JP4446776B2 - Method for producing anatase type titanium oxide crystal - Google Patents
Method for producing anatase type titanium oxide crystal Download PDFInfo
- Publication number
- JP4446776B2 JP4446776B2 JP2004099042A JP2004099042A JP4446776B2 JP 4446776 B2 JP4446776 B2 JP 4446776B2 JP 2004099042 A JP2004099042 A JP 2004099042A JP 2004099042 A JP2004099042 A JP 2004099042A JP 4446776 B2 JP4446776 B2 JP 4446776B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- polyamine
- anatase
- solution
- type titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 97
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 85
- 239000013078 crystal Substances 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 229920000768 polyamine Polymers 0.000 claims description 54
- 150000003609 titanium compounds Chemical class 0.000 claims description 31
- 150000001450 anions Chemical class 0.000 claims description 23
- -1 polyvinylamine Polymers 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000012736 aqueous medium Substances 0.000 claims description 16
- NEEAGZFWIFOFCK-UHFFFAOYSA-J 2-oxidopropanoate titanium(4+) dihydroxide Chemical compound CC(O[Ti](O)(O)OC(C)C([O-])=O)C([O-])=O NEEAGZFWIFOFCK-UHFFFAOYSA-J 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 150000001412 amines Chemical group 0.000 claims description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 229930187593 rose bengal Natural products 0.000 claims description 5
- 229940081623 rose bengal Drugs 0.000 claims description 5
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 5
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 4
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 claims description 4
- 229940011411 erythrosine Drugs 0.000 claims description 4
- 235000012732 erythrosine Nutrition 0.000 claims description 4
- 239000004174 erythrosine Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- DTQHSUHILQWIOM-UHFFFAOYSA-J 2-hydroxypropanoate titanium(4+) dihydroxide Chemical compound O[Ti++]O.CC(O)C([O-])=O.CC(O)C([O-])=O DTQHSUHILQWIOM-UHFFFAOYSA-J 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 108010039918 Polylysine Proteins 0.000 claims description 2
- BSZPYRJQDZNENV-UHFFFAOYSA-N [Na].c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3 Chemical compound [Na].c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3 BSZPYRJQDZNENV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N hydrogen bromide Substances Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000083 poly(allylamine) Polymers 0.000 claims description 2
- 229920000656 polylysine Polymers 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229940083542 sodium Drugs 0.000 claims description 2
- 229940063673 spermidine Drugs 0.000 claims description 2
- 229940063675 spermine Drugs 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001018 xanthene dye Substances 0.000 claims description 2
- VDNLFJGJEQUWRB-UHFFFAOYSA-N rose bengal free acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C(O)=C(I)C=C21 VDNLFJGJEQUWRB-UHFFFAOYSA-N 0.000 claims 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 53
- 239000000243 solution Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000002244 precipitate Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 25
- 239000000843 powder Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000007865 diluting Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910017008 AsF 6 Inorganic materials 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 230000005588 protonation Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- IYHIFXGFKVJNBB-UHFFFAOYSA-N 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonic acid Chemical compound C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S(O)(=O)=O IYHIFXGFKVJNBB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 108010038807 Oligopeptides Proteins 0.000 description 1
- 102000015636 Oligopeptides Human genes 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229920006187 aquazol Polymers 0.000 description 1
- 239000012861 aquazol Substances 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OKHMDSCYUWAQPT-UHFFFAOYSA-N n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.NCCNCCNCCN OKHMDSCYUWAQPT-UHFFFAOYSA-N 0.000 description 1
- VGICAQBLDJAGSJ-UHFFFAOYSA-N n'-[2-[2-(2-aminoethylamino)ethylamino]ethyl]ethane-1,2-diamine;pentahydrochloride Chemical compound Cl.Cl.Cl.Cl.Cl.NCCNCCNCCNCCN VGICAQBLDJAGSJ-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- NUSQOFAKCBLANB-UHFFFAOYSA-N phthalocyanine tetrasulfonic acid Chemical compound C12=CC(S(=O)(=O)O)=CC=C2C(N=C2NC(C3=CC=C(C=C32)S(O)(=O)=O)=N2)=NC1=NC([C]1C=CC(=CC1=1)S(O)(=O)=O)=NC=1N=C1[C]3C=CC(S(O)(=O)=O)=CC3=C2N1 NUSQOFAKCBLANB-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、光触媒や顔料として有用なアナターゼ型酸化チタン結晶の製法に関するものであり、より詳しくは、室温下における穏和な条件でのアナターゼ型酸化チタンの製法に関するものである。 The present invention relates to a method for producing anatase-type titanium oxide crystals useful as a photocatalyst or a pigment, and more particularly to a method for producing anatase-type titanium oxide under mild conditions at room temperature.
酸化チタンは白色顔料として古くから利用されてきたが、近年ではその高い屈折率に基づく光の反射・屈折現象を利用して、化粧料、干渉顔料等にも幅広く使用されており、フォトニック結晶の構成材料としての期待も高い。また光触媒としての有用性もよく知られており、太陽電池や、物質の光分解、酸化を利用した殺菌、抗菌、防臭システム等に応用されている。酸化チタンの結晶には、アナターゼ型、ルチル型、ブルッカイト型の結晶構造が知られているが、アナターゼ型酸化チタン結晶が光触媒としての活性が最も高い。以下従来の酸化チタン製造技術について説明する。 Titanium oxide has long been used as a white pigment, but in recent years it has been widely used in cosmetics, interference pigments, etc. by utilizing the light reflection and refraction phenomenon based on its high refractive index. Expectations are high as a constituent material In addition, its usefulness as a photocatalyst is well known, and it is applied to solar cells, photodecomposition of substances, sterilization utilizing oxidation, antibacterial, deodorizing systems and the like. Anatase type, rutile type, and brookite type crystal structures are known as titanium oxide crystals, and anatase type titanium oxide crystals have the highest activity as a photocatalyst. The conventional titanium oxide manufacturing technique will be described below.
酸化チタンを得る方法には、大別して気相法と液相法が用いられている。気相法においては、チタンテトライソプロポキシドを８７３Ｋ〜１０７３Ｋの温度で処理し、熱分解反応によるアナターゼ型酸化チタンの生成が確認されている（非特許文献１）。これら気相法では、アナターゼ型酸化チタンを得るために高温での処理が必要であり、製造過程で発生するガスに対応する設備も必要となるため生産コストが高いという問題点がある。 The method for obtaining titanium oxide is roughly classified into a gas phase method and a liquid phase method. In the gas phase method, titanium tetraisopropoxide is treated at a temperature of 873 K to 1073 K, and production of anatase-type titanium oxide by a thermal decomposition reaction has been confirmed (Non-patent Document 1). In these gas phase methods, a high temperature treatment is required in order to obtain anatase type titanium oxide, and there is a problem that the production cost is high because equipment corresponding to the gas generated in the production process is also required.
液相法は、気相法に比べて、反応温度を低く抑えることができ、また大量生産にも対応しやすいので、有用であり、種々の製造法が検討されている。例えば、「硫酸法」では、硫酸チタニルを加水分解して得た酸性チタニアゾルに水酸化ナトリウムを加えてｐＨ７に調節した後、ろ過、洗浄を行い、ついで得られた酸化チタン湿ケーキに水を加えてスラリーを形成する。このスラリーに水酸化ナトリウムを加えてｐＨ１０に調節した後、オートクレーブ中１５０℃の温度で３時間乾燥させて酸化チタンを得ている（特許文献１）。
The liquid phase method is useful as it can keep the reaction temperature lower than the gas phase method, and can easily cope with mass production, and various production methods are being studied. For example, in the “sulfuric acid method”, sodium hydroxide is added to acid titania sol obtained by hydrolyzing titanyl sulfate to adjust pH to 7, followed by filtration and washing, and then water is added to the obtained titanium oxide wet cake. To form a slurry. After adding sodium hydroxide to this slurry and adjusting to
「水熱法」では、チタンアルコキシドを希薄アルコール溶液中で加水分解し、さらにオートクレーブ中、２５０℃で水熱処理することによりアナターゼ型酸化チタンを得ている（非特許文献２、３）。また、チタンイソプロポキシドのイソプロパノール溶液に、塩酸と水を加えたイソプロパノールを滴下してチタニアゾル溶液を得、これを密閉容器内で加熱、加圧することによって８０〜１５０℃の比較的低い温度でアナターゼ型酸化チタンを製造する方法が開示されている（特許文献２）。これらは比較的工程数の少ない簡便な酸化チタンの製造法であるが、加圧処理のために特別な装置や容器を必要とする。 In the “hydrothermal method”, titanium alkoxide is hydrolyzed in a dilute alcohol solution and further hydrothermally treated at 250 ° C. in an autoclave to obtain anatase-type titanium oxide (Non-patent Documents 2 and 3). Further, titania sol solution is obtained by dropwise addition of isopropanol containing hydrochloric acid and water to isopropanol solution of titanium isopropoxide, and this is heated and pressurized in a sealed container at a relatively low temperature of 80 to 150 ° C. A method for producing type titanium oxide is disclosed (Patent Document 2). These are simple methods for producing titanium oxide with a relatively small number of steps, but require special equipment and containers for the pressure treatment.
