JPH04361619A - Carbon fiber and its production - Google Patents
Carbon fiber and its productionInfo
- Publication number
- JPH04361619A JPH04361619A JP13283991A JP13283991A JPH04361619A JP H04361619 A JPH04361619 A JP H04361619A JP 13283991 A JP13283991 A JP 13283991A JP 13283991 A JP13283991 A JP 13283991A JP H04361619 A JPH04361619 A JP H04361619A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- treatment
- anode
- measured
- fiber
- 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
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 138
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 138
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000011282 treatment Methods 0.000 claims abstract description 42
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 29
- 239000002344 surface layer Substances 0.000 claims description 13
- 230000005611 electricity Effects 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 9
- 238000001069 Raman spectroscopy Methods 0.000 claims description 8
- 229920002972 Acrylic fiber Polymers 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000007385 chemical modification Methods 0.000 claims description 5
- 238000004736 wide-angle X-ray diffraction Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 abstract description 16
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- 239000003792 electrolyte Substances 0.000 description 16
- 125000000524 functional group Chemical group 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000012937 correction Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010301 surface-oxidation reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- 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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229920001342 Bakelite® Polymers 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
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- -1 argon ion Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、炭素繊維及びその製造
方法に関するものである。さらに詳細には、母材樹脂と
の反応性に優れた特定の表面官能基を豊富に有し、母材
樹脂との接着力に優れた炭素繊維及びその製造方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to carbon fibers and methods for producing the same. More specifically, the present invention relates to a carbon fiber having an abundance of specific surface functional groups having excellent reactivity with a base resin and excellent adhesive strength to the base resin, and a method for producing the same.
【０００２】0002
【従来の技術】再生セルロース、ポリアクリロニトリル
、ピッチなどからなる繊維を酸化熱処理し、炭素化ない
し黒鉛化することによって得られる炭素繊維は、比強度
、比弾性率が大きいという力学的特性に基づき、複合材
料（コンポジット）の補強繊維として極めて優れた性能
を有する。この炭素繊維を補強繊維とする複合材料は航
空、宇宙用途或いは自動車、船舶等の輸送機械における
軽量化もしくは燃費低減の要請から、それらの構造材料
として広く、大量に使用されるようになってきた。[Prior Art] Carbon fibers obtained by subjecting fibers made of regenerated cellulose, polyacrylonitrile, pitch, etc. to oxidative heat treatment and carbonization or graphitization have mechanical properties such as high specific strength and specific modulus. It has extremely excellent performance as a reinforcing fiber for composite materials. Composite materials using carbon fiber as reinforcing fibers have come to be widely used in large quantities as structural materials for aviation and space applications, as well as for transportation machinery such as automobiles and ships, due to demands for weight reduction and fuel efficiency reduction. .
【０００３】しかしながら、炭素繊維の優れた力学的性
質を複合材料に反映させるためには複合材料の母材樹脂
と炭素繊維とが十分に接着し一体化する必要がある。一
般に炭素繊維は何等かの表面処理を行わないと母材樹脂
に対する接着性が十分でなく、母材樹脂からの“すぬけ
”が起き易く、複合材料としての曲げ、或いは剪断強度
が低くなり十分な補強効果を発揮しない。However, in order to reflect the excellent mechanical properties of carbon fibers in a composite material, it is necessary that the base resin of the composite material and the carbon fibers are sufficiently bonded and integrated. In general, carbon fibers do not have sufficient adhesion to the base resin unless they are subjected to some kind of surface treatment, and tend to "slip" from the base resin, resulting in low bending or shear strength as a composite material. It does not have a reinforcing effect.
【０００４】そこで、従来から炭素繊維には液相あるい
は気相での表面酸化処理が施されており、例えば、特開
昭６３−８５１６７号公報や特開昭６４−４５８６８号
公報には、酸性電解質中で電解酸化処理を行なった後に
、アルカリ性電解液中で電解処理を行なう方法が提案さ
れている。[0004] Therefore, carbon fibers have conventionally been subjected to surface oxidation treatment in a liquid phase or a gas phase. A method has been proposed in which electrolytic oxidation treatment is performed in an electrolyte and then electrolytic treatment is performed in an alkaline electrolyte.
【０００５】しかし、かかる技術によっても、結果とし
て得られるコンポジットの機械的特性は処理方法及び条
件により大きく影響を受け、例えば酸化処理程度の指標
として従来広く用いられているＸ線光電子分光法（以下
、ＥＳＣＡ）により得られる表面酸素濃度Ｏ／Ｃは増加
しても、炭素繊維と母材樹脂との接着力の指標であるコ
ンポジットの層間剪断強度ＩＬＳＳや９０°引張強度（
以下、９０°ＴＳ）などがこれに伴なって向上するとは
限らなかった。However, even with such technology, the mechanical properties of the resulting composite are greatly affected by the processing method and conditions. For example, X-ray photoelectron spectroscopy (hereinafter referred to as Even if the surface oxygen concentration O/C obtained by
Hereinafter, 90° TS) etc. were not necessarily improved accordingly.
【０００６】特に、熱処理温度を高めて弾性率を高めた
黒鉛繊維にかかる技術を適用した場合には、繊維表層の
黒鉛構造、換言すれば、炭素網面が発達していること等
に起因して、表面酸素濃度をいくら高めても、樹脂との
接着力は向上せず、前記コンポジット特性は、より弾性
率の低い炭素繊維に比べて低いものしか得られない。こ
れは、酸化処理により形成される官能基が炭素網面の端
に局在化するものと考えられ、炭素網面が発達している
黒鉛化繊維に対し酸化処理を施しても接着性に関与する
官能基を炭素繊維表面に均一に分散させて形成するのが
困難であるためと推定される。[0006] In particular, when applying technology to graphite fibers whose elastic modulus has been increased by increasing the heat treatment temperature, the graphite structure of the surface layer of the fibers, in other words, due to the development of the carbon network surface, etc. Therefore, no matter how much the surface oxygen concentration is increased, the adhesion to the resin does not improve, and the composite properties are only lower than those of carbon fiber, which has a lower modulus of elasticity. This is thought to be because the functional groups formed by oxidation treatment are localized at the edges of the carbon network surface, and even if oxidation treatment is applied to graphitized fibers with a well-developed carbon network surface, they do not affect adhesion. This is presumed to be because it is difficult to uniformly disperse and form functional groups on the surface of carbon fibers.
【０００７】一方、全体の官能基の量を増やそうとして
、単に処理電気量を上げるだけでは、処理すべき炭素繊
維、黒鉛繊維に損傷を与えることは避けられず、繊維の
基質強度を低下させてしまうという問題があり、炭素繊
維、黒鉛繊維コンポジットの構造部材への使用を制限し
てきた。On the other hand, simply increasing the amount of electricity processed in an attempt to increase the total amount of functional groups will inevitably damage the carbon fibers and graphite fibers to be processed, and will reduce the matrix strength of the fibers. This problem has limited the use of carbon fiber and graphite fiber composites for structural members.
【０００８】[0008]
【発明が解決しようとする課題】本発明の課題は、上記
問題点を解決すること、すなわち、炭素繊維の最表面に
露出した特定の表面官能基を豊富に有し、マトリックス
樹脂との接着力を向上させ、結果として得られるコンポ
ジットの機械的特性の良好なものとする炭素繊維および
その製造方法を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems, that is, to have carbon fibers with abundant specific surface functional groups exposed on the outermost surface, and to have adhesive strength with matrix resin. An object of the present invention is to provide a carbon fiber and a method for producing the same, which improve the mechanical properties of the resulting composite.
【０００９】[0009]
【課題を解決するための手段】上記した本発明の課題を
解決するために本発明の炭素繊維は、次のいずれかの構
成を有する。すなわち、ストランド弾性率が３０ｔ／ｍ
ｍ２ 以上であり、かつＥＳＣＡにより測定される炭素
繊維の表面酸素濃度Ｏ／Ｃが０．２０以下であり、かつ
Ｏ／Ｃと化学修飾ＥＳＣＡにより測定される炭素繊維の
表面水酸基濃度指数Ｓ及び表面カルボキシル基濃度指数
ＫがＳ−０．０１０≧０．１０（Ｏ／Ｃ）≧Ｋ−０．０
１５を満足することを特徴とする炭素繊維、または、ス
トランド強度が３５０ ｋｇ／ｍｍ２ 以上であり、広
角Ｘ線回折による結晶の大きさＬｃが４０オングストロ
ーム以上であり、Ｌｃとラマン分光法による炭素繊維表
層部の非晶化度Δν（ｃｍ−１）がΔν≧１２００／Ｌ
ｃ＋３０を満足することを特徴とする炭素繊維である。
ここで、表層部の非晶化度Δνはラマン分光法で観察さ
れる１５８０ｃｍ−１のラマンバンドの半価幅を表わす
。[Means for Solving the Problems] In order to solve the above problems of the present invention, the carbon fiber of the present invention has one of the following structures. That is, the strand elastic modulus is 30t/m
m2 or more, and the surface oxygen concentration O/C of the carbon fiber measured by ESCA is 0.20 or less, and the surface hydroxyl group concentration index S and surface of the carbon fiber measured by O/C and chemical modification ESCA. Carboxyl group concentration index K is S-0.010≧0.10 (O/C)≧K-0.0
15, or a carbon fiber having a strand strength of 350 kg/mm2 or more, a crystal size Lc measured by wide-angle X-ray diffraction of 40 angstroms or more, and a carbon fiber characterized by satisfying Lc and Raman spectroscopy. The amorphous degree Δν (cm-1) of the surface layer is Δν≧1200/L
It is a carbon fiber characterized by satisfying c+30. Here, the amorphous degree Δν of the surface layer portion represents the half width of the Raman band of 1580 cm −1 observed by Raman spectroscopy.
