JPH02289651A - Hybrid fiber-reinforced plastic composite material - Google Patents
Hybrid fiber-reinforced plastic composite materialInfo
- Publication number
- JPH02289651A JPH02289651A JP23693489A JP23693489A JPH02289651A JP H02289651 A JPH02289651 A JP H02289651A JP 23693489 A JP23693489 A JP 23693489A JP 23693489 A JP23693489 A JP 23693489A JP H02289651 A JPH02289651 A JP H02289651A
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- fiber
- carbon
- composite material
- inorganic
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims description 12
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims description 12
- 239000000835 fiber Substances 0.000 claims abstract description 179
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 80
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 229920003023 plastic Polymers 0.000 claims abstract description 21
- 239000004033 plastic Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 241000234282 Allium Species 0.000 claims abstract description 7
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- 239000012779 reinforcing material Substances 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 3
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 33
- -1 polycyclic aromatic compound Chemical class 0.000 claims description 30
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 25
- 229920006231 aramid fiber Polymers 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000004760 aramid Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000011882 ultra-fine particle Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract 1
- 238000005452 bending Methods 0.000 description 49
- 238000000034 method Methods 0.000 description 39
- 239000011295 pitch Substances 0.000 description 29
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 25
- 239000008096 xylene Substances 0.000 description 25
- 239000003822 epoxy resin Substances 0.000 description 20
- 229920000647 polyepoxide Polymers 0.000 description 20
- 229920005604 random copolymer Polymers 0.000 description 20
- 238000009987 spinning Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 229920001558 organosilicon polymer Polymers 0.000 description 19
- 239000002243 precursor Substances 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010304 firing Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920000271 Kevlar® Polymers 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000004761 kevlar Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IINOLFPQEZQVMB-UHFFFAOYSA-N ethanol;1,2-xylene Chemical group CCO.CC1=CC=CC=C1C IINOLFPQEZQVMB-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011316 heat-treated pitch Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- 238000012643 polycondensation polymerization Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000012783 reinforcing fiber Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011300 coal pitch Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000011301 petroleum pitch Substances 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004412 Bulk moulding compound Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 241000219122 Cucurbita Species 0.000 description 2
- 235000009852 Cucurbita pepo Nutrition 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000003677 Sheet moulding compound Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009730 filament winding Methods 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 2
- 229920003257 polycarbosilane Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 101000685083 Centruroides infamatus Beta-toxin Cii1 Proteins 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 101150023756 HSPA13 gene Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910007933 Si-M Inorganic materials 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910008318 Si—M Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005567 polycyclic polymer Polymers 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 239000002990 reinforced plastic Substances 0.000 description 1
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、特定の無機繊維と炭素繊維、ガラス繊維、ボ
ロン繊維、アルミナ繊維、窒化珪素繊維、アラミド繊維
、炭化珪素繊維、カーボンを芯線とする炭化珪素繊維及
びＳｉ−Ｍ−Ｃ−０繊維（ＭはＴｉ又はＺｒを示す。）
からなる繊維のうち少なくとも一種の繊維とのハイブリ
ッド繊維を強化材とし、プラスチックをマトリックスと
する機械的性質の優れたハイブリッド繊維強化プラスチ
ック複合材料に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention provides a method using specific inorganic fibers, carbon fibers, glass fibers, boron fibers, alumina fibers, silicon nitride fibers, aramid fibers, silicon carbide fibers, and carbon as core wires. silicon carbide fiber and Si-M-C-0 fiber (M represents Ti or Zr)
The present invention relates to a hybrid fiber-reinforced plastic composite material with excellent mechanical properties, which uses a hybrid fiber with at least one type of fiber consisting of as a reinforcing material and a plastic as a matrix.
（従来の技術及びその問題点）
従来、強化材として、各種素材の有する特性を活用する
ため、２種以上の繊維をマトリックス中に入れたハイブ
リッド繊維強化プラスチック複合材料の研究が進められ
ている．
例えば、エポキシ樹脂、変性エポキシ樹脂、ポリエステ
ル樹脂、ポリイミド樹脂等のプラスチック類を強化する
ハイブリッド繊維としては、力一ボン／ガラス、カーボ
ン／アラミド繊維（ケブラー）、ボロン／カーボン、ボ
ロン／ケブラー、ポロン／ガラス、セラミック繊維／ケ
ブラー、ケブラー／ガラスなどの研究がなされているが
、カーボン／ガラス、カーボン／ケブラーが圧倒的に多
く、実際の応用もほぼこの２種類に限定されている。(Prior art and its problems) In order to take advantage of the properties of various materials as reinforcing materials, research has been progressing on hybrid fiber-reinforced plastic composite materials in which two or more types of fibers are placed in a matrix. For example, hybrid fibers that strengthen plastics such as epoxy resin, modified epoxy resin, polyester resin, and polyimide resin include Rikibon/glass, carbon/aramid fiber (Kevlar), boron/carbon, boron/Kevlar, and poron/ Research has been conducted on glass, ceramic fiber/Kevlar, Kevlar/glass, etc., but carbon/glass and carbon/Kevlar are by far the most common, and actual applications are almost limited to these two types.
しかしながら、炭素繊維を用いる場合は、樹脂との濡れ
性が劣るため繊維の表面処理が必要であり、しかも表面
処理した炭素繊維を用いても、その複合材料は眉間剪断
強度が低く、繊維に垂直方向の引張強度が低いため樹脂
と繊維が剥がれやすく、疲労強度が低く、曲げ衝撃値が
低いため破壊が起こりやすく実用上問題となっている。However, when carbon fiber is used, surface treatment of the fiber is required due to poor wettability with resin, and even if surface-treated carbon fiber is used, the composite material has low glabella shear strength and perpendicular to the fiber. Because the tensile strength in the direction is low, the resin and fibers tend to separate, and the fatigue strength is low, and the bending impact value is low, making it easy to break, which poses a practical problem.
ガラス繊維を用いる場合は引張強度、弾性率が低いため
充分な補強効果が得られない。ボロン繊維及びカーボン
繊維を芯線とする炭化珪素繊維を用いる場合は、径が太
いためこれらの繊維を強化材とするプラスチック複合材
料は、繊維体積率の高いものが得られず、用途によって
は機械的特性が充分とは言えない。When glass fiber is used, a sufficient reinforcing effect cannot be obtained due to its low tensile strength and low elastic modulus. When silicon carbide fibers with boron fibers and carbon fibers as core wires are used, plastic composite materials reinforced with these fibers cannot be produced with a high fiber volume ratio due to their large diameters, and depending on the application, mechanical It cannot be said that the characteristics are sufficient.
アラミド繊維を用いる場合は圧縮に対して弱いため疲労
強度が低い。When using aramid fibers, fatigue strength is low because they are weak against compression.
これらの問題点を解決するため、特開昭６２−７７３７
号公報には、Ｓｉ−Ｍ−Ｃ−０繊維（ＭはＴｉ又はＺｒ
を示す。）と炭素繊維、ガラス繊維、ボロン繊維、アラ
ミド繊維及びカーボンを芯線とする炭化珪素繊維からな
る群から選ばれた少なくとも一種の繊維とのハイブリッ
ド繊維を強化材としたハイブリッド繊維強化プラスチッ
ク複合材料が開示されている。In order to solve these problems, Japanese Patent Application Laid-Open No. 62-7737
In the publication, Si-M-C-0 fiber (M is Ti or Zr
shows. ) and at least one type of fiber selected from the group consisting of carbon fiber, glass fiber, boron fiber, aramid fiber, and silicon carbide fiber having a carbon core as a reinforcing material. has been done.
本発明は、上記公報に開示されたハイブリッド繊維強化
プラスチック複合材料に比べ、弾性率がより改善され、
コスト的に大変優位なハイブリッド繊維強化プラスチッ
ク複合材料を提供する。The present invention has improved elastic modulus compared to the hybrid fiber-reinforced plastic composite material disclosed in the above publication,
We provide hybrid fiber-reinforced plastic composite materials that are extremely cost-effective.
（問題点を解決するための手段）
本発明は、ハイブリッド繊維の各素材が有する上記問題
点を改良し、機械的性質に優れたハイブリッド繊維強化
プラスチック複合材料を提供するものである．
本発明における無機繊維はプラスチックとの親和性が強
く、可撓性に冨むため容易に紡織が可能であり、上述の
他の繊維特有の欠点を補い補強効果を増強する。このた
め、本発明で特定した無機繊維を用いたハイブリッド繊
維による強化プラスチック複合材料では、眉間剪断強度
、曲げ衝撃値が大幅に改善される。(Means for Solving the Problems) The present invention aims to improve the above-mentioned problems of each hybrid fiber material and provide a hybrid fiber-reinforced plastic composite material with excellent mechanical properties. The inorganic fibers of the present invention have a strong affinity with plastics and are highly flexible, so they can be easily spun and woven, thereby compensating for the above-mentioned drawbacks peculiar to other fibers and enhancing the reinforcing effect. Therefore, the glabella shear strength and bending impact value of the reinforced plastic composite material made of hybrid fibers using the inorganic fibers specified in the present invention are significantly improved.
本発明の複合材料は、無機繊維と炭素繊維、ガラス繊維
、ボロン繊維、アルミナ繊維、窒化珪素繊維、アラミド
繊維、炭化珪素繊維、カーボンを芯線とする炭化珪素繊
維及びＳｉ−Ｍ−Ｃ−０繊維（ＭはＴｉ又はＺｒを示す
。）からなる群から選ばれた少なくとも一種の繊維との
ハイブリッド繊維を強化材とし、プラスチックをマトリ
ックスとするプラスチック複合材料において、前記無機
繊維がチタン、ジルコニウム及びハフニウムカラなる群
から選ばれる少なくとも一種類の元素及び珪素を含有す
る金属多環状芳香族重合体から得られる無機繊維であっ
て、その構成成分が、ａ）該重合体を構成するメソフヱ
ーズ状態にある多環状芳香族化合物から導かれるラジア
ル構造、オニオン構造、ランダム構造、コアラジアル構
造、スキンオニオン構造及びモザイク構造からなる群か
ら選ばれる少なくとも一種の結晶配列状態を示す炭素質
、
ｂ）該重合体を構成する有機溶媒不溶分を含む光学的等
方性の多環状芳香族化合物から導かれる、無配向状態の
結晶質炭素及び／又は非晶質炭素、及び
Ｃ）■Ｓｉ，Ｍ，Ｃ及びＯから実質的になる非晶質物質
、及び／又は
■実質的にβ−ＳｉＣ．．ＭＣ，β−ＳｉＣとＭＣの固
溶体及びＭＣ．．からなる粒径が５００人以下の結晶超
微粒子と、非晶質のＳｉＯｙ及びＭＯ．との集合体であ
り
構成元素の割合がＳｔ ；５〜７０重量％、Ｍ；０．５
〜４５重量％、Ｃ：２０〜４０重量％及びＯ ； ０．
０ １〜３０重量％である、Ｓｉ−Ｍ−Ｃ−０物！（
上記式中、ＭはＴｉ，Ｚｒ及びＨｆから選択される少な
くとも一種の元素であり、Ｏ＜ｘ＜１、０＜ｙ≦２、Ｏ
＜ｚ≦２である。）
であることを特徴とするハイブリッド繊維強化プラスチ
ック複合材料である。The composite material of the present invention includes inorganic fibers and carbon fibers, glass fibers, boron fibers, alumina fibers, silicon nitride fibers, aramid fibers, silicon carbide fibers, silicon carbide fibers having a carbon core, and Si-M-C-0 fibers. (M represents Ti or Zr), wherein the inorganic fibers include titanium, zirconium, and hafnium color. An inorganic fiber obtained from a metal polycyclic aromatic polymer containing silicon and at least one element selected from the group consisting of: a) a polycyclic polymer in a mesophase state constituting the polymer; a carbonaceous material exhibiting at least one type of crystal orientation selected from the group consisting of a radial structure, an onion structure, a random structure, a core radial structure, a skin onion structure, and a mosaic structure derived from an aromatic compound; b) constituting the polymer; Non-oriented crystalline carbon and/or amorphous carbon derived from an optically isotropic polycyclic aromatic compound containing organic solvent insoluble matter, and C) ■ Substantially from Si, M, C and O and/or ■ substantially β-SiC. ．． MC, a solid solution of β-SiC and MC, and MC. ．． crystalline ultrafine particles with a particle size of 500 or less, and amorphous SiOy and MO. The proportion of the constituent elements is St: 5 to 70% by weight, M: 0.5
-45% by weight, C: 20-40% by weight and O; 0.
0 1 to 30% by weight of Si-M-C-0! (
In the above formula, M is at least one element selected from Ti, Zr and Hf, O<x<1, 0<y≦2, O
<z≦2. ) is a hybrid fiber-reinforced plastic composite material.
本発明における無機繊維についてまず説明する。First, the inorganic fiber in the present invention will be explained.
以下の説明における「部」は全て「重量部」であり、「
％」は「重量％」である。All "parts" in the following explanations are "parts by weight", and "parts" are "parts by weight".
%” is “% by weight”.
本発明における無機繊維は、前述した構成成分ａ）、ｂ
）及びＣ）からなっており、Ｓｔ；０．０１〜３０％、
Ｍ ． ０． ０ １〜１０％、Ｃ；６５〜９９．９％
及びＯ；０．００１〜１０％、好ましくはＳ ｉ ；
０．１〜２５％、Ｍ；０．０１〜８％、Ｃ：７４〜９９
．８％及びｏ ． ｏ． ｏ ｉ〜８％から実質的に構
成されている。The inorganic fiber in the present invention has the above-mentioned components a) and b.
) and C), St; 0.01 to 30%,
M. 0. 0 1-10%, C; 65-99.9%
and O; 0.001 to 10%, preferably S i ;
0.1-25%, M; 0.01-8%, C: 74-99
．． 8% and o. o. oi~8%.
この無機繊維の構成成分である結晶質炭素は５００人以
下の結晶子サイズを有し、１．５人の分解能を有する高
分解能電子顕微鏡において、繊維軸方向に配向した３．
２人の（００２）面に相当する微細なラティスイメージ
像が観察されうる超微粒子のグラファイト結晶である。The crystalline carbon, which is a component of this inorganic fiber, has a crystallite size of 500 or less, and is oriented in the fiber axis direction under a high-resolution electron microscope with a resolution of 1.5.
It is an ultrafine graphite crystal in which a fine lattice image corresponding to two (002) planes can be observed.
無機繊維中の結晶質炭素は、ラジアル構造、オニオン構
造、ランダム構造、コアラジアル構造、スキンオニオン
構造、モザイク構造及び一部ラジアル構造を含むランダ
ム構造等をとることができる。これは、原料中にメソフ
ェーズ多環状芳香族化合物が存在することに起因する。The crystalline carbon in the inorganic fibers can have a radial structure, an onion structure, a random structure, a core radial structure, a skin onion structure, a mosaic structure, a random structure including a partial radial structure, and the like. This is due to the presence of mesophase polycyclic aromatic compounds in the raw materials.
この無機繊維における構成成分ａ）及びｂ》の総和１０
０部に対する構成成分Ｃ）の割合は０．０１５〜２００
部であり、且つ構成成分ａ）、ｂ）の比率は１：０．０
２〜４である。The total of constituent components a) and b) in this inorganic fiber is 10
The ratio of component C) to 0 parts is 0.015 to 200
and the ratio of constituent components a) and b) is 1:0.0
It is 2-4.
構成成分ａ）及びｂ）の総和１００部に対する構成成分
Ｃ）の割合が０．０１５未満の場合は、ほとんどピッチ
繊維と変わらず、耐酸化性や濡れ性の向上は望めず、上
記割合が２００部を越えた場合はグラファイトの微細結
晶が効果的には生成せず、高弾性率の繊維が得られない
。If the ratio of component C) to 100 parts of the total of components a) and b) is less than 0.015, it is almost the same as pitch fiber, and no improvement in oxidation resistance or wettability can be expected; If it exceeds 50%, fine graphite crystals will not be effectively generated and fibers with a high elastic modulus will not be obtained.
本発明における無機繊維は、
１）結合単位（Ｓ ｉ −ＣＨ． ） 、又は結合単位
（ＳｉＣＨ２）と結合単位（Ｓｉ−Ｓｔ）から主として
なり、珪素原子の側鎖に水素原子、低級アルキル基、フ
エニル基及びシリル基からなる群から選ばれる側鎖基を
有し、上記結合単位からなる主骨格の珪素原子に、チタ
ン、ジルコニウム及びハフニウムからなる群から選ばれ
る少なくとも一種類の原子が、直接又は酸素原子を介し
て、珪素原子の少なくとも一部と結合している遷移金属
含有有機珪素重合体の珪素原子の少なくとも一部が、石
油系又は石炭系のピッチあるいはその熱処理物の芳香族
環の炭素と結合したランダム共重合体及び
２）石油系又は石炭系ピッチを熱処理して得られるメソ
フェーズ状態又はメソフェーズと光学的等方相との両相
からなる多環状芳香族化合物（以下両者を総称して［メ
ソフエーズ多環状芳香族化合物」と言う。）を、
２００〜５００゜Ｃの範囲の温度で加熱反応及び／又は
加熱溶融して金属含有多環状芳香族重合体を得る第１工
程、
上記金属含有多環状芳香族重合体の紡糸原液を調製して
紡糸する第２工程、
該紡糸原糸を張力下あるいは無張力下で不融化する第３
工程、及び
不融化した前記紡糸繊維を真空中あるいは不活性ガス雰
囲気中で８００〜３ ０ ０ ０ ’Ｃの範囲の温度で
焼成する第４工程
からなる製造方法により提供される。The inorganic fiber in the present invention mainly consists of 1) a bonding unit (S i -CH.), or a bonding unit (SiCH2) and a bonding unit (Si-St), and has a hydrogen atom, a lower alkyl group, or a lower alkyl group in the side chain of a silicon atom. It has a side chain group selected from the group consisting of a phenyl group and a silyl group, and at least one type of atom selected from the group consisting of titanium, zirconium, and hafnium is directly or At least some of the silicon atoms of the transition metal-containing organosilicon polymer bonded to at least some of the silicon atoms via oxygen atoms are carbon atoms in the aromatic ring of petroleum-based or coal-based pitch or heat-treated products thereof. and 2) a mesophase state obtained by heat-treating petroleum-based or coal-based pitch, or a polycyclic aromatic compound consisting of both mesophase and optically isotropic phases (hereinafter both are collectively referred to as (referred to as "Mesophase polycyclic aromatic compound") at a temperature in the range of 200 to 500°C to obtain a metal-containing polycyclic aromatic polymer. A second step of preparing a spinning dope of a polycyclic aromatic polymer and spinning it, and a third step of infusibleizing the spinning yarn under tension or without tension.
and a fourth step of firing the infusible spun fibers at a temperature in the range of 800 to 3000'C in vacuum or in an inert gas atmosphere.
上記各工程について具体的に説明する。Each of the above steps will be specifically explained.
第１工程：
出発原料の一つである有機珪素重合体は、公知の方法で
合成することができ、例えば、ジメチルジク口ロシラン
と金属ナトリウムの反応により得られるポリメチルシラ
ンを不活性ガス中で４００゜Ｃ以上に加熱することによ
り得られる。First step: The organosilicon polymer, which is one of the starting materials, can be synthesized by a known method. For example, polymethylsilane obtained by the reaction of dimethyldicyclosilane and metallic sodium is heated for 400 min in an inert gas. Obtained by heating above °C.
上記有機珪素重合体は、結合単位（Ｓｔ ＣＨｚ）、
又は結合単位（Ｓｉ−Ｓｉ）と結合単位（Ｓｉ−ＣＨｚ
）より主としてなり、結合単位（ＳｔＣＨ．）の全数
対結合単位（Ｓｔ−Ｓｔ）の全数の比率は１：０〜２０
の範囲内にある．有機珪素重合体の重量平均分子量（Ｍ
１）は、一般的には３００〜１０００で、Ｍｗが４００
〜８００のものが、優れた炭素系無機繊維を得るための
中間原料であるランダム共重合体（２）を調製するため
に特に好ましい。The organosilicon polymer has a bonding unit (St CHz),
Or bond unit (Si-Si) and bond unit (Si-CHz
), and the ratio of the total number of bonding units (StCH.) to the total number of bonding units (St-St) is 1:0 to 20.
is within the range of Weight average molecular weight (M
1) is generally 300 to 1000, and Mw is 400
800 is particularly preferable for preparing the random copolymer (2), which is an intermediate raw material for obtaining excellent carbon-based inorganic fibers.
もう一つの出発原料である多環状芳香族化合物は石油類
及び／又は石炭類から得られるピッチで、特に好ましい
ピッチは石油類の流動接触分解により得られる重質油、
その重質油を蒸留して得た留出成分又は残渣油及びそれ
らを熱処理して得られるピッチである。Another starting material, the polycyclic aromatic compound, is pitch obtained from petroleum and/or coal, and particularly preferred pitch is heavy oil obtained by fluid catalytic cracking of petroleum,
These are distillate components or residual oil obtained by distilling the heavy oil, and pitch obtained by heat-treating them.
上記ピッチ中には、ベンゼン、トルエン、キシレン、テ
トラヒド口フランなどの有機溶媒に不溶の成分が５〜９
８％、特にｌＯ〜８０％含まれていることが好ましい。The above pitch contains 5 to 9 components insoluble in organic solvents such as benzene, toluene, xylene, and tetrahydrofuran.
It is preferably contained in an amount of 8%, particularly 10 to 80%.
上記の不溶成分が５重量％未満のピッチを原料として用
いた場合、強度、弾性率共に優れた無機質繊維は得られ
ず、また、９８重量％より多いピッチを原料として用い
た場合、共重合体の分子量上昇が激しく、一部コーキン
グの起こる場合もあり、紡糸困難な状態になる。If pitch containing less than 5% by weight of the above-mentioned insoluble components is used as a raw material, an inorganic fiber with excellent strength and elastic modulus cannot be obtained, and if pitch containing more than 98% by weight is used as a raw material, copolymer The molecular weight of the material increases rapidly, and coking may occur in some cases, making spinning difficult.
このピッチの重量平均分子量（Ｍ．）は、１００〜３０
００である。重量平均分子量は以下のようにして求めた
値である。即ち、ピッチがベンゼン、トルエン、キシレ
ン、テトラヒド口フラン、クロロホルム及びジクロ口ベ
ンゼン等のゲルパーミュエーションク口マトグラフ（Ｇ
ＰＣ）測定用有機溶媒不溶分を含有しない場合はそのま
まＧＰＣ測定し、ピッチが上記有機溶媒不溶分を含有す
る場合は、温和な条件で水添処理し、上記有機溶媒不溶
分を上記有機溶媒可溶な成分に変えて後ＧＰＣ測定する
。上記有機溶媒不溶分を含有する重合体の重量平均分子
量は、上記と同様の処理を施し求めた値である．
ピッチの使用割合は、有機珪素重合体１００部当たり８
３〜４９００部であることが好ましい。The weight average molecular weight (M.) of this pitch is 100 to 30
It is 00. The weight average molecular weight is a value determined as follows. That is, gel permeation chromatographs (G
PC) If the pitch does not contain any organic solvent insoluble matter, it is directly measured by GPC. If the pitch contains the above organic solvent insoluble matter, it is hydrogenated under mild conditions and the organic solvent insoluble matter is removed from the organic solvent insoluble matter. Change to a soluble component and then perform GPC measurement. The weight average molecular weight of the polymer containing organic solvent insoluble matter is the value obtained by performing the same treatment as above. The ratio of pitch used is 8 parts per 100 parts of organosilicon polymer.
It is preferable that it is 3-4900 parts.
ピッチの使用割合が過度に小さい場合は、得られる無機
繊維中の炭化珪素成分が多くなり、高弾性率を有する無
機繊維が得られなくなり、また、その割合が過度に多い
場合は、炭化珪素成分が少なくなり、マトリックスに対
する濡れ性や耐酸化性に優れた無機繊維が得られなくな
る．
上記反応の反応温度が過度に低いと、珪素原子と芳香族
炭素の結合が生成しにくくなり、反応温度が過度に高い
と、生成した前駆重合体（１）の分解及び高分子量化が
激しく起こり好ましぐない。If the ratio of pitch used is too small, the silicon carbide component in the resulting inorganic fiber will increase, making it impossible to obtain an inorganic fiber with a high modulus of elasticity. As a result, inorganic fibers with excellent matrix wettability and oxidation resistance cannot be obtained. If the reaction temperature of the above reaction is too low, it will be difficult to form bonds between silicon atoms and aromatic carbon, and if the reaction temperature is too high, the resulting precursor polymer (1) will be violently decomposed and its molecular weight will increase. I don't like it.
ここで言う前駆重合体（１）には、有機珪素重合体とピ
ッチが珪素一炭素連結基を介して結合した共重合体に加
え、有機珪素重合体及びピッチの各々の重縮合物が含ま
れる。The precursor polymer (1) mentioned here includes a copolymer in which an organosilicon polymer and pitch are bonded via a silicon-carbon linking group, as well as polycondensates of each of an organosilicon polymer and pitch. .
不活性ガスとしては、窒素、アルゴン等が好適に使用さ
れる。As the inert gas, nitrogen, argon, etc. are preferably used.
次に、前駆重合体（１）と式ＭＸ．で示される遷移金属
化合物とを１００〜５００゜Ｃの温度の範囲で反応させ
る．前記ＭＸ．において、ＭはＴｉ，Ｚｒ及びＨｆから
選択される少なくとも一種の元素であり、Ｘは縮合によ
り、Ｍが前駆重合体（１）の珪素と直接あるいは酸素原
子を介して結合しうるものであればよく、特に規定はな
いが、ハロゲン原子、アルコキシ基又はβ−ジケトンの
ような錯体形成基が好ましい．
反応温度が過度に低いと、前駆重合体（１）と弐ＭＸ４
との縮合反応が進行せず、反応温度が過度に高いと、Ｍ
を介した前駆重合体（１）の架橋反応が過度に進行しゲ
ル化が起こったり、前駆重合体（１）自体が縮合し高分
子量化したり、あるいは、場合によっては、Ｍ Ｘ ａ
が揮散して優れた無機繊維を得るための中間原料である
ランダム共重合体（２）が得られない。Next, precursor polymer (1) and formula MX. A transition metal compound represented by is reacted at a temperature of 100 to 500°C. Said MX. , M is at least one element selected from Ti, Zr and Hf, and X is an element that can be bonded to silicon of the precursor polymer (1) directly or via an oxygen atom by condensation. Although not particularly specified, complex-forming groups such as halogen atoms, alkoxy groups or β-diketones are preferred. If the reaction temperature is too low, the precursor polymer (1) and 2MX4
If the condensation reaction with M does not proceed and the reaction temperature is excessively high, M
In some cases, the crosslinking reaction of the precursor polymer (1) via
is volatilized, and the random copolymer (2), which is an intermediate raw material for obtaining excellent inorganic fibers, cannot be obtained.
一例を挙げれば、ＭがＴｉで、ＸがＱＣ．Ｈ．の場合、
反応温度は２００〜４００゜Ｃが適している。For example, M is Ti and X is QC. H. in the case of,
A suitable reaction temperature is 200-400°C.
この反応によって、前駆重合体（１）の珪素原子の少な
くとも一部をＭと直接あるいは酸素原子を介して結合さ
せたランダム共重合体（２）が調製される。Through this reaction, a random copolymer (2) in which at least some of the silicon atoms of the precursor polymer (1) are bonded to M directly or via oxygen atoms is prepared.
金属Ｍは前駆重合体（１）の珪素原子にーＭ Ｘ ’ｘ
あるいは一〇−ＭＸ．のような結合様式で側鎖状に結合
することもできるし、前駆重合体（１）の珪素原子を直
接又は酸素を介して架橋した結合様式もとり得る。The metal M is the silicon atom of the precursor polymer (1) -M
Or 10-MX. They can be bonded in the form of a side chain in the following bonding mode, or they may be bonded in a bonding mode in which the silicon atoms of the precursor polymer (1) are crosslinked directly or via oxygen.
ランダム共重合体（２）を調製する方法としては、前述
の方法以外に、有機珪素重合体とＭ Ｘ ４を反応させ
、得られた生成物にピッチをさらに反応させて調製する
方法も可能である。As a method for preparing the random copolymer (2), in addition to the method described above, it is also possible to prepare the random copolymer (2) by reacting an organosilicon polymer with M X 4 and further reacting the obtained product with pitch. be.
第１工程においては、最後にランダム共重合体（２）と
メソフェーズ多環状芳香族化合物を加熱反応及び／又は
加熱溶融して、金属含有多環状芳香族重合体を調製する
。In the first step, the random copolymer (2) and the mesophase polycyclic aromatic compound are finally reacted and/or heated and melted to prepare a metal-containing polycyclic aromatic polymer.
メソフェーズ多環状芳香族化合物は、例えば、石油系又
は石炭系ピッチを不活性ガス中で３００〜５００゜Ｃに
加熱し、生成する軟質留分を除去しながら縮重合するこ
とによって調製することができる。Mesophase polycyclic aromatic compounds can be prepared, for example, by heating petroleum-based or coal-based pitch to 300 to 500°C in an inert gas and subjecting it to condensation polymerization while removing the generated soft fraction. .
上記縮重合反応温度が過度に低いと縮合環の成長が充分
でなく、またその温度が過度に高いとコーキングにより
不溶、不融の生成物が生じる。If the temperature of the condensation polymerization reaction is too low, the growth of the condensed ring will not be sufficient, and if the temperature is too high, insoluble and infusible products will be produced due to coking.
上記のメソフェーズ多環状芳香族化合物は、融点が２０
０〜４００゜Ｃの範囲にあり、また、重量平均分子量が
２００〜ｔｏｏｏｏである。The above mesophase polycyclic aromatic compound has a melting point of 20
The temperature is in the range of 0 to 400°C, and the weight average molecular weight is in the range of 200 to toooo.
メソフエーズ多環状芳香族化合物の中でも、２０〜１０
０％の光学的異方性度を有し、３０〜１００％のベンゼ
ン、トルエン、キシレン又はテトラヒド口フランに対す
る不溶分を含むものが、機械的性能の優れた無機繊維を
得るために特に好ましい。Among mesophase polycyclic aromatic compounds, 20 to 10
Those having an optical anisotropy of 0% and containing 30 to 100% of insoluble matter in benzene, toluene, xylene or tetrahydrofuran are particularly preferred in order to obtain inorganic fibers with excellent mechanical performance.
メソフェーズ多環状芳香族化合物の使用割合はランダム
共重合体（２） １ ０ ０部当たり好ましくは５〜５
００００部、より好ましくは５〜１００００部であり、
５部未満では、生成物におけるメソフェーズ含有量が不
足するため、高弾性の焼成糸が得られず、また、５００
００部より多い場合は、珪素成分の不足のためマトリッ
クスに対する濡れ性、耐酸化性に優れた無機繊維が得ら
れなくなる．ランダム共重合体（２）とメソフエーズ多
環状芳香族化合物とを２００〜５００゜Ｃで加熱反応及
び／又は加熱溶融させることにより、ランダム共重合体
（２）の少なくとも一部がメソフェーズ多環状芳香族化
合物と結合した金属含有多環状芳香族重合体が得られる
。ただし、ここで言う結合とは、ランダム共重合体（２
）の珪素と多環状芳香族化合物の炭素との化学結合とラ
ンダム共重合体（２）中の珪素と化学結合した多環状芳
香族環部分とメソフヱーズ多環状芳香族化合物との間の
ファンデルワールス結合等の物理的結合を意味する。The proportion of the mesophase polycyclic aromatic compound used is preferably 5 to 5 per 100 parts of the random copolymer (2).
0,000 parts, more preferably 5 to 10,000 parts,
If the amount is less than 5 parts, the mesophase content in the product will be insufficient, making it impossible to obtain a fired yarn with high elasticity;
If the amount is more than 0.00 parts, inorganic fibers with excellent matrix wettability and oxidation resistance cannot be obtained due to the lack of silicon component. By heating the random copolymer (2) and the mesophase polycyclic aromatic compound at 200 to 500°C and/or heating and melting it, at least a part of the random copolymer (2) becomes a mesophase polycyclic aromatic compound. A metal-containing polycyclic aromatic polymer combined with a compound is obtained. However, the bond mentioned here refers to a random copolymer (2
) and the van der Waals between the polycyclic aromatic ring moiety chemically bonded to silicon in the random copolymer (2) and the mesophase polycyclic aromatic compound. It means a physical connection such as bonding.
上記溶融混合温度が２００゜Ｃより低いと不融部分が生
じ、系が不均一となり、無機繊維の強度、弾性率に悪影
響を及ぼし、また、溶融混合温度が５００゜Ｃより高い
と縮合反応が激しく進行し、生成重合体が高融点となり
、重合体の紡糸が著しく困難となる。If the above-mentioned melt-mixing temperature is lower than 200°C, unmelted portions will be generated, the system will become non-uniform, and the strength and elastic modulus of the inorganic fiber will be adversely affected, and if the melt-mixing temperature is higher than 500°C, the condensation reaction will occur. The process progresses violently, and the resulting polymer has a high melting point, making it extremely difficult to spin the polymer.
金属含有多環状芳香族重合体を調製する方法としては、
前述の方法以外に、有機珪素重合体とピッチを反応させ
、得られた生成物にメソフェーズピッチとＭＸ．を同時
に又は順次添加し、さらに反応させて調製する方法も可
能である。As a method for preparing a metal-containing polycyclic aromatic polymer,
In addition to the method described above, an organosilicon polymer and pitch may be reacted, and the resulting product may be mixed with mesophase pitch and MX. It is also possible to prepare by adding these simultaneously or sequentially and further reacting.
上記金属含有多環状芳香族重合体の重量平均分子量は２
００〜１１０００で、融点が２００〜４００゜Ｃである
。The weight average molecular weight of the metal-containing polycyclic aromatic polymer is 2
00-11000, and the melting point is 200-400°C.
第２工程：
第１工程で得られる金属含有多環状芳香族重合体である
紡糸ポリマーを加熱溶融させて、場合によってはこれを
濾過してミクロゲル、不純物等の紡糸に際して有害とな
る物質を除去し、これを通常用いられる合成繊維紡糸装
置により紡糸する。2nd step: The spinning polymer, which is a metal-containing polycyclic aromatic polymer obtained in the 1st step, is heated and melted, and in some cases, it is filtered to remove substances that are harmful during spinning, such as microgels and impurities. This is then spun using a commonly used synthetic fiber spinning device.
紡糸する際の紡糸原液の温度は原料ポリマーの軟化温度
によって異なるが、２２０〜４ ２ ０ ’Ｃの範囲の
温度が有利である。The temperature of the spinning dope during spinning varies depending on the softening temperature of the raw material polymer, but a temperature in the range of 220 to 420'C is advantageous.
前記紡糸装置において、必要に応じて紡糸筒を取付け、
該紡糸筒内の雰囲気を空気、不活性ガス、熱空気、熱不
活性ガス、スチーム、及びアンモニアガスからなる群か
ら選ばれる一種以上の雰囲気とした後、巻取り速度を大
きくすることにより細い直径の繊維を得ることができる
。前記溶融紡糸における紡糸速度は原料の平均分子量、
分子量分布、分子構造によって異なるが、５０〜５００
０ｍ／分の範囲であることが好ましい。In the spinning device, a spinning tube is attached as necessary,
After setting the atmosphere in the spinning tube to one or more atmospheres selected from the group consisting of air, inert gas, hot air, hot inert gas, steam, and ammonia gas, the winding speed is increased to create a thin diameter. fibers can be obtained. The spinning speed in the melt spinning is determined by the average molecular weight of the raw materials,
Although it varies depending on the molecular weight distribution and molecular structure, 50 to 500
A range of 0 m/min is preferable.
第３工程：
第２工程で得られる紡糸繊維を張力又は無張力の作用の
もとて不融化する。Third step: The spun fibers obtained in the second step are made infusible under tension or non-tension.
代表的な不融化方法は、紡糸繊維を酸化性雰囲気中で加
熱する方法である。不融化の温度は好ましくは５０〜４
０ ０ ”Ｃの範囲の温度である。不融化温度が過度
に低いと紡糸原糸を構成するポリマ一のはしかけが起こ
らず、また、この温度が過度に高いとボリマーが燃焼す
る。A typical infusibility method is to heat spun fibers in an oxidizing atmosphere. The infusibility temperature is preferably 50 to 4
The temperature is in the range of 0.00'' C. If the infusibility temperature is too low, the polymers constituting the spinning yarn will not be fused, and if the temperature is too high, the polymer will burn.
不融化の目的は、紡糸繊維を構成するポリマーを三次元
構造の不融・不溶のはしかけ状態にし、次工程の焼成の
際に熔融せず、且つ隣接した繊維と融着しないようにす
ることである。不融化の際の酸化性雰囲気を構成するガ
スとしては、空気、オゾン、酸素、塩素ガス、臭素ガス
、アンモニアガス、及びこれらの混合ガスが挙げられる
。The purpose of infusibility is to make the polymer that makes up the spun fibers into a three-dimensional structure that is infusible and insoluble, so that it does not melt during the next firing process and does not fuse with adjacent fibers. It is. Gases constituting the oxidizing atmosphere during infusibility include air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixed gases thereof.
上記とは別の不融化方法として、紡糸繊維に酸化性雰囲
気あるいは非酸化性雰囲気で、張力あるいは無張力で必
要に応じて低温加熱しながら、γ線照射、あるいは電子
線照射して不融化する方法も採用することができる。As an infusibilization method different from the above, the spun fibers are infusibilized by irradiation with gamma rays or electron beams in an oxidizing or non-oxidizing atmosphere, under tension or without tension, while heating at a low temperature as necessary. method can also be adopted.
このγ線あるいは電子線を照射する目的は、紡糸繊維を
形成するポリマーを、さらに重合させることによって、
紡糸原糸が融解し、繊維形状を失うことを防ぐことにあ
る。The purpose of irradiating with gamma rays or electron beams is to further polymerize the polymer that forms the spun fibers.
The purpose is to prevent the spun yarn from melting and losing its fiber shape.
Ｔ線あるいは電子線の照射線量は１０’〜１ｏ１０ラッ
ドが適当である。The appropriate irradiation dose of T-rays or electron beams is 10' to 1010 rad.
照射は真空、不活性ガス雰囲気下、あるいは空気、オゾ
ン、酸素、塩素ガス、臭素ガス、アンモニアガス及びこ
れらの混合ガスのような酸化性ガス雰囲気で行うことが
できる。Irradiation can be carried out in a vacuum, an inert gas atmosphere, or an oxidizing gas atmosphere such as air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixtures thereof.
照射による不融化は室温で行うこともでき、必要であれ
ば５０〜２００″Ｃの温度範囲で加熱しながら行うこと
によって不融化をより短時間で達成させることもできる
。Infusibility by irradiation can be carried out at room temperature, or, if necessary, by heating in the temperature range of 50 to 200''C, infusibility can be achieved in a shorter time.
不融化は、無張力下で行うと、前記紡糸繊維は収縮のた
め波状の形を呈するようになるが、次工程の焼成工程で
矯正できる場合もあり、張力は必ずしも必要ないが、張
力を作用させる場合には、その張力の大きさは不融化時
に紡糸繊維が収縮して波状となることを少なくとも防止
できる以上の張力を作用させると良い結果が得られる。If infusibility is carried out without tension, the spun fibers will shrink and take on a wavy shape, but this can sometimes be corrected in the next firing process, and tension is not necessarily required. In this case, good results can be obtained if the tension is greater than that which can at least prevent the spun fibers from shrinking and becoming wavy during infusibility.
不融化の際に、作用させる張力としては、１〜５ ０
０ ｇ ／ｔｍ”の範囲が好ましく、Ｉｇ／ａｍ”以下
の張力を作用させても繊維をたるませないような緊張を
与えることができず，’ ５ ０ ０ ｇ ／ｔｔｍ”
以上の張力を作用させると繊維が切断することがある。The tension to be applied during infusibility is 1 to 50
A range of 0 g/tm" is preferable; even if a tension of less than Ig/am" is applied, it is not possible to apply tension that will not cause the fibers to slack, and the range is 500 g/ttm.
If more tension is applied, the fibers may break.
第４工程：
第３工程で得られる不融化糸を、真空あるいは不活性ガ
ス雰囲気中で８００〜３ｏ００゜Ｃの範囲の温度で焼成
することによって、主として炭素、Ｍ、珪素及び酸素か
らなる無機繊維が得られる。Fourth step: By firing the infusible yarn obtained in the third step at a temperature in the range of 800 to 300°C in a vacuum or inert gas atmosphere, inorganic fibers mainly composed of carbon, M, silicon, and oxygen are produced. is obtained.
焼成工程において、張力を作用させることは必ずしも必
要ないが０．０ ０ １〜１ ０ ０ Ｋｇ／ｍｍ”
ＯＪＪ範囲で張力を作用させながら高温焼成すると屈曲
を少な《した強度の高い無機繊維を得ることができる。In the firing process, it is not necessarily necessary to apply tension, but it is 0.001 to 100 Kg/mm.
By firing at a high temperature while applying tension in the OJJ range, it is possible to obtain a high-strength inorganic fiber with less bending.
加熱過程において、約７００゜Ｃから無機化が激しくな
り、約８００゜Ｃでほぼ無機化が完了するものと推定さ
れる。従って、焼成は、８ ０ ０ ’Ｃ以上の温度で
行うことが好ましい。また、３ ０ ０ ０ ’Ｃより
高い温度を得るには高価な装置を必要とするため３００
０゜Ｃより高温での焼成は、コスト面からみて実際的で
ない。In the heating process, it is estimated that mineralization becomes intense at about 700°C and is almost completed at about 800°C. Therefore, the firing is preferably performed at a temperature of 800'C or higher. In addition, obtaining temperatures higher than 3000'C requires expensive equipment;
Firing at a temperature higher than 0°C is not practical from a cost standpoint.
なお、構成成分Ｃ）であるＳｉ−Ｍ−Ｃ−０吻質の形態
は、第１工程乃至第４工程で採用される製？条件によっ
て決定される。一般的に言えば、第４工程での焼成温度
が例えば１０００゜Ｃより低い場合、構成成分Ｃ）はＳ
ｉ，Ｍ，Ｃ、０からなる非晶質より実質的に構成される
。Note that the form of the Si-M-C-0 rostrum, which is the component C), is the same as that used in the first to fourth steps. Determined by conditions. Generally speaking, if the calcination temperature in the fourth step is lower than, for example, 1000°C, component C)
It is substantially composed of amorphous material consisting of i, M, C, and 0.
一方、第４工程での焼成温度が例えば１７００゜Ｃ以上
の場合、構成成分Ｃ）は実質的にβ−ＳｉＣ、ＭＣ、β
−ＳｉＣとＭＣの固溶体及びＭＣ．■（ただし、０＜ｘ
＜１）からなる粒径５００人以下の超微粒子及びＳｉｎ
ｙ （ただし、０＜ｙ≦２）、ＭＯ■ （ただし、Ｏ＜
ｚ≦２）からなる非晶質からなる集合体より実質的に構
成される。On the other hand, when the firing temperature in the fourth step is, for example, 1700°C or higher, the component C) is substantially β-SiC, MC, β
-Solid solution of SiC and MC and MC. ■(However, 0<x
<1) Ultrafine particles with a particle size of 500 or less and Sin
y (however, 0<y≦2), MO■ (however, O<
z≦2).
上記温度の中間では、構成成分Ｃ）は各集合体の混合系
より構成されている。また、無機繊維中の酸素量は、例
えば第１工程におけるＭＸ．の添加比率又は第３工程に
おける不融化条件により制御することができる。At intermediate temperatures, component C) consists of a mixed system of individual aggregates. In addition, the amount of oxygen in the inorganic fibers may be determined by, for example, MX in the first step. It can be controlled by the addition ratio of or the infusibility conditions in the third step.
また、構成成分Ｃ）の分布状態は、焼成時の雰囲気や原
料中のメソフエーズの大きさ、濃度によっても制御する
ことができる。例えば、メソフェーズを大きく成長させ
た場合、構成成分Ｃ）は繊維表面相に押し出されやすく
なる。Further, the distribution state of component C) can also be controlled by the atmosphere during firing and the size and concentration of mesophase in the raw material. For example, when the mesophase is grown to a large size, component C) is easily extruded into the fiber surface phase.
本発明において上記無機繊維と共にハイブリッド繊維を
構成する繊維は、炭素繊維、ガラス繊維、ボロン繊維、
アルミナ繊維、窒化珪素繊維、アラミド繊維、炭化珪素
繊維、カーボンを芯線とする炭化珪素繊維及びＳｉ−Ｍ
−Ｃ−０繊維（ＭはＴｉ又はＺｒを示す。）から選択さ
れる。In the present invention, the fibers constituting the hybrid fiber together with the above-mentioned inorganic fibers include carbon fiber, glass fiber, boron fiber,
Alumina fiber, silicon nitride fiber, aramid fiber, silicon carbide fiber, silicon carbide fiber with carbon core and Si-M
-C-0 fiber (M represents Ti or Zr).
上記のＳｉ−Ｍ−Ｃ−０繊維は、
（ｉ）Ｓｔ，Ｍ，Ｃ、及びＯから実質的になる非？Ｃの
固溶体及びＭＣＩ−ｘの粒径が５００人以下の各結晶質
超微粒子、及び非晶質のＳｉＯ２とＭＯ■からなる集合
体、又は
（ｉｊ）上記（１）の非晶質と上記（ｉｉ）の結晶質超
微粒子集合体の混合系、
（ただし、上式中のＭはＴｉ又はＺｒを示し、０＜ｘ＜
１を示す）
からなる無機繊維である。この無機繊維は、例えば、特
公昭６０−１４０５号公報、同５Ｂ−５２８６号公報、
同６０−２０４８５号公報、同５９４４４０３号公報に
記載の方法によって調製することができる。The above-mentioned Si-M-C-0 fiber is composed of (i) non-? A solid solution of C and each crystalline ultrafine particle with a particle size of 500 or less of MCI-x, and an aggregate consisting of amorphous SiO2 and MO■, or (ij) the amorphous of (1) above and the above ( ii) A mixed system of crystalline ultrafine particle aggregates, (where M in the above formula represents Ti or Zr, and 0<x<
1) is an inorganic fiber consisting of This inorganic fiber is disclosed in, for example, Japanese Patent Publication No. 60-1405, Japanese Patent Publication No. 5B-5286,
It can be prepared by the method described in JP 60-20485 and JP 5944403.
本発明において強化材として用いる繊維は繊維そのもの
を単軸方向、多軸方向に配合させる方法、あるいは平織
、朱子織、模紗織、綾織、からみ織、らせん織、三次元
織物などの各種織物にして使用する方法、あるいはチョ
ップドファイバーとして使用する方法等がある。The fibers used as reinforcing materials in the present invention can be prepared by blending the fibers themselves in a uniaxial or multiaxial direction, or by making them into various woven fabrics such as plain weave, satin weave, mock-satin weave, twill weave, leno weave, spiral weave, and three-dimensional weave. There are two methods: using it as a chopped fiber, and using it as a chopped fiber.
ハイブリッド繊維中の本発明で限定した無機繊維の割合
は１０％以上好ましくは２０％以上である。１０％より
低いと無機繊維によるプラスチックとの間の結合強さの
向上、強化効率の向上、疲労強度低下率の減少という本
発明の目的とする機械的性質の改善効果に乏しく、即ち
眉間剪断強度、曲げ衝撃値及び疲労強度の改善効果が減
少する。The proportion of the inorganic fibers defined in the present invention in the hybrid fibers is 10% or more, preferably 20% or more. If it is less than 10%, the effects of improving mechanical properties, which are the objectives of the present invention such as improving the bonding strength between the inorganic fiber and the plastic, improving reinforcing efficiency, and reducing the rate of decrease in fatigue strength, will be poor, that is, the glabella shear strength will be lowered. , the effect of improving bending impact value and fatigue strength is reduced.
ハイブリッド繊維のハイブリッド状態を形態別にみると
（１）ある種の繊維の層と別種の繊維の層を積層した眉
間ハイブリッド（２）一つの層の中ですでにハイブリッ
ド化されている層内ハイブリッドの２種類が基本で、（
３）それらの組合せがある。組合せの主な型は以下の６
種である。Looking at the hybrid state of hybrid fibers by form, we can look at (1) a glabella hybrid in which a layer of one type of fiber and a layer of another type of fiber are laminated, (2) an intralayer hybrid that has already been hybridized within one layer. There are two basic types (
3) There are combinations of them. The main types of combinations are the following 6
It is a seed.
（ａ）単層テープの積層（層単位で異質繊維を交互に積
層したもの）
（ｂ）サンドウィッチ型（層単位で異質繊維をサンドウ
ィッチに積層したもの）
（Ｃ）リブ補強
（ｄ）混織トウ（単繊維単位で異質の繊維をハイブリッ
ドしたもの）
（ｅ）混織テープの積層（糸条単位で異質の繊維を層内
でハイブリッドしたもの）
（ｆ）混織表層
本発明におけるプラスチックとしてはエボキシ系樹脂、
ポリエステル樹脂、フェノール樹脂、ポリイミド樹脂、
ポリウレタン樹脂、ボリアミド樹脂、ポリカーボネート
樹脂、シリコン樹脂、フッ素樹脂、ナイロン樹脂、ポリ
フェニレンサルファイド、ポリブチレンテレフタレート
、ポリエチレン、ポロプロピレン、変性ポリフェニレン
オキサイド、ポリスチレン、ＡＢＳ樹脂、塩化ビニル樹
脂、ポリエーテル・エーテルケトン樹脂、ビスマレイミ
ド樹脂等であり、これらの混合物でも良い．ハイブリッ
ド繊維強化プラスチック複合材料はそれ自体公知の方法
で製造することができ、例えば、（１）ハンドレイアッ
プ法、（２）マツチドメタルダイ法、（３）プレークア
ウエイ法、（４）フィラメント・ワインディング法、（
５）ホットプレス法、（６）オートクレープ法、（７）
連続引抜き法等の方法を採用することができる。(a) Lamination of single-layer tape (layers of different fibers are alternately layered) (b) Sandwich type (layers of different fibers are layered in a sandwich) (C) Rib reinforcement (d) Blended tow (Hybrid of different fibers in each single fiber unit) (e) Lamination of mixed tape (hybridized fibers of different types in each yarn unit) (f) Mixed fabric surface layer The plastic used in the present invention is epoxy. based resin,
polyester resin, phenolic resin, polyimide resin,
Polyurethane resin, polyamide resin, polycarbonate resin, silicone resin, fluororesin, nylon resin, polyphenylene sulfide, polybutylene terephthalate, polyethylene, polypropylene, modified polyphenylene oxide, polystyrene, ABS resin, vinyl chloride resin, polyether/ether ketone resin, Bismaleimide resin, etc., and mixtures thereof may also be used. Hybrid fiber-reinforced plastic composite materials can be manufactured by methods known per se, such as (1) hand lay-up method, (2) matted metal die method, (3) breakaway method, (4) filament Winding method, (
5) Hot press method, (6) Autoclape method, (7)
A method such as a continuous drawing method can be employed.
（１）ハンドレイア・ンフ゜法によれば、まずノ１イフ
゛り・冫ド繊維を裁断して型の上に敷き詰め、触媒を加
えたプラスチックをはけやローラでその上に塗り込めた
後自然に硬化させ、脱型して複合材料とすることができ
る。(1) According to the hand layering method, firstly, the fibrillated fiber is cut and spread on a mold, and then the plastic containing the catalyst is applied onto it using a brush or roller, and then it is dried naturally. It can be cured and demolded to form a composite material.
（２）マッチドメタルダイ法によれば、あらかじめ／Ｓ
イブリッド繊維にプラスチックと硬化剤、充填材、増粘
剤を加えて含浸したものを加熱加圧成形して複合材料と
することができる。成形時の材料の形態によりＳＭＣ法
（Ｓｈｅｅｔ Ｍｏｌｄｉｎｇ Ｃｏｍｐｏｕｎｄ）、
ＢＭＣ法（Ｂｕｌｋ Ｍｏｌｄｉｎｇ Ｃｏｍｐｏｕｎ
ｄ ）のどちらかを選択して用いることができる。(2) According to the matched metal die method, /S
A composite material can be obtained by impregnating hybrid fiber with plastic, a hardening agent, a filler, and a thickener and molding it under heat and pressure. Depending on the form of the material during molding, SMC method (Sheet Molding Compound),
BMC method (Bulk Molding Compound
d) can be selected and used.
（３）プレークアウエイ法によれば、ハイブリッド繊維
のシートにあらかじめプラスチックを含浸させ、予備硬
化させたプリプレグ（ｐｒｅρｒｅｇ ）を作り、これ
をテーパー付きの心金に巻付けて、硬化後に抜取り複合
材料とすることができる。(3) According to the pre-quake-away method, a sheet of hybrid fiber is pre-impregnated with plastic to create pre-cured prepreg, which is then wrapped around a tapered mandrel, and after curing is extracted and used as a composite material. can do.
（４）フィラメント・ワインディング法によれば、エボ
キシ樹脂、不飽和ポリエステル樹脂のような熱硬化性樹
脂を含浸したハイブリッド繊維をマンドレルに巻付け、
樹脂を硬化させた後、脱型して複合材料とすることがで
きる。この方法には、湿式法、乾式法（ブリプレグテー
プを使う方法）などがある。(4) According to the filament winding method, a hybrid fiber impregnated with a thermosetting resin such as epoxy resin or unsaturated polyester resin is wound around a mandrel.
After the resin is cured, it can be demolded to form a composite material. This method includes a wet method and a dry method (method using Bripreg tape).
（５）ホットプレス法によれば、ブリプレグシートを一
方向又は任意の角度に積層後、ホットプレスで加圧、加
熱して板状の複合材料とすることができる。(5) According to the hot press method, after laminating Bripreg sheets in one direction or at an arbitrary angle, a plate-shaped composite material can be obtained by pressing and heating with a hot press.
（６）オートクレープ法によれば、ブリブレグを成形金
型に積層し、特殊ラバーで包み、真空状態にして、高圧
釜に入れ、加熱、加圧して硬化させ複合材料とすること
ができる。複雑な成形に適している。(6) According to the autoclave method, blibregs are laminated in a mold, wrapped in a special rubber, placed in a vacuum state, placed in a high-pressure cooker, and cured by heating and pressurizing to form a composite material. Suitable for complex molding.
（７）連続引抜き法によれば、ハイブリッド繊維とプラ
スチックとを別々に分けて、成形機に供給し、成形金型
の手前で混合させ、途中で加熱炉のなかを通過させて連
続的に長尺な複合材料とすることができる。(7) According to the continuous pultrusion method, the hybrid fiber and plastic are separated separately, fed to a molding machine, mixed before the molding die, and passed through a heating furnace midway through to continuously lengthen the fibers. It can be made into a composite material.
ハイブリッド繊維とプラスチックマトリックスとから製
造された複合材料の引張強度（σＣ）は下記式で表され
る。The tensile strength (σC) of a composite material made from a hybrid fiber and a plastic matrix is expressed by the following formula.
σ０＝σ，■，＋σＭＶＭ
σＣ ：複合材料の引張強度
σｆ ：ハイブリッド繊維の引張強度
σ、：プラスチックマトリックスの引張強度■，：ハイ
ブリッド繊維の体積百分率
■κ：プラスチックマトリックスの体積百分率
上記式で示されるように、複合材料の強度は、複合材料
中のハイブリッド繊維の体積割合が、多くなるにしたが
って大きくなる。従って、強度の大きい複合材料を製造
するためには、複合させるハイブリッド繊維の体積割合
を多くする必要がある。しかしながら、ハイブリッド繊
維の体積割合が８０％を超えると、プラスチックマトリ
ックスの量が少ないため、ハイブリッド繊維の間隙を充
分にプラスチックマトリックスで充填することができな
くなるため、複合材料を製造しても前記式で示されるよ
うな強度が発揮されなくなる。また、繊維の体積割合を
低くしていくと前記式で示されるように複合材料の強度
は低下するから、実用性のある複合材料とするためには
１０％以上のハイブリッド繊維を複合させることが必要
である。従って、本発明のハイブリッド繊維強化プラス
チック複合材料の製造において、複合させるハイブリッ
ド繊維の体積割合を１０〜８０％、さらに好ましくは２
５〜７０％とすると最も良い効果が得られる。σ0=σ,■,+σMVM σC: Tensile strength of composite material σf: Tensile strength of hybrid fiber σ,: Tensile strength of plastic matrix ■,: Volume percentage of hybrid fiber ■κ: Volume percentage of plastic matrix Expressed by the above formula As such, the strength of the composite material increases as the volume fraction of hybrid fibers in the composite material increases. Therefore, in order to manufacture a composite material with high strength, it is necessary to increase the volume ratio of hybrid fibers to be composited. However, when the volume percentage of the hybrid fiber exceeds 80%, the amount of plastic matrix is small and the gaps between the hybrid fibers cannot be sufficiently filled with the plastic matrix. The strength shown will no longer be exerted. Furthermore, as the volume ratio of fibers is lowered, the strength of the composite material decreases as shown by the above formula, so in order to make a practical composite material, it is necessary to combine 10% or more of hybrid fibers. is necessary. Therefore, in producing the hybrid fiber-reinforced plastic composite material of the present invention, the volume ratio of the hybrid fibers to be composited is 10 to 80%, more preferably 2%.
The best effect can be obtained when it is set at 5 to 70%.
明細書における各種機械的特性は下記の測定法に従って
求めた。Various mechanical properties in the specification were determined according to the following measurement methods.
（ａ）層間剪断強度
曲率半径６柵φの２コのピン（長さ２０ｍｍ）の上に１
０Ｘ１２Ｘ２ｍｍの複合材料を置き、先端曲率半径３．
５ ｍｍ Ｒの圧子で圧縮、所謂３点曲げ方式で試験を
行い、層間剪断応力を測定する。剪断応力（ ｋｇ ／
印２）により表示す４る。(a) Interlaminar shear strength 1 on 2 pins (length 20 mm) with curvature radius 6
Place a composite material of 0x12x2mm and set the tip curvature radius to 3.
The test is performed by compression using a 5 mm R indenter and a so-called three-point bending method, and the interlaminar shear stress is measured. Shear stress (kg/
Indicated by mark 2).
（ｂ）曲げ衝撃値
３点曲げによるシャルピー試験法（ＪＩＳＫ７１１１）
により曲げ衝撃値を測定した。曲げ衝撃値（ｋｇ−ｃｍ
／ｃｍ” ）により表示する。(b) Bending impact value Charpy test method using 3-point bending (JISK7111)
The bending impact value was measured. Bending impact value (kg-cm
/cm”).
（Ｃ）引張強度、引張弾性率
試験片の厚さは２ｌＴＩｍで、中央部の板厚方向に１２
５１ＩＩｆｆｌＲの曲率をつけ厚さ約１ ｍｍに仕上げ
る。引張強度の測定は１ｍｍ／ｍｉｎで行った。引張強
度（ｋｇ／ｍｍ２） 、弾性率（１／鴫２）により表示
する。(C) Tensile strength, tensile modulus The thickness of the test piece is 2lTIm, and the thickness direction of the central part is 12
Add a curvature of 51IIfflR and finish to a thickness of approximately 1 mm. The tensile strength was measured at 1 mm/min. It is expressed by tensile strength (kg/mm2) and elastic modulus (1/2).
（ｄ）曲げ強度、曲げ弾性率
試験片の厚さは２胴で、中央部の板厚方向に１２５ｎ＋
ｍＲの曲率をつけ厚さ約１ ｍｍに仕上げる。３点曲げ
方式で試験を行い、曲げ強度（ｋｇ／ｍｍ２）、曲げ弾
性率（ｔ／ｍｍ”）により表示する。(d) Bending strength and bending modulus The thickness of the test piece is 2 cylinders, 125n+ in the thickness direction of the central part.
Add a curvature of mR and finish to a thickness of approximately 1 mm. The test is conducted using a three-point bending method, and is expressed in terms of bending strength (kg/mm2) and bending elastic modulus (t/mm'').
上記する各種機械的特性のうち、特に層間剪断強度及び
曲げ衝撃値は、プラスチックと繊維との間の結合強さを
表示する指標である。層間剪断強度が弱いと、樹脂と繊
維との間の結合強度が弱く、長期間の使用により繊維は
樹脂から剥離し易い。Among the various mechanical properties mentioned above, interlaminar shear strength and bending impact value in particular are indicators of the bond strength between plastic and fibers. If the interlayer shear strength is weak, the bonding strength between the resin and the fibers is weak, and the fibers are likely to peel off from the resin after long-term use.
また曲げ衝撃値が低いと瞬間的な衝撃による破壊という
実用上の問題を生じる。In addition, if the bending impact value is low, there will be a practical problem of destruction due to instantaneous impact.
（発明の効果）
本発明のハイブリッド繊維強化プラスチック複合材料は
、眉間剪断強度、曲げ衝撃値などの機械的特性に優れ、
プラスチックと繊維との間の結合強度に優れているため
、長期間の苛酷な環境下での使用に耐えるものである。(Effects of the Invention) The hybrid fiber-reinforced plastic composite material of the present invention has excellent mechanical properties such as glabella shear strength and bending impact value,
It has excellent bond strength between the plastic and fibers, so it can withstand long-term use in harsh environments.
このため、従来のハイブリッド繊維強化プラスチック複
合材料では満足に使用しえなかった各種分野で使用する
ことができる。そのような用途として、建築用材料、航
空機、宇宙開発用器材の材料、船舶用材料、陸上輸送機
器材料、耐食機器材料、電気材料、スポーツ用品、機械
要素、医療用機器材料、音響用機器材料などの各種分野
における用途を例示することができる。Therefore, it can be used in various fields where conventional hybrid fiber-reinforced plastic composite materials could not be used satisfactorily. Such uses include building materials, materials for aircraft and space exploration equipment, materials for ships, materials for land transportation equipment, materials for corrosion-resistant equipment, electrical materials, sporting goods, mechanical elements, medical equipment materials, and audio equipment materials. Examples of applications in various fields include:
（実施例） 以下実施例によって本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
参考例１（有機珪素重合体の製造）
５！の三口フラスコに無水キシレン２．５ｌ及びナトリ
ウム４００ｇを入れ、窒素ガス気流下でキシレンの沸点
まで加熱し、ジメチルジクロロシラン１ｌを１時間で滴
下した。滴下終了後、１０時間加熱還流し沈澱物を生成
させた。沈澱を濾過し、ンタノールついで水で洗浄して
、白色粉末のボリジメチルシラン４２０ｇを得た。Reference Example 1 (Production of organosilicon polymer) 5! 2.5 liters of anhydrous xylene and 400 g of sodium were placed in a three-necked flask, heated under a nitrogen gas stream to the boiling point of xylene, and 1 liter of dimethyldichlorosilane was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was heated under reflux for 10 hours to form a precipitate. The precipitate was filtered and washed with ethanol and then water to obtain 420 g of boridimethylsilane as a white powder.
このポリジメチルシラン４００ｇを、ガス導入管、攪拌
機、冷却器及び留出管を備えた３ｌの三口フラスコに仕
込み、攪拌しながら５０ｄ／分の窒素気流下に４２０゜
Ｃで加熱処理して、留出受器に３５０ｇの無色透明な少
し粘性のある液体を得た。400 g of this polydimethylsilane was charged into a 3-liter three-necked flask equipped with a gas inlet tube, a stirrer, a condenser, and a distillation tube, and heated at 420°C under a nitrogen flow of 50 d/min while stirring. 350 g of a colorless and transparent slightly viscous liquid was obtained in the receiver and receiver.
この液体の数平均分子量は蒸気圧浸透法で測定したとこ
ろ４７０であった。The number average molecular weight of this liquid was 470 as measured by vapor pressure osmosis.
この物質の赤外線吸収スペクトルを測定したところ、６
５ ０〜９ ０ ０ｃｍ−’と１２５０ｃｍ−’にＳ
ｉ−ＣＨ．の吸収、２ １ ０ ０ｃｌ’にＳｉ−Ｈの
吸収、１０２０ｃｍ−’付近と１ ３ ５ ５ｃｍ−’
にＳｉ ＣＨｚ−Ｓｉの吸収、２ ９ ０ ０ｃｍ−
’と２ ９ ５ ０ｃｍ−’にＣ一Ｈの吸収が認められ
、またこの物質の遠赤外線吸収スペクトルを測定したと
ころ、３８０ｃｍ−’にＳｉ−Ｓｔの吸収が認められる
ことから、得られた液状物質は、主として（Ｓｉ Ｃ
Ｈｚ）結合単位及び（Ｓｔ−Ｓｉ）結合単位からなり、
珪素の側鎖に水素原子及びメチル基を有する有機珪素重
合体であることが判明した。When the infrared absorption spectrum of this substance was measured, it was found that 6
S at 50~900cm-' and 1250cm-'
i-CH. absorption, absorption of Si-H at 2100cl', around 1020cm-' and 1355cm-'
Absorption of Si CHZ-Si, 2900 cm-
C-H absorption was observed at ' and 2950 cm-', and when the far-infrared absorption spectrum of this material was measured, Si-St absorption was observed at 380 cm-'. The material is mainly (Si C
Hz) bond unit and (St-Si) bond unit,
It turned out to be an organosilicon polymer having hydrogen atoms and methyl groups in silicon side chains.
核磁気共鳴分析及び赤外線吸収分析の測定結果から、こ
の有機珪素重合体は（ＳｉＣＨｚ）結合単位の全数対（
Ｓｉ−Ｓｉ）結合単位の全数の比率がほぼ１：３である
重合体であることが確認された。From the measurement results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer has a total number of pairs of (SiCHz) bonding units (
It was confirmed that the polymer had a ratio of the total number of (Si--Si) bond units of approximately 1:3.
上記有機珪素重合体３００ｇをエタノールで処理して低
分子量物を除去して、数平均分子量が１２００の重合体
４０ｇを得た。300 g of the above organosilicon polymer was treated with ethanol to remove low molecular weight substances to obtain 40 g of a polymer having a number average molecular weight of 1200.
この物質の赤外線吸収スペクトルを測定したところ、上
記と同様の吸収ピークが認められ、この物質は主として
（Ｓ ｉ −ＣＨｚ ）結合単位及び（Ｓｔ−Ｓｉ）結
合単位からなり、珪素の側鎖に水素原子及びメチル基を
有する有機珪素重合体であることが判明した。When the infrared absorption spectrum of this substance was measured, absorption peaks similar to those above were observed. It turned out to be an organosilicon polymer having atoms and methyl groups.
核磁気共鳴分析及び赤外線吸収分析の測定結果から、こ
の有機珪素重合体は（Ｓｉ ＣＨｚ）結合単位の全数
対（Ｓｔ−Ｓｉ）結合単位の全数の上記ＦＣＣスラリ一
オイル５００ｇを１！／分の窒素ガス気流下４５０゜Ｃ
で１時間加熱し、同温度における留出分を留去後、残渣
を２００゜Ｃにて熱時濾過を行い、同温度における不融
部を除去し、軽質分除去ピッチ２２５ｇを得た。From the measurement results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer has the total number of (Si CHZ) bond units to the total number of (St-Si) bond units when 500 g of the above FCC slurry oil is mixed with 1! /min nitrogen gas flow at 450°C
After heating for 1 hour at the same temperature and distilling off the distillate at the same temperature, the residue was filtered while hot at 200°C to remove the infusible part at the same temperature to obtain 225 g of pitch from which light components were removed.
この軽質分除去ピッチは７５％のキシレン不溶分を含む
光学的に等方性のピッチであった。This light fraction removed pitch was an optically isotropic pitch containing 75% xylene insoluble matter.
これと並行して、上記ＦＣＣスラリーオイル４００ｇを
、窒素ガス気流下４５０″Ｃに加熱し、同参考例２（無
機繊維Ｉの製造）
石油留分のうち、軽油以上の高沸点物をシリカ・アルミ
ナ系分解触媒の存在下、５００゜Ｃの温度で流動接触分
解・精留を行い、その塔底より残渣を得た。以下、この
残渣をＦＣＣスラリーオイルと呼ぶ。In parallel with this, 400 g of the above FCC slurry oil was heated to 450''C under a nitrogen gas flow, and silica and Fluid catalytic cracking and rectification were carried out at a temperature of 500°C in the presence of an alumina-based cracking catalyst, and a residue was obtained from the bottom of the column.Hereinafter, this residue will be referred to as FCC slurry oil.
このＦＣＣスラリーオイルは、元素分析の結果、炭素原
子対水素原子の原子比（Ｃ／Ｈ）が０．７５で、核磁気
共鳴分析による芳香炭素率が０．５５であった。As a result of elemental analysis, this FCC slurry oil had an atomic ratio of carbon atoms to hydrogen atoms (C/H) of 0.75, and an aromatic carbon ratio of 0.55 as determined by nuclear magnetic resonance analysis.
し、軽質分除去ピッチ１８０ｇを得た。得られた軽質分
除去ピッチ１８０ｇを窒素気流下、反応により生成する
軽質分を除去しながら４００゜Ｃで７時間縮重合を行い
、熱処理ピッチ８５ｇを得た。Then, 180 g of pitch from which light components were removed was obtained. 180 g of the obtained pitch from which light components were removed was subjected to condensation polymerization at 400° C. for 7 hours under a nitrogen stream while removing light components generated by the reaction, to obtain 85 g of heat-treated pitch.
この熱処理ピッチは融点２６８゜Ｃ、キシレン不溶分９
２％、キノリン不溶分１２％を含有しており、研磨面の
偏光顕微鏡観察による光学的異方性が８９％のメソフェ
ーズ多環状芳香族化合物であった。This heat-treated pitch has a melting point of 268°C and a xylene insoluble content of 9.
It was a mesophase polycyclic aromatic compound containing 2% and 12% of quinoline insoluble matter, and an optical anisotropy of 89% when observed with a polarized light microscope on the polished surface.
前記軽質分除去ピッチ４９ｇに参考例１で得た有機珪素
重合体２１ｇ及びキシレン２０−を加え、撹拌しながら
昇温し、キシレンを留去後、４００゜Ｃで６時間反応さ
せ３９ｇの前駆重合体（１）を得た。21 g of the organosilicon polymer obtained in Reference Example 1 and 20 g of xylene were added to 49 g of the light fraction removed pitch, the temperature was raised while stirring, the xylene was distilled off, and the mixture was reacted at 400°C for 6 hours to obtain a precursor weight of 39 g. Coalescence (1) was obtained.
この前駆重合体（１）は赤外線吸収スペクトル測定の結
果、有機珪素重合体中に存在するＳｉ−Ｈ結合（Ｉ Ｒ
： ２ １ ０ ０ｃｍ−’）の減少、及び新たなＳ
ｉ−Ｃ（ベンゼン環の炭素）結合（ＩＲ：１１３５ｃｍ
−’）の生成が認められることより有機珪素重多環状芳
香族化合物９０ｇを混合し、窒素雰囲気下、３１０゜Ｃ
で一時間溶融加熱し、均一な状態にある金属含有多環状
芳香族重合体を得た。As a result of infrared absorption spectrum measurement, this precursor polymer (1) was found to contain Si-H bonds (I R
: 2 1 0 0 cm-') and the new S
i-C (benzene ring carbon) bond (IR: 1135cm
Since the formation of
The mixture was melted and heated for one hour to obtain a metal-containing polycyclic aromatic polymer in a uniform state.
この重合体は、融点が２７２゜Ｃで、５９％のキシレン
不溶分を含んでいた。This polymer had a melting point of 272°C and contained 59% xylene insolubles.
上記高分子量物を紡糸用原料とし、ノズル径０．１５ｍ
ｍの金属製ノズルを用い、３４０゜Ｃで溶融紡糸を行い
、得られた紡糸原糸を、空気中、３００た。The above high molecular weight material is used as the raw material for spinning, and the nozzle diameter is 0.15 m.
Melt spinning was performed at 340° C. using a metal nozzle of 300° C., and the obtained spun yarn was heated in air for 300° C.
前駆重合体（１）３９ｇにテトラオクトキシチタン（Ｔ
ｉ （Ｏ Ｃｏ Ｈ＋ｔ）ａ） ２． ７ ５ ｇ
のキシレン溶液（２５％キシレン溶液１１ｇ）を加え、
キシレン留去後、３４０゜Ｃで２時間反応させ、ランダ
ム共重合体（２） ３ ８ ｇを得た。Tetraoctoxytitanium (T
i (O Co H+t)a) 2. 7 5 g
Add a xylene solution (11 g of 25% xylene solution),
After xylene was distilled off, the mixture was reacted at 340°C for 2 hours to obtain 38 g of random copolymer (2).
この共重合体は、キシレン不溶部を含まず重量平均分子
量は１６５０、融点は２７２゜Ｃであった．上記ランダ
ム共重合体（２） ３ ５ ｇとメソフェーズこの繊維
は引張強度が３２０Ｋｇ／ｍｍ”、引張弾性率３ ２
ｔ ／［ｌ１［ｌ”であり、破断面の走査型電子顕微鏡
を用いた観察より、結晶層が幾重にも重なった珊瑚様の
ランダム、ラジアル混在構造であった。This copolymer contained no xylene-insoluble parts, had a weight average molecular weight of 1650, and a melting point of 272°C. 35 g of the above random copolymer (2) and mesophase This fiber has a tensile strength of 320 Kg/mm'' and a tensile modulus of 32
t/[l1[l'', and observation of the fracture surface using a scanning electron microscope revealed that it had a coral-like random and radial mixed structure with multiple crystal layers.
参考例３（無機繊維Ｈの製造）
参考例２で得られた前駆重合体（１）３９ｇにテトラキ
スアセチルアセトナトジルコニウム５．４ｇのエタノー
ルーキシレン溶液（１．５％）を加え、キシレン及びエ
タノールを留去後２５０゜Ｃで１時間重合し３ ９．
５ ｇのランダム共重合体（２）を得た。Reference Example 3 (Production of Inorganic Fiber H) An ethanol-xylene solution (1.5%) of 5.4 g of tetrakisacetylacetonatozirconium was added to 39 g of the precursor polymer (1) obtained in Reference Example 2, and xylene and ethanol were added. After distilling off, polymerization was carried out at 250°C for 1 hour.39.
5 g of random copolymer (2) was obtained.
この重合体２０ｇと参考例２で得られたメソフェーズ多
環状芳香族化合物５０ｇを微粉砕混合し、紡糸筒内で３
５０゜Ｃで溶融し、ノズル径０．２Ｍのノズルを用い、
３４０゜Ｃで紡糸し、得られた紡糸原糸を空気中２５０
゜Ｃで不融化し、更にアルゴン雰囲気中１４００゜Ｃで
焼成、直径１１μの無機繊維■を得た。20 g of this polymer and 50 g of the mesophase polycyclic aromatic compound obtained in Reference Example 2 were pulverized and mixed, and
Melt at 50°C and use a nozzle with a nozzle diameter of 0.2M,
Spinning at 340°C, the obtained spun yarn was heated at 250°C in air.
The fibers were made infusible at 1400°C in an argon atmosphere to obtain inorganic fibers (2) with a diameter of 11 μm.
工一ズ多環状芳香族化合物８０ｇを微粉砕混合した後に
、紡糸筒内で３５０゜Ｃで溶融脱泡を行い、３５０゜Ｃ
で溶融紡糸し、２７０゜Ｃで不融化し、アルゴン中でｌ
２００゜Ｃで焼成することによって１２．５μの無機繊
維■を得た。After finely pulverizing and mixing 80 g of Koichi's polycyclic aromatic compound, melting and degassing was carried out at 350°C in a spinning cylinder.
Melt-spun at 270°C, infusible at 270°C, and l
By firing at 200°C, 12.5μ inorganic fibers (■) were obtained.
この繊維の引張強度は３１５ｋｇ／ｆｆＩＩｎ２、引張
弾性率３５ｔ／ｍｍ”であった。The tensile strength of this fiber was 315 kg/ffIIn2, and the tensile modulus was 35 t/mm''.
参考例５（無機繊維■の製造）
一参考例４（無機繊維■の製造）
軽質分除去ピッチ及び有機珪素重合体の使用量をそれぞ
れ６０ｇ及び４０ｇに変えた以外は参考例２と同様にし
て、５７ｇの前駆重合体（１）を得た。Reference Example 5 (Production of inorganic fiber ■) Reference Example 4 (Production of inorganic fiber ■) Same as Reference Example 2 except that the amounts of light fraction removal pitch and organic silicon polymer were changed to 60 g and 40 g, respectively. , 57 g of precursor polymer (1) was obtained.
この前駆共重合体（１）４０ｇにハフニウムクロライド
７．２ｇのエタノールーキシレン溶液（１．５％）を加
え、キシレン及びエタノールを留去後２５０゜Ｃで１時
間重合し４ ３． ５ ｇのランダム共重合体（２）を
得た。An ethanol-xylene solution (1.5%) containing 7.2 g of hafnium chloride was added to 40 g of this precursor copolymer (1), and after distilling off xylene and ethanol, polymerization was carried out at 250°C for 1 hour.43. 5 g of random copolymer (2) was obtained.
この重合体２０ｇと参考例２で得られたメソフ時間加熱
し、同温度における留出分を留去後、残渣を２００゜Ｃ
にて熱時濾過を行い、同温度における不融部を除去し、
軽質分除去ピッチ２００ｇを得た。20 g of this polymer was heated for the same period of time as obtained in Reference Example 2, and after distilling off the distillate at the same temperature, the residue was heated to 200°C.
Perform filtration while hot to remove infusible parts at the same temperature,
200 g of light content removed pitch was obtained.
この軽質分除去ピッチは２５％のキシレン不溶分を含む
光学的に等方性のピッチであった。This light fraction removed pitch was an optically isotropic pitch containing 25% xylene insoluble matter.
一方、上記軽質分除去ピッチ１８０ｇを窒素気流下、反
応により生成する軽質分を除去しながら４００゜Ｃで８
時間縮重合を行い、熱処理ピッチ９７．２ｇを得た。On the other hand, 180 g of the above light content removed pitch was heated at 400°C for 8 hours under a nitrogen stream while removing the light content generated by the reaction.
Time-condensation polymerization was performed to obtain 97.2 g of heat-treated pitch.
この熱処理ピッチは融点２６３゜Ｃ、軟化点３０８゜Ｃ
、キシレン不溶分７７％、キノリン不溶分３１％を含有
しており、研磨面の偏光顕微鏡観察による光学的異方性
が７５％のメソフエーズ多環状芳香族化合物であった。This heat-treated pitch has a melting point of 263°C and a softening point of 308°C.
It was a mesophase polycyclic aromatic compound containing 77% xylene insoluble matter and 31% quinoline insoluble matter, and had an optical anisotropy of 75% when observed with a polarized light microscope on the polished surface.
前記軽質分除去ピッチ５７ｇに参考例１で得た有機珪素
重合体２５ｇ及びキシレン２０ｒｄを加え、攪拌しなが
ら昇温し、キシレンを留去後、４００゜Ｃで４時間反応
させ５ ７． ４ ｇの前駆重合体（１）を得液（２５
％キシレン溶液１ ５． ５ ｇ ）を加え、キシレン
留去後、３４０゜Ｃで１時間反応させ、ランダム共重合
体（２） ５ ６ ｇを得た。25 g of the organosilicon polymer obtained in Reference Example 1 and 20 ml of xylene were added to 57 g of the pitch from which light fractions had been removed, the temperature was raised while stirring, the xylene was distilled off, and the mixture was reacted at 400° C. for 4 hours.57. 4 g of precursor polymer (1) was obtained using a solution (25
% xylene solution 1 5. After xylene was distilled off, the mixture was reacted at 340°C for 1 hour to obtain 56 g of random copolymer (2).
この共重合体は、キシレン不溶部を含まず重量平均分子
量は１５８０、融点は２５８゜Ｃで、軟化点２９２゜Ｃ
であった。This copolymer does not contain xylene-insoluble parts, has a weight average molecular weight of 1580, a melting point of 258°C, and a softening point of 292°C.
Met.
上記ランダム共重合体（２） ６． ４ ｇと前記メソ
フェーズ多環状芳香族化合物９０ｇを混合し、窒素雰の
結果、有機珪素重合体中に存在するＳｉ−Ｈ結合（Ｉ
Ｒ ： ２ １ ０ ０ｃｍ−’）の減少、及び新たな
Ｓｉ−Ｃ（ベンゼン環の炭素）結合（ＩＲ：１１３５ｃ
ｍ−’）の生成が認められることより有機珪素重合体の
珪素原子の一部が多環状芳香族環と直接結合した部分を
有する共重合体であることがわかった。The above random copolymer (2) 6. 4 g and 90 g of the mesophase polycyclic aromatic compound, and as a result of the nitrogen atmosphere, the Si-H bonds (I
R: 2 100 cm-') and a new Si-C (benzene ring carbon) bond (IR: 1135c
m-') was observed, indicating that the organosilicon polymer was a copolymer having a portion in which some of the silicon atoms were directly bonded to a polycyclic aromatic ring.
前駆重合体（１）５ ７． ４ ｇにテトラオクトキシ
チタン（Ｔ ｉ （Ｏ Ｃｓ Ｈ＋ｔ）ｉ） ３．
８ ７ ｇのキシレン？容この重合体は、融点が２６４
゜Ｃで、軟化点３０７℃、６８％のキシレン不溶分を含
んでいた。Precursor polymer (1) 5 7. 4 g of tetraoctoxytitanium (T i (OCs H+t)i) 3.
8 7 g of xylene? This polymer has a melting point of 264
It had a softening point of 307°C and contained 68% xylene insoluble matter.
上記高分子量物を紡糸用原料とし、ノズル径０．１５ａ
ｍの金属製ノズルを用い、３６０゜Ｃで溶融紡糸を行い
、得られた紡糸原糸を、空気中、３００゜Ｃで不融化し
、更にアルゴン雰囲気中、１３００℃で焼成を行い、直
径７．５μｍの無機繊維を得た。The above high molecular weight material is used as the raw material for spinning, and the nozzle diameter is 0.15a.
Melt spinning was carried out at 360°C using a metal nozzle with a diameter of 7 mm, and the resulting spun yarn was made infusible at 300°C in air, and then fired at 1300°C in an argon atmosphere to give a diameter of 7 mm. .5 μm inorganic fibers were obtained.
この繊維は引張強度が３ ５ ８ Ｋｇ／ｍｍ” 、引
張弾性率３ ２ ｔ ／ｍ”であり、破断面の走査型電
子顕微鏡を用いた観察より、結晶層が幾重にも重なった
珊瑚様のランダム、ラジアル混在構造であった。This fiber has a tensile strength of 358 Kg/mm" and a tensile modulus of 32 t/m", and observation of the fractured surface using a scanning electron microscope reveals a coral-like structure with many layers of crystals. It had a mixed random and radial structure.
この無機繊維を粉砕後、アルカリ溶融、塩酸処理を施し
、水溶液とした後高周波プラズマ発光分光分析（ＩＣＰ
）を行った結果、珪素含有率は０．９５％、チタン含有
率は０．０６％であった。After pulverizing the inorganic fibers, they were melted with alkali and treated with hydrochloric acid to form an aqueous solution, which was then subjected to high-frequency plasma emission spectroscopy (ICP).
), the silicon content was 0.95% and the titanium content was 0.06%.
参考例６（無機繊維■の製造）
参考例５で得られた前駆重合体（１） ３ ９ ｇにテ
ト）キスアセチルアセトナトジルコニウム５．４ｇのエ
タノールーキシレン溶液（１．５％）を加え、キシレン
及びエタノールを留去後２５０゜Ｃで１時間重合し３
９． ５ ｇのランダム共重合体（２）を得た。Reference Example 6 (Production of Inorganic Fiber ■) To 39 g of the precursor polymer (1) obtained in Reference Example 5, an ethanol-xylene solution (1.5%) of 5.4 g of tet)kisacetylacetonatozirconium was added. After distilling off xylene and ethanol, polymerization was carried out at 250°C for 1 hour.
9. 5 g of random copolymer (2) was obtained.
この重合体２０ｇと参考例５で得られたメソフ工一ズ多
環状芳香族化合物５０ｇを微粉砕混合し、３６０゜Ｃで
１時間溶融混合し、ノズル径０． ２ ｍｍのノズルを
用い、３５０゜Ｃで紡糸し、得られた紡糸原糸を空気中
２５０゜Ｃで不融化し、更にアルゴン雰囲気中１４００
゜Ｃで焼成、直径１１μの無機繊維Ｖを得た。20 g of this polymer and 50 g of Metsof Koichi's polycyclic aromatic compound obtained in Reference Example 5 were pulverized and mixed, and melt-mixed at 360°C for 1 hour. Spinning was carried out at 350°C using a 2 mm nozzle, and the resulting spun yarn was infusible at 250°C in air, and further heated at 1400°C in an argon atmosphere.
The inorganic fiber V having a diameter of 11 μm was obtained by firing at °C.
この繊維の引張強度は３ ４ ５ ｋｇ／ａｍ” 、引
張弾性率３５ｔ／ｍｍ２であった。This fiber had a tensile strength of 345 kg/am'' and a tensile modulus of 35 t/mm2.
参考例７（無機繊維■の製造）
軽質分除去ピッチ及び有機珪素重合体の使用量をそれぞ
れ６０ｇ及び４０ｇに変えた以外は参考例５と同様にし
て、５７ｇの前駆重合体（１）を得た。Reference Example 7 (Production of inorganic fiber ■) 57 g of precursor polymer (1) was obtained in the same manner as Reference Example 5, except that the amounts of light content removed pitch and organic silicon polymer were changed to 60 g and 40 g, respectively. Ta.
この前駆共重合体（１１４０ｇにハフニウムクロライド
７．２ｇのエタノールーキシレン溶液（１．５％）を加
え、キシレン及びエタノールを留去後２５０゜Ｃで１時
間重合し４ ３． ５ ｇのランダム共重合体（２）を
得た。An ethanol-xylene solution (1.5%) of 7.2 g of hafnium chloride was added to this precursor copolymer (1140 g), and after distilling off xylene and ethanol, polymerization was carried out at 250°C for 1 hour to obtain 43.5 g of random copolymer. Polymer (2) was obtained.
この重合体２０ｇと参考例５で得られたメソフェーズ多
環状芳香族化合物８０ｇを微粉砕混合した後に、３６０
゜Ｃで１時間溶融混合を行い、３６０゜Ｃで熔融紡糸し
、２７０゜Ｃで不融化し、アルゴン中で１２００゜Ｃで
焼成することによって１２．５μの無機繊維■を得た。After finely pulverizing and mixing 20 g of this polymer and 80 g of the mesophase polycyclic aromatic compound obtained in Reference Example 5,
Melt-mixing was carried out at 1 hour at 360°C, melt-spun at 360°C, infusible at 270°C, and calcined at 1200°C in argon to obtain 12.5μ inorganic fibers.
この繊維の引張強度は３３５ｋｇ／ｆｆｌｆｆ＋２、引
張弾性率３５ｔ／ｍｍ２であった。The tensile strength of this fiber was 335 kg/fflff+2, and the tensile modulus was 35 t/mm2.
参考例８（無機繊維■の製造）
参考例５と同様にして得たランダム共重合体（２）１．
８ｇと参考例５と同様にして得たメソフェーズ多環状芳
香族化合物９０ｇを、窒素気流下４００゜Ｃで１．５時
間溶融混合し、融点２６５゜Ｃ１キシレン不溶分５５％
の紡糸ドープを得た。このドープをノズル径０．１５ｍ
ｍのノズルを用い、３５０゜Ｃで溶融紡糸後、３００℃
で不融化後１７００゜Ｃで焼成し、直径８μの無機繊維
を得た。Reference Example 8 (Production of Inorganic Fiber (■)) Random copolymer (2) obtained in the same manner as Reference Example 51.
8g and 90g of a mesophase polycyclic aromatic compound obtained in the same manner as in Reference Example 5 were melt-mixed at 400°C for 1.5 hours under a nitrogen stream to obtain a melting point of 265°C1 xylene insoluble content of 55%.
A spinning dope was obtained. This dope is passed through a nozzle diameter of 0.15m.
After melt spinning at 350°C using a nozzle of
After making it infusible, it was fired at 1700°C to obtain inorganic fibers with a diameter of 8μ.
この無機繊維を粉砕後、アルカリ溶融、塩酸処理を施し
、水溶液とした後高周波プラズマ発光分光分析（ＩＣＰ
）を行った結果、珪素含有率は０．３％、チタン含有率
は０．０１５％であった。After pulverizing the inorganic fibers, they were melted with alkali and treated with hydrochloric acid to form an aqueous solution, which was then subjected to high-frequency plasma emission spectroscopy (ICP).
), the silicon content was 0.3% and the titanium content was 0.015%.
この繊維の引張強度は３ ３ ５ ｋｇ／ｍｍ” 、引
張弾性率４ ０ ｔ ／ｍｍｚであった。This fiber had a tensile strength of 335 kg/mm'' and a tensile modulus of 40 t/mmz.
参考例９ （Ｓｔ−Ｔｉ −Ｃ−０繊維の製法）ジメチ
ルジクロロシランを金属ナトリウムで脱塩素縮合して合
成されるボリジメチルシラン１００部に対しポリボロシ
ロキサンを３部の割合で添加し、窒素中、３５０゜Ｃで
熱縮合し、式（Ｓｉ−ＣＨ．）のカルボシラン単位から
主としてなる主鎖骨格を有し、該カルボシラン単位の珪
素原子に？素原子及びメチル基を有しているポリ力ルボ
シランを調製した。このポリ力ルボシランに、チタンア
ルコキシドを加えて、窒素中、３４０゜Ｃで架橋重合す
ることにより、カルボシラン単位１００部と式（Ｔｉ−
０）のチタノキサン１０部とからなるポリチタノカルボ
シランを得た。このポリマーを溶融紡糸し、空気中１９
０゜Ｃで不融化処理し、さらに引き続いて窒素中１３０
０゜Ｃで焼成して、繊維径１３μ、引張強度３ １ ０
ｋｇ／ ｍｍ２、弾性率１６ｔ／ａａ２ （モノフィ
ラメント法）の主として珪素、チタン、炭素及び酸素か
らなるチタン元素３％含有の無機繊維を得た。得られた
無機繊維はＳｔ，Ｔｉ，Ｃ及びＯからなる非晶質と、β
一ＳｉＣ，Ｔｉｃ，β−ＳｉＣとＴｉｃの固溶体及びＴ
ｉ Ｃｌ−Ｉ＋ （ただし、０＜ｘ＜１）の粒径が
約５０人の各結晶質超微粒子及び非晶質のＳｉＯ■とＴ
ｉＱ．からなる集合体との混合系からなるＳｉＴｉ−Ｃ
−０繊維であった。Reference Example 9 (Production method of St-Ti-C-0 fiber) Polyborosiloxane was added at a ratio of 3 parts to 100 parts of boridimethylsilane synthesized by dechlorination condensation of dimethyldichlorosilane with metallic sodium, and nitrogen The main chain skeleton is mainly composed of carbosilane units of the formula (Si-CH.), and the silicon atoms of the carbosilane units are thermally condensed at 350°C. A polycarbosilane containing elementary atoms and methyl groups was prepared. Titanium alkoxide is added to this polycarbosilane, and crosslinking polymerization is carried out at 340°C in nitrogen to form 100 parts of carbosilane units with the formula (Ti-
A polytitanocarbosilane consisting of 10 parts of titanoxane (0) was obtained. This polymer was melt-spun and 19
Infusible treatment at 0°C followed by 130°C in nitrogen
Sintered at 0°C, fiber diameter 13μ, tensile strength 310
An inorganic fiber containing 3% titanium element consisting mainly of silicon, titanium, carbon and oxygen and having an elastic modulus of 16 t/aa2 (monofilament method) was obtained. The obtained inorganic fiber is amorphous consisting of St, Ti, C and O, and β
-SiC, Tic, solid solution of β-SiC and Tic and T
i Cl-I+ (where 0<x<1) particle size is about 50 crystalline ultrafine particles and amorphous SiO■ and T
iQ. SiTi-C consisting of a mixed system with an aggregate consisting of
-0 fiber.
実施例１
ビスフェノールＡ型エポキシ樹脂（チバガイギ一社製Ｘ
Ｂ２８７９Ａ）１００部及びジシアンジアミド硬化剤（
チバガイギー社製ＸＢ２Ｂ７９Ｂ）２０部を均一に混合
した後に、混合物を重量比で１：１のメチルセロソルブ
とアセトンとの混合溶媒に溶解して、上記混合物の２８
％溶液を調製した。Example 1 Bisphenol A epoxy resin (X manufactured by Ciba-Geigi Co., Ltd.)
B2879A) 100 parts and dicyandiamide curing agent (
After uniformly mixing 20 parts of XB2B79B (manufactured by Ciba Geigy), the mixture was dissolved in a mixed solvent of methyl cellosolve and acetone at a weight ratio of 1:1, and 28 parts of the above mixture was dissolved.
% solution was prepared.
参考例２で得られた無機繊維Ｉに上記溶液を含浸した後
に、ドラムワイングーを用いて一方向に引き取り、熱循
環オーブン中１００゜Ｃで１４分間加熱することによっ
て半硬化状態の一方向に引き揃えられた無機繊維ブリプ
レグシ一トを調製した。After impregnating the inorganic fiber I obtained in Reference Example 2 with the above solution, it was pulled in one direction using a drum wine gourd, and heated in a heat circulation oven at 100°C for 14 minutes to make it semi-cured in one direction. A stretched inorganic fiber precipitate was prepared.
同様にして、表面処理をした炭素繊維（ポリアクリロニ
トリル系、繊維径７μ、引張強度３００Ｋｇ／ｍｍ”、
引張弾性率２ ４ ｔ ／ｍｍ” ）を用い半硬化状態
の一方向に引き揃えられた炭素繊維ブリプレグシートを
調製した。Similarly, surface-treated carbon fiber (polyacrylonitrile, fiber diameter 7μ, tensile strength 300Kg/mm),
A unidirectionally aligned carbon fiber blipreg sheet in a semi-cured state was prepared using a tensile modulus of elasticity of 2 4 t/mm''.
このようにして得た無機繊維Ｉと炭素繊維のブリプレグ
シ一トを軸方向を同じにして交互に積層した後ホットプ
レスして、ハイブリッド繊維（無機繊維／炭素繊維）強
化エポキシ複合材料を製造した。The thus obtained inorganic fiber I and the carbon fiber precipitate were alternately laminated with the same axial direction and then hot pressed to produce a hybrid fiber (inorganic fiber/carbon fiber) reinforced epoxy composite material.
この複合材料の繊維含有率は無機繊維３０体積％、炭素
繊維３０体積％、計６０体積％であった。The fiber content of this composite material was 30% by volume of inorganic fibers and 30% by volume of carbon fibers, for a total of 60% by volume.
得られた複合材料の０度方向の引張強度及び弓張弾性率
はそれぞれ１９１Ｋｇ／ｍｍ２ １６．８ｔ／ ｍｍ
２であり、０度方向の曲げ強度は１９５ＫｇＺ胴２で
あり、９０度方向の曲げ強度は７． ８ Ｋ ｇ／ ｍ
ｍ” 、層間剪断強度は８． ８ Ｋ ｇ／ｍｍ２、曲
げ衝撃値は２ ３ ０ Ｋ ｇ −ｃｍ／ｃＩｉ１であ
った。The tensile strength in the 0 degree direction and bow tensile modulus of the obtained composite material were 191 Kg/mm2 and 16.8 t/mm, respectively.
2, the bending strength in the 0 degree direction is 195KgZ body 2, and the bending strength in the 90 degree direction is 7. 8kg/m
m'', interlaminar shear strength was 8.8 K g/mm2, and bending impact value was 230 K g-cm/cIi1.
実施例２
炭素繊維の代わりに、参考例９に示したＳｉＴｉ−Ｃ−
０繊維を用いて実施例１と同様にしてハイブリッド繊維
強化エポキシ複合材料を製造した。この複合材料の繊維
含有率は無機繊維３０体積％、Ｓｉ−Ｔｉ−Ｃ−０繊維
３０体積％、計６０体積％である。得られた複合材料の
０度方向の引張強度及び引張弾性率はそれぞれ２００Ｋ
ｇ／ｍｎ” １５．９ｔ／鵬２であり、０度方向の
曲げ強度は、２ １ ５ Ｋｇ／ａｎ２、９ ０’方向
の曲げ強度は１２．８Ｋｇ／−２、眉間剪断強度は１
２． １ Ｋ ｇ／Ｉｎｌｌ１”、曲げ衝撃値は２ ８
２ Ｋｇ −ｃｍ／ｃｆｆｌであった。Example 2 Instead of carbon fiber, SiTi-C- shown in Reference Example 9
A hybrid fiber-reinforced epoxy composite material was produced in the same manner as in Example 1 using 0 fibers. The fiber content of this composite material is 30% by volume of inorganic fibers and 30% by volume of Si-Ti-C-0 fibers, for a total of 60% by volume. The tensile strength and tensile modulus of the obtained composite material in the 0 degree direction are each 200K.
g/mn" 15.9t/peng2, the bending strength in the 0 degree direction is 2 1 5 Kg/an2, the bending strength in the 90' direction is 12.8Kg/-2, and the glabella shear strength is 1
2. 1 K g/Inll1”, bending impact value is 2 8
It was 2 Kg-cm/cffl.
比較例１
引張強度３００Ｋｇ／ｆｆｌＩｌ１２、引張弾性率２１
ｔ／ ｆｆｌｆｆｉ ” 、繊維径７．５μのポリアク
リロニトリル系炭素繊維のみを用い、実施例１と同様に
して、半硬化状態の一方向に引き揃えられた炭素繊維ブ
リプレグシ一トを調製した。Comparative Example 1 Tensile strength 300Kg/fflI12, tensile modulus 21
Using only polyacrylonitrile-based carbon fibers with a fiber diameter of 7.5 μm and a fiber diameter of 7.5 μm, a semi-cured carbon fiber brisple resin sheet was prepared in the same manner as in Example 1.
このブリプレグシ一トを、繊維軸を同じにして、積層し
た後、ホットプレスして、炭素繊維強化エポキシ複合材
料を製造した。この複合材料の繊維含有率は６０体積％
である。得られた複合材料の０度方向の引張強度及び引
張弾性率はそれぞれ１５０Ｋｇ／閤２及び１４ｔ／鴫２
であり、０度方向の曲げ強度は、１ ７ ２ Ｋｇ／ｍ
ｍ” 、９ ０度方向の曲げ強度は６．２Ｋｇ／Ｍｚ、
層間剪断強度は８．１Ｋｇ／ｍｍ”、曲げ衝撃値は１
５ ０ Ｋ ｇ −ｃｒａ／ｃ［ａであった。This briple resin was laminated with the same fiber axis and then hot pressed to produce a carbon fiber-reinforced epoxy composite material. The fiber content of this composite material is 60% by volume
It is. The tensile strength and tensile modulus of the obtained composite material in the 0 degree direction are 150 Kg/Kg2 and 14 T/K2, respectively.
The bending strength in the 0 degree direction is 1 7 2 Kg/m
m”, bending strength in 90 degree direction is 6.2Kg/Mz,
Interlaminar shear strength is 8.1Kg/mm”, bending impact value is 1
It was 50 K g -cra/c[a.
比較例２
参考例９で得られたＳｉ−Ｔｉ−Ｃ−０繊維のみを用い
、実施例ｌと同様にして、Ｓｉ−ＴｉＣ−Ｏ繊維ブリプ
レグシ一トを調製し、比較例１と同様にして、Ｓｉ−Ｔ
ｉ−Ｃ−０繊維強化エポキシ複合材料を製造した。この
複合材料の繊維含有率は６０体積％である。得られた複
合材料のＯ度方向の引張弾性率１ １． ３ ｔ ／ｆ
ｆｕＩ１”であった。他の機械的強度は実施例２とほぼ
同程度の値であった。Comparative Example 2 Using only the Si-Ti-C-0 fibers obtained in Reference Example 9, a Si-TiC-O fiber precipitate was prepared in the same manner as in Example 1, and in the same manner as in Comparative Example 1. , Si-T
An i-C-0 fiber reinforced epoxy composite material was produced. The fiber content of this composite material is 60% by volume. Tensile modulus of the obtained composite material in the O degree direction: 1 1. 3t/f
fuI1''.Other mechanical strengths were approximately the same as in Example 2.
実施例３〜５
炭素繊維の代わりに第１表に示す特性を有するアルミナ
繊維、炭化珪素繊維またはガラス繊維（これらの繊維を
強化用第２繊維と呼ぶ。）を用いて、実施例１と同様に
してハイブリッド繊維強化エボキシ樹脂複合材料を製造
した。これらの複合材料の繊維含有率は、無機繊維３０
体積％、強化用第２繊維３０体積％、計６０体積％であ
った。Examples 3 to 5 Same as Example 1, using alumina fibers, silicon carbide fibers, or glass fibers (these fibers are referred to as second reinforcing fibers) having the characteristics shown in Table 1 instead of carbon fibers. A hybrid fiber-reinforced epoxy resin composite material was produced. The fiber content of these composite materials is 30% of the inorganic fibers.
% by volume, 30% by volume of the second reinforcing fiber, and 60% by volume in total.
得られたハイブリッド繊維強化エボキシ樹脂複合材料の
性能を第２表に示した。The performance of the obtained hybrid fiber-reinforced epoxy resin composite material is shown in Table 2.
第１表
第２表
比較例３〜５
アルミナ繊維、炭化珪素繊維またはガラス繊維を用い、
実施例１と同様にして、アルミナ繊維ブリプレグシ一ト
、炭化珪素繊維ブリプレグシ一ト及びガラス繊維ブリプ
レグシ一トを調製し、比較例１と同様にして、アルミナ
繊維強化エボキシ複合材料、炭化珪素繊維強化エボキシ
複合材料及びガラス繊維強化エポキシ複合材料を製造し
た。これらの複合材料の繊維含有率は６０体積％であっ
た。Table 1 Table 2 Comparative Examples 3 to 5 Using alumina fiber, silicon carbide fiber or glass fiber,
In the same manner as in Example 1, an alumina fiber bripreg sheet, a silicon carbide fiber bripreg sheet, and a glass fiber bripreg sheet were prepared, and in the same manner as in Comparative Example 1, an alumina fiber reinforced epoxy composite material, a silicon carbide fiber reinforced epoxy Composite materials and glass fiber reinforced epoxy composite materials were manufactured. The fiber content of these composite materials was 60% by volume.
得られた複合材料の機械的特性を第３表に示した。The mechanical properties of the obtained composite material are shown in Table 3.
第３表
実施例６
無機繊維として、参考例３で得られた無機繊維■を用い
、炭素繊維の代わりに、繊維直径１４０μ、引張強度３
５０Ｋｇ／胴２、引張弾性率４３ｔ／ｍｍ”のカーボン
を芯線とした炭化珪素繊維を用い、実施例１と同様にし
てハイブリッド繊維強化エポキシ樹脂複合材料を製造し
た。この複合材料の繊維含有率は、無機繊維が３０体積
％、力一ボンを芯線とした炭化珪素繊維が１６体積％で
、計４６体積％であった。 得られた複合材料のＯ度方
向の引張強度が１ ６ ８ Ｋｇ／ｍｍ２、０度方向の
引張弾性率が２ ２ ｔ／ｍｍ２、Ｏ度方向の曲げ強度
が２１３Ｋｇ／ｍｍ”及び９０度方向の曲げ強度が６．
７Ｋｇ／圓２であった。Table 3 Example 6 Inorganic fibers obtained in Reference Example 3 were used as the inorganic fibers, and the fiber diameter was 140μ and the tensile strength was 3 instead of the carbon fibers.
A hybrid fiber-reinforced epoxy resin composite material was produced in the same manner as in Example 1 using carbon-core silicon carbide fibers with a tensile modulus of 43 t/mm and a tensile modulus of 50 kg/2. The fiber content of this composite material was as follows. , 30% by volume of inorganic fibers, and 16% by volume of silicon carbide fibers with a core wire made of fibers, for a total of 46% by volume.The tensile strength of the obtained composite material in the O degree direction was 1 6 8 Kg/ mm2, the tensile modulus in the 0 degree direction is 2 2 t/mm2, the bending strength in the 0 degree direction is 213 Kg/mm", and the bending strength in the 90 degree direction is 6.
It was 7Kg/round 2.
比較例６
実施例６で用いたカーボンを芯線とした炭化珪素繊維を
用い、実施例１と同様にして、カーボンを芯線とした炭
化珪素繊維ブリプレグシートを調製し、比較例１と同様
にしてカーボンを芯線とした炭化珪素繊維強化エポキシ
樹脂複合材料を得た．カーボンを芯線とした炭化珪素繊
維は、繊維直径が大きいため繊維含有率は３３体積％に
過ぎなかった。Comparative Example 6 Using the carbon-core silicon carbide fiber used in Example 6, a carbon-core silicon carbide fiber preg sheet was prepared in the same manner as in Example 1, and in the same manner as in Comparative Example 1. A silicon carbide fiber-reinforced epoxy resin composite material with a carbon core was obtained. The silicon carbide fiber having a carbon core had a large fiber diameter, so the fiber content was only 33% by volume.
得られた複合材料の０度方向の引張強度が１４０Ｋｇ／
＋＋＋ｍ２、Ｑ度方向の引張弾性率が２３Ｌ／［ｌｔ［
Ｉｌ２、０度方向の曲げ強度が１９５Ｋｇ／ｍｍ２及び
９０度方向の曲げ強度が３．１Ｋｇ／ｍｍ２であった。The tensile strength of the obtained composite material in the 0 degree direction is 140 kg/
+++m2, the tensile modulus in the Q degree direction is 23L/[lt[
Il2, the bending strength in the 0 degree direction was 195 Kg/mm2, and the bending strength in the 90 degree direction was 3.1 Kg/mm2.
実施例７
無機繊維として、参考例４で得られた無機繊維■を用い
、炭素繊維の代わりに、繊維直径１４０μ、引張強度３
５７Ｋｇ／＋唾２、引張弾性率４１ｔ／ｍｍ”のボロン
繊維を用い、実施例１と同様にしてハイブリッド繊維強
化エポキシ樹脂複合材料を製造した。この複合材料の繊
維含有率は、無機繊維が３０体積％、ボロン繊維が２０
体積％で、計５０体積％であった。Example 7 Inorganic fibers obtained in Reference Example 4 were used as inorganic fibers, and the fiber diameter was 140μ and the tensile strength was 3 instead of carbon fibers.
A hybrid fiber-reinforced epoxy resin composite material was produced in the same manner as in Example 1 using boron fibers with a tensile modulus of 41 t/mm and a tensile modulus of 57 Kg/+2.The fiber content of this composite material was 30 Volume%, boron fiber is 20
The total amount was 50% by volume.
得られた複合材料の０度方向の引張強度が１７８Ｋｇ／
胴２、０度方向の引張弾性率が２ １ ｔ／ｍｍ”
Ｏ度方向の曲げ強度が２ １ ５ Ｋ ｇ／ｍｍ２及び
９０度方向の曲げ強度が７． ０ Ｋ ｇ ／ｍｍ”で
あった。The tensile strength of the obtained composite material in the 0 degree direction is 178 kg/
The tensile modulus of shell 2 in the 0 degree direction is 2 1 t/mm.
The bending strength in the 0 degree direction is 2 1 5 K g/mm2 and the bending strength in the 90 degree direction is 7. 0 Kg/mm".
比較例７
実施例７で用いたポロン繊維を単独で用い、実施例１と
同様にして、ボロン繊維ブリプレグシ一トを調製し、比
較例１と同様にしてボロン繊維強化エポキシ樹脂複合材
料を得た。ボロン繊維は、繊維直径が大きいため繊維含
有率は３１体積％に過ぎなかった。得られた複合材料の
０度方向の引張強度が１５４Ｋｇ／ｍＩ”、０度方向の
引張弾性率が２ ２ ｔ／ｍｎ” 、Ｏ度方向の曲げ強
度が１９３Ｋｇ／ｍｍ”及び９０度方向の曲げ強度が３
． ８ Ｋ ｇ／ｍｍ”であった。Comparative Example 7 Using the poron fiber used in Example 7 alone, a boron fiber brisple resin was prepared in the same manner as in Example 1, and a boron fiber reinforced epoxy resin composite material was obtained in the same manner as in Comparative Example 1. . The boron fiber had a large fiber diameter, so the fiber content was only 31% by volume. The resulting composite material has a tensile strength in the 0 degree direction of 154 Kg/mI", a tensile modulus in the 0 degree direction of 2 2 t/mn", a bending strength in the 0 degree direction of 193 Kg/mm", and a bending strength in the 90 degree direction. Strength is 3
．． 8 Kg/mm".
実施例８
炭素繊維の代わりに、引張強度２７０Ｋｇ／ｗ”、引張
弾性率１３ｔ／＋ｎｏ＋”のアラミド繊維を用いて実施
例１と同様にしてハイブリッド繊維強化エボキシ複合材
料を製造した。この複合材料の繊維含有率は無機繊維が
３０体積％で、アラミド繊維が３０体積％、計６０体積
％であった。 得られた複合材料の０度方向の引張強度
、引張弾性率及び曲げ強度はそれぞれ１５８Ｋｇ／ｍｍ
２ １２ｔ／ ｔｍ ”及び１６１Ｋｇ／ｍｍ”であ
り、アラミド繊維強化エボキシ樹脂と比べ大幅に強度、
弾性率が向上した（繊維含有率が６０体積％のアラミド
繊維強化エボキシ樹脂のＯ度方向の引張強度、引張弾性
率及び曲げ強度はそれぞれ９ ５ Ｋ ｇ ／ｍｍ２５
． ３ ｔ ／ ＩｎｏＩ”及び９３Ｋｇ／［ＩＩＩｌ
１２であった。）。Example 8 A hybrid fiber-reinforced epoxy composite material was produced in the same manner as in Example 1 using aramid fibers with a tensile strength of 270 Kg/w" and a tensile modulus of 13 t/+no+" instead of carbon fibers. The fiber content of this composite material was 30% by volume of inorganic fibers and 30% by volume of aramid fibers, for a total of 60% by volume. The tensile strength in the 0 degree direction, tensile modulus, and bending strength of the obtained composite material were each 158 Kg/mm.
2 12t/tm" and 161Kg/mm", significantly higher strength than aramid fiber reinforced epoxy resin.
Improved elastic modulus (tensile strength in the O degree direction, tensile modulus, and bending strength of aramid fiber-reinforced epoxy resin with a fiber content of 60% by volume are each 95 K g / mm25
．． 3t/InoI” and 93Kg/[IIIl
It was 12. ).
また、得られた複合材料の曲げ衝撃値は２７２Ｋｇ−ｃ
ｍｌｃ−で、アラミド繊維の特徴である耐衝撃性を大幅
に減じるものではなかった（繊維含有率が６０体積％の
アラミド繊維強化エボキシ樹脂の曲げ衝撃値は３０２Ｋ
ｇ−ｃｍ／ｃｆｆｌであった。）。Moreover, the bending impact value of the obtained composite material was 272Kg-c
mlc-, it did not significantly reduce the impact resistance, which is a characteristic of aramid fibers (the bending impact value of aramid fiber-reinforced epoxy resin with a fiber content of 60% by volume was 302K).
g-cm/cffl. ).
実施例９
ビスフェノールＡ型エボキシ樹脂（チバガイギー社製Ｘ
Ｂ２８７９Ａ）１００部及びジシアンジアミド硬化剤（
チバガイギー社製ＸＢ２８７９Ｂ）２０部を均一に混合
した後に、混合物を重量比でｌ：１のメチルセロソルブ
とアセトンとの混合溶媒に溶解して、上記混合物の２８
％溶液を調製した。Example 9 Bisphenol A type epoxy resin (X manufactured by Ciba Geigy)
B2879A) 100 parts and dicyandiamide curing agent (
After uniformly mixing 20 parts of XB2879B (manufactured by Ciba Geigy), the mixture was dissolved in a mixed solvent of methyl cellosolve and acetone at a weight ratio of 1:1, and 28 parts of the above mixture was dissolved.
% solution was prepared.
参考例５で得られた無機繊維■に上記溶液を含浸した後
に、ドラムワイングーを用いて一方向に引き取り、熱循
環オーブン中１００゜Ｃで１４分間加熱することによっ
て半硬化状態の一方向に引き揃えられた無機繊維ブリプ
レグシートを調製した。After the inorganic fibers obtained in Reference Example 5 were impregnated with the above solution, they were pulled in one direction using a drum wine gourd, and heated in a heat circulation oven at 100°C for 14 minutes to make them semi-cured in one direction. A aligned inorganic fiber Bripreg sheet was prepared.
同様にして、表面処理をした炭素繊維（ポリアクリロニ
トリル系、繊維径７μ、引張強度３００Ｋｇ／ｍｍ”、
引張弾性率２４ｔ／ｍｍ”）を用い半硬化状態の一方向
に引き揃えられた炭素繊維ブリプレグシ一トを調製した
。Similarly, surface-treated carbon fiber (polyacrylonitrile, fiber diameter 7μ, tensile strength 300Kg/mm),
Using a tensile modulus of elasticity of 24 t/mm"), a unidirectionally aligned carbon fiber bristle resin sheet in a semi-cured state was prepared.
このようにして得た無機繊維■と炭素繊維のブリプレグ
シートを軸方向を同じにして交互に積層した後ホットプ
レスして、ハイブリッド繊維（無機繊維／炭素繊維）強
化エポキシ複合材料を製造した。The thus obtained inorganic fiber (1) and carbon fiber Bripreg sheets were alternately laminated with the same axial direction and then hot pressed to produce a hybrid fiber (inorganic fiber/carbon fiber) reinforced epoxy composite material.
この複合材料の繊維含有率は無機繊維３０体積％、炭素
繊維３０体積％、計６０体積％であった。The fiber content of this composite material was 30% by volume of inorganic fibers and 30% by volume of carbon fibers, for a total of 60% by volume.
得られた複合材料のＯ度方向の引張強度及び引張弾性率
はそれぞれ１９７Ｋｇ／薗” １６．８ｔ／ＩＴＩ
Ｉ１２であり、０度方向の曲げ強度は１９９Ｋｇ／ ｍ
ｍ ”であり、９０度方向の曲げ強度は８． ０ Ｋ
ｇ／胴２、層間剪断強度は９． １ Ｋ ｇ ／ｔｉｎ
２、曲げ衝撃値は２ ３ ５ Ｋ ｇ −ｃｍ／ｃＪで
あった。The tensile strength and tensile modulus of the obtained composite material in the O degree direction were 197 Kg/Sono” 16.8 t/ITI, respectively.
I12, and the bending strength in the 0 degree direction is 199Kg/m
m”, and the bending strength in the 90 degree direction is 8.0 K
g/shell 2, interlaminar shear strength is 9. 1 kg/tin
2. The bending impact value was 235 K g -cm/cJ.
実施例１０
炭素繊維の代わりに、参考例９に示したＳｉＴｉ−Ｃ−
０繊維を用いて実施例９と同様にしてハイブリッド繊維
強化エポキシ複合材料を製造した。この複合材料の繊維
含有率は無機繊維３０体積％、Ｓｉ−Ｔｉ−Ｃ−０繊維
３０体積％、計６０体積％である。得られた複合材料の
０度方向の引張強度及び引張弾性率はそれぞれ２０７Ｋ
ｇ／ｍｍ” １５．９ｔ／鵬２であり、０度方向の
曲げ強度は、２２１Ｋｇ／ＩＩＩＩｏ２、９０゜方向の
曲げ強度は１３．１Ｋｇ／舗２、層間剪断強度は１ ２
． ９ Ｋ ｇ／ＩｌＩＩ１２、曲げ衝撃値は２ ９
０ Ｋｇ−ｃｍ／ｃｎｌであった。Example 10 Instead of carbon fiber, SiTi-C- shown in Reference Example 9
A hybrid fiber-reinforced epoxy composite material was produced in the same manner as in Example 9 using 0 fibers. The fiber content of this composite material is 30% by volume of inorganic fibers and 30% by volume of Si-Ti-C-0 fibers, for a total of 60% by volume. The tensile strength and tensile modulus of the obtained composite material in the 0 degree direction are 207K, respectively.
g/mm” 15.9t/Peng2, the bending strength in the 0 degree direction is 221Kg/IIIo2, the bending strength in the 90° direction is 13.1Kg/Peng2, and the interlaminar shear strength is 12
．． 9 K g/IlII12, bending impact value is 2 9
It was 0 Kg-cm/cnl.
実施例１１〜１３
炭素繊維の代わりに第１表に示す特性を有するアルミナ
繊維、炭化珪素繊維またはガラス繊維（これらの繊維を
強化用第２繊維と呼ぶ。）を用いて、実施例９と同様に
してハイブリッド繊維強化エポキシ樹脂複合材料を製造
した。これらの複合材料の繊維含有率は、無機繊維３０
体積％、強化用第２繊維３０体積％、計６０体積％であ
った。Examples 11 to 13 Same as Example 9, using alumina fiber, silicon carbide fiber, or glass fiber (these fibers are referred to as second reinforcing fibers) having the characteristics shown in Table 1 instead of carbon fiber. A hybrid fiber-reinforced epoxy resin composite material was produced. The fiber content of these composite materials is 30% of the inorganic fibers.
% by volume, 30% by volume of the second reinforcing fiber, and 60% by volume in total.
得られたハイブリッド繊維強化エボキシ樹脂複合材料の
性能を第４表に示した。Table 4 shows the performance of the obtained hybrid fiber-reinforced epoxy resin composite material.
第４表
実施例１４
無機繊維として、参考例６で得られた無機繊維■を用い
、炭素繊維の代わりに、繊維直径１４０μ、引張強度３
５ ０ Ｋｇ／圓２、引張弾性率４３ｔ／ｍｍ”のカ
ーボンを芯線とした炭化珪素繊維を用い、実施例１と同
様にしてハイブリッド繊維強化エボキシ樹脂複合材料を
製造した。この複合材料の繊維含有率は、無機繊維が３
０体積％、力一ボンを芯線とした炭化珪素繊維が１６体
積％で、計４６体積％であった。Table 4 Example 14 The inorganic fibers obtained in Reference Example 6 were used as the inorganic fibers, and instead of carbon fibers, the fiber diameter was 140μ and the tensile strength was 3.
A hybrid fiber-reinforced epoxy resin composite material was produced in the same manner as in Example 1 using silicon carbide fibers with a core of carbon having a tensile modulus of 43 t/mm and a tensile modulus of 50 Kg/field 2. The rate is 3 for inorganic fibers.
0% by volume, and 16% by volume of silicon carbide fibers having a core wire of Rikibon, for a total of 46% by volume.
得られた複合材料の０度方向の引張強度が１７１ Ｋｇ
／ｍ” 、Ｏ度方向の引張弾性率が２２ｔ／ＩＩＩ１２
、０度方向の曲げ強度が２１８Ｋｇ／ｍｍ”及び９０度
方向の曲げ強度が６． ９ Ｋ ｇ ／ｍｍ”であった
。The tensile strength of the resulting composite material in the 0 degree direction is 171 Kg.
/m”, tensile modulus in O degree direction is 22t/III12
The bending strength in the 0 degree direction was 218 Kg/mm'' and the bending strength in the 90 degree direction was 6.9 Kg/mm''.
実施例１５
無機繊維として、参考例７で得られた無機繊維■を用い
、炭素繊維の代わりに、繊維直径１４０μ、引張強度３
５ ７ Ｋｇ／ｍｍ” 、引張弾性率４１ｔ／ｒｍ”
のボロン繊維を用い、実施例９と同様にしてハイブリッ
ド繊維強化エボキシ樹脂複合材料を製造した。この複合
材料の繊維含有率は、無機繊維が３０体積％、ボロン繊
維が２０体積％で、計５０体積％であった。Example 15 Inorganic fibers obtained in Reference Example 7 were used as inorganic fibers, and instead of carbon fibers, the fiber diameter was 140μ and the tensile strength was 3.
5 7 Kg/mm", tensile modulus 41t/rm"
A hybrid fiber-reinforced epoxy resin composite material was produced in the same manner as in Example 9 using the boron fibers. The fiber content of this composite material was 30% by volume of inorganic fibers and 20% by volume of boron fibers, for a total of 50% by volume.
得られた複合材料の０度方向の引張強度が１８５ Ｋ
ｇ／ｍｍ” 、Ｑ度方向の引張弾性率が２１ｔ／ｆｆｌ
ＩＩｌ！、０度方向の曲げ強度が２１９Ｋｇ／ｍｍ２及
び９０度方向の曲げ強度が７．８Ｋｇ／ｍｍ”であった
。The tensile strength of the resulting composite material in the 0 degree direction is 185 K.
g/mm”, tensile modulus in Q degree direction is 21t/ffl
IIl! The bending strength in the 0 degree direction was 219 Kg/mm2, and the bending strength in the 90 degree direction was 7.8 Kg/mm''.
実施例１６
無機繊維として、参考例８で得られた無機繊維■を用い
、炭素繊維の代わりに、引張強度２７０Ｋｇ／ｔｍ”、
引張弾性率１３ｔ／ｍｍ”のアラミド繊維を用いて実施
例９と同様にしてハイブリッド繊維強化エボキシ複合材
料を製造した。この複合材料の繊維含有率は無機繊維が
３０体積％で、アラミド繊維が３０体積％、計６０体積
％であった。Example 16 Inorganic fibers obtained in Reference Example 8 were used as the inorganic fibers, and instead of carbon fibers, the tensile strength was 270 Kg/tm.
A hybrid fiber-reinforced epoxy composite material was produced in the same manner as in Example 9 using aramid fibers with a tensile modulus of 13 t/mm.The fiber content of this composite material was 30% by volume of inorganic fibers and 30% by volume of aramid fibers. The total amount was 60% by volume.
得られた複合材料のＯ度方向の引張強度、引張弾性率及
び曲げ強度はそれぞれ１ ６ ２ Ｋ ｇ／ｍｍ２１６
ｔ／■２及び１６６Ｋｇ／鵬２であり、アラミド繊維強
化エボキシ樹脂と比べ大幅に強度、弾性率が向上した（
繊維含有率が６０体積％のアラミド繊維強化エボキシ樹
脂の０度方向の引張強度、引張弾性率及び曲げ強度はそ
れぞれ９５Ｋｇ／ ｍｍ” 、５． ３ ｔ ／ ｍ”
及び９３Ｋｇ／ＩＩ＋１２であった。）。また、得られ
た複合材料の曲げ衝撃値は２ ７ ６Ｋｇ−ｃｔｔｒ／
ｃ４で、アラミド繊維の特徴である耐衝撃性を大幅に減
じるものではなかった（繊維含有率が６０体積％のアラ
ミド繊維強化エボキシ樹脂の曲げ衝撃値は３ ０ ２
Ｋ ｇ −Ｃ！ｌ／Ｃ−であった。）。The tensile strength, tensile modulus, and bending strength of the obtained composite material in the O degree direction are each 1 6 2 K g/mm 216
t/■2 and 166Kg/Peng2, significantly improving strength and elastic modulus compared to aramid fiber reinforced epoxy resin (
The tensile strength in the 0 degree direction, tensile modulus and bending strength of the aramid fiber reinforced epoxy resin with a fiber content of 60% by volume are 95 Kg/mm” and 5.3 t/m”, respectively.
and 93Kg/II+12. ). In addition, the bending impact value of the obtained composite material was 276Kg-cttr/
c4, it did not significantly reduce the impact resistance that is a characteristic of aramid fibers (the bending impact value of aramid fiber reinforced epoxy resin with a fiber content of 60% by volume is 3 0 2
Kg-C! l/C-. ).
Claims (1)
ナ繊維、窒化珪素繊維、アラミド繊維、炭化珪素繊維、
カーボンを芯線とする炭化珪素繊維及びＳｉ−Ｍ−Ｃ−
Ｏ繊維（ＭはＴｉ又はＺｒを示す。）からなる群から選
ばれた少なくとも一種の繊維とのハイブリッド繊維を強
化材とし、プラスチックをマトリックスとするプラスチ
ック複合材料において、前記無機繊維がチタン、ジルコ
ニウム及びハフニウムからなる群から選ばれる少なくと
も一種類の元素及び珪素を含有する金属含有多環状芳香
族重合体から得られる無機繊維であって、その構成成分
が、 ａ）該重合体を構成するメソフェーズ状態にある多環状
芳香族化合物から導かれるラジアル構造、オニオン構造
、ランダム構造、コアラジアル構造、スキンオニオン構
造及びモザイク構造からなる群から選ばれる少なくとも
一種の結晶配列状態を示す炭素質、 ｂ）該重合体を構成する有機溶媒不溶分を含む光学的等
方性の多環状芳香族化合物から導かれる、無配向状態の
結晶質炭素及び／又は非晶質炭素、及び ｃ）（１）Ｓｉ、Ｍ、Ｃ及びＯから実質的になる非晶質
物質、及び／又は （２）実質的にβ−ＳｉＣ、ＭＣ、β−ＳｉＣとＭＣの
固溶体及びＭＣ＿１＿−＿ｘからなる粒径が５００Å以
下の結晶超微粒子と、非晶質のＳｉＯ＿ｙ及びＭＯ＿ｚ
との集合体であり 構成元素の割合がＳｉ；５〜７０重量％、Ｍ；０．５〜
４５重量％、Ｃ；２０〜４０重量％及びＯ；０．０１〜
３０重量％である、Ｓｉ−Ｍ−Ｃ−Ｏ物質（上記式中、
ＭはＴｉ、Ｚｒ及びＨｆから選択される少なくとも一種
の元素であり、０＜ｘ＜１、０＜ｙ≦２、０＜ｚ≦２で
ある。） であることを特徴とするハイブリッド繊維強化プラスチ
ック複合材料。[Claims] Inorganic fibers and carbon fibers, glass fibers, boron fibers, alumina fibers, silicon nitride fibers, aramid fibers, silicon carbide fibers,
Silicon carbide fiber with carbon core and Si-M-C-
In a plastic composite material in which the reinforcing material is a hybrid fiber with at least one type of fiber selected from the group consisting of O fibers (M represents Ti or Zr) and the plastic matrix, the inorganic fibers include titanium, zirconium, and An inorganic fiber obtained from a metal-containing polycyclic aromatic polymer containing at least one element selected from the group consisting of hafnium and silicon, the constituent components of which are: a) in a mesophase state constituting the polymer; a carbon material exhibiting at least one type of crystal orientation selected from the group consisting of a radial structure, an onion structure, a random structure, a core radial structure, a skin onion structure, and a mosaic structure derived from a certain polycyclic aromatic compound; b) the polymer; unoriented crystalline carbon and/or amorphous carbon derived from an optically isotropic polycyclic aromatic compound containing an organic solvent insoluble component, and c) (1) Si, M, C and (2) crystalline ultrafine particles having a particle size of 500 Å or less and consisting essentially of β-SiC, MC, a solid solution of β-SiC and MC, and MC_1_-_x. , amorphous SiO_y and MO_z
The proportion of the constituent elements is Si: 5-70% by weight, M: 0.5-70% by weight.
45% by weight, C: 20-40% by weight and O: 0.01-
30% by weight of Si-M-C-O material (in the above formula:
M is at least one element selected from Ti, Zr, and Hf, and satisfies 0<x<1, 0<y≦2, and 0<z≦2. ) A hybrid fiber-reinforced plastic composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23693489A JPH0689259B2 (en) | 1989-02-14 | 1989-09-14 | Hybrid fiber reinforced plastic composite material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3280289 | 1989-02-14 | ||
| JP1-32802 | 1989-02-14 | ||
| JP23693489A JPH0689259B2 (en) | 1989-02-14 | 1989-09-14 | Hybrid fiber reinforced plastic composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02289651A true JPH02289651A (en) | 1990-11-29 |
| JPH0689259B2 JPH0689259B2 (en) | 1994-11-09 |
Family
ID=26371385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23693489A Expired - Lifetime JPH0689259B2 (en) | 1989-02-14 | 1989-09-14 | Hybrid fiber reinforced plastic composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689259B2 (en) |
-
1989
- 1989-09-14 JP JP23693489A patent/JPH0689259B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0689259B2 (en) | 1994-11-09 |
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