ゾル−ゲル反応を利用する製造法も知られている。これは、チタンアルコキシドの加水分解による水酸化チタンの生成と、水酸化チタンの重縮合による酸化チタンの生成の２段階からなる反応である（非特許文献４）。この方法は常圧下で行われるが、チタンアルコキシドは、非常に反応性が高く、空気中の水分とも反応するので、反応条件を精密にコントロールする必要がある。この高い反応性のために、得られる酸化チタンはアモルファスになり、アナターゼ型結晶を得るためには３００〜６００℃の高温で焼成を行わなければならない（非特許文献５）。 A production method using a sol-gel reaction is also known. This is a reaction composed of two stages, ie, production of titanium hydroxide by hydrolysis of titanium alkoxide and production of titanium oxide by polycondensation of titanium hydroxide (Non-patent Document 4). Although this method is carried out under normal pressure, titanium alkoxide is very reactive and reacts with moisture in the air, so it is necessary to precisely control the reaction conditions. Due to this high reactivity, the resulting titanium oxide becomes amorphous, and in order to obtain anatase-type crystals, firing must be performed at a high temperature of 300 to 600 ° C. (Non-patent Document 5).
反応性の高いチタンアルコキシドの代わりに、水中でも安定なチタニウム（ＩＶ）ビス（アンモニウムラクテート）ジヒドロキシドを用いる方法も検討されており、（非特許文献６）には、尿素の存在下、９０℃で加水分解を起こすことが報告されている。また、（非特許文献７）には、チタニウム（ＩＶ）ビス（アンモニウムラクテート）ジヒドロキシドの水溶液を封管中、１２０℃で２４時間処理することによるアナターゼ型の酸化チタンの製造法が開示されている。このチタン化合物は、本発明でも好適に用いられるものであるが、アナターゼ型酸化チタンの製造に、長時間の加熱操作を必要ととする。 A method of using titanium (IV) bis (ammonium lactate) dihydroxide that is stable in water instead of highly reactive titanium alkoxide has also been studied. (Non-Patent Document 6) includes 90 ° C. in the presence of urea. Has been reported to cause hydrolysis. (Non-patent Document 7) discloses a method for producing anatase-type titanium oxide by treating an aqueous solution of titanium (IV) bis (ammonium lactate) dihydroxide in a sealed tube at 120 ° C. for 24 hours. Yes. This titanium compound is preferably used in the present invention, but requires a long heating operation for the production of anatase-type titanium oxide.
また、同じチタン化合物を用いた、交互積層法による酸化チタンアナターゼ型酸化チタン膜の作製法が開示されている（非特許文献８）。この方法では、基材の上にカチオン性高分子の層を作り、これに、チタニウム（ＩＶ）ビス（アンモニウムラクテート）ジヒドロキシドを静電的に吸着させ、またカチオン性高分子、チタン化合物と、順次静電的に積層を繰り返してアモルファス膜を作製し、これを加熱処理してアナターゼ型酸化チタンを製造することが提示されている。
この方法で用いる物質の構成は、本発明と類似点があるが、カチオン性高分子とチタン化合物を、基材上に逐次積層しなければならないこと、アナターゼ型酸化チタンの製造に長時間の加熱処理を必要とする。
In addition, a method for producing a titanium oxide anatase-type titanium oxide film by an alternate lamination method using the same titanium compound is disclosed (Non-Patent Document 8). In this method, a layer of a cationic polymer is formed on a substrate, to which titanium (IV) bis (ammonium lactate) dihydroxide is electrostatically adsorbed, and a cationic polymer, a titanium compound, It has been proposed that an anatase-type titanium oxide is produced by sequentially repeating electrostatic lamination to produce an amorphous film and heat-treating it.
The composition of the substance used in this method is similar to that of the present invention, but the cationic polymer and the titanium compound must be sequentially laminated on the base material, and heating for a long time is required for the production of anatase type titanium oxide. Requires processing.
以上述べた様に、従来提案されてきたアナターゼ型酸化チタンの製造法は、反応条件を精密にコントロールしなければならず、また、高温での焼成や、長時間の処理を必要とする等の問題点があった。従って、より穏和な条件、より具体的には、加熱、加圧、積層工程等、反応条件の精密なコントロールを必要とせず、しかも処理に時間を要しないアナターゼ型酸化チタンの製造法が求められていた。 As described above, the anatase-type titanium oxide production method that has been proposed in the past requires precise control of the reaction conditions, and requires high-temperature firing and long-time treatment. There was a problem. Therefore, there is a need for a method for producing anatase-type titanium oxide that does not require milder conditions, more specifically, precise control of reaction conditions such as heating, pressurization, and lamination, and that does not require time for processing. It was.
本発明の解決しようとする課題は、穏和な条件において、より短時間で簡便にアナターゼ型酸化チタン結晶を製造する方法を提供することにある。 The problem to be solved by the present invention is to provide a method for easily producing anatase-type titanium oxide crystals in a shorter time under mild conditions.
本発明の上記課題は、親水性有機溶媒が含まれていてもよい水性媒体に、ポリアミンがプロトン化された状態で溶解した溶液（Ｘ）と、親水性有機溶媒が含まれていてもよい水性媒体に下記式（１） The object of the present invention is to provide a solution (X) in which a polyamine is dissolved in a protonated state in an aqueous medium that may contain a hydrophilic organic solvent, and an aqueous solution that may contain a hydrophilic organic solvent. The following formula (1)
又は、下記式（２）
Or the following formula (2)
で表されるチタン化合物が溶解した溶液（Ｙ）とを混合することにより達成される。
It achieves by mixing with the solution (Y) in which the titanium compound represented by this melt | dissolved.
本発明の製造方法によると、高温での処理や、雰囲気のコントロールなど、複雑な工程を必要とせず、２種類の水性媒体を、室温下で混合するだけで、アナターゼ型酸化チタン結晶を得ることができる。すなわち、本発明の製造方法は従来法に比べ、より簡便で、大量生産にも対応することが可能である。 According to the production method of the present invention, anatase-type titanium oxide crystals can be obtained by simply mixing two types of aqueous media at room temperature without requiring complicated processes such as high-temperature treatment and atmosphere control. Can do. That is, the production method of the present invention is simpler than the conventional method, and can cope with mass production.
また、本発明の製造方法においては、使用するポリアミンが、得られるアナターゼ型酸化チタン結晶中に包含されることから、溶媒への分散性や製膜性に優れたアナターゼ型酸化チタン結晶を得ることができる。 Further, in the production method of the present invention, since the polyamine to be used is included in the obtained anatase-type titanium oxide crystal, an anatase-type titanium oxide crystal excellent in dispersibility in a solvent and film forming property is obtained. Can do.
また、本発明の製造方法においては、ポリアミンがプロトン化された状態で溶解した溶液中のプロトン化されたポリアミンは、その対アニオンとして、各種対アニオンを取り得るため、対アニオンの有する機能や特性が付与されたアナターゼ型酸化チタン結晶が得られる。 Further, in the production method of the present invention, the protonated polyamine in the solution in which the polyamine is dissolved in a protonated state can take various counter anions as its counter anion. Anatase-type titanium oxide crystal to which is given is obtained.
本発明のアナターゼ型酸化チタン結晶の製造方法は、親水性有機溶媒が含まれていてもよい水性媒体に、ポリアミンがプロトン化された状態で溶解した溶液（Ｘ）と、親水性有機溶媒が含まれていてもよい水性媒体に、下記式（１） The method for producing anatase-type titanium oxide crystal of the present invention includes a solution (X) in which a polyamine is dissolved in a protonated state and a hydrophilic organic solvent in an aqueous medium which may contain a hydrophilic organic solvent. In the aqueous medium which may be prepared, the following formula (1)
又は、下記式（２）
Or the following formula (2)
で表されるチタン化合物が溶解した溶液（Ｙ）とを混合することでアナターゼ型酸化チタン結晶を得る方法である。
In this method, an anatase-type titanium oxide crystal is obtained by mixing a solution (Y) in which a titanium compound represented by formula (1) is dissolved.
本発明の製造方法によれば、温度や圧力、あるいは周囲の雰囲気等を精密に制御することなく、室温下で混合するだけで、アナターゼ型酸化チタン結晶を得ることが可能である。 According to the production method of the present invention, it is possible to obtain anatase-type titanium oxide crystals simply by mixing at room temperature without precisely controlling temperature, pressure, ambient atmosphere, or the like.
本発明において、アナターゼ型酸化チタン結晶が室温で形成される機構については明らかでないが、恐らくは、ポリアミンがプロトン化された状態で溶解した溶液（Ｘ）中のプロトン化されたポリアミンが、チタン化合物と静電的に引き合うことが重要であると考えられる。また、本発明で用いるプロトン化されたポリアミンは、一分子中に複数のアミンを有するので、チタン化合物を濃縮する効果があり、これがアナターゼ型酸化チタン結晶の生成に寄与すると考えられる。 In the present invention, the mechanism by which the anatase-type titanium oxide crystals are formed at room temperature is not clear, but the protonated polyamine in the solution (X) in which the polyamine is dissolved in a protonated state is probably combined with the titanium compound. It is considered important to attract electrostatically. Moreover, since the protonated polyamine used in the present invention has a plurality of amines in one molecule, it has an effect of concentrating the titanium compound, which is considered to contribute to the formation of anatase-type titanium oxide crystals.
本発明において用いる、親水性有機溶媒が含まれていてもよい水性媒体に、ポリアミンがプロトン化された状態で溶解した溶液（Ｘ）（以下、該溶液を単に溶液（Ｘ）と略記する。）中でプロトン化された状態となるポリアミンとしては、分子内に複数のアミン残基を有するものであれば良い。（本発明においては、分子中に複数のアミン残基を有するものをポリアミンと称する。）このようなポリアミンのなかでも、分子内に３以上のアミン残基を有する低分子又は高分子ポリアミンは、室温下で容易にアナターゼ型酸化チタン結晶を生成することができるため好ましい。 A solution (X) in which a polyamine is dissolved in a protonated state in an aqueous medium that may contain a hydrophilic organic solvent used in the present invention (hereinafter, the solution is simply referred to as a solution (X)). The polyamine that is in a protonated state may be any polyamine having a plurality of amine residues in the molecule. (In the present invention, those having a plurality of amine residues in the molecule are referred to as polyamines.) Among such polyamines, low-molecular or high-molecular polyamines having 3 or more amine residues in the molecule are: This is preferable because anatase-type titanium oxide crystals can be easily formed at room temperature.
上記の高分子ポリアミンの例としては、例えば、ポリエチレンイミン、ポリプロピレンイミン、ポリアリルアミン、ポリビニルアミン、ポリビニルピリジン、ポリリシン、ポリジメチルアミノエチルメタクリレート、ポリジメチルアミノアクリレート、キトサンの骨格が含まれるポリマーからなる群から選ばれる単独重合体または共重合体を取りあげることができる。 Examples of the polymer polyamine include, for example, a group consisting of a polymer containing a skeleton of polyethyleneimine, polypropyleneimine, polyallylamine, polyvinylamine, polyvinylpyridine, polylysine, polydimethylaminoethyl methacrylate, polydimethylaminoacrylate, and chitosan. Homopolymers or copolymers selected from can be taken up.
上記の低分子ポリアミンとしては、例えば、トリエチレンテトラミン、テトラエチレンペンタミン、スペルミジン、スペルミンなどを取りあげることができる。 Examples of the low molecular weight polyamine include triethylenetetramine, tetraethylenepentamine, spermidine, spermine and the like.
また、グリシン、アラニン、ロイシン、グルタミン、アスパラギン、リシン、アルギニンなどのアミノ酸残基の一種、もしくは複数種が、３以上結合したオリゴペプチド、またはポリペプチドの骨格が含まれる低分子・高分子化合物からなる群から選ばれる低分子・高分子化合物をあげることができる。 Also, from low molecular weight / high molecular weight compounds containing oligopeptides or polypeptide backbones of one or more amino acid residues such as glycine, alanine, leucine, glutamine, asparagine, lysine, arginine, etc. Examples thereof include low molecular and high molecular compounds selected from the group consisting of:
また、上記ポリアミンは、親水性有機溶媒が含まれていてもよい水性媒体中において、ポリアミン部分がプロトン化された状態で溶解していればよく、ポリアミンが基板や微粒子など、それ自身は水性媒体に溶解しない無機および有機基材の表面に結合されたものであっても良い。このようなポリアミンを用いると、アナターゼ型酸化チタン結晶で被覆された基板や微粒子を作製することが可能である。 The polyamine may be dissolved in a protonated state of the polyamine moiety in an aqueous medium that may contain a hydrophilic organic solvent. The polyamine itself is an aqueous medium such as a substrate or fine particles. It may be bonded to the surfaces of inorganic and organic base materials that do not dissolve in water. When such a polyamine is used, it is possible to produce a substrate or fine particles coated with anatase-type titanium oxide crystals.
また、上記ポリアミンは、親水性有機溶媒が含まれていてもよい水性媒体中において、ポリアミン部分がプロトン化された状態で溶解していればよいので、アルキル基やフェニル基などの疎水性の構造部分を有していもよく、また、アルキル基やフェニル基などの疎水性の構造部分を有する低分子、高分子と結合されたものを用いても良い。このような構造部分を有するものは、水性媒体中において分子が自己組織化し、ミセルなど特異な分子構造体を形成しやすく、この特異な構造を反映したアナターゼ型酸化チタン結晶の構造体を作製することもできる。 Further, the polyamine is only required to be dissolved in a protonated state in an aqueous medium that may contain a hydrophilic organic solvent, so that a hydrophobic structure such as an alkyl group or a phenyl group is used. It may have a moiety, and a low molecular weight or high molecular weight polymer having a hydrophobic structure such as an alkyl group or a phenyl group may be used. Those having such a structural part are easy to form a specific molecular structure such as a micelle by self-assembly of molecules in an aqueous medium, and a structure of anatase-type titanium oxide crystal reflecting this specific structure is produced. You can also.
通常、ポリアミンは、水性媒体中に若干プロトン化された状態で溶解しているが、酸を加えることによって、さらにプロトン化の割合を高めることができ、この溶液を本発明の溶液（Ｘ）として用いることができる。また、親水性有機溶媒が含まれていてもよい水性媒体中に、ポリアミンの塩を溶解することで、溶液（Ｘ）を得ることもできる。 Usually, the polyamine is dissolved in a slightly protonated state in an aqueous medium, but by adding an acid, the rate of protonation can be further increased, and this solution is used as the solution (X) of the present invention. Can be used. Moreover, the solution (X) can also be obtained by dissolving the salt of polyamine in an aqueous medium which may contain a hydrophilic organic solvent.
溶液（Ｘ）中には、プロトン化されたポリアミンの対アニオンが存在し、該対アニオンとしては、塩酸根、硫酸根、硝酸根、リン酸根、臭化水素酸根などの酸根、あるいは、［ＣｌＯ４］、［ＢＦ４］、［ＰＦ６］、［ＡｓＦ６］、［ＳｂＦ６］、［ＳｎＯ４］、［ＷＯ４］、［ＭｏＯ４］などの無機系の対アニオンが例として挙げられる。 In the solution (X), a protonated polyamine counteranion is present, and the counteranion includes an acid radical such as a hydrochloric acid radical, a sulfate radical, a nitrate radical, a phosphate radical, and a hydrobromide radical, or [ClO 4], [BF 4], [PF 6], [AsF 6], [SbF 6], [SnO 4], [WO 4], and the like as a counter anion example inorganic, such as [MoO 4].
また、対アニオンは無機系だけではなく、水溶性を有する有機系対アニオンも用いることができる。このような有機系対アニオンとしては、例えば、酢酸、トリフルオロ酢酸、安息香酸、フタロシアニンテトラスカルボン酸、ポルフィリンテトラカルボン酸などのカルボン酸の酸根、あるいはメチルスルホン酸、トリフルオロスルホン酸、トシル酸、フタロシアニンテトラスルホン酸、ポルフィリンテトラスルホン酸などのスルホン酸の酸根、エオシン、エリスロシン、ローズベンガルといったキサンテン系色素の色素アニオンなどの色素アニオンを好ましく使用できる。 The counter anion can be not only an inorganic type but also an organic type counter anion having water solubility. Examples of such organic counter anions include acid radicals of carboxylic acids such as acetic acid, trifluoroacetic acid, benzoic acid, phthalocyanine tetrascarboxylic acid, porphyrin tetracarboxylic acid, or methylsulfonic acid, trifluorosulfonic acid, and tosylic acid. A dye anion such as a dye anion of a sulfonic acid such as phthalocyanine tetrasulfonic acid or porphyrin tetrasulfonic acid, a xanthene dye such as eosin, erythrosine, or rose bengal can be preferably used.
これらの対アニオン、特に有機系酸根からなる対アニオンは酸化チタンと配位結合することにより、酸化チタンの表面に分子膜状態で存在しうるので、アナターゼ型酸化チタン結晶に多くの付加機能を付与することができる。 These counter anions, especially counter anions consisting of organic acid radicals, can be present in the form of molecular films on the surface of titanium oxide by coordinating with titanium oxide, giving many additional functions to anatase-type titanium oxide crystals. can do.
また、カルボン酸やスルホン酸類の酸根からなる有機系対アニオンのうち、重合性を持つものも好適に用いることができる。具体的には、アクリル酸、メタクリル酸、ビニルベンゼンスルホン酸などの重合性の酸根が例として挙げられる。これらの重合性の酸根は、得られる酸化チタンの表面に結合するため、それらを重合させることで、アナターゼ型酸化チタン結晶表面をポリマー膜で被覆することが可能となる。 Moreover, what has a polymeric property among the organic type | system | group anions which consist of an acid radical of carboxylic acid and sulfonic acids can also be used suitably. Specific examples include polymerizable acid radicals such as acrylic acid, methacrylic acid, and vinylbenzene sulfonic acid. Since these polymerizable acid radicals bind to the surface of the obtained titanium oxide, it is possible to coat the anatase-type titanium oxide crystal surface with a polymer film by polymerizing them.
色素アニオンを対アニオンとして用いる場合には、酸化チタンに色素の機能を付与することができ、可視光領域の吸収を示すので、光触媒や太陽電池として有用な酸化チタンを作製することができる。 In the case where a dye anion is used as a counter anion, the function of the dye can be imparted to titanium oxide, and absorption in the visible light region is exhibited, so that titanium oxide useful as a photocatalyst or a solar cell can be produced.
このように、本発明の製造方法においては、溶液（Ｘ）中のプロトン化されたポリアミンは、その対アニオンとして、各種機能や特性を有する対アニオンを取り得ることができることから、得られるアナターゼ型酸化チタン結晶に、これら対アニオンの有する機能や特性を付与することができる。 Thus, in the production method of the present invention, the protonated polyamine in the solution (X) can take counter anions having various functions and properties as the counter anion. Functions and characteristics of these counter anions can be imparted to the titanium oxide crystal.
上記ポリアミンの塩の形態としては、溶解してポリアミンがプロトン化されるものであれば特に制限されないが、塩酸塩、硫酸塩、硝酸塩、臭化水素酸塩又はリン酸塩のものを好ましく使用できる。また、イオン交換を行い、前記プロトン化されたポリアミンの対アニオンが、［ＣｌＯ４］−、［ＢＦ４］−、［ＰＦ６］−、［ＡｓＦ６］−、［ＳｂＦ６］−、［ＳｎＯ４］−、［ＷＯ４］−、あるいは［ＭｏＯ４］−のものを用いても良い。 The form of the polyamine salt is not particularly limited as long as it dissolves and the polyamine is protonated, but hydrochlorides, sulfates, nitrates, hydrobromides or phosphates can be preferably used. . Also, ion exchange is performed, and the counter anion of the protonated polyamine is [ClO 4 ] − , [BF 4 ] − , [PF 6 ] − , [AsF 6 ] − , [SbF 6 ] − , [SnO 4] -, [WO 4] -, or [MoO 4] - may also be used as.
上記ポリアミンの塩は、市販のものを用いても良いし、公知慣用の合成法により得られる低分子および高分子ポリアミンや生体から抽出されるポリプロピレンイミンのオリゴマーを、酸水溶液中でプロトン化させることによって、ポリアミンの塩を適宜調製してもよい。また、この塩をイオン交換することによって、種々の対アニオンとの組み合わせのものを利用できる。 Commercially available salts of the polyamine may be used, and low molecular and high molecular polyamines obtained by known and commonly used synthetic methods and polypropyleneimine oligomers extracted from living bodies are protonated in an acid aqueous solution. The salt of polyamine may be prepared as appropriate. Moreover, the combination with various counter anions can be utilized by ion-exchanging this salt.
本発明においてポリアミンは、溶液（Ｘ）中で全てのアミン残基が完全にプロトン化されている必要はなく、一部がプロトン化されない状態で存在しても良いが、低分子のポリアミンを使用する場合には、プロトン化されないアミン残基は少ない方がよい。プロトン化を促進するために加える酸の量は、ポリアミン分子中のアミン残基の数に応じて適宜選択すればよいが、アミン残基数の０．１〜２当量程度加えるのが良く、プロトン化されないアミン残基を少なくするためには、アミン残基数の１当量〜２当量程度の酸を加えるのが好ましい。 In the present invention, the polyamine does not need to be completely protonated in the solution (X), and may be present in a partially unprotonated state, but a low molecular polyamine is used. When doing so, it is better to have fewer amine residues that are not protonated. The amount of acid added to promote protonation may be appropriately selected according to the number of amine residues in the polyamine molecule, but it is preferable to add about 0.1 to 2 equivalents of the number of amine residues. In order to reduce the number of amine residues that are not converted, it is preferable to add an acid having about 1 to 2 equivalents of the number of amine residues.
本発明で用いるチタン化合物としては、上記式（１）もしくは式（２）で表される水溶性チタン化合物を好適に使用することができる。上記チタン化合物のなかでも、式（１）で表されるチタン化合物は、親水性有機溶媒が含まれていてもよい水性媒体中に溶解した際に、アニオン性を示すため、プロトン化されたポリアミンとの静電的相互作用が起こるので、特に好ましい。また、式（１）中のＲ１、Ｒ２が水素原子とメチル基との組み合わせである、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド、式（２）中のＲ３、Ｒ４が水素原子とメチル基との組み合わせである、チタニウム（ＩＶ）ビス（ラクテート）−ジヒドロキシドは安価に入手できることから、好適に用いることができる。このようなチタン化合物は、市販のものを用いても良いし、チタンアルコキシドとα−オキシカルボン酸とを反応させる方法（特開５８−１３４１６４）などにより合成して使用しても良い。 As a titanium compound used by this invention, the water-soluble titanium compound represented by the said Formula (1) or Formula (2) can be used conveniently. Among the above titanium compounds, the titanium compound represented by the formula (1) exhibits anionicity when dissolved in an aqueous medium which may contain a hydrophilic organic solvent, so that it is a protonated polyamine. Is particularly preferred because of the electrostatic interaction with the. In addition, R 1 and R 2 in the formula (1) are a combination of a hydrogen atom and a methyl group, titanium (IV) bis (ammonium lactate) -dihydroxide, and R 3 and R 4 in the formula (2) are Titanium (IV) bis (lactate) -dihydroxide, which is a combination of a hydrogen atom and a methyl group, can be suitably used because it can be obtained at low cost. As such a titanium compound, a commercially available product may be used, or it may be synthesized and used by a method of reacting titanium alkoxide with α-oxycarboxylic acid (Japanese Patent Laid-Open No. 58-134164).
本発明の一つの形態では、前記チタン化合物が溶解した溶液（Ｙ）に、前記酸化チタン化合物に加えて、さらに色素部分がアニオン性である色素を溶解した溶液を使用することもできる。色素部分がアニオン性である色素の例としては、エオシン、エリスロシン、ローズベンガル、フタロシアニンテトラスルホン酸ナトリウム、ポルフィリンテトラスルホン酸ナトリウムなどが好ましい例として挙げられる。また、コンゴーレッド、オレンジＩＩ、レーキレッドＣなど、一般に酸性染料と呼ばれる色素も好適に用いることができる。この方法では、色素が、プロトン化されたポリアミンとの静電相互作用によって、アナターゼ型酸化チタン結晶の形成と同時に取り込まれるので、色素の機能を持ったアナターゼ型酸化チタン結晶を製造することができる。溶解させる色素の量は、アナターゼ型酸化チタン結晶の形成を阻害しない量を適宜選択すればよいが、チタン化合物に対してモル比で２０％以下にするのがよい。 In one form of this invention, the solution (Y) in which the said titanium compound melt | dissolved can also use the solution which melt | dissolved the pigment | dye whose pigment part is anionic in addition to the said titanium oxide compound. Preferred examples of the dye having an anionic dye moiety include eosin, erythrosine, rose bengal, sodium phthalocyanine tetrasulfonate, sodium porphyrin tetrasulfonate, and the like. In addition, pigments generally called acid dyes such as Congo Red, Orange II, and Lake Red C can also be suitably used. In this method, since the dye is incorporated simultaneously with the formation of the anatase-type titanium oxide crystal by electrostatic interaction with the protonated polyamine, an anatase-type titanium oxide crystal having the function of a dye can be produced. . The amount of the dye to be dissolved may be appropriately selected as long as it does not inhibit the formation of anatase-type titanium oxide crystals, but it is preferably 20% or less in molar ratio with respect to the titanium compound.