【００１０】また、本発明の炭素繊維の製造方法は、次
の構成を有する。すなわち、ストランド弾性率が３０ｔ
／ｍｍ２ 以上である炭素繊維を陽極として電解質溶液
中で通電処理する炭素繊維の製造方法において、通電電
気量が１０〜１００クーロン／ｇ、通電処理回数を４回
以上とすることを特徴とする炭素繊維の製造方法である
。[0010] Furthermore, the method for manufacturing carbon fiber of the present invention has the following configuration. That is, the strand elastic modulus is 30t
/mm2 or more in a carbon fiber manufacturing method in which a carbon fiber having a carbon fiber size of 10 to 100 coulombs/g is used as an anode and is energized in an electrolyte solution, the carbon fiber being energized for 4 or more times. This is a method for producing fibers.
【００１１】まず、本発明の炭素繊維について詳細に説
明する。本発明は、ストランド弾性率３０ｔ／ｍｍ２
以上の炭素繊維を対象とするものである。ストランド弾
性率が３０ｔ／ｍｍ２ 未満の炭素繊維については、従
来公知の方法によっても比較的容易に母材樹脂との接着
力を向上させることができるから、本発明の対象外とし
た。なお、後述する本発明の処理方法の前後でストラン
ド弾性率の値そのものは変化しない。First, the carbon fiber of the present invention will be explained in detail. The present invention has a strand elastic modulus of 30t/mm2.
The above carbon fibers are targeted. Carbon fibers with a strand modulus of elasticity of less than 30 t/mm2 were excluded from the scope of the present invention because their adhesive strength with the base resin can be relatively easily improved by conventionally known methods. Note that the value of the strand elastic modulus itself does not change before and after the treatment method of the present invention, which will be described later.
【００１２】本発明において炭素繊維のストランド弾性
率とは、ＪＩＳ−Ｒ−７６０１の樹脂含浸ストランド試
験法に準じ、樹脂処方としては“ＢＡＫＥＬＩＴＥ”Ｅ
ＲＬ４２２１／３フッ化ホウ素モノエチルアミン／アセ
トン＝１００／３／４（重量部）を用いて測定した弾性
率をいう。In the present invention, the strand elastic modulus of carbon fiber is defined as "BAKELITE" E in accordance with the resin-impregnated strand test method of JIS-R-7601.
RL4221/3 refers to the elastic modulus measured using boron fluoride monoethylamine/acetone = 100/3/4 (parts by weight).
【００１３】本発明の炭素繊維は、ＥＳＣＡにより測定
される表面酸素濃度Ｏ／Ｃを０．２０以下とするもので
ある。該Ｏ／Ｃが０．２を越える炭素繊維は表面酸化処
理を強めに程こすことにより得られるのであるが、この
場合には、樹脂の官能基と炭素繊維最表面との化学結合
は強固になるものの、本来炭素繊維基質自身が有する強
度よりもかなり低い強度を有する酸化物層が炭素繊維表
層を被うことになるため、結果として得られるコンポジ
ットの機械的特性は低いものとなってしまう問題がある
。The carbon fiber of the present invention has a surface oxygen concentration O/C of 0.20 or less as measured by ESCA. Carbon fibers with O/C exceeding 0.2 can be obtained by subjecting them to strong surface oxidation treatment, but in this case, the chemical bonds between the resin functional groups and the outermost surface of the carbon fibers are not strong enough. However, since the carbon fiber surface layer is covered with an oxide layer that has a strength considerably lower than that of the carbon fiber matrix itself, the resulting composite has poor mechanical properties. There is.
【００１４】本発明において、ＥＳＣＡにより測定され
る表面酸素濃度Ｏ／Ｃとは、ＥＳＣＡにより次の手順に
従って求められる値をいう。先ず、溶媒でサイジング剤
などを除去した炭素繊維束をカットしてステンレス製の
試料支持台上に拡げて並べた後、光電子脱出角度を９０
゜とし、Ｘ線源としてＭｇＫα１，２ を用い、試料チ
ャンバー中を１×１０−８Ｔｏｒｒの真空度に保つ。測
定時の帯電に伴うピークの補正としてＣ１Ｓの主ピーク
の結合エネルギー値（Ｂ．Ｅ．）を２８４．６ ｅＶに
合わせる。Ｃ１Ｓピーク面積をＢ．Ｅ．として ２８２
〜２９６ ｅＶの範囲で直線のベースラインを引くこと
により求める。Ｏ１Ｓピーク面積をＢ．Ｅ．として ５
４０〜５２８ ｅＶの範囲で直線のベースラインを引く
ことにより求める。ここで、表面酸素濃度Ｏ／Ｃは、上
記Ｏ１Ｓピーク面積とＣ１Ｓピーク面積の比から、装置
固有の感度補正値で割ることにより算出した原子数比を
いうものである。なお、例えば、島津製作所（株）製Ｅ
ＳＣＡ−７５０を用いた場合には、上記装置固有の感度
補正値は２．８５となる。In the present invention, the surface oxygen concentration O/C measured by ESCA refers to a value determined by ESCA according to the following procedure. First, carbon fiber bundles from which the sizing agent and other substances have been removed with a solvent are cut, spread out and arranged on a stainless steel sample support stand, and then the photoelectron escape angle is adjusted to 90°.
The sample chamber was kept at a vacuum of 1 x 10-8 Torr using MgKα1,2 as an X-ray source. The binding energy value (B.E.) of the main peak of C1S is adjusted to 284.6 eV as a correction for the peak due to charging during measurement. The C1S peak area is expressed as B. E. as 282
It is determined by drawing a straight baseline in the range of ~296 eV. The O1S peak area is shown in B. E. as 5
It is determined by drawing a straight baseline in the range of 40 to 528 eV. Here, the surface oxygen concentration O/C is an atomic ratio calculated by dividing the ratio of the O1S peak area to the C1S peak area by a sensitivity correction value specific to the device. For example, E manufactured by Shimadzu Corporation
When SCA-750 is used, the sensitivity correction value unique to the above device is 2.85.
【００１５】また、本発明の炭素繊維は、Ｏ／Ｃと化学
修飾ＥＳＣＡにより測定される炭素繊維の表面水酸基濃
度指数Ｓ及び表面カルボキシル基濃度指数ＫがＳ−０．
０１０≧０．１０（Ｏ／Ｃ）≧Ｋ−０．０１５を満足す
るものである。Further, the carbon fiber of the present invention has a surface hydroxyl group concentration index S and a surface carboxyl group concentration index K measured by O/C and chemical modification ESCA of S-0.
010≧0.10 (O/C)≧K−0.015.
【００１６】かかる式を満足しない場合には、相対的に
水酸基よりもカルボキシル基の量が多いこととなり、こ
れでは、一般にコンポジットに使用される樹脂であるエ
ポキシ樹脂、ビスマレイミド樹脂、ポリイミド樹脂、ポ
リエーテルイミド樹脂、ポリアミド樹脂、ポリエステル
樹脂、ポリカーボネート樹脂などとの反応性及び結合性
が向上せず、ひいては、コンポジットのＩＬＳＳ及び９
０°ＴＳの向上は望めないし、また、樹脂の硬化速度を
遅延させることがあるなどの問題を有する。If this formula is not satisfied, the amount of carboxyl groups will be relatively greater than the amount of hydroxyl groups, and this will cause the resins generally used in composites, such as epoxy resins, bismaleimide resins, polyimide resins, and The reactivity and bonding properties with etherimide resin, polyamide resin, polyester resin, polycarbonate resin, etc. are not improved, and as a result, the ILSS and 9 of the composite are not improved.
It cannot be expected to improve the 0°TS, and it also has problems such as slowing down the curing speed of the resin.
【００１７】ここで、表面水酸基濃度指数Ｓとは、化学
修飾ＥＳＣＡにより、次の手順に従って求めた値をいう
。先ず、溶媒でサイジング剤などを除去した炭素繊維束
をカットして白金製の試料支持台上に拡げて並べ、０．
０４モル／ｌの無水３弗化酢酸気体を含んだ乾燥窒素ガ
ス中に３０℃で１０分間さらし、化学修飾処理した後、
Ｘ線光電子分光装置に光電子脱出角度を３５゜としてマ
ウントし、Ｘ線源としてＡｌＫα１，２ を用い、試料
チャンバー内を１×１０−８Ｔｏｒｒの真空度に保つ。
測定時の帯電に伴うピークの補正としてＣ１Ｓの主ピー
クの運動エネルギー値Ｂ．Ｅ．を２８４．６ ｅＶに合
わせる。Ｃ１Ｓピーク面積をＢ．Ｅ．として ２８２〜
２９６ ｅＶの範囲で直線のベースラインを引くことに
より求める。Ｆ１Ｓピーク面積をＢ．Ｅ．として ６８
２〜６９５ ｅＶの範囲で直線のベースラインを引くこ
とにより求める。ここで表面水酸基濃度指数Ｓは、上記
Ｆ１Ｓピーク面積とＣ１Ｓピーク面積の比を、装置固有
の感度補正値で割ることにより算出した原子数比をいう
ものである。なお、例えば、米国ＳＳＩ社製ＳＳＸ−１
００−２０６を用いた場合には上記装置固有の感度補正
値は３．９１９となる。[0017] Here, the surface hydroxyl group concentration index S refers to a value determined by chemically modified ESCA according to the following procedure. First, carbon fiber bundles from which the sizing agent and the like have been removed with a solvent are cut, spread out and arranged on a platinum sample support stand, and placed at 0.
After chemical modification treatment by exposing it to dry nitrogen gas containing 04 mol/l of anhydrous trifluoroacetic acid gas at 30°C for 10 minutes,
It is mounted on an X-ray photoelectron spectrometer with a photoelectron escape angle of 35°, AlKα1,2 is used as the X-ray source, and the inside of the sample chamber is maintained at a vacuum of 1×10 −8 Torr. The kinetic energy value B. of the main peak of C1S is used to correct the peak due to charging during measurement. E. is adjusted to 284.6 eV. The C1S peak area is expressed as B. E. As 282～
It is determined by drawing a straight baseline in the range of 296 eV. The F1S peak area is shown in B. E. as 68
It is determined by drawing a straight baseline in the range of 2 to 695 eV. Here, the surface hydroxyl group concentration index S is an atomic ratio calculated by dividing the ratio of the F1S peak area to the C1S peak area by a sensitivity correction value specific to the device. For example, SSX-1 manufactured by SSI, USA
When 00-206 is used, the sensitivity correction value unique to the above device is 3.919.
【００１８】また、表面カルボキシル基濃度指数Ｋとは
、化学修飾ＥＳＣＡにより、次の手順に従って求めた値
をいう。先ず、溶媒でサイジング剤などを除去した炭素
繊維束をカットして白金製の試料支持台上に拡げて並べ
、０．０２モル／ｌの３弗化エタノール気体，０．００
１モル／ｌのジシクロヘキシルカルボジイミド気体及び
０．０４モル／ｌのピリジン気体を含む空気中に６０℃
で８時間さらし、化学修飾処理した後、Ｘ線光電子分光
装置に光電子脱出角度を３５゜としてマウントし、Ｘ線
源としてＡｌＫα１，２ を用い、試料チャンバー内を
１×１０−８Ｔｏｒｒの真空度に保つ。測定時の帯電に
伴うピークの補正としてＣ１Ｓの主ピークの運動エネル
ギー値Ｂ．Ｅ．を２８４．６ ｅＶに合わせる。Ｃ１Ｓ
ピーク面積をＢ．Ｅ．として２８２〜２９６ ｅＶの範
囲で直線のベースラインを引くことにより求める。Ｆ１
Ｓピーク面積をＢ．Ｅ．として ６８２〜６９５ ｅＶ
の範囲で直線のベースラインを引くことにより求める。
ここで表面カルボキシル基濃度指数とは、上記Ｆ２ ピ
ーク面積とＣ１Ｓピーク面積の比を、装置固有の感度補
正値で割ることにより算出した原子数比をいうものであ
る。なお、例えば、米国ＳＳＩ社製ＳＳＸ−１００−２
０６を用いた場合には、上記感度補正値は３．９１９と
なる。Furthermore, the surface carboxyl group concentration index K refers to a value determined by chemically modified ESCA according to the following procedure. First, carbon fiber bundles from which sizing agents and the like have been removed with a solvent are cut, spread out and arranged on a platinum sample support stand, and treated with 0.02 mol/l of trifluoroethanol gas and 0.00 mol/l of trifluoroethanol gas.
60°C in air containing 1 mol/l dicyclohexylcarbodiimide gas and 0.04 mol/l pyridine gas.
After exposure for 8 hours and chemical modification treatment, it was mounted on an X-ray photoelectron spectrometer with a photoelectron escape angle of 35°, and using AlKα1,2 as the X-ray source, the inside of the sample chamber was kept at a vacuum level of 1 x 10-8 Torr. keep. The kinetic energy value B. of the main peak of C1S is used to correct the peak due to charging during measurement. E. is adjusted to 284.6 eV. C1S
The peak area is B. E. It is determined by drawing a straight baseline in the range of 282 to 296 eV. F1
The S peak area is expressed as B. E. as 682-695 eV
It is determined by drawing a straight baseline within the range of . Here, the surface carboxyl group concentration index refers to the atomic ratio calculated by dividing the ratio of the F2 peak area to the C1S peak area by a sensitivity correction value specific to the device. For example, SSX-100-2 manufactured by SSI, USA
06, the sensitivity correction value will be 3.919.
【００１９】また、本発明の課題は次の炭素繊維によっ
ても達成できる。すなわち、本発明の炭素繊維はストラ
ンド強度を３５０ ｋｇ／ｍｍ２ 以上とするものであ
る。ストランド強度は３５０ ｋｇ／ｍｍ２ 未満の場
合には補強繊維として優れた機能を示さないという問題
がある。ここで、本発明においてストランド強度は、前
記ストランド弾性率の測定と同条件でＪＩＳ−Ｒ−７６
０１の樹脂含浸ストランド試験法に準じて測定した強度
をいう。The objects of the present invention can also be achieved by the following carbon fibers. That is, the carbon fiber of the present invention has a strand strength of 350 kg/mm2 or more. When the strand strength is less than 350 kg/mm2, there is a problem that it does not exhibit an excellent function as a reinforcing fiber. Here, in the present invention, the strand strength is determined according to JIS-R-76 under the same conditions as the measurement of the strand elastic modulus.
This refers to the strength measured according to the resin-impregnated strand test method of No. 01.
【００２０】また、本発明の炭素繊維の広角Ｘ線回折に
よる結晶の大きさＬｃを４０オングストローム以上とす
るものである。該結晶の大きさＬｃが４０オングストロ
ーム未満の炭素繊維の場合には、表層の炭素網面があま
り発達していないため表面処理を特に厳しくしなくとも
官能基を多量に導入することが比較的容易であり、本発
明のようなマトリックス樹脂との接着力を向上させるた
めの技術を適用する必要性に乏しいからである。Further, the carbon fiber of the present invention has a crystal size Lc of 40 angstroms or more as measured by wide-angle X-ray diffraction. In the case of carbon fibers in which the crystal size Lc is less than 40 angstroms, the carbon network surface of the surface layer is not very developed, so it is relatively easy to introduce a large amount of functional groups without particularly severe surface treatment. This is because there is little need to apply the technique of the present invention for improving the adhesive force with the matrix resin.
【００２１】ここで、広角Ｘ線回折による結晶の大きさ
Ｌｃとは、広角Ｘ線回折により、次の手順に従って求め
た値をいう。すなわち、Ｘ線源として、Ｎｉフィルター
で単色化されたＣｕのＫα線を用い、２θ＝２６．０°
付近に観察される面指数（００２）のピークを赤道方向
にスキャンして得られたピークからその半価幅を求め、
次式により算出した値を結晶の大きさＬｃとする。[0021] Here, the crystal size Lc determined by wide-angle X-ray diffraction refers to a value determined by wide-angle X-ray diffraction according to the following procedure. That is, using Cu Kα rays monochromated with a Ni filter as an X-ray source, 2θ = 26.0°
Scan the peak of the surface index (002) observed nearby in the equator direction and find the half-width from the peak obtained,
Let the value calculated by the following formula be the crystal size Lc.
【００２２】Ｌｃ＝λ／（β０ ｃｏｓθ）ここで、
λ：Ｘ線の波長（この場合１．５４１８オングストロー
ム）、θ：回折角、β０ ：真の半価幅をいう。なお、
β０ は次式より算出される値を用いる。Lc=λ/(β0 cosθ) where,
λ: X-ray wavelength (1.5418 angstroms in this case), θ: diffraction angle, β0: true half-width. In addition,
For β0, use the value calculated from the following equation.
【００２３】β０ ＝（βｅ ２ −β１ ２ ）１／
２ ここで、βｅ ：見かけの半価幅、β１ ：装置定
数（理学電気社製４０３６Ａ２型Ｘ線発生装置を出力３
５ＫＶ， １５ｍＡで使用した場合には、１．０５×１
０−２ ｒａｄ）をいう。[0023] β0 = (βe 2 - β1 2 ) 1/
2 Here, βe: Apparent half-width, β1: Device constant (Rigaku Denki 4036A2 type X-ray generator output 3
When used at 5KV, 15mA, 1.05×1
0-2 rad).
【００２４】本発明の炭素繊維は、Ｌｃとラマン分光法
による炭素繊維表層部の非晶化度Δν（ｃｍ−１）がΔ
ν≧１２００／Ｌｃ＋３０を満足するものである。Ｌｃ
が大きくなるほど炭素網面が発達し、Ｌｃに応じて樹脂
との接着力を向上させるために必要な炭素繊維表層部の
非晶化度Δνの値の適正範囲が存在することが判明した
ものである。ＬｃとΔνがかかる関係を満足しない場合
には、接着性に関与する官能基を炭素繊維表面に均一に
分散させて形成することができず、樹脂との接着力が不
十分になる問題がある。The carbon fiber of the present invention has an amorphous degree Δν (cm-1) of the carbon fiber surface layer measured by Lc and Raman spectroscopy.
It satisfies ν≧1200/Lc+30. Lc
It was found that the carbon network surface develops as Lc increases, and that there is an appropriate range of the value of the amorphous degree Δν of the carbon fiber surface layer necessary to improve the adhesive strength with the resin, depending on Lc. be. If Lc and Δν do not satisfy this relationship, the functional groups involved in adhesiveness cannot be uniformly dispersed and formed on the carbon fiber surface, leading to a problem of insufficient adhesive force with the resin. .
【００２５】ここで、ラマン分光法による炭素繊維表層
部の非晶化度Δν（ｃｍ−１）とは、レーザーラマン分
光法により次の手順に従って求めた値をいう。すなわち
、炭素繊維束をそのまま解析に供し、励起波長５１４５
オングストロームのアルゴンイオンレーザー（ビーム径
：２００ μｍ×３００ μｍ）を用い、炭素繊維表面
のラマンスペクトルを測定し、１５８０ｃｍ−１近傍に
認められるピークの半価幅を炭素繊維表層部の非晶化度
Δν（ｃｍ−１）とする。[0025] Here, the amorphous degree Δν (cm-1) of the carbon fiber surface layer measured by Raman spectroscopy refers to a value determined by laser Raman spectroscopy according to the following procedure. That is, the carbon fiber bundle is subjected to analysis as it is, and the excitation wavelength is 5145.
The Raman spectrum of the carbon fiber surface was measured using an Angstrom argon ion laser (beam diameter: 200 μm x 300 μm), and the half-width of the peak observed near 1580 cm was calculated as the degree of amorphousness of the surface layer of the carbon fiber. Let it be Δν (cm-1).
【００２６】次に本発明の炭素繊維を得るための方法に
ついて説明する。表面酸化処理前の炭素繊維として特に
重要な特性は、後の表面酸化処理過程で酸化処理が炭素
繊維内部にまで進行し難い緻密な表面構造を有すること
である。表面緻密性の高い炭素繊維を得るためには、プ
リカーサーとして緻密な表面構造を形成させることが効
果的であり、例えば、ポリアクリロニトリル系炭素繊維
の場合、具体的には、プリカーサーの表面緻密性の尺度
であるヨウ素吸着法による明度差ΔＬが３０以下、さら
には、２０以下であるプリカーサーを用いることが好ま
しい。Next, a method for obtaining the carbon fiber of the present invention will be explained. A particularly important characteristic of carbon fibers before surface oxidation treatment is that they have a dense surface structure that prevents oxidation treatment from progressing into the interior of the carbon fibers during the subsequent surface oxidation treatment process. In order to obtain carbon fibers with high surface density, it is effective to form a dense surface structure as a precursor. For example, in the case of polyacrylonitrile carbon fibers, specifically, the surface density of the precursor is It is preferable to use a precursor whose lightness difference ΔL as measured by the iodine adsorption method is 30 or less, more preferably 20 or less.
【００２７】このような表面緻密性の高いプリカーサー
を焼成して炭素繊維に変換する。該プリカーサーの焼成
工程の条件、すなわち酸化（耐炎化）工程、炭化工程の
条件としては特に限定されるものではないが、プリカー
サーの緻密性を炭素繊維となった後も維持する条件が好
ましい。[0027] Such a precursor with high surface density is converted into carbon fiber by firing. The conditions for the firing step of the precursor, that is, the conditions for the oxidation (flame resistance) step and the carbonization step, are not particularly limited, but conditions that maintain the denseness of the precursor even after it becomes carbon fiber are preferred.
【００２８】例えば、窒素などの不活性雰囲気中での炭
化条件としては、３００〜７００℃ならびに１０００〜
１２００℃の温度領域における昇温速度を１０００℃／
分以下、好ましくは５００℃／分以下とすることが好ま
しい。For example, the carbonization conditions in an inert atmosphere such as nitrogen are 300-700°C and 1000-700°C.
The temperature increase rate in the 1200℃ temperature range is 1000℃/
The heating rate is preferably 500° C./min or less, preferably 500° C./min or less.
【００２９】また、後に続く表面酸化処理過程において
、酸化が繊維内部にまで進行し難くし、表面処理後の炭
素繊維の強度等が低下するのを防止する観点から、表面
処理を施すべき炭素繊維の弾性率を３０ｔ／ｍｍ２ 以
上、好ましくは４０ｔ／ｍｍ２ 以上とするものである
。かかる弾性率の炭素繊維は、より高温で炭化あるいは
黒鉛化することにより得ることができる。[0029] In addition, in the subsequent surface oxidation treatment process, carbon fibers to be subjected to surface treatment are made from the viewpoint of making it difficult for oxidation to progress to the inside of the fibers and preventing the strength etc. of the carbon fibers from decreasing after the surface treatment. The modulus of elasticity is 30 t/mm2 or more, preferably 40 t/mm2 or more. Carbon fibers having such an elastic modulus can be obtained by carbonization or graphitization at higher temperatures.
【００３０】かくして得られる炭素繊維を電解表面処理
する方式としては、図２に示す直接通電方式と図１に示
す非接触通電方式とがあるが、毛羽の発生、ロールへの
巻き付きを少なく、給電ロールと炭素繊維の間でのスパ
ークの発生などの問題を軽減する観点からは非接触通電
方式が好ましい。Methods for electrolytically surface-treating the carbon fibers thus obtained include the direct energization method shown in FIG. 2 and the non-contact energization method shown in FIG. 1. A non-contact energization method is preferable from the viewpoint of reducing problems such as generation of sparks between the roll and the carbon fibers.
【００３１】図１、図２、図３において、１は処理され
る炭素繊維、２は陰極層、３は陰極板、４は陽極層、５
は陽極板を示し、図２において、６は陽極ローラー、７
は浴中ガイドローラーを示す。なお、炭素繊維１は矢印
の方向に走行する。In FIGS. 1, 2, and 3, 1 is a carbon fiber to be treated, 2 is a cathode layer, 3 is a cathode plate, 4 is an anode layer, and 5 is a carbon fiber to be treated.
indicates an anode plate; in FIG. 2, 6 is an anode roller, 7 is an anode plate;
indicates an in-bath guide roller. Note that the carbon fiber 1 runs in the direction of the arrow.
【００３２】非接触通電方式で電解処理する場合、炭素
繊維が陰極として作用する電流給電槽すなわち陽極槽内
で、炭素繊維表面が還元されるため、図３に示すように
陰極槽２を１層配置しその後段に陽極層４を１層配置し
たのみの場合、陰極槽２において炭素繊維表面に生成し
た官能基は、引続き陽極槽４内を通過するに際して還元
され、せっかく生成した表面官能基の減少が起こること
となる。In the case of electrolytic treatment using the non-contact energization method, the surface of the carbon fiber is reduced in the current feeding tank, that is, the anode tank, where the carbon fiber acts as a cathode, so the cathode tank 2 is formed in one layer as shown in FIG. In the case where only one layer of the anode layer 4 is placed after the carbon fiber, the functional groups generated on the surface of the carbon fiber in the cathode bath 2 are reduced as they continue to pass through the anode bath 4, and the surface functional groups that have been generated are reduced. A decrease will occur.
【００３３】したがって、複数の陰極槽を配置し、該陰
極槽の間に陽極槽を配置した電解槽を用いて電解表面処
理を行うことにより、陽極槽での印加電圧を小さくして
還元反応を起き難くする必要があり、かかる観点から本
発明の製造方法においては、陰極槽２の数、すなわち、
通電処理回数を４回以上とするものである。なお、陰極
槽２の数、すなわち、通電処理回数が多いほど陽極と陰
極間の電圧は小さくなるが、無制限に段数を増すことは
工業上実際的ではなく、陰極層を５０槽以下、さらには
８槽以上１２槽以下とすることが好ましい。Therefore, by performing electrolytic surface treatment using an electrolytic cell in which a plurality of cathode cells are arranged and an anode cell is arranged between the cathode cells, the reduction reaction can be carried out by reducing the applied voltage in the anode cell. From this point of view, in the manufacturing method of the present invention, the number of cathode tanks 2, that is,
The number of times of energization processing is set to four or more times. Note that the voltage between the anode and the cathode decreases as the number of cathode tanks 2 increases, that is, the number of times of energization treatment increases, but it is not industrially practical to increase the number of stages indefinitely, and the number of cathode layers is limited to 50 or less, or even It is preferable that the number of tanks is 8 or more and 12 or less.
【００３４】また、このように通電処理回数を４回以上
、すなわち陰極槽の数を４層以上とし、該陰極槽の間に
陽極槽を配置した電解槽では、陽極と陰極の間にかける
電圧を後述の範囲内に容易に設定できるため、安全に操
業を行いうるという利点もある。In addition, in an electrolytic cell in which the number of times of energization is four or more, that is, the number of cathode cells is four or more layers, and an anode cell is arranged between the cathode cells, the voltage applied between the anode and the cathode is can be easily set within the range described below, which also has the advantage of allowing safe operation.
【００３５】電解処理に用いられる電解質としては、電
解処理に際して陽極から酸素を発生し得、かつ表面カル
ボキシル基濃度指数を小さくして、表面水酸基濃度指数
をできるかぎり大きくするものであれば限定されないが
、生成した水酸基が還元され易いため、前記した還元反
応を抑制することができる観点からは、特に、アルカリ
性の電解質を用いることが有効であり、さらに好ましく
はｐＨが１０以上である電解質水溶液を用いることが好
ましい。なお、請求項１の炭素繊維を得るためは、アル
カリ性電解質を用いる必要がある。一方、請求項２の炭
素繊維を得るにはかかる制限はなく、アルカリ性電解質
のみならず酸性電解質を用いてもよい。アルカリ性電解
質としては、例えば、水酸化ナトリウム、水酸化カリウ
ム、水酸化テトラメチルアンモニウム、水酸化テトラエ
チルアンモニウム等の無機あるいは有機の強アルカリあ
るいはそれらの混合物等を用いることができる。また、
酸性電解質としては、燐酸、硝酸、硫酸、ホウ酸、炭酸
等の無機塩、酢酸、酪酸、アクリル酸、マレイン酸、シ
ュウ酸等の有機酸、硝酸アンモニウム、硫酸アンモニウ
ム、硫化水素アンモニウム、燐酸二水素アンモニウム等
の無機塩を用いることができる。中性電解質としては、
硝酸ナトリウム、硝酸カリウム、硫酸ナトリウム等の無
機塩、ギ酸アンモニウム、酢酸アンモニウム、シュウ酸
アンモニウム等の有機塩を用いることができる。The electrolyte used in the electrolytic treatment is not limited as long as it can generate oxygen from the anode during the electrolytic treatment, and it can reduce the surface carboxyl group concentration index and increase the surface hydroxyl group concentration index as much as possible. Since the generated hydroxyl groups are easily reduced, it is particularly effective to use an alkaline electrolyte from the viewpoint of being able to suppress the reduction reaction described above, and more preferably to use an electrolyte aqueous solution having a pH of 10 or more. It is preferable. Note that in order to obtain the carbon fiber of claim 1, it is necessary to use an alkaline electrolyte. On the other hand, to obtain the carbon fiber of claim 2, there is no such restriction, and not only an alkaline electrolyte but also an acidic electrolyte may be used. As the alkaline electrolyte, for example, inorganic or organic strong alkalis such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or mixtures thereof can be used. Also,
Examples of acidic electrolytes include inorganic salts such as phosphoric acid, nitric acid, sulfuric acid, boric acid, and carbonic acid, organic acids such as acetic acid, butyric acid, acrylic acid, maleic acid, and oxalic acid, ammonium nitrate, ammonium sulfate, ammonium hydrogen sulfide, ammonium dihydrogen phosphate, etc. Inorganic salts of can be used. As a neutral electrolyte,
Inorganic salts such as sodium nitrate, potassium nitrate, and sodium sulfate, and organic salts such as ammonium formate, ammonium acetate, and ammonium oxalate can be used.
【００３６】電解処理の処理量としては、使用する炭素
繊維の弾性率により異なるが、小さすぎると酸化が有効
に進行せず、また大きすぎると前記した還元の悪影響も
顕著となる。具体的には、１つの槽における炭素繊維へ
の通電電気量が１０クーロン／ｇ以上、１００クーロン
／ｇ以下とするものであり、１０クーロン／ｇ以上、８
０クーロン／ｇ以下とすれば好ましい。１０クーロン／
ｇ未満では、表層の結晶性の低下が十分に進まず、処理
回数を多くする必要があり生産性が悪化する。一方、１
００クーロン／ｇを越える場合には炭素繊維基質の強度
低下が大きくなる。処理時間については、数秒から数十
分、さらには１０秒から２分程度が好ましい。また、表
層の結晶性の低下を適度な範囲に維持する観点からは、
通電処理の総電気量は１２０クーロン／ｇ以上１０００
クーロン／ｇ以下、さらには２００クーロン／ｇ以上５
００クーロン／ｇ以下とするのが好ましい。The amount of electrolytic treatment varies depending on the elastic modulus of the carbon fiber used, but if it is too small, oxidation will not proceed effectively, and if it is too large, the above-mentioned adverse effects of reduction will become significant. Specifically, the amount of electricity applied to the carbon fibers in one tank is 10 coulombs/g or more and 100 coulombs/g or less, and 10 coulombs/g or more and 8
It is preferable to set it to 0 coulomb/g or less. 10 coulombs/
If it is less than g, the crystallinity of the surface layer will not decrease sufficiently, and it will be necessary to increase the number of treatments, resulting in poor productivity. On the other hand, 1
If it exceeds 0.00 coulombs/g, the strength of the carbon fiber matrix will decrease significantly. The processing time is preferably from several seconds to several tens of minutes, and more preferably from about 10 seconds to 2 minutes. In addition, from the perspective of maintaining the decrease in crystallinity of the surface layer within an appropriate range,
The total amount of electricity for energization treatment is 120 coulombs/g or more 1000
Coulombs/g or less, even 200 coulombs/g or more5
It is preferable to set it to 00 coulombs/g or less.
【００３７】また、電解処理を行った後、水洗・乾燥す
る工程において、乾燥温度が高すぎると炭素繊維の最表
面に露出した官能基は熱分解により消失し易い。したが
って、できる限り低い温度で乾燥することが望ましく、
具体的には乾燥温度が２００℃以下、さらに好ましくは
１７０℃以下で乾燥することが望ましい。Furthermore, in the washing and drying steps after the electrolytic treatment, if the drying temperature is too high, the functional groups exposed on the outermost surface of the carbon fibers are likely to disappear due to thermal decomposition. Therefore, it is desirable to dry at the lowest possible temperature.
Specifically, it is desirable to dry at a drying temperature of 200°C or lower, more preferably 170°C or lower.
【００３８】[0038]
【実施例】以下、実施例により本発明をさらに具体的に
説明する。なお、実施例中、ストランド物性、ΔＬ、毛
羽発生数、ＩＬＳＳ及び９０°ＴＳは次の方法に従って
測定した。[Examples] The present invention will be explained in more detail with reference to Examples below. In the examples, strand physical properties, ΔL, number of fluffs, ILSS, and 90°TS were measured according to the following methods.
【００３９】＜プリカーサーの緻密性ΔＬ＞繊維長が５
〜７ｃｍの乾燥試料を約０．５ｇ精秤し、２００ｍｌの
共栓付き三角フラスコに採り、これにヨウ素溶液（Ｉ２
：５１ｇ，２，４−ジクロロフェノール：１０ｇ、酢
酸：９０ｇ、およびヨウ化カリウム：１００ｇを秤量し
、１ｌのメスフラスコに移して、水で溶かして定容とす
る）１００ｍｌを加えて、６０±０．５℃で５０分間振
とうしながら吸着処理を行う。ヨウ素を吸着した試料を
流水中で３０分間水洗した後、延伸脱水（２０００ｒｐ
ｍ，１分）を行い、すばやく風乾する。この試料を開繊
した後、ハンター型色差計で明度（Ｌ値）を測定する（
Ｌ１ ）。一方ヨウ素の吸着処理を行わない対応の試料
を開繊し、同様にハンター型色差計で明度を測定する（
Ｌ０ ）。Ｌ１ −Ｌ０ より明度差ΔＬを求める。な
お本発明者らは、カラーマシン（株）製、カラーマシン
ＣＭ−２５型のハンター型色差計を用いて測定した。<Precursor denseness ΔL> Fiber length is 5
Approximately 0.5 g of a ~7 cm dry sample was accurately weighed, placed in a 200 ml Erlenmeyer flask with a stopper, and iodine solution (I2
Weigh out 10 g of 2,4-dichlorophenol, 90 g of acetic acid, and 100 g of potassium iodide, transfer to a 1 L volumetric flask, dissolve with water to make a constant volume), add 100 ml, and add 100 ml of Adsorption treatment is performed while shaking at 0.5°C for 50 minutes. After washing the iodine-adsorbed sample in running water for 30 minutes, it was subjected to stretching dehydration (2000 rpm).
m, 1 minute) and quickly air-dry. After opening this sample, the lightness (L value) is measured using a Hunter color difference meter (
L1). On the other hand, a corresponding sample without iodine adsorption treatment was opened, and the brightness was similarly measured using a Hunter color difference meter (
L0). The brightness difference ΔL is determined from L1 −L0. The inventors of the present invention carried out the measurement using a Hunter type color difference meter, Model Color Machine CM-25, manufactured by Color Machine Co., Ltd.
【００４０】＜毛羽発生数＞電解処理後の乾燥工程を経
て走行する炭素繊維糸条に対し、側面から直角にレーザ
ー光線を照射し、発生した毛羽数を毛羽検出装置で検出
、カウントし、炭素繊維糸条１ｍ当りの毛羽個数（個／
ｍ）で表示した。<Number of fuzz generated> A laser beam is irradiated from the side at right angles to the carbon fiber thread running through the drying process after electrolytic treatment, and the number of fuzz generated is detected and counted by a fuzz detection device. Number of fuzz pieces per meter of yarn (pieces/
m).
【００４１】＜層間剪断強度ＩＬＳＳ＞■コンポジット
試験片の作製
円周約２．７ｍの鋼製ドラムに炭素繊維と組み合わせる
樹脂をシリコン塗布ペーパー上にコーティングした樹脂
フィルムを巻き、次に該樹脂フィルム上にクリールから
引き出した炭素繊維をトラバースを介して巻き取り、配
列して、さらにその繊維の上から前記樹脂フィルムを再
度かぶせた後、加圧ロールで回転加圧して樹脂を繊維内
に含浸せしめ、巾３００ｍｍ、長さ２．７ｍの一方向プ
リプレグを作製する。このとき、繊維間への樹脂含浸を
良くするためにドラムは５０〜６０℃に加熱し、またプ
リプレグの繊維目付はドラムの回転数とトラバースの送
り速度を調整することによって、繊維目付約２００ｇ／
ｍ２ 、樹脂量約３５重量％のプリプレグを作製した。
このように作製したプリプレグを裁断、一方向に積層し
、オートクレーブを用いて１８０℃、６ ｋｇ／ｃｍ２
下で２時間加熱硬化して、ＩＬＳＳ測定用として肉厚約
２ｍｍの一方向硬化板を作製した。このように作製した
一方向硬化板を、長さ方向に繊維が平行に配向するよう
に、巾１２．７ｍｍ、長さ２８ｍｍに切断して、ＩＬＳ
Ｓ用の試験片を作製した。
■ＩＬＳＳの測定
測定は通常の３点曲げ試験治具を用いて支持スパンを試
験片肉厚の４倍に設定し、島津製オートグラフを用いて
負荷速度２．５ｍｍ／ｍｉｎで測定した。なお、樹脂と
しては下記組成のものを用いた。
ＥＬＭ４３４［住友化学（株）］
：３５部
ＥＰ８２８ ［ペトロケミカルズ（株）］
：３５部 エピクロ
ン１５２ ［大日本インキ（株）］
：３０部 ４，４’−ジアミノジフェ
ニルスルフォン［住友化学（株）］：３２部 ３フッ
化ホウ素モノエチルアミン
： ０．５部<Interlaminar Shear Strength ILSS> ■ Preparation of Composite Test Piece A resin film in which a resin combined with carbon fiber is coated on silicone coated paper is wound around a steel drum with a circumference of about 2.7 m, and then a resin film is coated on silicone coated paper. The carbon fibers pulled out from the creel are wound up through a traverse and arranged, and the resin film is again placed over the fibers, and then the resin is impregnated into the fibers by rotating and pressurizing them with a pressure roll, A unidirectional prepreg with a width of 300 mm and a length of 2.7 m is produced. At this time, the drum is heated to 50 to 60°C to improve the resin impregnation between the fibers, and the fiber weight of the prepreg is adjusted to approximately 200 g/200 g by adjusting the rotation speed of the drum and the traverse feed speed.
m2 and a prepreg having a resin amount of about 35% by weight was produced. The prepreg prepared in this way was cut, laminated in one direction, and heated to 6 kg/cm2 at 180°C using an autoclave.
A unidirectionally cured plate with a wall thickness of approximately 2 mm was prepared for use in ILSS measurement by heating and curing for 2 hours. The unidirectionally cured board thus produced was cut into pieces of 12.7 mm in width and 28 mm in length so that the fibers were oriented parallel to each other in the length direction.
A test piece for S was prepared. (2) Measurement of ILSS Measurement was carried out using an ordinary three-point bending test jig, with the support span set to four times the thickness of the test piece, and using a Shimadzu Autograph at a loading rate of 2.5 mm/min. The resin used had the following composition. ELM434 [Sumitomo Chemical Co., Ltd.]
:35 copies
EP828 [Petrochemicals Co., Ltd.]
: 35 parts Epicron 152 [Dainippon Ink Co., Ltd.]
: 30 parts 4,4'-diaminodiphenylsulfone [Sumitomo Chemical Co., Ltd.]: 32 parts Boron trifluoride monoethylamine
: 0.5 part
【００４２】＜９０°
引張強度（９０°ＴＳ）＞■コンポジット試験片の作製
上記したＩＬＳＳ試験片の作製と同様の方法で作製した
一方向硬化板を、長さ方向に繊維が直角に配向するよう
に、巾２５．４ｍｍ、長さ２５０ｍｍに切断して、９０
°ＴＳ用の試験片を作製した。<90°
Tensile strength (90°TS)>■ Preparation of composite test piece A unidirectionally cured plate prepared in the same manner as the above-mentioned method for preparing the ILSS test piece was cured to a width of 25 mm so that the fibers were oriented at right angles in the length direction. Cut to 4 mm and 250 mm long, 90
A test piece for °TS was prepared.
【００４３】■９０°ＴＳの測定
測定は試験長１２７ｍｍに設定し、島津製オートグラフ
を用いて負荷速度１．０ｍｍ／ｍｉｎで測定した。■Measurement of 90°TS The test length was set to 127 mm, and the measurement was carried out using a Shimadzu autograph at a loading rate of 1.0 mm/min.
【００４４】なお、レーザーラマン分光法による炭素繊
維表層部の非晶化度Δνの測定は、フランス国Ｊｏｂｉ
ｎ−Ｙｖｏｎ社製Ｒａｍａｎｏｒ Ｕ−１０００マクロ
ラマンシステムを用いておこなった。[0044]Measurement of the amorphous degree Δν of the carbon fiber surface layer by laser Raman spectroscopy was carried out by Jobi, France.
This was carried out using a Ramanor U-1000 Macro Raman system manufactured by n-Yvon.
【００４５】（実施例１〜３、比較例１）アクリロニト
リル（以下、ＡＮ）９９．５モル％、イタコン酸０．５
モル％からなる固有粘度［η］が１．８０のＡＮ共重合
体のジメチルスルホキシド（以下、ＤＭＳＯ）溶液にア
ンモニアを吹き込み、該共重合体のカルボキシル末端基
をアンモニウム基で置換してポリマを変性し、この変性
ポリマの濃度が２０重量％であるＤＭＳＯ溶液を作成し
、紡糸原液とした。(Examples 1 to 3, Comparative Example 1) Acrylonitrile (hereinafter referred to as AN) 99.5 mol%, itaconic acid 0.5
Ammonia is blown into a dimethyl sulfoxide (DMSO) solution of an AN copolymer with an intrinsic viscosity [η] of 1.80 consisting of mol%, and the carboxyl terminal group of the copolymer is replaced with an ammonium group to modify the polymer. Then, a DMSO solution containing the modified polymer at a concentration of 20% by weight was prepared and used as a spinning stock solution.
【００４６】この紡糸原液を４５℃にて、孔径０．１５
ｍｍ、孔数１５００ホールの紡糸口金を通して、一旦空
気中に吐出させ、約３ｍｍの空間を走行させた後に、１
０℃の３０％ＤＭＳＯ水溶液中に導入して、凝固糸とし
た。この凝固糸条を水洗した後、温水中で４段の延伸を
行い、浴延伸糸を得た。延伸倍率は全体で４倍であり、
延伸浴の最高温度は６０℃であった。次に、この浴延伸
糸に変性シリコン系化合物を主成分とする油剤を付与し
た後、１３０℃の加熱ロールを用いて乾燥、および緻密
化を行った。さらに引き続いて、加圧スチーム中で３倍
に延伸して、単糸繊度が０．８デニール、トータル繊度
が１２００デニールのアクリル系繊維糸条を得た。ここ
で得られた繊維糸条のΔＬは１７であった。[0046] This spinning dope was heated to 45°C and the pore size was 0.15.
Once discharged into the air through a spinneret with 1,500 holes and running through a space of approximately 3 mm, 1
It was introduced into a 30% DMSO aqueous solution at 0°C to form a coagulated thread. After washing the coagulated yarn with water, it was drawn in four stages in warm water to obtain a bath-drawn yarn. The overall stretching ratio is 4 times,
The maximum temperature of the stretching bath was 60°C. Next, an oil agent containing a modified silicone compound as a main component was applied to the bath-drawn yarn, followed by drying and densification using a heated roll at 130°C. Subsequently, it was drawn three times in pressurized steam to obtain an acrylic fiber yarn having a single yarn fineness of 0.8 denier and a total fineness of 1200 denier. The fiber yarn obtained here had a ΔL of 17.
【００４７】このアクリル系繊維糸条を２４０〜２６０
℃の空気中で１．０５倍に延伸しながら耐炎化処理を行
い、引き続いて最高温度が１４００℃の窒素雰囲気中で
、３００〜７００℃の温度域における昇温速度を２５０
℃／分、１０００〜１２００℃の温度域における昇温速
度を４００℃／分に設定した炭化炉で処理を行い、炭素
繊維に変換した。得られた炭素繊維の目付は０．０６１
ｇ／ｍ、比重は１．８０、ストランド引張強度は５２０
ｋｇ／ｍｍ２ 、弾性率は３１ｔ／ｍｍ２ であった
。[0047] This acrylic fiber thread has a diameter of 240 to 260
Flame-retardant treatment is performed while stretching 1.05 times in air at a temperature of 1,400 °C, followed by a temperature increase rate of 250 °C in a temperature range of 300 to 700 °C in a nitrogen atmosphere with a maximum temperature of 1,400 °C.
The carbonization process was carried out in a carbonization furnace in which the heating rate in the temperature range of 1000 to 1200°C was set to 400°C/min, and the carbon fibers were converted into carbon fibers. The obtained carbon fiber has a basis weight of 0.061
g/m, specific gravity is 1.80, strand tensile strength is 520
kg/mm2, and the elastic modulus was 31t/mm2.
【００４８】かくして得られた原料炭素繊維糸条を図１
に示す陰極槽を４槽配置した非接触通電方式電解槽を用
いて、濃度０．１％の水酸化ナトリウム水溶液を電解液
として、糸速度１ｍ／分で、１つの陰極槽における通電
電気量を５，１０，３０，８０，１２０クーロン／ｇと
変更して電解処理した。このような電解処理の施された
炭素繊維糸条を続いて水洗し、１５０℃の加熱空気中で
乾燥した。The raw carbon fiber yarn thus obtained is shown in FIG.
Using a non-contact energizing electrolytic cell with four cathode cells arranged as shown in Figure 1, the amount of electricity energized in one cathode cell was calculated using an aqueous sodium hydroxide solution with a concentration of 0.1% as the electrolyte at a yarn speed of 1 m/min. The electrolytic treatment was performed by changing the coulombs/g to 5, 10, 30, 80, and 120 coulombs/g. The electrolytically treated carbon fiber yarn was then washed with water and dried in heated air at 150°C.
【００４９】このようにして得られた表面処理炭素繊維
糸条の力学特性および表面特性の評価結果を原料炭素繊
維と対比して表１に示す。また乾燥工程後の毛羽発生数
を表１に併せて示した。Table 1 shows the evaluation results of the mechanical properties and surface properties of the surface-treated carbon fiber yarn thus obtained, in comparison with the raw carbon fiber. Table 1 also shows the number of fluffs generated after the drying process.
【００５０】[0050]
【表１】[Table 1]
【００５１】（比較例２）電解処理装置として図３に示
す陰極槽を１段配置した非接触通電方式電解槽を用いた
以外は実施例３と同様の方法で表面処理炭素繊維糸条を
得た。得られた表面処理炭素繊維の糸条の力学特性及び
表面特性の評価結果を表１に示す。また乾燥工程後の毛
羽発生数を表１に併せて示した。(Comparative Example 2) A surface-treated carbon fiber yarn was obtained in the same manner as in Example 3, except that a non-contact energizing electrolytic cell having one stage of cathode cells shown in FIG. 3 was used as the electrolytic treatment apparatus. Ta. Table 1 shows the evaluation results of the mechanical properties and surface properties of the yarn of the surface-treated carbon fiber obtained. Table 1 also shows the number of fluffs generated after the drying process.
【００５２】（比較例３）電解液として０．１％の硝酸
水溶液を用いた以外は実施例２と同様の方法で表面処理
炭素繊維糸条を得た。得られた表面処理炭素繊維の糸条
の力学特性及び表面特性の評価結果を表１に示す。また
乾燥工程後の毛羽発生数を表１に併せて示した。(Comparative Example 3) A surface-treated carbon fiber yarn was obtained in the same manner as in Example 2 except that a 0.1% nitric acid aqueous solution was used as the electrolyte. Table 1 shows the evaluation results of the mechanical properties and surface properties of the yarn of the surface-treated carbon fiber obtained. Table 1 also shows the number of fluffs generated after the drying process.
【００５３】（実施例４）実施例１で用いたのと同様の
アクリル系繊維糸条を２４０〜２６０℃の空気中で１．
０５倍に延伸しながら耐炎化処理を行い、引き続いて最
高温度が１７００℃の窒素雰囲気中で、３００〜７００
℃の温度域における昇温速度を２５０℃／分、１０００
〜１２００℃の温度域における昇温速度を４００℃／分
に設定した炭化炉で処理を行った後、最高温度が２４０
０゜Ｃの窒素雰囲気中で１．０２倍の延伸を行いながら
１分間熱処理を行い、黒鉛繊維に変換した。得られた炭
素繊維の目付は０．０５７ｇ／ｍ、比重は１．８４、ス
トランド引張強度は５００ ｋｇ／ｍｍ２ 、弾性率は
４５ｔ／ｍｍ２ であった。(Example 4) Acrylic fiber yarn similar to that used in Example 1 was heated in air at 240 to 260°C for 1.
Flameproofing treatment is performed while stretching to 0.5 times, and then 300 to 700
Temperature increase rate in the temperature range of ℃ 250℃/min, 1000℃
After processing in a carbonization furnace with a heating rate of 400°C/min in the temperature range of ~1200°C, the maximum temperature was 240°C.
Heat treatment was performed for 1 minute while stretching 1.02 times in a nitrogen atmosphere at 0°C to convert it into graphite fiber. The obtained carbon fiber had a basis weight of 0.057 g/m, a specific gravity of 1.84, a strand tensile strength of 500 kg/mm2, and an elastic modulus of 45 t/mm2.
【００５４】かくして得られた原料黒鉛繊維糸条を、陰
極槽を８槽配置した非接触通電方式電解槽を用いて、濃
度０．１％の水酸化テトラエチルアンモニウム（以下、
ＴＥＡＨ）水溶液を電解液として、糸速度１ｍ／分で、
１槽当りの電気量が６０クーロン／ｇとなるよう電解処
理した。このような電解処理の施された炭素繊維糸条を
続いて水洗し、１５０℃の加熱空気中で乾燥した。[0054] The raw graphite fiber yarn obtained in this way was heated to 0.1% tetraethylammonium hydroxide (hereinafter referred to as
TEAH) aqueous solution as the electrolyte, at a yarn speed of 1 m/min,
Electrolytic treatment was performed so that the amount of electricity per tank was 60 coulombs/g. The electrolytically treated carbon fiber yarn was then washed with water and dried in heated air at 150°C.
【００５５】このようにして得られた表面処理炭素繊維
糸条の力学特性および表面特性の評価結果を原料炭素繊
維と対比して表２に示す。Table 2 shows the evaluation results of the mechanical properties and surface properties of the surface-treated carbon fiber yarn thus obtained, in comparison with the raw carbon fiber.
【００５６】[0056]
【表２】[Table 2]
【００５７】（実施例５）電解処理装置として図２に示
す直接通電方式電解槽を用いた以外は実施例４と同様の
方法で表面処理炭素繊維糸条を得た。得られた表面処理
炭素繊維の糸条の力学特性及び表面特性の評価結果を表
２に示す。(Example 5) A surface-treated carbon fiber yarn was obtained in the same manner as in Example 4, except that the direct current electrolytic cell shown in FIG. 2 was used as the electrolytic treatment apparatus. Table 2 shows the evaluation results of the mechanical properties and surface properties of the yarn of the surface-treated carbon fiber obtained.
【００５８】（比較例４）電解液として０．１％硫酸水
溶液を用いた以外は実施例４と同様の方法で表面処理炭
素繊維糸条を得た。得られた表面処理炭素繊維の糸条の
力学特性及び表面特性の評価結果を表２に併せて示す。(Comparative Example 4) A surface-treated carbon fiber yarn was obtained in the same manner as in Example 4, except that a 0.1% sulfuric acid aqueous solution was used as the electrolyte. Table 2 also shows the evaluation results of the mechanical properties and surface properties of the yarn of the surface-treated carbon fibers obtained.
【００５９】（実施例６〜８、比較例５、６）ＡＮ９９
．５モル％、イタコン酸０．５モル％の共重合体をアン
モニアで変性し、この共重合体の濃度が１３％であるＤ
ＭＳＯ溶液を紡糸原液に用いた。この原液中の共重合体
の極限粘度は１．８０であった。表４に示すように、種
々の共重合体の濃度と温度からなる紡糸原液を、孔径０
．１５ｍｍ、孔数３０００ホールの紡糸口金を通して、
一旦空気中に吐出させ、約３ｍｍの空間を走行させた後
に、５℃にコントロールした３０％ＤＭＳＯ水溶液中に
導入して、凝固糸とした。この凝固糸条を水洗した後、
温水中で４段の延伸を行い、浴延伸糸を得た。最終延伸
浴の温度は、単繊維同士の融着が発生しない範囲で、最
も高い温度に設定した。ここで得られた浴延伸糸に、乾
燥糸重量に対して０．７〜０．９％の付着量となるよう
に、実施例１と同様のシリコン系成分を含む油剤を付与
した後、１３０℃の加熱ロールを用いて乾燥、および緻
密化を行った。この乾燥緻密化後の糸条を、さらに、延
伸後に得られる前駆体繊維の伸度が１０．５〜１１．２
％となるように、３〜５ｋｇ／ｃｍ２・Ｇ の飽和スチ
ーム中で２〜３倍に延伸して、単糸繊度が０．８デニー
ル、トータル繊度が２４００デニールのアクリル系繊維
糸条を得た。(Examples 6 to 8, Comparative Examples 5 and 6) AN99
．． A copolymer containing 5 mol% of itaconic acid and 0.5 mol% of itaconic acid was modified with ammonia, and the concentration of this copolymer was 13%.
MSO solution was used as the spinning stock solution. The intrinsic viscosity of the copolymer in this stock solution was 1.80. As shown in Table 4, spinning stock solutions consisting of various copolymer concentrations and temperatures were mixed with a pore size of 0.
．． Through a spinneret with a diameter of 15 mm and 3000 holes,
Once it was discharged into the air and run through a space of about 3 mm, it was introduced into a 30% DMSO aqueous solution controlled at 5° C. to form a coagulated thread. After washing this coagulated thread with water,
Four stages of drawing were performed in warm water to obtain a bath-drawn yarn. The temperature of the final drawing bath was set at the highest temperature within the range where single fibers did not fuse together. The bath-drawn yarn obtained here was coated with an oil agent containing a silicone component similar to that in Example 1 so that the coating amount was 0.7 to 0.9% based on the weight of the dry yarn. Drying and densification were performed using a heating roll at .degree. The elongation of the precursor fiber obtained after drawing the yarn after drying and densification is 10.5 to 11.2.
%, it was drawn 2 to 3 times in saturated steam at 3 to 5 kg/cm2・G to obtain an acrylic fiber yarn with a single yarn fineness of 0.8 denier and a total fineness of 2400 denier. .
【００６０】このアクリル繊維糸条を炭化炉の最高温度
を１６００゜Ｃとした以外は実施例１と同様の方法で炭
素繊維に変換した。得られた炭素繊維の目付は０．１２
ｇ／ｍ、比重は１．８２、ストランド試験法により測定
される弾性率は３４ｔ／ｍｍ２ であった。[0060] This acrylic fiber yarn was converted into carbon fiber in the same manner as in Example 1 except that the maximum temperature of the carbonization furnace was 1600°C. The obtained carbon fiber has a basis weight of 0.12
g/m, the specific gravity was 1.82, and the elastic modulus measured by the strand test method was 34 t/mm2.
【００６１】かくして得られた原料炭素繊維糸条を図１
に示す陰極槽を４槽配置した非接触通電方式電解槽を用
いて、濃度０．１％の水酸化ナトリウム水溶液を電解液
として、糸速度０．５ｍ／分で、１槽当りの電気量が４
０クーロン／ｇとなるよう電解処理した。このような電
解処理の施された炭素繊維糸条を続いて水洗し、１５０
℃の加熱空気中で乾燥した。The raw carbon fiber yarn thus obtained is shown in FIG.
Using a non-contact energizing electrolytic cell with four cathode cells as shown in Figure 1, using a sodium hydroxide aqueous solution with a concentration of 0.1% as the electrolyte, at a thread speed of 0.5 m/min, the amount of electricity per cell was 4
Electrolytic treatment was carried out so that the concentration was 0 coulomb/g. The electrolytically treated carbon fiber yarn was then washed with water and heated to 150 ml.
Dry in heated air at °C.
【００６２】このようにして得られた表面処理炭素繊維
糸条の力学特性および表面特性の評価結果を表３に示す
。Table 3 shows the evaluation results of the mechanical properties and surface properties of the surface-treated carbon fiber yarn thus obtained.
【００６３】[0063]
【表３】[Table 3]
【００６４】（実施例９，比較例７，８）ＡＮ９９．４
モル％とメタクリル酸０．６モル％からなる共重合体を
用いて、乾湿式紡糸方法により単繊維デニール０．７ｄ
，フィラメント数１２０００のアクリル系繊維を得た。
得られた繊維束を２４０〜２８０℃の空気中で、延伸比
１．０５で加熱し、耐炎化繊維に転換し、ついで窒素雰
囲気中３００〜９００℃の温度領域での昇温速度を２０
０℃／分とし１０％の延伸を行なった後、１７００℃で
炭化し、更に窒素雰囲気中２４００℃で黒鉛化し、得ら
れた炭素繊維を、１．５重量％のＴＥＡＨ水溶液中、１
槽当りの電気量が６０Ｃ／ｇの電解酸化処理を電解槽８
槽を用いて行った。得られた炭素繊維のストランド強度
は４２０ ｋｇ／ｍｍ２ であり、ＩＬＳＳは８．０
ｋｇ／ｍｍ２ であった。１槽当りの電気量が４８０Ｃ
／ｇで１回処理を施した炭素繊維のストランド強度およ
びＩＬＳＳはそれぞれ、２９０ ｋｇ／ｍｍ２ ，６．
５ ｋｇ／ｍｍ２ であり、電解を繰り返すことにより
基質強度の低下を抑えてＩＬＳＳが大幅に向上したこと
がわかる。 得られた炭素繊維の特性を表４に示した
。(Example 9, Comparative Examples 7 and 8) AN99.4
Using a copolymer consisting of mol % and methacrylic acid 0.6 mol %, a single fiber denier of 0.7 d was produced by a dry-wet spinning method.
, an acrylic fiber having 12,000 filaments was obtained. The obtained fiber bundle was heated in air at 240 to 280°C at a drawing ratio of 1.05 to convert it into flame-resistant fibers, and then the temperature increase rate in the temperature range of 300 to 900°C was increased to 20°C in a nitrogen atmosphere.
After 10% stretching at 0°C/min, carbonization at 1700°C and further graphitization at 2400°C in a nitrogen atmosphere, the obtained carbon fiber was drawn in 1.5% by weight TEAH aqueous solution.
Electrolytic oxidation treatment with electricity amount per tank of 60C/g is carried out in electrolytic tank 8.
This was done using a tank. The strand strength of the obtained carbon fiber was 420 kg/mm2, and the ILSS was 8.0.
kg/mm2. Electricity amount per tank is 480C
The strand strength and ILSS of the carbon fiber treated once at 290 kg/mm2 and 6.
5 kg/mm2, and it can be seen that repeating electrolysis suppressed the decrease in substrate strength and significantly improved ILSS. Table 4 shows the properties of the obtained carbon fibers.
【００６５】[0065]
【表４】[Table 4]
【００６６】（実施例１０〜１２，比較例９〜１５）実
施例９において処理条件を表４のように変更した以外は
、実施例９と同様に処理して炭素繊維を得た。得られた
炭素繊維の特性を表４に併せて示した。本発明により、
繰り返し電解することにより基質強度の低下を抑えてＩ
ＬＳＳが大幅に向上したことがわかる。(Examples 10 to 12, Comparative Examples 9 to 15) Carbon fibers were obtained in the same manner as in Example 9, except that the treatment conditions were changed as shown in Table 4. The properties of the obtained carbon fibers are also shown in Table 4. According to the present invention,
By repeating electrolysis, the decrease in substrate strength is suppressed and I
It can be seen that LSS has been significantly improved.
【００６７】（実施例１３）２４００℃で黒鉛化処理を
行った炭素繊維を陽極として、１．０重量％の硫酸水溶
液中、１槽当りの電気量が６０Ｃ／ｇの電解酸化を電解
槽４槽用いて行い、水洗、乾燥を行ったのち、続けて得
られた炭素繊維を陽極として１．５重量％のＥＡＨ水溶
液中、１槽当りの電気量が６０Ｃ／ｇの電解酸化処理を
電解槽４槽用いて行った。得られた炭素繊維は、実施例
９より非晶化が進みＩＬＳＳは８．３ｋｇ／ｍｍ２ ま
で向上したことがわかる。(Example 13) Using a carbon fiber graphitized at 2400° C. as an anode, electrolytic oxidation was carried out in electrolytic bath 4 in a 1.0% by weight sulfuric acid aqueous solution with an amount of electricity of 60 C/g per bath. After washing with water and drying, electrolytic oxidation treatment was carried out using the obtained carbon fiber as an anode in a 1.5% by weight EAH aqueous solution with an amount of electricity of 60 C/g per tank in an electrolytic tank. The experiment was conducted using 4 tanks. It can be seen that the obtained carbon fiber was more amorphous than in Example 9, and the ILSS was improved to 8.3 kg/mm2.
【００６８】[0068]
【発明の効果】本発明の炭素繊維は、母材樹脂との結合
に直接関与する特定の表面官能基を豊富に有しているた
め、コンポジットの接着強度を著しく向上することが可
能となるため、樹脂との接着強度の不足により従来使用
が困難であった構造部材にも炭素繊維を使用できるよう
になり、材料設計の自由度を向上させることができる。[Effects of the Invention] The carbon fibers of the present invention have an abundance of specific surface functional groups that are directly involved in bonding with the base resin, making it possible to significantly improve the adhesive strength of the composite. Carbon fibers can now be used in structural members that were previously difficult to use due to lack of adhesive strength with resin, and the degree of freedom in material design can be improved.
【図１】本発明の炭素繊維を製造するのに好適な非接触
通電法による多段電解表面処理装置の一例を示す側面図
である。FIG. 1 is a side view showing an example of a multi-stage electrolytic surface treatment apparatus using a non-contact energization method suitable for producing the carbon fiber of the present invention.
【図２】本発明の炭素繊維を製造するのに用いられる直
接通電法による炭素繊維の多段電解表面処理装置の一例
を示す側面図である。FIG. 2 is a side view showing an example of an apparatus for multi-stage electrolytic surface treatment of carbon fibers using a direct energization method, which is used to produce the carbon fibers of the present invention.
【図３】比較例に用いられる非接触通電法による１段の
電解表面処理装置を示す側面図である。FIG. 3 is a side view showing a one-stage electrolytic surface treatment apparatus using a non-contact energization method used in a comparative example.
１：炭素繊維 ２：電解槽（陰極槽） ３：陰極板 ４：陽極槽 ５：陽極板 ６：陽極ローラー ７：浴中ガイドローラー 1: Carbon fiber 2: Electrolytic cell (cathode cell) 3: Cathode plate 4: Anode tank 5: Anode plate 6: Anode roller 7: Bath guide roller
Claims (7)
であり、かつＸ線光電子分光法により測定される炭素繊
維の表面酸素濃度Ｏ／Ｃが０．２０以下であり、かつＯ
／Ｃと化学修飾Ｘ線光電子分光法により測定される炭素
繊維の表面水酸基濃度指数Ｓ及び表面カルボキシル基濃
度指数Ｋが次式を満足することを特徴とする炭素繊維。 Ｓ−０．０１０≧０．１０（Ｏ／
Ｃ）≧Ｋ−０．０１５Claim 1: The strand elastic modulus is 30 t/mm2 or more, and the surface oxygen concentration O/C of the carbon fiber measured by X-ray photoelectron spectroscopy is 0.20 or less, and
/C and chemical modification A carbon fiber characterized in that a surface hydroxyl group concentration index S and a surface carboxyl group concentration index K, which are measured by X-ray photoelectron spectroscopy, satisfy the following formula. S-0.010≧0.10(O/
C)≧K-0.015
５０ ｋｇ／ｍｍ２ 以上であり、広角Ｘ線回折による
結晶の大きさＬｃが４０オングストローム以上であり、
Ｌｃとラマン分光法による炭素繊維表層部の非晶化度Δ
ν（ｃｍ−１）が次式を満足することを特徴とする炭素
繊維。 Δν≧１２００／Ｌｃ＋３０[Claim 2] Strand strength is 3
50 kg/mm2 or more, and the crystal size Lc by wide-angle X-ray diffraction is 40 angstroms or more,
Amorphousity Δ of carbon fiber surface layer measured by Lc and Raman spectroscopy
A carbon fiber characterized in that ν (cm-1) satisfies the following formula. Δν≧1200/Lc+30
である炭素繊維を陽極として電解質溶液中で通電処理す
る炭素繊維の製造方法において、通電電気量が１０〜１
００クーロン／ｇ、通電処理回数を４回以上とすること
を特徴とする炭素繊維の製造方法。3. A method for producing carbon fibers in which a carbon fiber having a strand modulus of elasticity of 30 t/mm2 or more is used as an anode and is energized in an electrolyte solution, wherein the amount of electricity to be energized is 10 to 1.
00 coulomb/g, and the number of times of energization treatment is 4 or more times.
用いることを特徴とする請求項３の炭素繊維の製造方法
。4. The method for producing carbon fibers according to claim 3, wherein an alkaline electrolyte solution is used as the electrolyte solution.
とを特徴とする請求項３または請求項４の炭素繊維の製
造方法。5. The method for producing carbon fibers according to claim 3 or 4, wherein the carbon fiber is subjected to a non-contact energization treatment in an electrolyte solution.
以上１０００クーロン／ｇ以下であることを特徴とする
請求項３、請求項４または請求項５の炭素繊維の製造方
法。Claim 6: The total amount of electricity in the energization process is 120 coulombs/g.
6. The method for producing carbon fibers according to claim 3, 4 or 5, wherein the carbon fiber is 1000 coulombs/g or less.
炭素繊維が、ヨウ素吸着法による表面緻密性ΔＬ３０以
下のアクリル繊維を前駆体繊維として得られるものであ
ることを特徴とする請求項３、請求項４、請求項５また
は請求項６記載の炭素繊維の製造方法。7. The carbon fiber having a strand elastic modulus of 30 t/mm 2 or more is obtained by using an acrylic fiber having a surface density ΔL of 30 or less by an iodine adsorption method as a precursor fiber. 4. The method for producing carbon fiber according to claim 5 or 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3132839A JP2530767B2 (en) | 1991-06-04 | 1991-06-04 | Carbon fiber and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3132839A JP2530767B2 (en) | 1991-06-04 | 1991-06-04 | Carbon fiber and manufacturing method thereof |
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| Publication Number | Publication Date |
|---|---|
| JPH04361619A true JPH04361619A (en) | 1992-12-15 |
| JP2530767B2 JP2530767B2 (en) | 1996-09-04 |
Family
ID=15090728
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3132839A Expired - Fee Related JP2530767B2 (en) | 1991-06-04 | 1991-06-04 | Carbon fiber and manufacturing method thereof |
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| Country | Link |
|---|---|
| JP (1) | JP2530767B2 (en) |
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|---|---|---|---|---|
| JPH02259118A (en) * | 1988-12-06 | 1990-10-19 | Mitsubishi Rayon Co Ltd | Graphite fiber having high tensile strength |
| JPH02269867A (en) * | 1989-04-11 | 1990-11-05 | Nippon Steel Corp | Method for carrying out surface electrolytic oxidation of carbon fiber tow having high elasticity |
| JPH02307967A (en) * | 1989-05-18 | 1990-12-21 | Mitsubishi Rayon Co Ltd | Production of surface-modified carbon fiber |
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1991
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02259118A (en) * | 1988-12-06 | 1990-10-19 | Mitsubishi Rayon Co Ltd | Graphite fiber having high tensile strength |
| JPH02269867A (en) * | 1989-04-11 | 1990-11-05 | Nippon Steel Corp | Method for carrying out surface electrolytic oxidation of carbon fiber tow having high elasticity |
| JPH02307967A (en) * | 1989-05-18 | 1990-12-21 | Mitsubishi Rayon Co Ltd | Production of surface-modified carbon fiber |
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