 2 and having a stroke cylinder 3 and a plunger 4 communicating with the space at the center of rotation. With the stroke cylinder 3 raised so that its tip does not come into contact with the space wall of the barrel 5, while the screw 2 is being rotated, the material is supplied from the material inlet 1 and melted, and the plunger 4 is gradually raised. The desired amount of molten material is taken into the stroke cylinder 3 and accumulated, and after a certain amount of accumulated material, the stroke cylinder 3 is lowered to raise its tip. Is brought into contact with the space wall, push down the cylinder 4, to obtain the intermediate material by extruding molten material through the nozzle 6. The use of such an extruder, unlike the previously described injection molding, results in almost no breakage of the reinforcing fibers. And
By selecting the nozzle hole shape of the nozzle 6, it is possible to obtain a linear intermediate material or a sheet-like intermediate material, and similar to the above-described method, heating, pressure molding or stamping is performed. It can be subjected to molding. Further, the molten material can be directly injected from the nozzle 6 into a mold having a cavity having a desired product shape to obtain a FRTP product. When this extruder is used, the stroke cylinder 3 and the plunger 4 may be removed, and the material may be melted and kneaded using only the screw 2 and then extruded from the nozzle 6.
【００２９】[0029]
実施例１ 東レ株式会社製ナイロン６“アミラン”ＣＭ１０１０
に、株式会社龍森製シリカ粉“アドマファイン”ＳＯ−
２５Ｒ（平均粒子径：０．８μｍ）をナイロン６に対し
て５体積％混入し、混合した後、２軸押出機を用いて２
３０℃で線状に押し出し、冷却後、長さ３mmにカットし
てペレットとした。Example 1 Nylon 6 "Amilan" CM1010 manufactured by Toray Industries, Inc.
And Tatsumori silica powder "Admafine" SO-
25R (average particle size: 0.8 μm) was mixed in 5% by volume with respect to nylon 6, and after mixing, 2
It was extruded linearly at 30 ° C., cooled, and then cut into a length of 3 mm to obtain pellets.
【００３０】次に、上記ペレットを２４０℃で溶融して
ダイに供給するとともに、ダイを通して、東レ株式会社
製炭素繊維束“トレカ”Ｔ３００−６Ｋ（平均単糸径：
７μｍ、単糸数：６，０００本、引張強度：３６０kgf
／mm2 、引張弾性率：２３，５００kgf ／mm2 ）を引き
抜き、炭素繊維束にペレットの溶融物を含浸、複合して
素材を得た。引抜速度は５ｍ／分とした。素材中におけ
る炭素繊維の量は、２５体積％であった。Next, the above pellets are melted at 240 ° C. and supplied to a die, and the carbon fiber bundle “Torayca” T300-6K (average single yarn diameter: manufactured by Toray Industries, Inc.) is passed through the die.
7μm, number of single yarn: 6,000, tensile strength: 360kgf
/ Mm 2 , tensile elastic modulus: 23,500 kgf / mm 2 ) was drawn out, and the carbon fiber bundle was impregnated with the melt of pellets to form a composite material. The drawing speed was 5 m / min. The amount of carbon fiber in the material was 25% by volume.
【００３１】次に、上記素材を長さ１２mmに切断した
後、図１に示した装置を用いてバルク状の材料を得た。
このとき、ストロークシリンダーの温度は２４０℃、ス
クリューの回転数は５０rpm とした。Next, after cutting the above material to a length of 12 mm, a bulk material was obtained by using the apparatus shown in FIG.
At this time, the temperature of the stroke cylinder was 240 ° C., and the rotation speed of the screw was 50 rpm.
【００３２】次に、上記バルク状材料を２０kgf ／cm2
でプレスし、厚みが１mmと２mmのＦＲＴＰシートを得
た。Next, the above bulk material is added to 20 kgf / cm 2
And pressed to obtain FRTP sheets with thicknesses of 1 mm and 2 mm.
【００３３】次に、厚みが１mmのシートを１５０mm角に
切り出し、アドバンテスト法にしたがって電磁波シール
ド特性を測定した。測定周波数は３００MHz とした。ま
た、厚みが２mmのシートについて、JIS K7055 に準拠
し、３点曲げ試験法による曲げ強度と曲げ弾性率とを測
定した。さらに、シートをぎ酸に浸漬して炭素繊維のみ
を取り出し、炭素繊維の長さと本数を調べた。また、シ
ートをエポキシ樹脂に包埋し、研磨してその断面を観察
し、ナイロン６の含浸性、ボイドの発生状況を調べた。
評価結果を以下に示す。Next, a sheet having a thickness of 1 mm was cut into a 150 mm square and the electromagnetic wave shielding property was measured according to the Advantest method. The measurement frequency was 300 MHz. Further, with respect to a sheet having a thickness of 2 mm, bending strength and bending elastic modulus were measured by a three-point bending test method according to JIS K7055. Further, the sheet was dipped in formic acid to take out only the carbon fiber, and the length and the number of carbon fiber were examined. Further, the sheet was embedded in an epoxy resin, polished, and the cross section thereof was observed to examine the impregnation property of nylon 6 and the occurrence of voids.
The evaluation results are shown below.
【００３４】電磁波シールド特性：５３ｄＢ 曲げ強度：３６．８kgf ／mm2 曲げ弾性率：２６７０kgf ／mm2 炭素繊維の数平均繊維長：４．９mm 含浸性・ボイドの有無：良好 実施例２ 東レ株式会社製ナイロン６“アミラン”ＣＭ１０１０
に、株式会社龍森製シリカ粉“アドマファイン”ＳＯ−
２５Ｒ（平均粒子径：０．８μｍ）をナイロン６に対し
て５体積％混入し、混合した後、２軸押出機を用いて２
３０℃で線状に押し出し、冷却後、長さ３mmにカットし
てペレットとした。Electromagnetic wave shielding property: 53 dB Bending strength: 36.8 kgf / mm 2 Bending elastic modulus: 2670 kgf / mm 2 Number average carbon fiber length: 4.9 mm Impregnating property / presence of voids: good Example 2 Toray Industries, Inc. Nylon 6 "Amilan" CM1010
And Tatsumori silica powder "Admafine" SO-
25R (average particle size: 0.8 μm) was mixed in 5% by volume with respect to nylon 6, and after mixing, 2
It was extruded linearly at 30 ° C., cooled, and then cut into a length of 3 mm to obtain pellets.
【００３５】次に、上記ペレットを２４０℃で溶融して
ダイから押し出すとともに、東レ株式会社製炭素繊維束
“トレカ”Ｔ３００−６Ｋ（平均単糸径：７μｍ、単糸
数：６，０００本、引張強度：３６０kgf ／mm2 、引張
弾性率：２３，５００kgf ／mm2 ）を接触させてその周
りに粉体を含む熱可塑性樹脂の外被層を形成し、素材を
得た。炭素繊維束の走行速度は１０ｍ／分とした。素材
中における炭素繊維の量は、２５体積％であった。以
下、実施例１と同様にしてシートを作り、評価した。評
価結果を以下に示す。Next, the pellets were melted at 240 ° C. and extruded from a die, and a carbon fiber bundle “Torayca” T300-6K manufactured by Toray Industries, Inc. (average single yarn diameter: 7 μm, number of single yarn: 6,000 yarns, tension) Strength: 360 kgf / mm 2 , tensile elastic modulus: 23,500 kgf / mm 2 ) were brought into contact with each other to form a thermoplastic resin-containing coating layer around the powder to obtain a raw material. The traveling speed of the carbon fiber bundle was 10 m / min. The amount of carbon fiber in the material was 25% by volume. Hereinafter, a sheet was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown below.
【００３６】電磁波シールド特性：５５ｄＢ 曲げ強度：３５．１kgf ／mm2 曲げ弾性率：２５３０kgf ／mm2 炭素繊維の数平均繊維長：５．１mm 含浸性・ボイドの有無：良好 実施例３ 日本電気硝子株式会社製ガラス繊維束ＥＲ５７５（平均
単糸径：１３μｍ、単糸数：１，６００本、引張強度：
１５０kgf ／mm2 、引張弾性率：７，４００kgf ／m
m2 ）を、開繊しながら、株式会社龍森製シリカ粉“ア
ドマファイン”ＳＯ−２５Ｒ（平均粒子径：３μｍ）の
流動床に通過させ、ガラス繊維束の単糸間にシリカ粉を
取り込んだ。Electromagnetic wave shielding property: 55 dB Bending strength: 35.1 kgf / mm 2 Bending elastic modulus: 2530 kgf / mm 2 Number average carbon fiber length: 5.1 mm Impregnating property / presence of voids: Good Example 3 Nippon Electric Glass Glass fiber bundle ER575 (average single yarn diameter: 13 μm, number of single yarn: 1,600, tensile strength:
150kgf / mm 2 , tensile modulus: 7,400kgf / m
m 2 ) while passing through a fluidized bed of Tatsumori Co., Ltd. silica powder “Admafine” SO-25R (average particle size: 3 μm), and the silica powder is incorporated between the single yarns of the glass fiber bundle. It is.
【００３７】次に、東レ株式会社製ナイロン６“アミラ
ン”ＣＭ１０１０のペレットを１軸押出機を用いて２４
０℃で溶融し、ワイヤコーティングダイから押し出すと
ともに、シリカ粉を取り込んだガラス繊維束を走行させ
ながら接触させて、ガラス繊維束の周りにナイロン６の
外被層を形成し、素材を得た。素材中における炭素繊維
の量は、２５体積％であった。Next, pellets of nylon 6 "Amilan" CM1010 manufactured by Toray Industries, Inc. were manufactured using a single-screw extruder.
While melting at 0 ° C and extruding from a wire coating die, a glass fiber bundle containing silica powder was brought into contact with the glass fiber bundle while running to form an outer coat layer of nylon 6 around the glass fiber bundle to obtain a raw material. The amount of carbon fiber in the material was 25% by volume.
【００３８】次に、上記素材を長さ１２mmに切断した
後、図１に示した装置を用いて溶融、混練し、金型に射
出成形して、JIS K7055 に準拠した短冊状の試験片を得
た。このとき、ストロークシリンダーの温度は２４０
℃、スクリューの回転数は５０rpm 、射出圧力は１，９
００kgf ／cm2 、金型温度は８０℃とした。以下、実施
例１と同様にしてシートを作り、評価した。評価結果を
以下に示す。Next, after cutting the above material to a length of 12 mm, it is melted and kneaded by using the apparatus shown in FIG. 1 and injection-molded in a die to obtain a strip-shaped test piece conforming to JIS K7055. Obtained. At this time, the temperature of the stroke cylinder is 240
℃, screw rotation speed 50 rpm, injection pressure 1,9
The mold temperature was 00 kgf / cm 2 and the mold temperature was 80 ° C. Hereinafter, a sheet was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown below.
【００３９】曲げ強度：１９．５kgf ／mm2 曲げ弾性率：１１３０kgf ／mm2 炭素繊維の数平均繊維長：４．３mm 含浸性・ボイドの有無：良好 実施例４ 実施例２で得られたペレット状の素材を、図１に示した
装置を用いて溶融、混練した後、扁平なノズルから押し
出し、厚みが１．５mmのシート状素材を得た。このと
き、ストロークシリンダーの温度は２４０℃、スクリュ
ーの回転数は５０rpm とした。Flexural strength: 19.5 kgf / mm 2 Flexural modulus: 1130 kgf / mm 2 Number average carbon fiber length: 4.3 mm Impregnability / Presence of voids: Good Example 4 Pellets obtained in Example 2 The raw material was melted and kneaded using the apparatus shown in FIG. 1 and then extruded from a flat nozzle to obtain a sheet material having a thickness of 1.5 mm. At this time, the temperature of the stroke cylinder was 240 ° C., and the rotation speed of the screw was 50 rpm.
【００４０】次に、上記シートをオーブン中にて２５０
℃によ予熱した後、１５０℃に予熱した、パーソナルコ
ンピューターの筐体の形状をしたキャビティを有する金
型に入れ、２００kgf ／cm2 の圧力で４０秒間加圧して
成形し、図２に示すような筐体を得た。図２において、
筐体は、枠８と、リブ９と、ボス１０とを有している。Next, the above sheet is placed in an oven at 250
After preheating at ℃, put it in a mold with a cavity in the shape of a personal computer housing preheated to 150 ℃, press at 200 kgf / cm 2 for 40 seconds to mold, as shown in FIG. I got a case. In FIG.
The housing has a frame 8, a rib 9, and a boss 10.
【００４１】得られた筐体は、板状部の厚みが１．２mm
で、炭素繊維の分布は極めて均一で、炭素繊維が枠８、
リブ９やボス１０にもよく分布していた。また、電磁は
シールド特性を測定したところ、５６dBであった。The thickness of the plate-shaped portion of the obtained housing was 1.2 mm.
And, the distribution of carbon fibers is extremely uniform, and the carbon fibers are
It was also well distributed on the ribs 9 and the bosses 10. Further, the electromagnetic wave had a shield characteristic of 56 dB.
【００４２】[0042]
比較例１ 粉体を使用しなかったほかは実施例１と同様にしてシー
トを作り、評価した。評価結果を以下に示す。Comparative Example 1 A sheet was prepared and evaluated in the same manner as in Example 1 except that the powder was not used. The evaluation results are shown below.
【００４３】次に、上記バルク状材料を２０kgf ／cm2
でプレスし、厚みが１mmと２mmのＦＲＴＰシートを得
た。Next, the above bulk material is added to 20 kgf / cm 2
And pressed to obtain FRTP sheets with thicknesses of 1 mm and 2 mm.
【００４４】電磁波シールド特性：４２ｄＢ 曲げ強度：２７．１kgf ／mm2 曲げ弾性率：１８４０kgf ／mm2 炭素繊維の数平均繊維長：３．２mm 含浸性・ボイドの有無：やや不良 比較例２ 粉体を使用しなかったほかは実施例２と同様にしてシー
トを作り、評価した。評価結果を以下に示す。Electromagnetic wave shielding property: 42 dB Bending strength: 27.1 kgf / mm 2 Bending elastic modulus: 1840 kgf / mm 2 Number average carbon fiber length: 3.2 mm Impregnating property / void presence / absence: Slightly defective Comparative Example 2 powder A sheet was prepared and evaluated in the same manner as in Example 2 except that the above was not used. The evaluation results are shown below.
【００４５】次に、上記バルク状材料を２０kgf ／cm2
でプレスし、厚みが１mmと２mmのＦＲＴＰシートを得
た。Next, the above bulk material is added to 20 kgf / cm 2
And pressed to obtain FRTP sheets with thicknesses of 1 mm and 2 mm.
【００４６】電磁波シールド特性：４３ｄＢ 曲げ強度：２７．３kgf ／mm2 曲げ弾性率：１６３０kgf ／mm2 炭素繊維の数平均繊維長：３．３mm 含浸性・ボイドの有無：不良 比較例３ 粉体を使用しなかったほかは実施例３と同様にしてシー
トを作り、評価した。評価結果を以下に示す。Electromagnetic wave shielding property: 43 dB Bending strength: 27.3 kgf / mm 2 Bending elastic modulus: 1630 kgf / mm 2 Number average carbon fiber length: 3.3 mm Impregnating ability / void presence / absence: Poor Comparative Example 3 A sheet was prepared and evaluated in the same manner as in Example 3 except that it was not used. The evaluation results are shown below.
【００４７】次に、上記バルク状材料を２０kgf ／cm2
でプレスし、厚みが１mmと２mmのＦＲＴＰシートを得
た。Next, the above bulk material is added to 20 kgf / cm 2
And pressed to obtain FRTP sheets with thicknesses of 1 mm and 2 mm.
【００４８】曲げ強度：１７．９kgf ／mm2 曲げ弾性率：８８０kgf ／mm2 炭素繊維の数平均繊維長：２．９mm 含浸性・ボイドの有無：不良Bending strength: 17.9 kgf / mm 2 Bending elastic modulus: 880 kgf / mm 2 Number average carbon fiber length: 2.9 mm Impregnating ability / Presence of voids: Poor
【００４９】[0049]
【発明の効果】この発明は、素材が粉体を含んでいて、
その粉体が素材溶融時にベアリング効果をもたらすの
で、素材溶融時において強化繊維束を構成している単糸
の滑り、移動がよくなり、単糸間の絡みを防いで、単糸
に作用する、単糸を屈曲させようとする力を低減させ、
混練や射出等の各過程で強化繊維が短く、しかも、不規
則な長さに折損してしまうのを防止することができるよ
うになり、たとえ薄くても力学的特性に優れたＦＲＴＰ
品を得ることができるようになる。しかも、そのような
素材は、熱可塑性樹脂と粉体との混合物を溶融してダイ
に供給するとともに、ダイを通して、単糸が一方向に延
在している強化繊維束を引き抜いてその強化繊維束に上
記混合物を含浸、複合するといったことで容易に製造す
ることができる。According to the present invention, the material contains powder,
Since the powder has a bearing effect when the material is melted, the single yarns that compose the reinforcing fiber bundle are better slipped and moved when the material is melted, preventing the entanglement between the single yarns and acting on the single yarns. The force to bend the single yarn is reduced,
In each process such as kneading and injection, it becomes possible to prevent the reinforcing fiber from being short and broken into irregular lengths. Even if it is thin, FRTP has excellent mechanical properties.
You will be able to get the goods. Moreover, such a material is obtained by melting a mixture of a thermoplastic resin and powder and supplying it to a die, and pulling out a reinforcing fiber bundle in which a single yarn extends in one direction through the die. It can be easily manufactured by impregnating the bundle with the above mixture and compounding.
【図１】この発明において好ましく用いられる押出機を
示す概略一部縦断面正面図である。FIG. 1 is a schematic partial vertical sectional front view showing an extruder preferably used in the present invention.
【図２】この発明の素材を用いた製造した電子・電気機
器用筐体の概略斜視図である。FIG. 2 is a schematic perspective view of a housing for electronic / electrical equipment manufactured using the material of the present invention.
１：素材投入口 ２：スクリュー ３：ストロークシリンダー ４：プランジャ ５：バレル ６：ノズル ７：溝 ８：枠 ９：リブ １０：ボス 1: Material input port 2: Screw 3: Stroke cylinder 4: Plunger 5: Barrel 6: Nozzle 7: Groove 8: Frame 9: Rib 10: Boss
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｋ 277:00 307:04 309:08 Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display area B29K 277: 00 307: 04 309: 08
Claims (32)
に、粉体を含む熱可塑性樹脂が含浸、複合されているＦ
ＲＴＰ品製造用素材。1. A reinforced fiber bundle in which single yarns extend in one direction is impregnated with a thermoplastic resin containing powder to form a composite F.
Material for manufacturing RTP products.
に、熱可塑性樹脂が含浸、複合され、かつ、複合体の表
面に粉体が担持されているＦＲＴＰ品製造用素材。2. A material for producing an FRTP product, in which a reinforcing fiber bundle in which single yarns extend in one direction is impregnated with a thermoplastic resin to form a composite, and a powder is carried on the surface of the composite.
に、粉体を含む熱可塑性樹脂の外被層が設けられている
ＦＲＴＰ品製造用素材。3. A material for producing a FRTP product, wherein a reinforcing fiber bundle in which single yarns extend in one direction is provided with an outer coat layer of a thermoplastic resin containing powder.
に、熱可塑性樹脂の外被層が設けられ、かつ、その外被
層の表面に粉体が担持されているＦＲＴＰ品製造用素
材。4. A FRTP product in which a reinforced fiber bundle in which single yarns extend in one direction is provided with an outer coat layer of a thermoplastic resin, and a powder is carried on the surface of the outer coat layer. Material for manufacturing.
向に延在している強化繊維束に、熱可塑性樹脂の外被層
が設けられているＦＲＴＰ品製造用素材。5. A material for producing an FRTP product, wherein a reinforcing fiber bundle, in which a single yarn extends in one direction, carries a powder on the surface thereof, and an outer coat layer of a thermoplastic resin is provided on the reinforcing fiber bundle.
方向に延在している強化繊維束に、熱可塑性樹脂の外被
層が設けられているＦＲＴＰ品製造用素材。6. A material for producing a FRTP product, wherein a reinforcing fiber bundle in which powder is carried between single yarns and in which the single yarns extend in one direction is provided with an outer coat layer of a thermoplastic resin. .
る、請求項３〜５のいずれかのＦＲＴＰ品製造用素材。7. The material for producing an FRTP product according to claim 3, wherein the powder is supported between the single yarns of the reinforcing fiber bundle.
２、４または５のＦＲＴＰ品製造用素材。8. The material for producing an FRTP product according to claim 2, 4 or 5, wherein the thermoplastic resin contains powder.
はポリアラミド繊維を少なくとも含んでいる、請求項１
〜８のいずれかのＦＲＴＰ品製造用素材。9. The reinforcing fiber bundle contains at least carbon fiber, glass fiber or polyaramid fiber.
Material for manufacturing FRTP products in any one of ~ 8.
範囲にあり、単糸数が５００〜５００，０００本の範囲
にある炭素繊維からなる、請求項１〜８のいずれかのＦ
ＲＴＰ品製造用素材。10. The reinforcing fiber bundle according to claim 1, wherein the reinforcing fiber bundle is composed of carbon fibers having a single yarn diameter of 1 to 50 μm and a single yarn number of 500 to 500,000.
Material for manufacturing RTP products.
テル、ポリスチレン、ＡＢＳ、ポリオレフィン、ポリカ
ーボネート、ポリアミドイミド、ポリフェニレンスルフ
ィド、ポリフェニレンオキシド、ポリスルホン、ポリエ
ーテルスルホン、ポリエーテルエーテルケトン、ポリエ
ーテルイミド、ポリアセタール、ポリイミド、ポリアミ
ドエラストマーまたはポリエステルエラストマーを少な
くとも含んでいる、請求項１〜１０のいずれかのＦＲＴ
Ｐ品製造用素材。11. A thermoplastic resin comprising polyamide, polyester, polystyrene, ABS, polyolefin, polycarbonate, polyamideimide, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyether sulfone, polyether ether ketone, polyether imide, polyacetal, polyimide, FRT according to any of claims 1 to 10, comprising at least a polyamide elastomer or a polyester elastomer.
Material for P product manufacturing.
からなる無機質粉体を少なくとも含んでいる、請求項１
〜１１のいずれかのＦＲＴＰ品製造用素材。12. The powder contains at least an inorganic powder made of ceramics, carbon or metal.
Material for manufacturing FRTP products according to any one of 11 to 11.
高い樹脂からなる有機質粉体を少なくとも含んでいる、
請求項１〜１１のいずれかのＦＲＴＰ品製造用素材。13. The powder contains at least an organic powder made of a resin having a melting point higher than that of the thermoplastic resin.
The material for producing a FRTP product according to claim 1.
範囲にある、請求項１〜１３のいずれかのＦＲＴＰ品製
造用素材。14. The material for producing an FRTP product according to claim 1, wherein the average particle size of the powder is in the range of 0.1 to 50 μm.
〜３０体積％の範囲にある、請求項１〜１４のいずれか
のＦＲＴＰ品製造用素材。15. The amount of powder relative to the thermoplastic resin is 0.1.
The material for producing an FRTP product according to any one of claims 1 to 14, which is in a range of -30% by volume.
１５のいずれかのＦＲＴＰ品製造用素材。16. The method according to claim 1, which has a pellet shape.
Material for manufacturing any of the 15 FRTP products.
ある、請求項１６のＦＲＴＰ品製造用素材。17. The material for producing a FRTP product according to claim 16, wherein the average length of the pellet is in the range of 3 to 50 mm.
てダイに供給するとともに、ダイを通して、単糸が一方
向に延在している強化繊維束を引き抜いてその強化繊維
束に上記混合物を含浸、複合する、ＦＲＴＰ品製造用素
材の製造方法。18. A mixture of a thermoplastic resin and powder is melted and supplied to a die, and a reinforcing fiber bundle in which single yarn extends in one direction is pulled out through the die and the reinforcing fiber bundle is formed into A method for producing a material for producing an FRTP product, which comprises impregnating and compounding a mixture.
とともに、ダイを通して、単糸が一方向に延在している
強化繊維束を引き抜いてその強化繊維束に上記熱可塑性
樹脂を含浸、複合した後、粉体と接触させて複合体の表
面に粉体を付着させる、ＦＲＴＰ品製造用素材の製造方
法。19. A thermoplastic resin is melted and supplied to a die, and a reinforcing fiber bundle having single yarns extending in one direction is pulled out through the die and the reinforcing fiber bundle is impregnated with the thermoplastic resin. A method for producing a material for producing an FRTP product, which comprises bringing the powder into contact with the powder and adhering the powder to the surface of the composite after the composite.
し、走行している、単糸が一方向に延在している強化繊
維束に接触させてその強化繊維束に上記混合物の外被層
を形成する、ＦＲＴＰ品製造用素材の製造方法。20. A mixture of a thermoplastic resin and powder is melted and brought into contact with a running reinforcing fiber bundle in which a single yarn extends in one direction, and the reinforcing fiber bundle is applied to the outside of the mixture. A method for producing a material for producing an FRTP product, which comprises forming a layer.
単糸が一方向に延在している強化繊維束に接触させてそ
の強化繊維束に上記熱可塑性樹脂の外被層を形成した
後、粉体と接触させて上記外被層の表面に粉体を付着さ
せる、ＦＲＴＰ品製造用素材の製造方法。21. A thermoplastic resin is melted and running.
After the single yarn is contacted with a reinforcing fiber bundle extending in one direction to form an outer coat layer of the thermoplastic resin on the reinforcing fiber bundle, the single yarn is contacted with a powder to form a powder on the surface of the outer coat layer. A method for producing a material for producing an FRTP product, which comprises attaching a body.
いる強化繊維束を粉体に接触させてその強化繊維束の表
面に粉体を付着させた後、溶融している熱可塑性樹脂に
接触させ、粉体が付着している強化繊維束に上記熱可塑
性樹脂の外被層を形成する、ＦＲＴＰ品製造用素材の製
造方法。22. A running single fiber, in which a single fiber extends in one direction, is brought into contact with the powder to adhere the powder to the surface of the fiber bundle and then melted. A method for producing a material for producing a FRTP product, which comprises bringing the thermoplastic resin into contact with a thermoplastic resin to form an outer coat layer of the thermoplastic resin on the reinforcing fiber bundle to which the powder adheres.
いる強化繊維束を解繊しながら粉体に接触させてその粉
体を強化繊維束の単糸間に取り込んだ後、溶融している
熱可塑性樹脂に接触させ、単糸間に粉体が取り込まれて
いる強化繊維束に上記熱可塑性樹脂の外被層を形成す
る、ＦＲＴＰ品製造用素材の製造方法。23. After running, the reinforced fiber bundle in which the single yarn extends in one direction is disintegrated and brought into contact with the powder, and the powder is taken in between the single yarns of the reinforced fiber bundle. A method for producing a material for producing an FRTP product, which comprises contacting with a molten thermoplastic resin to form an outer coat layer of the thermoplastic resin on a reinforcing fiber bundle in which powder is incorporated between single yarns.
維束を用いる、請求項２０〜２２のいずれかのＦＲＴＰ
品製造用素材の製造方法。24. The FRTP according to claim 20, wherein a reinforcing fiber bundle in which powder is incorporated between single yarns is used.
Manufacturing method of materials for product manufacturing.
項１９、２１または２２のいずれかのＦＲＴＰ品製造用
素材の製造方法。25. The method for producing a material for producing an FRTP product according to claim 19, 21 or 22, wherein a thermoplastic resin containing powder is used.
を溶融しながらダイから押し出す、ＦＲＴＰ品製造用中
間素材の製造方法。26. A method for producing an intermediate material for producing an FRTP product, which comprises extruding from a die while melting the material for production according to any one of claims 1 to 17.
間を有するバレルと、このバレルの空間内に設けたスク
リューと、このスクリューの先端に設けたノズルとを有
する押出機を用い、バレルの空間に請求項１〜１７のい
ずれかの製造用素材を供給してスクリューで溶融、混練
した後、混練された素材をノズルから押し出す、ＦＲＴ
Ｐ品製造用中間素材の製造方法。27. A barrel using an extruder having a barrel having a mortar-shaped space heated to a desired temperature, a screw provided in the space of the barrel, and a nozzle provided at the tip of the screw. The raw material for manufacturing according to any one of claims 1 to 17 is supplied to the space of No. 1 and melted and kneaded by a screw, and then the kneaded raw material is extruded from a nozzle.
Manufacturing method of intermediate material for P product manufacturing.
間を有するバレルと、このバレルの空間内に設けた、回
転中心に上記空間に連通可能なストロークシリンダおよ
びプランジャを備えたスクリューと、このスクリューの
先端に設けたノズルとを有する押出機を用い、バレルの
空間に請求項１〜１７のいずれかの製造用素材を供給し
てスクリューで溶融、混練した後、混練された素材をス
トロークシリンダに取り込み、プランジャでノズルから
押し出す、ＦＲＴＰ品製造用中間素材の製造方法。28. A barrel having a mortar-shaped space heated to a desired temperature, a screw provided in the space of the barrel and having a stroke cylinder and a plunger capable of communicating with the space at the center of rotation, Using an extruder having a nozzle provided at the tip of this screw, the material for production according to any one of claims 1 to 17 is supplied to the space of the barrel, melted and kneaded by the screw, and the kneaded material is stroked. A method of manufacturing an intermediate material for manufacturing FRTP products, which is taken into a cylinder and pushed out from a nozzle by a plunger.
って得られた中間素材を、所望の製品形状をしたキャビ
ティを有する型に供給し、加熱、加圧して成形する、Ｆ
ＲＴＰ品の製造方法。29. An intermediate material obtained by the method according to any one of claims 26 to 28 is supplied to a mold having a cavity having a desired product shape, and heated and pressed to mold.
RTP product manufacturing method.
って得られた中間素材を溶融し、射出成形する、ＦＲＴ
Ｐ品の製造方法。30. An FRT in which the intermediate material obtained by the method according to any one of claims 26 to 28 is melted and injection-molded.
Manufacturing method of P product.
間を有するバレルと、このバレルの空間内に設けた、回
転中心に上記空間に連通可能なストロークシリンダおよ
びプランジャを備えたスクリューと、このスクリューの
先端に設けたノズルとを有する押出機を用い、バレルの
空間に請求項１〜１７のいずれかの製造用素材を供給し
てスクリューで溶融、混練した後、混練された素材をス
トロークシリンダに取り込み、プランジャで、ノズルか
ら、所望の製品形状をしたキャビティを有する型に注入
し、成形する、ＦＲＴＰ品の製造方法。31. A barrel having a mortar-shaped space heated to a desired temperature, and a screw provided in the space of the barrel, the screw having a stroke cylinder and a plunger capable of communicating with the space at the center of rotation, Using an extruder having a nozzle provided at the tip of this screw, the material for production according to any one of claims 1 to 17 is supplied to the space of the barrel, melted and kneaded by the screw, and the kneaded material is stroked. A method for producing a FRTP product, which is taken into a cylinder, injected with a plunger from a nozzle into a mold having a cavity having a desired product shape, and molded.
つ、熱可塑性樹脂をマトリクスとするＦＲＴＰからなる
電子・電気機器用筐体。32. An electronic / electrical device housing made of FRTP containing a reinforcing discontinuous fiber and a powder, and comprising a thermoplastic resin as a matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7104126A JPH08294918A (en) | 1995-04-27 | 1995-04-27 | Raw material for manufacturing frtp product and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7104126A JPH08294918A (en) | 1995-04-27 | 1995-04-27 | Raw material for manufacturing frtp product and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08294918A true JPH08294918A (en) | 1996-11-12 |
Family
ID=14372434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7104126A Pending JPH08294918A (en) | 1995-04-27 | 1995-04-27 | Raw material for manufacturing frtp product and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08294918A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009242616A (en) * | 2008-03-31 | 2009-10-22 | Daikyonishikawa Corp | Resin injection-molded article and its molding method |
| WO2013031860A1 (en) * | 2011-08-31 | 2013-03-07 | 帝人株式会社 | Molded body having rising surface, and method for producing same |
| JP2014141582A (en) * | 2013-01-24 | 2014-08-07 | Toyota Motor Corp | Method of manufacturing frp sheet |
| JP2014162116A (en) * | 2013-02-26 | 2014-09-08 | Sekisui Chem Co Ltd | Fiber composite material, method for manufacturing fiber composite material, fiber bundle, and method for manufacturing fiber bundle |
| JP2019123984A (en) * | 2018-01-17 | 2019-07-25 | 積水化学工業株式会社 | Opened carbon fiber bundle, fiber-reinforced composite material, and method for producing opened carbon fiber bundle |
| JP2020524615A (en) * | 2017-06-22 | 2020-08-20 | アルケマ フランス | Fiber material impregnated with thermoplastic prepolymer |
| US11938656B2 (en) | 2017-06-22 | 2024-03-26 | Arkema France | Method for manufacturing a fibrous material impregnated with thermoplastic polymer |
-
1995
- 1995-04-27 JP JP7104126A patent/JPH08294918A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009242616A (en) * | 2008-03-31 | 2009-10-22 | Daikyonishikawa Corp | Resin injection-molded article and its molding method |
| WO2013031860A1 (en) * | 2011-08-31 | 2013-03-07 | 帝人株式会社 | Molded body having rising surface, and method for producing same |
| US10322559B2 (en) | 2011-08-31 | 2019-06-18 | Teijin Limited | Shaped product having standing plane, and method for manufacturing the same |
| JP2014141582A (en) * | 2013-01-24 | 2014-08-07 | Toyota Motor Corp | Method of manufacturing frp sheet |
| JP2014162116A (en) * | 2013-02-26 | 2014-09-08 | Sekisui Chem Co Ltd | Fiber composite material, method for manufacturing fiber composite material, fiber bundle, and method for manufacturing fiber bundle |
| JP2020524615A (en) * | 2017-06-22 | 2020-08-20 | アルケマ フランス | Fiber material impregnated with thermoplastic prepolymer |
| US11938656B2 (en) | 2017-06-22 | 2024-03-26 | Arkema France | Method for manufacturing a fibrous material impregnated with thermoplastic polymer |
| JP2019123984A (en) * | 2018-01-17 | 2019-07-25 | 積水化学工業株式会社 | Opened carbon fiber bundle, fiber-reinforced composite material, and method for producing opened carbon fiber bundle |
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