WO2012050171A1 - 炭素繊維前駆体繊維束、炭素繊維束、及びそれらの利用 - Google Patents
炭素繊維前駆体繊維束、炭素繊維束、及びそれらの利用 Download PDFInfo
- Publication number
- WO2012050171A1 WO2012050171A1 PCT/JP2011/073578 JP2011073578W WO2012050171A1 WO 2012050171 A1 WO2012050171 A1 WO 2012050171A1 JP 2011073578 W JP2011073578 W JP 2011073578W WO 2012050171 A1 WO2012050171 A1 WO 2012050171A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fiber
- carbon fiber
- fiber bundle
- cross
- carbon
- Prior art date
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 585
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 357
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 357
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 336
- 239000002243 precursor Substances 0.000 title claims abstract description 196
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 48
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 30
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 125
- 229920005989 resin Polymers 0.000 claims description 114
- 239000011347 resin Substances 0.000 claims description 114
- 229920001577 copolymer Polymers 0.000 claims description 73
- 229920000647 polyepoxide Polymers 0.000 claims description 69
- 239000003822 epoxy resin Substances 0.000 claims description 68
- 239000004744 fabric Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 39
- 238000007254 oxidation reaction Methods 0.000 claims description 34
- 238000005259 measurement Methods 0.000 claims description 33
- 238000000465 moulding Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 27
- -1 urea compound Chemical class 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 230000004907 flux Effects 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 229920002430 Fibre-reinforced plastic Polymers 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 230000020169 heat generation Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 241000282341 Mustela putorius furo Species 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011151 fibre-reinforced plastic Substances 0.000 claims description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 3
- 238000001020 plasma etching Methods 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 description 57
- 238000009987 spinning Methods 0.000 description 48
- 238000005470 impregnation Methods 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 42
- 239000000523 sample Substances 0.000 description 34
- 239000002131 composite material Substances 0.000 description 33
- 230000015271 coagulation Effects 0.000 description 30
- 238000005345 coagulation Methods 0.000 description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 28
- 229910052760 oxygen Inorganic materials 0.000 description 28
- 239000001301 oxygen Substances 0.000 description 28
- 238000004513 sizing Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 25
- 239000000178 monomer Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 18
- 238000003763 carbonization Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 15
- 244000046052 Phaseolus vulgaris Species 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 229920001342 Bakelite® Polymers 0.000 description 14
- 239000004637 bakelite Substances 0.000 description 14
- 238000012669 compression test Methods 0.000 description 14
- 230000001976 improved effect Effects 0.000 description 14
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- 238000009656 pre-carbonization Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 230000037303 wrinkles Effects 0.000 description 11
- 239000002759 woven fabric Substances 0.000 description 10
- 229920003319 Araldite® Polymers 0.000 description 9
- 238000005452 bending Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- ZWOULFZCQXICLZ-UHFFFAOYSA-N 1,3-dimethyl-1-phenylurea Chemical compound CNC(=O)N(C)C1=CC=CC=C1 ZWOULFZCQXICLZ-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 235000021251 pulses Nutrition 0.000 description 4
- 238000004904 shortening Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 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 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- KDQTUCKOAOGTLT-UHFFFAOYSA-N 3-[3-(dimethylcarbamoylamino)-4-methylphenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=C(C)C(NC(=O)N(C)C)=C1 KDQTUCKOAOGTLT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 2
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000010137 moulding (plastic) Methods 0.000 description 2
- VAUOPRZOGIRSMI-UHFFFAOYSA-N n-(oxiran-2-ylmethyl)aniline Chemical class C1OC1CNC1=CC=CC=C1 VAUOPRZOGIRSMI-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- CCYZSFPSPHPQPQ-UHFFFAOYSA-N 1,3,4,5,6,8-hexamethyl-2,7-bis(oxiran-2-ylmethoxy)-9-phenyl-9h-xanthene Chemical compound CC1=C2C(C=3C=CC=CC=3)C=3C(C)=C(OCC4OC4)C(C)=C(C)C=3OC2=C(C)C(C)=C1OCC1CO1 CCYZSFPSPHPQPQ-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- FLROJJGKUKLCAE-UHFFFAOYSA-N 3-amino-2-methylphenol Chemical compound CC1=C(N)C=CC=C1O FLROJJGKUKLCAE-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920002025 Pluronic® F 88 Polymers 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910000197 bakerite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011304 carbon pitch Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- KLFSCDLQXKYZFJ-UHFFFAOYSA-N ethanamine trihydrofluoride Chemical compound F.F.F.C(C)N KLFSCDLQXKYZFJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- 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
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
-
- 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
- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
- D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D7/00—Forming, maintaining, or circulating atmospheres in heating chambers
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3065—Including strand which is of specific structural definition
- Y10T442/3089—Cross-sectional configuration of strand material is specified
Definitions
- the present invention relates to a carbon fiber precursor fiber bundle, a flameproofing method, a carbon fiber bundle, and a method for producing a carbon fiber bundle.
- the present invention also relates to a carbon fiber prepreg, and more particularly to a carbon fiber prepreg having handleability and strength development suitable for a large molded product.
- the present invention further relates to a fiber reinforced fabric and a fiber reinforced plastic molding method.
- Patent Document 1 uses a carbon fiber precursor fiber bundle having a high roundness and a large single fiber fineness to suppress burning spots during the flameproofing treatment, and the total fineness is In spite of its large size, it has proposed a technique for obtaining a carbon fiber bundle that has few entanglements between single fibers, is excellent in spreadability, and is also excellent in productivity.
- Patent Document 2 proposes a polymer that does not require a flameproofing process. Furthermore, Patent Documents 3, 4, and 9 improve the oxygen permeability of the carbon fiber precursor fiber by using a monomer having a bulky side chain as a copolymerizable component of the copolymer, and thereby improve the inside of the flame resistant fiber. Has proposed a technique for uniformly controlling the oxygen concentration distribution of the carbon fiber and improving the tensile strength and tensile modulus of the resulting carbon fiber.
- Patent Document 5 suppresses heat accumulation inside the fiber bundle by promoting flame resistance of the PAN-based carbon fiber precursor fiber while passing heated air through the fiber bundle on a mesh-like roller. Proposing technology.
- Patent Document 6 discloses a flame resistance even when high-speed firing is performed by optimizing the content of the carboxylic acid group-containing vinyl monomer by measuring the isothermal exothermic curve of the carbon fiber precursor fiber bundle with a thermal flow rate type differential scanning calorimeter.
- Patent Document 7 proposes a technique for producing a high-performance carbon fiber bundle by copolymerizing acrylamide to obtain a highly hydrophilic polyacrylonitrile copolymer.
- stabilization of fibers in each process is a very important technique for reducing the production cost of carbon fibers.
- gelation of the spinning dope in the spinning process may directly lead to a process trouble, and improvement in the thermal stability of the spinning dope is required.
- Patent Document 8 dramatically improves the thermal stability when the spinning dope is held at a high temperature of about 80 ° C. by esterifying methacrylic acid, which is a component that accelerates the flameproofing reaction of the polymer.
- thermosetting resin mainly composed of a thermosetting resin. It is used for a wide range of applications ranging from. Molding of fiber reinforced composite material using an intermediate base material made of prepreg is performed by laminating a prepreg and then heating or heating and pressurizing it to cure a thermosetting resin that is a matrix resin. .
- the method using prepreg is superior to the VARTM method or the like in terms of fiber strength utilization rate.
- the matrix resin has a high flow. If the matrix resin has a low flow, it causes voids. However, if the matrix resin has a high flow, fiber micro-meandering occurs and the mechanical properties of the large-sized molded product deteriorate. The mechanical properties of large molded products are highly dependent on thickness, and the compressive strength decreases as the thickness of the molded products increases.
- Patent Documents 10 and 11 propose to prevent deterioration of various physical properties by making the matrix resin low flow.
- the cost of molding a fiber base with a large basis weight has been superior until now, but the resin impregnating properties are the viscosity of the resin, the basis weight of the textile fabric, the interfiber gap, the single fiber There was a problem of being greatly affected by the diameter.
- Patent Document 12 describes a single-fiber fiber in a carbon fiber bundle composed of a plurality of carbon fibers as a carbon fiber bundle that simultaneously satisfies the bundling property, resin impregnation property, and cross quality of the resulting cloth and has high strength.
- a carbon fiber bundle is proposed in which the ratio of the major axis to the minor axis (major axis / minor axis) of the cross section is 1.05 to 1.6.
- JP 2008-202207 A Japanese Patent Laid-Open No. 1-132832 Japanese Patent Laid-Open No. 2-84505 JP 2006-257580 A Japanese Patent Laid-Open No. 2-6625 JP 2000-119341 A JP-A-4-281008 JP 2007-204880 A Japanese Patent Laid-Open No. 2-84505 JP-A-1-161040 Japanese Patent Laid-Open No. 2-169658 JP 2002-242027 A
- Patent Document 1 Although the flameproofing process itself is shortened, a process of flameproofing the polymer is necessary, and therefore the entire carbon fiber manufacturing process has not been shortened.
- the strength of the carbon fiber of Patent Document 2 is remarkably low as compared with those using PAN or pitch as a raw material, and cannot meet the market demand.
- Patent Documents 10 and 11 it is possible to prevent the occurrence of micro-meandering of the fibers and the deterioration of the mechanical properties due to the low flow of the matrix resin, but this technique is applied to the molding of a large molding. Then, the point that defects, such as a void, arise is a problem.
- Patent Document 12 provides a carbon fiber bundle excellent in resin impregnation property with a carbon fiber bundle having a small number of yarns of 3,000, but the total fineness of the carbon fiber bundle is small, thereby reducing the cost. It is extremely difficult.
- the present invention relates to a high-quality carbon fiber bundle excellent in spreadability and a carbon fiber suitable for the production thereof, in which the single fiber fineness is small and the productivity of the single fiber within the fiber bundle is small and the productivity is excellent.
- An object is to provide a fiber precursor fiber.
- the present invention provides a carbon fiber precursor acrylic fiber bundle that can efficiently produce a high-quality carbon fiber bundle even if the single fiber fineness is large and the cross-sectional double structure of the flameproof fiber is suppressed in high-speed firing. And a method for producing a flame-resistant fiber bundle using the precursor acrylic fiber bundle.
- the present invention also provides a carbon fiber precursor acrylic fiber bundle that can be processed under economical flameproof heat treatment conditions to obtain a high-quality carbon fiber bundle even if the single fiber fineness is large, and the precursor acrylic fiber bundle.
- An object of the present invention is to provide a method of producing a carbon fiber bundle using a flame-resistant fiber using the above and a precursor acrylic fiber bundle thereof.
- An object of the present invention is to provide a carbon fiber prepreg that maintains a high flow of the matrix resin and has little decrease in compressive strength even when the thickness of the molded product after molding increases.
- An object of the present invention is to provide a carbon fiber bundle, a fiber reinforced fabric, and a fiber reinforced plastic molding method that have high strand tensile strength and excellent impregnation even if the diameter of the single fiber is large.
- a polyacrylonitrile copolymer comprising acrylonitrile units of 95.0 mol% or more and 99.0 mol% or less and hydroxyalkyl (meth) acrylate units of 1.0 mol% or more and 5.0 mol% or less.
- Body acrylic fiber bundle 1) The polyacrylonitrile copolymer is dissolved in dimethylformamide so as to have a mass concentration of 25% to prepare a copolymer solution. 2) The copolymer solution is applied on a glass plate. 3) The glass plate coated with the copolymer solution is dried in air at 120 ° C. for 6 hours to evaporate dimethylformamide to form a film having a constant thickness in the range of 20 ⁇ m to 40 ⁇ m.
- the obtained film is subjected to a flame resistance treatment by heat treatment at 240 ° C. in air for 60 minutes and further in air at 250 ° C. for 60 minutes to obtain a flame resistant film.
- the obtained flame resistant film is polished after embedding with resin, and a cross section perpendicular to the surface of the polished flame resistant film is observed at a magnification of 1500 times using a fluorescence microscope.
- a portion where oxidation has progressed is observed as a relatively dark layer, and a portion where oxidation has not progressed is observed as a relatively bright layer. Therefore, from the polished flameproof film surface, a dark layer and a bright layer are observed.
- the distance to the boundary is measured at least 5 points on one cross section, and the same measurement is performed on three cross sections, and the arithmetic average is defined as the oxidation depth De ( ⁇ m).
- Carbon fiber precursor acrylic fiber bundle satisfying the following conditions: 1) The single fiber fineness is 2.0 dtex or more and 5.0 dtex or less, 2) The calorific value per unit mass of 215 to 300 ° C. obtained by measurement using a heat flux type differential scanning calorimeter is 3200 kJ / kg or more (however, the rate of temperature increase in the measurement using the heat flux type differential scanning calorimeter 3) The full width at half maximum of the solid 1 H-NMR spectrum (measuring temperature 160 ° C.) is 10.0 kHz or more and 14.5 kHz or less.
- a polyacrylonitrile copolymer comprising acrylonitrile units of 95.0 mol% or more and 99.0 mol% or less and hydroxyalkyl (meth) acrylate units of 1.0 mol% or more and 5.0 mol% or less.
- the carbon fiber precursor acrylic fiber bundle according to any one of [1], [2], [5] to [8] and [11] to [14] is 220 ° C. or higher in an oxidizing atmosphere. 300 ° C. and treated oxidization at 90 minutes or less 30 minutes or more at a temperature of below oxidization processing method fiber density obtain flame-resistant fiber bundle 1.35 g / cm 3 or more 1.43 g / cm 3 or less.
- the carbon fiber precursor acrylic fiber bundle according to any one of [1], [2], [5] to [8] and [11] to [14] is 220 ° C. or higher in an oxidizing atmosphere. 300 ° C. and treated oxidization at 90 minutes or less 30 minutes or more at a temperature lower than the fiber density and 1.35 g / cm 3 or more 1.43 g / cm 3 or less of oxidized fiber bundle, further inert gas
- the diameter Di of the cross section perpendicular to the fiber axis of the single fiber is carbonized at a temperature of 800 ° C. or more and 2000 ° C. or less, and the shape of the cross section perpendicular to the fiber axis of the single fiber is roundness 0.90.
- the following is a method for producing a carbon fiber bundle:
- the diameter Di is obtained by the following method.
- the surface of the single fiber has a plurality of groove-like irregularities extending in the longitudinal direction of the single fiber, and the height difference between the highest and lowest parts is 80 nm or less within the circumferential length of 2 ⁇ m.
- Carbon fiber prepreg comprising a carbon fiber bundle having a single fiber fineness of 1.2 to 2.4 dtex and a roundness of 0.7 to 0.9 in a cross section perpendicular to the fiber axis of the single fiber and a matrix resin .
- a unidirectional fiber-reinforced fabric in which the carbon fiber bundles according to any one of [17] to [19] are arranged in a longitudinal direction.
- the number of filaments constituting the carbon fiber bundle is 15000 to 100,000, or the total fineness of the carbon fiber bundle is 9900 to 65000 dtex, according to any of the above [32] to [34]
- At least one or more layers of fiber reinforced fabric are laminated as a fiber base material on a mold, and a medium for diffusing the resin in the surface direction is placed thereon, and then the whole of the fiber base material and the medium is a bag film. Then, the bag film is vacuumed, and a room temperature curable resin is diffused on one side of the fiber base material to impregnate the fiber base material.
- a high-quality carbon fiber bundle having a single fiber fineness and a small amount of single-fiber entanglement in a fiber bundle despite excellent productivity, and suitable for manufacturing the same.
- Carbon fiber precursor fibers are provided.
- the present invention even when the single fiber fineness is large, the formation of a double-structured cross-section of flame-resistant fiber is suppressed in high-speed firing, and a carbon fiber precursor acrylic that can efficiently produce a high-quality carbon fiber bundle.
- a fiber bundle and a method for producing a flame-resistant fiber bundle using the precursor acrylic fiber bundle are provided.
- a carbon fiber bundle having a large single fiber fineness and appropriate physical properties is provided.
- the present invention it is possible to obtain a carbon fiber bundle, a fiber reinforced fabric and a fiber reinforced plastic having a large tow volume and excellent impregnation properties. For this reason, workability becomes easy in the prepreg use and textile use which are main uses of carbon fiber. Moreover, although the single fiber fineness is large compared with the conventional carbon fiber, the carbon fiber composite material which is high in tensile strength and excellent in strength expression can be manufactured.
- [Polyacrylonitrile copolymer] Inclusion of acrylonitrile units in a polyacrylonitrile-based copolymer (hereinafter also referred to as “copolymer”) constituting the carbon fiber precursor acrylic fiber bundle (hereinafter also referred to as “precursor fiber bundle”) of the present invention
- the amount is 95 to 99 mol%. If it is 95 mol% or more, the fall of the copolymerization rate of an acrylonitrile unit will not bring about the performance fall of carbon fiber. On the other hand, the upper limit of 99 mol% is defined by the necessary amount of the copolymerization component.
- the content of hydroxyalkyl (meth) acrylate units in the copolymer is 1 to 5 mol%.
- the carboxylic acid ester group of the hydroxyalkyl (meth) acrylate unit is thermally decomposed to a carboxylic acid group at a high temperature of 240 ° C. or higher.
- the carboxylic acid ester group of the hydroxyalkyl (meth) acrylate unit becomes a carboxylic acid group in the flameproofing step.
- a sufficient effect of promoting the flameproofing reaction can be obtained.
- the lower limit of the content of the hydroxyalkyl (meth) acrylate unit is preferably 1.2 mol% or more from the viewpoint of securing the denseness of the precursor fiber bundle, and is 1.5 in that a higher performance carbon fiber can be obtained. Mole% or more is more preferable.
- the upper limit of the content of the hydroxyalkyl (meth) acrylate unit is preferably 4.0 mol% or less from the viewpoint of suppressing the runaway reaction in the flameproofing step, and from the viewpoint of suppressing the decrease in the carbonization yield. 3.0 mol% or less is more preferable.
- the hydroxyalkyl (meth) acrylate used as the raw material for the hydroxyalkyl (meth) acrylate unit includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxy (meth) acrylate. Examples thereof include butyl and monoglyceryl (meth) acrylate. Further, a plurality of these monomers may be used in combination. When using together, if the total amount of a monomer is 5.0 mol% or less, the ratio can be set freely.
- 2-Hydroxyethyl (meth) acrylate has a hydroxyethyl group elimination temperature of 240 ° C. or higher in the flameproofing step, a bulkiness sufficient to improve oxygen permeability, a hydroxyethyl group From the standpoints that there is little decrease in mass when desorbed and it is easily industrially available, it is suitable as a constituent of the copolymer of the present invention.
- the copolymer of the present invention contains an acrylonitrile unit and a hydroxyalkyl (meth) acrylate unit, but may contain “another monomer unit” as necessary.
- another monomer unit As the “other monomer” used as a raw material for other monomer units, a vinyl monomer copolymerizable with acrylonitrile is preferable.
- (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate; Vinyl halides such as vinyl, vinyl bromide and vinylidene chloride; acids such as (meth) acrylic acid, itaconic acid and crotonic acid and their salts; maleic imide, phenylmaleimide, (meth) acrylamide, styrene, ⁇ - Examples include methylstyrene and vinyl acetate. These may be used alone or in combination of two or more.
- the content of other monomer units in the copolymer of the present invention is preferably 3.5 mol% or less in consideration of the content of acrylonitrile units and hydroxyalkyl (meth) acrylate units.
- the copolymer of the present invention preferably has a melting point of 160 to 175 ° C. under wet heat.
- the melting point under wet heat is 160 ° C. or higher, adhesion between single fibers in the precursor fiber bundle can be suppressed, and deterioration of the quality and mechanical properties of the obtained carbon fiber bundle can be suppressed.
- the melting point under wet heat is 175 ° C. or lower, for example, when the dried densified yarn is subjected to steam drawing during the spinning process, higher temperature, that is, higher-pressure steam is not required, and therefore the precursor is used under high-pressure steam. Since fluffing and rubbing that occur when the body fiber bundle moves up and down can be suppressed, deterioration of the quality and mechanical properties of the obtained carbon fiber bundle can be suppressed.
- the water contact angle of the copolymer of the present invention is preferably 40 ° or more and 70 ° or less. If the contact angle of the copolymer with water is 70 ° or less, in the spinning process when forming the precursor fiber bundle from the copolymer, particularly in the coagulation process, the organic solvent in the spinning stock solution and the coagulation bath liquid The exchange is performed slowly, and the denseness of the precursor fiber bundle is easily improved. Further, if the contact angle between the copolymer and water is 40 ° or more, the hydrophilicity of the copolymer is maintained properly, and efficiency is maintained without causing fusion between adjacent fibers in the spinning process, particularly in the coagulation process. Solidify well. From these viewpoints, the contact angle between the copolymer and water is preferably 55 ° or more and 65 ° or less, and more preferably 58 ° or more and 62 ° or less.
- the oxidation depth De during the flameproofing treatment of the film obtained from the copolymer of the present invention is the flameproofing reactivity of the precursor fiber bundle obtained from the copolymer of the present invention in the firing process, particularly the flameproofing process. It becomes an indicator. That is, as the oxidation depth De is larger, the oxygen diffusion into the single fiber of the precursor fiber bundle is sufficiently performed in the flameproofing process, and a uniform flameproofing process is possible. Therefore, the oxidation depth De is desirably 4.0 ⁇ m or more and 6.0 ⁇ m or less from the viewpoint of the oxidation reaction in the flameproofing reaction.
- the oxidation depth De is 4.0 ⁇ m or more, even in a carbon fiber precursor acrylic fiber bundle having a single fiber fineness of 2.0 dtex or more and 5.0 dtex, oxygen can be easily distributed to the inside of the fiber in the flameproofing process. It is possible to obtain high oxygen diffusivity and to easily obtain high-performance carbon fibers. On the other hand, if it is 6.0 ⁇ m or less, the degree of progress of the oxidation reaction in the flameproofing step can be easily within an appropriate range, and the yield of the obtained carbon fiber is unlikely to decrease. From these viewpoints, the oxidation depth De is more preferably 4.4 to 5.8 ⁇ m, and further preferably 4.6 to 5.6 ⁇ m. A method for measuring the oxidation depth De will be described later.
- the method for producing the copolymer is not particularly limited, and a known method such as solution polymerization or suspension polymerization can be employed.
- the polymerization initiator is not particularly limited, and an azo compound, an organic peroxide, or a redox catalyst such as persulfuric acid / sulfurous acid or ammonium salt of chloric acid / sulfurous acid can be used.
- each monomer, distilled water, ammonium persulfate, ammonium bisulfite and sulfuric acid are continuously supplied in a constant amount into an overflow type polymerization vessel, and stirring is continued while maintaining a constant temperature.
- a method of obtaining a copolymer by washing and drying the polymer slurry thus obtained can be used.
- the precursor fiber bundle of the present invention has a single fiber fineness of 1.5 dtex or more and 5.0 dtex or less, and a cross-sectional shape perpendicular to the fiber axis of the single fiber has a roundness of 0.90 or less.
- first group invention these precursor fiber bundles may be referred to as “first group invention” as appropriate.
- the single fiber fineness is preferably 2.0 dtex or more, and more preferably 2.5 dtex or more.
- the single fiber fineness is preferably 4.5 dtex or less, and more preferably 3.0 dtex or less.
- the cross-sectional shape of the single fiber of the precursor fiber bundle of the present invention has a roundness of 0.90 or less. Moreover, it is preferable that a cross-sectional shape is an empty bean type. If the cross-sectional shape is an empty bean type with a roundness of 0.90 or less, the flameproofing reaction proceeds sufficiently without insufficient oxygen diffusion into the single fibers constituting the precursor fiber bundle during the flameproofing treatment. As a result, fluffing in the carbonization process is suppressed, process passability is good, and the strength and elastic modulus of the obtained carbon fiber bundle can be properly maintained.
- the roundness of the single fibers constituting the carbon fiber bundle is preferably 0.70 or more, more preferably 0.75 or more, and further preferably 0.80 or more.
- the cross-sectional shape of the single fiber of the precursor fiber bundle of the present invention having the above structure can be uniformly flameproofed even if the single fiber fineness is increased to some extent because the distance from the inside of the fiber to the surface is shortened. Possible and high-performance carbon fiber bundles are easily obtained.
- the precursor fiber bundle of the present invention was measured at a heating rate of 10 ° C./min in an air stream of 100 ml / min (standard: 30 ° C., 0.10 MPa) using a heat flux type differential scanning calorimeter.
- a constant-temperature heating exothermic curve of 30 ° C. or higher and 450 ° C. or lower satisfies the following conditions.
- these precursor fiber bundles may be referred to as “second group invention”.
- the initial processing temperature is a temperature equal to or higher than the temperature at which the flameproofing reaction is started, and the precursor fiber. It is set within the range of the temperature below the temperature at which the bundle does not melt.
- a higher processing temperature can be set in order to efficiently perform the flameproofing process.
- the present inventors set this temperature range around 260 ° C. in the first half of the flame resistance process and the second half of the flame resistance process.
- the calorific value of 230 ° C or higher and 260 ° C or lower is defined as the calorific value Ja
- the calorific value of 260 ° C or higher and 290 ° C or lower is defined as the calorific value Jb. The quality and performance of fiber bundles were compared.
- the flameproofing reaction and oxygen diffusion are performed in a well-balanced manner, and the cross-sectional double structure of the flameproofing fiber is suppressed in the high-speed flameproofing treatment, resulting in high quality and performance. It was found that a carbon fiber bundle with good expression was efficiently obtained, and a precursor fiber bundle having a large single fiber fineness could be uniformly flame-resistant.
- the temperature setting during the flameproofing treatment was in the range of 220 to 300 ° C., and the optimum temperature setting for flameproofing the precursor fiber bundle to be used was set.
- the flameproofing reaction proceeds appropriately in the first half of the flameproofing process, and the precursor fiber bundle can be easily passed through without being melted by heat. Moreover, if it is 250 kJ / kg or less, in the first half of the flameproofing process, the flameproofing reaction does not proceed at a stretch, and it becomes easy to perform the flameproofing treatment uniformly even for the precursor fiber bundle having a large single fiber fineness.
- the amount of heat Ja is more preferably 120 kJ / kg or more from the viewpoint of productivity improvement by shortening the flameproofing treatment time, while 200 kJ / kg or less from the viewpoint of more uniformly flameproofing a precursor fiber bundle having a large single fiber fineness. Is more preferable, and 160 kJ / kg or less is particularly preferable.
- the precursor fiber bundle can be easily flameproofed to the target flameproof fiber density without impairing productivity in the flameproofing step.
- the flameproofing reaction proceeds slowly in the flameproofing step, and thus it becomes easy to uniformly flameproof the precursor fiber bundle having a large single fiber fineness, thereby forming a double cross-section structure. It becomes easy to suppress.
- the amount of heat Jb is preferably 600 kJ / kg or more from the viewpoint of improving productivity by shortening the flameproofing treatment time, and more preferably 700 kJ / kg or more from the viewpoint of further improving productivity.
- 950 kJ / kg or less is preferable from the viewpoint of more uniformly flame-proofing the precursor fiber bundle having a large single fiber fineness.
- the amount of heat Ja can be used as an index of flameproofing reactivity in the first half of the flameproofing process
- the amount of heat Jb can be used as an index of flameproofing reactivity in the second half of the flameproofing process.
- the amount of heat Ja and the amount of heat Jb can only be used as an index of the flame resistance reactivity of the precursor fiber bundle, and the processing temperature range applied to the actual flame resistance process is the amount of heat Ja or the amount of heat Jb. It may or may not contain a temperature range (that is, 230 to 260 ° C. or 260 to 290 ° C.), and is appropriately adjusted in the range of 220 to 300 ° C. depending on the precursor fiber bundle to be used. be able to.
- the precursor fiber bundle of the present invention has a calorific value per unit mass of 215 to 300 ° C. measured using a heat flux type differential scanning calorimeter (hereinafter sometimes referred to as “DSC”) 3200 to 3800 kJ.
- the half-width of the spectrum observed at 160 ° C. in solid 1 H-NMR is 10 kHz to 14.5 kHz.
- these precursor fiber bundles may be referred to as “third group invention”.
- the calorific value is a value obtained under the following measurement conditions. Measurement atmosphere: air, Gas flow rate: 100 ml / min, Temperature rising conditions: 20 ° C./min (room temperature to 210 ° C.), 2 ° C./min (210 to 300 ° C.), The calorific value is obtained by integrating the heat flow value from 215 to 300 ° C. with time, assuming the heat flow value at 215 ° C. as 0. The calorific value per unit mass is obtained by dividing the calorific value by the sample mass used for the measurement.
- the calorific value is 3200 kJ / kg or more, since there are many heat-stable structures after the flameproofing step, the elastic modulus does not decrease when carbon fibers are used.
- the calorific value is preferably 3300 kJ / kg or more.
- the half width of the spectrum observed at 160 ° C. is an index of molecular mobility, and the smaller the value, the better the molecular mobility. This value is almost the same if the composition of the polyacrylonitrile copolymer is the same.
- the half width of the spectrum is 14.5 kHz or less, the oxygen diffusibility at the time of flame resistance is good, and a stable structure can be formed even in the case where the single fiber fineness of the precursor fiber bundle is large. . Therefore, the strand elastic modulus of the carbon fiber does not decrease, and the strand strength does not decrease.
- the half-value width of the spectrum is 10.0 kHz or more, molecular motion is suppressed and the molecular orientation is easily maintained.
- the half width of the spectrum is preferably 10.0 kHz or more and 13.5 kHz or less.
- a commercially available apparatus can be used for solid 1 H-NMR, and the half width of the spectrum is a value obtained by measurement with a static probe in which a coil is fixed perpendicular to a magnetic field.
- the precursor fiber bundle which is the “first group invention” preferably further has the characteristics of the “second group invention” or the “third group invention”.
- the precursor fiber bundle of the present invention is prepared by, for example, spinning a stock solution having a copolymer concentration of 15 to 30% by mass obtained by dissolving the above-mentioned polyacrylonitrile copolymer in a solvent at a concentration of 30 to 70% by mass and a temperature of 20%. It can be produced by discharging into a coagulation bath at ⁇ 50 ° C. to obtain a coagulated yarn, and drawing this coagulated yarn by 2.5 to 6 times by wet heat. The spinning method will be described below.
- ⁇ Preparation of spinning dope> The above copolymer is dissolved in a solvent by a known method to obtain a spinning dope.
- a solvent organic solvents such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, and aqueous solutions of inorganic compounds such as zinc chloride and sodium thiocyanate can be used.
- An organic solvent is preferable because it contains no metal in the precursor fiber and the process is simplified.
- dimethylacetamide is preferably used because the denseness of the coagulated yarn and wet heat drawn yarn is high. .
- the spinning dope preferably has a copolymer concentration of a certain level or more so as to obtain a dense coagulated yarn and to have an appropriate viscosity and fluidity.
- concentration of the copolymer in the spinning dope is preferably in the range of 15 to 30% by mass, more preferably in the range of 18 to 25% by mass.
- the spinning method a known method can be employed, and specific examples include a wet spinning method, a dry wet spinning method, a dry spinning method, and the like. Among these, the wet spinning method is preferably used from the viewpoint of productivity.
- the spinning solution is discharged into a coagulation bath through a spinneret and spun to obtain a coagulated yarn.
- the roundness of the single fiber of the precursor fiber bundle can be controlled in the coagulation process in the spinning process.
- As the coagulation bath conditions a concentration of 30% by mass to 60% by mass and a temperature of 20 ° C. to 40 ° C. are preferable. If the coagulation bath conditions are within this range, a precursor fiber bundle having a roundness of 0.75 or more and 0.90 or less can be obtained while maintaining an appropriate coagulation rate.
- the coagulation bath concentration is 60% by mass or less, the exchange rate of the solvent and water on the surface of the spinning dope discharged into the coagulating bath exceeds the diffusion rate of water into the spinning dope, and the precursor fiber bundle The roundness is maintained within the above range, and a dense precursor fiber can be obtained. Furthermore, adhesion between the single yarns of the precursor fiber bundle can be suppressed.
- the concentration is preferably 55% by mass or less from the viewpoint of further suppressing adhesion between single yarns.
- the coagulation bath concentration is 30% by mass or more, it is possible to suppress that the exchange rate of the solvent and water on the surface of the spinning dope discharged into the coagulating bath significantly exceeds the diffusion rate of water into the spinning dope.
- the roundness of the precursor fiber bundle can be maintained within the above range within a range where rapid shrinkage of the coagulated yarn does not occur, and a dense precursor fiber bundle can be obtained.
- the coagulation bath temperature is 40 ° C. or less, the exchange rate of the solvent and water on the surface of the spinning dope discharged into the coagulation bath is significantly higher than the diffusion rate of water into the spinning dope.
- the circularity of the precursor fiber bundle can be maintained within the above range within a range where the shrinkage of the coagulated yarn does not occur, and a dense precursor fiber can be obtained.
- it is 20 degreeC or more, the replacement
- a bundle can be produced. Furthermore, it is not necessary to cool the coagulation bath excessively, capital investment and running costs can be suppressed, and the precursor fiber bundle can be produced at low cost.
- the properties of the coagulated yarn are extremely important, and it is preferable that the number of macrovoids is less than 1 in a length of 1 mm of the precursor fiber.
- the macro void is a general term for voids having a spherical shape, a spindle shape, or a cylindrical shape having a maximum diameter of 0.1 to several ⁇ m.
- the solidified yarn in the present invention does not have such macro voids and is obtained by sufficiently uniform solidification. If there are many macrovoids, the coagulated yarn is devitrified and becomes cloudy. However, the coagulated yarn of the present invention is hardly devitrified and hardly clouded because there are almost no macrovoids.
- the presence or absence of macrovoids can be easily determined by directly observing the coagulated yarn with an optical microscope or by cutting the coagulated yarn with an appropriate method and observing the cut surface with an optical microscope.
- wet heat drawing is performed on the obtained coagulated yarn.
- the orientation of the fiber can be further increased.
- the wet heat drawing is performed by drawing the coagulated yarn while being washed with water, or drawing in hot water. Stretching at the same time as washing with water is preferable from the viewpoint of simplification and efficiency of the spinning process, and stretching in hot water is preferable from the viewpoint of productivity.
- the stretching ratio in wet heat stretching is preferably 2.5 times or more, more preferably 3 times or more. If it is lower than 2.5 times, the effect of increasing the fiber orientation tends to be insufficient.
- the upper limit of the draw ratio is not particularly limited, but is preferably 6 times or less from the viewpoint of the stability of the spinning process.
- a silicon oil additive is added to the fiber bundle that has been subjected to wet heat drawing.
- the silicon-based oil a general silicon-based oil such as an aminosilicon-based oil can be used.
- the silicon-based oil agent is prepared to a concentration of 0.4 to 1.5% by mass. A more preferable range of the concentration of the silicone-based oil is 0.8 to 1.5 mass.
- the fiber bundle that has been subjected to the silicon oil addition process is dried.
- the obtained dried densified yarn is further stretched 1.2 to 4 times by steam stretching or dry heat stretching.
- the draw ratio is 1.2 times or more, preferably 1.3 times or more.
- the moisture content of the fiber bundle that has been subjected to steam drawing or dry heat drawing is adjusted with a touch roll as necessary, and then subjected to entanglement treatment by blowing air by a known method to obtain precursor fibers. Get a bunch.
- the entanglement treatment is not essential, but by providing entanglement between the filaments of the precursor fiber bundle, it is possible to obtain a fiber bundle that imparts convergence and retains the form of one tow. Moreover, it is difficult to disperse the fiber bundle, and the passability of the firing process can be improved.
- the moisture content of the fiber bundle before being entangled is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 3 to 5% by mass. When the moisture content exceeds 15% by mass, it becomes difficult for the single fibers to be entangled when the fiber bundle is entangled by blowing air.
- the moisture content in this specification is a value calculated
- required by following Formula. Moisture content (mass%) (W ⁇ W 0 ) ⁇ 100 / W 0 W: the mass of the fiber bundle in the wet state, W 0: Mass after drying a wet fiber bundle at 105 ° C. for 2 hours with a hot air dryer.
- the entanglement degree in the precursor fiber bundle subjected to the entanglement treatment is preferably in the range of 5 to 20 pieces / m, and more preferably in the range of 10 to 14 pieces / m. If the entanglement degree is 5 pieces / m or more, the fiber bundle is difficult to be separated and the passability of the firing process is good. Moreover, if the entanglement degree is 20 pieces / m or less, the resulting carbon fiber bundle has good resin impregnation and spreadability.
- the degree of entanglement of the precursor fiber bundle is a parameter indicating how many times one single fiber in the fiber bundle is entangled with other adjacent single fibers per 1 m of fiber length.
- the degree of entanglement is measured by the hook drop method.
- the manufacturing method of the carbon fiber of this invention is demonstrated.
- the precursor fiber bundle is subjected to flameproofing treatment at a temperature of 240 ° C. or higher and 300 ° C. or lower for 90 minutes or less in an oxidizing atmosphere to obtain a flame resistant fiber bundle.
- “under an oxidizing atmosphere” means in the air containing an oxidizing substance such as nitrogen dioxide, sulfur dioxide and oxygen.
- the temperature of the flameproofing treatment is preferably 250 ° C. or higher from the viewpoint of shortening the flameproofing processing time, and preferably 280 ° C. or lower from the viewpoint of suppressing the runaway of the flameproofing reaction.
- the flameproofing treatment time is preferably 10 to 90 minutes. If the flameproofing treatment time is 10 minutes or more, oxygen can be sufficiently diffused into the single fibers constituting the precursor fiber bundle. Moreover, if the flameproofing treatment time is 90 minutes or less, the carbon fiber bundle can be efficiently produced without causing the flameproofing treatment process to impair the productivity in the production process of the carbon fiber bundle. Further, from the viewpoint of improving the performance and productivity of the carbon fiber bundle, the flameproofing treatment time is more preferably 30 to 70 minutes.
- the density of the flameproof fiber bundle obtained by the flameproofing treatment is preferably 1.35 to 1.43 g / cm 3 . If it is 1.35 g / cm 3 or more, it is possible to produce carbon fibers without reducing the yield of carbon fiber bundles. In general, it is known that the higher the density of the flame-resistant fiber, the higher the yield of the carbon fiber bundle obtained, but the performance of the carbon fiber decreases.
- the density of the flame-resistant fiber bundle is 1.43 g / If it is cm 3 or less, it is possible to improve the yield of the obtained carbon fiber bundle while suppressing the deterioration of the performance of the carbon fiber. From the viewpoint of maintaining the performance of the obtained carbon fiber and improving the yield, the density of the flame-resistant fiber bundle is more preferably 1.38 to 1.41 g / cm 3 .
- the carboxylic acid hydroxyalkyl group of the hydroxyalkyl (meth) acrylate unit is a relatively bulky functional group, and has the effect of improving oxygen permeability in the flameproofing step. Because of these effects, oxygen is efficiently diffused to the inside of the single fiber while the progress of the flameproofing reaction is suppressed, so that the flameproofing treatment of the precursor fiber bundle having a large single fiber fineness is started at a high temperature. Even in a short time, the formation of a double-structured cross-section is suppressed, and a flame-resistant fiber having a uniform degree of flame resistance can be obtained.
- a precarbonization treatment After the flameproofing treatment and before the carbonization treatment, a precarbonization treatment can be performed in which the obtained flameproofed fiber bundle is treated in an inert gas at a maximum temperature of 550 ° C. or higher and 800 ° C. or lower.
- a carbon fiber bundle can be produced by subjecting the obtained flame resistant fiber bundle to carbonization treatment in an inert gas at a temperature of 800 ° C. or higher and 2000 ° C. or lower. Further, by treating this carbon fiber in an inert gas at a high temperature of about 2500 ° C. to 2800 ° C., a graphite fiber can be produced.
- the carbon fiber bundle obtained by the carbonization treatment has a single fiber diameter of 8 ⁇ m or more and a cross-sectional shape perpendicular to the fiber axis of the single fiber has a roundness of 0.90 or less.
- the cross-sectional shape is preferably an empty bean type.
- ⁇ Diameter (maximum ferret diameter) of single fiber of carbon fiber bundle> A cross section perpendicular to the fiber axis of a single fiber was observed with a scanning electron microscope (SEM), and the obtained image was subjected to cross-section analysis using image analysis software (product name: Image-Pro PLUS, manufactured by Nippon Roper Co., Ltd.). Measure the long diameter (maximum ferret diameter). The average value of the major axis of this cross section was defined as the diameter Di.
- the diameter Di is preferably 8 to 20 ⁇ m, particularly preferably 10 to 15 ⁇ m. A method for measuring the diameter Di will be described later.
- the carbon fiber bundle obtained by the production method of the present invention is composed of single fibers having a diameter Di of 8 ⁇ m or more, the bending rigidity of each single fiber is high, and the fibers may be entangled by disturbance during the production process. Since the number is small, the number of entanglements in the fiber bundle is reduced. Furthermore, when the single fiber is thick, the contact portion between the single fibers inside the fiber bundle is small and the frictional resistance between the single fibers is reduced, so that the carbon fiber bundle has very good spreadability even if the number of fibers is large. It is. For this reason, the diameter Di is more preferably 9 ⁇ m or more, and further preferably 10 ⁇ m or more.
- the diameter Di is preferably 17 ⁇ m or less, and more preferably 15 ⁇ m or less.
- the cross-sectional shape of the single fiber of the carbon fiber bundle obtained by the production method of the present invention is represented by the roundness of the cross section perpendicular to the fiber axis of the single fiber of the carbon fiber bundle.
- the roundness is defined by the formula (1) similarly to the roundness of the precursor fiber bundle.
- the cross-sectional shape of the single fiber of the carbon fiber bundle obtained by the production method of the present invention has a roundness of 0.70 or more and 0.90 or less. Furthermore, the cross-sectional shape is preferably an empty bean type.
- the cross-sectional shape By making the cross-sectional shape a relatively simple shape round bean type having a roundness of 0.70 or more and 0.90 or less, oxygen diffusion into the single fiber constituting the precursor fiber bundle is insufficient during the flameproofing treatment. Therefore, the flameproofing reaction has progressed sufficiently, and as a result, the fluff in the carbonization process is suppressed, the process passability is good, and the strength and elastic modulus of the obtained carbon fiber bundle can be properly maintained.
- the carbon fiber of the present invention having a roundness of 0.70 or more and 0.90 or less, even when the fineness of the single fiber is increased, than the carbon fiber having a cross-sectional shape close to a circle having a roundness of greater than 0.9
- the strand strength can maintain a high value. Further, since the single fibers can be densely packed, the fiber content in the prepreg is improved, and the mechanical properties of the composite material can be improved.
- the 0 ° compressive strength when a unidirectional prepreg is laminated to form a composite panel is more round when carbon fibers having a roundness of 0.70 or more and 0.90 or less are used. It shows a higher value than when carbon fibers having a cross-sectional shape close to a circle larger than 0.9 are used.
- the roundness of the single fiber constituting the carbon fiber bundle is 0.88 or less. More preferably, it is most preferably 0.86 or less.
- the roundness of the single fibers constituting the carbon fiber bundle is preferably 0.75 or more, and more preferably 0.80 or more.
- the carbon fiber bundle of the present invention preferably has wrinkles extending in the longitudinal direction of the fiber on the surface of the carbon fiber.
- the wrinkles extending in the longitudinal direction of the fiber play a very important role in expressing the mechanical properties of the fiber reinforced resin material using carbon fiber as a reinforcing material. This is directly related to the formation of the interfacial phase between the carbon fiber and the resin and its characteristics, and characterizes one of the three elements constituting the fiber reinforced resin material, the fiber, the matrix resin, and the interfacial phase. Because.
- the wrinkle on the surface of a single fiber refers to the form of irregularities having a certain length or more in a certain direction.
- a certain level or more is about 0.6 ⁇ m to 1.0 ⁇ m.
- the direction is not particularly limited, and the direction may be parallel or perpendicular to the fiber axis direction, or may have an angle. Due to a general method for producing carbon fiber bundles, wrinkles that are substantially parallel to the fiber axis direction exist on the surface of ordinary carbon fibers.
- the carbon fiber bundle of the present invention has a plurality of groove-like irregularities extending in the longitudinal direction of the single fiber on the surface of the single fiber, and the height difference between the highest part and the lowest part in the range of the circumferential length of the single fiber is 2 ⁇ m ( ⁇ Is preferably 80 nm or less. If the depth of the wrinkles becomes too deep, the fiber bundles are less converged, the passability of the firing process in producing the carbon fiber bundles deteriorates, and the carbon fiber bundles cannot be obtained stably. Moreover, the surface defect of a carbon fiber bundle increases and strand strength falls.
- the impregnation property is improved by using a carbon fiber bundle having a large fineness.
- the depth of the wrinkles in the cross section of the precursor fiber bundle and the carbon fiber bundle is determined by changing the coagulation bath concentration and temperature, and further the drawing conditions.
- the carbon fiber bundle of the present invention preferably has a strand tensile strength of 3000 MPa or more. If the strand tensile strength is extremely low, it will be unusable in most fields where carbon fibers are currently used, such as structural materials. Therefore, the tensile strength is more preferably 3500 MPa or more, and if it is 4000 MPa or more, it can be applied to most existing fields in industrial applications such as windmills, automobiles, and building materials.
- the carbon fiber bundle of the present invention preferably has a strand tensile modulus of 200 GPa or more. If the tensile modulus is extremely low, it will be unusable in most fields where carbon fibers are currently used, such as structural materials. Therefore, the tensile elastic modulus is more preferably 210 GPa or more, and if it is 220 GPa or more, application to most existing fields is possible.
- the carbon fiber bundle of the present invention preferably has a total fineness of 30000 to 90000 dtex.
- a carbon fiber bundle having a total fineness in this range is suitable for the production of large composite materials and molded products.
- a total fineness of 30000 dtex or more is preferable because productivity can be increased and production costs can be easily reduced.
- the total fineness is 90000 dtex or less, handling is easy, and from that point, 60000 dtex or less is more preferable, and 40000 dtex or less is more preferable.
- the carbon fiber bundle of the present invention may be subjected to a surface treatment before the sizing treatment step.
- a surface treatment for example, it is preferable to improve the affinity and adhesion between the carbon fiber and the matrix resin in the composite material by performing an electrolytic oxidation treatment in the electrolytic solution or by performing an oxidation treatment in a gas phase or a liquid phase. .
- the method of sizing treatment is not particularly limited as long as a desired sizing agent can be applied to the carbonized fiber bundle. Examples thereof include a roller sizing method, a roller dipping method, and a spray method.
- the sizing treatment liquid that can be used in the process of sizing the carbon fiber bundle of the present invention is not particularly limited, and those having characteristics suitable for various high-order processing can be selected.
- a solution containing a sizing agent can be put into an emulsion or suspension state, which is attached to a carbonized fiber bundle, and the solvent or dispersion medium can be removed by drying in a drying apparatus. If it is good.
- the main components of the sizing agent in the sizing solution are epoxy resin, epoxy-modified polyurethane resin, polyester resin, phenol resin, polyamide resin, polyurethane resin, polycarbonate resin, polyetherimide resin, polyamideimide resin, polyimide resin, bismaleimide Resins, urethane-modified epoxy resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, polyether sulfone resins and the like can be mentioned, and are not particularly limited.
- the content of the sizing agent in the sizing treatment liquid is not particularly limited, but is preferably 0.2 to 20% by mass, more preferably 3 to 10% by mass.
- the content of the sizing agent in the sizing treatment liquid is not particularly limited, but is preferably 0.2 to 20% by mass, more preferably 3 to 10% by mass.
- the solvent or dispersion medium used for the sizing treatment liquid is not particularly limited, it is preferable to use water from the viewpoint of handleability and safety.
- the adhesion amount of the sizing agent with respect to 100% by mass of the carbon fiber bundle is preferably 0.3 to 5% by mass, and more preferably 0.4 to 3% by mass.
- the adhesion amount of the sizing agent is 0.3% by mass or more, a desired function can be sufficiently imparted to the carbon fiber bundle.
- the adhesion amount of the sizing agent 3% by mass or less, the impregnation property of the matrix resin into the carbon fiber bundle at the time of manufacturing the composite material which is a subsequent process becomes good.
- the solvent or dispersion medium of the sizing process liquid is removed by drying.
- the conditions in this case are preferably a temperature of 120 to 300 ° C. and a range of 10 seconds to 10 minutes, and more preferably a temperature of 150 to 250 ° C. and a range of 30 seconds to 4 minutes.
- the drying temperature By setting the drying temperature to 120 ° C. or higher, the solvent can be sufficiently removed.
- the quality of the carbon fiber bundle by which the sizing process was carried out can be maintained by making drying temperature into 300 degrees C or less.
- the drying method is not particularly limited, and examples thereof include a method in which the carbon fiber bundle is brought into contact with a hot roll using steam as a heat source and a method in which the carbon fiber bundle is dried in an apparatus in which hot air is circulated. be able to.
- the carbon fiber bundle of the present invention can be suitably used for the following unidirectional fiber-reinforced fabric.
- the basis weight in which carbon fiber bundles are arranged in the longitudinal direction is preferably 300 to 1,000 g / m 2 .
- the basis weight of the fiber woven fabric is as small as about 200 g / m 2 , the interfiber spacing becomes large, so that the resin impregnation property is improved.
- the fabric weight of the fiber woven fabric is large, the inter-fiber gap becomes small, the fluidity of the resin becomes poor, and it takes a lot of time for impregnation failure and impregnation.
- methods for obtaining a fabric having a large fabric basis weight are roughly classified into two.
- One of them is a method of using a carbon fiber bundle having a general-purpose number of filaments of 12,000 and increasing the weave density of the fabric to obtain a fabric with a high basis weight.
- the second is a method of obtaining a fabric using a carbon fiber bundle having 48,000 filaments or more.
- it is much easier to fabricate a fabric using carbon fiber bundles called so-called large tows, which have a large number of filaments, in view of processability.
- the flowability of the resin is improved and the impregnation time is greatly shortened by using a carbon fiber bundle of large tow and a fiber having a large single fiber diameter for the fiber reinforced fabric.
- the reason for this is that by increasing the diameter of the single fiber, the gap between the fibers is increased and the flow of the resin is improved.
- a carbon fiber bundle in which the roundness of the single fiber defined above is 0.7 or more and 0.9 or less is preferable. When the roundness exceeds 0.9, the convergence tends to be too high. If the bundling property becomes too high, it becomes difficult to disperse the single fibers uniformly.
- the impregnation property of the resin is also reduced due to a decrease in the gaps between the single fibers.
- the roundness is less than 0.7, the convergence is deteriorated, the firing process in producing the carbon fiber bundle is deteriorated, and the carbon fiber bundle cannot be stably produced. Therefore, by using a single fiber having a roundness of 0.7 or more and 0.9 or less, it is possible to appropriately control the convergence of the carbon fiber bundle, and it is excellent in the balance between the convergence and the ease of dispersion, and the molding process.
- the resin impregnation property is also improved.
- the fabric used in the present invention is a unidirectional fiber reinforced fabric in which carbon fiber bundles are arranged in the longitudinal direction, and auxiliary yarns are used in the lateral direction.
- the basic structure of this fabric is already well known for use in seismic reinforcement.
- As the auxiliary yarn in order to improve the strength of the mechanical properties of the composite, a yarn having a fineness smaller than the carbon fiber bundle used in the longitudinal direction is usually used. That is, the carbon fiber bundles arranged in the vertical direction and the auxiliary yarns arranged in the horizontal direction are always interleaved one by one. Damaged.
- the degree of bending is proportional to the fineness of the auxiliary yarn, and the thicker the auxiliary yarn, the larger the bending of the carbon fiber bundle and the lower the mechanical properties. Therefore, an auxiliary thread that is as thin as possible is preferable, but there is no limitation as long as the shape of the woven fabric can withstand external force.
- glass fiber is generally used for the auxiliary yarn, it is not limited to this.
- the number of auxiliary yarns that are unidirectionally woven is usually relatively small, 10 yarns / inch or less, considering the handleability of the fabric, and the thin auxiliary yarns are interlaced with the warp yarns. And the handleability of the fabric is very poor. Therefore, the auxiliary yarn containing the low melting point polymer is used, and the carbon fiber and the auxiliary yarn are bonded to each other at the intersection through the polymer, so that the restraining force is maintained.
- the low-melting polymer fiber a low-melting-point heat-sealing fiber such as nylon or polyethylene is used.
- the auxiliary yarn and the heat-bonding fiber are composite yarns such as covering, combusting, and aligning bonding.
- the bonding method may be a method using a heat roll or a method using radiant heat such as a far infrared heater.
- CFRP molding method The CFRP molding method of the present invention will be described with reference to FIG.
- a mold release agent is applied to a mold 11 and a predetermined number of carbon fiber fabrics 12 of the present invention are laminated thereon as a fiber base material in a predetermined direction. Further, a peel ply 15 is laminated thereon, and a medium 14 for diffusing the resin is placed on the upper surface of the fiber substrate.
- the spiral tube 13 which deposits resin is arrange
- the whole is covered with a bag film 16 and the periphery of the bag film 16 is bonded to the mold 11 with a sealing material 17 so that air does not leak.
- the resin discharge port 20 injected from the resin tank is connected to the spiral tube 13.
- a resin tank (not shown), a room temperature curable thermosetting resin in the form of a syrup at room temperature with a predetermined amount of curing agent is placed.
- the effect of resin impregnation is large depending on the viscosity of the resin used.
- a low-viscosity product with good resin flowability is used.
- the viscosity at the time of resin injection is preferably 500 mPa ⁇ s or less, and more preferably 300 mPa ⁇ s or less.
- the fiber base material covered with the bag film 16 is brought into a vacuum state with a vacuum pressure of about 70 to 76 cmHg using a vacuum pump, and then the valve 19 is opened to inject the resin. Since the inside covered with the bag film 16 is in a vacuum state and the flow resistance of the resin is smaller in the direction of the surface of the medium than in the thickness direction of the fiber substrate, the resin is first diffused to the surface of the medium, and then the fiber base. Impregnation proceeds in the thickness direction of the material. However, the degree of impregnation is considerably influenced by the form of the carbon fiber fabric 12 used as the fiber base material. Naturally, the impregnation of the resin in the thickness direction is completed faster as the woven fabric has a gap between the fiber yarns.
- a mesh-like sheet using a monofilament such as polyethylene or polypropylene having a fiber diameter of about 0.2 to 0.5 mm, a sheet formed by Russell knitting, or the like can be used, and is not limited at all.
- the vacuum pump is preferably operated until at least the impregnation of the resin is completed, and the inside of the bag film is preferably kept in a vacuum state. After the resin is cured, the peel ply 15 is peeled off, the medium 14 and the bag film 16 are removed, and the mold is removed from the mold to obtain a CFRP molded product.
- the peel ply needs to allow the resin to pass through, and a nylon fiber fabric, a polyester fiber fabric, a glass fiber fabric, or the like can be used.
- the resin is cured and finally peeled, irregularities are generated on the surface of the fiber substrate. Therefore, it is preferable to select a resin that can pass through the resin as much as possible and is less likely to have unevenness on the surface.
- the bag film needs to be confidential, and a nylon film, a polyester film, or the like is used.
- the present invention also relates to a carbon fiber prepreg comprising a carbon fiber bundle and a matrix resin.
- the carbon fiber of the carbon fiber prepreg of the present invention is not particularly limited, and examples thereof include PAN-based carbon fibers and PITCH-based carbon fibers. Desirably, PAN-based carbon fiber is used.
- a single fiber fineness of 1.2 to 2.4 dtex is used, and the carbon fiber bundle of the present invention is particularly preferably used. When the single fiber fineness is 1.2 dtex or more, the compressive strength retention rate when the thickness of the molded article increases is increased. Further, when the single fiber fineness is 2.4 dtex or less, the mechanical strength of the molded product is good.
- One type of carbon fiber bundle may be used for the same prepreg, and a plurality of types of carbon fiber bundles may be used regularly or irregularly arranged.
- unidirectional prepreg is most suitable for applications that require high specific strength and specific modulus in a specific direction, but it should be pre-processed into sheet form such as long fiber mat or woven fabric. Is also possible.
- the matrix resin is not particularly limited, but preferably has a flow index of 5000 Pa ⁇ 1 or more.
- the matrix resin include epoxy resin, polyester resin, phenol resin, polyimide resin, maleimide resin, acetylene-terminated resin, vinyl-terminated resin, and cyanate ester-terminated resin.
- An epoxy resin is preferable.
- the “flow index” is as follows.
- the viscosity of the resin composition is measured using VAR-100 (manufactured by Rheometrics) at a gap of 0.5 mm, a measurement frequency of 10 rad / sec, a stress of 300 dyne / cm 2 and a measurement frequency of every 30 sec.
- the measurement temperature was set in the same manner as the curing conditions (FIG. 5), and the measurement was completed at a point where the viscosity was increased by two digits from the lowest viscosity of the resin composition.
- the flow index is defined by the following equation. However, ⁇ : viscosity, t: time, and n-th measurement values are ⁇ n and tn.
- Any epoxy resin can be used as the epoxy resin.
- polyfunctional epoxy resins to increase heat resistance epoxy resins with a rigid ring structure in the main chain, or low molecular weight epoxy resins or alicyclic to reduce the viscosity of the resin composition
- Any epoxy resin can be blended according to the purpose, such as blending an epoxy resin.
- a glycidyl ether type epoxy resin obtained from a compound having a hydroxyl group in the molecule and epichlorohydrin a glycidylamine type epoxy resin obtained from a compound having an amino group in the molecule and epichlorohydrin, a carboxyl group in the molecule
- a glycidyl ester type epoxy resin obtained from a compound having a glycidyl ester and epichlorohydrin an alicyclic epoxy resin obtained by oxidizing a compound having a double bond in the molecule, or two or more types selected from these
- An epoxy resin or the like in which groups are mixed in the molecule is used.
- glycidyl ether type epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, resorcinol type epoxy resin, phenol novolac type epoxy resin, other trisphenol novolak type epoxy resin, polyethylene glycol type epoxy resin, polypropylene glycol Type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, and their positional isomers, substituted groups with alkyl groups and halogens.
- bisphenol F type epoxy resins include jER806, jER807, jER1750 (Mitsubishi Chemical Corporation), Epicron 830 (DIC Corporation), Epototo YD-170, Epototo YD-175 (Nippon Steel Chemical Co., Ltd.) , Bakelite EPR169 (manufactured by Bakerite AG), GY281, GY282, and GY285 (above, manufactured by Huntsman Advanced Materials), and the like.
- Examples of commercially available resorcinol-type epoxy resins include Denacol EX-201 (manufactured by Nagase ChemteX Corporation).
- phenol novolac type epoxy resins examples include jER152, jER154 (above, manufactured by Mitsubishi Chemical Corporation), Epicron 740 (made by DIC), EPN179, EPN180 (above, made by Huntsman Advanced Materials), and the like. .
- trisphenol novolak type epoxy resin examples include Tactix 742 (manufactured by Huntsman Advanced Material), EPPN501H, EPPN501HY, EPPN502H, EPPN503H (manufactured by Nippon Kayaku Co., Ltd.), jER1032 (manufactured by Mitsubishi Chemical Corporation), and the like.
- glycidylamine type epoxy resin examples include tetraglycidyldiaminodiphenylmethanes, glycidyl compounds of aminophenol, glycidylanilines, and glycidyl compounds of xylenediamine.
- glycidyl compounds such as aminophenol and aminocresol include jER630 (Mitsubishi Chemical Corporation), Araldite MY0500, Araldite MY0510, Araldite MY0600 (manufactured by Huntsman Advanced Materials), Sumiepoxy ELM120, and Sumiepoxy ELM100. (Above, manufactured by Sumitomo Chemical Co., Ltd.).
- Examples of commercially available glycidyl anilines include GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.), Bakelite EPR493 (manufactured by Bakelite AG), and the like.
- Examples of the glycidyl compound of xylenediamine include TETRAD-X (manufactured by Mitsubishi Gas Chemical Company).
- glycidyl ester type epoxy resin examples include phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, dimer acid diglycidyl ester, and various isomers thereof.
- Examples of commercially available products of diglycidyl phthalate include Epomic R508 (manufactured by Mitsui Chemicals) and Denacol EX-721 (manufactured by Nagase ChemteX).
- Examples of commercially available hexahydrophthalic acid diglycidyl ester include Epomic R540 (Mitsui Chemicals) and AK-601 (Nippon Kayaku).
- dimer acid diglycidyl ester examples include jER871 (manufactured by Mitsubishi Chemical Corporation) and Epototo YD-171 (manufactured by Nippon Steel Chemical Co., Ltd.).
- alicyclic epoxy resins include Celoxide 2021P (Daicel Chemical Industries), CY179 (Huntsman Advanced Materials), Celoxide 2081 (Daicel Chemical Industries), and Celoxide 3000 (Daicel Chemical Industries). Manufactured).
- Examples of the epoxy resin having an oxazolidone ring in the skeleton include AER4152, AER4151, LSA4311, LSA4313, and LSA7001 (manufactured by Asahi Kasei E-Materials).
- Examples of the epoxy resin having a naphthalene skeleton in the skeleton include HP-4032, HP-4700 (manufactured by DIC), NC-7300 (manufactured by Nippon Kayaku).
- Examples of the epoxy resin having a dicyclopentadiene skeleton in the skeleton include XD-100 (manufactured by Nippon Kayaku Co., Ltd.) and HP7200 (manufactured by DIC).
- Examples of the epoxy resin having an anthracene skeleton in the skeleton include YL7172YX-8800 (above, manufactured by Mitsubishi Chemical Corporation).
- Examples of the epoxy resin having a xanthene skeleton in the skeleton include EXA-7335 (manufactured by DIC).
- a bisphenol A type epoxy resin or an epoxy resin having an oxazolidone ring in the skeleton is used.
- ⁇ Curing agent> As the curing agent for epoxy resin, amine type, acid anhydride, phenol, mercaptan type, Lewis acid amine complex, onium salt, imidazole, etc. are used, but any structure that can cure epoxy resin is used. But it ’s okay.
- aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea-added amines and isomers and modifications thereof. Particularly preferred is dicyandiamide.
- curing agents can be combined with an appropriate curing aid in order to increase the curing activity.
- Preferred examples include dicyandiamide and 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 3- (3-chloro-4 as a curing aid.
- urea compounds such as methylphenyl) -1,1-dimethylurea, 2,4-bis (3,3-dimethylureido) toluene, methylenediphenylbis (dimethylureido), phenyldimethylurea (PDMU);
- PDMU phenyldimethylurea
- Example of combining tertiary amine as curing aid with carboxylic anhydride or novolac resin urea compound such as imidazole compound, phenyldimethylurea (PDMU) as curing aid, diethyldiphenylsulfone, monoethylamine trifluoride, three
- combining amine complexes such as amine chloride complexes.
- 2,4-bis (3,3-dimethylureido) toluene is Omicure 24 (PTI Japan) and methylenediphenylbis (dimethylureido) is Micure 52 (PTI Japan).
- a preferred curing aid is 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU).
- composition of polyacrylonitrile copolymer was measured by 1 H-NMR method as follows. Using dimethyl sulfoxide-d6 solvent as a solvent, the copolymer was dissolved and measured with an NMR measuring apparatus (manufactured by JEOL Ltd., product name: GSZ-400 type) under the conditions of a total number of 40 times and a measurement temperature of 120 ° C. The ratio of each monomer unit was determined from the integral ratio of chemical shift.
- Oxidation depth De measurement of polyacrylonitrile copolymer> The copolymer was dissolved in dimethylformamide to prepare a copolymer solution having a mass concentration of 25%, and this copolymer solution was applied on a glass plate so as to have a constant thickness. Next, the glass plate coated with the copolymer solution is dried in air at 120 ° C. for 6 hours using a hot air dryer, and the solvent is evaporated to obtain a film having a constant thickness in the range of 20 to 40 ⁇ m. did. The obtained film was heat-treated at 240 ° C. in air for 60 minutes and further in air at 250 ° C. for 60 minutes using a hot air dryer to perform flameproofing treatment.
- the obtained flame resistant film was cut into a size of 30 mm length and 10 mm width, embedded in an epoxy resin, and polished so that the cross section of the flame resistant film was exposed.
- a cross section perpendicular to the polished flameproof film surface was observed at a magnification of 1500 times using a fluorescence microscope (trade name: MICROFLEX AFX DX).
- MICROFLEX AFX DX a fluorescence microscope
- Single fiber fineness of precursor fiber is the weight per 10,000 m of one fiber.
- Two fiber bundles having a length of 1 m are taken from an arbitrary portion of the precursor fiber bundle, each mass is measured, and each of these values is divided by the number of filaments (that is, the number of holes in the die), and then multiplied by 10,000. The average value of the two fiber bundles was calculated and used as the single fiber fineness.
- Precursor heating curve of precursor fiber bundle was measured by a heat flux type differential scanning calorimeter as follows. First, the precursor fiber bundle was cut into a length of 4.0 mm, 4.0 mg was precisely weighed, and packed in 50 ⁇ l (product name: P / N SSC000E030) made of a sealed sample container Ag manufactured by SII, The lid was covered with a mesh cover made by SII (trade name: P / N 50-037) (450 ° C./15 minutes, heat-treated in air).
- a heat flux type differential scanning calorimeter DSC / 220 manufactured by SII Co., Ltd., heating rate of 10 ° C./min, air supply rate of 100 ml / min (air supply rate standard: 30 ° C., 0.10 MPa) Measurement was performed from room temperature (30 ° C.) to 450 ° C. under the following conditions.
- the calorific value of 230 ° C. or higher and 260 ° C. or lower of the obtained constant-rate heating exothermic curve was defined as the calorific value Ja
- the calorific value of 260 ° C. or higher and 290 ° C. or lower was defined as the calorific value Jb.
- the apparatus uses a heat flux type differential scanning calorimeter: DSC / 220 manufactured by SII Corporation, and a temperature increase rate of 20 ° C./min between room temperature and 210 ° C. and 2 ° C./min between 210 and 300 ° C.
- the air supply rate was 100 ml / min (air supply rate reference: 30 ° C., 0.10 MPa).
- the time interval for taking in the heat flow is 0.5 seconds.
- the calorific value was obtained by integrating the heat flow rate from 215 to 300 ° C. over time with the heat flow rate at 215 ° C. being zero. Specifically, using the temperature and heat flow rate for each intake time, the sum of [heat flow rate ( ⁇ W) ⁇ 0.5 (s)] from 215 ° C. to 300 ° C. is taken, and the heat generation at 215 to 300 ° C. Asked. The calorific value was divided by the sample amount to determine the calorific value per unit mass.
- Method for Measuring Precursor Solid 1 H-NMR> A commercially available sample tube for NMR having an outer diameter of 5 mm was cut to 50 mm, and the precursor fiber bundle was packed so that there was no gap so that the longitudinal direction and the fiber axis coincided with each other.
- the fiber sample length in the sample tube was about 6 mm.
- the apparatus used was an AVANCE II 300 MHz magnet manufactured by Bruker Bio-Spin. The probe was set using a static probe so that the fiber axis was perpendicular to the magnetic field.
- the difference spectrum of A and B is C
- the half width of C Asked can be obtained with the attached analysis software, and the full width at half maximum can also be obtained with the attached analysis software.
- the measurement conditions are as follows. Measurement temperature: 160 ° C., measurement atmosphere: nitrogen, Hahn echo method, 90 ° pulse 5 ⁇ s, 180 ° pulse 10 ⁇ s, integration number: 8 times, repeat waiting time: 12 seconds.
- Impregnation evaluation> The evaluation of the impregnation property of the carbon fiber bundle will be described with reference to FIG.
- the carbon fiber bundle 5 was cut out to a length of 30 cm, coated with white powder (talc), and one end of the carbon fiber bundle was fastened with a clip 7.
- Formamide 9 is injected into the container and the side clipped so that the carbon fiber bundle is perpendicular to the liquid level is on the bottom.
- the clip was submerged in formamide, and when the clip was below the liquid level, settling was stopped and allowed to stand for 20 minutes to impregnate the carbon fiber bundle with formamide. After 20 minutes, the height impregnated with formamide was measured with a ruler 8. This operation was performed 6 times, and the average value was obtained as “rise height H”. The higher the rising height, the better the impregnation property.
- White powder (talc) is used to facilitate confirmation of the formamide impregnation height.
- the carbon fiber bundle of the present invention preferably has an impregnation height of
- a sheet to be removed after the resin is cured so-called peel ply (nylon taffeta # 15) is laminated, and a medium for diffusing the resin over the entire surface of the fiber substrate ( A polyethylene mesh material, AIRTECH GREENFLOE 75) was placed.
- a spiral tube (product number TSP-10 manufactured by Trusco Co., Ltd., material polyethylene, wall thickness 0.8 mm, outer diameter 10 mm, spiral pitch 11.4 mm) for depositing resin on both ends in the fiber axis direction of the fiber base is disposed.
- the suction port of the vacuum pump was attached. Further, these were entirely covered with a bag film (Lightlon # 8400), and the periphery of the bag film was adhered to a mold with a sealing material (vacuum sealant, RS200) so that air did not leak.
- the resin is an infusion molding epoxy resin (manufactured by Nagase Chemtech Co., Ltd., main agent: DENITEITE XNR6815, curing agent: DENATEITE XNH6815) in 100 parts by weight of the main agent and 27 parts by weight of the curing agent (mixture viscosity 260 mPa ⁇ S). Used.
- the fiber base material covered with the bag film using a vacuum pump was evacuated to a vacuum pressure of about 70 to 76 cmHg, and then the valve was opened to inject the resin.
- the resin impregnation property was evaluated by measuring the time until the resin impregnation was completed.
- the evaluation of resin impregnation was based on the time from the start of resin injection until the resin was impregnated into the entire three fabrics, and the impregnation was evaluated by the following evaluation. ⁇ : Impregnation time is less than 10 minutes, X: Impregnation time is 10 minutes or more.
- Example 1 Place 76.5 liters of deionized water in an aluminum polymerization kettle with a capacity of 80 liters (stirring wing: 240 ⁇ , 55 mm x 57 mm, 2 stages, 4 blades) so that the deionized water reaches the polymerization kettle overflow port. 0.01 g of ferrous iron (Fe 2 SO 4 .7H 2 O) was added and the reaction solution was adjusted with sulfuric acid so that the pH was 3.0, and the temperature in the polymerization kettle was maintained at 57 ° C.
- ferrous iron Fe 2 SO 4 .7H 2 O
- AN acrylonitrile
- HEMA 2-hydroxyethyl methacrylate
- polymer slurry For the polymer slurry, an aqueous solution of a polymerization terminator in which sodium oxalate 0.37 ⁇ 10 ⁇ 2 mol% and sodium bicarbonate 1.78 ⁇ 10 ⁇ 2 mol% was dissolved in deionized water was used. It added so that it might become 5.5-6.0.
- the polymer slurry was dehydrated with an Oliver type continuous filter, and 10 times the amount of deionized water (70 liters) was added to the polymer and dispersed again.
- the polymer slurry after re-dispersion is again dehydrated with an Oliver type continuous filter, pelletized, dried at 80 ° C.
- Polymer A was obtained.
- the composition of the obtained copolymer A was 98.5 mol% of AN units and 1.5 mol% of HEMA units, the specific viscosity was 0.21, and the melting point under wet heat was 170 ° C. Furthermore, the water contact angle of this copolymer A was 62.3 °, and the oxidation depth De was 4.5 ⁇ m.
- This copolymer was dissolved in an organic solvent such as dimethylacetamide to prepare a spinning stock solution having a concentration of 21% by mass.
- spinning was performed by a wet spinning method under coagulation bath conditions of a coagulation bath concentration of 60% by mass and a coagulation bath temperature of 35 ° C. to obtain a precursor fiber bundle.
- the single fiber fineness of this precursor fiber bundle was 2.0 dtex
- the number of filaments was 30000
- the fiber density was 1.18 g / cm 3
- the cross-sectional shape was an empty bean shape with a roundness of 0.85.
- the heat quantity Ja obtained from the heat flux type differential scanning calorimetry was 185 kJ / kg
- the heat quantity Jb was 740 kJ / kg.
- This precursor fiber bundle was subjected to a flameproofing treatment in a hot air circulation type flameproofing furnace at 250 ° C. to 290 ° C. in heated air at an elongation rate of + 2% for 60 minutes to obtain a flameproofed fiber bundle.
- the density of the obtained flameproofed fiber bundle was 1.392 g / cm 3 .
- this flame-resistant fiber bundle is subjected to low-temperature heat treatment in a nitrogen atmosphere at a maximum temperature of 660 ° C. and an elongation of 3.0% for 1.5 minutes, and further to a high-temperature heat treatment furnace having a maximum temperature of 1350 ° C. in a nitrogen atmosphere. Then, carbonization was performed at an elongation of -4.5% for about 1.5 minutes to obtain a carbon fiber bundle.
- the diameter Di of the obtained carbon fiber was 9.43 ⁇ m, and the roundness was 0.84. Furthermore, the strand tensile strength was 4300 MPa, and the strand tensile modulus was as high as 245 GPa. This is because the presence of HEMA units in the precursor fiber keeps the denseness or homogeneity sufficient for the performance of the carbon fiber, and even if the flameproofing treatment is performed at a high temperature for a short time. It has exothermic characteristics that oxygen diffuses sufficiently inside the fiber, and in addition, the distance from the fiber surface to the center of the cross section is short due to the fiber cross section of the precursor fiber being a hollow bean type, etc. This is because a uniform flameproofing treatment becomes possible.
- Copolymers A, B, C or F, G were obtained in the same manner as in Example 1 except that the monomer supply ratio (molar ratio) at the start of polymerization was changed to the values shown in Table 1 or Table 2.
- Table 1 or Table 2 HPMA is 2-hydroxypropyl methacrylate, and HEA is 2-hydroxyethyl acrylate.
- Table 1 or Table 2 shows the composition, specific viscosity, melting point under wet heat, the water contact angle of the film obtained from each copolymer, and the oxidation depth De.
- Example 2 Using these copolymers, a spinning dope was prepared and spun in the same manner as in Example 1 to obtain precursor fiber bundles.
- Table 1 or 2 shows the single fiber fineness, filament number, fiber density, coagulation bath condition, roundness, cross-sectional shape, heat quantity Ja, and heat quantity Jb of each precursor fiber bundle.
- each of these precursor fiber bundles was subjected to a flameproofing treatment in a heated air circulation type flameproofing furnace in a heated air having a temperature shown in Table 1 or 2 at an elongation rate and a time.
- the density of each flameproof fiber obtained is shown in Table 1 or Table 2.
- this flameproof fiber bundle was carbonized in the same manner as in Example 1 to obtain a carbon fiber bundle.
- Table 1 or Table 2 shows the diameter, roundness, openability, strand tensile strength, and strand elastic modulus of the obtained carbon fiber.
- the cross-sectional shape of the carbon fibers obtained in Examples 2 to 15 was an empty bean type with roundness of 0.78 to 0.88, and both the strand tensile strength and the strand tensile elastic modulus showed high values. This is because the precursor fibers have sufficient denseness or homogeneity as in Example 1, and a uniform flameproofing treatment is possible. Further, it was confirmed that the tow width was wide and the fiber opening property was excellent with respect to a carbon fiber bundle obtained from a precursor fiber bundle having the same single fiber fineness and a round cross section.
- a copolymer A, B, D or E was obtained in the same manner as in Example 1 except that the monomer supply ratio (molar ratio) at the start of polymerization was changed to the values shown in Table 3 or Table 4.
- AAm is acrylamide
- MAA is methacrylic acid
- IBMA is isobutyl methacrylate.
- Table 3 or Table 4 shows the composition, specific viscosity, melting point under wet heat, the water contact angle of the film obtained from each copolymer, and the oxidation depth De.
- a spinning dope was prepared and spun in the same manner as in Example 1 to obtain precursor fiber bundles.
- Table 3 or Table 4 shows the single fiber fineness, the number of filaments, the fiber density, the coagulation bath condition, the roundness, the cross-sectional shape, the heat amount Ja, and the heat amount Jb of each precursor fiber bundle.
- each of these precursor fiber bundles was subjected to a flameproofing treatment in a hot air circulation type flameproofing furnace in heated air at a temperature shown in Table 3 or Table 4 at an elongation rate and a time.
- the density of each flameproof fiber obtained is shown in Table 3 or Table 4.
- this flameproof fiber bundle was carbonized in the same manner as in Example 1 to obtain a carbon fiber bundle.
- Table 3 or Table 4 shows the diameter, roundness, openability, strand tensile strength, and strand elastic modulus of the obtained carbon fiber.
- the cross-sectional shape of the carbon fiber obtained in Comparative Example 1 was a round shape having a diameter of 7.6 ⁇ m and a roundness of 0.95. Furthermore, the strand tensile strength was 1910 MPa, and the strand tensile modulus was as low as 222 GPa. This is because the distance from the fiber surface to the center of the cross section is long because the fiber cross-sectional shape of the precursor fiber is round, and a uniform flame resistance treatment cannot be performed.
- the cross-sectional shape of the carbon fiber obtained in Comparative Example 2 was an empty bean shape with a diameter of 9.4 ⁇ m and a roundness of 0.85, but the strand tensile strength and the strand tensile modulus were lower than those in Example 1. showed that.
- the copolymer constituting the precursor fiber does not contain a monomer having a hydrophilic group such as a HEMA unit, so that the water contact angle of the film is very high at 74.4 °.
- the denseness or homogeneity of the body fiber bundle could not be maintained, and the amount of heat Ja was very small at 52 KJ / Kg, and the precursor fiber was plasticized before the flameproofing reaction proceeded. In the flameproofing process, This is because the fibers have stretched.
- the calorific value Jb is very small as 340 KJ / Kg, so the flame resistance reactivity is low, the flame resistance treatment takes a very long time, and the productivity is significantly impaired.
- the cross-sectional shape of the carbon fiber obtained in Comparative Example 3 was an empty bean shape having a diameter of 9.4 ⁇ m and a roundness of 0.81, but the strand tensile strength and the strand tensile modulus were lower than those in Example 1. showed that. This is because the portion of the carboxy group in the copolymer constituting the precursor fiber is not hydroxyalkylated, so the value of the heat quantity Jb is as high as 1150 kJ / kg, and the flameproofing reaction proceeds at a stretch.
- the cross-sectional shape of the carbon fiber obtained in Comparative Example 4 was an empty bean shape having a diameter of 11.9 ⁇ m and a roundness of 0.82, but the strand tensile strength and the strand tensile modulus were lower than those in Example 1. showed that. This is considered to be due to the same reason as in Comparative Example 3.
- the carbon fiber bundle could not be sampled. This is because the position of the carboxy group in the copolymer constituting the precursor fiber is not hydroxyalkylated, so the value of the heat quantity Jb is as high as 1150 kJ / kg, and the flameproofing reaction proceeds at a stretch. Oxygen diffuses to the inside of the precursor fiber having a large single fiber fineness because a double-cross-section structure is easily formed and the oxidation depth D of the film is as small as 3.0 ⁇ m and the oxygen permeability of the precursor fiber is low. This is because the flameproofing treatment was not uniform and the formation of a double-sectioned structure was remarkable.
- the cross-sectional shape of the carbon fiber obtained in Comparative Example 6 was an empty bean shape having a diameter of 11.7 ⁇ m and a roundness of 0.82, but the strand tensile strength and the strand tensile modulus were lower than those in Example 1. showed that. This is because the copolymer constituting the precursor fiber does not contain a monomer unit having a hydrophilic group such as a HEMA unit, so that the water contact angle of the film is very high as 76.2 °, This is because the denseness or homogeneity of the precursor fiber bundle could not be maintained.
- the copolymer H contains IA units, the value of the heat quantity Ja is as large as 178 kJ / kg, but the value of the heat quantity Jb is very small as 473 kJ / kg. This is because evenly flameproofing treatment cannot be performed.
- the cross-sectional shape of the carbon fiber obtained in Comparative Example 7 was an empty bean shape having a diameter of 12.3 ⁇ m and a roundness of 0.81, but the strand tensile strength and the strand tensile modulus were lower than those in Example 1. showed that. This is because the copolymer constituting the precursor fiber does not contain a monomer unit having a hydrophilic group such as a HEMA unit, so that the water contact angle of the film is as high as 71.1 °. This is because the denseness or homogeneity of the fiber bundle could not be maintained.
- the copolymer I contains an MAA unit, the value of the heat quantity Ja is very high as 262 kJ / kg, and the flameproofing reaction proceeds at a stretch, so that a cross-sectional double structure is easily formed. Since the oxidation depth De of the film is as small as 3.2 ⁇ m and the oxygen permeability of the precursor fiber is low, oxygen cannot be diffused into the precursor fiber having a large single fiber fineness and the flameproofing treatment cannot be performed uniformly. It is.
- the cross-sectional shape of the carbon fiber obtained in Comparative Example 8 was an empty bean shape having a diameter of 11.9 ⁇ m and a roundness of 0.83, but the strand tensile strength and the strand tensile elastic modulus were low compared to Example 1. The value is shown. This is considered to be caused by the following.
- AAm units in the copolymer constituting the precursor fiber, the denseness and homogeneity of the precursor fiber is maintained, but the carboxy group in the copolymer is hydroxyalkylated. This is because the amount of heat Ja is as very small as 82 kJ / kg, and the precursor fiber was plasticized before the flameproofing reaction proceeded, and the fiber was stretched in the flameproofing process.
- the value of the amount of heat Jb is as high as 1098 kJ / kg, and the flameproofing reaction proceeds at a stretch, so that a double cross-section structure is easily formed.
- the copolymer J does not contain a monomer unit containing a carboxylic acid group, and on the other hand, a bulky IBMA unit is introduced as the monomer unit. Is as large as 6.3 ⁇ m, and the oxygen permeability of the precursor fiber is sufficient, but because the flame resistance reactivity is inappropriate, uniform flame resistance treatment cannot be performed.
- the cross-sectional shape of the carbon fiber obtained in Comparative Example 9 was an empty bean shape having a diameter of 7.1 ⁇ m and a roundness of 0.84. Furthermore, the strand tensile strength and the strand tensile elastic modulus showed the same value as compared with Example 1, but the tow width, which is an index of the opening property, was 20.9 mm, which is the same for all the examples of the present invention. It showed a low value. This is because the single fiber fineness of the precursor fiber bundle is as thin as 1.0 dtex, so that the single fibers of the obtained carbon fiber bundle are easily entangled with each other, and the openability is lowered.
- the strand tensile strength and strand tensile modulus of the carbon fibers obtained in Comparative Examples 10 to 14 were lower than those in Example 1. This is because when the fiber cross-sectional shape of the precursor fiber is round, the distance from the surface of the fiber to the center of the cross-section is long, and uniform flameproofing treatment cannot be performed.
- Example 16 Acrylic copolymer A produced in the same manner as in Example 1 and having an AN unit of 98.0 mol% and a HEMA unit of 2.0 mol% and a specific viscosity of 0.21 was dissolved in dimethylacetamide, and spinning was performed. The stock solution was adjusted to a polymer concentration of 21% and a stock solution temperature of 60 ° C. Using this spinning dope, spinning was performed by a wet spinning method. The coagulation bath for spinning the spinning dope is a dimethylacetamide aqueous solution having a concentration of 45% by mass and a temperature of 25 ° C. The number of holes in the spinneret used is 3000.
- a coagulated yarn obtained by coagulation in a coagulation bath was washed and stretched and then thermally stretched to draw a total of 7.4 times to obtain a precursor fiber bundle A.
- the discharge amount was adjusted so that the single yarn fiber fineness of the precursor fiber bundle A was 2.5 dtex.
- the calorific value by a heat flux type differential scanning calorimeter was 3400 kJ / kg, and the H-NMR half width was 12.5 kHz.
- the precursor fiber bundle A was subjected to a flame resistance treatment at a stretch rate of 2% in a hot air circulation type flame resistance furnace at 230 ° C. to 270 ° C. for 70 minutes to obtain a flame resistant fiber bundle.
- the temperature of the flameproofing furnace was adjusted so that the density of the flameproofed fiber was about 1.35 g / cm 3 in 70 minutes.
- the density of the obtained flame-resistant fiber was 1.352 g / cm 3 .
- this flame-resistant fiber bundle was heat-treated for 1 minute (pre-carbonization treatment) at a maximum temperature of 690 ° C. and an elongation of 3.0% in a nitrogen atmosphere, and further, a high temperature having a maximum temperature of 1450 ° C. in a nitrogen atmosphere. Carbonization treatment was performed for 1 minute under an elongation of ⁇ 4.3% in a heat treatment furnace to obtain a carbon fiber bundle.
- the strand tensile strength was 4390 MPa, and the strand tensile modulus was as high as 251 GPa.
- Example 17 The precursor fiber bundle A produced in the same manner as in Example 16 was flameproofed in a hot air circulation type flameproofing furnace in a heated air of 230 ° C. to 270 ° C. for 90 minutes at an elongation rate of 2%.
- the temperature of the flameproofing furnace was adjusted to be about 1.40 g / cm 3 in 90 minutes.
- the density of the obtained flame-resistant fiber was 1.400.
- Example 16 pre-carbonization treatment and carbonization treatment were performed under the same conditions as in Example 16 to obtain a carbon fiber bundle.
- the strand tensile strength was 4280 MPa, and the strand tensile modulus was as high as 260 GPa.
- Example 18 to 27 and Comparative Examples 15 to 19 A spinning dope was prepared and spun in the same manner as in Example 16 except that the coagulation bath concentration and coagulation bath temperature were set to the values shown in Table 5 and the discharge rate was adjusted so that the resulting single fiber fineness was as shown in Table 5.
- Precursor fiber bundles BI were obtained.
- Table 6 shows the single fiber fineness of the obtained precursor fiber bundle, the calorific value by the heat flux type differential scanning calorimeter, and the 1 H-NMR half width.
- each of these precursor fiber bundles was subjected to flame resistance treatment in the hot air circulation type flame resistance furnace under the conditions of Example 16 or Example 17.
- Table 6 shows the density of each flame-resistant fiber obtained.
- Example 16 pre-carbonization treatment and carbonization treatment were carried out in the same manner as in Example 16 or Example 17 to obtain a carbon fiber bundle.
- Table 6 shows the strand tensile strength and strand elastic modulus of the obtained carbon fiber.
- Comparative Examples 15 and 16 since the calorific value per unit mass was smaller than 3200 kJ / kg, the strand elastic modulus was a small value compared to the Examples. In Comparative Examples 17 and 18, both the strand strength and the strand elastic modulus were good, but the target carbon fiber bundle was not obtained because the single fiber fineness was as small as 1.5 dtex.
- Example 28 Using the copolymer B having an AN unit of 98.5 mol% and a HEMA unit of 1.5 mol% and a specific viscosity of 0.21, produced in the same manner as in Example 15, the single fiber fineness was 2.0 dtex.
- the precursor fiber bundle J was obtained under the same conditions as in Example 16 except that the discharge amount was adjusted so that the coagulation bath conditions shown in Table 5 were used.
- the precursor fiber bundle J was subjected to a flameproofing treatment at a stretch rate of 2% in heated air at 230 ° C. to 270 ° C. for 60 minutes in a hot air circulation type flameproofing furnace to obtain a flameproofed fiber bundle.
- the temperature of the flameproofing furnace was adjusted so that the density of the flameproofed fiber after treatment was about 1.35 g / cm 3 in 60 minutes.
- a pre-carbonization treatment was performed under the same conditions as in Example 16, followed by a carbonization treatment to obtain a carbon fiber bundle.
- the evaluation results are shown in Table 6.
- Example 20 A spinning dope as in Example 16 using an acrylic copolymer D having 97.0 mol% AN units, 2.6 mol% AAm units, 0.4 mol% methacrylic acid units, and a specific viscosity of 0.21.
- Table 6 shows the single fiber fineness of the obtained precursor fiber bundle, the calorific value by the heat flux type differential scanning calorimeter, and the 1 H-NMR half width. Then, using this flameproof fiber bundle, the flameproofing temperature was adjusted so that the density of the flameproofed fiber became about 1.35 g / cm 3 in 70 minutes, and the flameproofing treatment was performed. Under these conditions, pre-carbonization treatment and carbonization treatment were performed to obtain a carbon fiber bundle. The evaluation results are shown in Table 6.
- the calorific value per unit mass is smaller than 3200 kJ / kg, and the 1 H-NMR half-value width is larger than 14.5 kHz, so that oxygen does not diffuse sufficiently and there are few stable structures. Therefore, both the strand tensile strength and the strand tensile elastic modulus were low.
- FIG. 6 shows the relationship between the strand elastic modulus and the calorific value per unit mass in Examples and Comparative Examples.
- the calorific value per unit mass is smaller than 3200 kJ / kg, it is apparent that the strand tensile elastic modulus is decreased and the physical properties are lowered regardless of the copolymer composition and the single fiber fineness.
- This copolymer was dissolved in dimethylacetamide to prepare a 21% by mass spinning stock solution.
- the fiber bundle to which the oil treatment liquid was applied was dried using a heating roll, and dry-heat-stretched 1.34 times between heating rolls whose rotation speed was adjusted to a predetermined condition.
- the total draw ratio from the swollen yarn was 7.4 times.
- the moisture content was adjusted by applying water to the fiber bundle with a touch roll to obtain a precursor fiber bundle having a single fiber fineness of 2.5 dtex.
- This precursor fiber bundle was subjected to a flame resistance treatment at a stretch rate of ⁇ 1.5% for 70 minutes in a heated air circulation type flame resistance furnace at 220 to 260 ° C. to obtain a flame resistant fiber bundle.
- the obtained flame-resistant fiber bundle was further pre-carbonized in a nitrogen atmosphere at 700 ° C. and an elongation rate of + 3% for 1.4 minutes, and then in a nitrogen atmosphere at 1,300 ° C. and an elongation rate of ⁇ 4.0%. And carbonized for 1.0 minute to obtain a carbon fiber bundle.
- the single fiber fineness of the obtained carbon fiber bundle was 1.3 dtex.
- the strand strength was 4300 MPa and the strand elastic modulus was 233 GPa.
- the roundness of the cross section of the carbon fiber was 0.75, and the depth of the wrinkles was 49.8 nm.
- the impregnation evaluation was performed, the height of the rise was 126 mm.
- the impregnation time was 9 minutes and the impregnation property was good.
- the single fiber fineness of the obtained carbon fiber bundle was 1.3 dtex.
- the strand strength was 4.2 GPa and the strand elastic modulus was 232 GPa.
- the roundness of the carbon fiber was 0.75, and the wrinkle depth was 50.0 nm.
- the impregnation evaluation was performed, the height of rise was 125 mm.
- the impregnation time was 9 minutes and the impregnation property was favorable.
- the above-mentioned precursor fiber bundle was subjected to a flameproofing treatment at a stretch rate of ⁇ 5.9% for 70 minutes in a heated air circulation type flameproofing furnace at 220 to 260 ° C. to obtain a flameproofed fiber bundle.
- the obtained flame resistant fiber bundle was further pre-carbonized in a nitrogen atmosphere at 700 ° C. and an elongation rate of + 3%, but yarn breakage frequently occurred in the pre-carbonization process because of insufficient flame resistance. Therefore, when the flameproofing treatment was performed for 300 minutes at an elongation rate of -5.9%, it was possible to pass the process without breakage in the pre-carbonization process.
- carbonization was performed in a nitrogen atmosphere at 1,300 ° C. and an elongation of ⁇ 4.0% for 3.2 minutes to obtain a carbon fiber bundle. Conditions other than these were obtained in the same manner as in Example 29 to obtain a carbon fiber bundle.
- Each evaluation result is shown in Table 7.
- the fiber bundle to which the oil agent treatment liquid was applied was dried using a heating roll, and dry-heat-stretched 1.3 times between heating rolls whose rotation speed was adjusted to a predetermined condition.
- the total draw ratio from the swollen yarn at this time was 7.3 times.
- the moisture content was adjusted by applying water to the fiber bundle with a touch roll to obtain a precursor fiber bundle having a single fiber fineness of 2.5 dtex.
- the above-mentioned precursor fiber bundle was subjected to a flameproofing treatment at a stretch rate of ⁇ 5.9% for 70 minutes in a heated air circulation type flameproofing furnace at 220 to 260 ° C. to obtain a flameproofed fiber bundle.
- An attempt was made to pre-carbonize the obtained flame-resistant fiber bundle in a nitrogen atmosphere at 700 ° C. and an elongation rate of + 3%, but yarn breakage frequently occurred in the pre-carbonization process because of insufficient flame resistance. . Therefore, when the flameproofing treatment was performed for 300 minutes at an elongation rate of -5.9%, it was possible to pass the process without breakage in the pre-carbonization process.
- Example 25 A fiber bundle (swelling yarn) was obtained by employing the spinning conditions shown in Table 7. Subsequently, this fiber bundle was stretched 4.8 times at the same time as washing with water, and an oil treatment solution was applied to the fiber bundle in the same manner as in Example 29. The fiber bundle was dried using a hot roll and subjected to steam stretching by 2.7 times with a steam stretching machine. The total draw ratio from the swollen yarn at this time was 12.7 times. Except these conditions, a precursor fiber bundle having a single fiber fineness of 1.2 dtex was obtained in the same manner as in Example 29.
- the precursor fiber bundle was subjected to a flame resistance treatment in a hot air circulation type flame resistance furnace at 220 to 260 ° C. in heated air at an elongation rate of ⁇ 6.0% for 60 minutes to obtain a flame resistant fiber bundle.
- the obtained flame-resistant fiber bundle was pre-carbonized in a nitrogen atmosphere at 700 ° C. and an elongation rate of + 3% for 1.6 minutes, and subsequently in a nitrogen atmosphere at 1,250 ° C. and an elongation rate of ⁇ 4.6%.
- Carbonization treatment was performed for 4 minutes to obtain a carbonized fiber bundle.
- Carbon fiber bundles were obtained in the same manner as in Example 29 except for these conditions. And the evaluation result of Table 7 was obtained.
- Example 26 A fiber bundle (swelling yarn) was obtained by employing the spinning conditions shown in Table 7. Subsequently, this fiber bundle was stretched 5.9 times simultaneously with washing with water, and an oil treatment solution was applied to the fiber bundle in the same manner as in Example 29. This fiber bundle was dried using a hot roll and subjected to steam drawing 2.1 times with a steam drawing machine. The total draw ratio from the swollen yarn at this time was 12.5 times. Except these conditions, a precursor fiber bundle having a single fiber fineness of 1.2 dtex was obtained in the same manner as in Example 29.
- Example 27 Conditions other than the spinning conditions shown in Table 7 were the same as in Example 29 to obtain a precursor fiber bundle having a single fiber fineness of 2.5 dtex. Using this precursor fiber bundle, an attempt was made to produce carbon fibers by the same method as in Example 29. However, the convergence of the fiber bundle was lowered, and the passing through the firing process was worsened when producing the carbon fiber bundle. The carbon fiber bundle could not be produced stably.
- the PAN-based carbon fiber 1 was produced under the same conditions as in Comparative Example 1 except that the number of filaments was changed to 50000.
- the PAN-based carbon fiber 2 was produced under the same conditions as in Example 3.
- the PAN-based carbon fiber 3 was produced under the same conditions as in Example 15 except that the number of filaments was changed to 12000.
- the PAN-based carbon fiber 4 was produced under the same conditions as in Comparative Example 12.
- the PAN-based carbon fiber 5 was produced under the same conditions as in Comparative Example 14, except that the number of filaments was 12000 and the fineness of the carbon fiber precursor was changed to 4.5 dtex.
- Epoxy resin jER828 Liquid bisphenol A type epoxy resin (Mitsubishi Chemical Corporation), AER4152: Oxazolidone type epoxy resin (Asahi Kasei E-Materials).
- Vinylec E Polyvinyl formal resin (manufactured by Chisso Corporation).
- DCMU Urea compound DCMU 99 (Hodogaya Chemical Co., Ltd.), PDMU: Urea compound Omicure 94 (manufactured by PiT i Japan).
- DICY Dicyandiamide DICY 15 (manufactured by Mitsubishi Chemical Corporation).
- Each carbon fiber bundle (any of PAN-based carbon fibers 1 to 5) is wound around a resin-coated surface of the obtained resin film T with a drum wind, and another resin film T is coated on the resin-coated surface with the coated surface below.
- the carbon fiber bundle is sandwiched between the carbon fiber bundles and impregnated with resin between the fibers of the carbon fiber bundle, so that the carbon fiber basis weight is 202 to 213 g / m 2 and the resin content is 32.0 to 34.3 mass.
- % Unidirectional prepreg. Table 9 shows the evaluation results.
- test piece was prepared by cutting it into a length (0 ° direction) of 80 mm and a width of 12.7 mm with a wet diamond cutter. did.
- the obtained test piece was subjected to a 0 ° compression test in accordance with SACMA 1R-94 using an Instron universal testing machine Instron 5882 and analysis software Bluehill, and 0 ° compressive strength and elastic modulus were calculated. Table 9 shows the evaluation results.
- the composite panel (10ply) obtained above was cut into dimensions of 127 mm in length (0 ° direction) and 12.7 mm in width (90 ° direction) with a wet diamond cutter to prepare a test piece.
- the composite panel (10ply) obtained above was cut into dimensions of 25.4 mm in length (0 ° direction) and 50 mm in width (90 ° direction) with a wet diamond cutter to prepare a test piece.
- Example 32 “PAN-based carbon fiber 3” having a fineness of 2.01 dtex was used. Both strength and elastic modulus in the 0 ° compression test were high values. The strength retention of 10 ply composite panel strength with respect to 6 ply molded body strength in the 0 ° compression test was high (98.7%).
- Comparative Example 31 This comparative example is an example in which the resin viscosity of comparative example 30 is increased. Although the flow index decreased to 1941 Pa ⁇ 1 , the strength of the 10 ply composite panel strength in the 0 ° compression test showed a low value, and the strength retention of the 10 ply composite panel strength to the 6 ply composite panel strength in the 0 ° compression test was slightly improved. Even so, the strength retention was low (87.1%).
- Comparative Example 32 This comparative example is an example in which the curing rate of comparative example 30 is increased. Although the flow index decreased to 2123 Pa ⁇ 1 , the strength of 10 ply composite panel strength in the 0 ° compression test showed a low value, and the strength retention of 10 ply composite panel strength with respect to 6 ply composite panel strength in the 0 ° compression test was slightly improved. Nevertheless, the strength retention was low (88.0%).
- the precursor fiber bundle having a large single fiber fineness and excellent productivity can be uniformly processed without reducing the productivity in the flameproofing treatment process, and further, the single fiber entanglement in the fiber bundle can be performed. And a high-quality carbon fiber bundle excellent in spreadability.
- the carbon fiber bundle of the present invention is used for aerospace materials such as airplanes and rockets, sports equipment materials such as tennis rackets, golf shafts and fishing rods, transportation machinery materials such as ships and automobiles, mobile phone and personal computer housings. It can be used in many fields including materials for electronic parts such as body and materials for fuel cell electrodes.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- General Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Inorganic Fibers (AREA)
- Reinforced Plastic Materials (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
特許文献6及び7の技術では、単繊維繊度が1.2dtex程度の小さい炭素繊維前駆体繊維束については、高速焼成を行っても耐炎化繊維の断面二重構造を抑制することは出来る。しかしながら、単繊維繊度が2.5dtex程度の大きい炭素繊維前駆体繊維束については、断面二重構造を抑制することが出来ない場合があった。
但し、真円度は下記式(1)にて求められる値であって、S及びLは、単繊維の繊維軸に垂直な断面をSEM観察し画像解析することにより得られる、単繊維の断面積及び周長である。
真円度=4πS/L2・・・(1)
等速昇温発熱曲線の230℃以上260℃以下の発熱速度を積分して求めた熱量Jaが100kJ/kg以上250kJ/kg以下、及び、260℃以上290℃以下の発熱速度を積分して求めた熱量Jbが550kJ/kg以上1050kJ/kg以下。
1)前記ポリアクリロニトリル系共重合体をジメチルホルムアミドに、質量濃度で25%となるよう溶解させ、共重合体溶液を調製する。
2)該共重合体溶液をガラス板上に塗布する。
3)該共重合体溶液を塗布したガラス板を、空気中120℃で6時間乾燥し、ジメチルホルムアミドを蒸発させて、20μm以上40μm以下の範囲で厚みが一定のフィルムとする。
4)得られたフィルムを、空気中240℃で60分、さらに空気中250℃で60分熱処理することにより耐炎化処理して、耐炎化フィルムを得る。
5)得られた耐炎化フィルムを樹脂包埋した後に研磨し、その研磨した耐炎化フィルムの表面に対して垂直な断面を、蛍光顕微鏡を用いて倍率1500倍で観察する。
6)該断面において酸化が進んだ部分は相対的に暗い層として、酸化が進んでいない部分は相対的に明るい層として観察されるので、研磨した耐炎化フィルム表面から、暗い層と明るい層との境界までの距離を1つの断面上で少なくとも5点計測し、更に3つの断面について同様の測定を行い、その算術平均を酸化深さDe(μm)とする。
1)単繊維繊度が2.0dtex以上5.0dtex以下、
2)熱流束型示差走査熱量計を用いた測定により得られる215~300℃の単位質量あたりの発熱量が3200kJ/kg以上(ただし、熱流束型示差走査熱量計を用いた測定における昇温速度は、2℃/min、雰囲気は空気。)、及び
3)固体1H-NMRスペクトル(測定温度160℃)の半値幅が、10.0kHz以上14.5kHz以下。
1)サンプルの作製;
長さ5cmに切断した炭素繊維束をエポキシ樹脂(エポマウント主剤:エポマウント硬化剤=100:9(質量比))に包埋し、2cmに切断して横断面を露出させ、鏡面処理する。
2)観察面のエッチング処理;
更に、繊維の外形を明瞭にするために、サンプルの横断面を次の方法でエッチング処理する。
・使用装置:日本電子(株)JP-170 プラズマエッチング装置、
・処理条件:(雰囲気ガス:Ar/O2=75/25、プラズマ出力:50W、真空度:約120Pa、処理時間:5min)。
3)SEM観察;
前記1)及び2)により得られたサンプルの横断面を、SEM(PHILIPS FEI-XL20)を用いて観察し、画面上に5個以上の繊維断面が写っている写真を任意に5枚撮影する。
4)炭素繊維束の単繊維断面の直径測定;
各サンプルについて5枚のSEM写真から任意に20個、ただし、1枚の写真から3個以上の単繊維断面を選んで、画像解析ソフトウェア(日本ローパー(株)製、製品名:Image-Pro PLUS)を用いて繊維断面の外形をトレースし、断面の長径(最大フェレ径)dを計測する。選んだ単繊維断面全ての長径の平均値を、炭素繊維束の単繊維の直径Diとする。
本発明の炭素繊維前駆体アクリル繊維束(以下「前駆体繊維束」という場合がある)を構成するポリアクリロニトリル系共重合体(以下「共重合体」という場合がある)中のアクリロニトリル単位の含有量は、95~99モル%である。95モル%以上であれば、アクリロニトリル単位の共重合率の低下が炭素繊維の性能低下をもたらすことがない。一方、上限の99モル%は共重合成分の必要量から規定されるものである。
本発明の共重合体は、アクリロニトリル単位と(メタ)アクリル酸ヒドロキシアルキル単位を含有するが、必要に応じて「他のモノマー単位」を含有してもよい。
他のモノマー単位の原料となる「他のモノマー」としては、アクリロニトリルと共重合可能なビニル系モノマーが好ましい。具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ヘキシル等の(メタ)アクリル酸エステル類;塩化ビニル、臭化ビニル、塩化ビニリデン等のハロゲン化ビニル類;(メタ)アクリル酸、イタコン酸、クロトン酸等の酸類及びそれらの塩類;マレイン酸イミド、フェニルマレイミド、(メタ)アクリルアミド、スチレン、α-メチルスチレン、酢酸ビニルなどが挙げられる。これらは1種単独で用いてもよく、2種以上を併用してもよい。
本発明の共重合体の湿熱下融点は160~175℃であることが好ましい。湿熱下融点が160℃以上であれば、前駆体繊維束における単繊維間の接着を抑制することができ、得られる炭素繊維束の品位、力学物性の低下を抑制することができる。また、湿熱下融点が175℃以下であれば、例えば、紡糸工程中の乾燥緻密化糸をスチーム延伸する際に、より高温すなわちより高圧力のスチームが不要となり、従って高圧力のスチーム下で前駆体繊維束が上下動等することによって発生する毛羽立ちや擦過などを抑えることができるので、得られる炭素繊維束の品位や力学特性の低下を抑制することが出来る。
本発明の共重合体の水接触角は、40°以上70°以下であることが好ましい。共重合体の水との接触角が70°以下であれば、共重合体から前駆体繊維束を形成する際の紡糸工程、特に凝固工程において、紡糸原液中の有機溶媒と、凝固浴液の交換が緩やかに行われ、前駆体繊維束の緻密性を高めやすくなる。また共重合体と水との接触角が40°以上であれば、共重合体の親水性が適正に保たれ、紡糸工程、特に凝固工程において、隣接する繊維間の融着が起こることなく効率良く凝固を行うことが出来る。これらの観点から、共重合体と水との接触角は55°以上65°以下が好ましく、58°以上62°以下がより好ましい。
本発明の共重合体から得られるフィルムの耐炎化処理時の酸化深さDeは、焼成工程、特に耐炎化工程において、本発明の共重合体より得られる前駆体繊維束の耐炎化反応性の指標となる。すなわち、酸化深さDeが大きいほど、耐炎化工程において、前駆体繊維束の単繊維内部への酸素拡散が十分に行われ、均一な耐炎化処理が可能となることを示すものである。したがって、酸化深さDeは、耐炎化反応における酸化反応の観点から、4.0μm以上6.0μm以下であることが望ましい。
共重合体の製造方法は、特に限定されず、溶液重合、懸濁重合など公知の方法を採用することができる。また、重合開始剤は、特に限定されず、アゾ系化合物、有機過酸化物、また、過硫酸/亜硫酸や塩素酸/亜硫酸のアンモニウム塩などのレドックス触媒を用いることができる。
本発明の前駆体繊維束は、単繊維繊度が1.5dtex以上5.0dtex以下であって単繊維の繊維軸に垂直な断面の形状が真円度0.90以下である。以下これらの前駆体繊維束を適宜『第一群の発明』という場合がある。
前駆体繊維束の単繊維繊度が1.5dtex以上であれば、前駆体繊維束内部における単繊維同士の接触部分があまり多くなることがなく、単繊維同士がからみ合い難く、炭素繊維束になった際に炭素繊維束の広がり性を保持できる。一方、前駆体繊維束の単繊維繊度が5.0dtex以下であれば、耐炎化工程において断面二重構造が顕著とならず、均一な品質の炭素繊維束を安定に生産できる。単繊維繊度は2.0dtex以上が好ましく、2.5dtex以上がさらに好ましい。また単繊維繊度は4.5dtex以下が好ましく、3.0dtex以下がさらに好ましい。
本発明の前駆体繊維束の単繊維の断面形状は、真円度が0.90以下である。また断面形状は空豆型であることが好ましい。断面形状が真円度0.90以下の空豆型であれば、耐炎化処理時に前駆体繊維束を構成する単繊維内部への酸素拡散が不足することなく、耐炎化反応が十分に進行する。その結果、炭素化工程での毛羽が抑えられ、工程通過性が良好で、得られる炭素繊維束の強度や弾性率を適正に維持できる。
真円度=4πS/L2・・・(1)
また本発明の前駆体繊維束は、熱流束型示差走査熱量計を用いて100ml/分(基準:30℃、0.10MPa)の空気気流中、昇温速度10℃/分で測定したときの30℃以上450℃以下の等速昇温発熱曲線が以下の条件を満たすものである。以下これらの前駆体繊維束を『第二群の発明』という場合がある。
(1)等速昇温発熱曲線の230℃以上260℃以下の発熱速度を積分して求めた熱量Jaが100kJ/kg以上250kJ/kg以下、かつ、
(2)等速昇温発熱曲線の260℃以上290℃以下の発熱速度を積分して求めた熱量Jbが550kJ/kg以上1050kJ/kg以下。
上述の等速昇温発熱曲線は、前駆体繊維束中で耐炎化反応が進行する時に発生する熱量を示している。
本発明の前駆体繊維束は、熱流束型示差走査熱量計(以下、「DSC」と記載することがある)を用いて測定される215~300℃の単位質量あたりの発熱量が3200~3800kJ/kgであり、かつ、固体1H-NMRにおいて160℃で観測されるスペクトルの半値幅が10kHz以上14.5kHz以下である。以下これらの前駆体繊維束を『第三群の発明』という場合がある。
ただし、発熱量は以下の測定条件で得られる値である。
測定雰囲気:空気、
ガス流量:100ml/min、
昇温条件:20℃/min(室温~210℃),2℃/min(210~300℃)、
発熱量は、215℃の熱流量の値を0として、215~300℃までの熱流量値を時間で積分して得る。単位質量あたりの発熱量は、発熱量を測定に供したサンプル質量で除して得る。
本発明の前駆体繊維束は、例えば、上述のポリアクリロニトリル系共重合体を溶剤に溶解して得た共重合体濃度15~30質量%の紡糸原液を、濃度30~70質量%、温度20~50℃の凝固浴中に吐出して凝固糸を得、この凝固糸を2.5倍以上6倍以下で湿熱延伸することによって製造することができる。以下紡糸方法を説明する。
上述の共重合体を溶剤に公知の方法で溶解して、紡糸原液とする。溶剤としては、ジメチルアセトアミド、ジメチルスルホキシド、ジメチルホルムアミドなどの有機溶剤や、塩化亜鉛、チオシアン酸ナトリウムなどの無機化合物の水溶液を用いることができる。前駆体繊維中に金属を含有せず、また、工程が簡略化される点で有機溶剤が好ましく、その中でも凝固糸及び湿熱延伸糸の緻密性が高いという点で、ジメチルアセトアミドを用いることが好ましい。
紡糸原液は、緻密な凝固糸を得るため、また、適正な粘度、流動性を有するように、ある程度以上の共重合体濃度を有することが好ましい。紡糸原液における共重合体の濃度は、15~30質量%の範囲にあることが好ましく、より好ましくは18~25質量%の範囲である。
次に、得られた凝固糸に対して湿熱延伸を行う。これにより繊維の配向をさらに高めることができる。湿熱延伸は、具体的には、凝固糸を、水洗に付しながらの延伸、あるいは熱水中での延伸によって行われる。水洗と同時の延伸は紡糸工程の簡略化、効率化の観点から好ましく、熱水中での延伸は生産性の観点から好ましい。湿熱延伸における延伸倍率は2.5倍以上が好ましく、3倍以上が更に好ましい。2.5倍よりも低いと、繊維の配向を高める効果が不十分となりやすい。延伸倍率の上限は特に限定されないが、紡糸工程の安定性の観点から6倍以下が好ましい。
次に、スチーム延伸あるいは乾熱延伸を行った繊維束に対して、必要に応じてタッチロールで水分率の調整を行った後、公知の方法でエアーを吹き付けて交絡処理を施し、前駆体繊維束を得る。本発明において交絡処理は必須ではないが、前駆体繊維束のフィラメント同士に交絡を付与する事で、集束性を付与して1本のトウの形態を保持する繊維束を得ることができる。また繊維束をばらけ難くして、焼成工程の通過性を向上させることができる。
水分率(質量%)=(W-W0)×100/W0
W:ウエット状態にある繊維束の質量、
W0:ウエット状態にある繊維束を105℃で2時間、熱風乾燥機で乾燥した後の質量。
次に、本発明の炭素繊維の製造方法を説明する。まず前駆体繊維束は、酸化性雰囲気下において、240℃以上300℃以下の温度で90分以下の時間で耐炎化処理されて、耐炎化繊維束とされる。なお、本発明において、「酸化性雰囲気下」とは、二酸化窒素、二酸化硫黄、酸素等の酸化性物質を含有する空気中を意味する。
耐炎化処理の温度が240℃以上であれば耐炎化反応を暴走させること無く、効率的に耐炎化処理を行うことができる。また、300℃以下であれば前駆体繊維のポリアクリロニトリル骨格を熱分解させることなく耐炎化処理することが可能であり、処理時間90分以下で耐炎化繊維束の密度を1.35~1.43g/cm3まで上げることができる。
耐炎化処理時間は、10~90分間であることが好ましい。耐炎化処理時間が10分間以上であれば、前駆体繊維束を構成する単繊維内部への酸素の拡散を充分に行うことが出来る。また、耐炎化処理時間が90分間以下であれば、炭素繊維束の製造工程において耐炎化処理工程が生産性を損なう原因となることなく、効率よく炭素繊維束を製造することが可能である。更に、炭素繊維束の性能及び生産性向上の観点から、耐炎化処理時間は、30~70分間がより好ましい。
耐炎化処理によって得られる耐炎化繊維束の密度は、1.35~1.43g/cm3であることが好ましい。1.35g/cm3以上であれば、炭素繊維束の収率を低下させること無く炭素繊維を製造することが可能である。一般的に、耐炎化繊維の密度が高いほど得られる炭素繊維束の収率は向上するが、炭素繊維の性能は低下することが知られており、耐炎化繊維束の密度が1.43g/cm3以下であれば、炭素繊維の性能低下を抑えつつ、得られる炭素繊維束の収率を向上することが可能である。得られる炭素繊維の性能保持と収率向上の観点から、耐炎化繊維束の密度は、1.38~1.41g/cm3がより好ましい。
本発明の前駆体繊維束を耐炎化処理する工程において、(メタ)アクリル酸ヒドロキシアルキル単位のカルボン酸ヒドロキシアルキル基(カルボン酸エステル基)が熱分解してカルボン酸基になるまでの間、耐炎化反応の進行が抑制される。これにより、酸素が単繊維の内部にまで拡散するのに十分な時間を確保した後、240℃以上の高温において、メタクリル酸ヒドロキシアルキル単位のカルボン酸ヒドロキシアルキル基の熱分解が起こってカルボン酸基になると、240℃以上の高温から素早く耐炎化処理を行うことが可能となる。
耐炎化処理後、炭素化処理前に、得られた耐炎化繊維束を不活性ガス中、最高温度が550℃以上800℃以下の温度で処理する前炭素化処理を行うこともできる。
得られた耐炎化繊維束を不活性ガス中、800℃以上2000℃以下の温度で炭素化処理することによって炭素繊維束を製造することができる。さらにこの炭素繊維を不活性ガス中、2500℃以上~2800℃以下程度の高温で処理することによって、黒鉛繊維を製造することもできる。炭素化処理によって得られる炭素繊維束は、単繊維の直径が8μm以上で、単繊維の繊維軸に垂直な断面の形状は真円度0.90以下である。断面形状は空豆型であることが好ましい。
単繊維の繊維軸に垂直な断面を走査型電子顕微鏡(SEM)により観察し、得られた画像について画像解析ソフトウェア(日本ローパー(株)製、製品名:Image-Pro PLUS)を用いて断面の長径(最大フェレ径)を測定する。この断面の長径の平均値を直径Diとした。直径Diは、8~20μmであることが好ましく、10~15μmであることが特に好ましい。尚、直径Diの測定方法は後述する。
本発明の製造方法で得られる炭素繊維束の単繊維の断面形状は、炭素繊維束の単繊維の繊維軸に垂直な断面の真円度で表される。真円度は、前駆体繊維束の真円度と同様に式(1)で定義される。
本発明の炭素繊維束は、炭素繊維の表面に繊維の長手方向に延びる皺が存在することが好ましい。繊維の長手方向に延びる皺は、炭素繊維を強化材とする繊維強化樹脂材料の機械特性の発現に非常に重要な役割を果たすものである。これは、炭素繊維と樹脂の界面相の形成とその特性に直接係わるものであり、繊維強化樹脂材料を構成する3つの要素である繊維、マトリックス樹脂および界面相の一つを特徴づけるものであるからである。単繊維の表面の皺とは、ある方向に一定以上の長さを有する凹凸の形態を指すものである。ここで一定以上とは、0.6μmから1.0μm程度である。またその方向には特に限定はなく、繊維軸方向に平行、あるいは垂直、あるいはある角度を有するものでもよい。炭素繊維束の一般的な製造方法から、通常の炭素繊維表面には繊維軸方向にほぼ平行な皺が存在する。
本発明の炭素繊維束は、ストランド引張強度が3000MPa以上であることが好ましい。ストランド引張強度が著しく低い場合、構造材など現在炭素繊維が使用されているほとんどの分野において、使用できないものとなってしまう。よって、かかる引張強度は3500MPa以上であることがより好ましく、4000MPa以上であれば風車や自動車、建材等を中心とする産業用途においては、既存のほとんどの分野への適用が可能となる。
本発明の炭素繊維束は、サイジング処理工程の前に、表面処理が行われても良い。例えば、電解液中で電解酸化処理を施したり、気相または液相での酸化処理を施したりすることによって、複合材料における炭素繊維とマトリックス樹脂との親和性や接着性を向上させることが好ましい。
炭素繊維束にサイジング処理する工程では、サイジング処理と乾燥処理を行う。サイジング処理の方法は特に限定されず、炭素化繊維束に所望のサイジング剤を付与することができれば良い。例えば、ローラーサイジング法、ローラー浸漬法およびスプレー法等を挙げることができる。
本発明炭素繊維束は以下の一方向性繊維強化織物に好適に使用可能である。本発明の一方向性繊維強化織物は、炭素繊維束が縦方向に配列された目付が、300~1,000g/m2であることが好ましい。一般に繊維織物の目付が200g/m2程度に小さければ、繊維間空隙が大きくなるため、樹脂の含浸性は良くなる。一方、繊維織物の目付が大きいと繊維間空隙が小さくなり、樹脂の流動性が悪くなり含浸不良や含浸に多くの時間が掛かることになる。加えて成形加工を施す際に繊維織物の目付が小さい織物を多数積層するよりも、繊維織物の目付が大きい織物を少数積層する方がコスト低減を図ることができるため、積層を必要とする成形加工では、できる限り目付が大きい繊維織物を用いた方が有利である。本発明の炭素繊維束を使用することで繊維織物の目付が300~1,000g/m2の範囲にあっても、樹脂の含浸性が良好であり、かつ長い含浸時間を要しない繊維織物が得られる。
本発明のCFRPの成形法を図4を用いて説明する。図4において、成形型11に離型剤を塗布し、その上に繊維基材として本発明の炭素繊維織物12を所定の方向に所定の枚数積層する。さらにその上にピールプライ15を積層し、その上に繊維基材の上面に樹脂を拡散させる為の媒体14を置く。また、繊維基材の繊維軸方向の両端に樹脂を堆積させるスパイラルチューブ13を配置させ、真空ポンプの吸引口18を取り付ける。これら全体をバッグフィルム16で覆い、空気が漏れないようにバッグフィルム16の周囲をシール材17で成形型11に接着する。樹脂タンクから注入される樹脂の吐出口20をスパイラルチューブ13に連結させる。樹脂タンク(不図示)には、硬化剤を所定量入れた常温でシロップ状の常温硬化型の熱硬化性樹脂を入れておく。なお、使用する樹脂の粘度により樹脂含浸性の影響は大きい。通常、RTM成形や真空バッグ成形では樹脂の流動性の良い低粘度品が用いられる。樹脂注入時の粘度として500mPa・s以下が好ましく、300mPa・s以下がより好ましい。
また本発明は、炭素繊維束とマトリックス樹脂からなる炭素繊維プリプレグに関する。本発明の炭素繊維プリプレグの炭素繊維は、特には限定されないが、PAN系炭素繊維、PITCH系炭素繊維が挙げられる。望ましくはPAN系炭素繊維である。単繊維繊度が1.2~2.4dtexのものが用いられ、特に、本発明の前記炭素繊維束が好適に用いられる。単繊維繊度が1.2dtex以上であると成形物の厚みが増した時の圧縮強度保持率が高くなる。また単繊維繊度が2.4dtex以下であると成形物の機械的強度が良好である。炭素繊維束は、同じプリプレグについて1種類のものを使用しても良く、複数種類のものを規則的にまたは不規則に並べて使用してもかまわない。通常、特定方向に比強度、比弾性率が高いことを要求される用途には単一方向プリプレグが最も適しているが、あらかじめ長繊維マットや織物などのシート形態に加工したものを使用することも可能である。
マトリックス樹脂は、特には限定されないが、フロー指数が5000Pa-1以上であることが好ましい。マトリックス樹脂としては、エポキシ樹脂、ポリエステル樹脂、フェノール樹脂、ポリイミド樹脂、マレイミド樹脂、アセチレン末端を有する樹脂、ビニル末端を有する樹脂、シアン酸エステル末端を有する樹脂等が挙げられる。好ましくはエポキシ樹脂である。
エポキシ樹脂の硬化剤は、アミン型、酸無水物、フェノール、メルカプタン型、ルイス酸アミン錯体、オニウム塩、イミダゾールなどが用いられるが、エポキシ樹脂を硬化させうるものであればどのような構造のものでも良い。好ましくは、ジアミノジフェニルメタン、ジアミノジフェニルスルフォンのような芳香族アミン、イミダゾール誘導体、ジシアンジアミド、テトラメチルグアニジン、チオ尿素付加アミンおよびそれらの異性体、変成体である。特に好ましくはジシアンジアミドである。
共重合体の組成(各単量体単位の比率(モル%))は、1H-NMR法により、以下のようにして測定した。溶媒としてジメチルスルホキシド-d6溶媒を用い、共重合体を溶解させ、NMR測定装置(日本電子社製、製品名:GSZ-400型)により、積算回数40回、測定温度120℃の条件で測定し、ケミカルシフトの積分比から各単量体単位の比率を求めた。
共重合体0.5gを100mlのジメチルホルムアミド中に分散し、75℃で40分間保持することで、共重合体溶液を得た。この溶液の粘度ηと溶媒の粘度η0をウベローデ型粘度計を用いて25℃で測定し、次式にて比粘度ηspを算出した。
ηsp=(η-η0)/5η0
共重合体を、目開き0.5mmの篩いに通し、5mgを精秤してエスアイアイ・ナノテクノロジー社製の密封試料容器Ag製15μl(DSC200系用)(300℃/30分Air中にて熱処理済)に入れ、純水5μlを加え密封した。セイコーインスツルメンツ(株)製DSC/220を用いて、10℃/分の昇温速度で、室温から230℃まで熱流束型示差走査熱量計による測定を実施し、150℃~200℃付近に現れる吸熱ピークの頂点に対応する温度を読取り、これを湿熱下融点Tm(℃)とした。
共重合体をジメチルアセトアミドに溶解させて、質量濃度21%の共重合体溶液を調製し、この共重合体溶液をガラス板上に、一定の厚みになるように塗布した。次に、この共重合体溶液を塗布したガラス板を、熱風乾燥機を用いて、空気中120℃で6時間乾燥し、溶媒を蒸発させて、厚み20~40μmのフィルムとした。このフィルムの表面に1μLの水を滴下し、接触角測定装置(協和界面科学社製、商品名:DM301)を用いて、滴下の3秒後から1秒間隔毎に、水接触角を5回測定し、その平均値θ’を求めた。さらに、水を滴下するフィルムの表面の位置を変えて、同様の操作を合計3回行い、3回の算術平均値を算出し、この算術平均値を共重合体の水接触角θとした。
共重合体をジメチルホルムアミドに溶解させて、質量濃度25%の共重合体溶液を調製し、この共重合体溶液をガラス板上に、一定の厚みになるように塗布した。次に、この共重合体溶液を塗布したガラス板を、熱風乾燥機を用いて、空気中120℃で6時間乾燥し、溶媒を蒸発させて、20~40μmの範囲で厚みが一定のフィルムとした。得られたフィルムを、熱風乾燥機を用いて、空気中240℃で60分、さらに空気中250℃で60分熱処理し、耐炎化処理を行った。得られた耐炎化フィルムを縦30mm、横10mmのサイズに切断して、エポキシ樹脂中に包埋し、耐炎化フィルムの横断面が露出するように研磨した。その研磨した耐炎化フィルム表面に対して垂直な断面を蛍光顕微鏡(商品名:MICROFLEX AFX DX)を用いて倍率1500倍で観察した。断面において酸化が進んだ部分は相対的に暗い層として、進んでいない部分は相対的に明るい層として観察されるので、フィルム表面から、暗い層と明るい層の境界までの距離を1つの断面上で少なくとも5点計測し、さらに、3つの断面について同様の測定を行い、その算術平均値を酸化深さDe(μm)とした。
単繊維繊度とは、繊維1本の10000m当りの重さである。前駆体繊維束の任意の箇所から長さ1mの繊維束を2本とり、各々の質量を測定し、これらの各値をフィラメント数(すなわち口金の孔数)で除した後、10000倍し、2本の繊維束の平均値を算出し、これを単繊維繊度とした。
(1)サンプルの作製
長さ200mm程度の前駆体繊維束(サンプル繊維)の長手方向の中心部付近に木綿糸を半巻きに引っかけ、木綿糸の両端を合わせて長さ約15mmのポリエチレン細管チューブ(三商(株)ヒビキ ポリエチレン細管 No.3)に通した。この時、サンプル繊維はチューブの端部分に止めておいた。次いで、サンプル繊維に静電気防止剤(三井物産プラスチックス(株)製、スタティサイド)をまんべんなく吹き付けた(約2秒間程度)。木綿糸を引いてサンプル繊維をチューブ内に導入し、サンプル繊維が入ったチューブをゴム板上で剃刀を用いて1~3mm程度にカットした。
SEM試料台にカーボン両面テープ(日新EM株式会社製、SEM用導電性カーボン両面テープ、幅8mm)を貼りつけ、その上に前記(1)により得られたサンプルチューブを繊維断面が真上になるように精密ピンセットを用いて貼りつけた。次いでSEM(PHILIPS FEI-XL20)を用いて観察し、画面上に5個以上の繊維断面が写っている写真を任意に5枚撮影した。
画像解析ソフトウェア(日本ローパー(株)製、製品名:Image-Pro PLUS)を用いて繊維断面の外形をトレースし、周長Lおよび面積Sを計測した。各サンプルについて5枚の写真から任意に20個、ただし、1枚の写真から3個以上の繊維断面を選んで計測し、LおよびSの平均値を求め、次式により真円度を算出した。
真円度=(4πS)/L2
前駆体繊維束の等速昇温発熱曲線は、熱流束型示差走査熱量計により、以下のようにして測定した。先ず、前駆体繊維束を4.0mmの長さに切断し、4.0mgを精秤して、エスアイアイ社製の密封試料容器Ag製50μl(商品名:P/N SSC000E030)中に詰め、エスアイアイ社製メッシュカバーCu製(商品名:P/N 50-037)(450℃/15分間、空気中で熱処理済)で蓋をした。次いで、熱流束型示差走査熱量計:エスアイアイ社製DSC/220を用いて、10℃/分の昇温速度、エアー供給量100ml/min(エアー供給量の基準:30℃、0.10MPa)の条件で、室温(30℃)から450℃まで測定した。得られた等速昇温発熱曲線の230℃以上260℃以下の発熱量を熱量Jaとし、260℃以上290℃以下の発熱量を熱量Jbとした。
前駆体繊維束を2.0mmの長さに切断し、約7.0mgをエスアイアイ社製のAl製オープンサンプルパン(商品名:P/N SSSC000E030 )中に詰め、エスアイアイ社製SUSメッシュカバー(商品名:P/N 50-038 )(450℃/15分間、空気中で熱処理済)で蓋をして、熱流量測定に供した。尚、サンプルパン、SUSメッシュ及び前駆体繊維束の質量は精密天秤を用いて100分の1mg単位まで秤量した。
市販の外径5mmのNMR用サンプル管を50mmに切断し作製したサンプル管に長手方向と繊維軸が一致するように隙間がないように前駆体繊維束をつめて測定に供した。サンプル管内の繊維サンプル長さは約6mmであった。装置はBruker Bio-Spin製 AVANCEII 300MHzマグネットを用いた。プローブはスタティックプローブを使用して繊維軸が磁場に対して垂直になるようにセットした。
測定温度:160℃、測定雰囲気:窒素、ハーンエコー法、90度パルス5μs、180度パルス10μs、積算回数:8回、繰り返し待ち時間:12s。
(1)サンプルの作製
長さ5cmに切断した炭素繊維束をエポキシ樹脂(エポマウント主剤:エポマウント硬化剤=100:9(質量比))に包埋し、2cmに切断して横断面を露出させ、鏡面処理した。
更に、繊維の外形を明瞭にするために、サンプルの横断面を次の方法でエッチング処理した。
・使用装置:日本電子(株)JP-170 プラズマエッチング装置、
・処理条件:(雰囲気ガス:Ar/O2=75/25、プラズマ出力:50W、真空度:約120Pa、処理時間:5min。)。
前記(1)及び(2)により得られたサンプルの横断面を、SEM(PHILIPS FEI-XL20)を用いて観察し、画面上に5個以上の繊維断面が写っている写真を任意に5枚撮影した。
各サンプルについて5枚のSEM写真から任意に20個、ただし、1枚の写真から3個以上の単繊維断面を選んで、画像解析ソフトウェア(日本ローパー(株)製、製品名:Image-Pro PLUS)を用いて繊維断面の外形をトレースし、断面の長径(最大フェレ径)dを計測した。選んだ単繊維断面全ての長径dの平均を、炭素繊維束の単繊維の直径Diとした。
画像解析ソフトウェア(日本ローパー(株)製、製品名:Image-Pro PLUS)を用いて繊維断面の外形をトレースし、周長Lおよび面積Sを計測した。各サンプルについて5枚の写真から任意に20個、ただし、1枚の写真から3個以上の繊維断面を選んで計測し、LおよびSの平均値を求め、次式により真円度を算出した。
真円度=(4πS)/L2
炭素繊維の物性(ストランド強度およびストランド弾性率)は、JIS R 7601に記載の方法に準じて測定した。
炭素繊維の単繊維を数本試料台上にのせ、両端を固定し、さらに周囲にドータイトを塗り測定サンプルとした。原子間力顕微鏡(セイコーインスツルメンツ社製、製品名:SPI3700/SPA-300)によりカンチレバー(シリコンナイトライド製)を使用してAFMモードにて測定を行った。単繊維の2~7μmの範囲を走査して得られた測定画像を二次元フーリエ変換にて低周波成分をカットしたのち逆変換を行い繊維の曲率を除去した。このようにして得られた平面画像の断面より皺の深さを5回定量し、その平均値を表面皺の深さとした。
炭素繊維束を一定張力下(0.075cN/dtex)、走行速度3.4m/minで金属ロール上を走行させた際のトウ幅をデジタル寸法測定器(キーエンス製 LS-7030M)で測定し開繊性の指標とした。
炭素繊維束の含浸性の評価について図3を用いて説明する。炭素繊維束5を30cmの長さで切り出して、白粉(タルク)をまぶし、炭素繊維束の一端をクリップ7で留めた。容器内にホルムアミド9を注入して、液面に対して炭素繊維束が垂直になるようにクリップで留めた側を下にする。クリップをホルムアミド中に沈めてゆき、クリップが液面より下になった時点で沈降を停止し、20分間静置させて炭素繊維束中にホルムアミドを含浸させた。20分間経過後に、ホルムアミドが含浸した高さを定規8で測定した。この操作を6回実施して平均値を求めて「上昇高さH」とした。上昇高さが高いほど含浸性は良好であることを示す。なお白粉(タルク)は、ホルムアミドの含浸高さの確認を容易にするために用いたものである。なお、本発明の炭素繊維束は、含浸高さが100mm以上であることが好ましい。
縦糸として本発明の炭素繊維束を用い、横糸として22.5texのガラス繊維(ユニチカグラスファイバー社製)に熱融着繊維(東レ株式会社製)を付着させた糸条を用い、レピア織機(津田駒製)を用いて、目付600g/m2の一方向性織物を製織した。得られた織物を縦500mm、横500mmの大きさにカットし、繊維軸方向を揃えて3枚積層した。この積層物(即ち、繊維基材)の上に、樹脂硬化後に除去するシート、いわゆるピールプライ(ナイロンタフタ♯15)を積層し、その上に繊維基材の全面に樹脂を拡散させる為の媒体(ポリエチレン製メッシュ材、AIRTECH GREENFLOE75)を置いた。
○:含浸時間が10分未満、
×:含浸時間が10分以上。
容量80リットルのタービン撹拌翼付きアルミニウム製重合釜(攪拌翼:240φ、55mm×57mmの2段4枚羽)に、脱イオン交換水が重合釜オーバーフロー口まで達するよう76.5リットル入れ、硫酸第一鉄(Fe2SO4・7H2O)を0.01g加え、反応液のpHが3.0になるように硫酸を用いて調節し、重合釜内の温度を57℃で保持した。
重合開始時の単量体の供給比(モル比)を表1または表2の値とした以外は、実施例1と同様の方法で共重合体A、B、CまたはF、Gを得た。尚、表1または表2中のHPMAはメタクリル酸2-ヒドロキシプロピル、またHEAはアクリル酸2-ヒドロキシエチルである。得られた共重合体の組成、比粘度、湿熱下融点、更に各々の共重合体より得られたフィルムの水接触角、及び、酸化深さDeを表1または表2に示した。
重合開始時の単量体の供給比(モル比)を表3または表4の値とした以外は、実施例1と同様の方法で共重合体A、B、DまたはEを得た。尚、表3または表4中のAAmはアクリルアマイド、MAAはメタクリル酸、またIBMAはメタクリル酸イソブチルである。得られた共重合体の組成、比粘度、湿熱下融点、更に各々の共重合体より得られたフィルムの水接触角、及び酸化深さDeを表3または表4に示した。
実施例1と同様にして製造されたAN単位98.0モル%、HEMA単位2.0モル%で、比粘度が0.21であるアクリル系共重合体Aをジメチルアセトアミドに溶解して、紡糸原液を重合体濃度21%、原液温度60℃に調整した。この紡糸原液を用いて湿式紡糸法により紡糸した。紡糸原液を紡出する凝固浴は、濃度45質量%、温度25℃のジメチルアセトアミド水溶液である。使用した紡糸口金のホール数は3000である。凝固浴中で凝固して得た凝固糸を、洗浄延伸、熱延伸してトータルで7.4倍延伸して前駆体繊維束Aを得た。前駆体繊維束Aの単糸繊維繊度は2.5dtexになるように吐出量を調節した。熱流束型示差走査熱量計による発熱量は3400kJ/kg、HーNMR半値幅は12.5kHzであった。
実施例16と同様にして製造された前駆体繊維束Aを熱風循環式耐炎化炉にて230℃~270℃の加熱空気中で、伸張率2%で90分間、耐炎化処理した。90分間で1.40g/cm3程度になるように耐炎化炉の温度を調節した。得られた耐炎化繊維の密度は、1.400であった。
凝固浴濃度と凝固浴温度を表5の値とし、得られる単繊維繊度を表5になるように吐出量を調節した以外は、実施例16と同様にして紡糸原液を調製して紡糸し、前駆体繊維束B~Iを得た。
得られた前駆体繊維束の単繊維繊度、熱流束型示差走査熱量計による発熱量、1H-NMR半値幅を表6に示した。
実施例15と同様にして製造されたAN単位98.5モル%、HEMA単位1.5モル%で、比粘度が0.21である共重合体Bを用いて、単繊維繊度が2.0dtexになるように吐出量を調整して、表5の凝固浴条件を使用した以外は、実施例16と同様の条件で、前駆体繊維束Jを得た。
AN単位97.0モル%、AAm単位2.6モル%、メタクリル酸単位0.4モル%、比粘度0.21であるアクリル系共重合体Dを用いて、実施例16と同様に紡糸原液を作製して、吐出量を調節して、表5に示す凝固浴条件で紡糸して、前駆体繊維束KおよびLを得た。得られた前駆体繊維束の単繊維繊度、熱流束型示差走査熱量計による発熱量、1H-NMR半値幅を表6に示した。そしてこの耐炎化繊維束を用いて、70分で耐炎化繊維の密度が1.35g/cm3程度になるように耐炎化温度を調節して、耐炎化処理を行ない、引き続き実施例16と同様の条件で、前炭素化処理、炭素化処理をして炭素繊維束を得た。評価結果を表6に示す。
アクリロニトリル、メタクリル酸2-ヒドロキシエチル、過硫酸アンモニウム-亜硫酸水素アンモニウムおよび硫酸鉄の存在下、水系懸濁重合により共重合し、アクリロニトリル単位/メタクリル酸2-ヒドロキシエチル単位=98.5/1.5(モル%)からなるアクリロニトリル系共重合体を得た。この共重合体をジメチルアセトアミドに溶解し、21質量%の紡糸原液を調製した。孔数24,000、孔直径60μmの紡糸口金(紡糸ノズル)を通して、濃度60質量%、温度35℃のジメチルアセトアミド水溶液からなる凝固浴中に吐出させ、紡糸口金面からの吐出線速度の0.32倍の速度で引き取ることで繊維束(膨潤糸条)を得た。
アクリロニトリル、メタクリル酸2-ヒドロキシエチル、過硫酸アンモニウム-亜硫酸水素アンモニウムおよび硫酸鉄の存在下、水系懸濁重合により共重合し、アクリロニトリル単位/メタクリル酸2-ヒドロキシエチル単位=98.0/2.0(モル%)としたこと以外は実施例29と同様にして炭素繊維束を得た。
表7に示す紡糸条件以外の条件は実施例29と同様にして単繊維繊度4.5dtexの前駆体繊維束を得た。
アクリロニトリル、アクリルアミド、及びメタクリル酸を、過硫酸アンモニウム-亜硫酸水素アンモニウムおよび硫酸鉄の存在下、水系懸濁重合により共重合し、アクリロニトリル単位/アクリルアミド単位/メタクリル酸単位=96/3/1(モル%)からなるアクリロニトリル系共重合体を得た。この共重合体を用いて実施例29と同様にして、紡糸原液の調製、紡糸、水洗、延伸、油剤処理を実施して、油剤処理液を繊維束に付与した。
表7に示す紡糸条件以外の条件は実施例29と同様にして単繊維繊度1.0dtexのPAN系前駆体繊維束を得、更に炭素繊維を製造し、表7の評価結果を得た。
表7に示す紡糸条件を採用して繊維束(膨潤糸条)を得た。ついでこの繊維束を水洗と同時に4.8倍に延伸し、さらに実施例29と同様にして油剤処理液を繊維束に付与した。この繊維束を熱ロールを用いて乾燥し、スチーム延伸機にて2.7倍にスチーム延伸をした。この時の膨潤糸条からの全延伸倍率は12.7倍であった。これら以外の条件は実施例29と同様にして、単繊維繊度1.2dtexの前駆体繊維束を得た。
表7に示す紡糸条件を採用して繊維束(膨潤糸条)を得た。ついでこの繊維束を水洗と同時に5.9倍に延伸し、さらに実施例29と同様にして油剤処理液を繊維束に付与した。この繊維束を熱ロールを用いて乾燥し、スチーム延伸機にて2.1倍にスチーム延伸した。この時の膨潤糸条からの全延伸倍率は12.5倍であった。これら以外の条件は実施例29と同様にして、単繊維繊度1.2dtexの前駆体繊維束を得た。
表7に示す紡糸条件以外の条件は実施例29と同様にして単繊維繊度2.5dtexの前駆体繊維束を得た。この前駆体繊維束を用いて、実施例29と同様の方法で炭素繊維を製造しようとしたが、繊維束の集束性が低下し、炭素繊維束を製造する際の焼成工程通過性が悪化し、炭素繊維束を安定して製造することができなかった。
<1.原料>
以下の実施例および比較例においては、原材料として下記のものを用いた。
(1-1.炭素繊維)
PAN系炭素繊維1(単繊維繊度:0.75dtex、真円度:0.70、直径Di:8.4μm、強度:4116MPa、弾性率:235GPa)、
PAN系炭素繊維2(単繊維繊度:1.24dtex、真円度:0.75、直径Di:11.9μm、強度:4226MPa、弾性率:229GPa)、
PAN系炭素繊維3(単繊維繊度:2.01dtex、真円度:0.73、直径Di:15.6μm、強度:3489MPa、弾性率:246GPa)、
PAN系炭素繊維4(単繊維繊度:1.21dtex、真円度:0.95、直径Di:9.6μm、強度:3989MPa、弾性率:227GPa)、
PAN系炭素繊維5(単繊維繊度:2.29dtex、真円度:0.95、直径Di:11.9μm、強度:3283MPa、弾性率:232GPa)。
PAN系炭素繊維1は、フィラメント数を50000に変更した以外は、比較例1と同条件で製造した。PAN系炭素繊維2は、実施例3と同条件で製造した。PAN系炭素繊維3は、フィラメント数を12000に変更した以外は、実施例15と同条件で製造した。PAN系炭素繊維4は、比較例12と同条件で製造した。PAN系炭素繊維5は、フィラメント数を12000にし、炭素繊維前駆体の繊度を4.5dtexに変更した以外は、比較例14と同条件で製造した。
jER828:液状ビスフェノールA型エポキシ樹脂(三菱化学社製)、
AER4152:オキサゾリドン型エポキシ樹脂(旭化成イーマテリアルズ社製)。
ビニレックE:ポリビニルホルマール樹脂(チッソ社製)。
DCMU:ウレア化合物 DCMU 99(保土ヶ谷化学社製)、
PDMU:ウレア化合物 オミキュア94(ピイ・テイ・アイ・ジャパン社製)。
DICY:ジシアンジアミド DICY 15(三菱化学社製)。
以下の実施例および比較例においては、下記の製造条件および評価条件等を採用した。
(2-1.エポキシ樹脂組成物の調製)
ニーダー中にエポキシ樹脂と熱可塑樹脂を所定量加え、混練しつつ160℃まで昇温し、160℃1時間混練することで透明な粘調液を得た。60℃まで混練しつつ降温させ、硬化助剤と硬化剤を所定量加え混練し、エポキシ樹脂組成物を得た。このエポキシ樹脂組成物の組成を表8に示した。
フロー指数の測定は、先に記載した方法によって実施した。
上記エポキシ樹脂組成物の調製で得られたエポキシ樹脂組成物を、フィルムコーターを用い、60℃において、樹脂目付50~55g/m2で離型紙上に塗布して、「樹脂フィルムT」を得た。
得られた樹脂フィルムTの樹脂塗布面上に各炭素繊維束(PAN系炭素繊維1~5のいずれか)をドラムワインドにて巻き付け、その上に別の樹脂フィルムTを、その塗布面が下側になるように置いて、炭素繊維束を挟み込み、炭素繊維束の繊維の間に樹脂を含浸させることで、炭素繊維目付202~213g/m2で樹脂含有率32.0~34.3質量%の一方向プリプレグを得た。評価結果を表9に示す。
得られた一方向プリプレグを、長さ(0°方向、繊維に平行方向)300mm、幅(90°方向、繊維直交方向)300mmにカットした。0°方向に揃えて6枚積層し、バギングした後、オーブンを用いて図6の硬化条件で真空バッグ成形を行い、コンポジットパネルを得た。評価結果を表9に示す。
得られた一方向プリプレグを、長さ(0°方向、繊維に平行方向)300mm、幅(90°方向、繊維直交方向)300mmにカットした。0°方向に揃えて10枚積層し、バギングした後、オーブンを用いて図5の硬化条件で真空バッグ成形を行い、コンポジットパネルを得た。
上記で得られたコンポジットパネルに前記コンポジットパネルと同じ材料で作成したタブを接着した後、湿式ダイヤモンドカッターにより長さ(0°方向)80mm、幅12.7mmの寸法に切断して試験片を作製した。得られた試験片にて、Instron社製万能試験機Instron5882と解析ソフトBluehillを用い、SACMA 1R-94準拠で0°圧縮試験を行い、0°圧縮強度、弾性率を算出した。評価結果を表9に示す。
上記で得られたコンポジットパネル(10ply)を湿式ダイヤモンドカッターにより長さ127mm(0°方向)、幅12.7mm(90°方向)の寸法に切断して試験片を作製した。得られた試験片を、Instron社製万能試験機Instron5565と解析ソフトBluehillを用い、ASTM D-790準拠(圧子R=5.0、L/D=40、クロスヘッドスピード5.26~5.52mm/分)で3点曲げ試験を行い、0°曲げ強度、0°曲げ弾性率を算出した。評価結果を表9に示す。
上記で得られたコンポジットパネル(10ply)を湿式ダイヤモンドカッターにより長さ25.4mm(0°方向)、幅50mm(90°方向)の寸法に切断して試験片を作製した。得られた試験片を、Instron社製万能試験機Instron5565と解析ソフトBluehillを用い、ASTM D-790準拠(圧子R=3.2、L/D=16、クロスヘッドスピード0.838~0.902mm/分)で3点曲げ試験を行い、90°曲げ強度、90°曲げ弾性率を算出した。評価結果を表9に示す。
上記で得られたコンポジットパネル(10ply)から湿式ダイヤモンドカッターにより試験片を作製し、ASTMD-2344に準拠して層間剪断強度を測定した。評価結果を表9に記す。
繊度が1.24dtexの「PAN系炭素繊維2」を用いた。0°圧縮試験における強度、弾性率共に高い値であった。0°圧縮試験における6ply成形体強度に対する10plyコンポジットパネル強度の強度保持率(=10ply成形体強度/6ply成形体強度×100)が高い値(97.6%)を示した。
繊度が2.01dtexの「PAN系炭素繊維3」を用いた。0°圧縮試験における強度、弾性率共に高い値であった。0°圧縮試験における6ply成形体強度に対する10plyコンポジットパネル強度の強度保持率が高い値(98.7%)を示した。
繊度が1.21dtexの「PAN系炭素繊維4」を用いた。0°圧縮試験における6plyコンポジットパネル強度の強度は、実施例31より低い値であり、使用できるレベルではなかった。
繊度が2.29dtexの「PAN系炭素繊維5」を用いた。0°圧縮試験における6plyコンポジットパネル強度の強度は、実施例32より低い値であり、使用できるレベルではなかった。
繊度が0.75dtexの「PAN系炭素繊維1」を用いた。0°圧縮試験における10plyコンポジットパネル強度の強度は低い値であり、使用できるレベルではなかった。また、0°圧縮試験における6ply成形体強度に対する10ply成形体強度の強度保持率が低い値(82.5%)を示した。
この比較例は、比較例30の樹脂粘度を上昇させた例である。フロー指数が1941Pa-1と低下し、0°圧縮試験における10plyコンポジットパネル強度の強度は低い値を示し、0°圧縮試験における6plyコンポジットパネル強度に対する10plyコンポジットパネル強度の強度保持率がやや向上したが、それでも強度保持率は低い値(87.1%)を示した。
この比較例は、比較例30の硬化速度を上昇させた例である。フロー指数が2123Pa-1と低下し、0°圧縮試験における10plyコンポジットパネル強度の強度は低い値を示し、0°圧縮試験における6plyコンポジットパネル強度に対する10plyコンポジットパネル強度の強度保持率がやや向上したが、それでも強度保持率は低い値(88.0%)を示した。
6:含浸高さ
7:クリップ
8:定規
9:ホルムアミド
10:アングル
11:成形型
12:炭素繊維織物
13:スパイラルチューブ
14:媒体
15:ピールプライ
16:バッグフィルム
17:シール材
18:真空ポンプの吸引口
19:バルブ
20:樹脂の吐出口
Claims (35)
- アクリロニトリル単位95~99モル%と(メタ)アクリル酸ヒドロキシアルキル単位1~5モル%のポリアクリロニトリル系共重合体からなり、単繊維繊度が1.5dtex以上5.0dtex以下、単繊維の繊維軸に垂直な断面の形状が真円度0.9以下である炭素繊維前駆体アクリル繊維束:
但し、真円度は下記式(1)にて求められる値であって、S及びLは、単繊維の繊維軸に垂直な断面をSEM観察し画像解析することにより得られる、単繊維の断面積及び周長である。
真円度=4πS/L2・・・(1) - 前記単繊維繊度が1.5dtex以上3.0dtex以下である請求項1に記載の炭素繊維前駆体アクリル繊維束。
- 前記単繊維の繊維軸に垂直な断面の形状が真円度0.7以上である請求項1または2に記載の炭素繊維前駆体アクリル繊維束。
- ポリアクリロニトリル系共重合体の湿熱下融点が160~175℃である請求項1または2に記載の炭素繊維前駆体アクリル繊維束。
- 熱流束型示差走査熱量計を用いて、30℃、0.10MPaにおいて100ml/分の空気気流中、昇温速度10℃/分で測定した30℃以上450℃以下の等速昇温発熱曲線が以下の条件を満たす炭素繊維前駆体アクリル繊維束:
等速昇温発熱曲線の230℃以上260℃以下の発熱速度を積分して求めた熱量Jaが100kJ/kg以上250kJ/kg以下、及び、260℃以上290℃以下の発熱速度を積分して求めた熱量Jbが550kJ/kg以上1050kJ/kg以下。 - アクリロニトリル単位が95.0モル%以上99.0モル%以下と、(メタ)アクリル酸ヒドロキシアルキル単位が1.0モル%以上5.0モル%以下とからなるポリアクリロニトリル系共重合体からなる請求項5に記載の炭素繊維前駆体アクリル繊維束。
- 単繊維繊度が1.5dtex以上5.0dtex以下である請求項6に記載の炭素繊維前駆体アクリル繊維束。
- 水接触角が40°以上70°以下である請求項6に記載の炭素繊維前駆体アクリル繊維束。
- 前記熱量Jaが160kJ/kg以下である請求項5~8のいずれかの一項に記載の炭素繊維前駆体アクリル繊維束。
- 前記ポリアクリロニトリル系共重合体の、以下の方法により得られる酸化深さDeが4.0μm以上6.0μm以下である請求項6~8のいずれかの1項に記載の炭素繊維前駆体アクリル繊維束:
1)前記ポリアクリロニトリル系共重合体をジメチルホルムアミドに、質量濃度で25%となるよう溶解させ、共重合体溶液を調製する。
2)該共重合体溶液をガラス板上に塗布する。
3)該共重合体溶液を塗布したガラス板を、空気中120℃で6時間乾燥し、ジメチルホルムアミドを蒸発させて、20μm以上40μm以下の範囲で厚みが一定のフィルムとする。
4)得られたフィルムを、空気中240℃で60分、さらに空気中250℃で60分熱処理することにより耐炎化処理して、耐炎化フィルムを得る。
5)得られた耐炎化フィルムを樹脂包埋した後に研磨し、その研磨した耐炎化フィルムの表面に対して垂直な断面を蛍光顕微鏡を用いて倍率1500倍で観察する。
6)該断面において酸化が進んだ部分は相対的に暗い層として、酸化が進んでいない部分は相対的に明るい層として観察されるので、該研磨した耐炎化フィルム表面から、暗い層と明るい層との境界までの距離を1つの該断面上で少なくとも5点計測し、更に3つの断面について同様の測定を行い、その算術平均を酸化深さDe(μm)とする。 - 以下の条件を満たす炭素繊維前駆体アクリル繊維束:
1)単繊維繊度が2.0dtex以上5.0dtex以下、
2)熱流束型示差走査熱量計を用いた測定により得られる215~300℃の単位質量あたりの発熱量が3200kJ/kg以上(ただし、熱流束型示差走査熱量計を用いた測定における昇温速度は、2℃/min、雰囲気は空気。)、及び
3)固体1H-NMRスペクトル(測定温度160℃)の半値幅が、10.0kHz以上14.5kHz以下。 - アクリロニトリル単位が95.0モル%以上99.0モル%以下と、(メタ)アクリル酸ヒドロキシアルキル単位が1.0モル%以上5.0モル%以下とからなるポリアクリロニトリル系共重合体からなる請求項11に記載の炭素繊維前駆体アクリル繊維束。
- 熱流束型示差走査熱量計を用いた測定により得られる215~300℃の発熱量が3300kJ/kg以上である請求項12に記載の炭素繊維前駆体アクリル繊維束。
- 固体1H-NMRスペクトル(測定温度160℃)の半値幅が、10.0kHz以上13.5kHz以下である請求項12に記載の炭素繊維前駆体アクリル繊維束。
- 請求項1、2、5~8及び11~14のいずれかの1項に記載の炭素繊維前駆体アクリル繊維束を、酸化性雰囲気下、220℃以上300℃以下の温度で30分以上90分以下の時間で耐炎化処理して、繊維密度が1.35g/cm3以上1.43g/cm3以下の耐炎化繊維束を得る耐炎化処理方法。
- 請求項1、2、5~8及び11~14のいずれかの1項に記載の炭素繊維前駆体アクリル繊維束を、酸化性雰囲気下、220℃以上300℃以下の温度で30分以上90分以下の時間で耐炎化処理して、繊維密度が1.35g/cm3以上1.43g/cm3以下の耐炎化繊維束とし、さらに不活性ガス中、800℃以上2000℃以下の温度で炭素化処理する、単繊維の繊維軸に垂直な断面の直径Diが8μm以上で、単繊維の繊維軸に垂直な断面の形状が真円度0.90以下である炭素繊維束の製造方法:
但し、直径Diは以下の方法によって求められる。
1)サンプルの作製;
長さ5cmに切断した炭素繊維束をエポキシ樹脂(エポマウント主剤:エポマウント硬化剤=100:9(質量比))に包埋し、2cmに切断して横断面を露出させ、鏡面処理する。
2)観察面のエッチング処理;
更に、繊維の外形を明瞭にするために、サンプルの横断面を次の方法でエッチング処理する。
・使用装置:日本電子(株)JP-170 プラズマエッチング装置、
・処理条件:(雰囲気ガス:Ar/O2=75/25、プラズマ出力:50W、真空度:約120Pa、処理時間:5min)。
3)SEM観察;
前記1)及び2)により得られたサンプルの横断面を、SEM(PHILIPS FEI-XL20)を用いて観察し、画面上に5個以上の繊維断面が写っている写真を任意に5枚撮影する。
4)炭素繊維束の単繊維断面の直径測定;
各サンプルについて5枚のSEM写真から任意に20個、ただし、1枚の写真から3個以上の単繊維断面を選んで、画像解析ソフトウェア(日本ローパー(株)製、製品名:Image-Pro PLUS)を用いて繊維断面の外形をトレースし、断面の長径(最大フェレ径)dを計測する。選んだ単繊維断面全ての長径の平均値を、炭素繊維束の単繊維の直径Diとする。 - 平均単繊維繊度が1.0~2.4dtex、単繊維の繊維軸に垂直な断面の形状が真円度0.7以上0.9以下である炭素繊維束。
- 前記単繊維の繊維軸に垂直な断面の直径Diが8~20μmである請求項17に記載の炭素繊維束。
- 前記単繊維の表面に単繊維の長手方向に延びる溝状の凹凸を複数有し、該単繊維の円周長さ2μmの範囲で最高部と最低部の高低差が80nm以下である請求項17に記載の炭素繊維束。
- ストランド引張強度が4000MPa以上である請求項17~19のいずれかの一項に記載の炭素繊維束。
- ストランド引張弾性率が200GPa以上である請求項17~19のいずれかの一項に記載の炭素繊維束。
- 総繊度が30000~90000dtexである請求項17~19のいずれかの一項に記載の炭素繊維束。
- 単繊維繊度が1.2~2.4dtex、単繊維の繊維軸に垂直な断面の真円度0.7以上0.9以下である炭素繊維束とマトリックス樹脂とからなる炭素繊維プリプレグ。
- 前記炭素繊維束がPAN系炭素繊維束である請求項23に記載の炭素繊維プリプレグ。
- 前記炭素繊維束の単繊維の繊維軸に垂直な直径Diが8~20μmである請求項23または24に記載の炭素繊維プリプレグ。
- 前記マトリックス樹脂のフロー指数が5000Pa-1以上である請求項23~25のいずれかの一項に記載の炭素繊維プリプレグ。
- 前記マトリックス樹脂がエポキシ樹脂である請求項23~26のいずれかの一項に記載の炭素繊維プリプレグ。
- 前記エポキシ樹脂がオキサゾリドン環構造を持つエポキシ樹脂を含んでなる請求項27に記載の炭素繊維プリプレグ。
- 前記エポキシ樹脂が熱可塑性樹脂を含んでなる請求項27または28に記載の炭素繊維プリプレグ。
- 前記エポキシ樹脂が硬化剤としてジシアンジアミドを含んでなる請求項27~29のいずれかの一項に記載の炭素繊維プリプレグ。
- 前記エポキシ樹脂が硬化助剤としてウレア化合物を含んでなる請求項27~30のいずれかの一項に記載の炭素繊維プリプレグ。
- 請求項17~19のいずれかの一項に記載の炭素繊維束が縦方向に配列された一方向性繊維強化織物。
- 前記一方向性繊維強化織物が横方向に補助糸を有し、該補助糸が縦方向の前記炭素繊維束と交錯している一方向性織物である請求項32に記載の繊維強化織物。
- 前記補助糸が低融点ポリマーを含んでおり、そのポリマーを介して前記炭素繊維束と前記補助糸とがその交点において、互いに接着してなる請求項33に記載の繊維強化織物。
- 前記炭素繊維束を構成するフィラメント数が15000~100000本であるか、あるいは前記炭素繊維束の総繊度が9900~65000dtexである、請求項32~34のいずれかの一項に記載の繊維強化織物を、繊維基材として少なくとも1層以上成形型に積層し、その上に、樹脂を面方向に拡散する為の媒体を置いた後、該繊維基材及び該媒体の全体をバッグフィルムで覆い、次いで該バッグフィルムの内部を真空状態にし、前記繊維基材の片面上に常温硬化型樹脂を拡散させ、前記繊維基材に含浸させる繊維強化プラスチックの成形方法。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2013004089A MX370355B (es) | 2010-10-13 | 2011-10-13 | Bloque de fibra precursora de fibra de carbono, bloque de fibra de carbono, y sus aplicaciones. |
JP2011545122A JP5682570B2 (ja) | 2010-10-13 | 2011-10-13 | 炭素繊維前駆体繊維束、炭素繊維束、及びそれらの利用 |
EP11832602.4A EP2628827B1 (en) | 2010-10-13 | 2011-10-13 | Carbon fiber bundle, and uses thereof |
US13/879,278 US9920456B2 (en) | 2010-10-13 | 2011-10-13 | Carbon-fiber-precursor fiber bundle, carbon fiber bundle, and uses thereof |
KR1020137009270A KR101518145B1 (ko) | 2010-10-13 | 2011-10-13 | 탄소 섬유 전구체 섬유속, 탄소 섬유속, 및 그들의 이용 |
CN201180049339.5A CN103154336B (zh) | 2010-10-13 | 2011-10-13 | 碳纤维前体纤维束、碳纤维束以及它们的用途 |
US15/888,230 US10233569B2 (en) | 2010-10-13 | 2018-02-05 | Carbon-fiber-precursor fiber bundle, carbon fiber bundle, and uses thereof |
US16/258,830 US10662556B2 (en) | 2010-10-13 | 2019-01-28 | Carbon-fiber-precursor fiber bundle, carbon fiber bundle, and uses thereof |
US16/860,191 US11332852B2 (en) | 2010-10-13 | 2020-04-28 | Carbon-fiber-precursor fiber bundle, carbon fiber bundle, and uses thereof |
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-230492 | 2010-10-13 | ||
JP2010230492 | 2010-10-13 | ||
JP2011-164596 | 2011-07-27 | ||
JP2011164596 | 2011-07-27 | ||
JP2011164597 | 2011-07-27 | ||
JP2011-164597 | 2011-07-27 | ||
JP2011-184328 | 2011-08-26 | ||
JP2011184328 | 2011-08-26 | ||
JP2011186859 | 2011-08-30 | ||
JP2011-186859 | 2011-08-30 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/879,278 A-371-Of-International US9920456B2 (en) | 2010-10-13 | 2011-10-13 | Carbon-fiber-precursor fiber bundle, carbon fiber bundle, and uses thereof |
US15/888,230 Continuation US10233569B2 (en) | 2010-10-13 | 2018-02-05 | Carbon-fiber-precursor fiber bundle, carbon fiber bundle, and uses thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012050171A1 true WO2012050171A1 (ja) | 2012-04-19 |
Family
ID=45938392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/073578 WO2012050171A1 (ja) | 2010-10-13 | 2011-10-13 | 炭素繊維前駆体繊維束、炭素繊維束、及びそれらの利用 |
Country Status (9)
Country | Link |
---|---|
US (4) | US9920456B2 (ja) |
EP (1) | EP2628827B1 (ja) |
JP (1) | JP5682570B2 (ja) |
KR (1) | KR101518145B1 (ja) |
CN (1) | CN103154336B (ja) |
HU (1) | HUE052010T2 (ja) |
MX (2) | MX370355B (ja) |
TW (1) | TWI553175B (ja) |
WO (1) | WO2012050171A1 (ja) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012188766A (ja) * | 2011-03-09 | 2012-10-04 | Mitsubishi Rayon Co Ltd | 炭素繊維前駆体繊維束および炭素繊維束 |
JP2012246583A (ja) * | 2011-05-27 | 2012-12-13 | Mitsubishi Rayon Co Ltd | 一方向強化織物とその製造方法、これを用いたプリプレグおよび炭素繊維複合材料 |
WO2013157613A1 (ja) * | 2012-04-18 | 2013-10-24 | 三菱レイヨン株式会社 | 炭素繊維束および炭素繊維束の製造方法 |
WO2013157612A1 (ja) * | 2012-04-18 | 2013-10-24 | 三菱レイヨン株式会社 | 炭素繊維束および炭素繊維の製造方法 |
WO2014054196A1 (ja) * | 2012-10-03 | 2014-04-10 | 三菱レイヨン株式会社 | 耐炎化繊維束、炭素繊維束及びそれらの製造方法 |
JP2014163016A (ja) * | 2013-02-26 | 2014-09-08 | Mitsubishi Rayon Co Ltd | 強化用多軸ステッチ基材、強化用織物および炭素繊維強化複合材料とその製造方法 |
GB2514189A (en) * | 2013-05-17 | 2014-11-19 | Gurit Uk Ltd | Carbon fibre-containing prepregs |
JP2015078310A (ja) * | 2013-10-17 | 2015-04-23 | 三菱レイヨン株式会社 | プリプレグ |
JP2015117442A (ja) * | 2013-12-18 | 2015-06-25 | 三菱レイヨン株式会社 | 補強繊維織物及びその製造方法 |
JP2016188271A (ja) * | 2015-03-30 | 2016-11-04 | 三菱レイヨン株式会社 | プリプレグの製造方法 |
EP3009056A4 (en) * | 2013-06-13 | 2017-04-26 | Novaralis Sl. | Method for producing a lightweight textured shower tray and lightweight textured shower tray produced by said method |
JP2018145541A (ja) * | 2017-03-02 | 2018-09-20 | 三菱ケミカル株式会社 | 炭素繊維束及びその製造方法 |
JP2018145540A (ja) * | 2017-03-02 | 2018-09-20 | 三菱ケミカル株式会社 | 炭素繊維束の製造方法 |
JP2019015013A (ja) * | 2017-06-05 | 2019-01-31 | ザ・ボーイング・カンパニーThe Boeing Company | 炭素繊維を製造するための方法及び装置 |
JP2019105023A (ja) * | 2013-12-18 | 2019-06-27 | 三菱ケミカル株式会社 | 補強繊維織物及びその製造方法 |
JP2019523833A (ja) * | 2016-05-11 | 2019-08-29 | フラウンホーファー−ゲゼルシャフト ツゥア フェアデルング デア アンゲヴァンドテン フォァシュング エー.ファウ. | マルチフィラメント糸の製造方法及びマルチフィラメント糸 |
JP2019202547A (ja) * | 2019-07-19 | 2019-11-28 | 三菱ケミカル株式会社 | プリプレグ |
WO2021157442A1 (ja) * | 2020-02-03 | 2021-08-12 | 東レ株式会社 | 成形材料および繊維強化複合材料 |
CN113402278A (zh) * | 2021-06-10 | 2021-09-17 | 福建立亚新材有限公司 | 一种用于高温试验的陶瓷纤维制备方法 |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5682570B2 (ja) | 2010-10-13 | 2015-03-11 | 三菱レイヨン株式会社 | 炭素繊維前駆体繊維束、炭素繊維束、及びそれらの利用 |
CN104321373B (zh) * | 2012-03-29 | 2018-04-06 | 三菱化学株式会社 | 碳纤维热塑性树脂预浸料、碳纤维复合材料以及制造方法 |
GB201217226D0 (en) | 2012-09-26 | 2012-11-07 | Hexcel Composites Ltd | Resin composition and composite structure containing resin |
CN104812957B (zh) * | 2012-11-26 | 2017-09-26 | 三菱化学株式会社 | 短切碳纤维束及短切碳纤维束的制造方法 |
DE102013206984A1 (de) * | 2013-04-18 | 2014-10-23 | Bayerische Motoren Werke Aktiengesellschaft | Verfahren zum Herstellen von Kohlefasern |
JP6695693B2 (ja) * | 2014-01-10 | 2020-05-20 | 小松マテーレ株式会社 | 繊維強化樹脂材料、その製造方法及び繊維強化樹脂材料を用いた繊維強化樹脂成形体 |
JP6523859B2 (ja) * | 2014-08-28 | 2019-06-05 | 帝人株式会社 | 切断体の製造方法、及び繊維強化樹脂の切断方法 |
CN104629264A (zh) * | 2015-02-06 | 2015-05-20 | 佛山星期六科技研发有限公司 | 一种应用于鞋中底板的碳纤维增强环氧树脂复合材料及其制备方法 |
DE102015214218A1 (de) * | 2015-07-28 | 2017-02-02 | Evonik Degussa Gmbh | Verfahren und Vorrichtung zur Herstellung von Vorprodukten für die Kohlenstofffaserherstellung |
EP3397797B1 (en) | 2015-12-31 | 2023-08-30 | UT-Battelle, LLC | Method of producing carbon fibers from multipurpose commercial fibers |
US10501595B2 (en) * | 2016-10-25 | 2019-12-10 | The Boeing Company | Insertion of catalyst into dry carbon fibers prior to resin impregnation |
TWI663124B (zh) * | 2016-11-23 | 2019-06-21 | 永虹先進材料股份有限公司 | Carbon fiber manufacturing method |
EP3590773B1 (en) | 2017-03-31 | 2023-01-04 | Seiren Co., Ltd. | Woven fabric for non-coated airbag and airbag |
WO2019107247A1 (ja) | 2017-11-29 | 2019-06-06 | 帝人株式会社 | 複合材料、成形体の製造方法、及び複合材料の製造方法 |
US20210079563A1 (en) * | 2018-03-06 | 2021-03-18 | Toray Industries, Inc. | Carbon fiber and method of manufacturing same |
CN110093677B (zh) * | 2019-05-20 | 2021-08-31 | 中国科学院山西煤炭化学研究所 | 一种聚丙烯腈纤维、聚丙烯腈基碳纤维及其制备方法 |
US11267166B2 (en) * | 2019-12-18 | 2022-03-08 | Toyota Motor Engineering & Manufacturing North America, Inc. | Devices, systems, and methods for generating a single fiber path of a composite material |
TWI762414B (zh) | 2021-08-25 | 2022-04-21 | 臺灣塑膠工業股份有限公司 | 碳纖維之製造方法 |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6111323B2 (ja) * | 1977-08-29 | 1986-04-02 | Toray Industries | |
JPH01132832A (ja) | 1987-08-21 | 1989-05-25 | Mitsui Mining Co Ltd | 炭素材料の製造方法 |
JPH01161040A (ja) | 1987-12-17 | 1989-06-23 | Nippon Steel Chem Co Ltd | マトリックス樹脂組成物 |
JPH026625A (ja) | 1988-06-23 | 1990-01-10 | Mitsubishi Rayon Co Ltd | 耐炎化繊維の製造法 |
JPH0284505A (ja) | 1988-04-26 | 1990-03-26 | Toray Ind Inc | 炭素繊維製造用プリカーサー |
JPH02169658A (ja) | 1988-12-22 | 1990-06-29 | Yokohama Rubber Co Ltd:The | エポキシ樹脂組成物 |
JPH04281008A (ja) | 1991-03-01 | 1992-10-06 | Mitsubishi Rayon Co Ltd | アクリロニトリル系前駆体繊維束 |
JP2535448B2 (ja) * | 1990-11-29 | 1996-09-18 | 東レ株式会社 | 異形断面炭素繊維および炭素繊維強化複合材料 |
JPH11124743A (ja) | 1997-10-20 | 1999-05-11 | Toray Ind Inc | 炭素繊維および炭素繊維強化複合材料 |
JP2000119341A (ja) | 1998-10-15 | 2000-04-25 | Mitsubishi Rayon Co Ltd | アクリロニトリル系ポリマーおよびそれを用いた炭素繊維用前駆体繊維 |
JP2002061035A (ja) * | 2000-08-10 | 2002-02-28 | Toray Ind Inc | 炭素繊維およびその製造方法ならびに炭素繊維強化複合材料 |
JP2002242027A (ja) | 2001-02-13 | 2002-08-28 | Mitsubishi Rayon Co Ltd | 炭素繊維束 |
JP2002266173A (ja) * | 2001-03-09 | 2002-09-18 | Mitsubishi Rayon Co Ltd | 炭素繊維および炭素繊維強化複合材料 |
JP2005226193A (ja) * | 2004-02-13 | 2005-08-25 | Mitsubishi Rayon Co Ltd | 強化繊維用サイジング剤、炭素繊維束、熱可塑性樹脂組成物及びその成形品 |
JP2006257580A (ja) | 2005-03-17 | 2006-09-28 | Toray Ind Inc | 炭素繊維前駆体繊維用ポリアクリロニトリル系重合体および炭素繊維前駆体繊維、炭素繊維の製造方法 |
JP2007204880A (ja) | 2006-02-02 | 2007-08-16 | Mitsubishi Rayon Co Ltd | 炭素繊維前駆体アクリル繊維用紡糸原液、炭素繊維前駆体アクリル繊維の製造方法並びにこれにて得られる炭素繊維前駆体アクリル繊維 |
JP2008202207A (ja) | 2007-01-26 | 2008-09-04 | Toray Ind Inc | 炭素繊維束およびその製造方法 |
JP2011046942A (ja) * | 2009-07-31 | 2011-03-10 | Mitsubishi Rayon Co Ltd | ポリアクリロニトリル系共重合体、炭素繊維用ポリアクリロニトリル系前駆体繊維、および炭素繊維の製造方法 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3923950A (en) | 1971-11-18 | 1975-12-02 | Celanese Corp | Production of stabilized acrylic fibers and films |
JPS5322575B2 (ja) * | 1974-05-14 | 1978-07-10 | ||
JPS5224134B2 (ja) * | 1974-11-07 | 1977-06-29 | ||
JPS616314A (ja) * | 1984-06-20 | 1986-01-13 | Teijin Ltd | ピツチ系炭素繊維 |
JPS6147826A (ja) * | 1984-08-15 | 1986-03-08 | Teijin Ltd | ピツチ系炭素繊維の製造法 |
JPS616313A (ja) * | 1984-06-20 | 1986-01-13 | Teijin Ltd | ピツチ系炭素繊維の製造方法 |
US4628001A (en) * | 1984-06-20 | 1986-12-09 | Teijin Limited | Pitch-based carbon or graphite fiber and process for preparation thereof |
JPS6111323A (ja) | 1984-06-26 | 1986-01-18 | 株式会社 フジヤマ技研 | 茶袋シ−ル機 |
JP2892127B2 (ja) * | 1989-09-05 | 1999-05-17 | 東レ株式会社 | 非円形断面炭素繊維、その製造方法および炭素繊維複合材料 |
KR0156870B1 (ko) * | 1989-09-05 | 1998-12-01 | 마에다 가쓰노스케 | 비원형단면 탄소섬유의 제조방법 및 이를 이용한 복합재료 |
JP2535448Y2 (ja) | 1991-12-16 | 1997-05-14 | 大和製罐株式会社 | 缶蓋巻締部の寸法自動測定装置 |
JPH06146120A (ja) * | 1992-10-31 | 1994-05-27 | Tonen Corp | 高強度、高弾性率ピッチ系炭素繊維及びその製造方法 |
US6066687A (en) * | 1994-06-24 | 2000-05-23 | Solutia Inc. | Acrylic fiber with high optical brightness |
SG73992A1 (en) * | 1995-12-18 | 2000-07-18 | Standard Oil Co | Melt spun acrylonitrile olefinically unsaturated fibers and a process to make fibers |
JPH10121325A (ja) | 1996-10-14 | 1998-05-12 | Toray Ind Inc | 炭素繊維用前駆体繊維束とその製造方法および炭素繊維の製造方法 |
HU227049B1 (en) | 1997-08-27 | 2010-05-28 | Mitsubishi Rayon Co | Acrylonitrile-based precursor fiber for carbon fiber, process for producing the same, and carbon fiber obtained from the precursor fiber |
KR100570592B1 (ko) | 1998-07-22 | 2006-04-13 | 미쯔비시 레이온 가부시끼가이샤 | 탄소 섬유용 아크릴로니트릴계 전구체 섬유 및 그 제조 방법 |
JP4407854B2 (ja) * | 2000-03-29 | 2010-02-03 | 東邦テナックス株式会社 | 電極材用炭素繊維フェルトおよびその製造方法 |
CN1918330B (zh) | 2004-02-13 | 2010-11-10 | 三菱丽阳株式会社 | 碳纤维前驱体纤维束、其制造方法及制造装置以及碳纤维及其制造方法 |
US8137810B2 (en) | 2005-12-13 | 2012-03-20 | Toray Industries, Inc. | Carbon fiber, process for production of polyacrylonitrile-base precursor fiber for carbon fiber production, and process for production of carbon fiber |
EP2305863A4 (en) | 2008-07-04 | 2011-11-30 | Hodogaya Chemical Co Ltd | CARBON FIBER AND COMPOSITE MATERIAL |
JP5682570B2 (ja) * | 2010-10-13 | 2015-03-11 | 三菱レイヨン株式会社 | 炭素繊維前駆体繊維束、炭素繊維束、及びそれらの利用 |
-
2011
- 2011-10-13 JP JP2011545122A patent/JP5682570B2/ja active Active
- 2011-10-13 WO PCT/JP2011/073578 patent/WO2012050171A1/ja active Application Filing
- 2011-10-13 EP EP11832602.4A patent/EP2628827B1/en active Active
- 2011-10-13 KR KR1020137009270A patent/KR101518145B1/ko active IP Right Grant
- 2011-10-13 CN CN201180049339.5A patent/CN103154336B/zh active Active
- 2011-10-13 MX MX2013004089A patent/MX370355B/es active IP Right Grant
- 2011-10-13 US US13/879,278 patent/US9920456B2/en active Active
- 2011-10-13 TW TW100137236A patent/TWI553175B/zh active
- 2011-10-13 HU HUE11832602A patent/HUE052010T2/hu unknown
-
2013
- 2013-04-11 MX MX2019014834A patent/MX2019014834A/es unknown
-
2018
- 2018-02-05 US US15/888,230 patent/US10233569B2/en active Active
-
2019
- 2019-01-28 US US16/258,830 patent/US10662556B2/en active Active
-
2020
- 2020-04-28 US US16/860,191 patent/US11332852B2/en active Active
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6111323B2 (ja) * | 1977-08-29 | 1986-04-02 | Toray Industries | |
JPH01132832A (ja) | 1987-08-21 | 1989-05-25 | Mitsui Mining Co Ltd | 炭素材料の製造方法 |
JPH01161040A (ja) | 1987-12-17 | 1989-06-23 | Nippon Steel Chem Co Ltd | マトリックス樹脂組成物 |
JPH0284505A (ja) | 1988-04-26 | 1990-03-26 | Toray Ind Inc | 炭素繊維製造用プリカーサー |
JPH026625A (ja) | 1988-06-23 | 1990-01-10 | Mitsubishi Rayon Co Ltd | 耐炎化繊維の製造法 |
JPH02169658A (ja) | 1988-12-22 | 1990-06-29 | Yokohama Rubber Co Ltd:The | エポキシ樹脂組成物 |
JP2535448B2 (ja) * | 1990-11-29 | 1996-09-18 | 東レ株式会社 | 異形断面炭素繊維および炭素繊維強化複合材料 |
JPH04281008A (ja) | 1991-03-01 | 1992-10-06 | Mitsubishi Rayon Co Ltd | アクリロニトリル系前駆体繊維束 |
JPH11124743A (ja) | 1997-10-20 | 1999-05-11 | Toray Ind Inc | 炭素繊維および炭素繊維強化複合材料 |
JP2000119341A (ja) | 1998-10-15 | 2000-04-25 | Mitsubishi Rayon Co Ltd | アクリロニトリル系ポリマーおよびそれを用いた炭素繊維用前駆体繊維 |
JP2002061035A (ja) * | 2000-08-10 | 2002-02-28 | Toray Ind Inc | 炭素繊維およびその製造方法ならびに炭素繊維強化複合材料 |
JP2002242027A (ja) | 2001-02-13 | 2002-08-28 | Mitsubishi Rayon Co Ltd | 炭素繊維束 |
JP2002266173A (ja) * | 2001-03-09 | 2002-09-18 | Mitsubishi Rayon Co Ltd | 炭素繊維および炭素繊維強化複合材料 |
JP2005226193A (ja) * | 2004-02-13 | 2005-08-25 | Mitsubishi Rayon Co Ltd | 強化繊維用サイジング剤、炭素繊維束、熱可塑性樹脂組成物及びその成形品 |
JP2006257580A (ja) | 2005-03-17 | 2006-09-28 | Toray Ind Inc | 炭素繊維前駆体繊維用ポリアクリロニトリル系重合体および炭素繊維前駆体繊維、炭素繊維の製造方法 |
JP2007204880A (ja) | 2006-02-02 | 2007-08-16 | Mitsubishi Rayon Co Ltd | 炭素繊維前駆体アクリル繊維用紡糸原液、炭素繊維前駆体アクリル繊維の製造方法並びにこれにて得られる炭素繊維前駆体アクリル繊維 |
JP2008202207A (ja) | 2007-01-26 | 2008-09-04 | Toray Ind Inc | 炭素繊維束およびその製造方法 |
JP2011046942A (ja) * | 2009-07-31 | 2011-03-10 | Mitsubishi Rayon Co Ltd | ポリアクリロニトリル系共重合体、炭素繊維用ポリアクリロニトリル系前駆体繊維、および炭素繊維の製造方法 |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012188766A (ja) * | 2011-03-09 | 2012-10-04 | Mitsubishi Rayon Co Ltd | 炭素繊維前駆体繊維束および炭素繊維束 |
JP2012246583A (ja) * | 2011-05-27 | 2012-12-13 | Mitsubishi Rayon Co Ltd | 一方向強化織物とその製造方法、これを用いたプリプレグおよび炭素繊維複合材料 |
US11970791B2 (en) | 2012-04-18 | 2024-04-30 | Mitsubishi Chemical Corporation | Carbon fiber bundle and method of producing carbon fiber bundle |
WO2013157612A1 (ja) * | 2012-04-18 | 2013-10-24 | 三菱レイヨン株式会社 | 炭素繊維束および炭素繊維の製造方法 |
US9873777B2 (en) | 2012-04-18 | 2018-01-23 | Mitsubishi Chemical Corporation | Carbon fiber bundle and method of producing carbon fibers |
WO2013157613A1 (ja) * | 2012-04-18 | 2013-10-24 | 三菱レイヨン株式会社 | 炭素繊維束および炭素繊維束の製造方法 |
JP5720783B2 (ja) * | 2012-04-18 | 2015-05-20 | 三菱レイヨン株式会社 | 炭素繊維束および炭素繊維束の製造方法 |
US10837127B2 (en) | 2012-04-18 | 2020-11-17 | Mitsubishi Chemical Corporation | Carbon fiber bundle and method of producing carbon fiber bundle |
KR101690437B1 (ko) * | 2012-10-03 | 2016-12-27 | 미쯔비시 레이온 가부시끼가이샤 | 내염화 섬유속, 탄소 섬유속 및 그들의 제조 방법 |
WO2014054196A1 (ja) * | 2012-10-03 | 2014-04-10 | 三菱レイヨン株式会社 | 耐炎化繊維束、炭素繊維束及びそれらの製造方法 |
JP2014074242A (ja) * | 2012-10-03 | 2014-04-24 | Mitsubishi Rayon Co Ltd | 炭素繊維束の製造方法 |
KR20150044942A (ko) * | 2012-10-03 | 2015-04-27 | 미쯔비시 레이온 가부시끼가이샤 | 내염화 섬유속, 탄소 섬유속 및 그들의 제조 방법 |
CN104662214A (zh) * | 2012-10-03 | 2015-05-27 | 三菱丽阳株式会社 | 预氧化纤维束、碳纤维束及它们的制造方法 |
CN104662214B (zh) * | 2012-10-03 | 2017-04-26 | 三菱丽阳株式会社 | 预氧化纤维束、碳纤维束及它们的制造方法 |
JP2014163016A (ja) * | 2013-02-26 | 2014-09-08 | Mitsubishi Rayon Co Ltd | 強化用多軸ステッチ基材、強化用織物および炭素繊維強化複合材料とその製造方法 |
GB2514189B (en) * | 2013-05-17 | 2018-11-14 | Gurit Uk Ltd | Carbon fibre-containing prepregs |
GB2514189A (en) * | 2013-05-17 | 2014-11-19 | Gurit Uk Ltd | Carbon fibre-containing prepregs |
EP3009056A4 (en) * | 2013-06-13 | 2017-04-26 | Novaralis Sl. | Method for producing a lightweight textured shower tray and lightweight textured shower tray produced by said method |
JP2015078310A (ja) * | 2013-10-17 | 2015-04-23 | 三菱レイヨン株式会社 | プリプレグ |
JP2019105023A (ja) * | 2013-12-18 | 2019-06-27 | 三菱ケミカル株式会社 | 補強繊維織物及びその製造方法 |
JP2015117442A (ja) * | 2013-12-18 | 2015-06-25 | 三菱レイヨン株式会社 | 補強繊維織物及びその製造方法 |
JP2016188271A (ja) * | 2015-03-30 | 2016-11-04 | 三菱レイヨン株式会社 | プリプレグの製造方法 |
JP2019523833A (ja) * | 2016-05-11 | 2019-08-29 | フラウンホーファー−ゲゼルシャフト ツゥア フェアデルング デア アンゲヴァンドテン フォァシュング エー.ファウ. | マルチフィラメント糸の製造方法及びマルチフィラメント糸 |
US11649567B2 (en) | 2016-05-11 | 2023-05-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing a multifilament yarn |
JP2018145540A (ja) * | 2017-03-02 | 2018-09-20 | 三菱ケミカル株式会社 | 炭素繊維束の製造方法 |
JP2018145541A (ja) * | 2017-03-02 | 2018-09-20 | 三菱ケミカル株式会社 | 炭素繊維束及びその製造方法 |
JP2019015013A (ja) * | 2017-06-05 | 2019-01-31 | ザ・ボーイング・カンパニーThe Boeing Company | 炭素繊維を製造するための方法及び装置 |
JP7169774B2 (ja) | 2017-06-05 | 2022-11-11 | ザ・ボーイング・カンパニー | 炭素繊維を製造するための方法及び装置 |
US11525193B2 (en) | 2017-06-05 | 2022-12-13 | The Boeing Company | Method and apparatus for manufacturing carbon fibers |
JP2019202547A (ja) * | 2019-07-19 | 2019-11-28 | 三菱ケミカル株式会社 | プリプレグ |
WO2021157442A1 (ja) * | 2020-02-03 | 2021-08-12 | 東レ株式会社 | 成形材料および繊維強化複合材料 |
CN113402278A (zh) * | 2021-06-10 | 2021-09-17 | 福建立亚新材有限公司 | 一种用于高温试验的陶瓷纤维制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2628827A4 (en) | 2014-07-09 |
US20130295811A1 (en) | 2013-11-07 |
JPWO2012050171A1 (ja) | 2014-02-24 |
CN103154336A (zh) | 2013-06-12 |
JP5682570B2 (ja) | 2015-03-11 |
US10662556B2 (en) | 2020-05-26 |
HUE052010T2 (hu) | 2021-04-28 |
MX2019014834A (es) | 2020-02-17 |
US11332852B2 (en) | 2022-05-17 |
TWI553175B (zh) | 2016-10-11 |
KR20130051505A (ko) | 2013-05-20 |
CN103154336B (zh) | 2015-08-12 |
EP2628827A1 (en) | 2013-08-21 |
KR101518145B1 (ko) | 2015-05-06 |
US20200263327A1 (en) | 2020-08-20 |
TW201226648A (en) | 2012-07-01 |
US20180155855A1 (en) | 2018-06-07 |
MX2013004089A (es) | 2013-10-25 |
MX370355B (es) | 2019-12-10 |
US9920456B2 (en) | 2018-03-20 |
US10233569B2 (en) | 2019-03-19 |
US20190153628A1 (en) | 2019-05-23 |
EP2628827B1 (en) | 2020-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5682570B2 (ja) | 炭素繊維前駆体繊維束、炭素繊維束、及びそれらの利用 | |
KR101340225B1 (ko) | 기계적 성능 발현이 우수한 탄소 섬유 다발 | |
KR101624839B1 (ko) | 사이징제 도포 탄소 섬유 다발, 탄소 섬유 다발의 제조 방법 및 프리프레그 | |
JP6051987B2 (ja) | サイジング剤塗布炭素繊維の製造方法 | |
JP2012056980A (ja) | トウプリプレグ用エポキシ樹脂組成物およびトウプリプレグ | |
WO1996021695A1 (fr) | Preimpregnes et materiau composite renforce par des fibres de carbone | |
JP4305081B2 (ja) | 炭素繊維製造用油剤及び炭素繊維の製造方法 | |
JP2002212320A (ja) | プリプレグおよび極低温タンク | |
JP2002266173A (ja) | 炭素繊維および炭素繊維強化複合材料 | |
JP2004238761A (ja) | 炭素繊維束および繊維強化複合材料 | |
JP2003055881A (ja) | 炭素繊維用プリカーサー、その製造方法および炭素繊維の製造方法 | |
WO2019203088A1 (ja) | 炭素繊維束とその製造方法、プリプレグおよび炭素繊維強化複合材料 | |
JP2013202803A (ja) | 炭素繊維強化複合材料 | |
JP4238436B2 (ja) | 炭素繊維の製造方法 | |
JP5561390B2 (ja) | プリプレグおよび炭素繊維強化複合材料 | |
JP5504859B2 (ja) | 炭素繊維前駆体繊維束および炭素繊維束とそれらの製造方法 | |
JP2024003966A (ja) | 炭素繊維束、炭素繊維束の製造方法、炭素繊維強化複合材料 | |
JP2022096210A (ja) | 炭素繊維の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180049339.5 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011545122 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11832602 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20137009270 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2013/004089 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011832602 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13879278 Country of ref document: US |