JPWO2007069511A1 - 炭素繊維、炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法、および、炭素繊維の製造方法 - Google Patents
炭素繊維、炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法、および、炭素繊維の製造方法 Download PDFInfo
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- JPWO2007069511A1 JPWO2007069511A1 JP2006554358A JP2006554358A JPWO2007069511A1 JP WO2007069511 A1 JPWO2007069511 A1 JP WO2007069511A1 JP 2006554358 A JP2006554358 A JP 2006554358A JP 2006554358 A JP2006554358 A JP 2006554358A JP WO2007069511 A1 JPWO2007069511 A1 JP WO2007069511A1
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- Prior art keywords
- carbon fiber
- polyacrylonitrile
- fiber
- producing
- based precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 192
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 192
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000000835 fiber Substances 0.000 title claims abstract description 143
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 101
- 239000002243 precursor Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 238000007380 fibre production Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 69
- 238000009987 spinning Methods 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 239000002772 conduction electron Substances 0.000 claims abstract description 29
- 238000004435 EPR spectroscopy Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000002166 wet spinning Methods 0.000 claims abstract description 7
- 238000001891 gel spinning Methods 0.000 claims abstract description 5
- 238000003763 carbonization Methods 0.000 claims description 35
- 230000005484 gravity Effects 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 8
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- 238000000578 dry spinning Methods 0.000 claims description 2
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- 230000001965 increasing effect Effects 0.000 description 16
- 230000007423 decrease Effects 0.000 description 15
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- 238000007334 copolymerization reaction Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
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- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
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- 238000006243 chemical reaction Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
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- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
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- 239000011976 maleic acid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000009730 filament winding Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
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- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
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- 238000005087 graphitization Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
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- 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
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- 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
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- 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
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
-
- 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
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Abstract
Description
従って、一定のフィラメント数の炭素繊維製造用ポリアクリロニトリル系前駆体繊維束を製造する場合、吐出線速度は、吐出量を変更するか、および/または、吐出孔径を変更することにより、任意の値に設定することができる。吐出量の増減は、得られる炭素繊維製造用ポリアクリロニトリル系前駆体繊維の単繊維繊度や、製糸設備の生産性の増減につながる場合があるため、必要な吐出量に合わせて、適切な吐出孔径を設定することが、より好ましい。
120℃の温度で2時間熱処理し乾燥したポリアクリロニトリル系重合体150mgを、60℃の温度において、50mlのチオシアン酸ナトリウム0.1mol/リットル添加ジメチルフォルムアミドに溶解する。得られた溶液について、25℃の温度においてオストワルド粘度計を用いて標線間の落下時間を1/100秒の精度で測定する。測定した落下時間をt(秒)とする。同様に、ポリアクリロニトリル系重合体を溶解していないチオシアン酸ナトリウム0.1mol/リットル添加ジメチルフォルムアミドについても測定し、その落下時間をt0(秒)とする。次式を用いて、極限粘度[η]を算出する。
ηsp=(t/t0)−1
なお、後述の実施例および比較例においては、上記チオシアン酸ナトリウム、および、ジメチルフォルムアミドとして、いずれも和光純薬社製特級を用いた。
測定に供するポリアクリロニトリル系重合体を、液体窒素中で凍結粉砕した後、目開き0.5mmの篩いを通し該重合体の粉体を得る。得られた粉体を5mg精秤し、DSC測定用サンプルを用意する。用意したサンプルを、耐圧2MPa以上の密閉可能なDSC用サンプルパンに、5mgの純水とともに密封する。次いで、このサンプルパンを用いて、10℃/分の昇温速度で、室温から220℃の温度までDSCを測定し、150乃至200℃の温度付近に現れる吸熱ピークの頂点に対応する温度を読み取り、湿熱下融点Tm(℃)とする。
測定に供する紡糸原液約10gを、その太さが2mm以下となるように水中に滴下し、凝固させる。凝固させた重合体を80℃の流水中で4時間洗浄する。洗浄した重合体を、熱風乾燥機により、120℃で2時間乾燥する。水中に滴下した紡糸原液の重量をA(g)、洗浄、乾燥後の重合体の重量をB(g)とし、次式により、紡糸原液中のポリアクリロニトリル系重合体濃度(%)を求める。
=B/A×100
<耐炎化繊維比重>
耐炎化繊維の比重は、JIS R7601(1986)記載の方法に従い、液置換法により測定する。浸せき液は、エタノールを精製せずに用いる。1.0乃至1.5gの耐炎化繊維を採取し、熱風乾燥機を用い、空気中120℃の温度で2時間乾燥する。乾燥質量A(g)を測定した後、比重既知(比重ρ)のエタノールに浸せきし、エタノール中の繊維質量B(g)を測定し、次式により、耐炎化繊維比重を求める。
なお、後述の実施例および比較例においては、上記エタノールとして、和光純薬社製特級を用いた。
炭素繊維の比重は、JIS R7601(1986)記載の方法に従い、液置換法により測定する。浸せき液は、オルトジクロロベンゼンを精製せずに用いる。1.0乃至1.5gの炭素繊維を採取し、該炭素繊維の重量を精秤し、繊維質量A(g)とする。引き続き、該炭素繊維を比重既知(比重ρ)のオルトジクロロベンゼンに浸せきし、オルトジクロロベンゼン中の繊維質量B(g)を測定し、次式により、炭素繊維比重を求める。
なお、後述の実施例および比較例においては、上記オルトジクロロベンゼンとして、和光純薬社製特級を用いた。
炭素繊維のストランド引張弾性率は、JIS R7601(1986)「樹脂含浸ストランド試験法」に従って求める。ここで、測定する炭素繊維の樹脂含浸ストランドは、3,4−エポキシシクロヘキシルメチル−3,4−エポキシ−シクロヘキサン−カルボキシレート(100重量部)/3フッ化ホウ素モノエチルアミン(3重量部)/アセトン(4重量部)を、炭素繊維に含浸させ、130℃の温度で30分間熱処理し硬化させて作製する。また、ストランドの測定本数は6本とし、各測定結果の算術平均値を、その炭素繊維のストランド引張弾性率とする。
測定に供する炭素繊維の重量を精秤した後、ESR装置を用い、下記条件のように、温度を変えて、g=2.002付近のシグナルを測定する。
・磁場掃引幅:200G
・変調:100kHz、2G
・マイクロ波:9.46GHz、1mW
・掃引時間:83.886秒×4回
・時定数:327.68ms
・データポイント数:1024点
・測定温度:10、50、100、150、200、250、296K。
測定に供する炭素繊維を引き揃え、コロジオン・アルコール溶液を用いて固めることにより、長さ4cm、1辺の長さが1mmの四角柱の測定試料を用意する。用意された測定試料について、広角X線回折装置を用いて、次の条件により測定を行う。
・検出器:ゴニオメーター+モノクロメーター+シンチレーションカウンター
・走査範囲:2θ=10乃至40°
・走査モード:ステップスキャン、ステップ単位0.02°、計数時間2秒。
但し、
K:1.0、λ:0.15418nm(X線の波長)
β0:(βE 2−β1 2)1/2
βE:見かけの半値幅(測定値)rad、β1:1.046×10−2rad
θB:Braggの回析角。
測定する多数本の炭素フィラメントからなる炭素繊維束について、単位長さ当たりの重量A(g/m)および比重B(g/cm3)を求める。測定する炭素繊維束のフィラメント数をCとし、炭素繊維の平均単繊維径(μm)を、下記式で算出する。
=((A/B/C)/π)(1/2)×2×103
<コンポジット圧縮強度の測定>
次に示す原料樹脂を混合し、30分間攪拌して樹脂組成物を得る。
・ビスフェノールAジグリシジルエーテル樹脂:30重量%
・フェノールノボラックポリグリシジルエーテル樹脂:27重量%
・ポリビニルホルマール樹脂:5重量%
・ジシアンジアミド:4重量%
・3−(3,4−ジクロロフェニル)−1,1−ジメチルウレア:4重量%
次に、得られた樹脂組成物を、シリコーンが塗布されている離型紙のシリコーン面に、塗布して、樹脂フィルムを用意する。用意された樹脂フィルムを、約2.7mの円周を有し、温度60乃至70℃に温調された鋼製ドラムの表面に、樹脂組成物の表面を外側にして、巻き付ける。
アクリロニトリルと表1に示した共重合量(mol%)の共重合成分とを、ジメチルスルホキシドを溶媒とし、アゾ系化合物を開始剤としたラジカル重合により共重合させ、表1に示した極限粘度を有するポリアクリロニトリル系共重合体(以下、単に、ポリアクリロニトリル系重合体と呼称する場合がある)を製造した。製造されたポリアクリロニトリル系重合体について、湿熱下融点Tm(℃)を測定した。測定結果を表1に示す。
得られた延伸繊維束を、温度170℃に加熱したローラーに接触させて走行させ、乾燥熱処理を行った。次いで、温度150乃至190℃の加圧スチーム中で、3.7倍延伸し、トータル延伸倍率13倍、単繊維繊度0.73dtex、フィラメント数6,000のポリアクリロニトリル系前駆体繊維を得た。得られたポリアクリロニトリル系前駆体繊維について、極限粘度、湿熱下融点(℃)を測定した。測定結果を表1に示す。
Claims (13)
- ストランド引張弾性率が、320乃至380GPaであり、かつ、電子スピン共鳴により測定される伝導電子量が、3.0×1019乃至7.0×1019スピン/gである炭素繊維。
- 前記ストランド引張弾性率が、330乃至380GPaであり、かつ、電子スピン共鳴により測定される伝導電子量が、4.0×1019乃至7.0×1019スピン/gである請求項1に記載の炭素繊維。
- 前記炭素繊維の結晶サイズが、1.8乃至2.6nmである請求項1あるいは2に記載の炭素繊維。
- 前記炭素繊維の比重が、1.75乃至1.85である請求項1あるいは2に記載の炭素繊維。
- 前記炭素繊維の平均単繊維径が、4.5乃至7.5μmである請求項1あるいは2に記載の炭素繊維。
- 極限粘度が2.0乃至10.0であるポリアクリロニトリル系重合体を含み、かつ、該ポリアクリロニトリル系重合体の濃度が10乃至25重量%である紡糸原液を、湿式紡糸法または乾湿式紡糸法により、紡糸口金から吐出させ紡糸する紡糸工程と、該紡糸工程で得られた繊維を乾燥熱処理する乾燥熱処理工程と、該乾燥熱処理工程で得られた繊維をスチーム延伸するスチーム延伸工程とからなる炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法において、前記ポリアクリロニトリル系重合体の前記紡糸口金からの吐出線速度が、2乃至15m/分である炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法。
- 前記吐出線速度が、2乃至10m/分である請求項6に記載の炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法。
- 前記紡糸法が、乾湿式紡糸法である請求項6あるいは7に記載の炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法。
- 前記ポリアクリロニトリル系重合体の示差走査熱量計により測定される湿熱下融点Tmが、186乃至200℃である請求項6あるいは7に記載の炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法。
- 前記ポリアクリロニトリル系重合体が、アクリロニトリルと共重合可能な成分を含む共重合体であり、その共重合可能な成分の量が、0.1乃至0.5mol%である請求項6あるいは7に記載の炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法。
- 前記炭素繊維製造用ポリアクリロニトリル系前駆体繊維の単繊維繊度が、0.7乃至1.0dtexである請求項6あるいは7に記載の炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法。
- 請求項6乃至11のいずれかに記載の炭素繊維製造用ポリアクリロニトリル系前駆体繊維の製造方法により製造された炭素繊維製造用ポリアクリロニトリル系前駆体繊維を、200乃至300℃の温度の空気中において延伸比0.80乃至1.20で延伸しながら耐炎化する耐炎化工程と、該耐炎化工程で得られた繊維を、300乃至800℃の温度の不活性雰囲気中において延伸比1.00乃至1.30で延伸しながら予備炭化する予備炭化工程と、該予備炭化工程で得られた繊維を、1,000乃至2,000℃の温度の不活性雰囲気中において延伸比0.96乃至1.05で延伸しながら炭化する炭化工程とからなる炭素繊維の製造方法。
- 前記耐炎化工程における延伸比が、0.90乃至1.20、前記予備炭化工程における延伸比が、1.10乃至1.30、および、前記炭化工程における延伸比が、0.97乃至1.05である請求項12に記載の炭素繊維の製造方法。
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EP1961847A1 (en) | 2008-08-27 |
EP1961847A4 (en) | 2009-10-14 |
CN101316956B (zh) | 2012-11-28 |
CN101316956A (zh) | 2008-12-03 |
TWI395849B (zh) | 2013-05-11 |
US20120126442A1 (en) | 2012-05-24 |
WO2007069511A1 (ja) | 2007-06-21 |
TW200728531A (en) | 2007-08-01 |
EP1961847B1 (en) | 2018-02-07 |
KR20080076937A (ko) | 2008-08-20 |
US20100143713A1 (en) | 2010-06-10 |
KR101335140B1 (ko) | 2013-12-03 |
US8137810B2 (en) | 2012-03-20 |
JP4957251B2 (ja) | 2012-06-20 |
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