JP7363630B2 - Prepreg laminate, fiber reinforced composite material and method for producing fiber reinforced composite material - Google Patents
Prepreg laminate, fiber reinforced composite material and method for producing fiber reinforced composite material Download PDFInfo
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- JP7363630B2 JP7363630B2 JP2020055301A JP2020055301A JP7363630B2 JP 7363630 B2 JP7363630 B2 JP 7363630B2 JP 2020055301 A JP2020055301 A JP 2020055301A JP 2020055301 A JP2020055301 A JP 2020055301A JP 7363630 B2 JP7363630 B2 JP 7363630B2
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- reinforced composite
- composite material
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- 239000000463 material Substances 0.000 title claims description 167
- 239000003733 fiber-reinforced composite Substances 0.000 title claims description 103
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229920005989 resin Polymers 0.000 claims description 131
- 239000011347 resin Substances 0.000 claims description 131
- 239000000835 fiber Substances 0.000 claims description 130
- 239000012783 reinforcing fiber Substances 0.000 claims description 54
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 41
- 239000004917 carbon fiber Substances 0.000 claims description 41
- 238000000465 moulding Methods 0.000 claims description 25
- 239000003365 glass fiber Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
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- 238000013461 design Methods 0.000 description 33
- 229920000647 polyepoxide Polymers 0.000 description 20
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- 239000003795 chemical substances by application Substances 0.000 description 14
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- 238000011282 treatment Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000010030 laminating Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000004760 aramid Substances 0.000 description 6
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- 239000004744 fabric Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002239 polyacrylonitrile Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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- 229920006122 polyamide resin Polymers 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 239000002964 rayon Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 239000011208 reinforced composite material Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
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- 229920002972 Acrylic fiber Polymers 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004883 computer application Methods 0.000 description 2
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- 229920006393 polyether sulfone Polymers 0.000 description 2
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- 229920001601 polyetherimide Polymers 0.000 description 2
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- 229920006324 polyoxymethylene Polymers 0.000 description 2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- DXBXIDZYBDDOJV-UHFFFAOYSA-N 2,3,3-trimethyl-2-phenyl-1h-indene Chemical group CC1(C)C2=CC=CC=C2CC1(C)C1=CC=CC=C1 DXBXIDZYBDDOJV-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- 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
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical class C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 229920006127 amorphous resin Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
- 235000005487 catechin Nutrition 0.000 description 1
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- 238000013016 damping Methods 0.000 description 1
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- 239000002781 deodorant agent Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 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
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical class CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
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- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、優れた意匠面を備えた繊維強化複合材料と繊維強化複合材料の製造方法、およびそれに好適に用いられるプリプレグ積層体に関するものである。 The present invention relates to a fiber-reinforced composite material with an excellent design, a method for manufacturing the fiber-reinforced composite material, and a prepreg laminate suitably used therein.
繊維強化複合材料は、強度、剛性および導電性等に優れていることから有用であり、航空機構造部材、風車の羽根、自動車の外装材、自動車の内装材およびＩＣトレイやノートパソコンの筐体（ハウジング）などのコンピュータ用途等に広く展開され、その需要は年々増加しつつある。 Fiber-reinforced composite materials are useful because they have excellent strength, rigidity, and electrical conductivity, and are used in aircraft structural components, windmill blades, automobile exterior materials, automobile interior materials, and IC trays and notebook computer casings ( They are widely used in computer applications such as housings), and their demand is increasing year by year.
繊維強化複合材料は、強化繊維と樹脂を必須の構成要素とするプリプレグを成形してなる材料であり、その場合、成形前や成形中にプリプレグの樹脂部分に空気や揮発成分が残存していると得られる繊維強化複合材料は表面にピンホールや内部にボイドが発生することが知られている。そのため、プリプレグから得られる繊維強化複合材料の表面のピンホールや内部のボイドを低減させることを目的に、種々の技術が提案されている。また、プリプレグの賦形性や成形ロバスト性を向上させることを目的にも、種々の技術が提案されている。 Fiber-reinforced composite materials are materials made by molding prepreg, which has reinforcing fibers and resin as essential components, and in this case, air and volatile components remain in the resin part of the prepreg before and during molding. It is known that the resulting fiber-reinforced composite material has pinholes on the surface and voids inside. Therefore, various techniques have been proposed for the purpose of reducing pinholes and internal voids on the surface of fiber-reinforced composite materials obtained from prepreg. Various techniques have also been proposed for the purpose of improving the shapeability and molding robustness of prepreg.
その中の一つに、強化繊維に樹脂を含浸させたプリプレグと、樹脂が未含浸の基材を積層したプリプレグ積層体から繊維強化複合材料を成形することが提案されている（特許文献１参照）。この技術では、繊維強化複合材料に優れた意匠面を提供することが提案されている。また別に、樹脂組成物が含浸した強化繊維を含む層を有するプリプレグで、プリプレグ中における樹脂組成物の含有率が所定の範囲内であり、複数の切込によって少なくとも一部が所定の繊維長さの強化繊維で構成され、三次元形状への賦形性に優れ、部材強度低下を引き起こすような成形欠陥を抑制する成形ロバスト性に優れたことを特徴としたプリプレグを与える技術が提案されている（特許文献２参照）。さらに、三軸織物と不織布を積層することで、繊維強化複合材料と同様の強度、弾性率及び高い比強度を有し、かつ金属材料に匹敵する導電性、絶縁性、熱伝導性、断熱性の少なくともいずれかを有する複合材料、成形物及びプリプレグを与える技術が提案されている（特許文献３参照）。 One of these proposals is to mold a fiber-reinforced composite material from a prepreg laminate made by laminating a prepreg in which reinforcing fibers are impregnated with a resin and a base material not impregnated with a resin (see Patent Document 1). ). This technology is proposed to provide fiber-reinforced composite materials with an excellent design. Separately, there is also a prepreg having a layer containing reinforcing fibers impregnated with a resin composition, wherein the content of the resin composition in the prepreg is within a predetermined range, and at least a part of the fibers has a predetermined length by a plurality of cuts. A technology has been proposed to provide a prepreg that is composed of reinforcing fibers, has excellent formability into three-dimensional shapes, and has excellent molding robustness that suppresses molding defects that cause a decrease in component strength. (See Patent Document 2). Furthermore, by laminating triaxial fabric and nonwoven fabric, it has strength, elastic modulus, and high specific strength similar to fiber-reinforced composite materials, and has electrical conductivity, insulation, thermal conductivity, and heat insulation properties comparable to metal materials. A technique for providing a composite material, a molded product, and a prepreg having at least one of the above has been proposed (see Patent Document 3).
ところが、これらの技術では、繊維強化複合材料の優れた意匠面を備えること、プリプレグの賦形性、成形ロバスト性を向上させること、繊維強化複合材料の導電性、絶縁性、熱伝導性、断熱性の少なくともいずれかを向上させることはできるが、プリプレグの賦形性と繊維強化複合材料に優れた意匠面を備えることを両立する点については困難であった。 However, with these technologies, it is necessary to provide fiber-reinforced composite materials with an excellent design, improve the shapeability and molding robustness of prepreg, and improve the electrical conductivity, insulation, thermal conductivity, and heat insulation of fiber-reinforced composite materials. Although it is possible to improve at least one of the properties, it has been difficult to achieve both the shapeability of the prepreg and the excellent design of the fiber reinforced composite material.
本発明の目的は、優れた意匠面を備えた炭素繊維強化複合材料と繊維強化複合材料の製造方法、およびそれに好適に用いられる賦形性に優れたプリプレグ積層体を提供することである。 An object of the present invention is to provide a carbon fiber-reinforced composite material with an excellent design, a method for producing the fiber-reinforced composite material, and a prepreg laminate with excellent shapeability that is suitably used therein.
本発明は、上記目的を達成するために次のいずれかの構成を有するものである。 In order to achieve the above object, the present invention has any of the following configurations.
本発明は、樹脂が含浸されていない繊維基材［ｂ］の一方の表面に、強化繊維に樹脂を含浸させたプリプレグであって、複数の切込によって少なくとも一部の前記強化繊維が繊維長さ（Ｌ）１０～３００ｍｍの強化繊維で構成され、かつ、強化繊維の体積含有率Ｖｆが４５～６５％の範囲内である切込プリプレグ［ａ］を１層または複数層積層させるとともに、前記繊維基材［ｂ］の他方の表面に樹脂を連続繊維の強化繊維に含浸させたプリプレグ［ｃ］を１層あるいは複数層積層させたサンドイッチ構造を有する、プリプレグ積層体である。 The present invention provides a prepreg in which reinforcing fibers are impregnated with a resin on one surface of a fiber base material [b] that is not impregnated with a resin, and in which at least some of the reinforcing fibers have a fiber length by a plurality of cuts. Laminating one or more layers of cut prepreg [a] composed of reinforcing fibers having a length (L) of 10 to 300 mm and having a volume content Vf of the reinforcing fibers in the range of 45 to 65%, and It is a prepreg laminate having a sandwich structure in which one or more layers of prepreg [c] in which reinforcing continuous fibers are impregnated with resin are laminated on the other surface of the fiber base material [b].
本発明のプリプレグ積層体の好ましい態様によれば、前記プリプレグ積層体の少なくとも一方の表面が意匠面であり、前記繊維基材［ｂ］が前記意匠面側から２層目または３層目に積層された、プリプレグ積層体である。 According to a preferred embodiment of the prepreg laminate of the present invention, at least one surface of the prepreg laminate is a designed surface, and the fiber base material [b] is laminated as the second or third layer from the designed surface side. This is a prepreg laminate.
本発明のプリプレグ積層体の好ましい態様によれば、前記切込プリプレグ［ａ］の厚さが３０～３００μｍである、プリプレグ積層体である。 According to a preferred embodiment of the prepreg laminate of the present invention, it is a prepreg laminate in which the cut prepreg [a] has a thickness of 30 to 300 μm.
本発明のプリプレグ積層体の好ましい態様によれば、前記切込プリプレグ［ａ］を構成する前記強化繊維が炭素繊維であり、前記樹脂が熱硬化性樹脂である、プリプレグ積層体である。 According to a preferred embodiment of the prepreg laminate of the present invention, the reinforcing fibers constituting the cut prepreg [a] are carbon fibers, and the resin is a thermosetting resin.
本発明のプリプレグ積層体の好ましい態様によれば、前記繊維基材［ｂ］が、炭素繊維またはガラス繊維を含み、前記炭素繊維またはガラス繊維が不連続であり、目付量が５～１００ｇ／ｍ２である、プリプレグ積層体である。 According to a preferred embodiment of the prepreg laminate of the present invention, the fiber base material [b] contains carbon fibers or glass fibers, the carbon fibers or glass fibers are discontinuous, and the basis weight is 5 to 100 g/m. 2 , which is a prepreg laminate.
