WO2019188834A1 - 金属酸化物繊維の製造方法および金属酸化物繊維 - Google Patents
金属酸化物繊維の製造方法および金属酸化物繊維 Download PDFInfo
- Publication number
- WO2019188834A1 WO2019188834A1 PCT/JP2019/012225 JP2019012225W WO2019188834A1 WO 2019188834 A1 WO2019188834 A1 WO 2019188834A1 JP 2019012225 W JP2019012225 W JP 2019012225W WO 2019188834 A1 WO2019188834 A1 WO 2019188834A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal oxide
- polymetalloxane
- group
- oxide fiber
- metal
- Prior art date
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 199
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 179
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 179
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 229910052751 metal Chemical group 0.000 claims abstract description 74
- 239000002184 metal Chemical group 0.000 claims abstract description 74
- 125000004429 atom Chemical group 0.000 claims abstract description 67
- 238000009987 spinning Methods 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 25
- 229910052718 tin Inorganic materials 0.000 claims abstract description 21
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 11
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 11
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- -1 silicate ester Chemical class 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 68
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 26
- 238000010304 firing Methods 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229920000620 organic polymer Polymers 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000000578 dry spinning Methods 0.000 claims description 7
- 238000001523 electrospinning Methods 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 136
- 230000015572 biosynthetic process Effects 0.000 description 51
- 238000003786 synthesis reaction Methods 0.000 description 50
- 239000002904 solvent Substances 0.000 description 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 238000001308 synthesis method Methods 0.000 description 23
- 239000010936 titanium Substances 0.000 description 23
- 238000006460 hydrolysis reaction Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 230000007062 hydrolysis Effects 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 229910003849 O-Si Inorganic materials 0.000 description 12
- 229910003872 O—Si Inorganic materials 0.000 description 12
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 11
- 230000002194 synthesizing effect Effects 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 239000002685 polymerization catalyst Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- WHKFNWLWQPPDBQ-UHFFFAOYSA-N CC(C)O[Ti](OC(C)C)(OC(C)C)O[Si](C)(C)C Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)O[Si](C)(C)C WHKFNWLWQPPDBQ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- NJUDTVAXKXBAHG-UHFFFAOYSA-N C(CC)O[Zr](O[Si](C)(C)C)(OCCC)OCCC Chemical compound C(CC)O[Zr](O[Si](C)(C)C)(OCCC)OCCC NJUDTVAXKXBAHG-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- BSFPEQZYFKGGQH-UHFFFAOYSA-N di(butan-2-yloxy)alumanyloxy-trimethylsilane Chemical compound C(C)(CC)O[Al](O[Si](C)(C)C)OC(C)CC BSFPEQZYFKGGQH-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- 229940093858 ethyl acetoacetate Drugs 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QVQGTNFYPJQJNM-UHFFFAOYSA-N dicyclohexylmethanamine Chemical compound C1CCCCC1C(N)C1CCCCC1 QVQGTNFYPJQJNM-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- RAXHZDXXIBGFBD-UHFFFAOYSA-N 2,2,4,4-tetramethylpiperidine Chemical compound CC1(C)CCNC(C)(C)C1 RAXHZDXXIBGFBD-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 2
- BNDRWEVUODOUDW-UHFFFAOYSA-N 3-Hydroxy-3-methylbutan-2-one Chemical compound CC(=O)C(C)(C)O BNDRWEVUODOUDW-UHFFFAOYSA-N 0.000 description 2
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003966 growth inhibitor Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- CLZGJKHEVKJLLS-UHFFFAOYSA-N n,n-diheptylheptan-1-amine Chemical compound CCCCCCCN(CCCCCCC)CCCCCCC CLZGJKHEVKJLLS-UHFFFAOYSA-N 0.000 description 2
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 2
- NJWMENBYMFZACG-UHFFFAOYSA-N n-heptylheptan-1-amine Chemical compound CCCCCCCNCCCCCCC NJWMENBYMFZACG-UHFFFAOYSA-N 0.000 description 2
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 2
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- OHRSSDYDJRJIMN-UHFFFAOYSA-N 1-[2-[2-(2-butoxypropoxy)propoxy]propoxy]butane Chemical compound CCCCOCC(C)OCC(C)OCC(C)OCCCC OHRSSDYDJRJIMN-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- QKVUSSUOYHTOFQ-UHFFFAOYSA-N 3-methyl-n,n-bis(3-methylbutyl)butan-1-amine Chemical compound CC(C)CCN(CCC(C)C)CCC(C)C QKVUSSUOYHTOFQ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JSHPTIGHEWEXRW-UHFFFAOYSA-N 5-hydroxypentan-2-one Chemical compound CC(=O)CCCO JSHPTIGHEWEXRW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- MENJIQNPWJPNRH-UHFFFAOYSA-N C(CC)O[Ti](O[Si](C)(C)C)(OCCC)OCCC Chemical compound C(CC)O[Ti](O[Si](C)(C)C)(OCCC)OCCC MENJIQNPWJPNRH-UHFFFAOYSA-N 0.000 description 1
- OXNJXBGKUKUJLQ-UHFFFAOYSA-N C(CCC)O[Ti](O[Si](C)(C)C)(OCCCC)OCCCC Chemical compound C(CCC)O[Ti](O[Si](C)(C)C)(OCCCC)OCCCC OXNJXBGKUKUJLQ-UHFFFAOYSA-N 0.000 description 1
- NEDHKQAKCNUGJI-UHFFFAOYSA-N C(CCC)O[Zr](O[Si](C)(C)C)(OCCCC)OCCCC Chemical compound C(CCC)O[Zr](O[Si](C)(C)C)(OCCCC)OCCCC NEDHKQAKCNUGJI-UHFFFAOYSA-N 0.000 description 1
- FIBVIQGKUAFZHL-UHFFFAOYSA-N CC(C)O[Zr](OC(C)C)(OC(C)C)O[Si](C)(C)C Chemical compound CC(C)O[Zr](OC(C)C)(OC(C)C)O[Si](C)(C)C FIBVIQGKUAFZHL-UHFFFAOYSA-N 0.000 description 1
- RASBDVLERRNNLJ-UHFFFAOYSA-N CCCCO[Ti] Chemical compound CCCCO[Ti] RASBDVLERRNNLJ-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- WPCPXPTZTOMGRF-UHFFFAOYSA-K di(butanoyloxy)alumanyl butanoate Chemical compound [Al+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O WPCPXPTZTOMGRF-UHFFFAOYSA-K 0.000 description 1
- JEGNMOIIQPASIC-UHFFFAOYSA-N dibutoxyalumanyloxy(trimethyl)silane Chemical compound CCCCO[Al](O[Si](C)(C)C)OCCCC JEGNMOIIQPASIC-UHFFFAOYSA-N 0.000 description 1
- TWXWPPKDQOWNSX-UHFFFAOYSA-N dicyclohexylmethanone Chemical compound C1CCCCC1C(=O)C1CCCCC1 TWXWPPKDQOWNSX-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- ROPILACPUDGYBZ-UHFFFAOYSA-N dipropoxyalumanyloxy(trimethyl)silane Chemical compound CCCO[Al](O[Si](C)(C)C)OCCC ROPILACPUDGYBZ-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- GNZVOBJWPAARFX-UHFFFAOYSA-N propan-2-olate;trimethylsilyloxyaluminum(2+) Chemical compound CC(C)[O-].CC(C)[O-].C[Si](C)(C)O[Al+2] GNZVOBJWPAARFX-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62236—Fibres based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/6225—Fibres based on zirconium oxide, e.g. zirconates such as PZT
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62254—Fibres based on copper oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62259—Fibres based on titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6264—Mixing media, e.g. organic solvents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/6325—Organic additives based on organo-metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/10—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/12—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing tin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5264—Fibers characterised by the diameter of the fibers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
Definitions
- the present invention relates to a method for producing metal oxide fibers and metal oxide fibers.
- a fiber made of a metal oxide (hereinafter, appropriately referred to as a metal oxide fiber) has properties such as high heat resistance, high strength, and surface activity, and is expected to have useful properties for various applications.
- a fiber mainly composed of alumina (Al 2 O 3 ) as a metal oxide is excellent in heat resistance, and has high strength and high elastic modulus. Therefore, a high-temperature heat insulating material, metal, ceramic, plastic, etc. It is used as a reinforcing fiber.
- a metal oxide fiber containing zirconia (ZrO 2 ) has been proposed as a fiber having higher strength (see, for example, Patent Document 1).
- the fiber mainly composed of titania (TiO 2 ) photocatalytic properties can be imparted in addition to high heat resistance and high strength, so that it is expected to be used for environmental purification such as decomposition of volatile organic compounds.
- photocatalytic properties can be imparted in addition to high heat resistance and high strength, so that it is expected to be used for environmental purification such as decomposition of volatile organic compounds.
- a melt fiberization method is known. This method is as follows. For example, a metal oxide raw material and a low melting point compound such as silica are mixed. The mixture is then melted in a high temperature furnace and the melt is removed as a trickle. The trickle stream is rapidly cooled by blowing high-pressure air or applying centrifugal force to form metal oxide fibers (see, for example, Patent Document 3).
- melt fiberization method a technique that enables fiberization by adding an alkali metal or an alkaline earth metal as a raw material to lower the melt is known (for example, see Patent Document 4). .
- a fiber precursor is generally produced using a spinning solution containing a metal oxide source and a thickener, and organic substances are removed by heating the fiber precursor.
- a spinning solution containing a metal oxide source and a thickener
- organic substances are removed by heating the fiber precursor.
- Patent Document 5 uses aluminum oxychloride or aluminum lactate as an alumina source, adds silica sol to suppress grain growth, and further adds polyethylene glycol and polyethylene oxide as thickeners. It is related with the manufacturing method of the alumina fiber which heat-processes the fibrous precursor obtained by making this into a viscous liquid and spinning this. However, such a method has a problem that the heat resistance of the fiber is lowered by the silica component. In addition, when the thickener is burned off during the heating process, there is a problem that pores and cracks are generated and the strength is insufficient. Further, when aluminum oxychloride is used as a raw material, chlorine gas is generated in the heat treatment process, which causes a problem that the heating furnace and the duct are corroded.
- the present invention has been made in view of the above-mentioned problems, and its purpose is a dense, which does not require an additive for suppressing grain growth (hereinafter referred to as “grain growth inhibitor”) or a thickener. It is providing the manufacturing method of a metal oxide fiber, and a metal oxide fiber.
- a method for producing a metal oxide fiber according to the present invention includes a spinning step of spinning a composition containing a polymetalloxane and an organic solvent to obtain a filament, Firing the filamentous material obtained by the spinning process at a temperature of 200 ° C. or more and 2000 ° C.
- the polymetalloxane contains Al, Sc, Ti, V, Metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd, Ag, In, Sn, Sb, Hf, Ta, W, and Bi It has a repeating structure of atoms and oxygen atoms, and the polymetalloxane has a weight average molecular weight of 20,000 to 2,000,000.
- the metal oxide fiber manufacturing method according to the present invention is characterized in that, in the above invention, the composition has a viscosity at 25 ° C. of 10 P or more and 50000 P or less.
- the metal oxide fiber manufacturing method according to the present invention is characterized in that, in the above invention, the average fiber diameter is 0.01 ⁇ m or more and 1000 ⁇ m or less.
- the composition contains an organic polymer, and the content of the organic polymer in the composition is in the composition. It is 1 weight% or less with respect to the weight of the said polymetalloxane contained, It is characterized by the above-mentioned.
- the metal oxide fiber manufacturing method according to the present invention is characterized in that, in the above invention, the composition does not contain any alkali metal or alkaline earth metal.
- the composition does not contain any of silicic acid, silicate, silica gel, silicate ester, boric acid, borate and borate ester. It is characterized by that.
- the polymetalloxane is a structural unit represented by the following general formula (1) and a structure represented by the following general formula (2). It is a polymetalloxane having at least one of the units.
- R 1 and R 3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms .R 2 where chosen arbitrarily from groups or having a metalloxane bond, Hydroxy group, alkyl group having 1 to 12 carbon atoms, alicyclic alkyl group having 5 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aromatic group having 6 to 30 carbon atoms, and 6 to 30 carbon atoms phenoxy group, .R 1, R 2 and R 3 which chosen arbitrarily from among the naphthoxy group having 10 to 30 carbon atoms is good .R 4 be different even for the same, respectively if there are a plurality Among hydroxy groups, alkyl groups having 1 to 12 carbon atoms, alicyclic alkyl groups having 5 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aromatic groups having 6 to 30 carbon atoms, and groups having a siloxane bond Arbitrarily selected from
- the polymetalloxane has at least a structural unit represented by the general formula (1), and the general formula (1) At least one of R 2 in the formula is a hydroxy group.
- the metal oxide fiber manufacturing method according to the present invention is characterized in that, in the above invention, the polymetalloxane has at least a structural unit represented by the general formula (2).
- the metal atom M in the polymetalloxane is one kind of metal atom selected from the group consisting of Al, Ti, Zr and Sn. Including the above.
- the metal atom M in the polymetalloxane contains Ti, and in all the metal atoms M in the metal oxide fiber.
- the ratio of Ti is in the range of 5 mol% or more and 100 mol% or less.
- the metal atom M in the polymetalloxane contains Zr, and in all the metal atoms M in the metal oxide fiber.
- the ratio of Zr is in the range of 5 mol% or more and 100 mol% or less.
- the metal oxide fiber manufacturing method according to the present invention is characterized in that, in the above invention, the spinning step is a step of spinning the composition by a dry spinning method or an electrospinning method.
- the metal oxide fiber according to the present invention includes Si, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd. And one or more metal atoms selected from the group consisting of Ag, In, Sn, Sb, Hf, Ta, W and Bi, and the content of the SiO 2 component in the metal oxide is 0.5 It is characterized by being not more than wt%.
- the metal oxide fiber according to the present invention is characterized in that, in the above-mentioned invention, the average fiber diameter is 0.01 ⁇ m or more and 1000 ⁇ m or less.
- the metal atom in the metal oxide includes one or more metal atoms selected from the group consisting of Al, Ti, Zr and Sn. It is characterized by.
- the metal atom in the metal oxide contains Ti, and the ratio of Ti in all the metal atoms contained is 5 mol% or more and 100 mol. % Or less.
- the metal atom in the metal oxide contains Zr, and the ratio of Zr in all the metal atoms contained is 5 mol% or more and 100 mol. % Or less.
- the metal atom in the metal oxide includes two or more metal atoms selected from the group consisting of Al, Ti, Zr and Sn. It is characterized by.
- a grain growth inhibitor and a thickener are not required, so that a dense metal oxide fiber can be obtained. Therefore, there is an effect that a metal oxide fiber having characteristics such as high heat resistance, high strength, and surface activity can be easily obtained.
- the content of SiO 2 component such as silica causing heat resistance to be reduced is 0.5% by weight or less, it is possible to realize a metal oxide fiber having high heat resistance. There is an effect that can be done.
- a method for producing a metal oxide fiber according to Embodiment 1 of the present invention includes a spinning step of spinning a composition containing a polymetalloxane and an organic solvent to obtain a filamentous product, and a filamentous product obtained by the spinning step. Firing at a temperature of 200 ° C. to 2000 ° C. to obtain metal oxide fibers.
- polymetalloxane is Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd.
- this polymetalloxane has a repeating structure of metal atoms and oxygen atoms selected from the group consisting of. Moreover, the weight average molecular weight of this polymetalloxane is 20,000 or more and 2 million or less.
- the polymetalloxane and the organic solvent in the present invention are appropriately referred to as polymetalloxane (a) and organic solvent (b), respectively.
- the polymetalloxane is generally a polymer having a metal-oxygen-metal bond as a main chain.
- the metal atoms constituting the polymetalloxane (a) are Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo. , Pd, Ag, In, Sn, Sb, Hf, Ta, W, and Bi.
- the metal atom is preferably a metal atom selected from the group consisting of Al, Ti, Zr and Sn.
- the metal atom in the polymetalloxane (a) preferably contains one or more metal atoms selected from the group consisting of Al, Ti, Zr and Sn.
- the polymetalloxane (a) contains the above-mentioned preferred metal atoms, metal alkoxides, which will be described later as the raw material for synthesizing polymetalloxane, are stably present, so that it becomes easy to obtain a high-molecular-weight polymetalloxane.
- the weight average molecular weight of the polymetalloxane (a) is 20,000 or more as a lower limit, preferably 50,000 or more, more preferably 200,000 or more. Moreover, the weight average molecular weight of polymetalloxane (a) is 2 million or less as an upper limit, Preferably it is 1.5 million or less, More preferably, it is 1 million or less.
- the weight average molecular weight of the polymetalloxane (a) is at least the lower limit value, the crack resistance of the filamentous material is improved, and a homogeneous metal oxide fiber having no cracks can be obtained even in the firing step described later.
- the weight average molecular weight in this invention says the value of polystyrene conversion measured by gel permeation chromatography (GPC).
- the weight average molecular weight of the polymetalloxane (a) is determined by the following method. For example, polymetalloxane (a) is dissolved in a developing solvent so as to be 0.2 wt% to obtain a sample solution. Next, the sample solution is injected into a column filled with a porous gel and a developing solvent. By detecting the column eluate with a differential refractive index detector and analyzing the elution time, the weight average molecular weight is determined.
- a solvent capable of dissolving polymetalloxane (a) at a concentration of 0.2 wt% is selected.
- this solution is used as a developing solvent.
- the structural unit of the polymetalloxane (a) is not particularly limited, but the polymetalloxane (a) is a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). Of these, polymetalloxane having at least one of them is preferred.
- R 1 and R 3 are arbitrarily selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a group having a metalloxane bond.
- R 2 is a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or 6 carbon atoms. It is arbitrarily selected from phenoxy groups having ⁇ 30 and naphthoxy groups having 10 to 30 carbon atoms. When a plurality of R 1 , R 2 and R 3 are present, they may be the same or different.
- R 4 includes a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a siloxane bond. It is arbitrarily selected from the groups having.
- Metal atoms M are Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd, Ag, In, Sn, Sb, Hf.
- the integer m is an integer indicating the valence of the metal atom M.
- the integer a is an integer from 0 to (m ⁇ 2).
- the integer b is an integer from 1 to (m ⁇ 2).
- alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.
- Examples of the alicyclic alkyl group having 5 to 12 carbon atoms include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group.
- alkoxy group having 1 to 12 carbon atoms examples include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentoxy group, hexyloxy group, heptoxy group, octoxy group Group, 2-ethylhexyloxy group, nonyl group, decyloxy group and the like.
- Examples of the aromatic group having 6 to 30 carbon atoms include a phenyl group, a phenoxy group, a benzyl group, a phenylethyl group, and a naphthyl group.
- phenoxy group having 6 to 30 carbon atoms examples include phenoxy group, methylphenoxy group, ethylphenoxy group, propylphenoxy group, methoxyphenoxy group, ethoxyphenoxy group, and propoxyphenoxy group.
- Examples of the naphthoxy group having 10 to 30 carbon atoms include a naphthoxy group, a methyl naphthoxy group, an ethyl naphthoxy group, a propyl naphthoxy group, a methoxy naphthoxy group, an ethoxy naphthoxy group, and a propoxy naphthoxy group.
- R 1 and R 3 are a group having a metalloxane bond means that R 1 and R 3 are bonded to another polymetalloxane molecule via an oxygen atom.
- the polymetalloxane (a) has at least one of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), the polymetalloxane (a) The compatibility of is improved. Therefore, since it can superpose
- the polymetalloxane (a) preferably has at least a structural unit represented by the general formula (1), and at least one of R 2 in the general formula (1) is preferably a hydroxy group.
- R 2 in the general formula (1) is preferably a hydroxy group.
- R 4 in the general formula (2) is a group having a siloxane bond indicates that R 4 is bonded to other Si via an oxygen atom.
- polymetalloxane (a) has at least the structural unit represented by General formula (2).
- the polymetalloxane (a) having the structural unit represented by the general formula (2) has a (R 4 3 SiO—) group, thereby significantly improving the compatibility with other components. Therefore, this polymetalloxane (a) exists stably in an organic solvent. Furthermore, in the firing step of forming the metal oxide fiber described later, since the polymetalloxane (a) has an (R 4 3 SiO—) group, the condensation stress of the polymetalloxane (a) is relieved, A homogeneous metal oxide fiber that is less prone to cracking can be obtained.
- the polymetalloxane (a) has a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2).
- the (R 4 3 SiO—) group in the general formula (2) includes a trihydroxysiloxy group, a trimethylsiloxy group, a triethylsiloxy group, a tripropylsiloxy group, a triisopropylsiloxy group, a tributylsiloxy group, a triisobutylsiloxy group, Tri-s-butylsiloxy group, tri-t-butylsiloxy group, tricyclohexylsiloxy group, trimethoxysiloxy group, triethoxysiloxy group, tripropoxysiloxy group, triisopropoxysiloxy group, tributoxysiloxy group, triphenylsiloxy group Group, hydroxydiphenylsiloxy group, methyldiphenylsiloxy group, ethyldiphenylsiloxy group, propyldiphenylsiloxy group, dihydroxy (phenyl) siloxy group, dimethyl (phenyl) si
- R 4 is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.
- the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and t-butyl group.
- preferred (R 4 3 SiO—) groups include trimethylsiloxy group, triethylsiloxy group, tripropylsiloxy group, triisopropylsiloxy group, tributylsiloxy group, triisobutylsiloxy group, tri-s-butylsiloxy group, tri -T-butylsiloxy group, methyldiphenylsiloxy group, ethyldiphenylsiloxy group, propyldiphenylsiloxy group, dihydroxy (phenyl) siloxy group, dimethyl (phenyl) siloxy group, diethyl (phenyl) siloxy group, dipropyl (phenyl) siloxy group, etc. Is mentioned.
- the content of the (R 4 3 SiO—) group is 1 mol% or more in terms of the ratio of the number of moles of Si (silicon atoms) to the number of moles of metal atoms M in the polymetalloxane (a). It is preferably 250 mol% or less, more preferably 10 mol% or more and 200 mol% or less.
- the metal atom M in the general formula (1) and the general formula (2) described above, that is, the metal atom M in the polymetalloxane (a) is a metal atom selected from the group consisting of Al, Ti, Zr and Sn. It is preferable to include 1 or more types. Thereby, since the metal alkoxide used as a synthesis raw material of polymetalloxane (a) exists stably, it becomes easy to obtain high molecular weight polymetalloxane (a).
- the metal atom M in the polymetalloxane (a) contains Ti (titanium atom), and the ratio of Ti in all the metal atoms M in the metal oxide fiber is in the range of 5 mol% or more and 100 mol% or less. It is preferable. By setting the Ti ratio within the above range, titanium dioxide crystals are produced in the metal oxide fiber. Therefore, photocatalytic characteristics peculiar to titanium dioxide can be imparted to the metal oxide fiber.
- the metal atom M in the polymetalloxane (a) contains Zr (zirconium atom), and the ratio of Zr in all the metal atoms M in the metal oxide fiber is in the range of 5 mol% to 100 mol%. It is preferable. By setting the Zr ratio in the above range, crystals of zirconium dioxide are generated in the metal oxide fiber. Since the melting point of zirconium dioxide is as high as 2715 ° C., metal oxide fibers having excellent heat resistance can be obtained.
- the method for synthesizing the polymetalloxane (a) in the present invention is not particularly limited, but at least one of the compound represented by the following general formula (3) and the compound represented by the following general formula (4), It is preferable to include a condensation polymerization step in which hydrolysis is performed as necessary, followed by partial condensation and polymerization.
- R 5 is the same as R 1 in General Formula (1) described above, and R 6 is the same as R 3 in General Formula (2) described above. It is.
- partial condensation refers to not condensing all M-OH in the hydrolyzate, but in the resulting polymetalloxane (a), some M-OH of all the M-OHs. Refers to leaving OH. Under the general condensation conditions described later, it is common that the part of M-OH remains in the polymetalloxane (a). The amount of M—OH remaining is not particularly limited.
- reaction conditions for the hydrolysis are preferably such that water is added to the metal alkoxide in a solvent over 1 to 180 minutes and then reacted at room temperature to 110 ° C. for 1 to 180 minutes.
- the reaction temperature for the hydrolysis is preferably 30 ° C. to 150 ° C.
- reaction conditions for partial condensation and polymerization are such that the hydrolyzate is obtained by hydrolysis reaction of the metal alkoxide, and then the reaction solution is heated as it is at 50 ° C. to 180 ° C. for 1 to 100 hours. Is preferred.
- the produced alcohol or the like may be removed by distilling and removing an appropriate amount by at least one of heating and decompression, and then an arbitrary solvent may be added.
- the solvent is not particularly limited, but a compound having an alcoholic hydroxyl group (that is, an alcohol solvent), esters, ethers, and ketones are preferably used. By using these solvents, the stability of the polymetalloxane (a) can be improved.
- alcohol solvents examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetol, 3-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2-pentanone.
- ester solvent examples include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, and 3-methyl-3.
- ether solvents include diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether. Is mentioned.
- ketone solvent examples include methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, and dicyclohexyl ketone.
- solvents that can be used include propylene carbonate, N-methylpyrrolidone, and the like.
- adjusting the hydrolysis rate of at least one of the compound represented by General formula (3) and the compound represented by General formula (4) by adjusting the addition amount of the water used for a hydrolysis reaction. Can do.
- the amount of water added is preferably 0.1 mol or more and 2 mol or less with respect to 1 mol of the alkoxy group.
- the catalyst added as necessary is not particularly limited, but an acidic catalyst or a basic catalyst is preferably used.
- the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydride thereof, and ion exchange resin.
- Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, dipropylamine, dibutylamine, diisobutylamine, dipentylamine, dihexylamine.
- Diheptylamine, dioctylamine, triethanolamine, diethanolamine, dicyclohexylamine, dicyclohexylmethylamine, 2,6-lutidine, 2,2,4,4-tetramethylpiperidine, 2,2,4,4-tetramethylpipe Examples include redone, an alkoxysilane having an amino group, and an ion exchange resin.
- a more preferable catalyst is a base catalyst.
- a base catalyst By using a base catalyst, a particularly high molecular weight polymetalloxane (a) can be obtained.
- base catalysts tripropylamine, triisobutylamine, tripentylamine, triisopentylamine, trihexylamine, triheptylamine, trioctylamine, dibutylamine, diisobutylamine, dipentylamine, dihexylamine, diheptylamine, Dioctylamine, dicyclohexylamine, dicyclohexylmethylamine, 2,6-lutidine, 2,2,4,4-tetramethylpiperidine, 2,2,4,4-tetramethylpiperidone are particularly preferred.
- the polymetalloxane solution after hydrolysis should not contain the above catalyst. Is preferred. For this reason, the catalyst is removed as necessary.
- the method for removing the catalyst is not particularly limited, but at least one of water washing and ion exchange resin treatment is preferred from the viewpoint of ease of operation and removability.
- Water washing is a removal method of diluting a polymetalloxane solution with an appropriate hydrophobic solvent and then concentrating the organic layer obtained by washing several times with water with an evaporator or the like.
- the treatment with an ion exchange resin is a removal method in which a polymetalloxane solution is brought into contact with an appropriate ion exchange resin.
- the composition used in the method for producing a metal oxide fiber according to Embodiment 1 of the present invention contains polymetalloxane (a) and organic solvent (b). This composition can be adjusted to an arbitrary viscosity by including the organic solvent (b). This makes it possible to achieve both the spinnability and fluidity of the composition.
- organic solvent (b) a solvent contained in a polymetalloxane solution obtained by synthesis of polymetalloxane (a) can be used.
- the organic solvent (b) may be added to the polymetalloxane solution.
- the organic solvent (b) is not particularly limited, but is preferably the same as the solvent used in the synthesis of the polymetalloxane (a).
- a more preferable organic solvent (b) is an aprotic polar solvent.
- aprotic polar solvent examples include, for example, acetone, tetrahydrofuran, ethyl acetate, dimethoxyethane, N, N-dimethylformamide, dimethylacetamide (DMAc, 165 ° C.), dipropylene glycol dimethyl ether, tetramethyl urea, diethylene glycol ethyl methyl.
- examples include ether, dimethyl sulfoxide, N-methylpyrrolidone, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone, propylene carbonate, and N, N′-dimethylpropylene urea.
- composition used in the method for producing a metal oxide fiber according to Embodiment 1 of the present invention may contain other components.
- other components include a surfactant, a crosslinking agent, and a crosslinking accelerator.
- the surfactant is preferably used for controlling the drying rate of the organic solvent (b) during the spinning process.
- the surfactant may remain in the filamentous material obtained by the spinning process, or may remain in the metal oxide fiber obtained by firing the filamentous material.
- surfactant there is no particular limitation on the type of surfactant.
- the content of the surfactant in the composition is preferably 0.001 part by weight or more and 10 parts by weight or less, and 0.01 part by weight or more with respect to 100 parts by weight of the polymetalloxane (a). More preferably, it is 1 part by weight or less.
- the crosslinking agent and the crosslinking accelerator are preferably used for improving the strength of the metal oxide fiber.
- the content of the crosslinking agent and crosslinking accelerator in the composition is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the polymetalloxane (a) as a total amount. More preferably, it is 1 part by weight or more and 20 parts by weight or less.
- the cross-linking agent and the cross-linking accelerator may be used alone or in combination.
- the lower limit of the viscosity of the composition at 25 ° C. is preferably 10P or more, more preferably 20P or more, further preferably 100P or more, and further preferably 500P or more. 800P or more is even more preferable.
- the viscosity at 25 ° C. of the composition is preferably 50000P or less, more preferably 20000P or less, further preferably 10,000P or less, and still more preferably 5000P or less as an upper limit.
- the composition used for the method for producing a metal oxide fiber according to Embodiment 1 of the present invention preferably contains an organic polymer.
- An organic polymer refers to a polymer containing carbon in the main chain. Specific examples of the organic polymer include polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polyvinyl pyrrolidone, polyvinyl alcohol, cellulose, acrylic resin, and the like.
- the content of the organic polymer in the composition is preferably 1% by weight or less and preferably 0.5% by weight or less based on the weight of the polymetalloxane (a) contained in the composition. Further preferred.
- the organic polymer By including the organic polymer at the above-described concentration, it is possible to suppress the occurrence of voids and cracks in the obtained metal oxide fiber in the firing step of firing the filamentous material obtained by spinning as described later. Thereby, the strength of the metal oxide fiber is improved.
- the composition used in the method for producing a metal oxide fiber according to Embodiment 1 of the present invention does not contain any alkali metal or alkaline earth metal. If an alkali metal or alkaline earth metal is contained in the composition, it causes a reduction in the degree of crosslinking in the firing step of firing the filamentous material obtained by spinning as described later. Therefore, by containing neither an alkali metal nor an alkaline earth metal, it becomes highly crosslinked and the strength of the resulting metal oxide fiber is improved. It is particularly preferable that the composition used in the method for producing a metal oxide fiber according to Embodiment 1 of the present invention does not contain any of Na, Mg, K, and Ca atoms.
- the composition used in the method for producing a metal oxide fiber according to Embodiment 1 of the present invention does not contain any of silicic acid, silicate, silica gel, silicate ester, boric acid, borate and borate ester. Is preferred.
- the composition contains the above compound, the resulting metal oxide fiber has a low melting point. Therefore, by not containing the said compound, it becomes a high melting metal oxide fiber and the heat resistance of the said metal oxide fiber improves.
- the method for producing metal oxide fibers according to Embodiment 1 of the present invention includes a spinning step of spinning the above composition to obtain a filamentous product, and a filamentous product obtained by the spinning step of 200 ° C. or more and 2000 ° C. or less. Firing at a temperature to obtain a metal oxide fiber.
- spinning process In the spinning step, a known method can be used as a method for spinning the composition.
- the spinning method include a dry spinning method, a wet spinning method, a dry and wet spinning method, and an electrospinning method.
- the dry spinning method is a method in which a composition is filled, extruded from a die having pores into an atmosphere by a load, and an organic solvent is evaporated to form a filamentous material.
- the composition may be heated after filling to reduce the viscosity during extrusion.
- the composition may be extruded into a heated atmosphere to control the evaporation rate of the organic solvent.
- the filamentous material can be stretched by a rotating roller or a high-speed air stream.
- Wet spinning is a method in which a composition is extruded from a die having pores into a coagulation bath by a load to remove an organic solvent to form a filamentous material.
- a coagulation bath water or a polar solvent is preferably used.
- Dry-wet spinning is a method in which the composition is extruded into an atmosphere and then immersed in a coagulation bath to remove the organic solvent and form a filament.
- the electrospinning method In the electrospinning method, a high voltage is applied to the nozzle filled with the composition, so that electric charges are accumulated in the droplets at the tip of the nozzle, and the droplets repel each other, spreading the droplets and stretching the solution flow. This is a spinning method. With this method, it is possible to obtain a thread having a small diameter. Therefore, according to the electrospinning method, a thin thread having a diameter of several tens nm to several ⁇ m can be obtained.
- a dry spinning method or an electrospinning method can be particularly preferably used as the spinning method in the spinning step in the present invention. That is, this spinning step is preferably a step of spinning the composition by dry spinning or electrospinning.
- the obtained filamentous material may be subjected to a drying treatment, a steam treatment, a hot water treatment, or a combination thereof, as necessary, before firing.
- the filamentous material obtained by spinning in the spinning step is fired at a temperature of 200 ° C. or more and 2000 ° C. or less, whereby organic components such as organic groups are removed and the strength is increased as the crosslinking reaction proceeds.
- An excellent metal oxide fiber can be obtained.
- the firing temperature in this firing step is more preferably 400 ° C. or higher and 1500 ° C. or lower.
- the firing method is not particularly limited. Examples of the firing method include a method of firing in an air atmosphere, a method of firing in an inert atmosphere such as nitrogen and argon, and a method of firing in a vacuum.
- the obtained metal oxide fiber may be further fired in a reducing atmosphere such as hydrogen.
- the filamentous material or metal oxide fiber may be fired while applying tension.
- the average fiber diameter of the obtained metal oxide fiber is obtained by the following method. For example, an adhesive tape is affixed to the mount, and a single fiber whose fiber diameter is to be measured is adhered horizontally to the single fiber test piece. This single fiber test piece is observed from the upper surface with an electron microscope, and the width of the image is taken as the fiber diameter. The fiber diameter is measured three times along the length direction and averaged. This operation is performed for 20 single fibers selected at random, and the obtained fiber diameters are averaged to obtain an average fiber diameter.
- the average fiber diameter of the metal oxide fiber is preferably 0.01 ⁇ m or more and 1000 ⁇ m or less, and more preferably 0.10 ⁇ m or more and 200 ⁇ m or less.
- the metal oxide fiber can be a uniform fiber without cracks.
- the lower limit of the average fiber diameter is more preferably 1 ⁇ m or more, and further preferably 3 ⁇ m or more.
- the upper limit of the average fiber diameter is more preferably 100 ⁇ m or less, and further preferably 70 ⁇ m or less.
- the metal oxide fiber according to Embodiment 2 of the present invention has the following characteristic configuration. That is, the metal oxide fiber according to the second embodiment includes Si (silicon atoms), Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, One or more metal atoms selected from the group consisting of Zr, Nb, Mo, Pd, Ag, In, Sn, Sb, Hf, Ta, W and Bi (hereinafter referred to as “first characteristics”) As appropriate).
- the content of the SiO 2 component in the metal oxide constituting the metal oxide fiber is 0.5% by weight or less (hereinafter referred to as “second feature” as appropriate).
- the metal oxide fiber according to Embodiment 2 is a fiber made of a metal oxide containing polymetalloxane (a).
- the polymetalloxane (a) has a repeating structure of Si (silicon atom) and one or more metal atoms selected from the group of metal atoms and oxygen atoms.
- the structural unit of the polymetalloxane (a) include the structural unit represented by the general formula (2) described above.
- the metal oxide fiber having the first and second characteristics described above is a metal oxide fiber in which a part of the metal constituting the crystal part or amorphous part of the metal oxide is replaced with Si.
- a metal oxide fiber has a good flexibility because the molecular arrangement is disturbed as compared with a metal oxide fiber not containing Si.
- the content of the SiO 2 component in the metal oxide is 0.5% by weight or less as an upper limit, preferably 0.2% by weight or less. is there.
- the metal oxide fiber suppresses the formation of a low heat-resistant portion having a low melting point such as silica, and thus the metal oxide fiber is a highly heat-resistant metal oxide fiber. be able to.
- the content of SiO 2 component of the metal oxide constituting the metal oxide fibers according to the second embodiment is represented by SiO 2 component ratio of the metal oxide.
- the SiO 2 component ratio refers to a ratio obtained by a wide-angle X-ray diffraction method (hereinafter abbreviated as XRD).
- the SiO 2 component ratio in the metal oxide by XRD can be determined by the following method. For example, a metal oxide fiber sample is placed on a silicon non-reflective plate and irradiated with X-rays by an X-ray diffractometer. The measurement range (2 ⁇ ) is 10 to 80 °, and after obtaining a diffraction pattern, it is compared with standard data to determine the presence or absence of a peak derived from the SiO 2 component. If there is no peak, the SiO 2 component was not detected (no detection).
- the integrated value of the strongest peak derived from that component divided by the reference intensity ratio and the integrated value of the strongest peak derived from the metal oxide component are expressed by the reference intensity ratio.
- the ratio to the one divided is the SiO 2 component ratio in the metal oxide of the metal oxide fiber.
- the metal oxide fiber according to the second embodiment of the present invention includes the metal oxide fiber manufactured by the manufacturing method according to the first embodiment described above, except that the first and second characteristics described above are included. Have the same configuration. That is, the metal oxide fiber according to the second embodiment is the same as the metal oxide fiber according to the first embodiment with respect to the average fiber diameter, the type and content ratio of metal atoms in the metal oxide, and the like. In particular, in the metal oxide fiber according to the second embodiment, it is more preferable that the metal atom in the metal oxide includes two or more metal atoms selected from the group consisting of Al, Ti, Zr and Sn.
- the manufacturing method of the metal oxide fiber which concerns on Embodiment 2 of this invention is 1 or more types of metal atoms chosen from Si (silicon atom) and the said metal atom group as polymetalloxane (a). This is the same as Embodiment 1 described above except that a polymetalloxane having a repeating structure of oxygen atoms is used.
- the metal oxide fiber obtained by the production method according to the present invention is a continuous dense metal oxide fiber, it has characteristics such as high heat resistance, high strength, and surface activity. Therefore, the metal oxide fiber can be used as a heat insulating material such as an electric furnace or a building material or a heat radiating material by utilizing the characteristics of the high heat-resistant fiber. Moreover, the said metal oxide fiber can be utilized as composite materials, such as fiber reinforcement (FRP), utilizing the characteristic of a high strength fiber. Furthermore, the metal oxide fiber can be used as a member such as an aircraft engine turbine or a space aircraft member by utilizing the characteristics of the high heat resistance and high strength fiber. Further, since the metal oxide fiber mainly composed of titanium dioxide has photocatalytic activity, it can be used for a filter for purifying water and air.
- FRP fiber reinforcement
- the solid content concentration of the polymetalloxane solution was determined by the following method. Specifically, 1.0 g of polymetalloxane solution is weighed in an aluminum cup, heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid, and the solid content remaining in the heated aluminum cup is removed. The solid content concentration of the polymetalloxane solution was determined by weighing.
- Viscosity was measured by the following method. Specifically, the temperature of the sample is set to 25 ° C., and the viscosity of the sample is measured at a rotation speed of 3 rpm using a B-type viscometer with a digital calculation function (DV-II, manufactured by Brookfield, USA). Thereby, the target viscosity was obtained.
- FT-IR Fourier transform infrared spectroscopy
- the weight average molecular weight (Mw) was determined by the following method. Specifically, lithium chloride was dissolved in N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) as a developing solvent to prepare a 0.02 mol / dm 3 lithium chloride and NMP solution. A polymetalloxane was dissolved in a developing solvent so as to be 0.2 wt%, and this was used as a sample solution. A developing solvent was packed in a porous gel column (TSKgel (one each of ⁇ -M and ⁇ -3000) manufactured by Tosoh Corporation) at a flow rate of 0.5 mL / min, and a sample solution (0.2 mL) was injected therein. The column eluate was detected with a differential refractive index detector (RI-201, manufactured by Showa Denko KK), and the elution time was analyzed to determine the weight average molecular weight (Mw).
- NMP N-methyl-2-pyrrolidone
- Solution 1 The whole amount of Solution 1 was charged into a 500 mL three-necked flask, and this three-necked flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes. Thereafter, the entire amount of the solution 2 was filled in a dropping funnel for the purpose of hydrolysis, and added to the three-necked flask over 1 hour. During the addition of Solution 2, no precipitation occurred in the liquid in the three-necked flask, and this solution was a uniform colorless and transparent solution. After addition of Solution 2, the mixture was further stirred for 1 hour to produce a hydroxy group-containing metal compound. Thereafter, the temperature of the oil bath was raised to 140 ° C. over 30 minutes for the purpose of polycondensation.
- the internal temperature of the solution reached 100 ° C., and the solution was then heated and stirred for 2 hours.
- the internal temperature of the solution at this time was 100 to 130 ° C.
- IPA and water distilled off.
- the solid content concentration of the polymetalloxane (T-1) solution was 45.7%, and the viscosity of the solution was 3500P.
- the polymetalloxane (T-1) solution was analyzed by FT-IR, an absorption peak (958 cm ⁇ 1 ) of Ti—O—Si was confirmed. From this, it was confirmed that the polymetalloxane (T-1) in the polymetalloxane (T-1) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (T-1) was 400,000 in terms of polystyrene.
- Synthesis Example 2 A method for synthesizing the polymetalloxane (T-2) solution of Synthesis Example 2 will be described.
- synthesis was performed in the same manner as in Synthesis Example 1 except that ⁇ -butyrolactone (15.8 g) was mixed as a solvent instead of NMP (15.8 g) as the solvent in Synthesis Example 1.
- ⁇ -butyrolactone is abbreviated as GBL.
- the solution obtained by the synthesis method of Synthesis Example 2 was designated as polymetalloxane (T-2) solution.
- the appearance of the polymetalloxane (T-2) solution was colorless and transparent.
- the solid content concentration of the polymetalloxane (T-2) solution was 44.5%, and the viscosity of the solution was 6000 P.
- an absorption peak (958 cm ⁇ 1 ) of Ti—O—Si was confirmed. From this, it was confirmed that the polymetalloxane (T-2) in the polymetalloxane (T-2) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (T-2) was 49,000 in terms of polystyrene.
- Synthesis Example 3 A method for synthesizing the polymetalloxane (T-3) solution of Synthesis Example 3 will be described.
- synthesis example 1 was used except that dicyclohexylmethylamine (2.0 g (0.01 mol)) was mixed as a polymerization catalyst in place of tributylamine (1.9 g) which is the polymerization catalyst of synthesis example 1.
- the synthesis was performed in the same manner as above.
- the solution obtained by the synthesis method of Synthesis Example 3 was designated as polymetalloxane (T-3) solution.
- the appearance of the polymetalloxane (T-3) solution was light yellow and transparent.
- the solid concentration of the polymetalloxane (T-3) solution was 46.8%, and the viscosity of the solution was 4500P.
- an absorption peak (958 cm ⁇ 1 ) of Ti—O—Si was confirmed. From this, it was confirmed that the polymetalloxane (T-3) in the polymetalloxane (T-3) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (T-3) was 520,000 in terms of polystyrene.
- the solid content concentration of the polymetalloxane (T-4) solution was 45.0%, and the viscosity of the solution was 4000P.
- the polymetalloxane (T-4) solution was analyzed by FT-IR, an absorption peak (958 cm ⁇ 1 ) of Ti—O—Si was confirmed. From this, it was confirmed that the polymetalloxane (T-4) in the polymetalloxane (T-4) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (T-4) was 450,000 in terms of polystyrene.
- the solution obtained by the synthesis method of Synthesis Example 5 was designated as polymetalloxane (Z-1) solution.
- the appearance of the polymetalloxane (Z-1) solution was colorless and transparent.
- the solid content concentration of the polymetalloxane (Z-1) solution was 43.1%, and the viscosity of the solution was 7500 P.
- an absorption peak (968 cm ⁇ 1 ) of Zr—O—Si was confirmed. From this, it was confirmed that the polymetalloxane (Z-1) in the polymetalloxane (Z-1) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (Z-1) was 900,000 in terms of polystyrene.
- the solution obtained by the synthesis method of Synthesis Example 6 was designated as polymetalloxane (A-1) solution.
- the appearance of the polymetalloxane (A-1) solution was colorless and transparent.
- the solid content concentration of the polymetalloxane (A-1) solution was 42.1%, and the viscosity of the solution was 2000P.
- an absorption peak (780 cm ⁇ 1 ) of Al—O—Si was confirmed. From this, it was confirmed that the polymetalloxane (A-1) in the polymetalloxane (A-1) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (A-1) was 190,000 in terms of polystyrene.
- the solution obtained by the synthesis method of Synthesis Example 7 was designated as polymetalloxane (TZ-1) solution.
- the appearance of the polymetalloxane (TZ-1) solution was light yellow and transparent.
- the solid content concentration of the polymetalloxane (TZ-1) solution was 44.4%, and the viscosity of the solution was 5000P.
- the polymetalloxane (TZ-1) solution was analyzed by FT-IR, an absorption peak of Ti—O—Si (958 cm ⁇ 1 ) and an absorption peak of Zr—O—Si (968 cm ⁇ 1 ) were confirmed. .
- the polymetalloxane (TZ-1) in the polymetalloxane (TZ-1) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (TZ-1) was 600,000 in terms of polystyrene.
- the solution obtained by the synthesis method of Synthesis Example 8 was designated as polymetalloxane (TA-1) solution.
- the appearance of the polymetalloxane (TA-1) solution was light yellow and transparent.
- the solid content concentration of the polymetalloxane (TA-1) solution was 46.2%, and the viscosity of the solution was 2500P.
- the polymetalloxane (TZ-1) solution was analyzed by FT-IR, an absorption peak of Ti—O—Si (958 cm ⁇ 1 ) and an absorption peak of Al—O—Si (780 cm ⁇ 1 ) were confirmed. .
- the polymetalloxane (TA-1) in the polymetalloxane (TA-1) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (TA-1) was 280,000 in terms of polystyrene.
- the solution obtained by the synthesis method of Synthesis Example 9 was designated as polymetalloxane (ZA-1) solution.
- the appearance of the polymetalloxane (ZA-1) solution was light yellow and transparent.
- the solid content concentration of the polymetalloxane (ZA-1) solution was 44.5%, and the viscosity of the solution was 4500P.
- the polymetalloxane (ZA-1) solution was analyzed by FT-IR, an absorption peak of Zr—O—Si (968 cm ⁇ 1 ) and an absorption peak of Al—O—Si (780 cm ⁇ 1 ) were confirmed. .
- the polymetalloxane (ZA-1) in the polymetalloxane (ZA-1) solution was a polymetalloxane having a trimethylsiloxy group.
- the weight average molecular weight (Mw) of the polymetalloxane (ZA-1) was 500,000 in terms of polystyrene.
- the average fiber diameter of the filamentous material and the metal oxide fiber was measured by the following method.
- an adhesive tape carbon double-sided tape for SEM (aluminum substrate), manufactured by Nissin EM Co., Ltd.
- the filament or metal oxide fiber to be measured for the fiber diameter is horizontally adhered to it.
- This single fiber test piece was observed from the upper surface with an electron microscope, and the width of the image was taken as the fiber diameter.
- the fiber diameter was measured three times along the length direction and averaged. This operation was performed on 20 randomly selected filamentous or metal oxide fibers, and the average value of the obtained fiber diameters was defined as the average fiber diameter.
- the tensile strength was measured by the following method. Specifically, using a Tensilon universal tensile tester (ORIENTEC, RTM-100), the sample was pulled at a measurement length of 25 mm and a tensile speed of 1 mm / min, and the strength at which the sample (fiber) breaks was determined as the tensile strength. It was. In addition, the measured value of tensile strength is an average value of the tensile strength of 20 samples selected at random.
- ORIENTEC Tensilon universal tensile tester
- the content of alkali metal and alkaline earth metal in the composition was measured as follows. Specifically, the composition was weighed in a platinum crucible and incinerated in order with a burner and an electric furnace. The ashed product was thermally decomposed with hydrofluoric acid to obtain a constant volume. Quantitative analysis of Na, Mg, K and Ca in the obtained constant volume liquid was performed using Agilent 8800 (ICP mass spectrometer, manufactured by Agilent Technologies).
- the contents of silicic acid, silicate, silica gel, silicate ester, boric acid, borate and borate in the composition were measured as follows. Specifically, the composition is filled into a 5 mm ⁇ glass tube, and 29 Si NMR measurement and 11 B NMR measurement are performed using ECA600 (trade name, manufactured by JEOL RESONANCE), and the presence or absence of a peak derived from the target substance. It was confirmed.
- ECA600 trade name, manufactured by JEOL RESONANCE
- Example 1 In Example 1, NMP (1.25 g) was added to the polymetalloxane (T-1) solution (8.75 g) to give a solid content concentration of 40.0% to obtain a composition. The viscosity of this composition was 2000P.
- the organic polymer was analyzed for the composition of Example 1. As a result, an absorption peak (451 cm ⁇ 1 ) of Ti—O—Ti was observed for all of the eluates at each elution time. From this, the eluate was polymetalloxane, and no organic polymer was detected.
- Example 1 the composition was filled into a 10 mL syringe for dispenser (Musashi Engineering Co., Ltd.), and a plastic needle for dispenser (inner diameter 0.20 mm, manufactured by Musashi Engineering Co.) was attached to the syringe as an adapter. A tube (Musashi Engineering Co., Ltd.) was attached. The adapter tube was connected to a compressed air line, and the composition was extruded into an air atmosphere at 25 ° C. at a pressure of 0.4 MPa to obtain a filamentous material. The average fiber diameter of the filamentous material was 60 ⁇ m.
- the obtained filamentous material was dried at 25 ° C. for 24 hours, and then fired at 600 ° C. for 60 minutes in an air atmosphere at a heating rate of 10 ° C./minute using an electric muffle furnace (manufactured by ADVANTEC, FUW263PA).
- a metal oxide fiber was obtained.
- the average fiber diameter of this metal oxide fiber was 40 ⁇ m.
- the tensile strength of this metal oxide fiber was 1.2 GPa.
- the composition and measurement results of the composition of Example 1 are summarized in Table 2 described later.
- Examples 2 to 11 In Examples 2 to 11, thread-like materials were obtained for the compositions shown in Table 2 in the same manner as in Example 1. Subsequently, the filamentous material was fired at the firing temperature shown in Table 2 in the same manner as in Example 1 to obtain metal oxide fibers.
- Example 2 the viscosity of the composition, the average fiber diameter of the filamentous material, the average fiber diameter of the metal oxide fiber, and the tensile strength of the metal oxide were measured.
- the measurement results of Examples 2 to 11 are summarized in Table 2.
- Comparative Example 1 B-10 (trade name, manufactured by Nippon Soda Co., Ltd., butoxytitanium oligomer, weight average molecular weight 2200) was used as the polymetalloxane, and NMP (6.0 g) was added to B-10 (4.00 g). In addition, the solid content concentration was 40.0% to obtain a composition. The viscosity of this composition was 0.1P. In Comparative Example 1, the composition was extruded from the needle in the same manner as in Example 1, but it became droplets and no filamentous material was obtained.
- Comparative Example 2 In Comparative Example 2, a composition having a solid content concentration of 100.0% without adding an organic solvent to B-10 as polymetalloxane was used. The viscosity of this composition was 20P. In Comparative Example 2, the composition was extruded from the needle in the same manner as in Example 1, but it became droplets and no filamentous material was obtained.
- Example 12 the elemental composition of the metal oxide fiber produced in Example 1 described above was quantified by X-ray photoelectron spectroscopy (hereinafter abbreviated as XPS).
- XPS X-ray photoelectron spectroscopy
- the elemental composition analysis by XPS was performed by the following method. Specifically, using an X-ray photoelectron spectrometer (Quanta SXM, manufactured by PHI), an excitation X-ray (monochromatic Al K ⁇ 1,2 line (1486.6 eV)) is set to the sample, and the X-ray diameter is set to 200 ⁇ m.
- the photoelectron escape angle was set to 45 °, and photoelectrons emitted from the surface were detected by an analyzer.
- the elemental composition was quantified based on the detected peak position, peak shape, and peak area ratio of the photoelectron spectrum.
- Example 12 The elemental composition of the metal oxide fiber produced in Example 1 is shown in Table 3 below.
- Example 12 the structural analysis of the metal oxide fiber produced in Example 1 was performed by a wide angle X-ray diffraction method (hereinafter abbreviated as XRD).
- the structural analysis by XRD was performed by the following method. Specifically, using an X-ray diffractometer (manufactured by Bruker AXS, D8 ADVANCE), the measurement range (2 ⁇ ) was set to 10 to 80 °, and a diffraction pattern was obtained, followed by comparison with standard data and identification.
- Table 3 The results of structural analysis of the metal oxide fibers produced in Example 1 are shown in Table 3.
- Example 13 to 22 In Examples 13 to 22, as shown in Table 2, the elemental composition analysis by XPS and the structural analysis by XRD were performed on the metal oxide fibers produced in Examples 2 to 11 as in Example 12. The analysis results of Examples 13 to 22 are shown in Table 3.
- the metal oxide fiber manufacturing method and metal oxide fiber according to the present invention are suitable for easy realization of metal oxide fibers having characteristics such as high heat resistance, high strength, and surface activity.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Textile Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明の実施の形態1に係る金属酸化物繊維の製造方法は、ポリメタロキサンおよび有機溶剤を含む組成物を紡糸して糸状物を得る紡糸工程と、この紡糸工程によって得られた糸状物を200℃以上2000℃以下の温度で焼成して、金属酸化物繊維を得る焼成工程と、を含む。この金属酸化物繊維の製造方法において、ポリメタロキサンは、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Pd、Ag、In、Sn、Sb、Hf、Ta、WおよびBiからなる群より選ばれる金属原子と酸素原子との繰り返し構造を有する。また、このポリメタロキサンの重量平均分子量は、2万以上200万以下である。以下、本発明におけるポリメタロキサンおよび有機溶剤は、各々、ポリメタロキサン(a)、有機溶剤(b)と適宜称する。
ポリメタロキサンとは、一般に、金属-酸素-金属結合を主鎖とする高分子である。本発明において、ポリメタロキサン(a)を構成する金属原子は、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Pd、Ag、In、Sn、Sb、Hf、Ta、WおよびBiからなる群より選ばれる。ポリメタロキサン(a)が上記金属原子を含むことにより、耐熱性の高い金属酸化物繊維を得ることができる。上記金属原子は、好ましくは、Al、Ti、ZrおよびSnからなる群より選ばれる金属原子である。詳細には、ポリメタロキサン(a)中の金属原子は、Al、Ti、ZrおよびSnからなる群より選ばれる金属原子を1種以上含むことが好ましい。ポリメタロキサン(a)が上記の好ましい金属原子を含むことにより、後述するポリメタロキサンの合成原料となる金属アルコキシドが安定に存在するため、高分子量のポリメタロキサンを得ることが容易となる。
本発明におけるポリメタロキサン(a)の合成方法は、特に制限はないが、下記一般式(3)で表される化合物および下記一般式(4)で表される化合物のうち少なくとも一つを、必要に応じて加水分解し、その後、部分縮合および重合させる縮重合工程を含むことが好ましい。
本発明の実施の形態1に係る金属酸化物繊維の製造方法に供される組成物は、上述したように、ポリメタロキサン(a)および有機溶剤(b)を含有する。この組成物は、有機溶剤(b)を含むことにより、任意の粘度に調節され得る。それにより、この組成物の曳糸性と流動性とを両立させることが可能となる。
本発明の実施の形態1に係る金属酸化物繊維の製造方法に供される組成物は、上述したポリメタロキサン(a)および有機溶剤(b)に加え、その他の成分を含んでいてもよい。その他の成分としては、界面活性剤、架橋剤、架橋促進剤などが挙げられる。
本発明の実施の形態1に係る金属酸化物繊維の製造方法は、上記組成物を紡糸して糸状物を得る紡糸工程と、この紡糸工程によって得られた糸状物を200℃以上2000℃以下の温度で焼成して、金属酸化物繊維を得る焼成工程とを含む。
紡糸工程において、組成物を紡糸する方法としては、公知の方法を用いることができる。例えば、この紡糸の方法として、乾式紡糸法、湿式紡糸法、乾湿式紡糸法、エレクトロスピニング法が挙げられる。
焼成工程では、上記紡糸工程で紡糸して得られた糸状物を200℃以上2000℃以下の温度で焼成し、これにより、架橋反応の進行とともに、有機基などの有機成分が除去され、強度に優れた金属酸化物繊維を得ることができる。この焼成工程における焼成の温度は、より好ましくは、400℃以上1500℃以下である。
(金属酸化物繊維)
本発明の実施の形態2に係る金属酸化物繊維は、以下に示す特徴的な構成を有する。すなわち、この実施の形態2に係る金属酸化物繊維は、Si(シリコン原子)と、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Pd、Ag、In、Sn、Sb、Hf、Ta、WおよびBiからなる群より選ばれる金属原子のうち1種以上と、を含む(以下、「第1の特徴」と適宜いう)。また、この金属酸化物繊維を構成する金属酸化物中のSiO2成分の含有量は、0.5重量%以下である(以下、「第2の特徴」と適宜いう)。
本発明に係る製造方法により得られる金属酸化物繊維は、連続した緻密な金属酸化物繊維であることから、高耐熱、高強度、表面活性などの特性を有する。そのため、当該金属酸化物繊維は、高耐熱繊維の特性を活かして、電気炉や建材などの断熱材や、放熱材として用いることができる。また、当該金属酸化物繊維は、高強度繊維の特性を活かして、繊維強化(FRP)などの複合材料として利用することができる。さらに、当該金属酸化物繊維は、高耐熱・高強度繊維の特性を活かして、航空機のエンジンタービンなどの部材や、宇宙航空機の部材として用いることができる。また、二酸化チタン主体の金属酸化物繊維によれば、光触媒活性を有するため、水および大気の浄化用フィルターなどに用いることができる。
合成例1のポリメタロキサン(T-1)溶液の合成方法について説明する。この合成方法では、トリイソプロポキシ(トリメチルシロキシ)チタン(31.4g(0.10mol))と、溶媒としてのNMP(15.8g)とを混合し、これを溶液1とした。また、水(5.4g(0.30mol))と、水希釈溶媒としてのイソプロピルアルコール(50.0g)と、重合触媒としてのトリブチルアミン(1.9g(0.01mol))とを混合し、これを溶液2とした。以下、イソプロピルアルコールは、IPAと略記する。
合成例2のポリメタロキサン(T-2)溶液の合成方法について説明する。この合成方法では、合成例1の溶媒であるNMP(15.8g)に替えて、γ-ブチロラクトン(15.8g)を溶媒として混合したこと以外は、合成例1と同様に合成を行った。以下、γ-ブチロラクトンは、GBLと略記する。
合成例3のポリメタロキサン(T-3)溶液の合成方法について説明する。この合成方法では、合成例1の重合触媒であるトリブチルアミン(1.9g)に替えて、ジシクロヘキシルメチルアミン(2.0g(0.01mol))を重合触媒として混合したこと以外は、合成例1と同様に合成を行った。
合成例4のポリメタロキサン(T-4)溶液の合成方法について説明する。この合成方法では、トリイソプロポキシ(トリメチルシロキシ)チタン(15.7g(0.05mol))と、テトラブトキシチタン(17.0g(0.05mol))と、溶媒としてのNMP(16.4g)とを混合し、これを溶液1とした。また、水(5.4g(0.30mol))と、水希釈溶媒としてのIPA(50.0g)と、重合触媒としてのトリブチルアミン(1.9g(0.01mol))とを混合し、これを溶液2とした。
合成例5のポリメタロキサン(Z-1)溶液の合成方法について説明する。この合成方法では、トリプロポキシ(トリメチルシロキシ)ジルコニウム(35.4g(0.10mol))と、溶媒としてのNMP(17.5g)とを混合し、これを溶液1とした。また、水(5.4g(0.30mol))と、水希釈溶媒としてのIPA(50.0g)と、重合触媒としてのトリブチルアミン(1.9g(0.01mol))とを混合し、これを溶液2とした。
合成例6のポリメタロキサン(A-1)溶液の合成方法について説明する。この合成方法では、ジ-s-ブトキシ(トリメチルシロキシ)アルミニウム(24.6g(0.10mol))と、溶媒としてのNMP(12.1g)とを混合し、これを溶液1とした。また、水(5.4g(0.30mol))と、水希釈溶媒としてのIPA(50.0g)と、重合触媒としてのトリブチルアミン(1.9g(0.01mol))とを混合し、これを溶液2とした。
合成例7のポリメタロキサン(TZ-1)溶液の合成方法について説明する。この合成方法では、トリイソプロポキシ(トリメチルシロキシ)チタン(15.7g(0.05mol))と、トリプロポキシ(トリメチルシロキシ)ジルコニウム(17.7g(0.05mol))と、溶媒としてのNMP(16.6g)とを混合し、これを溶液1とした。また、水(5.4g(0.30mol))と、水希釈溶媒としてのIPA(50.0g)と、重合触媒としてのトリブチルアミン(1.9g(0.01mol))とを混合し、これを溶液2とした。
合成例8のポリメタロキサン(TA-1)溶液の合成方法について説明する。この合成方法では、トリイソプロポキシ(トリメチルシロキシ)チタン(15.7g(0.05mol))と、ジ-s-ブトキシ(トリメチルシロキシ)アルミニウム(12.3g(0.05mol))と、溶媒としてのNMP(16.6g)とを混合し、これを溶液1とした。また、水(5.4g(0.30mol))と、水希釈溶媒としてのIPA(50.0g)と、重合触媒としてのトリブチルアミン(1.9g(0.01mol))とを混合し、これを溶液2とした。
合成例9のポリメタロキサン(ZA-1)溶液の合成方法について説明する。この合成方法では、トリプロポキシ(トリメチルシロキシ)ジルコニウム(17.7g(0.05mol))と、ジ-s-ブトキシ(トリメチルシロキシ)アルミニウム(12.3g(0.05mol))と、溶媒としてのNMP(16.6g)とを混合し、これを溶液1とした。また、水(5.4g(0.30mol))と、水希釈溶媒としてのIPA(50.0g)と、重合触媒としてのトリブチルアミン(1.9g(0.01mol))とを混合し、これを溶液2とした。
実施例1では、ポリメタロキサン(T-1)溶液(8.75g)にNMP(1.25g)を加え、固形分濃度を40.0%とし、組成物とした。この組成物の粘度は、2000Pであった。
実施例2~11では、表2に示した組成物につき、実施例1と同様に、糸状物を得た。次いで、表2に示した焼成温度で、実施例1と同様に糸状物を焼成し、金属酸化物繊維を得た。
比較例1では、ポリメタロキサンとしてB-10(商品名、日本曹達社製、ブトキシチタンオリゴマー、重量平均分子量2200)を用い、このB-10(4.00g)にNMP(6.0g)を加え、固形分濃度を40.0%とし、組成物とした。この組成物の粘度は、0.1Pであった。比較例1では、実施例1と同様にニードルから組成物を押し出したが、液滴となり、糸状物は得られなかった。
比較例2では、ポリメタロキサンとしてB-10に有機溶剤を加えずに、固形分濃度が100.0%の組成物とした。この組成物の粘度は、20Pであった。比較例2では、実施例1と同様にニードルから組成物を押し出したが、液滴となり、糸状物は得られなかった。
実施例12では、上述した実施例1で作製した金属酸化物繊維につき、元素組成をX線光電子分光法(以下、XPSと略す)により定量化した。XPSによる元素組成分析は、以下の方法で行った。具体的には、X線光電子分光装置(PHI社製、Quantera SXM)を用いて、試料に励起X線(monochromatic Al Kα1,2線(1486.6eV))を、X線径を200μmに設定して照射し、光電子脱出角度を45°とし、表面から放出される光電子をアナライザーで検出した。検出した光電子スペクトルのピーク位置およびピーク形状、ピーク面積比により、元素組成を定量した。
実施例13~22では、表2に示したように、実施例2~11で作製した金属酸化物繊維につき、実施例12と同様に、XPSによる元素組成分析およびXRDによる構造分析を行った。実施例13~22の分析結果は、表3に示した。
Claims (19)
- ポリメタロキサンおよび有機溶剤を含む組成物を紡糸して糸状物を得る紡糸工程と、
前記紡糸工程によって得られた前記糸状物を200℃以上2000℃以下の温度で焼成して、金属酸化物繊維を得る焼成工程と、
を含み、
前記ポリメタロキサンは、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Pd、Ag、In、Sn、Sb、Hf、Ta、WおよびBiからなる群より選ばれる金属原子と酸素原子との繰り返し構造を有し、
前記ポリメタロキサンの重量平均分子量は、2万以上200万以下である、
ことを特徴とする金属酸化物繊維の製造方法。 - 前記組成物の25℃における粘度が10P以上50000P以下である、
ことを特徴とする請求項1に記載の金属酸化物繊維の製造方法。 - 平均繊維径が0.01μm以上1000μm以下である、
ことを特徴とする請求項1または2に記載の金属酸化物繊維の製造方法。 - 前記組成物が、有機高分子を含み、
前記組成物中の前記有機高分子の含有量が、前記組成物中に含まれる前記ポリメタロキサンの重量に対し、1重量%以下である、
ことを特徴とする請求項1~3のいずれか一つに記載の金属酸化物繊維の製造方法。 - 前記組成物が、アルカリ金属およびアルカリ土類金属をいずれも含まない、
ことを特徴とする請求項1~4のいずれか一つに記載の金属酸化物繊維の製造方法。 - 前記組成物が、珪酸、珪酸塩、シリカゲル、珪酸エステル、ホウ酸、ホウ酸塩およびホウ酸エステルをいずれも含まない、
ことを特徴とする請求項1~5のいずれか一つに記載の金属酸化物繊維の製造方法。 - 前記ポリメタロキサンが、下記一般式(1)で表される構造単位および下記一般式(2)で表される構造単位のうち少なくとも一つを有するポリメタロキサンである、
ことを特徴とする請求項1~6のいずれか一つに記載の金属酸化物繊維の製造方法。
- 前記ポリメタロキサンが、前記一般式(1)で表される構造単位を少なくとも有し、
前記一般式(1)中のR2の少なくとも一つは、ヒドロキシ基である、
ことを特徴とする請求項7に記載の金属酸化物繊維の製造方法。 - 前記ポリメタロキサンが、前記一般式(2)で表される構造単位を少なくとも有する、
ことを特徴とする請求項7または8に記載の金属酸化物繊維の製造方法。 - 前記ポリメタロキサン中の前記金属原子Mが、Al、Ti、ZrおよびSnからなる群より選ばれる金属原子を1種以上含む、
ことを特徴とする請求項7~9のいずれか一つに記載の金属酸化物繊維の製造方法。 - 前記ポリメタロキサン中の前記金属原子Mは、Tiを含み、
前記金属酸化物繊維中の全ての前記金属原子MにおけるTiの比率が、5mol%以上100mol%以下の範囲である、
ことを特徴とする請求項7~10のいずれか一つに記載の金属酸化物繊維の製造方法。 - 前記ポリメタロキサン中の前記金属原子Mは、Zrを含み、
前記金属酸化物繊維中の全ての前記金属原子MにおけるZrの比率が、5mol%以上100mol%以下の範囲である、
ことを特徴とする請求項7~10のいずれか一つに記載の金属酸化物繊維の製造方法。 - 前記紡糸工程が、乾式紡糸法またはエレクトロスピニング法によって前記組成物を紡糸する工程である、
ことを特徴とする請求項1~12のいずれか一つに記載の金属酸化物繊維の製造方法。 - Siと、
Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Nb、Mo、Pd、Ag、In、Sn、Sb、Hf、Ta、WおよびBiからなる群より選ばれる金属原子のうち1種以上と、
を含み、
金属酸化物中のSiO2成分の含有量が、0.5重量%以下である、
ことを特徴とする金属酸化物繊維。 - 平均繊維径が0.01μm以上1000μm以下である、
ことを特徴とする請求項14に記載の金属酸化物繊維。 - 前記金属酸化物中の前記金属原子が、Al、Ti、ZrおよびSnからなる群より選ばれる金属原子を1種以上含む、
ことを特徴とする請求項14または15に記載の金属酸化物繊維。 - 前記金属酸化物中の前記金属原子が、Tiを含み、
含有される全ての前記金属原子におけるTiの比率が、5mol%以上100mol%以下の範囲である、
ことを特徴とする請求項14または15に記載の金属酸化物繊維。 - 前記金属酸化物中の前記金属原子が、Zrを含み、
含有される全ての前記金属原子におけるZrの比率が、5mol%以上100mol%以下の範囲である、
ことを特徴とする請求項14または15に記載の金属酸化物繊維。 - 前記金属酸化物中の前記金属原子が、Al、Ti、ZrおよびSnからなる群より選ばれる金属原子を2種以上含む、
ことを特徴とする請求項14または15に記載の金属酸化物繊維。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019516724A JP7264048B2 (ja) | 2018-03-29 | 2019-03-22 | 金属酸化物繊維の製造方法 |
KR1020207026576A KR20200138206A (ko) | 2018-03-29 | 2019-03-22 | 금속 산화물 섬유의 제조 방법 및 금속 산화물 섬유 |
EP19777894.7A EP3779001A4 (en) | 2018-03-29 | 2019-03-22 | METAL OXIDE FIBER AND METAL OXIDE FIBER PRODUCTION METHOD |
CN201980023196.7A CN111971425A (zh) | 2018-03-29 | 2019-03-22 | 金属氧化物纤维的制造方法和金属氧化物纤维 |
US16/982,658 US20210108339A1 (en) | 2018-03-29 | 2019-03-22 | Method for producing metal oxide fibers, and metal oxide fibers |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018064028 | 2018-03-29 | ||
JP2018-064029 | 2018-03-29 | ||
JP2018-064028 | 2018-03-29 | ||
JP2018064029 | 2018-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019188834A1 true WO2019188834A1 (ja) | 2019-10-03 |
Family
ID=68061852
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/012225 WO2019188834A1 (ja) | 2018-03-29 | 2019-03-22 | 金属酸化物繊維の製造方法および金属酸化物繊維 |
PCT/JP2019/012228 WO2019188835A1 (ja) | 2018-03-29 | 2019-03-22 | ポリメタロキサン、組成物、硬化膜、部材、電子部品、繊維、セラミックス成型用結着剤、硬化膜の製造方法、および繊維の製造方法 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/012228 WO2019188835A1 (ja) | 2018-03-29 | 2019-03-22 | ポリメタロキサン、組成物、硬化膜、部材、電子部品、繊維、セラミックス成型用結着剤、硬化膜の製造方法、および繊維の製造方法 |
Country Status (8)
Country | Link |
---|---|
US (2) | US20210108339A1 (ja) |
EP (2) | EP3779001A4 (ja) |
JP (2) | JP7334619B2 (ja) |
KR (2) | KR20200138206A (ja) |
CN (2) | CN111971425A (ja) |
SG (1) | SG11202009303SA (ja) |
TW (2) | TW201942211A (ja) |
WO (2) | WO2019188834A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022054552A1 (ja) * | 2020-09-11 | 2022-03-17 | 東レ株式会社 | ポリメタロキサン含有組成物、硬化体、部材、電子部品および繊維 |
WO2022138541A1 (ja) * | 2020-12-25 | 2022-06-30 | 東レ株式会社 | ポリメタロキサン、その組成物、硬化膜およびその製造方法、それを具備する部材および電子部品、繊維およびその製造方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022065127A1 (ja) * | 2020-09-24 | 2022-03-31 | 東レ株式会社 | 組成物、硬化体およびその製造方法、ならびに部材、電子部品および繊維 |
CN115746309B (zh) * | 2022-11-04 | 2023-08-29 | 复旦大学 | 一种主链为金属元素的高分子及其制备方法和应用 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6046927A (ja) | 1983-08-24 | 1985-03-14 | Natl Inst For Res In Inorg Mater | チタニア繊維の製造法 |
JPS60215815A (ja) * | 1984-04-10 | 1985-10-29 | Sumitomo Chem Co Ltd | 無機質繊維の製造方法 |
JPH03190931A (ja) * | 1989-12-20 | 1991-08-20 | Nitto Boseki Co Ltd | チタノシロキサン重合体の製造方法 |
JPH0578489A (ja) * | 1991-02-08 | 1993-03-30 | Nitto Boseki Co Ltd | ジルコノシロキサン重合体及びその製造方法 |
JPH06108315A (ja) * | 1992-09-22 | 1994-04-19 | Mitsui Mining Co Ltd | リチウムアルミネ−ト繊維の製造方法 |
JPH09276705A (ja) | 1996-04-11 | 1997-10-28 | Sumitomo Chem Co Ltd | 光触媒体 |
JPH09291421A (ja) | 1996-04-22 | 1997-11-11 | Isolite Kogyo Kk | アルミナジルコニア繊維及びその製造方法 |
JPH09316733A (ja) | 1996-05-27 | 1997-12-09 | Isolite Kogyo Kk | アルミナ繊維の製造方法 |
JP2000045127A (ja) | 1998-05-19 | 2000-02-15 | Toshiba Monofrax Co Ltd | 無機繊維及び耐火断熱材 |
WO2017090512A1 (ja) * | 2015-11-26 | 2017-06-01 | 東レ株式会社 | ポリメタロキサン、その製造方法、その組成物、硬化膜およびその製造方法ならびにそれを備えた部材および電子部品 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5898428A (ja) * | 1982-09-27 | 1983-06-11 | Sumitomo Chem Co Ltd | 無機質繊維の製造方法 |
US4495121A (en) * | 1981-11-30 | 1985-01-22 | Sumitomo Chemical Company, Ltd. | Process for producing inorganic fiber |
JPS5895611A (ja) * | 1981-11-30 | 1983-06-07 | Sumitomo Chem Co Ltd | 無機質焼成体の製造方法 |
JPH01129032A (ja) | 1987-11-12 | 1989-05-22 | Nippon Soda Co Ltd | ラダー状ポリチタノキサンおよびその製造方法 |
US5418298A (en) * | 1993-03-19 | 1995-05-23 | Regents Of The University Of Michigan | Neutral and mixed neutral/anionic polymetallooxanes |
WO2005113142A1 (ja) * | 2004-05-21 | 2005-12-01 | Nippon Soda Co., Ltd. | 光触媒活性薄膜 |
JP2009013398A (ja) * | 2007-06-05 | 2009-01-22 | Nippon Shokubai Co Ltd | ボンド磁石用熱硬化性バインダー樹脂組成物 |
WO2009051023A1 (ja) * | 2007-10-16 | 2009-04-23 | Hitachi Chemical Company, Ltd. | 樹脂組成物及びこれを用いた膜状光学部材並びに樹脂組成物の製造方法 |
JP5682063B2 (ja) * | 2008-10-30 | 2015-03-11 | ナガセケムテックス株式会社 | 硬化性組成物 |
CN101899725B (zh) * | 2010-03-31 | 2014-06-11 | 清华大学 | 金属氧化物的纳米纤维及其制造方法 |
JP2014058423A (ja) * | 2012-09-18 | 2014-04-03 | Nichias Corp | 耐熱性を有する生体溶解性無機繊維及びその組成物 |
WO2014049988A1 (ja) * | 2012-09-27 | 2014-04-03 | ニチアス株式会社 | 生体溶解性無機繊維及びその組成物 |
JP6175320B2 (ja) | 2013-05-24 | 2017-08-02 | マツモトファインケミカル株式会社 | 高屈折率膜材料の製造方法 |
RU2649392C2 (ru) * | 2014-04-11 | 2018-04-03 | Федеральное государственное бюджетное учреждение науки Институт синтетических полимерных материалов им. Н.С. Ениколопова Российской академии наук (ИСПМ РАН) | Функциональные металлосилоксаны, продукты их частичного гидролиза и их применение |
US20160299451A1 (en) * | 2015-04-10 | 2016-10-13 | Canon Kabushiki Kaisha | Charging member, process cartridge, and electrophotographic image forming apparatus |
-
2019
- 2019-03-22 JP JP2019516547A patent/JP7334619B2/ja active Active
- 2019-03-22 SG SG11202009303SA patent/SG11202009303SA/en unknown
- 2019-03-22 US US16/982,658 patent/US20210108339A1/en not_active Abandoned
- 2019-03-22 EP EP19777894.7A patent/EP3779001A4/en not_active Withdrawn
- 2019-03-22 WO PCT/JP2019/012225 patent/WO2019188834A1/ja active Application Filing
- 2019-03-22 CN CN201980023196.7A patent/CN111971425A/zh not_active Withdrawn
- 2019-03-22 CN CN201980023188.2A patent/CN111886280B/zh not_active Expired - Fee Related
- 2019-03-22 EP EP19778312.9A patent/EP3778715B1/en active Active
- 2019-03-22 US US16/980,645 patent/US20210371599A1/en not_active Abandoned
- 2019-03-22 JP JP2019516724A patent/JP7264048B2/ja active Active
- 2019-03-22 KR KR1020207026576A patent/KR20200138206A/ko active Search and Examination
- 2019-03-22 WO PCT/JP2019/012228 patent/WO2019188835A1/ja active Application Filing
- 2019-03-22 KR KR1020207026575A patent/KR20200138205A/ko unknown
- 2019-03-27 TW TW108110726A patent/TW201942211A/zh unknown
- 2019-03-27 TW TW108110760A patent/TW201942062A/zh unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6046927A (ja) | 1983-08-24 | 1985-03-14 | Natl Inst For Res In Inorg Mater | チタニア繊維の製造法 |
JPS60215815A (ja) * | 1984-04-10 | 1985-10-29 | Sumitomo Chem Co Ltd | 無機質繊維の製造方法 |
JPH03190931A (ja) * | 1989-12-20 | 1991-08-20 | Nitto Boseki Co Ltd | チタノシロキサン重合体の製造方法 |
JPH0578489A (ja) * | 1991-02-08 | 1993-03-30 | Nitto Boseki Co Ltd | ジルコノシロキサン重合体及びその製造方法 |
JPH06108315A (ja) * | 1992-09-22 | 1994-04-19 | Mitsui Mining Co Ltd | リチウムアルミネ−ト繊維の製造方法 |
JPH09276705A (ja) | 1996-04-11 | 1997-10-28 | Sumitomo Chem Co Ltd | 光触媒体 |
JPH09291421A (ja) | 1996-04-22 | 1997-11-11 | Isolite Kogyo Kk | アルミナジルコニア繊維及びその製造方法 |
JPH09316733A (ja) | 1996-05-27 | 1997-12-09 | Isolite Kogyo Kk | アルミナ繊維の製造方法 |
JP2000045127A (ja) | 1998-05-19 | 2000-02-15 | Toshiba Monofrax Co Ltd | 無機繊維及び耐火断熱材 |
WO2017090512A1 (ja) * | 2015-11-26 | 2017-06-01 | 東レ株式会社 | ポリメタロキサン、その製造方法、その組成物、硬化膜およびその製造方法ならびにそれを備えた部材および電子部品 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022054552A1 (ja) * | 2020-09-11 | 2022-03-17 | 東レ株式会社 | ポリメタロキサン含有組成物、硬化体、部材、電子部品および繊維 |
WO2022138541A1 (ja) * | 2020-12-25 | 2022-06-30 | 東レ株式会社 | ポリメタロキサン、その組成物、硬化膜およびその製造方法、それを具備する部材および電子部品、繊維およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP3778715A1 (en) | 2021-02-17 |
EP3779001A4 (en) | 2021-10-13 |
EP3779001A1 (en) | 2021-02-17 |
TW201942062A (zh) | 2019-11-01 |
KR20200138205A (ko) | 2020-12-09 |
JPWO2019188835A1 (ja) | 2021-03-11 |
JPWO2019188834A1 (ja) | 2021-02-12 |
EP3778715A4 (en) | 2021-06-30 |
US20210371599A1 (en) | 2021-12-02 |
SG11202009303SA (en) | 2020-10-29 |
US20210108339A1 (en) | 2021-04-15 |
WO2019188835A1 (ja) | 2019-10-03 |
JP7264048B2 (ja) | 2023-04-25 |
CN111886280A (zh) | 2020-11-03 |
TW201942211A (zh) | 2019-11-01 |
CN111971425A (zh) | 2020-11-20 |
JP7334619B2 (ja) | 2023-08-29 |
EP3778715B1 (en) | 2022-05-25 |
KR20200138206A (ko) | 2020-12-09 |
CN111886280B (zh) | 2022-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7264048B2 (ja) | 金属酸化物繊維の製造方法 | |
JP2012255070A (ja) | 無機酸化物粒子とシリコーン樹脂との複合組成物及び透明複合体 | |
CN109437862A (zh) | 一种含1~5wt%B2O3的氧化铝基陶瓷连续纤维的制备方法 | |
RU2551431C1 (ru) | Волокнообразующие органоиттрийоксаналюмоксаны | |
WO1985004678A1 (en) | Process for preparing inorganic fibers | |
JPWO2008038529A1 (ja) | シリカ基複合光触媒及びその製造方法 | |
WO2022202398A1 (ja) | 金属-酸素-金属結合を主鎖とする高分子、その組成物、固体物およびその製造方法、ならびに電子部品および繊維 | |
Gunji et al. | Synthesis of polytitanosiloxanes and their transformation to SiO2–TiO2 ceramic fibers | |
FR2655327A1 (fr) | Composition vitroceramique li-al-si-o et son procede de fabrication. | |
JP2022161583A (ja) | 強化用繊維含有セラミックス組成物、繊維強化セラミックス基複合体、および繊維強化セラミックス基複合体の製造方法 | |
JP2022142854A (ja) | 金属酸化物繊維の製造方法 | |
WO2007145172A1 (ja) | 有機無機ハイブリッドガラス状物質 | |
TW202216857A (zh) | 組成物、硬化體及其製造方法以及構件、無機固體物圖案的製造方法、電子零件及纖維及其製造方法 | |
JPH04263615A (ja) | アルミノシリケート系粘性ゾルの製造方法 | |
WO2022138541A1 (ja) | ポリメタロキサン、その組成物、硬化膜およびその製造方法、それを具備する部材および電子部品、繊維およびその製造方法 | |
TW202210559A (zh) | 組成物、硬化體及其製造方法、無機固體物圖案的製造方法、構件、電子零件及纖維及其製造方法、以及金屬氧化物纖維的製造方法 | |
RU2530033C1 (ru) | СПОСОБ ПОЛУЧЕНИЯ КЕРАМИЧЕСКОГО ВОЛОКНА НА ОСНОВЕ ZrO2 И SiO2 | |
CN115852528B (zh) | 一种规模化生产连续钇铝石榴石长丝的方法 | |
JP2022048417A (ja) | 無機含有有機膜の製造方法 | |
JPS5891721A (ja) | 芳香族コポリエステル | |
RU2314994C1 (ru) | Способ получения нановолокон гликолята титана | |
CN117986015A (zh) | 一种氧化铪聚合物陶瓷前驱体及其制备方法 | |
JP5399697B2 (ja) | 無機含有有機膜の製造方法及び無機含有有機膜 | |
JP2001279098A (ja) | 有機ケイ素重合体、炭化ケイ素系無機繊維及びそれらの製造方法 | |
JP2008038000A (ja) | 有機無機ハイブリッドガラス状物質 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2019516724 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19777894 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2019777894 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2019777894 Country of ref document: EP Effective date: 20201029 |