本発明においては、上記したポリアミンの塩、及び上記式（１）又は（２）で表されるチタン化合物は、それぞれ親水性有機溶媒が含まれていてもよい水性媒体に溶解し、溶液（Ｘ）、及び溶液（Ｙ）として使用する。ここで親水性有機溶媒が含まれていてもよい水性媒体としては、水、あるいはメタノール、エタノール、２−プロパノール、などの有機アルコール類と水との混合溶媒などが例として挙げられる。 In the present invention, the above-mentioned polyamine salt and the titanium compound represented by the above formula (1) or (2) are dissolved in an aqueous medium which may contain a hydrophilic organic solvent, respectively, and the solution (X ) And solution (Y). Examples of the aqueous medium that may contain a hydrophilic organic solvent include water or a mixed solvent of water and an organic alcohol such as methanol, ethanol, 2-propanol, and the like.
本発明において、混合する溶液（Ｘ）、及び溶液（Ｙ）の２種類の溶液の濃度は、それぞれ０．１ｗｔ％〜５０ｗｔ％のものを好適に使用することができる。濃度が高すぎると生成するアナターゼ型酸化チタン結晶が凝集するおそれがあり、また濃度が低すぎる場合には生成したアナターゼ型酸化チタン結晶の捕集が困難である。より好適には、溶液（Ｘ）は０．２ｗｔ％〜２ｗｔ％、溶液（Ｙ）は、５〜３０ｗｔ％の濃度範囲のものを好適に使用することができる。この際、各溶液の混合量は、混合した溶液中でのポリアミンのアミン数と水溶性チタンの比が１：１０〜１０：１程度になるように調整するのが好ましく、凝集の抑制や捕集の簡便さから、より好適には１：５〜５：１程度にするのが良い。 In the present invention, the concentrations of the two types of solutions (X) and (Y) to be mixed can preferably be 0.1 wt% to 50 wt%, respectively. If the concentration is too high, the produced anatase-type titanium oxide crystals may aggregate, and if the concentration is too low, it is difficult to collect the produced anatase-type titanium oxide crystals. More preferably, the solution (X) having a concentration range of 0.2 wt% to 2 wt% and the solution (Y) having a concentration range of 5 to 30 wt% can be preferably used. At this time, the mixing amount of each solution is preferably adjusted so that the ratio of the amine number of the polyamine to the water-soluble titanium in the mixed solution is about 1:10 to 10: 1. From the convenience of collection, it is more preferable that the ratio is about 1: 5 to 5: 1.
本発明において、２種類の溶液の混合方法については特に制限はないが、生成したアナターゼ型酸化チタン結晶の凝集を抑制するために、一方の水溶液を攪拌しておき、これに他方の水溶液を徐々に滴下することが望ましい。 In the present invention, the mixing method of the two types of solutions is not particularly limited, but in order to suppress aggregation of the produced anatase-type titanium oxide crystals, one aqueous solution is stirred and the other aqueous solution is gradually added thereto. It is desirable to drop it into
本発明において、アナターゼ型酸化チタン結晶を生成する反応は滴下直後に起こるので、生成した酸化チタンをすぐに捕集しても良いが、さらに１０〜３０分程度攪拌を継続することにより、未反応のチタン化合物を減じることができる。特に用いるポリアミンの分子内アミン数が少ない低分子の場合には、より長い時間、攪拌を継続しても良い。 In the present invention, since the reaction for producing anatase-type titanium oxide crystals occurs immediately after the dropping, the produced titanium oxide may be collected immediately, but by further stirring for about 10 to 30 minutes, unreacted The titanium compound can be reduced. In particular, in the case of a low molecular weight polyamine having a small number of amines in the molecule, stirring may be continued for a longer time.
また、本発明において、アナターゼ型酸化チタン結晶を生成する反応は室温で可能であるが、５０℃程度に加温することで、さらに反応を促進することもできる。 In the present invention, the reaction for producing anatase-type titanium oxide crystals is possible at room temperature, but the reaction can be further promoted by heating to about 50 ° C.
上記方法により得られるアナターゼ型酸化チタン結晶は、良好な製膜性を有し、水洗によって、余剰のポリアミンの塩やチタン化合物を充分除去した後にも、透明フィルムを形成することができる。これは、上記方法により得られるアナターゼ型酸化チタン結晶が、ポリアミンを含有することに起因すると考えられる。 The anatase-type titanium oxide crystal obtained by the above method has a good film-forming property, and can form a transparent film even after sufficiently removing excess polyamine salts and titanium compounds by washing with water. This is considered to be caused by the fact that the anatase-type titanium oxide crystal obtained by the above method contains a polyamine.
また、上記方法により得られるアナターゼ型酸化チタン結晶は、水又は水と親水性有機溶媒の混合溶媒に、容易に再分散させることができ、種々のバインダーとの混合が可能である。これは、上記方法により得られるアナターゼ型酸化チタン結晶の表面に、原料のチタン化合物から生成した乳酸が配位して、酸化チタン表面を化学修飾したのと同様の効果を与えるためと考えられる。同様な原理であるが、有機酸根を対アニオンとして用いた場合、その有機酸根が酸化チタン表面に配位結合させることもできる。 In addition, the anatase-type titanium oxide crystal obtained by the above method can be easily redispersed in water or a mixed solvent of water and a hydrophilic organic solvent, and can be mixed with various binders. This is considered to be because the lactic acid produced from the raw material titanium compound is coordinated to the surface of the anatase-type titanium oxide crystal obtained by the above method, and the same effect as that obtained by chemically modifying the titanium oxide surface is given. Although it is the same principle, when an organic acid radical is used as a counter anion, the organic acid radical can be coordinated to the titanium oxide surface.
このようなアナターゼ型酸化チタン結晶は、その製膜性、分散性の良さから、加工性が高く、高屈折率の光学部品や化粧料、干渉顔料等へ応用が可能である。また、光触媒能を有する膜の形成や、太陽電池への応用も可能である。 Such anatase-type titanium oxide crystals have high processability due to their good film formability and dispersibility, and can be applied to high refractive index optical parts, cosmetics, interference pigments, and the like. In addition, it is possible to form a film having photocatalytic activity and to apply to a solar cell.
以下に実施例を示して本発明を詳細に記載する。
実施例、比較例における操作及び測定方法は下記の通りである。
（遠心分離）
日立工機社製の高速遠心器「ＨＩＭＡＣ ＳＣＲ２０ＢＢ」を使用して、各条件により遠心分離を行った。
（Ｘ線回折）
理学電機製の広角Ｘ線装置「Ｒｉｎｔ−Ｕｌｔｉｍａ＋」を使用して、各実施例で得られた粉末のＸ線回折測定を行った。
（ＩＲスペクトル）
日本分光工業（株）製の赤外分光装置「Ｍｉｃｒｏ ＦＴ−ＩＲ―１００」に、ＺｎＳｅ製の全反射セルをセットして、粉末表面のＩＲスペクトルを測定した。
Hereinafter, the present invention will be described in detail with reference to examples.
The operations and measurement methods in Examples and Comparative Examples are as follows.
(Centrifuge)
Using a high-speed centrifuge “HIMAC SCR20BB” manufactured by Hitachi Koki Co., Ltd., centrifugation was performed according to each condition.
(X-ray diffraction)
Using a wide-angle X-ray apparatus “Rint-Ultima +” manufactured by Rigaku Corporation, X-ray diffraction measurement of the powder obtained in each example was performed.
(IR spectrum)
A total reflection cell made of ZnSe was set in an infrared spectrometer “Micro FT-IR-100” manufactured by JASCO Corporation, and the IR spectrum of the powder surface was measured.
（実施例１）
５Ｍの塩酸水溶液に、ポリ（２−エチル−２−オキサゾリン）（アルドリッチ社製、分子量５００００）を、オキサゾリンのモノマー単位に対して、モル比で塩酸が３倍量となるように加え、９時間攪拌を行うことにより、白色の沈殿物を得た。この沈殿物をろ別、乾燥することにより、線状ポリエチレンイミン塩酸塩の白色粉末を得た。この線状ポリエチレンイミンの塩酸塩１００ｍｇを水１０ｍｌに溶解した水溶液（Ｘ１）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を２倍に希釈した水溶液（Ｙ１）を調製し、攪拌した水溶液（Ｘ１）１０ｍｌに水溶液（Ｙ１）を５ｍｌ滴下したところ、（Ｙ１）の滴下直後から液が白濁した。（Ｙ１）の滴下後、さらに１０分間攪拌を継続した。
Example 1
Poly (2-ethyl-2-oxazoline) (manufactured by Aldrich, molecular weight 50000) was added to a 5M hydrochloric acid aqueous solution so that the molar ratio of hydrochloric acid was 3 times that of the monomer unit of oxazoline, and 9 hours By stirring, a white precipitate was obtained. The precipitate was filtered and dried to obtain a white powder of linear polyethyleneimine hydrochloride. An aqueous solution (X1) obtained by dissolving 100 mg of this linear polyethyleneimine hydrochloride in 10 ml of water and an aqueous solution obtained by diluting a titanium (IV) bis (ammonium lactate) -dihydroxide aqueous solution (manufactured by Aldrich, 50 wt%) twice ( Y1) was prepared, and 5 ml of the aqueous solution (Y1) was dropped into 10 ml of the stirred aqueous solution (X1). As a result, the solution became cloudy immediately after the dropwise addition of (Y1). After the dropwise addition of (Y1), stirring was continued for another 10 minutes.
この液に水を加えて５０ｍｌにし、６０００ｒｐｍ、３０分間の遠心分離を行ったところ、遠沈管底部に白色の沈殿物が得られた。この沈殿物を再度５０ｍｌの水に分散して遠心分離する操作を２回繰返し、未反応のチタン化合物を除去した。得られた沈殿物を真空乾燥したところ、４３０ｍｇの白色粉末を得た。得られた粉末のＸ線回折を測定したところ、アナターゼ型酸化チタン結晶に由来する回折ピークが確認された。 Water was added to this solution to make 50 ml, and centrifugation was performed at 6000 rpm for 30 minutes. As a result, a white precipitate was obtained at the bottom of the centrifuge tube. The operation of dispersing the precipitate again in 50 ml of water and centrifuging was repeated twice to remove the unreacted titanium compound. The obtained precipitate was vacuum-dried to obtain 430 mg of white powder. When X-ray diffraction of the obtained powder was measured, a diffraction peak derived from anatase-type titanium oxide crystals was confirmed.
（実施例２）
実施例１と同様にして得た、線状ポリエチレンイミンの塩酸塩５０ｍｇを水１０ｍｌに溶解した水溶液（Ｘ２）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を２倍に希釈した水溶液（Ｙ２）を調製し、攪拌した水溶液（Ｘ２）１０ｍｌに水溶液（Ｙ２）を１ｍｌ滴下したところ、（Ｙ２）の滴下直後から液が白濁した。（Ｙ２）の滴下後、さらに１０分間攪拌を継続した。
(Example 2)
An aqueous solution (X2) obtained by dissolving 50 mg of linear polyethyleneimine hydrochloride in 10 ml of water and an aqueous solution of titanium (IV) bis (ammonium lactate) -dihydroxide (manufactured by Aldrich, 50 wt%) obtained in the same manner as in Example 1. An aqueous solution (Y2) in which the aqueous solution (Y2) was diluted 2 times was prepared, and 1 ml of the aqueous solution (Y2) was dropped into 10 ml of the stirred aqueous solution (X2), and the liquid became cloudy immediately after the dropwise addition of (Y2). After the dropwise addition of (Y2), stirring was continued for another 10 minutes.
この液に水を加えて５０ｍｌにし、６０００ｒｐｍ、３０分間の遠心分離を行ったところ、遠沈管底部に白色の沈殿物が得られた。この沈殿物を再度５０ｍｌの水に分散して遠心分離する操作を２回繰返し、未反応のチタン化合物を除去した。この沈殿物を真空乾燥したところ、薄黄色透明のフィルム状の固形物８３ｍｇを得た。このフィルム状塊を粉砕し、得られた粉末表面のＩＲスペクトルを測定したところ、１６２０ｃｍ−１付近にピークが認められた。これは、Ｔａｄａｓｈｉ Ａｗａｔａｎｉ、他４名、ケミストリーレターズ、１９９８年、ｐ．８４９−８５０に記載があるように、ＴｉＯ２上に配位結合した乳酸に由来するピークと帰属される（図１参照）。得られた粉末のＸ線回折を測定したところ、アナターゼ型酸化チタン結晶に由来する回折ピークが確認された（図２（ａ）参照）。 Water was added to this solution to make 50 ml, and centrifugation was performed at 6000 rpm for 30 minutes. As a result, a white precipitate was obtained at the bottom of the centrifuge tube. The operation of dispersing the precipitate again in 50 ml of water and centrifuging was repeated twice to remove the unreacted titanium compound. When this precipitate was vacuum-dried, 83 mg of a light yellow transparent film-like solid was obtained. When this film-like lump was pulverized and the IR spectrum of the obtained powder surface was measured, a peak was observed in the vicinity of 1620 cm −1 . Tadashi Awatani, 4 others, Chemistry Letters, 1998, p. As described in 849-850, it is attributed to a peak derived from lactic acid coordinated on TiO 2 (see FIG. 1). When X-ray diffraction of the obtained powder was measured, a diffraction peak derived from anatase-type titanium oxide crystals was confirmed (see FIG. 2A).
（比較例１）
実施例１と同様にして得た、線状ポリエチレンイミンの塩酸塩を２５ｗｔ％のアンモニア水に加えてｐＨ７にすることで透明な液を得、透析により水洗を行うことにより、白色の沈殿を得た。この沈殿をろ別した後、アセトンで洗浄し、自然乾燥した。さらに、４０℃で１２時間乾燥を行い、水分を１５〜２０ｗｔ％含有する中性線状ポリエチレンイミンの白色固体を得た。この中性の線状ポリエチレンイミン１３ｍｇを水１０ｍｌに溶解した水溶液（Ｈ１）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を２倍に希釈した水溶液（Ｈ２）を調製し、８０℃において、攪拌した水溶液（Ｈ１）１０ｍｌに水溶液（Ｈ２）を１ｍｌ滴下したが、液は無色透明のままであった。その後、室温での静置１月経過後も液は無色透明のままであった。
(Comparative Example 1)
A transparent solution is obtained by adding linear polyethyleneimine hydrochloride obtained in the same manner as in Example 1 to 25 wt% aqueous ammonia to adjust the pH to 7, and washed with water by dialysis to obtain a white precipitate. It was. The precipitate was filtered off, washed with acetone and air dried. Furthermore, it dried at 40 degreeC for 12 hours, and obtained the white solid of neutral linear polyethyleneimine containing 15-20 wt% of water | moisture contents. An aqueous solution (H1) obtained by dissolving 13 mg of this neutral linear polyethyleneimine in 10 ml of water and an aqueous solution obtained by diluting a titanium (IV) bis (ammonium lactate) -dihydroxide aqueous solution (Aldrich, 50 wt%) twice ( 1 ml of the aqueous solution (H2) was added dropwise to 10 ml of the stirred aqueous solution (H1) at 80 ° C., but the solution remained colorless and transparent. Thereafter, the liquid remained colorless and transparent even after one month of standing at room temperature.
（実施例３）
５Ｍの塩酸水溶液に、エチレンイミン単位が塩酸に対して１．５倍量となるように、分岐状ポリエチレンイミン（アルドリッチ社製）を加え、一日攪拌することにより、分岐状ポリエチレンイミンの塩酸塩を得た。この分岐状ポリエチレンイミンの塩酸塩５０ｍｇを水１０ｍｌに溶解した水溶液（Ｘ３）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を４倍に希釈した水溶液（Ｙ３）を調製し、攪拌した水溶液（Ｘ３）１０ｍｌに水溶液（Ｙ３）を１ｍｌ滴下したところ、（Ｙ３）の滴下直後から液が白濁した。（Ｙ３）の滴下後、さらに１０分間攪拌を継続した。
Example 3
Branched polyethyleneimine hydrochloride is added to a 5M aqueous hydrochloric acid solution by adding branched polyethyleneimine (manufactured by Aldrich) so that the ethyleneimine unit is 1.5 times the amount of hydrochloric acid and stirring for one day. Got. An aqueous solution (X3) obtained by dissolving 50 mg of this branched polyethyleneimine hydrochloride in 10 ml of water and an aqueous solution obtained by diluting the titanium (IV) bis (ammonium lactate) -dihydroxide aqueous solution (manufactured by Aldrich, 50 wt%) four times ( Y3) was prepared, and 1 ml of the aqueous solution (Y3) was added dropwise to 10 ml of the stirred aqueous solution (X3). As a result, the solution became cloudy immediately after the addition of (Y3). After the dropwise addition of (Y3), stirring was continued for another 10 minutes.
この液に水を加えて５０ｍｌにし、６０００ｒｐｍ、３０分間の遠心分離を行ったところ、遠沈管底部に白色の沈殿物が得られた。この沈殿物を再度５０ｍｌの水に分散して遠心分離する操作を２回繰返し、未反応のチタン化合物を除去した。この沈殿物を真空乾燥したところ、８４ｍｇの白色粉末を得た。得られた粉末の粉末Ｘ線回折を測定したところ、アナターゼ型酸化チタン結晶に由来する回折ピークが確認された（図２（ｂ）参照）。 Water was added to this solution to make 50 ml, and centrifugation was performed at 6000 rpm for 30 minutes. As a result, a white precipitate was obtained at the bottom of the centrifuge tube. The operation of dispersing the precipitate again in 50 ml of water and centrifuging was repeated twice to remove the unreacted titanium compound. This precipitate was vacuum-dried to obtain 84 mg of white powder. When the powder X-ray diffraction of the obtained powder was measured, a diffraction peak derived from the anatase-type titanium oxide crystal was confirmed (see FIG. 2B).
（実施例４）
ポリアリルアミンの塩酸塩（アルドリッチ社製）４０ｍｇを水１０ｍｌに溶解した水溶液（Ｘ４）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を２倍に希釈した水溶液（Ｙ４）を調製し、攪拌した水溶液（Ｘ４）１０ｍｌに水溶液（Ｙ４）を１ｍｌ滴下したところ、（Ｙ４）の滴下直後から液が白濁した。（Ｙ４）の滴下後、さらに１０分間攪拌を継続した。
(Example 4)
An aqueous solution (X4) obtained by dissolving 40 mg of polyallylamine hydrochloride (manufactured by Aldrich) in 10 ml of water and an aqueous solution of titanium (IV) bis (ammonium lactate) -dihydroxide (manufactured by Aldrich, 50 wt%) were diluted twice. When an aqueous solution (Y4) was prepared and 1 ml of the aqueous solution (Y4) was dropped into 10 ml of the stirred aqueous solution (X4), the solution became cloudy immediately after the dropwise addition of (Y4). After the dropwise addition of (Y4), stirring was continued for another 10 minutes.
この液に水を加えて５０ｍｌにし、６０００ｒｐｍ、３０分間の遠心分離を行ったところ、遠沈管底部に白色の沈殿物が得られた。この沈殿物を再度５０ｍｌの水に分散して遠心分離する操作を２回繰返し、未反応のチタン化合物を除去した。この沈殿物を真空乾燥したところ、薄黄色透明のフィルム状の固形物５４ｍｇを得た。このフィルム状の固形物を粉砕し、得られた粉末のＸ線回折を測定したところ、アナターゼ型酸化チタン結晶に由来する回折ピークが確認された（図２（ｃ）参照）。 Water was added to this solution to make 50 ml, and centrifugation was performed at 6000 rpm for 30 minutes. As a result, a white precipitate was obtained at the bottom of the centrifuge tube. The operation of dispersing the precipitate again in 50 ml of water and centrifuging was repeated twice to remove the unreacted titanium compound. When this precipitate was vacuum-dried, 54 mg of a light yellow transparent film-like solid was obtained. When this film-form solid was pulverized and the X-ray diffraction of the obtained powder was measured, a diffraction peak derived from anatase-type titanium oxide crystals was confirmed (see FIG. 2 (c)).
（実施例５）
トリエチレンテトラミン四塩酸塩（東京化成社製）６３ｍｇを水１０ｍｌに溶解した水溶液（Ｘ５）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を２倍に希釈した水溶液（Ｙ５）を調製し、攪拌した水溶液（Ｘ５）１０ｍｌに水溶液（Ｙ５）を１ｍｌ滴下したところ、（Ｙ５）の滴下直後から液が白濁した。（Ｙ５）の滴下後、さらに１０分間攪拌を継続した。
(Example 5)
Double an aqueous solution (X5) obtained by dissolving 63 mg of triethylenetetramine tetrahydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 ml of water and an aqueous solution of titanium (IV) bis (ammonium lactate) -dihydroxide (manufactured by Aldrich, 50 wt%). A diluted aqueous solution (Y5) was prepared, and when 1 ml of the aqueous solution (Y5) was dropped into 10 ml of the stirred aqueous solution (X5), the solution became cloudy immediately after the dropwise addition of (Y5). After the dropwise addition of (Y5), stirring was continued for another 10 minutes.
この液に水を加えて５０ｍｌにし、６０００ｒｐｍ、３０分間の遠心分離を行ったところ、遠沈管底部に白色の沈殿物が得られた。この沈殿物を再度５０ｍｌの水に分散して遠心分離する操作を２回繰返し、未反応のチタン化合物を除去した。この沈殿物を真空乾燥したところ、薄黄色透明のフィルム状の固形物１３ｍｇを得た。このフィルム状の固形物を粉砕し、得られた粉末のＸ線回折を測定したところ、アナターゼ型酸化チタン結晶に由来する回折ピークが確認された（図３（ｄ）参照）。 Water was added to this solution to make 50 ml, and centrifugation was performed at 6000 rpm for 30 minutes. As a result, a white precipitate was obtained at the bottom of the centrifuge tube. The operation of dispersing the precipitate again in 50 ml of water and centrifuging was repeated twice to remove the unreacted titanium compound. When this precipitate was vacuum-dried, 13 mg of a light yellow transparent film-like solid was obtained. When this film-like solid was pulverized and the X-ray diffraction of the obtained powder was measured, a diffraction peak derived from anatase-type titanium oxide crystals was confirmed (see FIG. 3 (d)).
（実施例６）
テトラエチレンペンタミン五塩酸塩（アルドリッチ社製）６４ｍｇを水１０ｍｌに溶解した水溶液（Ｘ６）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を２倍に希釈した水溶液（Ｙ６）を調製し、攪拌した水溶液（Ｘ６）１０ｍｌに水溶液（Ｙ６）を１ｍｌ滴下したところ、（Ｙ６）の滴下直後から液が白濁した。（Ｙ６）の滴下後、さらに１０分間攪拌を継続した。
(Example 6)
Double an aqueous solution (X6) obtained by dissolving 64 mg of tetraethylenepentamine pentahydrochloride (manufactured by Aldrich) in 10 ml of water and an aqueous solution of titanium (IV) bis (ammonium lactate) -dihydroxide (manufactured by Aldrich, 50 wt%). A diluted aqueous solution (Y6) was prepared, and when 1 ml of the aqueous solution (Y6) was dropped into 10 ml of the stirred aqueous solution (X6), the solution became cloudy immediately after the dropwise addition of (Y6). After dropwise addition of (Y6), stirring was continued for another 10 minutes.
この液に水を加えて５０ｍｌにし、６０００ｒｐｍ、３０分間の遠心分離を行ったところ、遠沈管底部に白色の沈殿物が得られた。この沈殿物を再度５０ｍｌの水に分散して遠心分離する操作を２回繰返し、未反応のチタン化合物を除去した。この沈殿物を真空乾燥したところ、薄黄色透明のフィルム状の固形物３３ｍｇを得た。このフィルム状の固形物を粉砕し、得られた粉末のＸ線回折を測定したところ、アナターゼ型酸化チタン結晶に由来する回折ピークが確認された（図３（ｅ）参照）。 Water was added to this solution to make 50 ml, and centrifugation was performed at 6000 rpm for 30 minutes. As a result, a white precipitate was obtained at the bottom of the centrifuge tube. The operation of dispersing the precipitate again in 50 ml of water and centrifuging was repeated twice to remove the unreacted titanium compound. When this precipitate was vacuum-dried, 33 mg of a light yellow transparent film-like solid was obtained. When this film-like solid was pulverized and the X-ray diffraction of the obtained powder was measured, a diffraction peak derived from anatase-type titanium oxide crystals was confirmed (see FIG. 3 (e)).
（実施例７）
スペルミン四塩酸塩（シグマ社製）２５０ｍｇを水１０ｍｌに溶解した水溶液（Ｘ７）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を２倍に希釈した水溶液（Ｙ７）を調製し、攪拌した水溶液（Ｘ７）１０ｍｌに水溶液（Ｙ７）を１ｍｌ滴下したところ、（Ｙ７）の滴下直後から液が白濁した。（Ｙ７）の滴下後、さらに１０分間攪拌を継続した。
(Example 7)
An aqueous solution (X7) obtained by dissolving 250 mg of spermine tetrahydrochloride (manufactured by Sigma) in 10 ml of water and an aqueous solution obtained by diluting a titanium (IV) bis (ammonium lactate) -dihydroxide aqueous solution (manufactured by Aldrich, 50 wt%) twice. When (Y7) was prepared and 1 ml of the aqueous solution (Y7) was dropped into 10 ml of the stirred aqueous solution (X7), the solution became cloudy immediately after the dropwise addition of (Y7). After dropping (Y7), stirring was continued for another 10 minutes.
この液に水を加えて５０ｍｌにし、６０００ｒｐｍ、３０分間の遠心分離を行ったところ、遠沈管底部に白色の沈殿物が得られた。この沈殿物を再度５０ｍｌの水に分散して遠心分離する操作を２回繰返し、未反応のチタン化合物を除去した。この沈殿物を真空乾燥したところ、薄黄色透明のフィルム状の固形物６７ｍｇを得た。このフィルム状の固形物を粉砕し、得られた粉末のＸ線回折を測定したところ、アナターゼ型酸化チタン結晶に由来する回折ピークが確認された（図３（ｆ）参照）。 Water was added to this solution to make 50 ml, and centrifugation was performed at 6000 rpm for 30 minutes. As a result, a white precipitate was obtained at the bottom of the centrifuge tube. The operation of dispersing the precipitate again in 50 ml of water and centrifuging was repeated twice to remove the unreacted titanium compound. When this precipitate was vacuum-dried, 67 mg of a light yellow transparent film-like solid was obtained. When this film-like solid was pulverized and the X-ray diffraction of the obtained powder was measured, a diffraction peak derived from anatase-type titanium oxide crystals was confirmed (see FIG. 3F).
（実施例８）
実施例１と同様にして得た、線状ポリエチレンイミンの塩酸塩５０ｍｇを水１０ｍｌに溶解した水溶液（Ｘ８）と、チタニウム（ＩＶ）ビス（アンモニウムラクテート）−ジヒドロキシド水溶液（アルドリッチ社製、５０ｗｔ％）を２倍に希釈した水溶液（Ｙ８）中に、さらにローズベンガル３．８ｍｇを溶解した水溶液（Ｚ８）を調製し、攪拌した水溶液（Ｘ８）１０ｍｌに水溶液（Ｚ８）を１ｍｌ滴下したところ、（Ｚ８）の滴下直後から液が懸濁した。（Ｚ８）の滴下後、さらに１０分間攪拌を継続した。
(Example 8)
An aqueous solution (X8) obtained by dissolving 50 mg of linear polyethyleneimine hydrochloride in 10 ml of water obtained in the same manner as in Example 1, and an aqueous solution of titanium (IV) bis (ammonium lactate) -dihydroxide (Aldrich, 50 wt%) An aqueous solution (Z8) in which 3.8 mg of rose bengal was further dissolved in an aqueous solution (Y8) diluted twice, and 1 ml of the aqueous solution (Z8) was added dropwise to 10 ml of the stirred aqueous solution (X8). The liquid was suspended immediately after the addition of Z8). After the dropwise addition of (Z8), stirring was continued for another 10 minutes.
この液に水を加えて５０ｍｌにし、６０００ｒｐｍ、３０分間の遠心分離を行ったところ、遠沈管底部に赤色の沈殿物が得られた。この沈殿物を再度５０ｍｌの水に分散して遠心分離する操作を２回繰返し、未反応のチタン化合物を除去した。この沈殿物を真空乾燥したところ、赤色透明のフィルム状の固形物３８ｍｇを得た。得られた粉末のＸ線回折を測定したところ、色素を加えない場合と同様に、アナターゼ型酸化チタン結晶に由来する回折ピークが確認された。 Water was added to this solution to make 50 ml, and centrifugation was performed at 6000 rpm for 30 minutes. As a result, a red precipitate was obtained at the bottom of the centrifuge tube. The operation of dispersing the precipitate again in 50 ml of water and centrifuging was repeated twice to remove the unreacted titanium compound. When this precipitate was vacuum-dried, 38 mg of a red transparent film-like solid was obtained. When the X-ray diffraction of the obtained powder was measured, the diffraction peak derived from the anatase type titanium oxide crystal was confirmed like the case where a pigment | dye was not added.
Claims (12)
又は、下記式（２）
で表されるチタン化合物が溶解した溶液（Ｙ）とを混合することを特徴とするアナターゼ型酸化チタン結晶の製造方法。 A solution (X) in which a polyamine is dissolved in a protonated state in an aqueous medium which may contain a hydrophilic organic solvent, and an aqueous medium which may contain a hydrophilic organic solvent have the following formula (1)
Or the following formula (2)
And a solution (Y) in which a titanium compound represented by the formula (1) is dissolved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004099042A JP4446776B2 (en) | 2004-03-30 | 2004-03-30 | Method for producing anatase type titanium oxide crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004099042A JP4446776B2 (en) | 2004-03-30 | 2004-03-30 | Method for producing anatase type titanium oxide crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005281080A JP2005281080A (en) | 2005-10-13 |
| JP4446776B2 true JP4446776B2 (en) | 2010-04-07 |
Family
ID=35179864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004099042A Expired - Fee Related JP4446776B2 (en) | 2004-03-30 | 2004-03-30 | Method for producing anatase type titanium oxide crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4446776B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012193048A (en) * | 2011-03-14 | 2012-10-11 | Itec Co Ltd | Method for producing titanium oxide fine particle, and titanium oxide fine particle produced by the production method |
| JP5871317B2 (en) * | 2012-03-15 | 2016-03-01 | 国立大学法人信州大学 | Cosmetic composition and method for producing the same |
| JP6015224B2 (en) * | 2012-08-09 | 2016-10-26 | Dic株式会社 | Method for producing metal oxide nanostructure |
| JP7679616B2 (en) * | 2020-11-10 | 2025-05-20 | Dic株式会社 | Paint and articles coated with said paint |
| JP7679615B2 (en) * | 2020-11-10 | 2025-05-20 | Dic株式会社 | Water-based paint and article coated with said water-based paint |
-
2004
- 2004-03-30 JP JP2004099042A patent/JP4446776B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005281080A (en) | 2005-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sanchez et al. | Design of functional nano-structured materials through the use of controlled hybrid organic–inorganic interfaces | |
| Naghibi et al. | Application of the statistical Taguchi method to optimize TiO2 nanoparticles synthesis by the hydrothermal assisted sol–gel technique | |
| CN102216221B (en) | Titanium oxide sol manufacturing method | |
| US8017542B2 (en) | Method for production of doped titanium oxide, doped titanium oxide, and visible light-responsive photocatalyst comprising the doped titanium oxide | |
| JP4704515B2 (en) | Rutile type titanium oxide crystal and mid-infrared filter using the same | |
| CN100509149C (en) | Method for preparing porous bismuth titanate photocatalyst | |
| JPWO2011135974A1 (en) | Infrared absorbing thin film containing rutile type titanium oxide crystal and method for producing the same | |
| US20090005238A1 (en) | Modified Nanostructured Titania Materials and Methods of Manufacture | |
| CN104903242B (en) | The manufacture method of chiral metal oxide structure body and chiral cell structure | |
| Łabuz et al. | Visible light photoactive titanium dioxide aqueous colloids and coatings | |
| JP2003137549A (en) | Method for producing tubular titanium oxide particles and tubular titanium oxide particles | |
| Kimizuka | Self-assembly of supramolecular nanofibers | |
| JP4446776B2 (en) | Method for producing anatase type titanium oxide crystal | |
| Galkina et al. | Surfactant‐assisted sol‐gel synthesis of TiO2 with uniform particle size distribution | |
| CN1067911A (en) | Preparation | |
| JP2000335919A (en) | Method for producing titanium oxide fine particles containing brookite-type crystals | |
| JP6015224B2 (en) | Method for producing metal oxide nanostructure | |
| JP4226016B2 (en) | Monodispersed silica fine particles containing polyamine and method for producing the same | |
| CN109674670B (en) | A kind of manganese oxide nano-cluster and its preparation method and application | |
| CN1235677C (en) | Aqueous colloidal dispersion based on at least one metal compound and complexing agent, preparation method and use | |
| JP3978443B2 (en) | Silica / metal complex composite material and method for producing the same | |
| JP4101271B2 (en) | Acicular surface fine particles and method for producing the same | |
| Shiba et al. | Synthesis of cytocompatible luminescent titania/fluorescein hybrid nanoparticles | |
| JP5038636B2 (en) | Titanium oxide / polymer composite and method for producing the same | |
| JP7391328B2 (en) | Method for producing chiral metal oxide structures, and block copolymers, chiral complexes, and chiral metal oxide complexes suitable therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070226 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20070226 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070404 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090724 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090728 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090826 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100114 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100119 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130129 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130129 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140129 Year of fee payment: 4 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |