WO2021124907A1 - 繊維強化樹脂複合シート、繊維強化樹脂複合材およびそれを備える樹脂成形品 - Google Patents
繊維強化樹脂複合シート、繊維強化樹脂複合材およびそれを備える樹脂成形品 Download PDFInfo
- Publication number
- WO2021124907A1 WO2021124907A1 PCT/JP2020/045029 JP2020045029W WO2021124907A1 WO 2021124907 A1 WO2021124907 A1 WO 2021124907A1 JP 2020045029 W JP2020045029 W JP 2020045029W WO 2021124907 A1 WO2021124907 A1 WO 2021124907A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fiber
- reinforced resin
- resin composite
- composite material
- laminated
- Prior art date
Links
- 239000000805 composite resin Substances 0.000 title claims abstract description 183
- 239000000463 material Substances 0.000 title claims description 175
- 229920005989 resin Polymers 0.000 title claims description 44
- 239000011347 resin Substances 0.000 title claims description 43
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 108
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 92
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000004985 diamines Chemical class 0.000 claims abstract description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims description 88
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 19
- 239000004917 carbon fiber Substances 0.000 claims description 19
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 1
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 65
- 238000012360 testing method Methods 0.000 description 57
- 238000010521 absorption reaction Methods 0.000 description 49
- 238000000034 method Methods 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 25
- 230000008859 change Effects 0.000 description 23
- 229920002292 Nylon 6 Polymers 0.000 description 20
- 230000000704 physical effect Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 16
- 230000007246 mechanism Effects 0.000 description 15
- 238000005452 bending Methods 0.000 description 13
- 238000003475 lamination Methods 0.000 description 13
- 229920005992 thermoplastic resin Polymers 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000010030 laminating Methods 0.000 description 9
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000011151 fibre-reinforced plastic Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- -1 aliphatic diamine Chemical class 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920000299 Nylon 12 Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920002239 polyacrylonitrile Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 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
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 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
- 238000009751 slip forming Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- WKRCUUPMCASSBN-UHFFFAOYSA-N 2,2-diethylbutanedioic acid Chemical compound CCC(CC)(C(O)=O)CC(O)=O WKRCUUPMCASSBN-UHFFFAOYSA-N 0.000 description 1
- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- JZUMVFMLJGSMRF-UHFFFAOYSA-N 2-Methyladipic acid Chemical compound OC(=O)C(C)CCCC(O)=O JZUMVFMLJGSMRF-UHFFFAOYSA-N 0.000 description 1
- ZVMAGJJPTALGQB-UHFFFAOYSA-N 2-[3-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=CC(OCC(O)=O)=C1 ZVMAGJJPTALGQB-UHFFFAOYSA-N 0.000 description 1
- DNXOCFKTVLHUMU-UHFFFAOYSA-N 2-[4-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=C(OCC(O)=O)C=C1 DNXOCFKTVLHUMU-UHFFFAOYSA-N 0.000 description 1
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- FJSUFIIJYXMJQO-UHFFFAOYSA-N 3-methylpentane-1,5-diamine Chemical compound NCCC(C)CCN FJSUFIIJYXMJQO-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- 229920002748 Basalt fiber Polymers 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Chemical group 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical class COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
- B29C70/0035—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties comprising two or more matrix materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
- B29C70/14—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat oriented
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
- B29C70/545—Perforating, cutting or machining during or after moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
- B32B37/025—Transfer laminating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/10—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer reinforced with filaments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
- B29K2105/128—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles in the form of a mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
- B29K2105/14—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles oriented
- B29K2105/145—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles oriented and crossing at substantial angles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/44—Number of layers variable across the laminate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
- B32B2419/06—Roofs, roof membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2603/00—Vanes, blades, propellers, rotors with blades
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/10—Trains
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/12—Ships
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/18—Aircraft
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
Definitions
- the present invention relates to a fiber-reinforced resin composite sheet containing a polyamide resin film and reinforcing fibers.
- the fiber reinforced resin composite material is lightweight, high strength, and highly rigid, it is widely used from sports and leisure applications to industrial applications such as automobiles and aircraft.
- a method for producing such a fiber-reinforced resin composite material there is a method of using an intermediate material, that is, a prepreg, in which a reinforcing material made of long fibers (continuous fibers) such as reinforcing fibers is impregnated with a matrix resin. According to this method, there is an advantage that the content of the reinforcing fiber of the obtained fiber-reinforced resin composite material can be easily controlled and the content can be designed to be higher. By laminating a plurality of these prepregs and heating and curing them, a molded product of a fiber reinforced resin composite material can be obtained.
- thermosetting resin has been widely used as a matrix resin from the viewpoint of being excellent in strength and rigidity in the production of a fiber reinforced resin composite material (see, for example, Patent Document 1).
- the preprig using the thermosetting resin has a problem that the impact resistance is low and the secondary processability and mass productivity are difficult. Therefore, in recent years, prepregs in which reinforcing fibers are impregnated with a thermoplastic resin as a matrix resin have been widely developed. Since such a preprig is easily melted by heating and solidified by cooling, it is excellent in operability during molding of the fiber reinforced resin composite material, and is expected to have effects such as shortening of production time, leading to cost reduction.
- a polyamide resin may be used as the thermoplastic resin from the viewpoint of excellent physical properties such as impact resistance, toughness and flexibility. ..
- polyamide 6 polycarbonate
- polyamide 6 is generally used in many cases. This is because polyamide 6 is inexpensive and available in large quantities, it is easy to maintain strength in a wide temperature range, it has excellent impregnation into reinforcing fibers, and it is compatible with sizing agents and is easy to handle. Because it is.
- polyamide 6 does not have sufficiently low water absorption, it may affect the physical characteristics of the fiber-reinforced resin composite material by absorbing water. Specifically, absorption of water may cause a decrease in physical property values such as strength of the fiber reinforced resin composite material and a dimensional change. Therefore, the polyamide 6 may be unsuitable for application to, for example, a molded product that may get wet with water or infiltrate into water, a molded product used in rainwater or a humid surrounding environment, and the like.
- the dimensional change is a concept including the meaning of the mass change.
- polyamide 12 (polydodecane amide) has remarkably low water absorption among polyamide resins.
- the polyamide 12 has a low glass transition temperature Tg and a low melting point Tm in terms of its physical properties. Therefore, it is assumed that a fiber-reinforced resin composite material having sufficient strength cannot be produced.
- the fiber reinforced resin composite sheet which is an intermediate material of the fiber reinforced resin composite material, has low water absorption, does not cause dimensional change due to water absorption, and has sufficient strength, the fiber reinforced resin composite material and the final It is preferable because a resin molded product, which is a typical molded product, can be used in a wider range of applications and in an ambient environment.
- an object of the present invention is to provide a fiber reinforced resin composite sheet having low water absorption and excellent strength.
- the fiber-reinforced resin composite sheet includes a polyamide resin film containing a dicarboxylic acid component (a) and a diamine component (b), and a plurality of reinforcing fibers opened from a reinforcing fiber bundle on the polyamide resin film.
- the thickness of the fiber-reinforced resin composite sheet is 20 ⁇ m or more and 70 ⁇ m or less.
- the fiber-reinforced resin composite sheet according to the present invention not only has excellent strength, but also has physical properties such as strength that do not change due to dimensional changes due to water absorption. It is suitably used as a material for producing a molded product that may be infiltrated, a molded product that is used in a rainwater or a humid ambient environment, and the like.
- the fiber-reinforced resin composite sheet in the present embodiment includes a polyamide resin film and a plurality of reinforcing fibers laminated on the polyamide resin film.
- the plurality of reinforcing fibers are laminated on the polyamide resin film in a state in which the plurality of reinforcing fibers opened from the reinforcing fiber bundles are oriented in the same direction.
- the term “laminated” used in the phrase “laminated on a polyamide resin film” refers to the physical property value, shape, and type of treatment performed for laminating the polyamide resin film. And, depending on the conditions, etc., the meanings of "lamination after fusion at least in part”, “lamination after adhesion in at least part” and “lamination after pressure bonding in at least part” also mean. Including. More specifically, at the time of “lamination”, heating, cooling and / or pressure treatment may be performed as necessary.
- the polyamide resin film can be obtained by forming a polyamide resin composed of a dicarboxylic acid component (a) and a diamine component (b) into a film.
- the polyamide resin film may contain other thermoplastic resins, other additives, and the like, in addition to the polyamide resin composed of the dicarboxylic acid component (a) and the diamine component (b).
- each component contained in the polyamide resin film will be described.
- (Polyamide resin) -Dicarboxylic acid component (a) in the polyamide resin, 60 mol% or more and 100 mol% or less of the dicarboxylic acid component (a) is terephthalic acid. This is because when the terephthalic acid in the dicarboxylic acid component (a) is less than 60 mol%, the physical properties such as heat resistance and chemical resistance of the obtained polyamide resin are deteriorated.
- terephthalic acid is preferably 75 mol% or more, more preferably 80 mol% or more, still more preferably 85 mol% or more, or even more preferably 90 mol% or more, 95 mol% or more. , 99 mol% or more, 99.9 mol% or more, or 100 mol%.
- the dicarboxylic acid component (a) other than terephthalic acid is not particularly limited, and is, for example, an aliphatic dicarboxylic acid (malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyl).
- Adipic acid pimeric acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, etc.
- alicyclic dicarboxylic acid (1,3-cyclopentanedicarboxylic acid, 1,3 4-Cyclohexanedicarboxylic acid, etc.)
- aromatic dicarboxylic acid isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenylic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfon-4,4'-dicarboxylic acid, 4,4 '-B
- dicarboxylic acid components (a) other than terephthalic acid do not impair the effects of the fiber-reinforced resin composite sheet of the present embodiment having low water absorption and excellent strength when the fiber-reinforced resin composite sheet is manufactured. It can also be used within the range.
- Diamine component (b) in the polyamide resin, 60 mol% or more and 100 mol% or less of the diamine component (b) is 1,9-nonanediamine and 2-methyl-1,8 octanediamine.
- 60 mol% or more of the diamine component (b) 1,9-nonanediamine and 2-methyl-1,8 octanediamine it is excellent in low water absorption, high heat resistance and impact resistance, and the moldable temperature range is widened. A wide polyamide resin can be obtained.
- 1,9-nonandiamine and 2-methyl-1,8 octanediamine are preferably 75 mol% or more, more preferably 80 mol% or more, still more preferably 85 mol%, based on the total amount of the diamine component (b). Above, or even more preferably, it accounts for 90 mol% or more, 95 mol% or more, 99 mol% or more, 99.9 mol% or more, or 100 mol%.
- the diamine component (b) either 1,9-nonandiamine or 2-methyl-1,8 octanediamine may be contained. In this case, it is preferable to contain 1,9-nonanediamine because it does not easily affect the low water absorption physical properties of the obtained polyamide resin.
- the molar ratio of 1,9-nonandiamine to 2-methyl-1,8-octanediamine is It is preferably 60:40 to 99: 1, more preferably 70:30 to 95: 5, and even more preferably 80:20 to 95: 5.
- the moldable temperature range is wide and the moldability is wide. Is remarkably excellent, and a polyamide resin having excellent impact resistance can be obtained.
- the diamine component (b) other than 1,9-nonanediamine and 2-methyl-1,8-octanediamine is not particularly limited, and is, for example, an aliphatic diamine (ethylenediamine, propylenediamine, 1,4-butanediamine).
- diamine components (b) other than 1,9-nonanediamine and 2-methyl-1,8-octanediamine provide the low water absorption and excellent strength of the present invention when the fiber reinforced resin composite sheet is produced. It can also be used within a range that does not impair the effect of having.
- the molar amount of the entire diamine component (b) is preferably 0.9 or more and 1.2 or less, more preferably 0.95 or more, with respect to the total molar amount of 1 of the dicarboxylic acid component (a). It is 1.1 or less, more preferably 0.98 or more and 1.05 or less.
- the polyamide resin composed of these components can be produced by any method known to those skilled in the art as a method for producing the polyamide resin. For example, it is obtained by (i) a heat-melt polycondensation method in which a mixture of a dicarboxylic acid component (a) and a diamine component (b) is heated and polymerized while maintaining a molten state, and (ii) a heat-melt polycondensation method.
- a hot melt polymerization / solid phase polymerization method in which the degree of polymerization is increased while maintaining the solid state of the polyamide resin at a temperature below the melting point, and (iii) a mixture of a dicarboxylic acid component (a) and a diamine component (b) is in a solid state.
- Examples thereof include a solid-phase polymerization method in which polymerization is carried out while maintaining the above.
- the ends of the obtained polyamide resin are sealed with any end-sealing agent known to those skilled in the art.
- the terminal encapsulant is not particularly limited, and examples thereof include monocarboxylic acid, monoamine, acid anhydride, monoisocyanate, monoacid halide, monoesters, and monoalcohols. These end sealants may be used alone or in combination of two or more as appropriate.
- Polyamide resins end-sealed with an end-sealing agent tend to be superior in heat resistance, fluidity, toughness, low water absorption and rigidity.
- the polyamide resin film obtained by forming the monomer unit contained in the polyamide resin to be filmed as described above and the fiber-reinforced resin composite sheet according to the present embodiment produced by using the same have low water absorption and. It has physical properties such as high heat resistance.
- polyamide 9T polynonamethylene terephthalamide
- Table 1 below shows the approximate physical property values of the polyamide 9T compared with the polyamide 6 and the polyamide 12 for reference.
- the water absorption rate (%) in Table 1 below is a measured value under the conditions of 23 ° C., relative humidity (RH) 100%, and 24 hours (for polyamide 6 and polyamide 12, "revised new edition engineering polymer”. (Chemical Daily Industry Co., Ltd.), see page 174, and for polyamide 9T, refer to the basic physical property values of PA9T of "Genesta" (registered trademark) manufactured by Kuraray).
- polyamide 9T has a significantly lower water absorption rate than polyamide 6, which is about one-seventh. Further, the polyamide 9T has a higher glass transition temperature Tg and a melting point Tm than the polyamide 6 and the polyamide 12. Therefore, when polyamide 9T is applied to a fiber-reinforced resin composite sheet, a fiber-reinforced resin composite material using the same, and a resin molded product, low water absorption and high heat resistance are expected.
- a polyamide 9T has, for example, "Genesta” (registered trademark) (manufactured by Kuraray) having a melting point Tm (° C.) of 250 ° C. to 320 ° C. (grades: N1000A, N1001A, N1002A, N1006A, N1006D, N1001D, etc.) and the like.
- the polyamide resin film may contain a thermoplastic resin other than the polyamide resin composed of the above-mentioned dicarboxylic acid component (a) and diamine component (b). This is to improve the resin flow control when the reinforcing fibers are laminated on the polyamide resin film, and / or to give the fiber-reinforced resin composite sheet additional functions such as toughness.
- thermoplastic resins are not particularly limited, but for example, polyester, polyamide not corresponding to the above-mentioned polyamide resin, polycarbonate, polyethersulfone, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polyetherketone, and the like.
- These thermoplastic resins can be used alone or in combination of two or more as appropriate.
- the content thereof is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the above-mentioned polyamide resin. Yes, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less.
- the content of the thermoplastic resin other than the above-mentioned polyamide resin is 20 parts by mass or less, it is possible to easily add additional functions while maintaining the effects of low water absorption and impact resistance of the polyamide resin film. it can.
- the polyamide resin film may contain various known additives as long as the effects of the present invention are not impaired.
- an antioxidant in order to improve the storage stability of the polyamide resin film and avoid discoloration or deterioration of the cured product, an antioxidant, a light stabilizer, a weather resistance improving material and the like can be added.
- thermosetting elastomers for example, thermosetting elastomers, thermoplastic elastomers, flame retardants (for example, phosphorus-containing polyamide resins, red phosphorus, phosphazenic compounds, phosphates, phosphate esters, etc.), silicone oils, wet dispersants, defoaming agents, etc.
- flame retardants for example, phosphorus-containing polyamide resins, red phosphorus, phosphazenic compounds, phosphates, phosphate esters, etc.
- silicone oils for example, silicone oils, wet dispersants, defoaming agents, etc.
- Defoaming agents natural waxes, synthetic waxes, metal salts of linear fatty acids, acid amides, esters, mold release agents such as paraffins, crystalline silica, molten silica, calcium silicate, alumina, calcium carbonate, Powders such as talc and barium sulfate, metal oxides, metal hydroxides, glass fibers, carbon nanotubes, inorganic fillers such as fullerene, organic fillers such as carbon fibers and cellulose nanofibers, colorants such as red iron oxide, and silane coupling. Examples thereof include agents, conductive materials, slip agents, leveling agents, polymerization inhibitors such as hydroquinone monomethyl ethers, and ultraviolet absorbers. These additives may be used alone or in combination of two or more as appropriate.
- the polyamide resin film containing the above-mentioned components can be produced by applying any method known to those skilled in the art.
- the method for producing the film is not particularly limited, and examples thereof include a roll coat, a reverse coat, a comma coat, a knife coat, a die coat, a gravure coat, a melt extrusion method, a solution casting method, a T die method, and a calendar method. Be done. Further, by using the coextrusion method or the laminating method, it is possible to increase the thickness or to laminate resin films having different resin compositions.
- the lower limit of the thickness of the polyamide resin film is not particularly limited, but preferably 5 ⁇ m or more makes it easy to maintain a good morphology of the film during film molding.
- the thickness of the polyamide resin film is preferably 50 ⁇ m or less, more preferably 45 ⁇ m or less, still more preferably 40 ⁇ m or less, still more preferably 30 ⁇ m or less.
- Such a polyamide resin film is an intermediate material for producing the fiber reinforced resin composite sheet in the present embodiment. This is carried out by laminating a plurality of reinforcing fibers opened from a reinforcing fiber bundle on one or both surfaces of a polyamide resin film in a state of being oriented in the same direction, and heating, cooling and / or pressurizing the fibers. A fiber-reinforced resin composite sheet in the form is obtained.
- the reinforcing fibers are laminated on the above-mentioned polyamide resin film in a state in which a plurality of reinforcing fibers opened from the reinforcing fiber bundles are oriented in the same direction.
- the "state in which a plurality of reinforcing fibers are oriented in the same direction" means a state in which each reinforcing fiber extends in a substantially parallel direction with respect to the plurality of reinforcing fibers.
- the material of the reinforcing fiber is not particularly limited, but it may be appropriately selected from known reinforcing fibers as the reinforcing fibers constituting the fiber-reinforced resin composite sheet according to the application and the like.
- various inorganic fibers or organic fibers such as carbon fiber, aramid fiber, nylon fiber, high-strength polyester fiber, glass fiber, boron fiber, alumina fiber, silicon nitride fiber, and basalt fiber can be used.
- carbon fibers, aramid fibers, glass fibers, boron fibers, alumina fibers, and silicon nitride fibers are preferable from the viewpoint of specific strength and specific elasticity.
- carbon fiber is more preferable because the strength and corrosion resistance of the molded product using the fiber-reinforced resin composite sheet in the present embodiment can be improved.
- the carbon fiber it is preferable to use a PAN (polyacrylonitrile) -based carbon fiber having particularly high strength.
- the surface treatment with metal may be applied to the carbon fiber.
- the reinforcing fibers opened from these reinforcing fiber bundles can be used alone or in combination of two or more as long as they are oriented in the same direction.
- the volume content Vf of the reinforcing fibers with respect to the fiber-reinforced resin composite sheet is 20% or more and 70% or less.
- the volume content Vf of the reinforcing fibers is preferably 25% or more, more preferably 30% or more, still more preferably 40% or more, still more preferably 45% or more.
- the volume content Vf of the reinforcing fiber is preferably 65% or less, more preferably 60% or less, still more preferably 55% or less.
- the volume content Vf of the reinforcing fibers in the fiber-reinforced resin composite sheet is not only the type and thickness of the reinforcing fibers, the fiber width in which the reinforcing fibers are oriented, the thickness of the polyamide resin film, etc., but also the fiber-reinforced resin composite sheet. It can be adjusted within the above range by appropriately controlling the temperature and pressure applied during production.
- the volume content Vf of the reinforcing fiber can be measured by a combustion method, a nitric acid decomposition method, a sulfuric acid decomposition method, or the like, but the volume content Vf of the reinforcing fiber in the present specification is the same as in the examples by the combustion method. The value to be measured.
- the thickness of the fiber reinforced resin composite sheet in the present embodiment is 20 ⁇ m or more and 70 ⁇ m or less.
- the thickness of the fiber-reinforced resin composite sheet is preferably 25 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 35 ⁇ m or more, still more preferably 40 ⁇ m or more.
- the thickness of the fiber-reinforced resin composite sheet is preferably 65 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 55 ⁇ m or less.
- the polyamide resin and the reinforcing fibers are mostly fused and then laminated, so that the strength of the reinforcing fibers can be increased. You will be able to fully demonstrate it.
- delamination of the laminate made of the fiber-reinforced composite sheet (fiber-reinforced resin composite material described later) is unlikely to occur, and the fatigue characteristics are also excellent.
- the molding processability when using the fiber reinforced resin composite sheet is more excellent.
- the thickness of the fiber-reinforced resin composite sheet is also affected by the thickness of the polyamide resin film, but can be kept within the above range by appropriately controlling the temperature and pressure applied during the production of the fiber-reinforced resin composite sheet.
- the fiber-reinforced resin composite sheet in the present embodiment not only has low water absorption and high heat resistance, but also has excellent reinforcement by the volume content Vf of the reinforcing fiber which occupies a sufficient value. It has excellent molding processability due to its effectiveness, fatigue resistance, and the relatively thin thickness of the fiber reinforced resin composite sheet. That is, since the fiber-reinforced resin composite sheet in the present embodiment has low water absorption, it is used in, for example, a resin molded product that may get wet or infiltrate into water, rainwater, or a humid surrounding environment. It is suitably used as a material for producing resin molded products and the like.
- a plurality of fiber-reinforced resin composite sheets can be laminated to form various shapes at high density while reducing voids as much as possible, so that excellent strength can be obtained. It is possible to manufacture a fiber-reinforced resin composite material and a resin molded product.
- each reference numeral is a fiber reinforced resin composite sheet manufacturing apparatus 1, a reinforcing fiber bundle F0, a reinforcing fiber (reinforcing fiber opened (from the reinforcing fiber bundle)) F, a polyamide resin film R0, a heating roller 2, and a cooling roller 3. , Endless belt 4, pull-out roller 5, bobbin 6, and fiber reinforced resin composite sheet S.
- the fiber-reinforced resin composite sheet S can be continuously manufactured by using, for example, the fiber-reinforced resin composite sheet manufacturing apparatus 1 shown in FIG.
- the fiber-reinforced resin composite sheet manufacturing apparatus 1 is an apparatus for continuously producing a fiber-reinforced resin composite sheet S from a reinforcing fiber bundle F0 and a polyamide resin film R0.
- the fiber-reinforced resin composite sheet manufacturing apparatus 1 includes a plurality of pairs of heating rollers 2 arranged vertically (two pairs in FIG. 1) and a plurality of pairs arranged vertically below the heating rollers 2 (two pairs in FIG. 1). ), A pair of endless belts 4 hung between the heating roller 2 and the cooling roller 3, a pair of pull-out rollers 5 located below the endless belt 4, and under the pull-out roller 5. It is provided with a winding bobbin 6 arranged on the side.
- a fiber opening mechanism for opening the reinforcing fiber bundle F0 and spreading it in a band shape is provided in the vicinity of the heating roller 2 on the uppermost stage.
- this fiber opening mechanism can form a large number of continuous reinforcing fibers F while spreading them so as to be oriented in the same direction and extend.
- the fiber opening mechanism may be any mechanism capable of such processing, such as a mechanism for striking and expanding the reinforcing fiber bundle F0, a mechanism for blowing and expanding the reinforcing fiber bundle F0, and a mechanism for applying ultrasonic waves to the reinforcing fiber bundle F0.
- Various mechanisms such as a mechanism for spreading can be used.
- the fiber opening mechanism includes a mechanism for supplying the reinforcing fiber F after opening to one surface of the polyamide resin film R0 and a reinforcing fiber F after opening to the other surface of the polyamide resin film R0.
- the former mechanism is provided so as to introduce the reinforcing fiber F between one surface of the polyamide resin film R0 and the heating roller 2 in contact with the surface, and the latter mechanism is provided with the other surface of the polyamide resin film R0.
- the reinforcing fiber F is provided so as to be introduced between the surface and the heating roller 2 in contact with the surface.
- the fiber opening mechanism may supply the reinforcing fibers F only to one surface of the polyamide resin film R0.
- the heating roller 2 is a high-temperature roller heated by an electric heater, a heating medium, or the like (for example, a heating fluid).
- the two pairs of heating rollers 2 heat the polyamide resin film R0 and the reinforcing fibers F introduced on both sides thereof while sandwiching the reinforcing fibers F from both sides via the endless belt 4, so that the reinforcing fibers F are continuously formed on the polyamide resin film R0.
- the reinforcing fibers F are laminated on the polyamide resin film R0 in a state of being oriented in the same direction (a state of being aligned in the vertical direction of FIG. 1).
- the cooling roller 3 is a low-temperature roller cooled by a cooling medium or the like (for example, a cooling fluid).
- the cooling roller 3 fixes the reinforcing fibers F to the polyamide resin film R0 by cooling the polyamide resin film R0 in which the reinforcing fibers F are laminated while sandwiching the polyamide resin film R0 from both sides via the endless belt 4.
- the fiber reinforced resin composite sheet S in which the polyamide resin film R0 (matrix resin) and the reinforcing fibers F are integrated is formed.
- the pull-out roller 5 is a roller that pulls out the molded fiber-reinforced resin composite sheet S downward while applying tension to it.
- the bobbin 6 for winding is a core material for winding the fiber reinforced resin composite sheet S.
- the bobbin 6 is rotationally driven by a drive source such as a motor, and the fiber-reinforced resin composite sheet S drawn out by the drawing roller 5 is sequentially wound up to form a roll-shaped fiber-reinforced resin composite sheet S.
- the fiber-reinforced resin composite sheet S can also be produced by a method in which the polyamide resin film R0 and the opened reinforcing fibers are flowed together in the same direction and wound up without using the endless belt 4 shown in FIG. Is.
- the reinforcing fibers F shown in FIG. 1 are not sent from both sides, but on one side.
- a fiber-reinforced resin composite sheet S in which reinforcing fibers F are laminated on one surface of a polyamide resin film can be obtained.
- the fiber-reinforced resin composite material in the present embodiment is a fiber-reinforced composite material in which a plurality of fiber-reinforced resin composite sheets in the above-described embodiment are laminated in the thickness direction.
- the “lamination” used in "the fiber reinforced resin composite sheet (or its chop material) is laminated” means the physical properties of the fiber reinforced resin composite sheet (or its chop material).
- “lamination after fixing at least partly”, “lamination after bonding at least partly”, “at least partly bonding” It also includes the meanings of "lamination after fusion in a part”, “lamination after adhesion in at least a part”, and “lamination after pressure bonding in at least a part”. More specifically, at the time of "lamination”, heating, cooling and / or pressure treatment may be performed as necessary.
- the fiber-reinforced resin composite sheet to be laminated may be laminated by being shredded or the like as necessary according to the desired shape of the fiber-reinforced resin composite material.
- the number of laminated fiber-reinforced resin composite sheets is also not particularly limited, and may be appropriately set according to the desired size of the fiber-reinforced resin composite material and the like.
- the fiber-reinforced resin composite sheet may be laminated in any state with respect to the fiber direction of the reinforcing fiber, but preferably, the fiber directions of the reinforcing fibers of the plurality of fiber-reinforced resin composite sheets differ in two-dimensional directions. It is laminated in a state of having.
- a plurality of fiber-reinforced resin composite sheets have an angle difference of approximately 45 ° in the fiber direction of the reinforcing fibers in the two-dimensional direction, in other words, 0 °, 45 °, ⁇ 45 ° and 90 in the two-dimensional plane.
- fiber reinforced composite materials are available.
- the fiber-reinforced resin composite sheet in the above-described embodiment may be laminated in the shape of a plurality of chops in the thickness direction.
- a plurality of chop materials can be produced, for example, by shredding the fiber-reinforced resin composite sheet S shown in FIG. 1 in the above-described embodiment in the longitudinal direction and the width direction.
- a chop material can be produced by the following procedure.
- each reference numeral represents a fiber-reinforced resin composite sheet S, a section I, a notch X continuous in the longitudinal direction, a section II, a notch Y continuous from one end to the other end in the width direction, and a chop material C.
- a notch X extending in the longitudinal direction is formed. That is, while feeding the fiber-reinforced resin composite sheet S in the longitudinal direction, a large number of cuts X continuous in the longitudinal direction are formed in the section I in the middle of the feeding path.
- the cut X can be formed by using, for example, a shredding device including a large number of blades arranged at equal intervals in the width direction of the fiber reinforced resin composite sheet S.
- a continuous notch Y is formed from one end to the other end of the fiber reinforced resin composite sheet S in the width direction.
- the notch Y can be formed by using, for example, a rotary cutter or the like.
- the notch Y is formed each time the fiber reinforced resin composite sheet S is fed out by a fixed distance in the longitudinal direction. As a result, a large number of rectangular chop materials C having a short side having a length corresponding to the pitch of the cut X and a long side having a length corresponding to the pitch of the cut Y are cut out.
- the fiber-reinforced resin composite sheet S is a sheet in which a large number of reinforcing fibers F are laminated in the same direction in the longitudinal direction thereof. Therefore, each chop material C cut out from the fiber-reinforced resin composite sheet S is also laminated in a state in which a large number of reinforcing fibers F are oriented in the same direction in the longitudinal direction (long side direction). That is, the chop material C contains a polyamide resin film R0 and a large number of reinforcing fibers F laminated on the polyamide resin film R0 in the same direction.
- the size of the chop material C can be appropriately set to an appropriate size in consideration of the shapeability of the fiber reinforced resin composite material and the resin molded product manufactured using the chop material C.
- the chop material C is formed in a rectangular shape having a short side length of 2 mm or more and 50 mm or less and a long side length of 2 mm or more and 80 mm or less.
- the fiber-reinforced resin composite material and resin molded product manufactured using it are not extremely large in size or need to be mass-produced in a short time, the lengths of the short side and the long side of the chop material C are not required. The smaller the value, the more effectively the strength of the fiber-reinforced resin composite material and the resin molded product can be increased.
- the fiber reinforced resin composite material and the resin molded product are made by increasing the lengths of the short side and the long side of the chop material C to such an extent that the strength is not extremely impaired. Can be manufactured more efficiently in a short time.
- the length of the short side of the chop material C is preferably 2 mm or more, more preferably 3 mm or more, further preferably 4 mm or more, still more preferably 4.5 mm or more, and preferably 50 mm or less, more preferably 40 mm. Hereinafter, it is more preferably 30 mm or less, or even more preferably 20 mm or less, 15 mm or less, or 10 mm or less.
- the length of the long side of the chop material C is preferably 2 mm or more, more preferably 4 mm or more, further preferably 6 mm or more, or even more preferably 8 mm or more or 10 mm or more, and preferably 80 mm or less. It is preferably 70 mm or less, more preferably 60 mm or less, or even more preferably 50 mm or less or 45 mm or less.
- the thickness of the chop material C is the same as the thickness of the fiber-reinforced resin composite sheet in the above-described embodiment, and is 20 ⁇ m or more and 70 ⁇ m or less.
- the preferable thickness is also the same as the thickness of the fiber reinforced resin composite sheet in the above-described embodiment. That is, similarly to the fiber-reinforced resin composite sheet in the above-described embodiment, a plurality of sheets can be laminated in a small size as the chop material C while reducing the voids as much as possible due to its thinness. Therefore, it is possible to manufacture a fiber-reinforced resin composite material having a significantly higher density and remarkably excellent strength and low water absorption, and a resin molded product using the same. Further, by forming the chop material C into a shape, the shapeability is improved, and a resin molded product having a complicated shape can be manufactured.
- such a plurality of chop materials C may be laminated in any state of the fiber directions of the reinforcing fibers, but the fiber directions of the reinforcing fibers of the plurality of chop materials C.
- the fibers are laminated in a two-dimensionally random state (pseudo-isotropic).
- a large number of chop materials C are arranged while being dispersed on the upper surface of a belt conveyor that is arranged substantially horizontally and is rotating.
- a drop device that drops the chop material C while vibrating from above the belt conveyor can be used.
- the density and the number of laminated chop materials C on the upper surface of the belt conveyor are increased.
- the fiber direction of the reinforcing fiber F contained in each chop material C (in other words, the longitudinal direction of the chop material C) varies in various directions on the horizontal plane, and a plurality of chop materials C are formed in the thickness direction. A large number of chop materials C are laminated on the belt conveyor so as to be stacked.
- the chop material C laminated on the upper surface of the belt conveyor is pressurized and heat-treated using a heat-resistant endless belt or a heating roller via a release film.
- a large number of chop materials C are integrated. That is, the laminated chop materials C are bonded to each other by pressurization and heat treatment using the heating roller.
- the dispersion and lamination of a large number of chop materials C on the upper surface of the belt conveyor and the pressurization and heat treatment using the heating roller are continuously performed.
- the dropping operation of the chop material C may be repeated at a plurality of places in the rotation direction of the belt conveyor, as in the example of the manufacturing method when the carrier sheet is used as described later, and as a result, the density of the chop material C may be repeated. And the number of stacked sheets may be increased.
- a laminated chopped sheet a laminated chopped sheet in which a plurality of chopping materials C are integrated and laminated with each other is continuously formed in a scroll shape.
- a partial cross section of the scroll-shaped laminated chopped sheet has a shape in which the carrier sheet R is omitted in FIG. 4 described later.
- the thickness of this laminated chopped sheet can be appropriately set.
- each reference numeral represents the thickness t of the carrier sheet R, the section XI, the chopped material C, the section XII, the section XIII, the laminated chopped sheet (fiber reinforced composite material) CS, and the laminated chopped sheet CS.
- a large number of chop materials C are dispersed and arranged on the upper surface of the carrier sheet R.
- a dropping device similar to the above can be used from above the carrier sheet R. Then, by repeating the drop operation of the chop material C using such a drop device at a plurality of places in the feed direction of the carrier sheet R, the density of the chop material C on the carrier sheet R and the number of laminated sheets are increased. That is, in a plurality of sections XI, section XII, section XIII, ...
- the chop material C is contained in each chop material C by repeatedly dropping the chop material C using the drop device.
- a large number of chop materials C are laminated on the carrier sheet R so that the fiber directions of the reinforcing fibers F vary in various directions on the horizontal plane and a plurality of chop materials C are stacked in the thickness direction.
- the carrier sheet R and the chop material C on the carrier sheet R are pressurized and heat-treated using a heating roller to integrate the carrier sheet R and the chop material C with each other. That is, by pressurizing and heat-treating using the heating roller, the chop material C is supported on the carrier sheet R in a laminated state, and the laminated chop materials C are bonded to each other.
- a laminated chopped sheet CS in which a plurality of chopping materials C are laminated on the upper surface of the carrier sheet R is formed.
- the thickness t of the laminated chopped sheet CS that is, the total thickness of the carrier sheet R and the chop material C in which a plurality of sheets or more are laminated on the carrier sheet R can be appropriately set.
- the material of the carrier sheet R basically the same polyamide resin as the resin of the chop material C, or other thermoplastic resin as described above can be used.
- FIGS. 3 and 4 the case where the chopped material C is laminated only on the upper surface of the carrier sheet R to produce the laminated chopped sheet CS is illustrated, but the chop material C may be laminated on both sides of the carrier sheet R.
- the work of laminating the chop material C on the carrier sheet R that is, the work of arranging the chop materials C in multiple random manners to heat and pressurize
- the carrier sheet R is turned upside down so that the lower surface of the carrier sheet R is on top, and the operation of laminating the chop material C in that state is repeated in the same manner.
- a laminated chopped sheet in which the chopping material C is laminated on both sides of the carrier sheet R can be produced.
- the resin molded product in this embodiment includes the fiber reinforced resin composite material in the above-described embodiment.
- the resin molded product may be any molded product having an arbitrary shape that can be manufactured by using the fiber-reinforced resin composite material in the above-described embodiment by any molding method known to those skilled in the art.
- molded products for general industrial use, sports use, aerospace use and the like can be mentioned. Specific examples thereof include various vehicles such as automobiles, bicycles, motorcycles and railroad vehicles, and molded products used for moving bodies such as ships. More specifically, for example, molded products for various vehicles such as brake pedals, undercovers, front ends, seat shells, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, papermaking rollers, roofing materials, etc.
- Other molded products such as cables, repair reinforcements, golf shafts, fishing rods, tennis and badminton rackets, hockey sticks, ski poles and the like can be mentioned.
- the method for producing the resin molded product in this embodiment is not particularly limited.
- a plurality of laminated chopped sheet CS described in the above-described embodiment, which are plate-shaped cut out to a predetermined size, are prepared, and these are stacked in the thickness direction in a mold such as a heat press machine. Place in.
- a resin molded product can be manufactured by performing a heating and / or pressure treatment and, if necessary, a cooling treatment on a plurality of stacked laminated chopped sheet CS.
- the low water absorption polyamide resin film R0 is used as the thermoplastic resin, it is possible to obtain a resin molded product in which the physical property value of the resin molded product is unlikely to decrease or the dimensional change due to water absorption. it can. Further, since the resin molded product is molded using the laminated chopped sheet CS containing a sufficient amount of the reinforcing fiber F so that the volume content Vf of the reinforcing fiber is 20% or more and 70% or less, the reinforcing fiber F is used. An excellent reinforcing effect can be obtained, and the strength of the resin molded product can be increased.
- the laminated chopped sheet CS which is laminated in a state where the fiber directions of the reinforcing fibers F of the plurality of chop materials C are two-dimensionally random (pseudo isotropic), is when the laminated chopped sheet CS is pressed.
- the possibility that the reinforcing fiber F is shredded can be reduced, and the flow of the resin during press working can be promoted to increase the degree of freedom in the shape of the resin molded product.
- resin molded products having various shapes can be molded without any trouble while exhibiting the reinforcing effect of the reinforcing fibers F isotropically.
- the fiber-reinforced resin composite sheet includes a polyamide resin film containing a dicarboxylic acid component (a) and a diamine component (b), and a plurality of reinforcing fibers opened from a reinforcing fiber bundle on the polyamide resin film. It is a fiber-reinforced resin composite sheet containing a plurality of reinforcing fibers laminated in the same direction, and 60 mol% or more and 100 mol% or less of the dicarboxylic acid component (a) is terephthalic acid, and the diamine component.
- the thickness of the fiber-reinforced resin composite sheet is 20 ⁇ m or more and 70 ⁇ m or less.
- the fiber reinforced resin composite sheet having such a structure has low water absorption and excellent strength.
- the fiber-reinforced resin composite sheet not only has excellent strength, but also its physical properties such as strength do not change due to dimensional changes due to water absorption. Therefore, for example, it gets wet with water or is infiltrated into water. It is suitably used as a material for producing a molded product having a possibility of being used, a molded product used in a rainwater or a humid surrounding environment, and the like.
- the polyamide resin film has a thickness of 5 ⁇ m or more and 50 ⁇ m or less, and the reinforcing fibers are laminated on one or both surfaces of the polyamide resin film.
- the reinforcing fiber is a carbon fiber.
- the fiber-reinforced resin composite material according to another aspect of the present invention is a fiber-reinforced composite material in which a plurality of fiber-reinforced resin composite sheets according to one aspect of the present invention are laminated in the thickness direction.
- the materials are laminated in a state in which the fiber directions of the reinforcing fibers of the plurality of fiber-reinforced resin composite sheets have an angle difference in the two-dimensional direction.
- the fiber reinforced resin composite material having such a structure has low water absorption and excellent strength.
- the fiber-reinforced resin composite material according to another aspect of the present invention is a fiber-reinforced composite material laminated in the thickness direction in the form of a plurality of chop materials, and the chop material is the fiber-reinforced resin composite sheet. Is formed so as to exhibit a rectangular shape in which the length of the short side is 2 mm or more and 50 mm or less and the length of the long side is 2 mm or more and 80 mm or less. The fibers are laminated in a state in which the fiber directions are two-dimensionally random.
- the fiber reinforced resin composite material having such a structure has low water absorption and excellent strength.
- the fiber-reinforced resin composite material further includes a carrier sheet, and the carrier sheet supports the plurality of chop materials in a laminated state on one or both surfaces thereof. It is preferable to do so.
- the resin molded product according to still another aspect of the present invention includes the fiber-reinforced resin composite material according to the other aspect of the present invention described above.
- a resin molded product having such a structure has low water absorption and excellent strength.
- the resin molded product not only has excellent strength, but also its physical properties such as strength do not change due to dimensional changes due to water absorption, so that it may get wet or infiltrate into water, for example. It can be suitably used even in an environment where there is a certain environment, rainwater or a humid surrounding environment.
- test pieces of the fiber-reinforced resin composite material in Examples 1 and 2 and Comparative Examples 1 and 2 were prepared as follows.
- a polyamide resin film was prepared.
- Polyamide 9T manufactured by Kuraray, "Genesta” (registered trademark) pellets are molded using an extrusion molding machine equipped with a T-die under conditions of molding temperature of 290 ° C to 310 ° C, and polyamide 9T with a thickness of 20 ⁇ m is formed. Polyamide resin film was obtained.
- the fiber-reinforced resin composite sheet of the present embodiment described above was obtained while opening the carbon fiber bundle by the manufacturing apparatus shown in 1. At this time, the roll temperature (the temperature of the heating roller 2 shown in FIG. 1) was 280 ° C., and the feed rate was 20 m / min. The obtained fiber-reinforced resin composite sheet is obtained by laminating open fiber bundles on both sides of a polyamide resin film.
- the volume content Vf of the carbon fibers with respect to the fiber-reinforced resin composite sheet was similarly 53%, and the thickness of the fiber-reinforced resin composite sheet was 40 ⁇ m to 50 ⁇ m.
- the volume content Vf of the reinforcing fiber was measured by the combustion method.
- the laminated fiber-reinforced resin composite sheet was put into a mold and pressurized while heating at 300 ° C. and 2 MPa for 15 minutes, and then pressurized while cooling at room temperature and 3 MPa for 10 minutes.
- a fiber reinforced resin composite material of 300 mm ⁇ 300 mm ⁇ 2 mm (thickness) is taken out from the mold, the fiber reinforced plastic composite material is cut out to various predetermined sizes, and finally, a four-axis structure having a laminated structure with an angle difference of 45 ° is obtained.
- a test piece of a fiber-reinforced resin composite material in the direction was obtained.
- the test piece of the fiber-reinforced resin composite material has a size of 25 mm (length in the minor axis direction) x 250 mm (length in the major axis direction) x 2 mm (thickness), and 15 mm (length in the minor axis direction) x 100 mm (length in the minor axis direction). It was cut out into a size of (length in the major axis direction) ⁇ 2 mm (thickness) and a size of 50 mm ⁇ 50 mm ⁇ 2 mm (thickness). The volume content Vf of the carbon fiber of the test piece was also 53%.
- Example 2 The fiber-reinforced resin composite sheet obtained by the same method as in Example 1 is shredded by the method shown in FIG. 2 to obtain a chop material having a rectangular shape with a short side length of 5 mm and a long side length of 20 mm. Multiple pieces were prepared. The thickness of the chop material is 40 ⁇ m to 50 ⁇ m because it is the same as that of the fiber reinforced resin composite sheet.
- the opened carbon fibers have a pseudo-isotropic shape as shown in FIGS. 2 to 4, that is, the fiber directions of the carbon fibers of the chop material are two-dimensionally random (pseudo-isotropic). It was put into a mold and laminated. The laminated chop material in the mold was pressurized while heating at 300 ° C.
- a fiber reinforced resin composite material having a size of 300 mm ⁇ 300 mm ⁇ 2 mm (thickness) is taken out from the mold, the fiber reinforced plastic composite material is cut out to various predetermined sizes, and finally, the fiber reinforced plastic having a pseudo-isotropic laminated structure is obtained.
- a test piece of a resin composite material was obtained.
- the test piece of the fiber-reinforced resin composite material has a size of 25 mm (length in the minor axis direction) x 250 mm (length in the major axis direction) x 2 mm (thickness), and 15 mm (length in the minor axis direction) x 100 mm (length in the minor axis direction). It was cut out into a size of (length in the major axis direction) ⁇ 2 mm (thickness) and a size of 50 mm ⁇ 50 mm ⁇ 2 mm (thickness). The volume content Vf of the carbon fiber of the test piece was 50%.
- the tensile strength and tensile elastic modulus, bending strength and flexural modulus of the test piece of the fiber-reinforced resin composite material cut out were measured by the methods shown below, and the water absorption was further evaluated by the method shown below.
- tensile strength (MPa) and tensile modulus (GPa) The tensile strength and the tensile elastic modulus were measured using a test piece of a fiber-reinforced resin composite material having a size of 25 mm (length in the minor axis direction) ⁇ 250 mm (length in the major axis direction) ⁇ 2 mm (thickness). Specifically, the tensile strength and tensile elastic modulus of the test pieces of the fiber-reinforced resin composite materials of Examples 1 and 2 and Comparative Examples 1 and 2 were measured according to JIS K 7164: 2005.
- the water absorption was evaluated using a test piece of a fiber reinforced resin composite material having a size of 50 mm ⁇ 50 mm ⁇ 2 mm (thickness).
- a test piece of the fiber-reinforced resin composite material was placed in an oven at 80 ° C. for 6 hours to be absolutely dried.
- water at room temperature was placed in a 210 mm ⁇ 297 mm stainless steel vat to a depth of about 10 mm, and a test piece of a fiber reinforced resin composite material that had been absolutely dried was immersed in the vat.
- the surrounding environment was set to the atmospheric atmosphere.
- a test piece of the fiber reinforced resin composite material was taken out from the water, and the mass was measured with an electronic balance.
- Two evaluation tests were performed on each of the test pieces of the fiber-reinforced resin composite material of Example 1 and Comparative Example 1, and the average mass (g) and the average mass change from the absolute dry state (average mass over time-).
- the average mass) (g) and the average mass change rate (average mass change amount / average mass in the absolutely dry state) (%) in the absolutely dry state were calculated.
- the test pieces of the fiber-reinforced resin composite material produced by using the polyamide 9T film have generally excellent tensile properties and generally excellent tensile properties as compared with the case where the polyamide 6 film is used. It can be seen that it has bending characteristics and has sufficiently excellent strength. Further, as is clear from the results in Table 3 above, the test piece of the fiber-reinforced resin composite material produced by using the film of polyamide 9T is remarkably water-absorbent as compared with the case of using the film of polyamide 6. The average mass change rate remained 0.2% or less even when measured from 24 hours to 149 hours after the start of immersion, and almost no mass change occurred.
- the laminated structure was cut out as a test piece of the fiber reinforced resin composite material by the same method as in Example 1 and Comparative Example 1 described above, and the laminated structure had an angle difference of 45.
- test piece of the fiber reinforced plastic composite material used is different, and the ambient environment when the test piece of the fiber reinforced plastic composite material is immersed is a constant temperature and constant humidity of 23 ° C. and 50% RH.
- the test piece of the fiber reinforced plastic composite material was taken out from the water and the mass was measured with an electronic balance at predetermined time intervals by the same method as the above-mentioned water absorption evaluation test except that it was in an environment. ..
- Table 4 summarizes the results of additional tests for water absorption under a constant temperature and humidity environment.
- Example 1 As is clear from the results in Table 4 above, the test piece in Example 1 produced using the polyamide 9T film has an average mass change rate of 0.26% even after 864 hours have passed since the start of immersion. , Almost no change in mass occurred even in a constant temperature / humidity environment. On the other hand, the test piece in Comparative Example 1 produced by using the film of polyamide 6 had an average mass change rate of 2.42% at 864 hours after the start of immersion, and the mass change occurred due to water absorption. ..
- test pieces of Example 1 and Comparative Example 1 after water absorption which were immersed in water for 864 hours in a constant temperature / humidity environment of 23 ° C. and 50% RH, were used as the test pieces of Example 3 and the test pieces of Comparative Example 1, respectively.
- test pieces of Comparative Example 3 the tensile strength, tensile elastic modulus, bending strength and bending elastic modulus of these test pieces were measured.
- the measuring method is the same as the method described above.
- test piece of Example 3 prepared using the polyamide 9T film is remarkable as compared with the test piece of Comparative Example 3 prepared using the polyamide 6 film. It had excellent tensile and bending properties. It is considered that this is because the test piece of Comparative Example 3 produced by using the film of polyamide 6 had a mass change due to water absorption, so that the physical property values such as strength decreased.
- the fiber-reinforced resin composite sheet of the example of the present invention produced by using the polyamide 9T film not only has sufficient strength, but also does not significantly deteriorate physical properties such as strength due to water absorption. It was found that it can be preferably used even in an environment such as getting wet with water or immersing it in water.
- the fiber-reinforced resin composite sheet produced by using the polyamide 6 film has a reduced crystallinity due to the bond between the amide group and the water molecule in an environment where it gets wet with water such as moisture and rainwater. Therefore, it was found that the dimensional change (specifically, the mass change) was caused, and the physical property values such as strength were remarkably lower than those of the example of the present invention.
- the fiber-reinforced resin composite sheet of the present invention is used, for example, when manufacturing a resin molded product that may get wet or infiltrate into water, a resin molded product used in rainwater or a humid surrounding environment, and the like. As a material for, it can be suitably used for a wide range of products.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Mathematical Physics (AREA)
- Physics & Mathematics (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
本実施形態における繊維強化樹脂複合シートは、ポリアミド樹脂フィルムと、当該ポリアミド樹脂フィルムに積層された複数の強化繊維とを含む。複数の強化繊維は、ポリアミド樹脂フィルムに、強化繊維束から開繊した複数の強化繊維が同一方向に配向した状態で積層されている。
ポリアミド樹脂フィルムは、具体的には、ジカルボン酸成分(a)およびジアミン成分(b)からなるポリアミド樹脂をフィルム化することにより得ることができる。なお、必要に応じて、ポリアミド樹脂フィルムは、ジカルボン酸成分(a)およびジアミン成分(b)からなるポリアミド樹脂以外にも、他の熱可塑性樹脂、他の添加物等を含んでもよい。以下、ポリアミド樹脂フィルムに含まれる各成分を説明する。
・ジカルボン酸成分(a)
本実施形態では、ポリアミド樹脂において、ジカルボン酸成分(a)の60モル%以上100モル%以下がテレフタル酸である。これは、ジカルボン酸成分(a)中のテレフタル酸が60モル%未満の場合には、得られるポリアミド樹脂の耐熱性、耐薬品性等の物性が低下してしまうためである。テレフタル酸は、ジカルボン酸成分(a)において、好ましくは75モル%以上、より好ましくは80モル%以上、さらに好ましくは85モル%以上、または、よりさらに好ましくは90モル%以上、95モル%以上、99モル%以上、99.9モル%以上もしくは100モル%の割合を占める。
本実施形態では、ポリアミド樹脂において、ジアミン成分(b)の60モル%以上100モル%以下が1,9-ノナンジアミンおよび2-メチル-1,8オクタンジアミンである。ジアミン成分(b)の60モル%以上を1,9-ノナンジアミンおよび2-メチル-1,8オクタンジアミンとすることによって、低吸水性、高耐熱性、耐衝撃性に優れ、成形可能温度範囲が広いポリアミド樹脂を得ることができる。1,9-ノナンジアミンおよび2-メチル-1,8オクタンジアミンは、ジアミン成分(b)の全体量に対して、好ましくは75モル%以上、より好ましくは80モル%以上、さらに好ましくは85モル%以上、または、よりさらに好ましくは90モル%以上、95モル%以上、99モル%以上、99.9モル%以上もしくは100モル%の割合を占める。
ポリアミド樹脂フィルムは、必要に応じて、前述のジカルボン酸成分(a)およびジアミン成分(b)からなるポリアミド樹脂以外の他の熱可塑性樹脂を含んでもよい。これは、ポリアミド樹脂フィルムに強化繊維が積層される際の樹脂フロー制御を良好にするため、および/または繊維強化樹脂複合シートに靱性等の追加機能を与えるためである。
ポリアミド樹脂フィルムは、必要に応じて、本発明の効果を損なわない範囲で、公知の様々な添加剤を含んでもよい。例えば、ポリアミド樹脂フィルムの貯蔵安定性向上、硬化物の変色または変質の回避のために、酸化防止剤、光安定剤、耐候性改良材等を添加することができる。
強化繊維は、前述のポリアミド樹脂フィルムに、強化繊維束から開繊した複数の強化繊維が同一方向に配向した状態で積層されている。本明細書において、「複数の強化繊維が同一方向に配向した状態」とは、複数の強化繊維について、各々の強化繊維が略平行方向に延びている状態を意味する。
本実施形態における繊維強化樹脂複合材は、前述の実施形態における繊維強化樹脂複合シートが、厚さ方向に複数積層された繊維強化複合材である。
本実施形態における樹脂成形品は、前述の実施形態における繊維強化樹脂複合材を備える。
まず、繊維強化樹脂複合シートを作製するために、ポリアミド樹脂フィルムを作製した。ポリアミド9T(クラレ製、「ジェネスタ」(登録商標))のペレットを、Tダイが取り付けられた押出成形機を用いて成形温度290℃~310℃の条件下で成形し、厚さ20μmのポリアミド9Tのポリアミド樹脂フィルムを得た。
実施例1と同じ方法で得られた繊維強化樹脂複合シートを図2で示した方法によって細断して、短辺の長さが5mmかつ長辺の長さが20mmの矩形を呈するチョップ材を複数作製した。チョップ材の厚さは、繊維強化樹脂複合シートと同様であるため、40μm~50μmである。開繊した炭素繊維が図2~図4において示したような疑似等方を有する、すなわちチョップ材の炭素繊維の繊維方向が二次元的にランダムになる状態(疑似等方)となるように、金型内に投入および積層した。金型内における積層されたチョップ材を、300℃、2MPaの条件下において15分間加熱しながら加圧し、その後、常温、3MPaの条件下において10分間冷却しながら加圧した。金型から300mm×300mm×2mm(厚さ)の繊維強化樹脂複合材を取り出し、当該繊維強化樹脂複合材を所定の各種サイズに切り出して、最終的に、積層構造が疑似等方である繊維強化樹脂複合材の試験片を得た。繊維強化樹脂複合材の試験片は、25mm(短軸方向の長さ)×250mm(長軸方向の長さ)×2mm(厚さ)のサイズ、15mm(短軸方向の長さ)×100mm(長軸方向の長さ)×2mm(厚さ)のサイズ、および、50mm×50mm×2mm(厚さ)のサイズに切り出した。当該試験片の炭素繊維の体積含有率Vfは50%であった。
ポリアミド樹脂として、ポリアミド6(三菱ケミカル社製、「ダイアミロン」、グレード:C-Z(融点Tm225℃))を用いた以外は、実施例1と同じ方法で厚さ20μmのポリアミド6のポリアミド樹脂フィルムを得て、最終的に、積層構造が角度差45°の4軸方向である、25mm(短軸方向の長さ)×250mm(長軸方向の長さ)×2mm(厚さ)のサイズ、15mm(短軸方向の長さ)×100mm(長軸方向の長さ)×2mm(厚さ)のサイズ、および、50mm×50mm×2mm(厚さ)のサイズの繊維強化樹脂複合材の試験片を得た。
ポリアミド樹脂として、ポリアミド6(三菱ケミカル社製、「ダイアミロン」、グレード:C-Z(融点Tm225℃))を用いた以外は、実施例1と同じ方法で厚さ20μmのポリアミド6のポリアミド樹脂フィルムを得た後、実施例2と同じ方法で、最終的に、積層構造が疑似等方である、25mm(短軸方向の長さ)×250mm(長軸方向の長さ)×2mm(厚さ)のサイズ、15mm(短軸方向の長さ)×100mm(長軸方向の長さ)×2mm(厚さ)のサイズ、および、50mm×50mm×2mm(厚さ)のサイズの繊維強化樹脂複合材の試験片を得た。
引張強度および引張弾性率は、25mm(短軸方向の長さ)×250mm(長軸方向の長さ)×2mm(厚さ)のサイズの繊維強化樹脂複合材の試験片を用いて測定した。具体的には、実施例1~2および比較例1~2の繊維強化樹脂複合材の試験片の引張強度および引張弾性率について、JIS K 7164:2005に準じて測定した。
曲げ強度および曲げ弾性率は、15mm(短軸方向の長さ)×100mm(長軸方向の長さ)×2mm(厚さ)のサイズの繊維強化樹脂複合材の試験片を用いて測定した。具体的には、実施例1~2および比較例1~2の繊維強化樹脂複合材の試験片の引張強度および引張弾性率について、JIS K 7074:1988の炭素繊維強化プラスチックの4点曲げ(B法)による曲げ試験方法に準じて測定した。
吸水性は、50mm×50mm×2mm(厚さ)のサイズの繊維強化樹脂複合材の試験片を用いて評価した。繊維強化樹脂複合材の試験片を80℃のオーブン内に6時間入れて絶対乾燥状態にした。次いで、210mm×297mmのステンレスバット内に常温の水を深さ10mm程度まで入れて、当該バットの中に絶対乾燥状態にした繊維強化樹脂複合材の試験片を浸漬した。この時、周囲環境は大気雰囲気下とした。所定の時間経過毎に、繊維強化樹脂複合材の試験片を水中から取り出して、電子天秤にて質量を計測した。実施例1および比較例1の繊維強化樹脂複合材の試験片についてそれぞれ2つずつ評価試験を行い、平均質量(g)、ならびに絶対乾燥状態からの平均質量変化量(時間経過時における平均質量-絶対乾燥状態における平均質量)(g)および平均質量変化率(平均質量変化量/絶対乾燥状態における平均質量)(%)を算出した。
使用する繊維強化樹脂複合材の試験片のサイズが異なること、および、繊維強化樹脂複合材の試験片を浸漬する際の周囲環境が23℃の温度かつ50%RHの湿度の恒温・恒湿度の環境下であること以外は、前述の吸水性の評価試験と同様の方法によって、所定の時間経過毎に、繊維強化樹脂複合材の試験片を水中から取り出して、電子天秤にて質量を計測した。この追加試験では、前述したサイズにおける実施例1および比較例1の繊維強化樹脂複合材の試験片についてそれぞれ6つずつ評価試験を行い、平均質量(g)、ならびに、絶対乾燥状態からの平均質量変化量(g)および平均質量変化率(平均質量変化量/絶対乾燥状態における平均質量)(%)を前述と同様に算出した。
Claims (7)
- ジカルボン酸成分(a)およびジアミン成分(b)を含むポリアミド樹脂フィルムと、前記ポリアミド樹脂フィルムに強化繊維束から開繊した複数の強化繊維が同一方向に配向した状態で積層された複数の強化繊維とを含む繊維強化樹脂複合シートであり、
前記ジカルボン酸成分(a)の60モル%以上100モル%以下がテレフタル酸であり、前記ジアミン成分(b)の60モル%以上100モル%以下が1,9-ノナンジアミンおよび2-メチル-1,8オクタンジアミンであり、
前記強化繊維の体積含有率Vfは、20%以上70%以下であり、
前記繊維強化樹脂複合シートの厚さは、20μm以上70μm以下である、繊維強化樹脂複合シート。 - 前記ポリアミド樹脂フィルムは、5μm以上50μm以下の厚さを有し、
前記強化繊維は、前記ポリアミド樹脂フィルムの一方または両方の面に積層されている、請求項1に記載の繊維強化樹脂複合シート。 - 前記強化繊維は、炭素繊維である、請求項1または2に記載の繊維強化樹脂複合シート。
- 請求項1~3のいずれか1項に記載の繊維強化樹脂複合シートが、厚さ方向に複数積層された繊維強化複合材であり、
前記繊維強化複合材は、複数の前記繊維強化樹脂複合シートの前記強化繊維の繊維方向が二次元方向に角度差を有する状態で積層されている、繊維強化樹脂複合材。 - 請求項1~3のいずれか1項に記載の繊維強化樹脂複合シートが、複数のチョップ材の形状で、厚さ方向に積層された繊維強化複合材であり、
前記チョップ材は、前記繊維強化樹脂複合シートが短辺の長さが2mm以上50mm以下で、かつ長辺の長さが2mm以上80mm以下の矩形を呈するように形成されており、
前記繊維強化複合材は、複数の前記チョップ材の前記強化繊維の繊維方向が二次元的にランダムになる状態で積層されている、繊維強化樹脂複合材。 - 前記繊維強化樹脂複合材は、キャリアシートをさらに備え、
前記キャリアシートは、その一方または両方の面において、前記複数のチョップ材を積層状態で支持している、請求項5に記載の繊維強化樹脂複合材。 - 請求項4~6のいずれか1項に記載の繊維強化樹脂複合材を備える、樹脂成形品。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/784,774 US20230025079A1 (en) | 2019-12-17 | 2020-12-03 | Fiber-reinforced resin composite sheet, fiber-reinforced resin composite material, and molded resin article including same |
EP20900982.8A EP4052894A4 (en) | 2019-12-17 | 2020-12-03 | FIBER REINFORCED RESIN COMPOSITE SHEET, FIBER REINFORCED RESIN COMPOSITE MATERIAL AND MOLDED RESIN ARTICLE THEREFROM |
KR1020227022105A KR20220107258A (ko) | 2019-12-17 | 2020-12-03 | 섬유 강화 수지 복합 시트, 섬유 강화 수지 복합재 및 이를 구비하는 수지 성형품 |
CN202080084135.4A CN114829144A (zh) | 2019-12-17 | 2020-12-03 | 纤维增强树脂复合片材、纤维增强树脂复合材料、以及具备该纤维增强树脂复合材料的树脂成形品 |
JP2021565458A JP7368499B2 (ja) | 2019-12-17 | 2020-12-03 | 繊維強化樹脂複合シート、繊維強化樹脂複合材およびそれを備える樹脂成形品 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019227455 | 2019-12-17 | ||
JP2019-227455 | 2019-12-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021124907A1 true WO2021124907A1 (ja) | 2021-06-24 |
Family
ID=76477294
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/045029 WO2021124907A1 (ja) | 2019-12-17 | 2020-12-03 | 繊維強化樹脂複合シート、繊維強化樹脂複合材およびそれを備える樹脂成形品 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230025079A1 (ja) |
EP (1) | EP4052894A4 (ja) |
JP (1) | JP7368499B2 (ja) |
KR (1) | KR20220107258A (ja) |
CN (1) | CN114829144A (ja) |
WO (1) | WO2021124907A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022145155A1 (ja) * | 2020-12-28 | 2022-07-07 | フクビ化学工業株式会社 | 繊維強化樹脂シート及び繊維強化複合材並びに成形品 |
WO2023120462A1 (ja) * | 2021-12-20 | 2023-06-29 | 株式会社クラレ | 複合体 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08118381A (ja) | 1994-10-19 | 1996-05-14 | Mitsubishi Rayon Co Ltd | Cfrp成形物の製造方法 |
JP2006083227A (ja) * | 2004-09-14 | 2006-03-30 | Mitsubishi Engineering Plastics Corp | 長繊維強化ポリアミド樹脂製外装成形体 |
JP2006274061A (ja) * | 2005-03-29 | 2006-10-12 | Kuraray Co Ltd | 長繊維強化半芳香族ポリアミド樹脂組成物 |
JP2010084111A (ja) * | 2008-10-03 | 2010-04-15 | Kuraray Co Ltd | 長繊維強化ポリアミド組成物 |
JP2011068874A (ja) * | 2009-08-25 | 2011-04-07 | Asahi Kasei Chemicals Corp | ポリアミド組成物を含む自動車部品 |
JP2012031371A (ja) * | 2010-07-01 | 2012-02-16 | Daicel Polymer Ltd | 炭素繊維巻きテープとその製造方法 |
JP2012131918A (ja) * | 2010-12-22 | 2012-07-12 | Daicel Polymer Ltd | 耐摩耗性成形体用の樹脂組成物 |
JP2014111757A (ja) * | 2012-11-12 | 2014-06-19 | Kuraray Co Ltd | 長繊維強化ポリアミド樹脂組成物 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2137477C (en) * | 1993-12-24 | 2002-05-07 | Hideaki Oka | Polyamide and polyamide composition |
CA2600334C (en) * | 2005-03-18 | 2013-07-23 | Kuraray Co., Ltd. | Semi-aromatic polyamide resin |
CA2656541A1 (en) * | 2006-08-18 | 2008-02-21 | Fukui Prefectural Government | Multiaxially reinforced laminated moldings and process for production thereof |
CN101466535B (zh) * | 2006-11-22 | 2013-05-22 | 福井县 | 热塑性树脂多层增强片材及其制造方法、以及热塑性树脂复合材料成形品的成形方法 |
WO2013080820A1 (ja) * | 2011-11-29 | 2013-06-06 | 東レ株式会社 | 炭素繊維強化熱可塑性樹脂組成物、そのペレットおよび成形品 |
KR20160070062A (ko) * | 2013-10-11 | 2016-06-17 | 도레이 카부시키가이샤 | 탄소 섬유 강화 수지 조성물, 펠릿, 성형품 및 전자 기기 하우징 |
JP6638131B2 (ja) * | 2014-07-08 | 2020-01-29 | 福井県 | 擬似等方補強シート材及びその製造方法 |
CN106604818A (zh) * | 2014-09-30 | 2017-04-26 | 积水化成品工业株式会社 | 树脂复合体 |
CN113334792B (zh) * | 2015-12-24 | 2023-08-11 | 三菱化学株式会社 | 纤维强化树脂材料成型体及其制造方法以及纤维强化树脂材料的制造方法 |
JP2018161799A (ja) * | 2017-03-27 | 2018-10-18 | 三菱ケミカル株式会社 | 炭素繊維強化シートおよびその製造方法 |
JP6866245B2 (ja) * | 2017-06-30 | 2021-04-28 | 株式会社クラレ | 繊維強化ポリアミドシートまたはテープ |
CN110315660B (zh) * | 2018-03-28 | 2022-06-10 | 福美化学工业株式会社 | 准各向同性补强片材、frp成型体和frp成型体的制造方法 |
-
2020
- 2020-12-03 KR KR1020227022105A patent/KR20220107258A/ko not_active Application Discontinuation
- 2020-12-03 JP JP2021565458A patent/JP7368499B2/ja active Active
- 2020-12-03 CN CN202080084135.4A patent/CN114829144A/zh active Pending
- 2020-12-03 US US17/784,774 patent/US20230025079A1/en not_active Abandoned
- 2020-12-03 WO PCT/JP2020/045029 patent/WO2021124907A1/ja unknown
- 2020-12-03 EP EP20900982.8A patent/EP4052894A4/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08118381A (ja) | 1994-10-19 | 1996-05-14 | Mitsubishi Rayon Co Ltd | Cfrp成形物の製造方法 |
JP2006083227A (ja) * | 2004-09-14 | 2006-03-30 | Mitsubishi Engineering Plastics Corp | 長繊維強化ポリアミド樹脂製外装成形体 |
JP2006274061A (ja) * | 2005-03-29 | 2006-10-12 | Kuraray Co Ltd | 長繊維強化半芳香族ポリアミド樹脂組成物 |
JP2010084111A (ja) * | 2008-10-03 | 2010-04-15 | Kuraray Co Ltd | 長繊維強化ポリアミド組成物 |
JP2011068874A (ja) * | 2009-08-25 | 2011-04-07 | Asahi Kasei Chemicals Corp | ポリアミド組成物を含む自動車部品 |
JP2012031371A (ja) * | 2010-07-01 | 2012-02-16 | Daicel Polymer Ltd | 炭素繊維巻きテープとその製造方法 |
JP2012131918A (ja) * | 2010-12-22 | 2012-07-12 | Daicel Polymer Ltd | 耐摩耗性成形体用の樹脂組成物 |
JP2014111757A (ja) * | 2012-11-12 | 2014-06-19 | Kuraray Co Ltd | 長繊維強化ポリアミド樹脂組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4052894A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022145155A1 (ja) * | 2020-12-28 | 2022-07-07 | フクビ化学工業株式会社 | 繊維強化樹脂シート及び繊維強化複合材並びに成形品 |
WO2023120462A1 (ja) * | 2021-12-20 | 2023-06-29 | 株式会社クラレ | 複合体 |
Also Published As
Publication number | Publication date |
---|---|
EP4052894A4 (en) | 2024-02-14 |
JP7368499B2 (ja) | 2023-10-24 |
US20230025079A1 (en) | 2023-01-26 |
JPWO2021124907A1 (ja) | 2021-06-24 |
CN114829144A (zh) | 2022-07-29 |
KR20220107258A (ko) | 2022-08-02 |
EP4052894A1 (en) | 2022-09-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6140862B2 (ja) | 複合ポリアミド物品 | |
CN103221208B (zh) | 聚酰胺复合结构及其制备方法 | |
KR102006511B1 (ko) | 개선된 충격 강도를 갖는 복합 라미네이트 및 그의 용도 | |
JP3466821B2 (ja) | ポリアミド12マトリックスを基材とする熱可塑的に成形可能な複合材料の製造方法 | |
JP4789940B2 (ja) | 等方性の繊維強化熱可塑性樹脂シートとその製造方法並びに成形板 | |
JP5551386B2 (ja) | 繊維・樹脂複合化シート及びfrp成形体 | |
US20120238164A1 (en) | Composite polyamide article | |
WO2021124907A1 (ja) | 繊維強化樹脂複合シート、繊維強化樹脂複合材およびそれを備える樹脂成形品 | |
NO338721B1 (no) | Epoksyharpiks impregnert garn og dets anvendelse for fremstilling av en forform | |
US20130115836A1 (en) | Composite polyamide article | |
JP6699986B2 (ja) | プリフォーム、および一体化シート材料の製造方法 | |
WO2018143068A1 (ja) | 繊維強化樹脂成形材料 | |
TWI804599B (zh) | 纖維強化塑膠成形用材料及成形物 | |
KR20180044896A (ko) | 장섬유강화 복합재료 및 성형품 | |
JP6453575B2 (ja) | 繊維強化樹脂組成物 | |
JP2018062641A5 (ja) | ||
JP2018187944A (ja) | 繊維強化樹脂組成物 | |
WO2020246440A1 (ja) | 繊維強化樹脂成形体 | |
JP2014145048A (ja) | 炭素繊維強化熱可塑性樹脂プリプレグシートまたは成形品 | |
WO2022181804A1 (ja) | プリプレグ及びその製造方法と、成形体 | |
MATSUMOTO et al. | Method of producing complex shaped composites with xylylenediamine derived polyamide matrix |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20900982 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021565458 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2020900982 Country of ref document: EP Effective date: 20220603 |
|
ENP | Entry into the national phase |
Ref document number: 20227022105 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |