JP6284310B2 - Fiber base tape or sheet, method for producing the same, and fiber reinforced composite material - Google Patents
Fiber base tape or sheet, method for producing the same, and fiber reinforced composite material Download PDFInfo
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- JP6284310B2 JP6284310B2 JP2013146622A JP2013146622A JP6284310B2 JP 6284310 B2 JP6284310 B2 JP 6284310B2 JP 2013146622 A JP2013146622 A JP 2013146622A JP 2013146622 A JP2013146622 A JP 2013146622A JP 6284310 B2 JP6284310 B2 JP 6284310B2
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- 239000000835 fiber Substances 0.000 title claims description 296
- 239000000463 material Substances 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000003733 fiber-reinforced composite Substances 0.000 title description 5
- 239000012783 reinforcing fiber Substances 0.000 claims description 96
- 229920001169 thermoplastic Polymers 0.000 claims description 76
- 239000004416 thermosoftening plastic Substances 0.000 claims description 76
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 17
- 239000004917 carbon fiber Substances 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000004697 Polyetherimide Substances 0.000 claims description 11
- 229920001601 polyetherimide Polymers 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 10
- 238000010030 laminating Methods 0.000 claims description 9
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 8
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- 239000004744 fabric Substances 0.000 claims description 7
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
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- 239000003365 glass fiber Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
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- 125000003118 aryl group Chemical group 0.000 claims description 4
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 230000003014 reinforcing effect Effects 0.000 description 2
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- 238000003892 spreading Methods 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 229920004747 ULTEM® 1000 Polymers 0.000 description 1
- 229920004699 VICTREX® PEEK 150G Polymers 0.000 description 1
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
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- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、優れた力学物性と耐熱性、難燃性、寸法安定性を兼ね備えた繊維強化熱可塑性樹脂複合材料などを形成するために用いられる、強化繊維が一方向に配列した繊維基材テープまたはシート、およびその製造方法に関する。特に、本発明は、一方向にテープまたはシート状に引き揃えられた強化繊維と、同方向にテープまたはシート状に引き揃えられた熱可塑性樹脂からなる繊維（以下、「熱可塑性繊維」と称することがある。）と、を積層し、熱可塑性繊維を軟化させて強化繊維間を接合して形成した繊維基材テープまたはシートおよびその製造方法に関する。さらに、本発明は、この繊維基材テープまたはシートを前駆体とし、該前駆体を加熱成形してなる繊維強化熱可塑性樹脂複合材料に関する。 The present invention is a fiber base tape in which reinforcing fibers are unidirectionally arranged to form a fiber reinforced thermoplastic resin composite material having excellent mechanical properties, heat resistance, flame retardancy, and dimensional stability. Alternatively, the present invention relates to a sheet and a manufacturing method thereof. In particular, the present invention relates to a fiber (hereinafter referred to as “thermoplastic fiber”) composed of reinforcing fibers arranged in a tape or sheet in one direction and a thermoplastic resin arranged in a tape or sheet in the same direction. And a fiber base tape or sheet formed by softening thermoplastic fibers and bonding between reinforcing fibers, and a method for producing the same. Furthermore, this invention relates to the fiber reinforced thermoplastic resin composite material which uses this fiber base tape or sheet as a precursor, and heat-molds this precursor.
炭素繊維やガラス繊維等の強化繊維とマトリックス樹脂からなる繊維強化複合材料は、軽量であり、且つ比強度、比剛性に優れていることから、電気・電子分野、土木・建築、航空機・自動車・鉄道・船舶分野等において広く用いられている。特に、土木分野や輸送機器分野における主要な構造部材として用いられる場合には、材料には極めて優れた力学特性や、高温下使用に耐えうる耐熱性、耐久性、難燃性等が求められる。 Fiber reinforced composite materials made of reinforced fibers such as carbon fibers and glass fibers and matrix resins are lightweight and have excellent specific strength and specific rigidity, so they can be used in the electrical / electronic field, civil engineering / architecture, aircraft / automobile / Widely used in the railway and ship fields. In particular, when used as a main structural member in the field of civil engineering and transportation equipment, the material is required to have extremely excellent mechanical properties, heat resistance that can withstand use at high temperatures, durability, flame resistance, and the like.
こうした部材で用いられる繊維強化複合材料としては、高い力学物性を発揮するために、一般的に強化繊維として炭素繊維等の連続繊維を用いることが知られている。特に、一方向における力学物性が要求される場合には、強化繊維の強力利用率が高いことから、強化繊維が一方向に引き揃えられた材料を用いる場合がある。このような強化繊維が引き揃えられた材料のマトリックスとしてなる樹脂は、エポキシ樹脂やフェノール樹脂のような熱硬化性樹脂が用いられることが知られており、既に航空機分野等においても広く使用されている。 As a fiber reinforced composite material used in such a member, it is generally known to use continuous fibers such as carbon fibers as reinforcing fibers in order to exhibit high mechanical properties. In particular, when mechanical properties in one direction are required, a material in which the reinforcing fibers are aligned in one direction may be used because the strength utilization rate of the reinforcing fibers is high. It is known that a resin serving as a matrix of such a material in which reinforcing fibers are aligned is used as a thermosetting resin such as an epoxy resin or a phenol resin, and has already been widely used in the aircraft field and the like. Yes.
熱硬化性樹脂をマトリックスとする繊維強化複合材料は、硬化前の熱硬化樹脂の粘度が低く、強化繊維への含浸性が良好であることから、優れた力学物性を発揮する。一方で、成形において硬化工程が必要であり、該工程は長時間を要することから量産性や成形コスト面での問題がある。 A fiber reinforced composite material having a thermosetting resin as a matrix exhibits excellent mechanical properties since the viscosity of the thermosetting resin before curing is low and the impregnation property of the reinforcing fibers is good. On the other hand, in the molding, a curing process is required, and this process takes a long time, and thus there are problems in terms of mass productivity and molding cost.
そこで近年注目を集めるのは、熱可塑性樹脂をマトリックスとする繊維強化複合材料であり、これら材料は短い成形サイクルを可能とし、ハイサイクル生産の実現、つまりは単位時間当たりの生産性を高めることができることから、従来問題となっていた成形コストの問題を解決できる可能性がある。又、熱可塑性樹脂複合材料は、リサイクル性、リペア性にも優れ、環境面にも配慮した材料として幅広い分野において用いることが可能である。更には、熱可塑性樹脂が本来持つ高靭性の特性を活かし、損傷許容量を高めることができることから航空機の構造部材としても期待できる。 Therefore, fiber reinforced composite materials that use thermoplastic resin as a matrix have attracted attention in recent years, and these materials enable short molding cycles and realize high cycle production, that is, increase productivity per unit time. Therefore, there is a possibility that the problem of molding cost, which has been a conventional problem, can be solved. Further, the thermoplastic resin composite material is excellent in recyclability and repairability, and can be used in a wide range of fields as an environmentally friendly material. Furthermore, it can be expected as a structural member of an aircraft because the damage tolerance can be increased by utilizing the high toughness characteristic inherent in thermoplastic resins.
熱可塑性樹脂複合材料用の繊維基材テープまたはシートを製造する方法としては、（１）強化繊維束、或いは織物、編み物等のシート状物へ熱可塑性樹脂からなるフィルム成形物を重ね合わせ、加熱・加圧を施す方法（例えば、特許文献１及び２）、（２）同じく強化繊維シート状物へ熱可塑性樹脂の粉体（パウダー状物）を塗布し、これを加熱・加圧を施す方法（例えば、特許文献３及び４）、（３）更にもう１つは強化繊維シート状物へ熱可塑性樹脂を溶解させた溶剤を含浸させ、該溶剤を揮発させることにより熱可塑性樹脂を強化繊維シート状物へ担持させる方法（例えば、特許文献５）が知られている。さらに、（４）強化繊維に組み合わせる熱可塑性樹脂成分として、熱可塑性繊維を用いる方法が提案されている（特許文献６）。 As a method for producing a fiber base tape or sheet for a thermoplastic resin composite material, (1) a film molded product made of a thermoplastic resin is superposed on a reinforcing fiber bundle, or a sheet-like material such as woven fabric or knitted fabric, and heated.・ Methods of applying pressure (for example, Patent Documents 1 and 2), (2) Method of applying thermoplastic resin powder (powder) to a reinforced fiber sheet, and heating / pressing the same (For example, Patent Documents 3 and 4), (3) The other is that the reinforcing fiber sheet is impregnated with a solvent in which a thermoplastic resin is dissolved, and the solvent is volatilized to volatilize the thermoplastic resin. There is known a method (for example, Patent Document 5) for supporting a material. Furthermore, (4) a method using a thermoplastic fiber as a thermoplastic resin component combined with a reinforcing fiber has been proposed (Patent Document 6).
前記（１）のフィルム成形物を重ね合わせる方法においては、十分に樹脂が含浸できていないことから、得られる複合材料の力学物性は不十分なものに留まる。フィルム成形物の使用に当たっては、通常フィルム成形物は厚みを調整するために、延伸されていることが一般的であり、加熱成形時においてフィルム成形物が収縮するとの問題点がある。とくに、熱可塑性樹脂は溶融粘度が高いため、含浸する強化繊維シート状物の強化繊維が高度に引き揃えられている場合においては、強化繊維間に樹脂が流動する隙間が少ないことから、十分に樹脂を含浸できないとの問題点がある。 In the method of superimposing the film molded product of (1), since the resin is not sufficiently impregnated, the mechanical properties of the obtained composite material remain insufficient. When using a film molded product, the film molded product is generally stretched to adjust the thickness, and there is a problem that the film molded product shrinks during heat molding. In particular, since the thermoplastic resin has a high melt viscosity, when the reinforcing fibers of the reinforcing fiber sheet to be impregnated are highly aligned, there are few gaps for the resin to flow between the reinforcing fibers. There is a problem that the resin cannot be impregnated.
前記（２）の方法、熱可塑性樹脂の粉体（パウダー状物）を強化繊維シート状物上へまぶす手法においては、パウダー状物を均一にまぶすことが難しく、又材料パウダーの粒径を揃えることも難しいことから、強化繊維シート状物へ熱可塑性樹脂を均一に付着させることが難しいとの問題点がある。 In the method (2) described above, in which the thermoplastic resin powder (powder-like material) is applied onto the reinforcing fiber sheet, it is difficult to uniformly coat the powder-like material, and the particle sizes of the material powders are made uniform. Since this is difficult, there is a problem that it is difficult to uniformly attach the thermoplastic resin to the reinforcing fiber sheet.
前記（３）の方法、熱可塑性樹脂を溶解させた溶剤を用いて強化繊維シート状物へ含浸する手法は、強化繊維シート状物へ高比率で樹脂を含浸させることは難しい他、十分な含浸を行うためには含浸工程と溶剤を乾燥させる工程を繰り返す必要があり、取扱い性が悪いとの問題がある。更に、主に有機溶剤を用いることから、成形前には十分に溶剤を乾燥除去させることが必要であり、溶剤除去が不十分な場合には加熱成形時に溶剤が揮発する結果となり、成形体の中での発泡それに伴う物性低下、或いは揮発した溶剤を体内へ吸引する等の人体への影響も懸念される。 In the method (3), the method of impregnating the reinforcing fiber sheet using a solvent in which a thermoplastic resin is dissolved is difficult to impregnate the reinforcing fiber sheet in a high ratio, and sufficient impregnation. In order to perform this, it is necessary to repeat the impregnation step and the step of drying the solvent, and there is a problem that the handleability is poor. Furthermore, since an organic solvent is mainly used, it is necessary to dry and remove the solvent sufficiently before molding. If the solvent removal is insufficient, the solvent volatilizes at the time of heat molding. There are also concerns about the effects on the human body, such as the deterioration of physical properties associated with foaming in the inside or the inhalation of a volatilized solvent into the body.
前記（４）の方法では、熱可塑性樹脂繊維は、強化繊維基材の繊維束層と繊維束層とを接着して、強化繊維基材の形態を保持するために用いられており、成形材料の形成は別途添加しているマトリックス樹脂粉末の含浸によって行っており、このため、前記（２）の方法における問題点の解決には至っていない。 In the method (4), the thermoplastic resin fiber is used for adhering the fiber bundle layer and the fiber bundle layer of the reinforcing fiber base material to maintain the form of the reinforcing fiber base material. The formation of is performed by impregnation with a matrix resin powder added separately. Therefore, the problem in the method (2) has not been solved.
本発明の目的は、上述の先行技術の問題点を解消するために、繊維強化熱可塑性樹脂複合材料を形成するために用いられる、一方向に配列した強化繊維からなり、強化繊維間に熱可塑性樹脂が充分に含浸されるとともに、強化繊維間の接合が均一に行われた繊維基材テープまたはシートを提供することであり、その製造方法を、溶剤除去のようなプロセスに依存することなく提供することである。 The object of the present invention consists of unidirectionally arranged reinforcing fibers used to form a fiber-reinforced thermoplastic resin composite material to solve the above-mentioned problems of the prior art, and thermoplasticity between the reinforcing fibers. It is to provide a fiber base tape or sheet in which the resin is sufficiently impregnated and the reinforcing fibers are uniformly bonded, and its manufacturing method is provided without depending on a process such as solvent removal. It is to be.
本発明のさらなる目的は、上記の新規な繊維基材テープまたはシートを用いて、優れた力学物性と耐熱性、難燃性、寸法安定性を兼ね備えた繊維強化熱可塑性樹脂複合材料を提供することである。 A further object of the present invention is to provide a fiber reinforced thermoplastic resin composite material having excellent mechanical properties, heat resistance, flame retardancy, and dimensional stability by using the above novel fiber base tape or sheet. It is.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、一方向にテープまたはシート状に配列した複数の強化繊維と同方向にテープまたはシート状に配列した複数の熱可塑性繊維とを積層して、加熱・加圧を行うことにより、熱可塑性繊維が軟化して強化繊維間に接合が形成されることにより、熱可塑性繊維が均一に含有されるとともに強化繊維間が均一に接合された繊維基材テープまたはシートが得られることを見出し、上記の目的が達成されることを見出した。 As a result of intensive studies in order to solve the above problems, the present inventors have obtained a plurality of thermoplastic fibers arranged in a tape or a sheet in the same direction as a plurality of reinforcing fibers arranged in a tape or a sheet in one direction. Are laminated and heated / pressurized to soften the thermoplastic fibers and form a bond between the reinforcing fibers, so that the thermoplastic fibers are uniformly contained and the reinforcing fibers are uniformly distributed. It has been found that a bonded fiber base tape or sheet can be obtained, and that the above object has been achieved.
本発明第１の構成は、一方向にテープまたはシート状に配列した複数の強化繊維と同方向にテープまたはシート状に配列した複数の熱可塑性繊維とが積層されて形成されたテープまたはシート状の繊維基材であって、前記繊維基材の繊維配列方向に垂直方向の断面における少なくとも前記積層界面において、前記強化繊維の単繊維と前記熱可塑性繊維の単繊維の断面が混合して分布しており、前記熱可塑性繊維の少なくとも一部の断面が前記強化繊維の断面と断面との間を融着していることを特徴とする、前記強化繊維と前記熱可塑性繊維とが一方向に配列した繊維基材テープまたはシートである。 The first configuration of the present invention is a tape or sheet formed by laminating a plurality of reinforcing fibers arranged in a tape or sheet in one direction and a plurality of thermoplastic fibers arranged in a tape or sheet in the same direction. The cross-section of the single fiber of the reinforcing fiber and the single fiber of the thermoplastic fiber is mixed and distributed at least at the lamination interface in the cross section perpendicular to the fiber arrangement direction of the fiber base material. The reinforcing fiber and the thermoplastic fiber are arranged in one direction, wherein at least a part of the cross section of the thermoplastic fiber is fused between the cross section of the reinforcing fiber. Fiber base tape or sheet.
前記の繊維基材テープまたはシートにおいて、前記の一方向にテープまたはシート状に配列した複数の強化繊維の片面または両面に前記の同方向にテープまたはシート状に配列された複数の熱可塑性繊維が積層されていることが好ましい。 In the fiber-based tape or sheet, a plurality of thermoplastic fibers arranged in the same direction in a tape or a sheet are provided on one or both sides of the plurality of reinforcing fibers arranged in a tape or a sheet in the one direction. It is preferable that they are laminated.
前記の繊維基材テープまたはシートにおいて、前記の一方向にテープまたはシート状に配列した複数の強化繊維と同方向にテープまたはシート状に配列した複数の熱可塑性繊維とが一段または多段に積層されていることが好ましい。 In the fiber base tape or sheet, a plurality of reinforcing fibers arranged in a tape or sheet in one direction and a plurality of thermoplastic fibers arranged in a tape or sheet in the same direction are laminated in one or more stages. It is preferable.
上記の繊維基材テープまたはシートは、以下の条件を全て満たすことが好ましい。
（１）前記繊維基材の全繊維重量に対して、前記強化繊維の割合が１０重量％〜９０重量％である。
（２）前記繊維基材を構成する前記熱可塑性繊維の単繊維の繊度が０．５〜１０ｄｔｅｘであり、フィラメント数が１０〜２４０００本である。
（３）前記テープまたはシートの幅が０．１〜５０ｍｍであり、厚みが０．１〜１０ｍｍである。
The fiber base tape or sheet preferably satisfies all the following conditions.
(1) The ratio of the reinforcing fibers is 10% by weight to 90% by weight with respect to the total fiber weight of the fiber base material.
(2) The fineness of the single fiber of the thermoplastic fiber constituting the fiber base material is 0.5 to 10 dtex, and the number of filaments is 10 to 24,000 .
(3) The tape or sheet has a width of 0.1 to 50 mm and a thickness of 0.1 to 10 mm.
前記の一方向にテープまたはシート状に配列した複数の強化繊維と前記の同方向にテープまたはシート状に配列した複数の熱可塑性繊維とに、さらにバインダーが加えられて前記バインダーによる繊維間の接合が形成されている、繊維基材テープまたはシートであることが好ましい。 A binder is further added to the plurality of reinforcing fibers arranged in a tape or sheet in the one direction and the plurality of thermoplastic fibers arranged in a tape or sheet in the same direction, and the fibers are joined by the binder. It is preferably a fiber base tape or sheet in which is formed.
前記熱可塑性繊維が、ポリエーテルイミド系繊維、ポリエーテルエーテルケトン系繊維、ポリエーテルケトンケトン系繊維、ポリフェニレンサルファイド繊維、ポリスルフォン繊維、熱可塑性ポリイミド系繊維、ポリカーボネート系繊維および半芳香族ポリアミド系繊維からなる群より選ばれた少なくとも１種であることが好ましい。 The thermoplastic fibers are polyetherimide fibers, polyetheretherketone fibers, polyetherketoneketone fibers, polyphenylene sulfide fibers, polysulfone fibers, thermoplastic polyimide fibers, polycarbonate fibers and semi-aromatic polyamide fibers. It is preferably at least one selected from the group consisting of
前記強化繊維が、炭素繊維、ガラス繊維、全芳香族ポリエステル繊維、アラミド繊維、セラミック繊維およびメタル繊維からなる群より選ばれた少なくとも１種であることが好ましい。 The reinforcing fiber is preferably at least one selected from the group consisting of carbon fiber, glass fiber, wholly aromatic polyester fiber, aramid fiber, ceramic fiber and metal fiber.
本発明第２の構成は、一方向に引き揃えられ、幅方向に拡げられた強化繊維の連続繊維束と同方向に引き揃えられ、幅方向に拡げられた熱可塑性繊維の連続繊維束を、積層して一体化し、ついで、加熱・加圧装置を通過させて、前記熱可塑性繊維の少なくとも一部を軟化させながら前記強化繊維の繊維間を接合して、テープまたはシート状の繊維基材を製造することを特徴とする、前記強化繊維と前記熱可塑性繊維とが一方向に配列した繊維基材テープまたはシートの製造方法である。 The second configuration of the present invention is a continuous fiber bundle of thermoplastic fibers that is aligned in one direction and is aligned in the same direction as a continuous fiber bundle of reinforcing fibers that is expanded in the width direction, and is expanded in the width direction. Laminate and integrate, and then pass through a heating / pressurizing apparatus to join the fibers of the reinforcing fibers while softening at least a part of the thermoplastic fibers to form a tape or sheet-like fiber substrate. It is a manufacturing method of a fiber base tape or sheet in which the reinforcing fibers and the thermoplastic fibers are arranged in one direction.
上記の方法において、前記加熱・加圧装置が、プレスローラであることが好ましい。 In the above method, the heating / pressurizing device is preferably a press roller.
本発明第３の構成は、前記の繊維基材テープまたはシートを織製または編製して形成された布帛であり、織製された布帛は、繊維基材テープまたはシートを経糸および／または緯糸として用いて織製されていてよい。 The third configuration of the present invention is a fabric formed by weaving or knitting the fiber base tape or sheet, and the woven fabric uses the fiber base tape or sheet as warp and / or weft. It may be woven using.
本発明第４の構成は、前記繊維基材テープまたはシートを加熱成形してなる繊維強化熱可塑性樹脂複合材料である。 A fourth configuration of the present invention is a fiber reinforced thermoplastic resin composite material obtained by thermoforming the fiber base tape or sheet.
本発明第１の構成により得られる、強化繊維と熱可塑性繊維とが一方向に配列した繊維基材テープまたはシートを用いて熱可塑性樹脂複合材料を形成すると、一方向に配列した強化繊維層中に、熱可塑性樹脂が十分かつ均一に含浸された繊維強化熱可塑性樹脂複合材料を得ることができるという利点がある。 When the thermoplastic resin composite material is formed by using the fiber base tape or sheet in which the reinforcing fibers and the thermoplastic fibers are arranged in one direction, which is obtained by the first configuration of the present invention, in the reinforcing fiber layer arranged in one direction Further, there is an advantage that a fiber reinforced thermoplastic resin composite material in which the thermoplastic resin is sufficiently and uniformly impregnated can be obtained.
本発明第２の構成によれば、一方向に配列した強化繊維束を幅方向にテープ状またはシート状に拡げながら、同時に、別途、一方向に配列した熱可塑性繊維束を幅方向にテープ状またはシート状に拡げながら、両方のテープまたはシート状物を積層しながら、加熱・加圧手段により加熱・加圧処理することにより、熱可塑性繊維を軟化させて強化繊維間を接合することにより繊維基材テープまたはシートを製造することができるので、基本的な製造方式としては、強化繊維間の接合のためのプロセスに溶媒の使用を必要とせず、したがって、従来技術におけるような環境上、作業員の健康上の負担を軽減することができる。 According to the second configuration of the present invention, the reinforcing fiber bundle arranged in one direction is expanded in a tape shape or a sheet shape in the width direction, and at the same time, the thermoplastic fiber bundle arranged in one direction is separately taped in the width direction. Or by spreading both tapes or sheet-like materials while spreading them into a sheet, heating / pressurizing by heating / pressurizing means, softening the thermoplastic fibers and joining the reinforcing fibers Since the base tape or sheet can be produced, the basic production method does not require the use of a solvent in the process for bonding between the reinforcing fibers, and therefore works environmentally as in the prior art. The burden on the health of employees can be reduced.
本発明第３の構成によれば、上記の本発明第１の構成に係る強化繊維と熱可塑性繊維とが一方向に配列した繊維基材テープまたはシートを経糸および／または緯糸として使用して織製する、あるいは繊維基材テープまたはシートを編製することにより形成される布帛は、一方向ＦＲＰ用ではなく、織物、編物等を補強材とするＦＲＰ用として好適に用いられる。この場合も、強化繊維と熱可塑性繊維とが一方向に配列した繊維基材テープまたはシートから布帛が形成されるため、力学的性能などに優れた布帛補強熱可塑性樹脂複合材料が得られる。 According to the third configuration of the present invention, a fiber base tape or sheet in which the reinforcing fiber and the thermoplastic fiber according to the first configuration of the present invention are arranged in one direction is used as a warp and / or a weft. Fabrics that are manufactured or formed by knitting fiber-based tapes or sheets are suitably used not for unidirectional FRP but for FRP using a woven fabric, knitted fabric or the like as a reinforcing material. Also in this case, since the fabric is formed from the fiber base tape or sheet in which the reinforcing fibers and the thermoplastic fibers are arranged in one direction, a fabric-reinforced thermoplastic resin composite material excellent in mechanical performance and the like can be obtained.
本発明第４の構成によれば、優れた力学物性と耐熱性、難燃性、寸法安定性を兼ね備え、特に一方向における高い力学物性と耐熱性、難燃性、寸法安定性が要求される用途に適した繊維強化熱可塑性樹脂複合材料を提供することが可能である。更に、本発明の繊維強化熱可塑性樹脂複合材料は、特別な成形方法を用いることなく、熱可塑性樹脂の強化繊維束への高い含浸性を達成し、その結果、高い力学物性を有する熱可塑性樹脂複合材料を工業的に効率良く、且つ経済的に製造することができる。更に、本発明の繊維強化熱可塑性樹脂複合材料は、その高い力学物性を活かし、一般産業資材分野、電気・電子分野、土木・建築分野等の幅広い分野において有効に用いることができ、特に航空機・自動車、鉄道・船舶等の輸送機器分野においては、その主要な構造を成す部材として有効に用いることができる。 According to the fourth configuration of the present invention, it has excellent mechanical properties, heat resistance, flame retardancy, and dimensional stability, and particularly requires high mechanical properties, heat resistance, flame retardancy, and dimensional stability in one direction. It is possible to provide a fiber reinforced thermoplastic resin composite material suitable for an application. Furthermore, the fiber reinforced thermoplastic resin composite material of the present invention achieves high impregnation of the thermoplastic resin into the reinforcing fiber bundle without using a special molding method. As a result, the thermoplastic resin has high mechanical properties. The composite material can be produced industrially efficiently and economically. Furthermore, the fiber reinforced thermoplastic resin composite material of the present invention can be effectively used in a wide range of fields such as general industrial material fields, electrical / electronic fields, civil engineering / architecture fields, taking advantage of its high mechanical properties. In the field of transportation equipment such as automobiles, railways and ships, it can be effectively used as a member constituting its main structure.
(繊維基材テープまたはシートの構成)
本発明の繊維基材テープまたはシートは、（１）一方向にテープまたはシート状に配列した複数の強化繊維と同方向にテープまたはシート状に配列した複数の熱可塑性繊維とが積層されて形成され、（２）繊維基材の繊維配列方向に垂直方向の断面における少なくとも前記積層界面において、前記強化繊維の単繊維と前記熱可塑性繊維の単繊維の断面が混合して分布しており、前記熱可塑性繊維の少なくとも一部の断面が前記強化繊維の断面と断面との間を融着している。
本発明の繊維基材テープまたはシートを製造するための出発原料としては、一方向に配列した強化繊維束および熱可塑性繊維束が用いられるが、この強化繊維束および熱可塑性繊維束をテープ状またはシート状に幅を拡げながら、テープまたはシート状に拡げられた一方向配列強化繊維（Ａ）と同様にテープまたはシート状に拡げられた同方向配列熱可塑性繊維（Ｂ）とが積層される。積層は、それぞれ１層が積層されるＡ−Ｂ型、強化繊維または熱可塑性繊維のどちらか１層の両面に他層が形成されたＡ−Ｂ−Ａ型、Ｂ−Ａ−Ｂ型、これらの単位が重ねあわされた、Ａ−Ｂ−Ａ−Ｂ、Ａ−Ｂ−Ａ−Ｂ−Ａ−Ｂ型など、要求性能に応じて積層数は適宜選択可能である。
テープまたはシート状強化繊維とテープまたはシート状熱可塑性繊維は、少なくとも積層界面においては、この二つの繊維の単繊維は入り乱れて存在しており、そして熱可塑性繊維の少なくとも一部が軟化して、強化繊維の単繊維間を融着しており、この融着により繊維基材シートまたはテープが形成されている。
本発明において、「少なくとも一部の断面」における「少なくとも一部」とは、本発明に係る繊維基材テープまたはシートを形成可能な程度に、強化繊維の断面と断面とが融着していることを意味する。
本発明において、「繊維基材」とは、強化繊維を単層または複層のテープ状またはシート状にした、繊維強化熱可塑性樹脂複合材料の前駆体を意味する。
本発明において、テープとは、強化繊維束または熱可塑性繊維束が開繊拡幅されて、平行に引き揃えて面状に並べたものを意味し、その幅が２５０ｍｍ未満のものを言い、シートとは、その幅が２５０ｍｍ以上のものをいう。
(Configuration of fiber base tape or sheet)
The fiber base tape or sheet of the present invention is formed by laminating (1) a plurality of reinforcing fibers arranged in a tape or sheet in one direction and a plurality of thermoplastic fibers arranged in a tape or sheet in the same direction. And (2) at least at the lamination interface in the cross section perpendicular to the fiber arrangement direction of the fiber base material, the single fiber of the reinforcing fiber and the single fiber of the thermoplastic fiber are mixed and distributed, At least a part of the cross section of the thermoplastic fiber is fused between the cross section of the reinforcing fiber.
As a starting material for producing the fiber base tape or sheet of the present invention, a reinforced fiber bundle and a thermoplastic fiber bundle arranged in one direction are used. The unidirectionally aligned thermoplastic fibers (B) expanded in the form of a tape or a sheet are laminated together with the unidirectionally aligned reinforcing fibers (A) expanded in the form of a tape or a sheet while expanding the width in the form of a sheet. Lamination is A-B type in which one layer is laminated, A-B-A type in which other layers are formed on both sides of either one of reinforcing fiber or thermoplastic fiber, B-A-B type, these The number of layers can be selected as appropriate according to the required performance, such as A-B-A-B or A-B-A-B-A-B type, in which the units are overlapped.
In the tape or sheet-like reinforcing fiber and the tape or sheet-like thermoplastic fiber, at least at the lamination interface, the single fiber of the two fibers is confused and at least a part of the thermoplastic fiber is softened, Single fibers of reinforcing fibers are fused together, and a fiber base sheet or tape is formed by this fusion.
In the present invention, “at least a part” in “at least a part of the cross section” means that the cross section and the cross section of the reinforcing fiber are fused to such an extent that the fiber base tape or sheet according to the present invention can be formed. Means that.
In the present invention, the “fiber substrate” means a precursor of a fiber reinforced thermoplastic resin composite material in which reinforcing fibers are formed into a single-layer or multi-layer tape or sheet.
In the present invention, the tape means that the reinforcing fiber bundle or the thermoplastic fiber bundle is spread and widened, aligned in parallel and arranged in a plane, and the width is less than 250 mm, Means that the width is 250 mm or more.
（熱可塑性繊維）
本発明で用いられる熱可塑性樹脂からなる繊維（熱可塑性繊維）は、加熱溶融或いは加熱流動するものであれば特に制限されることはないが、力学物性や耐熱性、難燃性、寸法安定性の観点から、ポリエーテルイミド系繊維、ポリエーテルエーテルケトン系繊維、ポリエーテルケトンケトン系繊維、ポリフェニレンサルファイド系繊維、ポリスルフォン系繊維、熱可塑性ポリイミド系繊維、ポリカーボネート系繊維、半芳香族ポリアミド系繊維が好適に用いられる。特に、本発明の熱可塑性樹脂複合材料を航空宇宙分野で用いるために、難燃性及び耐熱性に優れるという理由から、ポリエーテルイミド系繊維、ポリエーテルエーテルケトン系繊維、ポリエーテルケトンケトン系繊維、熱可塑性ポリイミド系繊維を用いることが好ましく、自動車分野で用いるために、耐熱性に優れるという理由から、半芳香族ポリアミド系繊維を用いることがより好ましい。特に、高い耐熱性、難燃性、寸法安定性が要求される航空宇宙、自動車、船舶等の輸送機器分野においては、前記性能に優れるポリエーテルイミド系繊維、ポリエーテルエーテルケトン系繊維、ポリエーテルケトンケトン系繊維、熱可塑性ポリイミド系繊維、半方向族ナイロン系繊維を好適に用いることができる。これらは単独で用いてもよく、２種以上の繊維を組み合わせて用いても良い。
また、異種または同種で特性の異なる熱可塑性樹脂の組合せからなる、芯鞘型やサイドバイサイド型の複合繊維も用いることができる。
(Thermoplastic fiber)
The fiber (thermoplastic fiber) made of the thermoplastic resin used in the present invention is not particularly limited as long as it is heat-melted or heat-flowable, but mechanical properties, heat resistance, flame retardancy, and dimensional stability. From the viewpoint of polyetherimide fiber, polyether ether ketone fiber, polyether ketone ketone fiber, polyphenylene sulfide fiber, polysulfone fiber, thermoplastic polyimide fiber, polycarbonate fiber, semi-aromatic polyamide fiber Are preferably used. In particular, since the thermoplastic resin composite material of the present invention is used in the aerospace field, it is excellent in flame retardancy and heat resistance, so that it is a polyetherimide fiber, a polyether ether ketone fiber, a polyether ketone ketone fiber. It is preferable to use a thermoplastic polyimide fiber, and it is more preferable to use a semi-aromatic polyamide fiber because it is excellent in heat resistance for use in the automobile field. In particular, in the field of transportation equipment such as aerospace, automobiles, ships, etc. that require high heat resistance, flame retardancy, and dimensional stability, polyetherimide fibers, polyetheretherketone fibers, polyethers having excellent performance Ketone ketone fibers, thermoplastic polyimide fibers, and semi-directional nylon fibers can be suitably used. These may be used alone or in combination of two or more kinds of fibers.
Further, core-sheath type or side-by-side type composite fibers made of a combination of different types or the same type of thermoplastic resins having different characteristics can also be used.
本発明で用いる熱可塑性繊維は、本発明の効果を損なわない範囲で、酸化防止剤、帯電防止剤、ラジカル抑制剤、艶消し剤、顔料、染料、紫外線吸収剤、相容化剤、難燃剤、無為物等を含んでいても良い。かかる無機物の具体例としては、黒鉛、カーボンブラック、カーボンナノチューブ、フラーレン、ガラス、タルク、ゼオライト、マイカ、クレー、シリカ、ベンナイト、スメクタイト等に代表されるケイ酸塩、酸化マグネシウム、アルミナ、酸化チタン、酸化鉄等の金属酸化物、炭酸カルシウム、炭酸マグネシウム等の炭酸塩、硫酸カルシウム、硫酸バリウム等の硫酸塩、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の水酸化物等が用いられる。 The thermoplastic fiber used in the present invention is an antioxidant, an antistatic agent, a radical inhibitor, a matting agent, a pigment, a dye, an ultraviolet absorber, a compatibilizer, and a flame retardant, as long as the effects of the present invention are not impaired. It may contain involuntary items. Specific examples of such inorganic substances include graphite, carbon black, carbon nanotubes, fullerene, glass, talc, zeolite, mica, clay, silica, bennite, smectite and the like, silicates, magnesium oxide, alumina, titanium oxide, Metal oxides such as iron oxide, carbonates such as calcium carbonate and magnesium carbonate, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide are used.
本発明で用いる熱可塑性繊維の製造方法は、特に制限されることはないが、公知の溶融紡糸装置を用いて製造することができる。すなわち、溶融押出し機で熱可塑性樹脂のペレットや粉体を溶融混練し、溶融樹脂を紡糸筒に導き、続いてギヤポンプで軽量し、紡糸ノズルから吐出させて糸条を巻取り機にて巻き取ることにより得られる。その際の引き取り速度は特に限定されるものではないが、５００〜４０００ｍ／分の範囲で引き取ることが好ましい。５００ｍ／分未満にでは生産性の観点から好ましくなく、一方で４０００ｍ／分を超えるような高速での巻き取りは、繊維化が難しくなり、断糸が頻発するため生産性が低下し、更に得られる糸は紡糸線上での分子配向が進行するため、その後の熱成形時において高温に晒された際に繊維が大きく収縮することから好ましくない。 Although the manufacturing method of the thermoplastic fiber used by this invention is not restrict | limited in particular, It can manufacture using a well-known melt spinning apparatus. In other words, thermoplastic resin pellets and powder are melted and kneaded with a melt extruder, the molten resin is guided to a spinning cylinder, subsequently lightened with a gear pump, discharged from a spinning nozzle, and wound with a winder. Can be obtained. The take-up speed at that time is not particularly limited, but it is preferably taken in the range of 500 to 4000 m / min. If it is less than 500 m / min, it is not preferable from the viewpoint of productivity. On the other hand, winding at a high speed exceeding 4000 m / min makes it difficult to fiberize, and the yarn is frequently broken, resulting in lower productivity. The resulting yarn undergoes molecular orientation on the spinning line, which is not preferable because the fiber contracts greatly when exposed to a high temperature during subsequent thermoforming.
本発明で用いられる熱可塑性繊維の製造においては、耐熱性樹脂成形体の製造工程での工程通過性や得られる成形体の寸法安定性を確保するために、延伸工程を施さないことが好ましい。従来の繊維製造工程で実施されるような延伸を施すと、加熱成形時に分子運動の増大に起因するエントロピー収縮が起こり、大きな収縮を伴うことになり、繊維基材を加熱成形する際の工程通過性を悪化させ、得られた成形体の外観不良や十分な力学物性が発現しない等の懸念がある。 In the production of the thermoplastic fiber used in the present invention, it is preferable not to perform the stretching step in order to ensure the process passability in the production process of the heat resistant resin molded body and the dimensional stability of the obtained molded body. When stretching is performed as in the conventional fiber manufacturing process, entropy shrinkage occurs due to an increase in molecular motion during thermoforming, which is accompanied by large shrinkage, and passes through the process when thermoforming a fiber substrate. There is a concern that the appearance of the obtained molded product is poor and sufficient mechanical properties are not exhibited.
本発明で用いられる熱可塑性繊維に付与するサイズ剤は特に制限されることはないが、公知のサイズ剤を付与することができる。特に、紡糸工程、引き揃え糸作成工程に必要なサイズ剤を付与することができ、成形物となるまでにいくつかある各工程において、それらを洗浄により取り除き、新たに付与することもできる。 The sizing agent applied to the thermoplastic fiber used in the present invention is not particularly limited, but a known sizing agent can be applied. In particular, a sizing agent necessary for the spinning process and the draw yarn forming process can be applied, and in some processes until forming a molded product, they can be removed by washing and newly applied.
本発明で用いられる熱可塑性繊維は、フィラメント形態のものを拡幅して用いられることが望ましく、その単繊維の平均繊度は、０．５〜１０ｄｔｅｘが好ましい。平均繊度が細くなるほど、同重量下における繊維表面積が大きくなることから、加熱成形する際には熱可塑性繊維がより融解しやすい状態となる。又、繊維を拡幅する際にはより薄い引き揃えテープまたはシートを作成することができ、より薄い繊維基材、或いは複合材料の作成にも適している。一方で、単糸繊度が０．５ｄｔｅｘ以下となる場合には、繊維製造や拡幅が難しくなる他、繊維同士が絡まること等から、取扱い性が低下することが懸念される。好ましくは、単繊維の平均繊度は、１．０〜５．０ｄｔｅｘ、好ましくは、１．５〜４．０ｄｔｅｘ、更に好ましくは、２．０〜３．０ｄｔｅｘである。 The thermoplastic fiber used in the present invention is desirably widened in filament form, and the average fineness of the single fiber is preferably 0.5 to 10 dtex. Since the fiber surface area under the same weight increases as the average fineness decreases, the thermoplastic fibers are more easily melted during thermoforming. Further, when the fibers are widened, a thinner alignment tape or sheet can be produced, which is suitable for producing a thinner fiber substrate or composite material. On the other hand, when the single yarn fineness is 0.5 dtex or less, fiber manufacture and widening become difficult, and the fibers are entangled with each other. Preferably, the average fineness of the single fiber is 1.0 to 5.0 dtex, preferably 1.5 to 4.0 dtex, and more preferably 2.0 to 3.0 dtex.
更に、繊維基材テープまたはシートを形成する熱可塑性繊維の総フィラメント数は、１０〜２４０００本が好ましく、更に好ましくは２０〜１２０００本である。総フィラメント数は、繊維束を拡幅し、一方向引き揃えのテープ状物とした際の、テープ幅やテープの厚みに影響を及ぼす。フィラメント数が多すぎる場合には、薄く且つ小さい幅のテープの作成が難しくなり、逆にフィラメント数が小さすぎる場合には、取扱いに十分な幅のテープを作成することが困難となる。 Furthermore, the total number of filaments of the thermoplastic fiber forming the fiber base tape or sheet is preferably 10 to 24,000, and more preferably 20 to 12,000. The total number of filaments affects the tape width and the tape thickness when the fiber bundle is widened to obtain a one-way aligned tape-like product. When the number of filaments is too large, it is difficult to produce a thin tape having a small width, and conversely, when the number of filaments is too small, it is difficult to produce a tape having a width sufficient for handling.
（強化繊維）
本発明で用いる強化繊維については、本発明の効果を損なわない限りにおいては特に制限されず、例えば、ガラス繊維、炭素繊維、炭化ケイ素繊維、アルミナ繊維、セラミックファイバー、金、銀、銅、鉄、ニッケル、チタン等の各種金属繊維、パラ系アラミド繊維、全芳香族ポリエステル繊維を例示することができる。
(Reinforced fiber)
The reinforcing fiber used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, for example, glass fiber, carbon fiber, silicon carbide fiber, alumina fiber, ceramic fiber, gold, silver, copper, iron, Examples include various metal fibers such as nickel and titanium, para-aramid fibers, and wholly aromatic polyester fibers.
これら強化繊維のうち、力学物性や難燃性、耐熱性、入手し易さの観点から、炭素繊維、ガラス繊維、全芳香族ポリエステル繊維、パラ系アラミド繊維が好適に用いられる。この中でも特に炭素繊維は、非常に高い強度、弾性率、耐熱性、及び難燃性を有し、且つ近年多くの企業が製造に参入していることから比較的入手もし易い、更には、炭素繊維を広幅のテープ状にする拡幅技術も目覚しく、容易に可能となることから好適に用いることができる。 Of these reinforcing fibers, carbon fibers, glass fibers, wholly aromatic polyester fibers, and para-aramid fibers are preferably used from the viewpoints of mechanical properties, flame retardancy, heat resistance, and availability. Among them, carbon fiber in particular has very high strength, elastic modulus, heat resistance, and flame retardancy, and is relatively easy to obtain because many companies have recently entered the manufacturing process. A widening technique for forming fibers into a wide tape shape is also remarkable and can be suitably used because it can be easily performed.
繊維基材テープまたはシートを形成する上記強化繊維の総フィラメント数は、１０〜２４０００本が好ましく、更に好ましくは２０〜１２０００本である。総フィラメント数は、繊維束を拡幅し、一方向引き揃えのテープ状物とした際の、テープ幅やテープの厚みに影響を及ぼす。フィラメント数が多すぎる場合には、薄く且つ小さい幅のテープの作成が難しくなり、逆にフィラメント数が小さすぎる場合には、取扱いに十分な幅のテープを作成することが困難となる。 The total number of filaments of the reinforcing fibers forming the fiber base tape or sheet is preferably 10 to 24,000, and more preferably 20 to 12,000. The total number of filaments affects the tape width and the tape thickness when the fiber bundle is widened to obtain a one-way aligned tape-like product. When the number of filaments is too large, it is difficult to produce a thin tape having a small width, and conversely, when the number of filaments is too small, it is difficult to produce a tape having a width sufficient for handling.
（バインダー）
本発明の繊維基材テープまたはシートにおいて、テープまたはシート状の熱可塑性繊維及び強化繊維の、それぞれの繊維と繊維の間における接合、或いはテープまたはシート状の熱可塑性繊維と強化繊維との積層界面における接合を、バインダーを加えてバインダーにより補強してもよい。バインダーにより、繊維間を接合させることにより、加熱成形前の繊維基材テープまたはシートの取扱い性を向上させ、加熱成形前或いは加熱成形時において、一方向に引き揃えられた強化繊維の方向性が乱れることを防ぎ、その結果、力学物性が高く、外観の良好な熱可塑性樹脂複合材料を得ることが可能となる。
(binder)
In the fiber-based tape or sheet of the present invention, the tape or sheet-like thermoplastic fiber and the reinforcing fiber are bonded to each other, or the laminated interface between the tape or sheet-like thermoplastic fiber and the reinforcing fiber is used. The bonding may be reinforced with a binder by adding a binder. By bonding the fibers with a binder, the handling property of the fiber base tape or sheet before heat forming is improved, and the directionality of the reinforcing fibers aligned in one direction before or during heat forming is improved. As a result, it is possible to obtain a thermoplastic resin composite material having high mechanical properties and good appearance.
上述のバインダーは、繊維基材テープまたはシートの全重量に対する割合が、０〜３０％であることが好ましい。バインダー成分が３０％を越える場合には、熱可塑性樹脂複合材料の力学物性や耐熱性、難燃性、寸法安定性等の性能について、マトリックスを形成する熱可塑性樹脂による特徴に影響を及ぼすことが懸念される。バインダーは、より好ましくは０〜１０％、更に好ましくは０〜５％である。 The above binder preferably has a ratio of 0 to 30% with respect to the total weight of the fiber base tape or sheet. When the binder component exceeds 30%, the properties of the thermoplastic resin forming the matrix may be affected by the properties such as mechanical properties, heat resistance, flame retardancy, and dimensional stability of the thermoplastic resin composite material. Concerned. The binder is more preferably 0 to 10%, still more preferably 0 to 5%.
本発明で用いるバインダーとして、ポリエステル、ポリビニルアルコール、ポリエチレンビニルアルコール、ポリアセテート、エチレンビニルアセテート、ポリアクリル酸、ポリアクリル酸エステル、ポリウレタン、メラミン樹脂、フェノール樹脂、エポキシ樹脂などを用いることができる。 As the binder used in the present invention, polyester, polyvinyl alcohol, polyethylene vinyl alcohol, polyacetate, ethylene vinyl acetate, polyacrylic acid, polyacrylic ester, polyurethane, melamine resin, phenol resin, epoxy resin and the like can be used.
また、本発明で用いるバインダーの形態は、特に限定されるものではなく、粉体（パウダー状物）；フィラメント、ステープル、ショートカット等の形態の繊維状物；或いは、水又は有機溶剤を分散媒とするエマルジョン分散液等を使用することができる。
上述したように、成形時における強化繊維の方向性が乱れることを防ぐ方法として、繊維基材テープまたはシート内にバインダーを配し、強化繊維を固定化させる方法について述べたが、これらを効率的に活用するために、上述した熱可塑性繊維が流動する温度での加熱・加圧成形の前に、バインダー成分が溶融する温度域にて予備加熱してもよい。
In addition, the form of the binder used in the present invention is not particularly limited, and is a powder (powder); a fiber in the form of filament, staple, shortcut, etc .; or water or an organic solvent as a dispersion medium An emulsion dispersion or the like can be used.
As described above, as a method for preventing the directionality of the reinforcing fiber during molding from being disturbed, a method for fixing the reinforcing fiber by arranging a binder in the fiber base tape or sheet has been described. In order to utilize it, you may pre-heat in the temperature range which a binder component fuse | melts before the heating and press-molding in the temperature which the thermoplastic fiber mentioned above flows.
（強化繊維と熱可塑性繊維との積層）
本発明の繊維基材テープまたはシートは、一方向に引き揃えられた強化繊維からなる連続繊維束を拡幅してテープまたはシート状にした物と、同じく一方向に引き揃えられた熱可塑性繊維からなる連続繊維束を拡幅してテープまたはシート状にした物とを積層・複合化した、繊維基材テープまたはシートである。このように、熱可塑性繊維及び強化繊維をそれぞれ一方向に引き揃えることで、積層した際にテープまたはシート状の熱可塑性繊維層とテープまたはシート状の強化繊維層とが隙間なく密着するため、熱成形した際に、容易に強化繊維と強化繊維の間に熱可塑性繊維が溶融して熱可塑性樹脂が含浸し、高い含浸率の複合材料を容易に得ることができ、結果として得られた複合材料は高い力学物性を有する。面内に含まれる強化繊維の量が多くなり、マトリックスである熱可塑性樹脂に対する補強効果が大きくなる。
(Lamination of reinforced fiber and thermoplastic fiber)
The fiber-based tape or sheet of the present invention is obtained by widening a continuous fiber bundle composed of reinforcing fibers aligned in one direction into a tape or sheet, and a thermoplastic fiber aligned in one direction. It is a fiber base tape or sheet in which a continuous fiber bundle is widened and combined with a tape or sheet. In this way, by aligning the thermoplastic fibers and the reinforcing fibers in one direction respectively, the tape or sheet-like thermoplastic fiber layer and the tape or sheet-like reinforcing fiber layer are closely adhered to each other when laminated, When thermoformed, the thermoplastic fiber is easily melted between the reinforcing fibers and impregnated with the thermoplastic resin, and a composite material with a high impregnation rate can be easily obtained, and the resulting composite The material has high mechanical properties. The amount of reinforcing fibers contained in the surface increases, and the reinforcing effect on the thermoplastic resin as a matrix increases.
繊維基材の全繊維重量に対する強化繊維の割合は、１０〜９０重量％が好ましく（熱可塑性繊維の割合は、９０〜１０重量％）、更に好ましくは、強化繊維の割合は３０〜７０重量％（熱可塑性繊維の割合は、７０〜３０重量％）である。強化繊維が１０重量％未満となる場合では強化繊維の割合が少ないため、補強効果が少なくなるため、高い力学物性の複合材料を得ることができない。一方で９０重量％を超えるとマトリックスとなる樹脂が少なく、強化繊維束に十分に樹脂が含浸しないため、望ましい力学物性の材料を得ることができないため好ましくない。 The ratio of the reinforcing fiber to the total fiber weight of the fiber base is preferably 10 to 90% by weight (the ratio of the thermoplastic fiber is 90 to 10% by weight), more preferably the ratio of the reinforcing fiber is 30 to 70% by weight. (The ratio of the thermoplastic fiber is 70 to 30% by weight). When the reinforcing fiber is less than 10% by weight, the reinforcing fiber ratio is small and the reinforcing effect is reduced, so that a composite material having high mechanical properties cannot be obtained. On the other hand, if it exceeds 90% by weight, the resin used as a matrix is small, and the reinforcing fiber bundle is not sufficiently impregnated with the resin, so that a material having desirable mechanical properties cannot be obtained.
一方向に引き揃えられた熱可塑性繊維からなる連続繊維束、及び一方向に引き揃えられた強化繊維からなる連続繊維束をそれぞれ開繊拡幅してテープまたはシート状物とする方法は、特に制限されることはなく、公知の方法により作成することができる。一方向に引き揃えた際の幅が０．１〜５０ｍｍ、厚みが０．１〜１０ｍｍであることが好ましい。幅が０．１ｍｍ未満となる場合には、熱可塑性繊維と強化繊維との張り合わせやその後の成形における取扱い性が悪くなるとの懸念があり、一方で幅が５０ｍｍを超える場合には、繊維引き揃えの斑が発生するとの懸念があるため好ましくない。また、厚みが０．１ｍｍ未満の場合には、厚み斑等の問題が発生し、また１０ｍｍを超える場合には、成形時における樹脂含浸が難しくなるとの懸念がある。 There is a particular limitation on the method of expanding the continuous fiber bundle composed of thermoplastic fibers aligned in one direction and the continuous fiber bundle composed of reinforcing fibers aligned in one direction into a tape or a sheet. It can be created by a known method. The width when aligned in one direction is preferably 0.1 to 50 mm and the thickness is 0.1 to 10 mm. When the width is less than 0.1 mm, there is a concern that the handling property in the lamination and the subsequent molding of the thermoplastic fiber and the reinforcing fiber is deteriorated. On the other hand, when the width exceeds 50 mm, the fibers are aligned. This is not preferable because there is a concern that the spots of the skin may occur. In addition, when the thickness is less than 0.1 mm, problems such as unevenness of thickness occur, and when it exceeds 10 mm, there is a concern that resin impregnation during molding becomes difficult.
本発明の繊維基材テープまたはシートの製造は、熱可塑性繊維と強化繊維をそれぞれ別個に一度幅広に開繊して一方向に引き揃えた後、互いに積層し、再び所望の厚みへと調整して複合テープ状物を得ることが好ましい。このように、一度開繊工程を経ることにより、強化繊維束への熱可塑性樹脂の含浸が容易になることから、より高い力学物性の複合材料を得ることが可能となる。ここで用いる開繊方法は、特に限定されることはなく、公知の方法を用いることができる（例えば、特許第３０６４０１９号公報）。 In the production of the fiber base tape or sheet of the present invention, the thermoplastic fibers and the reinforcing fibers are separately spread apart once and aligned in one direction, then laminated together, and adjusted again to the desired thickness. It is preferable to obtain a composite tape. As described above, once the fiber opening process is performed, the reinforcing fiber bundle can be easily impregnated with the thermoplastic resin, so that a composite material having higher mechanical properties can be obtained. The opening method used here is not particularly limited, and a known method can be used (for example, Japanese Patent No. 3064019).
（積層後の加熱・加圧）
本発明の熱可塑性樹脂複合材料は、上述した一方向に引き揃えられたテープまたはシート状の強化繊維と一方向に引き揃えられたテープまたはシート状の熱可塑性繊維とを積層したシート状物、或いはテープまたはシート状の両方の繊維を平行に並べたシート状物を積層して形成されたテープまたはシート状物を、熱可塑性繊維の流動開始温度以上の温度で加熱・加圧成形することにより得られる。
(Heating and pressurization after lamination)
The thermoplastic resin composite material of the present invention is a sheet-like material obtained by laminating the tape or sheet-like reinforcing fibers aligned in one direction and the tape or sheet-like thermoplastic fibers aligned in one direction, Alternatively, by heating and pressure-molding a tape or sheet formed by laminating sheets in which both fibers of tape or sheet are arranged in parallel at a temperature higher than the flow start temperature of the thermoplastic fiber can get.
加熱・加圧成形方法については特に制限はなく、加熱手段を備えた加圧成形装置、圧縮成形装置、真空圧着成形装置、ロールプレス等を用いることができる。成形に必要な温度は、マトリックス素材として用いる熱可塑性繊維の材質によるが、該繊維の流動開始温度と熱分解温度を考慮して設定すれば良い。
更に、加熱温度と加圧圧力及び成形時間を調整することにより、熱可塑性繊維が強化繊維束へ完全な含浸（繊維形態をとどめることなく溶融）をしていない半含浸の状態とすることが可能である。このような半含浸の状態の繊維基材テープまたはシートは、十分に樹脂が含浸していないことから、期待する力学物性を発現することはできないが、十分な含浸が達成された素材と比較して柔軟性を有しており、成形の自由度が増すため、賦形成形に適している。また、このような工程を経ることにより、繊維基材テープまたはシートを薄くし、半含浸ではあるものの、未含浸部分を少なくすることに寄与しており、結果として最終的な本成形後の樹脂含浸性を上げることが可能となる。
There is no restriction | limiting in particular about the heating and pressure molding method, The pressure molding apparatus provided with the heating means, the compression molding apparatus, the vacuum press molding apparatus, a roll press etc. can be used. The temperature required for molding depends on the material of the thermoplastic fiber used as the matrix material, but may be set in consideration of the flow start temperature and the thermal decomposition temperature of the fiber.
Furthermore, by adjusting the heating temperature, pressure, and molding time, it is possible to achieve a semi-impregnated state in which the thermoplastic fiber is not completely impregnated (melted without stopping the fiber form) into the reinforcing fiber bundle. It is. Such a semi-impregnated fiber-based tape or sheet is not sufficiently impregnated with resin, and thus cannot exhibit the expected mechanical properties, but compared with a material that has achieved sufficient impregnation. It is flexible and has a high degree of freedom in molding, so it is suitable for forming. In addition, through such a process, the fiber base tape or sheet is thinned, and although it is semi-impregnated, it contributes to reducing the unimpregnated portion, and as a result, the resin after final final molding Impregnation can be improved.
（繊維基材テープまたはシートから繊維強化熱可塑性樹脂複合材料の成形）
本発明の繊維強化熱可塑性樹脂複合材料を得る方法としては、例えば、細幅の一方向に引き揃えられた繊維基材テープを経糸や緯糸、或いはその両方として用いた織物とし、これらを加熱成形する方法や、本発明の一方向に引き揃えられた繊維基材テープまたはシートを平行に並べて成形する方法などが挙げられるが、必ずしもこれらに限定されない。織物を加熱成形する方法では、薄肉且つ含浸性が良好であり、結果として力学物性に優れた熱可塑性樹脂複合材料を得ることができる。また、繊維基材テープまたはシートを平行に並べて成形する方法では、ある一方向に極めて優れた力学物性を有する薄物の繊維強化熱可塑性複合材料のシート状物を得ることが可能であり、該シート状物をさらに様々な方向性を持たせて積層し、これを加熱成形して得られる熱可塑性樹脂複合材料は、薄肉で且つあらゆる方向において優れた力学物性を有する。
本発明においては、繊維基材テープまたはシートは、熱可塑性繊維を含んで形成されているので、繊維基材テープまたはシートを積層して成形材料を製造するにあたり、繊維基材シートと繊維基材シートとの間に熱可塑性樹脂フィルムを挟むことなく、積層・加熱プレスすることにより成形材料を製造することが可能である。この積層・加熱プレスにおいて、繊維基材テープまたはシート中の熱可塑性繊維は溶融して繊維形態をとどめることなく、強化繊維間のマトリックス樹脂として機能している。
(Molding of fiber reinforced thermoplastic resin composite material from fiber base tape or sheet)
As a method for obtaining the fiber reinforced thermoplastic resin composite material of the present invention, for example, a fiber base tape aligned in one direction of a narrow width is used as a woven fabric using warp and weft, or both, and these are thermoformed. And a method of arranging fiber base tapes or sheets aligned in one direction of the present invention in parallel, but not necessarily limited thereto. In the method of heat forming a woven fabric, a thermoplastic resin composite material that is thin and has good impregnation properties and, as a result, excellent mechanical properties can be obtained. Further, in the method in which the fiber base tapes or sheets are arranged in parallel, it is possible to obtain a sheet-like material of a thin fiber-reinforced thermoplastic composite material having extremely excellent mechanical properties in a certain direction. A thermoplastic resin composite material obtained by laminating a material with various orientations and thermoforming the laminate is thin and has excellent mechanical properties in all directions.
In the present invention, since the fiber base tape or sheet is formed to contain thermoplastic fibers, the fiber base sheet and the fiber base are produced when the fiber base tape or sheet is laminated to produce a molding material. A molding material can be produced by laminating and hot pressing without sandwiching a thermoplastic resin film between the sheet and the sheet. In this lamination / heating press, the thermoplastic fiber in the fiber base tape or sheet functions as a matrix resin between the reinforcing fibers without melting and keeping the fiber form.
本発明の一方向に引き揃えられた強化繊維と熱可塑性繊維から構成される繊維基材テープまたはシートは、筒状の金型に巻きつけることにより容易にパイプ形状の複合材料を得ることができる。作成方法は特に限定さえることはないが、筒状金型にテープを巻きつけた後、これをオートクレーブで加熱・加圧することにより得られる。また、フィラメントワインディング法等を用いて、例えばガスタンクのような形状とすることも容易にできる。 A fiber base tape or sheet composed of reinforcing fibers and thermoplastic fibers aligned in one direction of the present invention can be easily obtained as a pipe-shaped composite material by winding it around a cylindrical mold. . Although the production method is not particularly limited, it can be obtained by winding a tape around a cylindrical mold and then heating and pressing it with an autoclave. Moreover, it can also be easily made into the shape like a gas tank, for example using a filament winding method.
（用途）
本発明の繊維強化熱可塑性樹脂複合材料は、その特徴を活かし、一般産業資材分野、電気・電子分野、土木・建築分野等の幅広い分野において有効に用いることができ、特に航空機・自動車、鉄道・船舶等の輸送機器分野においては、その主要な構造を成す部材として有効に用いることができる。
本発明の熱可塑性樹脂複合材料は、優れた力学物性と耐熱性、難燃性、寸法安定性等の機能特性を兼ね備えていることから、一般産業資材分野、電気・電子分野、土木・建築分野などの幅広い分野において有効に用いることができ、特に、航空機・自動車、鉄道・船舶等の輸送機器分野等の幅広い分野においては、その主要な構造をなす部材として有効に用いることができる。
例えば、パソコン、ディスプレイ、ＯＡ機器、携帯電話、携帯情報端末、デジタルビデオカメラ、光学機器、オーディオ、エアコン、照明機器、玩具用品、その他家電製品などの筐体、トレイ、シャーシ、内装部材、またはそのケースなどの電気、電子機器部品、支柱、パネル、補強材などの土木、建材用部品、各種メンバ、各種フレーム、各種ヒンジ、各種アーム、各種車軸、各種車輪用軸受、各種ビーム、各種ピラー、各種メンバ、各種フレーム、各種ビーム、各種サポート、各種レール、各種ヒンジなどの、外板、またはボディー部品、バンパー、モール、アンダーカバー、エンジンカバー、整流板、スポイラー、カウルルーバー、エアロパーツなど外装部品、インストルメントパネル、シートフレーム、ドアトリム、ピラートリム、ハンドル、各種モジュールなどの内装部品、またはモーター部品、ＣＮＧタンク、ガソリンタンク、燃料ポンプ、エアーインテーク、インテークマニホールド、キャブレターメインボディー、キャブレタースペーサー、各種配管、各種バルブなどの燃料系、排気系、または吸気系部品などの自動車、二輪車用構造部品、ランディングギアポッド、ウィングレット、スポイラー、エッジ、ラダー、エレベーター、フェイリング、リブなどの航空機用部品に好適に用いられる。
(Use)
The fiber reinforced thermoplastic resin composite material of the present invention can be effectively used in a wide range of fields such as general industrial material fields, electrical / electronic fields, civil engineering / architecture fields, taking advantage of the characteristics thereof. In the field of transportation equipment such as ships, it can be used effectively as a member constituting its main structure.
The thermoplastic resin composite material of the present invention has excellent mechanical properties and functional properties such as heat resistance, flame retardancy, and dimensional stability, so that it is a general industrial material field, electrical / electronic field, civil engineering / architecture field. It can be effectively used in a wide range of fields such as aircraft / automobiles, and in a wide range of fields such as transportation equipment such as railways / ships, and can be effectively used as a member constituting the main structure.
For example, a case such as a personal computer, a display, an OA device, a mobile phone, a portable information terminal, a digital video camera, an optical device, an audio, an air conditioner, a lighting device, a toy product, and other household appliances, a tray, a chassis, an interior member, or the like Electrical parts such as cases, electronic equipment parts, supports, panels, reinforcing materials, etc., building materials, various members, various frames, various hinges, various arms, various axles, various wheel bearings, various beams, various pillars, various Outer parts such as members, various frames, various beams, various supports, various rails, various hinges, etc., body parts, bumpers, moldings, under covers, engine covers, current plates, spoilers, cowl louvers, aero parts, Instrument panel, seat frame, door trim, pillar trim, Interior parts such as cylinders, various modules, or motor parts, CNG tanks, gasoline tanks, fuel pumps, air intakes, intake manifolds, carburetor main bodies, carburetor spacers, various piping, various valves, etc., fuel systems, exhaust systems, or intake systems It is suitably used for aircraft parts such as automobile parts such as system parts, structural parts for motorcycles, landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, and ribs.
以下、実施例により本発明を詳細に説明するが、本発明は本実施例により何ら限定されるものではない。尚、以下の実施例において、各種評価により得られた数値等のデータは、下記の方法により測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by this Example. In the following examples, data such as numerical values obtained by various evaluations were measured by the following methods.
［平均繊度 ｄｔｅｘ］
熱可塑性繊維の平均繊度は、マルチフィラメントから無作為に１００本抜き出し、それぞれの繊度を測定して平均を求めた。
[Average fineness dtex]
The average fineness of the thermoplastic fiber was randomly extracted from the multifilament and 100 averages were obtained by measuring the respective finenesses.
［平均巾 ｍｍ］
熱可塑性繊維束及び強化繊維束を一方向に引き揃えてテープ状にした際の平均巾は、無作為に１０箇所を選定し、それぞれの巾長を測定して平均を求めた。
[Average width mm]
The average width when the thermoplastic fiber bundle and the reinforcing fiber bundle were aligned in one direction to form a tape was selected at 10 locations at random, and the respective width lengths were measured to obtain the average.
［曲げ強度 ＭＰａ、曲げ弾性率 ＧＰａ］
繊維基材テープまたはシートから得られた熱可塑性樹脂複合材料の２４℃ならびに１００℃における曲げ強度ならびに曲げ弾性率は、ＡＳＴＭ７９０に準拠して測定した。
[Bending strength MPa, flexural modulus GPa]
The bending strength and bending elastic modulus at 24 ° C. and 100 ° C. of the thermoplastic resin composite material obtained from the fiber base tape or sheet were measured according to ASTM 790.
［含浸率 ％]
熱可塑性樹脂複合材料の含浸率は、断面を切り出し、走査型電子顕微鏡にて観察し、単位面積当たりにおける未含浸部分（空隙部分）の面積の割合を測定することにより求めて、これから含浸部分の割合を求めた。
[Impregnation rate%]
The impregnation ratio of the thermoplastic resin composite material is obtained by cutting out a section, observing with a scanning electron microscope, and measuring the ratio of the area of the non-impregnated part (void part) per unit area. The percentage was determined.
［難燃性］
熱可塑性樹脂複合材料の難燃性は、ＵＬ９４Ｖ規格の方法に準拠して測定した。
[Flame retardance]
The flame retardancy of the thermoplastic resin composite material was measured according to the method of UL94V standard.
［実施例１］
（１）ポリエーテルイミド系ポリマー（サービックイノベイティブプラスチックス社製「ＵＬＴＥＭ９００１」）を１５０℃で１２時間真空乾燥した。
（２）上記（１）のポリマーを紡糸ヘッド温度３９０℃、紡糸速度１５００ｍ／分、吐出量５０ｇ／分の条件で丸孔ノズルより吐出し、２６４０ｄｔｅｘ／１２００ｆのマルチフィラメントを得た。
（３）上記（２）で得られたポリエーテルイミド系繊維のマルチフィラメントを３本あわせた後、これらを２０ｍｍ巾へと拡幅し、一方向に配列したテープ状にし、このテープ状物を別途一方向に引き揃えた１２Ｋの炭素繊維束（単繊維の繊度：０．７ｄｔｅｘ）を２０ｍｍ巾へと拡幅したテープ状物と積層した後、２２０℃、２ＭＰａのローラープレスを通して、炭素繊維とポリエーテルイミド系繊維からなり、軟化（部分溶融）したポリエーテルイミド系繊維を介して炭素繊維間に接合が形成された、複合繊維基材テープを得た。
（４）得られた複合繊維基材テープを、繊維配列方向を同一にして、１８枚積層させた後、３２０℃で５分間圧縮成形して、ポリエーテルイミド系繊維が完全溶融し、炭素繊維間に含浸した、厚さ約１ｍｍの平棒状の繊維強化熱可塑性樹脂複合材料を作成した。
（５）得られた繊維強化熱可塑性樹脂複合材料は強化繊維束の配向乱れも殆どなく、外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、１．５ＧＰａ、１１５ＧＰａ、であった。含浸率は９６％と比較的良好であり、難燃性はＵＬ９４規格Ｖ−０に合格した。
[Example 1]
(1) A polyetherimide polymer (“ULTEM 9001” manufactured by Servic Innovative Plastics) was vacuum-dried at 150 ° C. for 12 hours.
(2) The polymer of (1) was discharged from a round hole nozzle under the conditions of a spinning head temperature of 390 ° C., a spinning speed of 1500 m / min, and a discharge amount of 50 g / min to obtain a 2640 dtex / 1200 f multifilament.
(3) After combining the three polyetherimide fiber multifilaments obtained in (2) above, they are expanded to a width of 20 mm and arranged in one direction. A 12K carbon fiber bundle (single fiber fineness: 0.7 dtex) aligned in one direction is laminated with a tape-like material widened to a width of 20 mm, and then passed through a roller press at 220 ° C. and 2 MPa, and the carbon fiber and the polyether. A composite fiber base tape was obtained which was composed of imide fibers and was joined between carbon fibers via softened (partially melted) polyetherimide fibers.
(4) The obtained composite fiber base tape was laminated in the same fiber array direction, and after 18 sheets were laminated, it was compression molded at 320 ° C. for 5 minutes to completely melt the polyetherimide fiber, and carbon fiber A flat rod-like fiber reinforced thermoplastic resin composite material having a thickness of about 1 mm impregnated therebetween was produced.
(5) The obtained fiber reinforced thermoplastic resin composite material has almost no orientation disorder of the reinforced fiber bundle, has a good appearance, and has bending strength and bending elastic modulus at room temperature of 1.5 GPa and 115 GPa, respectively. It was. The impregnation rate was relatively good at 96%, and the flame retardancy passed UL94 standard V-0.
［実施例２］
（１）ポリエーテルエーテルケトン系ポリマー（ビクトレックス社製「Ｖｉｃｔｒｅｘ ＰＥＥＫ１５０Ｇ」）を１５０℃で１２時間真空乾燥した。
（２）上記（１）のポリマーを紡糸ヘッド温度３７０℃、紡糸速度１５００ｍ／分、吐出量５０ｇ／分の条件で丸孔ノズルより吐出し、２６４０ｄｔｅｘ／１２００ｆのマルチフィラメントを得た。
（３）上記（２）で得られたポリエーテルエーテルケトン系繊維のマルチフィラメントを３本あわせた後、これらを２０ｍｍ巾へと拡幅し、一方向に配列したテープ状にし、このテープ状物を別途一方向に引き揃えた１２Ｋの炭素繊維束を２０ｍｍ巾へと拡幅したテープ状物と積層した後、３３０℃、２ＭＰａのローラープレスを通して、炭素繊維とポリエーテルエーテルケトン繊維からなり、炭素繊維間に接合が形成された、複合繊維基材テープを得た。
（４）得られた複合繊維基材テープを１８枚積層させた後、３７０℃で５分間圧縮成形して厚さ約１ｍｍの平棒状の繊維強化熱可塑性樹脂複合材料を作成した。
（５）得られた繊維強化熱可塑性樹脂複合材料は強化繊維束の配向乱れも殆どなく、外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、１．４ＧＰａ、１２０ＧＰａ、であった。含浸率は９８％と比較的良好であり、難燃性はＵＬ９４規格Ｖ−０に合格した。
[Example 2]
(1) A polyether ether ketone polymer (“Victrex PEEK150G” manufactured by Victrex) was vacuum-dried at 150 ° C. for 12 hours.
(2) The polymer of (1) was discharged from a round hole nozzle under the conditions of a spinning head temperature of 370 ° C., a spinning speed of 1500 m / min, and a discharge rate of 50 g / min, to obtain 2640 dtex / 1200 f multifilament.
(3) After combining three polyether ether ketone fiber multifilaments obtained in (2) above, these were expanded to a width of 20 mm and formed into a tape array arranged in one direction. After laminating a 12K carbon fiber bundle separately aligned in one direction with a tape-like material widened to a width of 20 mm, it is composed of carbon fiber and polyether ether ketone fiber through a roller press at 330 ° C. and 2 MPa. A composite fiber base tape having a bond formed thereon was obtained.
(4) After 18 sheets of the obtained composite fiber base tape were laminated, compression molding was performed at 370 ° C. for 5 minutes to prepare a flat rod-like fiber reinforced thermoplastic resin composite material having a thickness of about 1 mm.
(5) The obtained fiber reinforced thermoplastic resin composite material has almost no disorder in the orientation of the reinforced fiber bundle, has a good appearance, and has bending strength and bending elastic modulus at room temperature of 1.4 GPa and 120 GPa, respectively. It was. The impregnation rate was relatively good at 98%, and the flame retardancy passed UL94 standard V-0.
［実施例３］
（１）半芳香族ポリアミド系ポリマー（クラレ社製「ジェネスタ」）を１２０℃で１２時間真空乾燥した。
（２）上記（１）のポリマーを紡糸ヘッド温度３３０℃、紡糸速度１５００ｍ／分、吐出量５０ｇ／分の条件で丸孔ノズルより吐出し、２６４０ｄｔｅｘ／１２００ｆのマルチフィラメントを得た。
（３）上記（２）で得られた半芳香族ポリアミド系繊維のマルチフィラメントを３本あわせた後、これらを２０ｍｍ巾へと拡幅し、一方向に配列したテープ状にし、このテープ状物を別途一方向に引き揃えた１２Ｋの炭素繊維束を２０ｍｍ巾へと拡幅したテープ状物と積層した後、３００℃、２ＭＰａのローラープレスを通して、炭素繊維と半芳香族ポリアミド繊維からなり、炭素繊維間に接合が形成された、複合繊維基材テープを得た。
（４）得られた複合繊維基材テープを１８枚積層させた後、３２０℃で５分間圧縮成形して厚さ約１ｍｍの平棒状の繊維強化熱可塑性樹脂複合材料を作成した。
（５）得られた繊維強化熱可塑性樹脂複合材料は強化繊維束の配向乱れも殆どなく、外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、１．４ＧＰａ、１１８ＧＰａ、であった。含浸率は９６％と比較的良好であった。ただし、難燃性はＵＬ９４規格に合格しなかった。
[Example 3]
(1) A semi-aromatic polyamide-based polymer (“Genesta” manufactured by Kuraray Co., Ltd.) was vacuum-dried at 120 ° C. for 12 hours.
(2) The polymer of (1) was discharged from a round hole nozzle under the conditions of a spinning head temperature of 330 ° C., a spinning speed of 1500 m / min, and a discharge amount of 50 g / min to obtain a 2640 dtex / 1200 f multifilament.
(3) After combining three semi-aromatic polyamide fiber multifilaments obtained in (2) above, these were expanded to a width of 20 mm and formed into a tape arranged in one direction. After laminating a 12K carbon fiber bundle separately aligned in one direction with a tape-like material widened to a width of 20 mm, it is composed of carbon fibers and semi-aromatic polyamide fibers through a roller press at 300 ° C. and 2 MPa. A composite fiber base tape having a bond formed thereon was obtained.
(4) After 18 sheets of the obtained composite fiber base tape were laminated, compression molding was performed at 320 ° C. for 5 minutes to prepare a flat rod-like fiber reinforced thermoplastic resin composite material having a thickness of about 1 mm.
(5) The obtained fiber reinforced thermoplastic resin composite material has almost no disorder in the orientation of the reinforced fiber bundle, has a good appearance, and has bending strength and bending elastic modulus at room temperature of 1.4 GPa and 118 GPa, respectively. It was. The impregnation rate was relatively good at 96%. However, the flame retardancy did not pass the UL94 standard.
［比較例１］
（１）ポリエーテルイミド系ポリマーフィルム（住友ベークライト社製「スミライトＦＳ１４５０」）を２０ｍｍ巾へと切り出し、別途２０ｍｍ巾へと拡幅して一方向に引き揃えた１２Ｋの炭素繊維束のテープ状物と積層した後、２２０℃、２ＭＰａのローラープレスを通して複合テープ状物を得た。
（２）得られた複合テープ状物を１８枚積層させた後、３２０℃で５分間圧縮成形して厚さ約１ｍｍの平棒状の繊維強化熱可塑性樹脂複合材料を作成した。
（３）得られた繊維強化熱可塑性樹脂複合材料は強化繊維束の配向乱れも殆どなく、外観は良好であり、室温での曲げ強度、曲げ弾性率はそれぞれ、１．３ＧＰａ、１０２ＧＰａ、であった。含浸率は９１％とやや低く、それに伴い力学物性も本発明の実施例と比較して低いものに留まる。ただし、難燃性はＵＬ９４規格Ｖ−０に合格した。
[Comparative Example 1]
(1) A 12K carbon fiber bundle tape-like material obtained by cutting a polyetherimide polymer film (“Sumilite FS1450” manufactured by Sumitomo Bakelite Co., Ltd.) into a width of 20 mm, separately expanding to a width of 20 mm and aligning in one direction. After lamination, a composite tape-like product was obtained through a roller press at 220 ° C. and 2 MPa.
(2) After 18 sheets of the obtained composite tape were laminated, compression molding was carried out at 320 ° C. for 5 minutes to prepare a flat rod-like fiber reinforced thermoplastic resin composite material having a thickness of about 1 mm.
(3) The obtained fiber reinforced thermoplastic resin composite material has almost no disorder in the orientation of the reinforcing fiber bundle, has a good appearance, and has bending strength and bending elastic modulus at room temperature of 1.3 GPa and 102 GPa, respectively. It was. The impregnation rate is slightly low at 91%, and accordingly, the mechanical properties remain low compared to the examples of the present invention. However, the flame retardancy passed UL94 standard V-0.
［比較例２］
（１）ポリエーテルイミド系ポリマーフィルム（サービックイノベーティブプラスチック
ス社製「ＵＬＴＥＭ１０００」）を粉砕機にかけて粉末（０．１〜３００μｍの広範囲な粒径分布を有する）にした後、これを別途一方向に引き揃えた１２Ｋの炭素繊維束を２０ｍｍ巾へと拡幅したテープ状物上へ塗布し、２２０℃、２ＭＰａのローラープレスを通して複合テープを得た。
（２）得られた複合テープを１８枚積層させた後、３２０℃で５分間圧縮成形して厚さ約１ｍｍの平棒状の熱可塑性樹脂複合材料を作成した。
（３）得られた熱可塑性樹脂複合材料はパウダー塗布斑による外観不良が部分的に発生した。室温での曲げ強度、曲げ弾性率はそれぞれ、１．３ＧＰａ、１００ＧＰａ、であった。含浸率は、部分的な斑も発生しており、且つ８９％とやや低く、難燃性は、ＵＬ９４規格Ｖ−０に合格した。
[Comparative Example 2]
(1) A polyetherimide polymer film ("ULTEM1000" manufactured by Servic Innovative Plastics Co., Ltd.) is put into a powder (having a wide particle size distribution of 0.1 to 300 µm) by a pulverizer, and then separately in one direction. The aligned 12K carbon fiber bundles were applied onto a tape-like material widened to a width of 20 mm, and a composite tape was obtained through a roller press at 220 ° C. and 2 MPa.
(2) After 18 sheets of the obtained composite tape were laminated, compression molding was carried out at 320 ° C. for 5 minutes to prepare a flat rod-shaped thermoplastic resin composite material having a thickness of about 1 mm.
(3) Appearance defects due to powder coating spots were partially generated in the obtained thermoplastic resin composite material. The bending strength and bending elastic modulus at room temperature were 1.3 GPa and 100 GPa, respectively. The impregnation rate was partially low and slightly low at 89%, and the flame retardance passed UL94 standard V-0.
本発明に係る、強化繊維が一方向に配列した繊維基材テープまたはシートは、強化繊維間の接合がテープまたはシート内部まで強固に形成されているので、複合材料形成用の繊維基材テープまたはシートとして優れているので、複合材料分野において産業上の利用可能性がある。 In the fiber base tape or sheet in which the reinforcing fibers are arranged in one direction according to the present invention, since the joining between the reinforcing fibers is firmly formed up to the inside of the tape or the sheet, the fiber base tape for forming the composite material or Since it is excellent as a sheet, it has industrial applicability in the field of composite materials.
以上、本発明の好ましい実施態様を例示的に説明したが、当業者であれば、特許請求の範囲に開示した本発明の範囲および精神から逸脱することなく多様な修正、付加および置換ができることが理解されるであろう。
Although the preferred embodiments of the present invention have been described above by way of example, those skilled in the art can make various modifications, additions and substitutions without departing from the scope and spirit of the present invention disclosed in the claims. Will be understood.
Claims (11)
（１）前記繊維基材の全繊維重量に対して、前記強化繊維の割合が１０重量％〜９０重量％である。
（２）前記繊維基材を構成する前記熱可塑性繊維の単繊維の繊度が０．５〜１０ｄｔｅｘであり、フィラメント数が１０〜２４０００本である。
（３）前記テープまたはシートの幅が０．１〜５０ｍｍであり、厚みが０．１〜１０ｍｍである。 All the following conditions are satisfy | filled, The fiber base tape or sheet | seat of any one of Claims 1-3 characterized by the above-mentioned.
(1) The ratio of the reinforcing fibers is 10% to 90% by weight with respect to the total fiber weight of the fiber base material.
(2) The fineness of the single fiber of the thermoplastic fiber constituting the fiber base material is 0.5 to 10 dtex, and the number of filaments is 10 to 24,000.
(3) The tape or sheet has a width of 0.1 to 50 mm and a thickness of 0.1 to 10 mm.
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