また、本発明の繊維強化複合材料は、前記プリプレグ積層体を用いて、前記切込プリプレグ［ａ］に由来する繊維強化複合材料層［Ａ］と、前記切込プリプレグ［ａ］または前記プリプレグ［ｃ］に含浸されていた樹脂を含有する前記繊維基材［ｂ］に由来する繊維強化複合材料層［Ｂ］とを少なくとも含む、繊維強化複合材料である。 Further, the fiber reinforced composite material of the present invention uses the prepreg laminate to form a fiber reinforced composite material layer [A] originating from the cut prepreg [a] and the cut prepreg [a] or the prepreg [a]. The fiber-reinforced composite material includes at least a fiber-reinforced composite material layer [B] derived from the fiber base material [b] containing the resin impregnated in the fiber-reinforced composite material layer [B].
本発明の炭素繊維強化複合材料の好ましい態様によれば、前記繊維強化複合材料層［Ａ］の繊維体積含有率ＶｆＡ（％）と、前記繊維強化複合材料層［Ｂ］の繊維体積含有率ＶｆＢ（％）とがＶｆＡ＞ＶｆＢの関係を有する、繊維強化複合材料である。 According to a preferred embodiment of the carbon fiber reinforced composite material of the present invention, the fiber volume content VfA (%) of the fiber reinforced composite material layer [A] and the fiber volume content VfB of the fiber reinforced composite material layer [B] (%) is a fiber reinforced composite material having a relationship of VfA>VfB.
また、本発明の繊維強化複合材料の製造方法は、前記プリプレグ積層体を加熱しつつ前記プリプレグ積層体外部を加圧する成形工程を有する、繊維強化複合材料の製造方法である。 Moreover, the method for producing a fiber-reinforced composite material of the present invention is a method for producing a fiber-reinforced composite material, which includes a molding step of applying pressure to the outside of the prepreg laminate while heating the prepreg laminate.
本発明の炭素繊維強化複合材料の製造方法の好ましい態様によれば、前記成形工程において、さらに前記プリプレグ積層体内部を－８０ｋＰａ以下（ゲージ圧）の圧力で行う工程を含む、繊維強化複合材料の製造方法である。 According to a preferred embodiment of the method for producing a carbon fiber reinforced composite material of the present invention, the forming step further includes a step of applying a pressure of -80 kPa or less (gauge pressure) inside the prepreg laminate. This is the manufacturing method.
本発明の炭素繊維強化複合材料の製造方法の好ましい態様によれば、前記成形工程において、前記切込プリプレグ［ａ］または前記プリプレグ［ｃ］に含まれる樹脂を繊維基材［ｂ］に含浸させる、繊維強化複合材料の製造方法である。 According to a preferred embodiment of the method for producing a carbon fiber reinforced composite material of the present invention, in the molding step, the fiber base material [b] is impregnated with the resin contained in the cut prepreg [a] or the prepreg [c]. , a method for producing fiber-reinforced composite materials.
本発明によれば、切込プリプレグをプリプレグ積層体に積層することでプリプレグの賦形性に優れ、また成形して得られる繊維強化複合材料に優れた意匠面を備えることを両立することができる。 According to the present invention, by laminating the cut prepreg into the prepreg laminate, it is possible to achieve both excellent formability of the prepreg and an excellent design in the fiber-reinforced composite material obtained by molding. .
以下、実施の形態について図面を用いて説明する。なお、本発明は図や実施例に何ら限定されるものではない。 Embodiments will be described below with reference to the drawings. Note that the present invention is not limited to the figures or examples.
本発明に係るプリプレグ積層体は、図１に示すように、少なくとも強化繊維に樹脂を含浸させた切込プリプレグ［ａ］２、樹脂が含浸されていない繊維基材［ｂ］３を積層させたプリプレグ積層体１０であることが重要である。また、図２に示すように、樹脂が含浸されていない繊維基材［ｂ］３の両側に、強化繊維に樹脂を含浸させた切込プリプレグ［ａ］２を積層させたサンドイッチ構造のプリプレグ積層体も好ましく用いられる。さらに、図３に示すように、樹脂が含浸されていない繊維基材［ｂ］３の一方の表面に、強化繊維に樹脂を含浸させた切込プリプレグ［ａ］２を積層させるとともに、樹脂を連続繊維の強化繊維に含浸させたプリプレグ［ｃ］４を積層させたサンドイッチ構造のプリプレグ積層体１０も好ましく用いられる。 As shown in FIG. 1, the prepreg laminate according to the present invention includes at least a cut prepreg [a] 2 whose reinforcing fibers are impregnated with a resin, and a fiber base material [b] 3 which is not impregnated with a resin. It is important that the prepreg laminate 10 is used. In addition, as shown in FIG. 2, a prepreg laminate with a sandwich structure in which cut prepreg [a] 2 made of reinforcing fibers impregnated with resin is laminated on both sides of a fiber base material [b] 3 that is not impregnated with resin. The body is also preferably used. Furthermore, as shown in FIG. 3, a cut prepreg [a] 2 made of reinforcing fibers impregnated with resin is laminated on one surface of the fiber base material [b] 3 that is not impregnated with resin. A prepreg laminate 10 having a sandwich structure in which prepreg [c] 4 impregnated with continuous reinforcing fibers is laminated is also preferably used.
プリプレグ積層体１０をプレス等により圧縮成形する際、プリプレグ［ａ］２あるいはプリプレグ［ｃ］４に含浸されている樹脂が、繊維基材［ｂ］３に移動し繊維間に含浸する。プリプレグ［ａ］２あるいはプリプレグ［ｃ］４を積層することで、繊維基材［ｂ］３へ十分な樹脂が含浸されることで、意匠面となるプリプレグ［ａ］２あるいはプリプレグ［ｃ］４に含まれる樹脂とともに空気や揮発成分を繊維基材［ｂ］３に移すことにより、優れた意匠面１を有する繊維強化複合材料を得ることができる。 When the prepreg laminate 10 is compression-molded by a press or the like, the resin impregnated in the prepreg [a] 2 or the prepreg [c] 4 moves to the fiber base material [b] 3 and impregnates between the fibers. By laminating the prepreg [a] 2 or prepreg [c] 4, the fiber base material [b] 3 is impregnated with sufficient resin, thereby forming the prepreg [a] 2 or prepreg [c] 4 that becomes the design surface. By transferring air and volatile components together with the resin contained in the fiber base material [b] 3, a fiber reinforced composite material having an excellent design surface 1 can be obtained.
本発明に用いられる切込プリプレグ［ａ］２は、少なくとも強化繊維に樹脂を含浸させたものである。 The cut prepreg [a] 2 used in the present invention is made by impregnating at least reinforcing fibers with a resin.
切込プリプレグ［ａ］２に用いられる強化繊維としては、特に制限はなく、例えば、アルミニウム繊維、黄銅繊維、ステンレス繊維などの金属繊維や、ＰＡＮ系炭素繊維、レーヨン系炭素繊維、リグニン系炭素繊維、ピッチ系炭素繊維の炭素繊維や、黒鉛繊維や、ガラス繊維などの絶縁性繊維や、アラミド繊維、ＰＢＯ繊維、ポリフェニレンスルフィド繊維、ポリエステル繊維、アクリル繊維、ナイロン繊維、ポリエチレン繊維などの有機繊維や、シリコンカーバイト繊維、シリコンナイトライド繊維などの無機繊維が挙げられる。また、これらの繊維に表面処理が施されているものであってもよい。表面処理としては、導電体として金属の被着処理のほかに、カップリング剤による処理、サイジング剤による処理、結束剤による処理、添加剤の付着処理などがある。また、これらの強化繊維は１種類を単独で用いてもよいし、２種類以上を併用してもよい。 There are no particular restrictions on the reinforcing fibers used in the cut prepreg [a] 2, and examples include metal fibers such as aluminum fibers, brass fibers, and stainless steel fibers, PAN-based carbon fibers, rayon-based carbon fibers, and lignin-based carbon fibers. , pitch-based carbon fibers, graphite fibers, insulating fibers such as glass fibers, organic fibers such as aramid fibers, PBO fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, polyethylene fibers, Examples include inorganic fibers such as silicon carbide fiber and silicon nitride fiber. Moreover, these fibers may be surface-treated. Surface treatments include treatment with a coupling agent, treatment with a sizing agent, treatment with a binding agent, treatment with an additive, and the like, in addition to treatment with a metal as a conductor. Moreover, these reinforcing fibers may be used alone or in combination of two or more types.
中でも、軽量化効果の観点から、比強度、比剛性に優れるＰＡＮ系炭素繊維、ピッチ系炭素繊維、レーヨン系炭素繊維などの炭素繊維が好ましく用いられる。また、得られる積層体の経済性を高める観点からは、ガラス繊維が好ましく用いられ、とりわけ力学特性と経済性のバランスから炭素繊維とガラス繊維を併用することが好ましい。さらに、得られる積層体の衝撃吸収性や賦形性を高める観点からは、アラミド繊維が好ましく用いられ、とりわけ力学特性と衝撃吸収性のバランスから炭素繊維とアラミド繊維を併用することが好ましい。また、得られる積層体の導電性を高める観点からは、ニッケルや銅やイッテルビウムなどの金属を被覆した強化繊維を用いることもできる。これらの中で、強度と弾性率などの力学的特性に優れるＰＡＮ系炭素繊維をより好ましく用いることができる。 Among these, carbon fibers such as PAN-based carbon fibers, pitch-based carbon fibers, and rayon-based carbon fibers, which are excellent in specific strength and specific rigidity, are preferably used from the viewpoint of weight reduction effects. Further, from the viewpoint of increasing the economic efficiency of the resulting laminate, glass fiber is preferably used, and in particular, from the viewpoint of a balance between mechanical properties and economic efficiency, it is preferable to use carbon fiber and glass fiber in combination. Furthermore, from the viewpoint of improving the shock absorbing properties and formability of the resulting laminate, aramid fibers are preferably used, and in particular, it is preferable to use carbon fibers and aramid fibers in combination from the viewpoint of the balance between mechanical properties and shock absorbing properties. Furthermore, from the viewpoint of increasing the conductivity of the resulting laminate, reinforcing fibers coated with metal such as nickel, copper, or ytterbium can also be used. Among these, PAN-based carbon fibers, which are excellent in mechanical properties such as strength and elastic modulus, can be more preferably used.
切込プリプレグ［ａ］２に用いられる強化繊維は、強化繊維を一方向に引き揃えた一方向基材や、二方向織物、多軸織物、不織布材料、マット、編物、組紐等の形態を採用することができるが、いずれも強化繊維が連続した布帛状基材の形態として用いることが好ましい。強化繊維の形態は、用途や使用領域によってこれらを自由に選択することができる。中でも繊維が一方向に配列した一方向基材は、繊維のパッキングがよく効率的にＶｆを向上することができるため、力学特性を最も高く発現させることができることから好ましい。切込プリプレグ［ａ］２は、この連続繊維で構成された基材に繊維長さ（Ｌ）となるように切込を入れたものである。繊維長さ（Ｌ）については、少なくとも一部の繊維が１０～３００ｍｍの強化繊維で構成されていることが重要である。強化繊維の繊維長さ（Ｌ）がこの範囲内にあることにより、成形時における面外方向への気体の脱気パス数を確保することと、ブリッジング抑制を効果的に実現することができる。Ｌを１０ｍｍ以上にすると、切込同士の距離が離れるため、そのような切込プリプレグを用いて成形された繊維強化プラスチックに荷重が負荷された場合には、クラックが連結しにくく強度が高いものとなる。成形時における形状追従性、ボイド等の成形不具合の抑制効果と成形された繊維強化プラスチックの力学特性との関係を鑑みると、切込によって分断された強化繊維の繊維長さＬのより好ましい範囲は１０～１００ｍｍである。 The reinforcing fibers used in the cut prepreg [a] 2 are in the form of a unidirectional base material in which reinforcing fibers are aligned in one direction, bidirectional fabrics, multiaxial fabrics, nonwoven materials, mats, knitted fabrics, braided cords, etc. However, it is preferable to use any of them in the form of a fabric-like base material with continuous reinforcing fibers. The form of the reinforcing fibers can be freely selected depending on the purpose and area of use. Among these, a unidirectional base material in which fibers are arranged in one direction is preferable because the fibers can be packed well and Vf can be efficiently improved, so that the mechanical properties can be exhibited to the highest degree. The cut prepreg [a] 2 is made by cutting a base material made of this continuous fiber so as to have the fiber length (L). Regarding the fiber length (L), it is important that at least some of the fibers are composed of reinforcing fibers with a length of 10 to 300 mm. By setting the fiber length (L) of the reinforcing fibers within this range, it is possible to ensure the number of gas degassing passes in the out-of-plane direction during molding and to effectively suppress bridging. . When L is set to 10 mm or more, the distance between the notches increases, so when a load is applied to fiber-reinforced plastic molded using such a notch prepreg, cracks will not connect easily and the product will have high strength. becomes. Considering the relationship between the shape followability during molding, the effect of suppressing molding defects such as voids, and the mechanical properties of the molded fiber-reinforced plastic, a more preferable range of the fiber length L of the reinforcing fibers separated by the cuts is It is 10 to 100 mm.
また、切込プリプレグ［ａ］２の強化繊維の体積含有率Ｖｆが４５～６５％の範囲内にあることが重要である。強化繊維の体積含有率Ｖｆは６５％以下とすることで切込部の強化繊維のずれがおき、ブリッジングを効果的に抑制し、形状追従性とボイド等の成形不具合の抑制効果を得ることができる。かかる観点からＶｆが６０％以下であることがより好ましい。また、Ｖｆは低いほどブリッジングは抑制できるが、Ｖｆが４５％より小さくなると、構造材に必要な高力学特性が得られにくくなる。かかる観点からＶｆが５５％以上であることがより好ましい。なお、強化繊維の体積含有率Ｖｆの測定は、実施例に記載の方法にてプリプレグを硬化した後、光学顕微鏡やレーザー顕微鏡による画像を処理することにより行うことができる。 Furthermore, it is important that the volume content Vf of reinforcing fibers in the cut prepreg [a] 2 is within the range of 45 to 65%. By setting the volume content Vf of the reinforcing fibers to 65% or less, the reinforcing fibers are displaced at the cut portion, effectively suppressing bridging, and obtaining shape followability and the effect of suppressing molding defects such as voids. I can do it. From this point of view, it is more preferable that Vf is 60% or less. Furthermore, the lower Vf is, the more bridging can be suppressed, but when Vf is less than 45%, it becomes difficult to obtain the high mechanical properties required for the structural material. From this point of view, it is more preferable that Vf is 55% or more. The volume content Vf of the reinforcing fibers can be measured by curing the prepreg by the method described in Examples and then processing the image with an optical microscope or a laser microscope.
また、切込プリプレグ［ａ］２に用いられる樹脂としては、特に制限はなく、熱硬化性樹脂、熱可塑性樹脂ともに好適に用いることができる。 Furthermore, the resin used for the cut prepreg [a] 2 is not particularly limited, and both thermosetting resins and thermoplastic resins can be suitably used.
熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、ビニルエステル樹脂、ベンゾオキサジン樹脂、ポリイミド樹脂、オキセタン樹脂、マレイミド樹脂、不飽和ポリエステル樹脂、ユリア樹脂、メラミン樹脂などの熱硬化性樹脂などを好ましく用いることができる。これらは、２種以上をブレンドした樹脂などを適用しても良い。この中でも、エポキシ樹脂、フェノール樹脂、ビニルエステル樹脂が積層体の力学特性、耐熱性の観点から好ましい。特に、エポキシ樹脂は、積層体の力学特性や、耐熱性に加え取扱性の観点からより好ましい。エポキシ樹脂は、その優れた力学特性を発現するために、使用する樹脂の主成分として含まれるのが好ましく、具体的には樹脂組成物当たり６０重量％以上含まれることが好ましい。 As the thermosetting resin, thermosetting resins such as epoxy resin, phenol resin, vinyl ester resin, benzoxazine resin, polyimide resin, oxetane resin, maleimide resin, unsaturated polyester resin, urea resin, melamine resin, etc. are preferably used. be able to. For these resins, resins made by blending two or more types may be used. Among these, epoxy resins, phenol resins, and vinyl ester resins are preferred from the viewpoint of mechanical properties and heat resistance of the laminate. In particular, epoxy resins are more preferred from the viewpoints of mechanical properties of the laminate, heat resistance, and handleability. In order to exhibit its excellent mechanical properties, the epoxy resin is preferably contained as a main component of the resin used, and specifically, it is preferably contained in an amount of 60% by weight or more based on the resin composition.
エポキシ樹脂としては、アミン類、フェノール類、炭素－炭素二重結合を有する化合物を前駆体とするエポキシ樹脂が好ましく用いられる。 As the epoxy resin, epoxy resins whose precursors are amines, phenols, or compounds having a carbon-carbon double bond are preferably used.
エポキシ樹脂の硬化剤としては、エポキシ基と反応し得る活性基を有する化合物であればこれを用いることができる。硬化剤としては、アミノ基、酸無水物基およびアジド基を有する化合物が適している。硬化剤としては、より具体的には、例えば、ジシアンジアミド、ジアミノジフェニルメタンやジアミノジフェニルスルホンの各種異性体、アミノ安息香酸エステル類、各種酸無水物、フェノールノボラック樹脂、クレゾールノボラック樹脂、ポリフェノール化合物、イミダゾール誘導体、脂肪族アミン、テトラメチルグアニジン、チオ尿素付加アミン、メチルヘキサヒドロフタル酸無水物のようなカルボン酸無水物、カルボン酸ヒドラジド、カルボン酸アミド、ポリメルカプタンおよび三フッ化ホウ素エチルアミン錯体のようなルイス酸錯体などが挙げられる。これらの硬化剤は、単独で使用しても併用してもよい。 As the curing agent for the epoxy resin, any compound having an active group capable of reacting with an epoxy group can be used. As the curing agent, compounds having an amino group, an acid anhydride group and an azide group are suitable. More specifically, the curing agent includes, for example, dicyandiamide, various isomers of diaminodiphenylmethane and diaminodiphenylsulfone, aminobenzoic acid esters, various acid anhydrides, phenol novolak resin, cresol novolak resin, polyphenol compounds, imidazole derivatives. , aliphatic amines, tetramethylguanidine, thiourea-adducted amines, carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, carboxylic acid hydrazides, carboxylic acid amides, polymercaptans, and Lewis compounds such as boron trifluoride ethylamine complexes. Examples include acid complexes. These curing agents may be used alone or in combination.
上記熱硬化性樹脂に、熱可塑性樹脂を溶解して用いることも好適である。このような熱可塑性樹脂としては、一般に、主鎖に、炭素－炭素結合、アミド結合、イミド結合、エステル結合、エーテル結合、カーボネート結合、ウレタン結合、チオエーテル結合、スルホン結合およびカルボニル結合から選ばれた結合を有する熱可塑性樹脂であることが好ましいが、部分的に架橋構造を有していても差し支えない。また、結晶性を有していても非晶性であってもよい。特に、ポリアミド樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、ポリフェニレンオキシド樹脂、ポリフェニレンスルフィド樹脂、ポリアリレート樹脂、ポリエステル樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、フェニルトリメチルインダン構造を有するポリイミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリエーテルケトン樹脂、ポリエーテルエーテルケトン樹脂、ポリアラミド樹脂、ポリエーテルニトリル樹脂およびポリベンズイミダゾール樹脂からなる群から選ばれた少なくとも１種の樹脂が、熱硬化性樹脂に溶解していることが好適である。 It is also suitable to use a thermoplastic resin dissolved in the thermosetting resin. Such thermoplastic resins generally include carbon-carbon bonds, amide bonds, imide bonds, ester bonds, ether bonds, carbonate bonds, urethane bonds, thioether bonds, sulfone bonds, and carbonyl bonds in the main chain. Although it is preferable that the thermoplastic resin has a bond, it may have a partially crosslinked structure. Further, it may be crystalline or amorphous. In particular, polyamide resin, polycarbonate resin, polyacetal resin, polyphenylene oxide resin, polyphenylene sulfide resin, polyarylate resin, polyester resin, polyamideimide resin, polyimide resin, polyetherimide resin, polyimide resin having a phenyltrimethylindane structure, polysulfone resin, At least one resin selected from the group consisting of polyether sulfone resin, polyether ketone resin, polyether ether ketone resin, polyaramid resin, polyether nitrile resin and polybenzimidazole resin is dissolved in a thermosetting resin. It is preferable to be present.
また、熱可塑性樹脂としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリブチレン樹脂等のポリオレフィン樹脂や、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリトリメチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、液晶ポリエステル等のポリエステル樹脂や、ポリアミド樹脂、ポリオキシメチレン樹脂、ポリフェニレンスルフィド樹脂などのポリアリーレンスルフィド樹脂、ポリケトン樹脂、ポリエーテルケトン樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルケトンケトン樹脂、ポリエーテルニトリル樹脂、ポリテトラフルオロエチレン樹脂などのフッ素系樹脂、液晶ポリマー樹脂などの結晶性樹脂、ポリスチレン樹脂の他、ポリカーボネート樹脂、ポリメチルメタクリレート樹脂、ポリ塩化ビニル樹脂、ポリフェニレンエーテル樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリサルホン樹脂、ポリエーテルサルホン樹脂、ポリアリレート樹脂などの非晶性樹脂、その他、フェノール系樹脂、フェノキシ樹脂、更にポリスチレン樹脂系、ポリオレフィン樹脂系、ポリウレタン樹脂系、ポリエステル樹脂系、ポリアミド樹脂系、ポリブタジエン樹脂系、ポリイソプレン樹脂系、フッ素系樹脂、およびポリアクリロニトリル樹脂系等の熱可塑エラストマー等や、これらの共重合体および変性体等から選ばれる熱可塑性樹脂が挙げられる。中でも、得られる積層体の軽量性の観点からはポリオレフィン樹脂が好ましく、強度の観点からはポリアミド樹脂が好ましく、表面外観の観点からポリエステル樹脂が好ましく用いられる。 Examples of thermoplastic resins include polyolefin resins such as polyethylene resin, polypropylene resin, and polybutylene resin, and polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin, polyethylene naphthalate resin, and liquid crystal polyester. and polyarylene sulfide resins such as polyamide resins, polyoxymethylene resins, and polyphenylene sulfide resins, polyketone resins, polyetherketone resins, polyetheretherketone resins, polyetherketoneketone resins, polyethernitrile resins, and polytetrafluoroethylene resins. In addition to fluorine resins such as, crystalline resins such as liquid crystal polymer resins, polystyrene resins, polycarbonate resins, polymethyl methacrylate resins, polyvinyl chloride resins, polyphenylene ether resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone Resin, amorphous resin such as polyether sulfone resin, polyarylate resin, etc., phenolic resin, phenoxy resin, polystyrene resin, polyolefin resin, polyurethane resin, polyester resin, polyamide resin, polybutadiene resin. Examples include thermoplastic resins selected from thermoplastic elastomers such as polyisoprene resins, polyisoprene resins, fluororesins, and polyacrylonitrile resins, as well as copolymers and modified products thereof. Among these, polyolefin resins are preferred from the viewpoint of lightweight of the resulting laminate, polyamide resins are preferred from the viewpoint of strength, and polyester resins are preferably used from the viewpoint of surface appearance.
前記群に例示された熱可塑性樹脂は、本発明の目的を損なわない範囲で、エラストマーあるいはゴム成分などの耐衝撃性向上剤、他の充填材や添加剤を含有しても良い。これらの例としては、無機充填材、難燃剤、導電性付与剤、結晶核剤、紫外線吸収剤、酸化防止剤、制振剤、抗菌剤、防虫剤、防臭剤、着色防止剤、熱安定剤、離型剤、帯電防止剤、可塑剤、滑剤、着色剤、顔料、染料、発泡剤、制泡剤、あるいは、カップリング剤が挙げられる。 The thermoplastic resins exemplified in the above group may contain impact resistance improvers such as elastomers or rubber components, other fillers, and additives within a range that does not impair the object of the present invention. Examples of these include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, color inhibitors, and heat stabilizers. , a mold release agent, an antistatic agent, a plasticizer, a lubricant, a colorant, a pigment, a dye, a foaming agent, an antifoaming agent, or a coupling agent.
また、熱硬化性樹脂や熱可塑性樹脂などの樹脂にフィラーを添加して用いることもできる。フィラーとしては、連続した強化繊維、炭酸カルシウム、タルク、シリカ、クレー、ガラスフレーク、カテキン、ゼオライト、シリカバルーン、ガラスバルーン、シラスバルーン、カーボンブラック、カーボンナノチューブ、フラーレン、黒鉛、金属粉、金属箔、フェライト材料、アルミナ、チタン酸バリウム、チタン酸ジルコン酸鉛、硫酸バリウム、酸化チタン、ガラスビーズ、アルミナ、酸化アンチモン、ハイドロタルサイト、赤燐、炭酸亜鉛、酸化カルシウムなどが挙げられる。中でも連続した強化繊維を含む中間基材が成形性の観点から好ましい。 Further, a filler can be added to resin such as a thermosetting resin or a thermoplastic resin. Fillers include continuous reinforcing fibers, calcium carbonate, talc, silica, clay, glass flakes, catechin, zeolite, silica balloons, glass balloons, shirasu balloons, carbon black, carbon nanotubes, fullerene, graphite, metal powder, metal foil, Examples include ferrite materials, alumina, barium titanate, lead zirconate titanate, barium sulfate, titanium oxide, glass beads, alumina, antimony oxide, hydrotalcite, red phosphorus, zinc carbonate, calcium oxide, and the like. Among these, an intermediate base material containing continuous reinforcing fibers is preferred from the viewpoint of moldability.
切込プリプレグ［ａ］の厚さは、３０～３００μｍの範囲内であることが好ましい。これにより、プリプレグ積層体１０の成形性の向上と繊維強化複合材料の意匠性の両立を図ることができる。厚さが３０μｍ未満の場合は、得られる繊維強化複合材料の意匠面にピンホールが多く出ることがあり、厚さが３００μｍを超える場合は、プリプレグに切込を入れる際に問題が出ることがある。 The thickness of the cut prepreg [a] is preferably within the range of 30 to 300 μm. Thereby, it is possible to improve both the moldability of the prepreg laminate 10 and the design of the fiber-reinforced composite material. If the thickness is less than 30 μm, many pinholes may appear on the design surface of the resulting fiber-reinforced composite material, and if the thickness exceeds 300 μm, problems may occur when cutting into the prepreg. be.
本発明に用いられる繊維基材［ｂ］３は、樹脂を含浸されやすくするため、繊維から構成される基材である。 The fiber base material [b] 3 used in the present invention is a base material composed of fibers in order to be easily impregnated with resin.
繊維基材［ｂ］３に用いられる繊維としては、特に制限はなく、例えば、アルミニウム繊維、黄銅繊維、ステンレス繊維などの金属繊維や、ＰＡＮ系他炭素繊維、レーヨン系炭素繊維、リグニン系炭素繊維、ピッチ系炭素繊維の炭素繊維や、黒鉛繊維や、ガラス繊維などの絶縁性繊維や、アラミド繊維、ＰＢＯ繊維、ポリフェニレンスルフィド繊維、ポリエステル繊維、アクリル繊維、ナイロン繊維、ポリエチレン繊維などの有機繊維や、シリコンカーバイト繊維、シリコンナイトライド繊維などの無機繊維が挙げられる。また、これらの繊維に表面処理が施されているものであってもよい。表面処理としては、導電体として金属の被着処理のほかに、カップリング剤による処理、サイジング剤による処理、結束剤による処理、添加剤の付着処理などがある。また、これらの強化繊維は１種類を単独で用いてもよいし、２種類以上を併用してもよい。 The fibers used for the fiber base material [b] 3 are not particularly limited, and include, for example, metal fibers such as aluminum fibers, brass fibers, and stainless steel fibers, PAN-based carbon fibers, rayon-based carbon fibers, and lignin-based carbon fibers. , pitch-based carbon fibers, graphite fibers, insulating fibers such as glass fibers, organic fibers such as aramid fibers, PBO fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, polyethylene fibers, Examples include inorganic fibers such as silicon carbide fiber and silicon nitride fiber. Moreover, these fibers may be surface-treated. Surface treatments include treatment with a coupling agent, treatment with a sizing agent, treatment with a binding agent, treatment with an additive, and the like, in addition to treatment with a metal as a conductor. Moreover, these reinforcing fibers may be used alone or in combination of two or more types.
中でも、軽量化効果の観点から、比強度、比剛性に優れるＰＡＮ系炭素繊維、ピッチ系炭素繊維、レーヨン系炭素繊維などの炭素繊維が好ましく用いられる。また、得られるプリプレグ積層体の経済性を高める観点からは、ガラス繊維が好ましく用いられ、とりわけ力学特性と経済性のバランスから炭素繊維とガラス繊維を併用することが好ましい。さらに、得られる積層体の衝撃吸収性や賦形性を高める観点からは、アラミド繊維が好ましく用いられ、とりわけ力学特性と衝撃吸収性のバランスから炭素繊維とアラミド繊維を併用することが好ましい。また、得られる積層体の導電性を高める観点からは、ニッケルや銅やイッテルビウムなどの金属を被覆した強化繊維を用いることもできる。これらの中で、強度と弾性率などの力学的特性に優れるＰＡＮ系炭素繊維、得られる積層体の経済性を高める観点からはガラス繊維をより好ましく用いることができる。 Among these, carbon fibers such as PAN-based carbon fibers, pitch-based carbon fibers, and rayon-based carbon fibers, which are excellent in specific strength and specific rigidity, are preferably used from the viewpoint of weight reduction effects. Furthermore, from the viewpoint of increasing the economic efficiency of the obtained prepreg laminate, glass fiber is preferably used, and in particular, from the viewpoint of a balance between mechanical properties and economic efficiency, it is preferable to use carbon fiber and glass fiber in combination. Furthermore, from the viewpoint of improving the shock absorbing properties and formability of the resulting laminate, aramid fibers are preferably used, and in particular, it is preferable to use carbon fibers and aramid fibers in combination from the viewpoint of the balance between mechanical properties and shock absorbing properties. Furthermore, from the viewpoint of increasing the conductivity of the resulting laminate, reinforcing fibers coated with metal such as nickel, copper, or ytterbium can also be used. Among these, PAN-based carbon fibers have excellent mechanical properties such as strength and elastic modulus, and glass fibers are more preferably used from the viewpoint of improving the economic efficiency of the resulting laminate.
繊維基材［ｂ］の目付量は、５～１００ｇ／ｍ２の範囲内であることが好ましい。これにより、プリプレグ積層体１０の成形性の向上と繊維強化複合材料の意匠性の両立を図ることができる。好ましくは、５～８０ｇ／ｍ２、さらに好ましくは、５～５０ｇ／ｍ２である。 The basis weight of the fiber base material [b] is preferably within the range of 5 to 100 g/m 2 . Thereby, it is possible to improve both the moldability of the prepreg laminate 10 and the design of the fiber-reinforced composite material. Preferably, it is 5 to 80 g/m 2 , more preferably 5 to 50 g/m 2 .
目付量が５ｇ／ｍ２未満の場合は、得られる繊維強化複合材料の意匠面１にピンホールが多くなることがあり、１００ｇ／ｍ２を超えると、得られる繊維強化複合材料の含浸性に問題が出ることがある。 If the basis weight is less than 5 g/m 2 , there may be many pinholes on the design surface 1 of the resulting fiber-reinforced composite material, and if it exceeds 100 g/m 2 , the impregnability of the resulting fiber-reinforced composite material may be affected. Problems may occur.
繊維基材［ｂ］３は、樹脂が含浸されていないものであればよく、形態としては、例えば、不織布、織物、編物、マットが挙げられ、樹脂の含浸性の点で不連続繊維であることが好ましい。 The fiber base material [b] 3 may be any material that is not impregnated with resin, and its form includes, for example, nonwoven fabric, woven fabric, knitted fabric, and mat, and is a discontinuous fiber in terms of resin impregnability. It is preferable.
また、繊維基材［ｂ］３の厚さは、０．１～１．５ｍｍの範囲内であることが好ましい。これにより、繊維基材［ｂ］３への含浸性と繊維強化複合材料の意匠性の両立を図ることができる。好ましくは０．１～１ｍｍ、より好ましくは０．１～０．５ｍｍである。厚さが０．１ｍｍ未満の場合は、得られる繊維強化複合材料の意匠面にピンホールが多くなる場合があり、１．５ｍｍを超えると得られる繊維強化複合材料の含浸性に問題が出る場合がある。 Further, the thickness of the fiber base material [b] 3 is preferably within the range of 0.1 to 1.5 mm. Thereby, it is possible to achieve both impregnability into the fiber base material [b] 3 and designability of the fiber reinforced composite material. Preferably it is 0.1 to 1 mm, more preferably 0.1 to 0.5 mm. If the thickness is less than 0.1 mm, there may be many pinholes on the design surface of the fiber-reinforced composite material obtained, and if it exceeds 1.5 mm, there may be a problem with the impregnability of the fiber-reinforced composite material obtained. There is.
本発明に用いられる樹脂を連続繊維の強化繊維に含浸させたプリプレグ［ｃ］は、少なくとも強化繊維と樹脂を含んでいるものであることが好ましい。 The prepreg [c] in which continuous reinforcing fibers are impregnated with resin used in the present invention preferably contains at least reinforcing fibers and resin.
プリプレグ［ｃ］に用いられる強化繊維としては、特に制限はなく、切込プリプレグ［ａ］に記載と同様の強化繊維が用いられる。 The reinforcing fibers used in the prepreg [c] are not particularly limited, and the same reinforcing fibers as those described in the cut prepreg [a] can be used.
強化繊維の形態については、連続した形態であり、強化繊維が、一方向に引き揃えた長繊維、織物、トウおよびロービング等連続繊維の形態であることが好ましい。 The form of the reinforcing fibers is preferably continuous, and the reinforcing fibers are preferably in the form of continuous fibers such as long fibers aligned in one direction, woven fabrics, tows, and rovings.
また、プリプレグ［ｃ］に用いられる樹脂としては特に制限はなく、切込プリプレグ［ａ］に記載と同様の樹脂を用いることができる。 Further, the resin used for the prepreg [c] is not particularly limited, and the same resin as described for the cut prepreg [a] can be used.
プリプレグ積層体１０は、プリプレグ積層体１０の少なくとも一方の表面が意匠面１であり、繊維基材［ｂ］３が意匠面１側の最外層から２層目または３層目に積層された構成とすることが好ましい。 The prepreg laminate 10 has a structure in which at least one surface of the prepreg laminate 10 is the design surface 1, and the fiber base material [b] 3 is laminated as the second or third layer from the outermost layer on the design surface 1 side. It is preferable that
意匠面１側の最外層から２層目に繊維基材［ｂ］３を積層させた構成としては、図１に示すように、意匠面１から切込プリプレグ［ａ］２、次いで繊維基材［ｂ］３を配置したプリプレグ積層体１０とすることにより、意匠面１となる切込プリプレグ［ａ］２の空気や揮発成分を樹脂とともに繊維基材［ｂ］３へ含浸するため、繊維強化複合材料の優れた意匠面を得られる点で好ましい。 As shown in FIG. 1, the structure in which the fiber base material [b] 3 is laminated as the second layer from the outermost layer on the design surface 1 side is as shown in FIG. By forming the prepreg laminate 10 in which [b] 3 is arranged, the air and volatile components of the cut prepreg [a] 2, which forms the design surface 1, are impregnated into the fiber base material [b] 3 together with the resin. This is preferable in that an excellent design aspect of the composite material can be obtained.
また、プリプレグ積層体１０の好ましい積層態様として、図２に示すように、意匠面１から切込プリプレグ［ａ］２ｂ、次いで繊維基材［ｂ］３、切込プリプレグ［ａ］２ａを配置したプリプレグ積層体１０とすることができる。このような積層構成とすることにより、積層工程が複雑でなく、また、意匠面１となる切込プリプレグ［ａ］２の空気や揮発成分を樹脂とともに繊維基材［ｂ］３へ含浸するため、繊維強化複合材料の優れた意匠面１を得られる点で好ましい。切込プリプレグ［ａ］２ａおよび切込プリプレグ［ａ］２ｂは複数枚を積層することも好ましい態様である。 In addition, as a preferable lamination mode of the prepreg laminate 10, as shown in FIG. 2, the cut prepreg [a] 2b is arranged from the design surface 1, followed by the fiber base material [b] 3 and the cut prepreg [a] 2a. It can be a prepreg laminate 10. By having such a laminated structure, the lamination process is not complicated, and the air and volatile components of the cut prepreg [a] 2, which forms the design surface 1, are impregnated into the fiber base material [b] 3 together with the resin. , is preferable in that an excellent design surface 1 of the fiber-reinforced composite material can be obtained. It is also a preferred embodiment to laminate a plurality of cut prepreg [a] 2a and cut prepreg [a] 2b.
さらに、プリプレグ積層体１０の別の好ましい積層態様として、図３に示すように、プリプレグ積層体１０にさらに切込プリプレグ［ａ］２、次いで繊維基材［ｂ］３、プリプレグ［ｃ］４を配置したプリプレグ積層体１０も好ましく使用できる。切込プリプレグ［ａ］２およびプリプレグ［ｃ］４は複数枚を積層することも好ましく使用できる。 Furthermore, as another preferable lamination mode of the prepreg laminate 10, as shown in FIG. The arranged prepreg laminate 10 can also be preferably used. It is also preferable to use a plurality of cut prepregs [a] 2 and prepregs [c] 4 stacked together.
本発明の繊維強化複合材料は、少なくとも樹脂を強化繊維に含浸させた切込プリプレグ［ａ］に由来する繊維強化複合材料層［Ａ］と、前記切込プリプレグ［ａ］または前記プリプレグ［ｃ］に含浸されていた樹脂を含有する繊維基材［ｂ］に由来する繊維強化複合材料層［Ｂ］とを少なくとも含む繊維強化複合材料であることが好ましい。樹脂を連続繊維の強化繊維に含浸させたプリプレグ［ｃ］を積層する場合、樹脂を連続繊維の強化繊維に含浸させたプリプレグ［ｃ］からなる繊維強化複合材料層［Ｃ］を含ませることができる。 The fiber-reinforced composite material of the present invention includes a fiber-reinforced composite material layer [A] derived from a cut prepreg [a] in which reinforcing fibers are impregnated with at least a resin, and a fiber-reinforced composite material layer [A] derived from the cut prepreg [a] or the prepreg [c]. It is preferable that the fiber-reinforced composite material includes at least a fiber-reinforced composite material layer [B] derived from a fiber base material [b] containing a resin impregnated with a fiber-reinforced composite material layer [B]. When laminating prepreg [c] in which reinforcing fibers of continuous fibers are impregnated with resin, it is possible to include a fiber reinforced composite material layer [C] consisting of prepreg [c] in which reinforcing fibers of continuous fibers are impregnated with resin. can.
プリプレグ積層体１０を構成する切込プリプレグ［ａ］２、繊維基材［ｂ］３またはプリプレグ［ｃ］４について複数層積層する場合、繊維種類、樹脂種類、繊維体積含有率、プリプレグの目付、強化繊維の目付、プリプレグの厚さ等の異なる切込プリプレグ［ａ］２、繊維基材［ｂ］３またはプリプレグ［ｃ］４を組み合わせて使用しても良い。その場合、繊維強化複合材料の力学特性や繊維強化複合材料の厚さ等に合わせてプリプレグ積層体１０を設計することができる。 When laminating multiple layers of the cut prepreg [a] 2, fiber base material [b] 3, or prepreg [c] 4 constituting the prepreg laminate 10, the fiber type, resin type, fiber volume content, prepreg basis weight, It is also possible to use a combination of cut prepregs [a] 2, fiber base materials [b] 3, or prepregs [c] 4 having different fabric weights of reinforcing fibers, prepreg thicknesses, etc. In that case, the prepreg laminate 10 can be designed in accordance with the mechanical properties of the fiber-reinforced composite material, the thickness of the fiber-reinforced composite material, and the like.
本発明に係る繊維強化複合材料のうち、切込プリプレグ［ａ］２に由来する繊維強化複合材料層［Ａ］は、切込プリプレグ［ａ］２の樹脂を硬化あるいは固化させた繊維強化複合材料である。また、繊維基材［ｂ］３に由来する繊維強化複合材料層［Ｂ］は、切込プリプレグ［ａ］２あるいはプリプレグ［ｃ］４に含浸されていた樹脂を含有する繊維基材［ｂ］３であり、含有させた樹脂を硬化あるいは固化させた繊維強化複合材料である。さらに、プリプレグ［ｃ］４からなる繊維強化複合材料層［Ｃ］は、プリプレグ［ｃ］４の樹脂を硬化あるいは固化させた繊維強化複合材料である。 Among the fiber-reinforced composite materials according to the present invention, the fiber-reinforced composite material layer [A] derived from the cut prepreg [a]2 is a fiber-reinforced composite material obtained by curing or solidifying the resin of the cut prepreg [a]2. It is. In addition, the fiber reinforced composite material layer [B] derived from the fiber base material [b] 3 is a fiber base material [b] containing the resin impregnated in the cut prepreg [a] 2 or the prepreg [c] 4. 3, and is a fiber-reinforced composite material made by curing or solidifying the resin contained therein. Furthermore, the fiber-reinforced composite material layer [C] made of prepreg [c]4 is a fiber-reinforced composite material obtained by curing or solidifying the resin of prepreg [c]4.
本発明に係る繊維強化複合材料は、繊維強化複合材料層［Ａ］の繊維体積含有率ＶｆＡ（％）と、繊維強化複合材料層［Ｂ］の繊維体積含有率ＶｆＢ（％）とがＶｆＡ＞ＶｆＢの関係を有することが好ましい。具体的には、ＶｆＡが５０％以上、ＶｆＢが５０％以下であることが繊維強化複合材料の意匠性の点から好ましい。 In the fiber reinforced composite material according to the present invention, the fiber volume content VfA (%) of the fiber reinforced composite material layer [A] and the fiber volume content VfB (%) of the fiber reinforced composite material layer [B] are VfA> It is preferable to have a relationship of VfB. Specifically, it is preferable for VfA to be 50% or more and VfB to be 50% or less from the viewpoint of the design of the fiber-reinforced composite material.
さらに、繊維強化複合材料層［Ａ］の繊維体積含有率ＶｆＡとしては、それぞれ５５％以上９０％以下であることが繊維強化複合材料の力学特性と意匠性の観点から好ましい。好ましくは６０～９０％、さらに好ましくは６０から７０％である。５５％未満であると、繊維強化複合材料層［Ａ］の樹脂層が多くなり、空気や揮発成分が繊維強化複合材料層［Ｂ］へ移りにくくなり繊維強化複合材料の意匠面の意匠性を満足できない場合がある。 Furthermore, the fiber volume content VfA of the fiber-reinforced composite material layer [A] is preferably 55% or more and 90% or less from the viewpoint of mechanical properties and design of the fiber-reinforced composite material. Preferably it is 60 to 90%, more preferably 60 to 70%. If it is less than 55%, the resin layer of the fiber reinforced composite material layer [A] will increase, making it difficult for air and volatile components to transfer to the fiber reinforced composite material layer [B], which will reduce the design quality of the fiber reinforced composite material. You may not be satisfied.
本発明に係る繊維強化複合材料において、繊維強化複合材料層［Ｂ］の繊維体積含有率ＶｆＢとしては、１～６０％であることがプリプレグの含浸性の観点から好ましく、好ましくは５～５０％、さらに好ましくは５～２０％である。 In the fiber-reinforced composite material according to the present invention, the fiber volume content VfB of the fiber-reinforced composite material layer [B] is preferably 1 to 60% from the viewpoint of impregnating the prepreg, and preferably 5 to 50%. , more preferably 5 to 20%.
また、繊維強化複合材料層［Ｃ］の繊維体積含有率としては、それぞれ５５％以上９０％以下であることが繊維強化複合材料の力学特性と意匠性の観点から好ましい。好ましくは６０～９０％、さらに好ましくは６０から７０％である。５５％未満であると、繊維強化複合材料層［Ｃ］の樹脂層が多くなり、空気や揮発成分が繊維強化複合材料層［Ｂ］へ移りにくくなり繊維強化複合材料の意匠面が満足しない場合がある。 Further, the fiber volume content of the fiber-reinforced composite material layer [C] is preferably 55% or more and 90% or less from the viewpoint of mechanical properties and design of the fiber-reinforced composite material. Preferably it is 60 to 90%, more preferably 60 to 70%. If it is less than 55%, the resin layer of the fiber-reinforced composite material layer [C] increases, making it difficult for air and volatile components to transfer to the fiber-reinforced composite material layer [B], and the design aspect of the fiber-reinforced composite material is not satisfactory. There is.
次に、本発明に係る繊維強化複合材料の製造方法について説明する。本発明に係る繊維強化複合材料の製造方法は、プリプレグ積層体を加熱しつつ、プリプレグ積層体外部を加圧する成形工程を有することを特徴とするものである。 Next, a method for manufacturing a fiber-reinforced composite material according to the present invention will be explained. The method for producing a fiber-reinforced composite material according to the present invention is characterized by having a molding step of heating the prepreg laminate while pressurizing the outside of the prepreg laminate.
本発明に係る繊維強化複合材料の製造方法において、プリプレグ積層体を加熱しつつ、プリプレグ積層体外部を加圧する成形工程において、プリプレグ積層体内部を－８０ｋＰａ以下（ゲージ圧）の圧力で行う工程を含むことが、得られる繊維強化複合材料のボイドを減少させる観点から好ましい。プリプレグ積層体内部の圧力（ゲージ圧）としては、好ましくは－９０ｋＰａ以下、さらに好ましくは－９５ｋＰａ以下である。 In the method for producing a fiber-reinforced composite material according to the present invention, in the molding step of heating the prepreg laminate while applying pressure to the outside of the prepreg laminate, the step of applying pressure to the inside of the prepreg laminate at a pressure of -80 kPa or less (gauge pressure) is performed. Inclusion is preferable from the viewpoint of reducing voids in the resulting fiber-reinforced composite material. The pressure (gauge pressure) inside the prepreg laminate is preferably -90 kPa or less, more preferably -95 kPa or less.
また、本発明に係る繊維強化複合材料の製造方法において、プリプレグ積層体を加熱しつつ、プリプレグ積層体外部を加圧する成形工程において、切込プリプレグ［ａ］またはプリプレグ［ｃ］に含まれる樹脂を繊維基材［ｂ］に含浸させることが、得られる繊維強化複合材料の意匠面を向上させる観点から好ましい。 In addition, in the method for producing a fiber reinforced composite material according to the present invention, in the molding step of heating the prepreg laminate and pressurizing the outside of the prepreg laminate, the resin contained in the cut prepreg [a] or the prepreg [c] is It is preferable to impregnate the fiber base material [b] from the viewpoint of improving the design of the resulting fiber-reinforced composite material.
本発明の繊維強化複合材料の製造方法としては、例えば、成形型を用いたプレス成形、真空バッグ成形、オートクレーブ成形等の適用が挙げられる。 Examples of the method for manufacturing the fiber reinforced composite material of the present invention include press molding using a mold, vacuum bag molding, autoclave molding, and the like.
かかる本発明の繊維強化複合材料の用途としては、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、ファクシミリ、コンパクトディスク、ポータブルＭＤ、携帯用ラジオカセット、ＰＤＡ（電子手帳などの携帯情報端末）、ビデオカメラ、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、娯楽用品、玩具用品、その他家電製品などの筐体、トレイ、シャシー、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、プロペラシャフト、ホイール、ギアボックスなどの、サスペンション、アクセル、またはステアリング部品」、「フード、ルーフ、ドア、フェンダ、トランクリッド、サイドパネル、リアエンドパネル、アッパーバックパネル、フロントボディー、アンダーボディー、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、バンパービーム、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、メーターバイザー、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、「その他、オルタネーターターミナル、オルタネーターコネクター、ＩＣレギュレーター、ライトディヤー用ポテンショメーターベース、エンジン冷却水ジョイント、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、タービンべイン、ワイパーモーター関係部品、ディストリビュター、スタータースィッチ、スターターリレー、ウィンドウオッシャーノズル、エアコンパネルスィッチ基板、燃料関係電磁気弁用コイル、バッテリートレイ、ＡＴブラケット、ヘッドランプサポート、ペダルハウジング、プロテクター、ホーンターミナル、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ノイズシールド、スペアタイヤカバー、ソレノイドボビン、エンジンオイルフィルター、点火装置ケース、スカッフプレート、フェイシャー」、などの自動車用部品、二輪車用部品、「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が挙げられる。力学特性の観点からは、自動車の内外装、電気・電子機器筐体、自転車、スポーツ用品用構造材、航空機内装材、輸送用箱体に好ましく用いられる。 Applications of the fiber reinforced composite material of the present invention include, for example, personal computers, displays, OA equipment, mobile phones, personal digital assistants, facsimile machines, compact discs, portable MDs, portable radio cassettes, PDAs (electronic notebooks, etc.) Information terminals), video cameras, digital video cameras, optical equipment, audio equipment, air conditioners, lighting equipment, entertainment products, toys, and other home appliances, etc. Electronic equipment parts, parts for civil engineering and building materials such as "pillars, panels, reinforcing materials", "various members, various frames, various hinges, various arms, various axles, various wheel bearings, various beams, propeller shafts, wheels, gears" Suspension, accelerator, or steering parts such as boxes, hoods, roofs, doors, fenders, trunk lids, side panels, rear end panels, upper back panels, front bodies, under bodies, various pillars, various members, various frames, External panels or body parts such as various beams, various supports, various rails, various hinges, etc.'' Exterior parts such as bumpers, bumper beams, moldings, undercovers, engine covers, rectifier plates, spoilers, cowl louvers, aero parts, etc.'' , "Interior parts such as instrument panels, seat frames, door trims, pillar trims, handles, meter visors, various modules, etc.", or "Motor parts, CNG tanks, gasoline tanks, fuel pumps, air intakes, intake manifolds, carburetor main bodies, Structural parts for automobiles and motorcycles such as fuel system, exhaust system, or intake system parts such as carburetor spacers, various piping, and various valves, etc., alternator terminals, alternator connectors, IC regulators, potentiometer bases for light wheels, engines, etc. Cooling water joints, thermostat bases for air conditioners, heating hot air flow control valves, brush holders for radiator motors, turbine vanes, wiper motor related parts, distributors, starter switches, starter relays, window washers nozzles, air conditioner panel switch boards, Fuel-related electromagnetic valve coil, battery tray, AT bracket, headlamp support, pedal housing, protector, horn terminal, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise shield, spare tire cover, solenoid bobbin , engine oil filters, ignition cases, scuff plates, fascias, etc., motorcycle parts, and aircraft parts such as ``landing gear pods, winglets, spoilers, edges, rudders, elevators, faillings, ribs.'' Examples include parts. From the viewpoint of mechanical properties, it is preferably used for the interior and exterior of automobiles, electrical and electronic equipment casings, bicycles, structural materials for sporting goods, aircraft interior materials, and transportation boxes.
以下、実施例によって、本発明について、より具体的に説明する。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
樹脂を強化繊維に含浸させた切込プリプレグ［ａ］、樹脂が未含浸の繊維基材［ｂ］、樹脂を連続繊維の強化繊維に含浸させたプリプレグ［ｃ］、プリプレグ積層体の賦形性、繊維強化複合材料の繊維体積含有率の測定方法、繊維強化複合材料の表面品位の測定方法を以下に示す。実施例におけるプリプレグ積層体及び繊維強化複合材料の作製環境および評価は、特に断りのない限り、温度２５℃±２℃、相対湿度５０％の雰囲気で行ったものである。また、本発明は、これらの実施例によって限定されるものではない。 Cut prepreg [a] in which reinforcing fibers are impregnated with resin, fiber base material not impregnated with resin [b], prepreg [c] in which reinforcing fibers of continuous fibers are impregnated with resin, shapeability of prepreg laminates , a method for measuring the fiber volume content of a fiber-reinforced composite material, and a method for measuring the surface quality of a fiber-reinforced composite material are shown below. The production environment and evaluation of prepreg laminates and fiber-reinforced composite materials in Examples were conducted in an atmosphere with a temperature of 25° C.±2° C. and a relative humidity of 50%, unless otherwise specified. Furthermore, the present invention is not limited to these Examples.
＜樹脂を強化繊維に含浸させた切込プリプレグ［ａ］＞
・下記の製造方法で得られた切込プリプレグＡ
［エポキシ樹脂組成物］
混練装置で、３５質量部の“ｊＥＲ”（登録商標）４００７Ｐ（ジャパンエポキシレジン（株）製）と３５質量部のリグリシジル－ｐ－アミノフェノール（“アラルダイド”（登録商標）ＭＹ０５１０（ハンツマン・アドバンスト・マテリアルズ社製））と３０質量部のビスフェノールＦ型エポキシ樹脂（“エピクロン”（登録商標）８３０（ＤＩＣ（株）製））に、３質量部の“ビニレック”（登録商標）ＰＶＦ－Ｋ（ポリビニルホルマール）（チッソ（株）製））を配合して、熱可塑性樹脂（ＰＶＦ－Ｋ）をエポキシ樹脂中に溶解した。その後、硬化剤であるジシアンジアミド（硬化剤、ＤＩＣＹ－７、三菱化学（株）製）を５質量部、さらに硬化補助剤であるＤＣＭＵ９９（３－（３，４－ジクロロフェニル）－１，１－ジメチルウレア、硬化促進剤（保土ヶ谷化学工業（株）製））を３質量部混練して、エポキシ樹脂組成物を作製した。
<Cut prepreg [a] in which reinforcing fibers are impregnated with resin>
・Incision prepreg A obtained by the following manufacturing method
[Epoxy resin composition]
In a kneading device, 35 parts by mass of "jER" (registered trademark) 4007P (manufactured by Japan Epoxy Resins Co., Ltd.) and 35 parts by mass of liglycidyl-p-aminophenol ("Araldide" (registered trademark) MY0510 (Huntsman Advanced - 3 parts by mass of "Vinylec" (registered trademark) PVF-K to 30 parts by mass of bisphenol F type epoxy resin ("Epicron" (registered trademark) 830 (manufactured by DIC Corporation))) (Polyvinyl formal) (manufactured by Chisso Corporation) was blended to dissolve the thermoplastic resin (PVF-K) into the epoxy resin. Thereafter, 5 parts by mass of dicyandiamide (hardening agent, DICY-7, manufactured by Mitsubishi Chemical Corporation) as a hardening agent, and further DCMU99 (3-(3,4-dichlorophenyl)-1,1-dimethyl) as a hardening agent. Three parts by mass of urea and a curing accelerator (manufactured by Hodogaya Chemical Industry Co., Ltd.) were kneaded to prepare an epoxy resin composition.
［炭素繊維］
・“トレカ（登録商標）”Ｔ７００Ｓ－１２Ｋ（東レ（株）製）
［切込プリプレグ［ａ］］
調製したエポキシ樹脂組成物を、ナイフコーターを用いて離型紙上に塗布して５２ｇ／ｍ２の樹脂フィルムを、２枚作製した。次に、前記のように得られた樹脂フィルムを、一方向に配列させたシート状の炭素繊維の両面に積層し、加熱加圧により樹脂を含浸させた後、炭素繊維の目付が１９０ｇ／ｍ２でマトリックス樹脂の質量分率が３５．４％、プリプレグの目付が２９４ｇ／ｍ２、プリプレグの厚さが１８９μｍの一方向プリプレグを作製した。
[Carbon fiber]
・“Trading Card (registered trademark)” T700S-12K (manufactured by Toray Industries, Inc.)
[Incision prepreg [a]]
The prepared epoxy resin composition was applied onto release paper using a knife coater to produce two resin films each weighing 52 g/m 2 . Next, the resin film obtained as described above was laminated on both sides of sheet-shaped carbon fibers arranged in one direction, and after impregnating with resin by heating and pressing, the basis weight of the carbon fibers was 190 g/m. A unidirectional prepreg having a matrix resin mass fraction of 35.4%, a prepreg basis weight of 294 g/m 2 , and a prepreg thickness of 189 μm was prepared using Example No. 2 .
次に、シリンダーに刃を配置したローラーカッターに得られた前記一方向プリプレグシートを繊維方向に挿入し、断続的な直線状の切込を図４のカットパターンで切込を挿入した。繊維長さＬは２４ｍｍ、θは±１４°で切込を切込プリプレグの面内における強化繊維の垂直方向に投影した投影長さＷｓは０．２５ｍｍであった。＋１４°の切込と－１４°の切込は前記一方向プリプレグシートのプリプレグ中に同数挿入された。全ての切込は切込角度の正負が逆の切込が最近接で、同符号の切込角度の近接の切込より近い距離に４つの切込角度の正負が逆の切込が存在した。また、切込のあらゆる点から切込長さＹの半径内に近接の切込はなかった。切込の列は切込長さＹ１ｍｍの切込が１ｍｍピッチで配置されたものであり、切込の列１つおきに対応する切込によって繊維を分断し、切込プリプレグシートを作製した。同一直線上の近接する切込間距離はＹのおよそ１０倍であった。切込挿入後の離型紙の断面を光学顕微鏡で観察したところ、離型紙の厚み方向に４０％まで切込が侵入していた。 Next, the obtained unidirectional prepreg sheet was inserted in the fiber direction into a roller cutter having a blade arranged in a cylinder, and intermittent linear cuts were inserted in the cut pattern shown in FIG. 4. The fiber length L was 24 mm, θ was ±14°, and the projected length Ws of the cut in the plane of the prepreg in the vertical direction of the reinforcing fibers was 0.25 mm. The same number of +14° cuts and −14° cuts were inserted into the prepreg of the unidirectional prepreg sheet. For all cuts, the nearest cut with the opposite sign of the cutting angle was the cut with the opposite sign, and there were four cuts with the opposite sign of the cut angle at a closer distance than the adjacent cuts with the same sign of the cutting angle. . Further, there was no adjacent notch within the radius of the notch length Y from any point of the notch. The rows of cuts were arranged with cuts having a cut length Y of 1 mm at a pitch of 1 mm, and the fibers were divided by the cuts corresponding to every other row of cuts to produce a cut prepreg sheet. The distance between adjacent notches on the same straight line was approximately 10 times Y. When the cross section of the release paper after the cut was inserted was observed with an optical microscope, it was found that the cut penetrated up to 40% in the thickness direction of the release paper.
得られた切込プリプレグを０°方向に２５ｃｍ角の大きさにカットし、繊維方向をそろえて８層積層し、オートクレーブにて、１３０℃の温度で２時間、０．５ＭＰａの圧力下、昇温速度１．６℃／分で成形して、繊維強化プラスチックの平板を作製した。成形した平板の略中央から略繊維直角方向断面を含むように１０ｍｍ×１０ｍｍの小片を切り出し、エポキシ樹脂により包埋し、略繊維直角方向断面を研磨した。研磨された断面を光学顕微鏡により２００倍以上に拡大し、３００μｍ×３００μｍの領域を９００ピクセル×９００ピクセルのデジタル画像として取得した。得られたデジタル画像において繊維部に該当するピクセルを１、樹脂に該当するピクセルを０となるよう二値化し、繊維部に該当するピクセル数のデジタル画像の総ピクセル数における割合から略繊維直角方向断面における炭素繊維の面積率を取得した。炭素繊維は長手方向に一方向に配置されているため、該面積率を炭素繊維の体積含有率Ｖｆとみなした。２つの小片から無作為に計１０箇所のデジタル画像を、領域が重ならないように取得し、炭素繊維の体積含有率Ｖｆの平均値を計算したところ、５６％であった。 The obtained prepreg was cut into 25 cm square pieces in the 0° direction, stacked in 8 layers with the fiber directions aligned, and heated in an autoclave at a temperature of 130°C for 2 hours under a pressure of 0.5 MPa. A flat plate of fiber-reinforced plastic was produced by molding at a temperature rate of 1.6° C./min. A small piece of 10 mm x 10 mm was cut out from approximately the center of the molded flat plate so as to include the cross section in the direction substantially perpendicular to the fibers, embedded in epoxy resin, and the cross section in the direction substantially perpendicular to the fibers was polished. The polished cross section was magnified 200 times or more using an optical microscope, and a 300 μm×300 μm area was obtained as a 900 pixel×900 pixel digital image. The obtained digital image is binarized so that pixels corresponding to the fiber part are 1 and pixels corresponding to the resin are 0, and from the ratio of the number of pixels corresponding to the fiber part to the total number of pixels of the digital image, the direction approximately perpendicular to the fibers is determined. The area ratio of carbon fiber in the cross section was obtained. Since the carbon fibers were arranged in one direction in the longitudinal direction, the area ratio was regarded as the volume content ratio Vf of the carbon fibers. A total of 10 digital images were taken at random from the two pieces so that the areas did not overlap, and the average value of the carbon fiber volume content Vf was calculated to be 56%.
＜樹脂が未含浸の繊維基材［ｂ］＞
・繊維基材Ａ：“トレカ（登録商標）”ＣＯ６１５１Ｂ（東レ（株）製）（目付量：９２ｇ／ｍ２、厚さ：０．１１ｍｍ）
・繊維基材Ｂ：サーフェイスマット、ＦＣ－３０Ｓ（セントラルグラスファイバー（株）製））（目付量：３０ｇ／ｍ２、厚さ：０．２３ｍｍ）
<Fiber base material not impregnated with resin [b]>
・Fiber base material A: "Torayca (registered trademark)" CO6151B (manufactured by Toray Industries, Inc.) (area weight: 92 g/m 2 , thickness: 0.11 mm)
・Fiber base material B: Surface mat, FC-30S (manufactured by Central Glass Fiber Co., Ltd.) (Area weight: 30 g/m 2 , Thickness: 0.23 mm)
＜樹脂を連続繊維の強化繊維に含浸させたプリプレグ［ｃ］＞
・下記の製造方法で得られたプリプレグＣ
［エポキシ樹脂組成物］
混練装置で、３５質量部の“ｊＥＲ”（登録商標）４００７Ｐ（ジャパンエポキシレジン（株）製）と３５質量部のリグリシジル－ｐ－アミノフェノール（“アラルダイド”（登録商標）ＭＹ０５１０（ハンツマン・アドバンスト・マテリアルズ社製））と３０質量部のビスフェノールＦ型エポキシ樹脂（“エピクロン”（登録商標）８３０（ＤＩＣ（株）製））に、３質量部の“ビニレック”（登録商標）ＰＶＦ－Ｋ（ポリビニルホルマール）（チッソ（株）製））を配合して、熱可塑性樹脂（ＰＶＦ－Ｋ）をエポキシ樹脂中に溶解した。その後、硬化剤であるジシアンジアミド（硬化剤、ＤＩＣＹ－７、三菱化学（株）製）を５質量部、さらに硬化補助剤であるＤＣＭＵ９９（３－（３，４－ジクロロフェニル）－１，１－ジメチルウレア、硬化促進剤（保土ヶ谷化学工業（株）製））を３質量部混練して、エポキシ樹脂組成物を作製した。
<Prepreg [c] in which reinforcing continuous fibers are impregnated with resin>
・Prepreg C obtained by the following manufacturing method
[Epoxy resin composition]
In a kneading device, 35 parts by mass of "jER" (registered trademark) 4007P (manufactured by Japan Epoxy Resins Co., Ltd.) and 35 parts by mass of liglycidyl-p-aminophenol ("Araldide" (registered trademark) MY0510 (Huntsman Advanced - 3 parts by mass of "Vinylec" (registered trademark) PVF-K to 30 parts by mass of bisphenol F type epoxy resin ("Epicron" (registered trademark) 830 (manufactured by DIC Corporation))) (Polyvinyl formal) (manufactured by Chisso Corporation) was blended to dissolve the thermoplastic resin (PVF-K) into the epoxy resin. Thereafter, 5 parts by mass of dicyandiamide (hardening agent, DICY-7, manufactured by Mitsubishi Chemical Corporation) as a hardening agent, and further DCMU99 (3-(3,4-dichlorophenyl)-1,1-dimethyl) as a hardening agent. Three parts by mass of urea and a curing accelerator (manufactured by Hodogaya Chemical Industry Co., Ltd.) were kneaded to prepare an epoxy resin composition.
［炭素繊維］
・“トレカ（登録商標）”Ｔ７００Ｓ－１２Ｋ（東レ（株）製）
［プリプレグ［ｃ］］
調製したエポキシ樹脂組成物を、ナイフコーターを用いて離型紙上に塗布して５２ｇ／ｍ２の樹脂フィルムを、２枚作製した。次に、前記のように得られた樹脂フィルムを、一方向に配列させたシート状の炭素繊維の両面に積層し、加熱加圧により樹脂を含浸させた後、炭素繊維の目付が１９０ｇ／ｍ２でマトリックス樹脂の質量分率が３５．４％、プリプレグの目付が２９４ｇ／ｍ２、プリプレグの厚さが１８９μｍの一方向プリプレグを作製した。
[Carbon fiber]
・“Trading Card (registered trademark)” T700S-12K (manufactured by Toray Industries, Inc.)
[Prepreg [c]]
The prepared epoxy resin composition was applied onto release paper using a knife coater to produce two resin films each weighing 52 g/m 2 . Next, the resin film obtained as described above was laminated on both sides of sheet-shaped carbon fibers arranged in one direction, and after impregnating with resin by heating and pressing, the basis weight of the carbon fibers was 190 g/m. A unidirectional prepreg having a matrix resin mass fraction of 35.4%, a prepreg basis weight of 294 g/m 2 , and a prepreg thickness of 189 μm was prepared using Example No. 2 .
（１）プリプレグ積層体の賦形性
プリプレグ積層体から、縦２４０ｍｍ×横３４０ｍｍのサンプルを切り出し、６０℃のオーブンに２０分入れた後に取り出し、縦４０ｍｍ×横８０ｍｍ×高さ３５ｍｍの鉄製の直方体形状の５面（縦４０ｍｍ×横８０ｍｍの１面以外の５面）への賦形性を評価した。
(1) Shaping property of prepreg laminate A sample measuring 240 mm long x 340 mm wide was cut out from the prepreg laminate, placed in an oven at 60°C for 20 minutes, taken out, and shaped into an iron rectangular parallelepiped measuring 40 mm long x 80 mm wide x 35 mm high. The shapeability on 5 sides of the shape (5 sides other than 1 side of 40 mm long x 80 mm wide) was evaluated.
プリプレグ積層体の賦形性の判定基準として、直方体形状で切込プリプレグあるいはプリプレグに、皺あるいは裂けがなく賦形できた場合は◎、切込プリプレグあるいはプリプレグに、皺あるいは裂けが合計１か所で発生した場合は○、切込プリプレグあるいはプリプレグに、皺あるいは裂けが合計２か所以上で発生した場合は△とした。 The criteria for determining the shapeability of prepreg laminates are: ◎ if the cut prepreg or prepreg can be shaped into a rectangular parallelepiped shape without wrinkles or tears, and there is a total of 1 wrinkle or tear in the cut prepreg or prepreg. If wrinkles or tears occurred in two or more places in the cut prepreg or prepreg, the mark was △.
（２）繊維強化複合材料の繊維体積含有率の測定方法
プリプレグ積層体を、オートクレーブにて、１３０℃の温度で２時間、０．５ＭＰａの圧力下、昇温速度１．６℃／分で成形して６個の繊維強化複合材料を作製した。これらの各繊維強化複合材料から、積層方向とは垂直な面内方向において、縦２０ｍｍ×横２０ｍｍのサンプルを切り出し、その断面を研磨後、レーザー顕微鏡（ＫＥＹＥＮＣＥ ＶＫ－９５１０）で２００倍以上に拡大し繊維の層と繊維の層が２層以上視野内に納まるようにして写真撮影した。同様の操作から各層について１０箇所を任意に選択した。各層の厚さ、繊維の目付と繊維比重から、各繊維体積含有率を求めて、１０箇所の平均を繊維体積含有率とした。
(2) Method for measuring fiber volume content of fiber reinforced composite material The prepreg laminate is molded in an autoclave at a temperature of 130°C for 2 hours under a pressure of 0.5 MPa at a temperature increase rate of 1.6°C/min. Six fiber-reinforced composite materials were produced. A sample measuring 20 mm long x 20 mm wide was cut out from each of these fiber-reinforced composite materials in the in-plane direction perpendicular to the stacking direction, and the cross section was polished and enlarged more than 200 times using a laser microscope (KEYENCE VK-9510). Photographs were taken so that two or more fiber layers were within the field of view. Ten locations were arbitrarily selected for each layer from a similar operation. Each fiber volume content was determined from the thickness of each layer, fiber basis weight, and fiber specific gravity, and the average of 10 locations was taken as the fiber volume content.
（３）繊維強化複合材料の表面品位の測定方法
（２）で作製した繊維強化複合材料を目視で、意匠面のピンホールを検査した。判定基準として、ピンホール数が１０個以下の場合は◎、１１個以上３０個以下の場合は、○、３１個以上の場合は△とした。
(3) Method for measuring surface quality of fiber-reinforced composite material The fiber-reinforced composite material produced in (2) was visually inspected for pinholes on the designed surface. As a criterion, if the number of pinholes was 10 or less, it was rated ◎, if it was 11 or more and 30 or less, it was rated ○, and if it was 31 or more, it was rated △.
（実施例１）
意匠面から切込プリプレグＡ、繊維基材Ａの順番で２層を積層しプリプレグ積層体を作製した。
(Example 1)
From a design perspective, two layers of cut prepreg A and fiber base material A were laminated in this order to produce a prepreg laminate.
得られたプリプレグ積層体を用い、上記の（１）プリプレグ積層体の賦形性、（２）繊維強化複合材料の繊維体積含有率の測定方法と（３）繊維強化複合材料の表面品位の測定方法を記載のとおりに実施して繊維強化複合材料を得て、プリプレグ積層体の賦形性、繊維強化複合材料の繊維体積含有率、繊維強化複合材料の表面品位を測定した。結果を表１に示す。 Using the obtained prepreg laminate, the above (1) shapeability of the prepreg laminate, (2) method for measuring the fiber volume content of the fiber reinforced composite material, and (3) measurement of the surface quality of the fiber reinforced composite material were carried out. The method was carried out as described to obtain a fiber-reinforced composite material, and the formability of the prepreg laminate, the fiber volume content of the fiber-reinforced composite material, and the surface quality of the fiber-reinforced composite material were measured. The results are shown in Table 1.
（実施例２～６、比較例１～４）
プリプレグ積層体の樹脂を強化繊維に含浸させた切込プリプレグ［ａ］、樹脂が未含浸の繊維基材［ｂ］、樹脂を連続繊維の強化繊維に含浸させたプリプレグ［ｃ］、積層構成を表１と表２に示すように変更したこと以外は、実施例１と同様にしてプリプレグ積層体を作製した。作製したプリプレグ積層体を用いて、プリプレグ積層体の賦形性を測定した。また、作製したプリプレグ積層体を用いて、繊維強化複合材料を得て、繊維体積含有率、表面品位を測定した。得られた結果を表１と表２にまとめて示す。
(Examples 2 to 6, Comparative Examples 1 to 4)
A cut prepreg [a] in which reinforcing fibers are impregnated with the resin of the prepreg laminate, a fiber base material not impregnated with resin [b], a prepreg [c] in which reinforcing fibers of continuous fibers are impregnated with resin, and a laminated structure. A prepreg laminate was produced in the same manner as in Example 1 except for the changes shown in Tables 1 and 2. Using the prepared prepreg laminate, the shapeability of the prepreg laminate was measured. Furthermore, a fiber-reinforced composite material was obtained using the prepared prepreg laminate, and the fiber volume content and surface quality were measured. The obtained results are summarized in Tables 1 and 2.
実施例１～６と比較例１～４との対比により、本発明のプリプレグ積層体は、樹脂を強化繊維に含浸させた切込プリプレグ、樹脂が未含浸の繊維基材を含む構成を含んでおり、成形中に意匠面に配置されたプリプレグから樹脂が、樹脂が未含浸の繊維基材へと含浸される際に意匠面のピンホールの原因となる空気や揮発成分も樹脂が未含浸の基材へ移るため、得られる繊維強化複合材料は優れた意匠面を実現していることが分かる。またプリプレグ積層体は切込プリプレグを積層しているため、プリプレグ積層体の賦形性に優れていることが分かる。 By comparing Examples 1 to 6 and Comparative Examples 1 to 4, the prepreg laminate of the present invention includes a structure including a cut prepreg in which reinforcing fibers are impregnated with resin, and a fiber base material not impregnated with resin. Therefore, when the resin is impregnated from the prepreg placed on the design surface into the unimpregnated fiber base material during molding, the air and volatile components that cause pinholes on the design surface are also removed from the unimpregnated resin. It can be seen that the resulting fiber-reinforced composite material has an excellent design because it is transferred to the base material. Furthermore, since the prepreg laminate is made by laminating cut prepregs, it can be seen that the prepreg laminate has excellent shapeability.
本発明によれば、優れたプリプレグ積層体の賦形性と優れた意匠面を備えた繊維強化複合材料が得られるため、テニスラケットやゴルフシャフトなどのスポーツ用品、バンパーやドアなどの自動車の外装材、シャシーやフロントサイドメンバなど自動車の構造材、又はステアリングやメーターバイザー、航空機構造部材、風車の羽根、自動車の外装材、自動車の内装材、又はＩＣトレイやノートパソコンの筐体（ハウジング）などのコンピュータ用途等に広く展開でき、有用である。 According to the present invention, a fiber-reinforced composite material with excellent prepreg laminate formability and excellent design can be obtained, so it can be used for sports equipment such as tennis rackets and golf shafts, and for automobile exteriors such as bumpers and doors. Automobile structural materials such as chassis and front side members, steering wheels, meter visors, aircraft structural members, windmill blades, automobile exterior materials, automobile interior materials, IC trays and laptop computer housings, etc. It is useful and can be widely used in computer applications.
１ 意匠面
２、２ａ、２ｂ 切込プリプレグ［ａ］
３ 繊維基材［ｂ］
４ プリプレグ［ｃ］
５ 断続的な斜め切込（繊維方向に対して正の角度）
６ 断続的な斜め切込（繊維方向に対して負の角度）
７ 繊維方向
８ 繊維直交方向
１０ プリプレグ積層体
1 Design surface 2, 2a, 2b Notch prepreg [a]
3 Fiber base material [b]
4 Prepreg [c]
5 Intermittent diagonal cuts (positive angle to fiber direction)
6 Intermittent diagonal cuts (negative angle to the fiber direction)
7 Fiber direction 8 Fiber orthogonal direction 10 Prepreg laminate
Claims (10)
の製造方法。 The method for producing a fiber-reinforced composite material according to claim 8 or 9 , wherein in the molding step, the fiber base material [b] is impregnated with the resin contained in the cut prepreg [a] or the prepreg [c].
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| JP2009286817A (en) | 2008-05-27 | 2009-12-10 | Toray Ind Inc | Laminated substrate, fiber-reinforced plastic, and methods for producing them |
| WO2016043156A1 (en) | 2014-09-19 | 2016-03-24 | 東レ株式会社 | Notched pre-preg and notched pre-preg sheet |
| JP2017052246A (en) | 2015-09-11 | 2017-03-16 | 三菱レイヨン株式会社 | Manufacturing method of thermoformed articles and material for thermoforming |
| WO2018079475A1 (en) | 2016-10-26 | 2018-05-03 | 東レ株式会社 | Prepreg laminate, fiber-reinforced composite material, and method for producing fiber-reinforced composite material |
| WO2019031111A1 (en) | 2017-08-10 | 2019-02-14 | 東レ株式会社 | Prepreg laminate, method for manufacturing fiber-reinforced plastic using prepreg laminate, and fiber-reinforced plastic |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009286817A (en) | 2008-05-27 | 2009-12-10 | Toray Ind Inc | Laminated substrate, fiber-reinforced plastic, and methods for producing them |
| WO2016043156A1 (en) | 2014-09-19 | 2016-03-24 | 東レ株式会社 | Notched pre-preg and notched pre-preg sheet |
| JP2017052246A (en) | 2015-09-11 | 2017-03-16 | 三菱レイヨン株式会社 | Manufacturing method of thermoformed articles and material for thermoforming |
| WO2018079475A1 (en) | 2016-10-26 | 2018-05-03 | 東レ株式会社 | Prepreg laminate, fiber-reinforced composite material, and method for producing fiber-reinforced composite material |
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