JP4800914B2 - Method for producing metal oxide film - Google Patents
Method for producing metal oxide film Download PDFInfo
- Publication number
- JP4800914B2 JP4800914B2 JP2006325012A JP2006325012A JP4800914B2 JP 4800914 B2 JP4800914 B2 JP 4800914B2 JP 2006325012 A JP2006325012 A JP 2006325012A JP 2006325012 A JP2006325012 A JP 2006325012A JP 4800914 B2 JP4800914 B2 JP 4800914B2
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- metal
- raw material
- oxide film
- producing
- 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.)
- Active
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 95
- 150000004706 metal oxides Chemical class 0.000 title claims description 95
- 238000004519 manufacturing process Methods 0.000 title claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000002994 raw material Substances 0.000 claims description 48
- 238000000576 coating method Methods 0.000 claims description 36
- 238000006460 hydrolysis reaction Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 34
- 230000007062 hydrolysis Effects 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 239000010419 fine particle Substances 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 150000002736 metal compounds Chemical class 0.000 claims description 23
- 238000009835 boiling Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 150000004696 coordination complex Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 125000005594 diketone group Chemical group 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011358 absorbing material Substances 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 56
- 239000000243 solution Substances 0.000 description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 14
- 239000002609 medium Substances 0.000 description 14
- 239000011941 photocatalyst Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- 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 10
- 239000002245 particle Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- OHTQAXHNTFKKJM-UHFFFAOYSA-N zinc dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] OHTQAXHNTFKKJM-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000003779 heat-resistant material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical class 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C01G23/047—Titanium dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- 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
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は金属酸化物の合成において、高温での加熱焼成処理を行うことなく、結晶化した酸化物粉体や酸化物膜を製造することのできる、金属酸化物膜の製造方法に関するものである。
The present invention relates to a method for producing a metal oxide film, which is capable of producing a crystallized oxide powder or oxide film without performing a baking process at a high temperature in the synthesis of a metal oxide. .
従来より金属酸化物は、顔料、光学材料、電子材料、触媒、触媒担体、吸着剤、薄膜材料など、各産業分野において機能性材料として幅広く用いられており、これら機能性金属酸化物の特性は、結晶構造、粒子サイズ、表面特性、あるいは構造欠陥等、種々の物性により左右される。 Conventionally, metal oxides have been widely used as functional materials in various industrial fields such as pigments, optical materials, electronic materials, catalysts, catalyst carriers, adsorbents, thin film materials, and the characteristics of these functional metal oxides are It depends on various physical properties such as crystal structure, particle size, surface characteristics, or structural defects.
たとえば、光触媒材料として知られる酸化チタンの場合、高い光触媒活性を得るためには、紫外線照射の際に発生した電子とホールの再結合を抑制する必要がある。よって、結晶性を向上させるために、最終的には３００℃以上の温度で加熱処理を施す必要がある。 For example, in the case of titanium oxide known as a photocatalytic material, in order to obtain high photocatalytic activity, it is necessary to suppress recombination of electrons and holes generated during ultraviolet irradiation. Therefore, in order to improve crystallinity, it is necessary to finally perform heat treatment at a temperature of 300 ° C. or higher.
しかし、高温で処理することによって、得られる酸化チタン結晶の表面積が低下し、触媒としての吸着能が低下するというデメリットがあるため、過度の高温で処理する方法は光触媒材料の製法としては好ましくないといえる。 However, the treatment at a high temperature has the disadvantage that the surface area of the resulting titanium oxide crystal is reduced and the adsorptivity as a catalyst is lowered. Therefore, the treatment at an excessively high temperature is not preferable as a method for producing a photocatalytic material. It can be said.
一方、酸化チタン光触媒において高い表面積を維持するために３００℃以下の低温で焼成した場合は、結晶化しないかまたは結晶性が悪くなり、原料由来の有機物や無機イオンが結晶内に残存する場合が多くなる。これらはいずれも、電子とホールの再結合に寄与することとなるため、量子効率が低下し、その結果、光触媒活性が低下するという問題がある。このような課題に対し、従来、低温結晶化のための様々な検討が行われてはいる。 On the other hand, if the titanium oxide photocatalyst is fired at a low temperature of 300 ° C. or lower in order to maintain a high surface area, it may not crystallize or crystallinity may deteriorate, and organic materials and inorganic ions derived from the raw material may remain in the crystal. Become more. All of these contribute to the recombination of electrons and holes, resulting in a problem that the quantum efficiency is lowered, and as a result, the photocatalytic activity is lowered. Conventionally, various studies for low-temperature crystallization have been performed for such problems.
たとえば、焼成過程を含まずに結晶化したナノ微粒子を作成する方法としては水熱合成法が挙げられるが、原料を１００℃以上の温度および大気圧（１．０１＊１０５Ｐａ）以上の高圧下で反応させる特殊反応場が必要となるため、コスト面からも設備面からも、大量生産には好ましくない。
For example, a hydrothermal synthesis method can be cited as a method for producing crystallized nanoparticles without including a firing process. The raw material is heated at a temperature of 100 ° C. or higher and at a high pressure of atmospheric pressure (1.01 * 105 Pa) or higher. Since a special reaction field for reaction is required, it is not preferable for mass production from the viewpoint of cost and equipment.
また、従来、焼成工程を含まず液相中における反応のみで、金属酸化物粒子を製造する方法がいくつか報告されている（たとえば特許文献１〜２）。このうち、特許文献１に開示されている技術は、チタン化合物の加熱または加水分解によって生成した光触媒前駆体ゾルを、アルカリ処理してゲル状物を得、これを２００℃以下で乾燥することによる酸化チタンの製造方法である。
Conventionally, several methods for producing metal oxide particles by only reaction in a liquid phase without including a firing step have been reported (for example,
また、特許文献２に開示されている技術は、透明性と紫外線遮断効果に優れた塗膜を得ることのできる酸化亜鉛の製法として、亜鉛塩をアルコールまたはアルコールを含む水との混合液中で、ｐＨ９以上のアルカリ性下で加水分解を行い、平均粒径０．０５μｍ以下の酸化亜鉛微粒子を製造する方法である。
Moreover, the technique currently disclosed by
しかしながら上記の各方法では、熱アルカリ条件下、もしくは最終的にアルカリで処理する工程を含み、これらの処理は、得られた金属酸化物表面に吸着イオンとして残留することがしばしばある。これを除去するために、洗浄または焼成工程が必要となる場合があり、安全性や製造コストの面では好ましくない。 However, each of the above-mentioned methods includes a step of treating with hot alkali conditions or finally with alkali, and these treatments often remain as adsorbed ions on the surface of the obtained metal oxide. In order to remove this, a cleaning or baking process may be required, which is not preferable in terms of safety and manufacturing cost.
たとえば、電子表示機器に用いられる透明導電膜（ＩＴＯ膜）等は、一般にスパッタリング法を用いて製膜される。金属酸化膜の合成方法としては、熱分噴霧分解法、ゾルゲル法、ＣＶＤ法等の化学的手法、スパッタリング法、レーザーアブレーション等の物理的手法を含め、数多くの報告がある。しかし、化学的手法を用いた場合、大量生産は可能であるが、機能性金属酸化物の所望の特性を発現・制御するためには、最終的に高温での加熱処理が必要となる場合が多い。 For example, a transparent conductive film (ITO film) used for an electronic display device is generally formed using a sputtering method. As a method for synthesizing a metal oxide film, there are many reports including a chemical method such as a thermal spray decomposition method, a sol-gel method, and a CVD method, and a physical method such as a sputtering method and laser ablation. However, when chemical methods are used, mass production is possible, but in order to develop and control the desired properties of functional metal oxides, heat treatment at high temperatures may eventually be required. Many.
一方、物理的手法を用いた場合は、真空下において３００℃程度の比較的低温で金属酸化膜を製造することが可能ではあるが、真空チャンバー等の大型設備が必要となる上、大面積基材への製膜には限界がある。 On the other hand, when a physical method is used, a metal oxide film can be produced at a relatively low temperature of about 300 ° C. in a vacuum, but a large facility such as a vacuum chamber is required, and a large area substrate is required. There is a limit to film formation on materials.
また、高温下での製膜は、基材の変形および熱分解を引き起こす原因ともなるため、基材がプラスチック等の非耐熱性材料である場合、これらへの適用は困難であり、自ずと基材の材料選択は制限されることとなる。 In addition, since film formation under high temperature may cause deformation and thermal decomposition of the base material, when the base material is a non-heat resistant material such as plastic, it is difficult to apply to these, Material selection will be limited.
本願が解決しようとする課題は、このような従来事情に鑑み、高温での加熱焼成処理を行うことなく、結晶化した金属酸化物微粒子、粉体、および酸化物膜を製造することのできる、金属酸化物膜の製造方法を提供することである。また、コスト面および設備面からも大量生産に適し、製造過程の安全性にも問題のない、金属酸化物膜の製造方法を提供することである。さらにまた本願の課題は、金属酸化物微粒子を分散させた、非耐熱性基材にも製膜可能なコーティング液の製造方法を提供することである。
The problem to be solved by the present application is that, in view of such conventional circumstances, it is possible to produce crystallized metal oxide fine particles, powder, and oxide film without performing heating and baking treatment at a high temperature. It is to provide a method for producing a metal oxide film . Another object of the present invention is to provide a method for producing a metal oxide film , which is suitable for mass production from the viewpoint of cost and equipment and has no problem in the safety of the production process. Furthermore, the subject of this application is providing the manufacturing method of the coating liquid which can form into a non-heat-resistant base material which disperse | distributed the metal oxide microparticles | fine-particles.
本願発明者は上記課題について検討した結果、金属含有化合物または金属含有化合物を含む溶液を用いて、加水分解または中和反応時の条件を制御することで、原料溶液および溶媒の沸点以下の温度条件で結晶化した金属酸化物微粒子の合成が可能であることを見出し、本発明に至った。すなわち、上記課題を解決するための手段として本願で特許請求される発明、もしくは少なくとも開示される発明は以下の通りである。 As a result of studying the above problems, the present inventor has controlled the conditions at the time of hydrolysis or neutralization reaction using a metal-containing compound or a solution containing a metal-containing compound, so that the temperature conditions are below the boiling point of the raw material solution and the solvent. The inventors have found that the metal oxide fine particles crystallized with can be synthesized, and have reached the present invention. That is, the invention claimed in the present application as means for solving the above-described problems, or at least the invention disclosed is as follows.
（１）金属化合物原料、または金属酸化物原料溶液に加水分解用の媒体を添加して、該原料または該原料溶液をその沸点以下の温度で加水分解する過程を経ることによって金属酸化物膜を得る、３００℃以上の高温加熱処理を用いずに大気圧下において行う金属酸化物膜の製造方法であって、得られる金属酸化物が少なくともＴｉまたはＺｎを含むものであり、該金属化合物原料を加水分解する媒体が水とアルコールを混合した溶液であり、該加水分解の過程後に得られる金属酸化物を乾燥処理することにより金属酸化物微粒子を得、該金属酸化物微粒子を水、アルコールもしくは水−アルコール混合溶液に懸濁させて懸濁液とし、酢酸、硝酸、塩酸もしくは硫酸の少なくとも一種類を加えて分散させる過程か、または該懸濁液を超音波処理によって分散させる過程を経ることによって、金属酸化物微粒子を含むコーティング液を得、該コーティング液を基材に塗布し、これにより得られた塗膜を１５℃以上２５０℃以下で乾燥処理することによって、加熱焼成処理を行うことなく金属酸化物膜を得ることを特徴とする、金属酸化物膜の製造方法。
（２）前記金属化合物原料が、金属塩、金属アルコキシドまたは金属錯体の少なくとも一種類を含むものであることを特徴とする、（１）に記載の金属酸化物膜の製造方法。
（３）前記金属化合物原料または原料溶液には、ジケトン類またはジオール類の少なくともいずれかが添加されることを特徴とする、（１）または（２）に記載の金属酸化物膜の製造方法。
（４）前記加水分解の温度が７０℃以上１０５℃以下であることを特徴とする、（１）ないし（３）のいずれかに記載の金属酸化物膜の製造方法。
(1) A metal oxide film is obtained by adding a hydrolysis medium to a metal compound raw material or a metal oxide raw material solution and hydrolyzing the raw material or the raw material solution at a temperature below its boiling point. A method for producing a metal oxide film obtained under atmospheric pressure without using a high-temperature heat treatment at 300 ° C. or higher, wherein the obtained metal oxide contains at least Ti or Zn, The medium to be hydrolyzed is a solution in which water and alcohol are mixed, and metal oxide fine particles are obtained by drying the metal oxide obtained after the hydrolysis process, and the metal oxide fine particles are obtained by water, alcohol or water. -A process of suspending in an alcohol mixed solution to form a suspension, and adding and dispersing at least one of acetic acid, nitric acid, hydrochloric acid or sulfuric acid, or sonicating the suspension Thus, by passing through the process of dispersion, a coating liquid containing metal oxide fine particles is obtained, the coating liquid is applied to a substrate, and the coating film obtained thereby is dried at 15 ° C. or higher and 250 ° C. or lower. A method for producing a metal oxide film , characterized in that a metal oxide film is obtained without performing a heating and baking treatment.
(2) The method for producing a metal oxide film according to (1), wherein the metal compound raw material contains at least one of a metal salt, a metal alkoxide, and a metal complex.
(3) The method for producing a metal oxide film according to (1) or (2), wherein at least one of diketones or diols is added to the metal compound raw material or the raw material solution.
(4) The method for producing a metal oxide film according to any one of (1) to (3), wherein the hydrolysis temperature is 70 ° C. or higher and 105 ° C. or lower.
（５）前記金属酸化物微粒子における、Ｘ線回折パターンに基づきシェラー式により求められる平均一次結晶粒径が１ｎｍ以上５０ｎｍ以下の範囲内であることを特徴とする、（１）ないし（４）のいずれかに記載の金属酸化物膜の製造方法。
（６）（１）ないし（５）のいずれかに記載の金属酸化物膜の製造方法により得られた金属酸化物膜を使用してなる、下記（Ａ）のいずれかの製品。
（Ａ）触媒、触媒担体、吸着材、保護膜、熱線反射材、ガスセンサー、発光素子、圧電素子、調光材、導電膜、電磁波吸収材
(5) The average primary crystal grain size determined by the Scherrer formula based on the X-ray diffraction pattern in the metal oxide fine particles is in the range of 1 nm or more and 50 nm or less. (1) to (4) The manufacturing method of the metal oxide film in any one.
(6) A product according to any of the following (A), wherein the metal oxide film obtained by the method for producing a metal oxide film according to any one of (1) to (5) is used.
(A) Catalyst, catalyst carrier, adsorbent, protective film, heat ray reflective material, gas sensor, light emitting element, piezoelectric element, light modulating material, conductive film, electromagnetic wave absorbing material
つまり本発明は、金属含有化合物の加水分解または中和反応によって水酸化物または含水酸化物を合成、製造する際の反応場の条件を制御することで、高温・高圧下のような特殊な反応系や特殊な原料化合物を用いることなく、低温・大気圧下において結晶化した金属酸化物微粒子を合成、製造し、金属酸化物膜を得られることを可能とするものであるといえる。 In other words, the present invention controls the reaction field conditions when synthesizing and producing a hydroxide or a hydrous oxide by hydrolysis or neutralization reaction of a metal-containing compound, thereby enabling a special reaction such as under high temperature and high pressure. It can be said that a metal oxide film can be obtained by synthesizing and producing metal oxide fine particles crystallized at low temperature and atmospheric pressure without using a system or a special raw material compound.
本発明の金属酸化物膜の製造方法は上述のように構成されるため、これによれば、高温での加熱焼成処理を行うことなく、しかも特殊な反応系や原料化合物を用いることなく、低温・大気圧下において、容易に、結晶化した金属酸化物微粒子、粉体、および酸化物膜を得ることができる。さらに、金属酸化物微粒子を分散させた非耐熱性基材にも製膜可能なコーティング液をも得ることができ、たとえばプラスチック、紙、繊維等の非耐熱性基材への適用も充分可能となる。また、本発明製法による金属酸化物膜製造は、コスト面、設備面でも大量生産に適しており、製造過程の安全性も高い。
Since the method for producing a metal oxide film according to the present invention is configured as described above, according to this, a low temperature can be obtained without performing a heat baking treatment at a high temperature, and without using a special reaction system or a raw material compound. -Crystallized metal oxide fine particles, powder, and oxide film can be easily obtained under atmospheric pressure. Furthermore, it is possible to obtain a coating liquid capable of forming a film even on a non-heat-resistant substrate in which metal oxide fine particles are dispersed, and can be sufficiently applied to non-heat-resistant substrates such as plastic, paper, and fiber. Become. In addition, the metal oxide film production by the production method of the present invention is suitable for mass production in terms of cost and equipment, and the safety of the production process is high.
以下、本発明をより詳細に説明する。
本発明の金属酸化物膜の製造方法は、従来のような高温加熱処理を用いることなしに行われるものであり、目的とする金属酸化物を構成する金属を含有する化合物（以下、「金属含有化合物」あるいは「金属化合物原料」ともいう。）または化合物の溶液に加水分解用の媒体を添加して加水分解する際、該化合物または該化合物の溶液の沸点付近の温度で、反応させることを特徴とする。これには、急速に反応させる場合を含む。
Hereinafter, the present invention will be described in more detail.
The method for producing a metal oxide film of the present invention is carried out without using a conventional high-temperature heat treatment, and a compound containing a metal constituting the target metal oxide (hereinafter referred to as “metal-containing”). It is also referred to as “compound” or “metal compound raw material”) or a hydrolysis medium by adding a hydrolysis medium to the compound solution, and reacting at a temperature near the boiling point of the compound or the compound solution. And This includes the case of rapid reaction.
また、ここでいう「沸点付近」の沸点とは、水（以下、「水」とは、脱塩水もしくは蒸留水。また、脱塩水を「純水」ともいう。）を溶媒とした場合に限定するものではない。つまり、該原料に用いてこれを原料溶液とするための溶媒としては、水に対して適宜の酸、アルカリ、アルコール、無機塩、その他の溶質を混合溶解してなる水溶液を用いることができ、かかる場合にはその水溶液の沸点をいう。 The boiling point in the vicinity of “boiling point” here is limited to a case where water (hereinafter, “water” is demineralized water or distilled water. Demineralized water is also referred to as “pure water”) is used as a solvent. Not what you want. That is, as a solvent for using the raw material as a raw material solution, an aqueous solution obtained by mixing and dissolving an appropriate acid, alkali, alcohol, inorganic salt, or other solute in water can be used. In such a case, it refers to the boiling point of the aqueous solution.
また「沸点付近」は、該原料または該原料溶液の沸点と同一の温度、または沸点とほとんど同等で沸点よりも高いか低い温度をいう。特に良好な結果を得るためには、水を溶媒とした場合には沸点−５℃以上、沸点＋５℃の範囲であることが望ましい。また、水に対してアルコールを容量比で５０％以下混合した溶液を溶媒とする場合には、沸点−５℃以上、沸点＋５℃の範囲であることが望ましい。
Further, “near the boiling point” means the same temperature as the boiling point of the raw material or the raw material solution, or a temperature almost equal to the boiling point and higher or lower than the boiling point. In order to obtain particularly good results, when water is used as a solvent, the boiling point is preferably in the range of −5 ° C. or higher and the boiling point + 5 ° C. Moreover, when using as a solvent the solution which mixed
また本発明の製造方法において「沸点付近」は、後述する実施例のように、該原料または該原料溶液の沸点以下の温度に限定するものとすることもできる。 In the production method of the present invention, “near the boiling point” can be limited to a temperature not higher than the boiling point of the raw material or the raw material solution, as in the examples described later.
前記金属含有化合物および化合物溶液としては、最終的に本製法によって得られる金属酸化物を、Ａｌ、Ｓｉ、Ｔｉ、Ｖ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｙ、Ｚｒ、Ｇａ、Ｎｂ、Ｉｎ、Ｓｎ、Ｓｂ、Ｂａ、Ｗ、からなる群より選ばれる少なくともいずれか一つの金属を含むものとし得るものを、用いるものとすることができる。 As the metal-containing compound and the compound solution, the metal oxide finally obtained by this production method is Al, Si, Ti, V, Fe, Co, Ni, Cu, Zn, Y, Zr, Ga, Nb, In , Sn, Sb, Ba, W, which can contain at least one metal selected from the group consisting of, can be used.
該金属含有化合物（金属化合物原料）としては、塩化物、硝酸化合物、硫酸化合物のような無機系化合物（金属塩）や、金属アルコキシド、アセチルアセトナト錯体その他の金属錯体等の有機系化合物が挙げられ、少なくともこれらのうちの一種類を金属化合物原料に含めて用いることが望ましい。これらのうち、取り扱いやコストの観点からは特に、無機系化合物を用いることが好ましい。ただしこれに限定されるものではなく、特に本製法を触媒または触媒担体製造用として用いる場合において、表面残査イオン等の影響も考慮する場合はこの限りではない。 Examples of the metal-containing compound (metal compound raw material) include inorganic compounds (metal salts) such as chlorides, nitric acid compounds, and sulfuric acid compounds, and organic compounds such as metal alkoxides, acetylacetonato complexes, and other metal complexes. It is desirable to use at least one of these in the metal compound raw material. Among these, it is particularly preferable to use an inorganic compound from the viewpoint of handling and cost. However, the present invention is not limited to this. In particular, when the present production method is used for the production of a catalyst or a catalyst support, this does not apply when the influence of surface residual ions and the like is taken into consideration.
前記原料化合物に加え、添加剤としてジケトン類、ジオール類からなる有機化合物より選ばれる少なくとも一種類を原料または原料溶液に添加してもよい。これらを添加することによって、加水分解の速度をコントロールし、不均一な粒子の成長を抑え、均一な酸化物微粒子が得られるという効果が得られる。 In addition to the raw material compound, at least one selected from organic compounds consisting of diketones and diols may be added to the raw material or raw material solution as an additive. By adding these, the effect of controlling the rate of hydrolysis, suppressing the growth of non-uniform particles, and obtaining uniform oxide fine particles can be obtained.
金属化合物原料を加水分解する媒体としては、水（純水）を用いることができる。また、水とアルコールを適宜容量比にて混合した溶液すなわち水−アルコール混合溶液を用いてもよい。 Water (pure water) can be used as a medium for hydrolyzing the metal compound raw material. Alternatively, a solution in which water and alcohol are appropriately mixed at a volume ratio, that is, a water-alcohol mixed solution may be used.
金属含有化合物および金属含有化合物溶液の加水分解には、水酸化ナトリウム、アンモニア水、尿素、水、硝酸、塩酸、硫酸、のいずれかを使用することができる。これらの添加により上記化合物の加水分解反応を良好に進ませることができる。 For the hydrolysis of the metal-containing compound and the metal-containing compound solution, any of sodium hydroxide, ammonia water, urea, water, nitric acid, hydrochloric acid, and sulfuric acid can be used. By adding these, the hydrolysis reaction of the compound can be favorably advanced.
前記金属含有化合物の加水分解反応においての加熱温度は、７０℃以上とすることが好ましい。さらに該加熱温度は、原料である金属含有化合物および金属含有化合物溶液の沸点以下とすることが好ましい。なおさらに、加水分解用の媒体を水もしくは水−アルコール混合溶液とし、加水分解の温度を７０℃以上１０５℃以下と限定するものとすることもできる。 The heating temperature in the hydrolysis reaction of the metal-containing compound is preferably 70 ° C. or higher. Further, the heating temperature is preferably set to be equal to or lower than the boiling point of the metal-containing compound and the metal-containing compound solution as raw materials. Still further, the hydrolysis medium may be water or a water-alcohol mixed solution, and the hydrolysis temperature may be limited to 70 ° C. or higher and 105 ° C. or lower.
以上のように加水分解を行うことで、目的とする金属を含んだ酸化物ゲルまたはスラリーが得られるので、必要に応じてろ過等の手段により分離採取してもよい。また、これら沈殿物への吸着イオンを除去する目的で、蒸留水またはアルコールを用いて洗浄する工程を含めてもよい。 By performing hydrolysis as described above, an oxide gel or slurry containing the target metal can be obtained, and may be separated and collected by means such as filtration as necessary. Moreover, you may include the process wash | cleaned using distilled water or alcohol in order to remove the adsorption | suction ion to these precipitates.
本発明製法により製造される金属酸化物は、Ｘ線回折パターンに基づきシェラー式により求められる平均一次結晶粒径が、１ｎｍ以上１００ｎｍ以下の範囲内の金属酸化物微粒子とすることができる。また、１ｎｍ以上５０ｎｍ以下の範囲内の金属酸化物微粒子とすることもできる。かかる微粒子化は、表面積を増大させて、各金属化合物特有の機能発現を高めるものであり、望ましい。さらには、３０ｎｍ以下の一次結晶粒子径を有していることが、より望ましい。かかる粒径の微粒子は、前記加水分解の過程後、得られる金属酸化物を適宜条件で乾燥処理することによって得ることができる。乾燥方法は熱乾燥に限定されず、真空乾燥その他の乾燥方法でもよい。要するに、水分を蒸発させられればよい。また、乾燥状態でのＢＥＴ法による比表面積が１００ｍ２／ｇ以上であることが望ましい。 The metal oxide produced by the production method of the present invention can be metal oxide fine particles having an average primary crystal grain size determined by the Scherrer formula based on an X-ray diffraction pattern in a range of 1 nm to 100 nm. Moreover, it can also be set as the metal oxide fine particle in the range of 1 nm or more and 50 nm or less. Such micronization is desirable because it increases the surface area and enhances the expression of functions unique to each metal compound. Furthermore, it is more desirable to have a primary crystal particle size of 30 nm or less. Fine particles having such a particle size can be obtained by subjecting the obtained metal oxide to a drying treatment under appropriate conditions after the hydrolysis process. The drying method is not limited to heat drying, and may be vacuum drying or other drying methods. In short, it is only necessary to evaporate moisture. Moreover, it is desirable that the specific surface area by the BET method in a dry state is 100 m 2 / g or more.
上記本発明の製造方法によって、高温での加熱処理をすることなく、金属酸化物粉体および金属酸化物コーティング液を作成することができる。これらは高い表面積を有し、触媒、触媒担体として優れている他、プラスチック等の非耐熱性基材への適用も可能となる。 By the manufacturing method of the present invention, a metal oxide powder and a metal oxide coating liquid can be prepared without performing a heat treatment at a high temperature. These have a high surface area and are excellent as catalysts and catalyst carriers, and can also be applied to non-heat-resistant substrates such as plastics.
上述の金属酸化物沈殿の分離採取に際して、必要に応じて、酸・アルカリによる中和処理を施してからろ過してもよい。このようにして得られた金属酸化物を、必要に応じて水で洗浄した後、乾燥、粉砕処理すれば、金属酸化物粉体（金属酸化物粉末材料）が得られる。乾燥処理条件としては、大気圧下８０℃以上２００℃未満での熱乾燥処理を好適に用いることができる。 When separating and collecting the above-mentioned metal oxide precipitate, if necessary, it may be filtered after neutralizing with acid / alkali. A metal oxide powder (metal oxide powder material) can be obtained by washing the metal oxide thus obtained with water as necessary, followed by drying and pulverization. As a drying treatment condition, a thermal drying treatment at 80 ° C. or more and less than 200 ° C. under atmospheric pressure can be suitably used.
あるいはまた、上述の中和処理、ろ過を経て得られた金属酸化物を水、アルコールまたは水−アルコール混合溶液中に分散させて、金属酸化物が分散したコーティング液とすることもできる。 Alternatively, the metal oxide obtained through the above-described neutralization treatment and filtration can be dispersed in water, alcohol, or a water-alcohol mixed solution to obtain a coating liquid in which the metal oxide is dispersed.
ここで得られるコーティング液は懸濁状態であるが、これに対して必要に応じて、酢酸、硝酸、塩酸もしくは硫酸の少なくとも一種類を加えて分散させる過程、または懸濁液を超音波処理によって分散させる過程を経ることによって、より分散状態が良好、安定なコーティング液としてもよい。なお、周波数４５ｋＨｚの超音波処理の場合であれば、３０分間以上の処理は、安定・良好な分散状態を得るのに充分である。 The coating solution obtained here is in a suspended state, but if necessary, at least one of acetic acid, nitric acid, hydrochloric acid or sulfuric acid is added and dispersed, or the suspension is subjected to ultrasonic treatment. By passing through the process of dispersing, it is possible to obtain a coating liquid having a better dispersion state and stable. In the case of ultrasonic treatment at a frequency of 45 kHz, treatment for 30 minutes or more is sufficient to obtain a stable and good dispersion state.
本発明製法により得られた金属酸化物は、上述のコーティング液としてそのまま用いることも可能であるが、必要に応じて溶剤やバインダーを添加して金属酸化物膜に形成してもよい。基材との密着性に優れたバインダー等を添加することにより、機能膜の基材との密着性を向上させることができる。バインダー等は基材の種類により適宜選択すればよいが、シリカゾル、アルミナゾル等の無機系バインダーが好ましい。 The metal oxide obtained by the production method of the present invention can be used as it is as the above-mentioned coating solution, but may be formed into a metal oxide film by adding a solvent or a binder as necessary. By adding a binder having excellent adhesion to the substrate, the adhesion of the functional film to the substrate can be improved. The binder and the like may be appropriately selected depending on the type of the substrate, but inorganic binders such as silica sol and alumina sol are preferable.
本発明の金属酸化物膜の製造方法は上述の通り、従来のような３００℃以上の高温加熱焼成処理が不要であるため、金属酸化物膜製造に用いる基材は特に限定されない。熱処理金属、セラミックスなどの耐熱性材はもちろん、プラスチック、フィルム、紙、繊維、木材等の非耐熱性材に分類される基材であってもよい。
As described above, the method for producing a metal oxide film according to the present invention does not require a conventional high-temperature heating and baking treatment at 300 ° C. or higher. As well as heat-resistant materials such as heat-treated metals and ceramics, base materials classified into non-heat-resistant materials such as plastic, film, paper, fiber, and wood may be used.
金属酸化物膜は、得られた金属酸化物微粒子を含むコーティング液を適宜の基材に塗布し、これにより得られた塗膜を乾燥処理することによって得ることができる。膜形成後の乾燥には特に高温は不要である。たとえば室温でも可能である。したがって、実際の製造条件としては、塗膜の乾燥処理温度を１５℃以上２５０℃以下としてもよい。 The metal oxide film can be obtained by applying the coating liquid containing the obtained metal oxide fine particles to an appropriate substrate and drying the coating film obtained thereby. High temperature is not particularly required for drying after film formation. For example, it is possible even at room temperature. Therefore, as actual manufacturing conditions, the drying treatment temperature of the coating film may be 15 ° C. or more and 250 ° C. or less.
図１は、以上説明した本発明の金属酸化物膜の製造方法を示すフロー図である。もっとも上述説明の通り、このフローに記載された過程を必ずしもすべて含まないものであっても、本発明の範囲内である。図示するように本発明製法の典型的なフローは、原料または原料溶液Ｒを所定温度条件下で加水分解する加水分解工程Ｓ１、ついで、加水分解反応の系においてスラリー等の状態となっている金属酸化物にろ過等の分離手段を施すことによって、結晶化した金属酸化物微粒子（以下、「一次金属化合物」ともいう。）を得る分離工程Ｓ２を経ることを基本とし、ここまでの工程により、一次金属化合物Ｍが得られる。
FIG. 1 is a flowchart showing the method for producing the metal oxide film of the present invention described above. However, as described above, it is within the scope of the present invention even if it does not necessarily include all the processes described in this flow. As shown in the drawing, a typical flow of the production method of the present invention is a hydrolysis step S1 in which a raw material or raw material solution R is hydrolyzed under a predetermined temperature condition, and then a metal in a slurry state in the hydrolysis reaction system. By performing separation step S2 to obtain crystallized metal oxide fine particles (hereinafter also referred to as “primary metal compound”) by applying separation means such as filtration to the oxide, A primary metal compound M is obtained.
ついで、一次金属酸化物Ｍを、洗浄・乾燥処理などのなされる粉体化工程Ｓ３に供することによって、金属酸化物粉体Ｐ１が得られる。また一方、一次金属酸化物Ｍを、水その他の適宜の分散媒中に分散させる分散工程Ｓ４に供することによって、金属酸化物コーティング液Ｐ２が得られる。さらに金属酸化物コーティング液Ｐ２を用いて適宜の基材に対して被覆処理（製膜処理）を施すコーティング工程Ｓ５によって、金属酸化物薄膜Ｐ３を得ることができる。 Next, the metal oxide powder P1 is obtained by subjecting the primary metal oxide M to a pulverization step S3 in which washing and drying are performed. On the other hand, the metal oxide coating liquid P2 is obtained by subjecting the primary metal oxide M to the dispersion step S4 in which the primary metal oxide M is dispersed in water or other appropriate dispersion medium. Furthermore, the metal oxide thin film P3 can be obtained by a coating step S5 in which a coating process (film forming process) is performed on an appropriate base material using the metal oxide coating liquid P2.
本発明製造方法により得られる金属酸化物微粒子、粉体、コーティング液または膜は、各金属酸化物が備える特性、機能により、様々な分野において種々の製品に応用することができる。たとえば下記の通りである。
The metal oxide fine particles, powder, coating liquid or film obtained by the production method of the present invention can be applied to various products in various fields depending on the characteristics and functions of each metal oxide. For example:
〈ａ〉触媒・触媒担体としては、一例を挙げれば、パラモリブデン酸アンモニウムや塩化バナジウムを金属化合物原料として、ＭｏＯ３やＶ２Ｏ５を得、これをオキシ塩化ジルコニウムやチタニウムテトライソプロポキシドを原料として作製したＴｉＯ２担体やＺｒＯ２担体に担持して用いることができる。
触媒利用可能な金属の例は、他にもＣｕＯ、ＮｉＯ、Ｆｅ２Ｏ３等が上げられる。
〈ｂ〉特に光触媒としては、チタニウムテトライソプロポキシドを金属化合物原料として、酸化チタン微粒子を得、これを粉体や膜に形成して用いることができる。
<a> As an example of the catalyst / catalyst support, ammonium paramolybdate or vanadium chloride is used as a metal compound raw material to obtain MoO 3 or V 2 O 5. It can be used by being supported on a TiO 2 carrier or ZrO 2 carrier produced as a raw material.
Other examples of metals that can be used as a catalyst include CuO, NiO, Fe 2 O 3 and the like.
<B> Particularly as a photocatalyst, titanium tetraisopropoxide can be used as a metal compound raw material to obtain titanium oxide fine particles, which can be used as powders or films.
〈ｃ〉吸着材や、〈ｄ〉保護膜としては、塩化アルミニウムやテトラエチルオルトシリケートを金属化合物原料として、アモルファスなＡｌ２Ｏ３やＳｉＯ２を得、これを粉体や膜に形成して用いることができる。
〈ｅ〉導電膜、熱線反射材、電磁波吸収剤としては、酢酸亜鉛、塩化錫を金属化合物原料として、分散液、膜に形成された金属酸化物の状態で用いることができる。
<C> Adsorbent and <d> Protective film are obtained by forming amorphous Al 2 O 3 or SiO 2 using aluminum chloride or tetraethylorthosilicate as a metal compound raw material, and forming this into a powder or film. be able to.
<E> As a conductive film, a heat ray reflective material, and an electromagnetic wave absorber, zinc acetate and tin chloride can be used as a metal compound raw material in the form of a dispersion and a metal oxide formed in the film.
〈ｆ〉ガスセンサーとしては、硝酸亜鉛や塩化鉄を金属化合物原料として、ＺｎＯやＦｅ２Ｏ３を得、これを膜として用いることができる。
〈ｇ〉蛍光素子としては、硝酸亜鉛や硫化ナトリウムを金属化合物原料として、ＺｎＳ（金属酸化物）を得、これを粉体や分散液、膜に形成して用いることができる。
〈ｈ〉圧電素子としては、硫酸バリウムや塩化チタンを金属化合物原料として、ＢａＴｉＯ３を得、これを粉体、膜状に形成して用いることができる。
<F> As the gas sensor, zinc nitrate or iron chloride is used as a metal compound raw material to obtain ZnO or Fe 2 O 3 , which can be used as a film.
<G> As a fluorescent element, zinc nitrate or sodium sulfide can be used as a metal compound raw material to obtain ZnS (metal oxide), which can be used as a powder, dispersion, or film.
<H> As the piezoelectric element, BaTiO 3 can be obtained by using barium sulfate or titanium chloride as a metal compound raw material, and this can be used in the form of powder or film.
〈ｉ〉調光材としては、タングステン酸アンモニウムを金属化合物原料として、ＷＯ３を得、これを酸化チタンと組み合わせて膜として用いることもできる。 <I> As a light modulating material, WO 3 can be obtained by using ammonium tungstate as a metal compound raw material, and this can be used as a film in combination with titanium oxide.
以下、本発明の実施例として酸化チタン、酸化亜鉛の製造例について説明するが、本発明はこれらの実施例に限定されるものではない。
＜１．本方法による酸化チタン微粒子の作製＞
１．１ 実施例１
加水分解用の媒体とする蒸留水５００ｇをホットスターラーを用いて加熱、攪拌し、温度９５〜１００℃の温水を得た。この温水にチタニウムテトライソプロポキシド１００ｇを、２０ｇ／ｍｉｎの速度で滴下した。その後、３０ｍｉｎ加熱攪拌し、酸化チタンスラリーを得た。こうして得られた酸化チタンスラリーを、１５０℃で１時間乾燥した粉末のＢＥＴ比表面積は、４７０ｍ２／ｇであった。
Hereinafter, although the manufacture example of a titanium oxide and a zinc oxide is demonstrated as an Example of this invention, this invention is not limited to these Examples.
<1. Preparation of titanium oxide fine particles by this method>
1.1 Example 1
Distilled water 500 g used as a medium for hydrolysis was heated and stirred using a hot stirrer to obtain warm water having a temperature of 95 to 100 ° C. 100 g of titanium tetraisopropoxide was added dropwise to the warm water at a rate of 20 g / min. Thereafter, the mixture was heated and stirred for 30 minutes to obtain a titanium oxide slurry. The BET specific surface area of the powder obtained by drying the titanium oxide slurry thus obtained at 150 ° C. for 1 hour was 470 m 2 / g.
得られた酸化チタンスラリーに、酸化チタンの固形分濃度で１０〜１５ｗｔ％になるように蒸留水を加え、３０ｍｉｎの超音波処理（周波数４５ｋＨｚ）を施し、酸化チタンコーティング液を得た。上述の方法で得られた酸化チタンコーティング液を高純度シリカフィルター（ＡＤＶＡＮＴＥＣ ＱＲ−１００）に塗布し、１５０℃で３０ｍｉｎ乾燥し、光触媒シートを得た。 Distilled water was added to the obtained titanium oxide slurry so that the solid content concentration of titanium oxide was 10 to 15 wt%, and ultrasonic treatment (frequency 45 kHz) was performed for 30 minutes to obtain a titanium oxide coating solution. The titanium oxide coating solution obtained by the above method was applied to a high purity silica filter (ADVANTEC QR-100) and dried at 150 ° C. for 30 minutes to obtain a photocatalytic sheet.
なお、加水分解用の媒体を高沸点（沸点約２０１℃）の１，３−ブタンジオールに替え、反応温度１８０℃で実施例１と同様の方法で酸化チタンを合成したところ、結晶にはなるものの、光触媒活性は示さなかった。また、水と１，３−ブタンジオールを混合した溶液を加水分解用の媒体として、温度１２０℃で、実施例１と同様条件にて合成した場合も同じであった。これは、高沸点の溶媒を用いると、合成された物質の表面に溶媒が残存し、表面を被覆するため、触媒活性が失われるものである。残存溶媒を除去するためには洗浄工程が必要となるが、ナノサイズの微粒子を完全に洗浄するのは困難である。また、熱処理により残存成分を除去する方法もあるが、そのためには結果的に２００℃を超える高温で加熱処理することが必要となり、従来行われている水熱合成と大差ない条件となってしまい、上述の本発明課題を解決し得る手段としては採用されない。 In addition, when the medium for hydrolysis was changed to 1,3-butanediol having a high boiling point (boiling point: about 201 ° C.) and titanium oxide was synthesized by the same method as in Example 1 at a reaction temperature of 180 ° C., crystals were formed. However, it did not show photocatalytic activity. The same result was obtained when the solution prepared by mixing water and 1,3-butanediol was synthesized at a temperature of 120 ° C. under the same conditions as in Example 1 using a medium for hydrolysis. This is because when a high-boiling solvent is used, the solvent remains on the surface of the synthesized substance and coats the surface, so that the catalytic activity is lost. A cleaning step is required to remove the residual solvent, but it is difficult to completely clean the nano-sized fine particles. In addition, there is a method of removing residual components by heat treatment, but as a result, it is necessary to perform heat treatment at a high temperature exceeding 200 ° C., and the conditions are not much different from conventional hydrothermal synthesis. It is not adopted as means for solving the above-described problems of the present invention.
１．２ 実施例２
蒸留水２５０ｍｌとイソプロピルアルコール２５０ｍｌを混合した溶液をホットスターラーを用いて加熱、攪拌し、温度８０〜８２℃の温水を得た。この温水にチタニウムテトライソプロポキシド１００ｇを２０ｇ／ｍｉｎの速度で滴下した。その後、３０ｍｉｎ加熱攪拌し、酸化チタンスラリーを得た。得られた酸化チタンスラリーに、酸化チタンの固形分濃度で１０〜１５ｗｔ％になるように蒸留水を加え、３０ｍｉｎの超音波処理（周波数４５ｋＨｚ）を施し、酸化チタンコーティング液を得た。このようにして得られた酸化チタンコーティング液を高純度シリカフィルター（ＡＤＶＡＮＴＥＣ ＱＲ−１００）に塗布し１５０℃で３０ｍｉｎ乾燥し、光触媒シートを得た。
1.2 Example 2
A solution obtained by mixing 250 ml of distilled water and 250 ml of isopropyl alcohol was heated and stirred using a hot stirrer to obtain hot water having a temperature of 80 to 82 ° C. 100 g of titanium tetraisopropoxide was added dropwise to the warm water at a rate of 20 g / min. Thereafter, the mixture was heated and stirred for 30 minutes to obtain a titanium oxide slurry. Distilled water was added to the obtained titanium oxide slurry so that the solid content concentration of titanium oxide was 10 to 15 wt%, and ultrasonic treatment (frequency 45 kHz) was performed for 30 minutes to obtain a titanium oxide coating solution. The titanium oxide coating solution thus obtained was applied to a high purity silica filter (ADVANTEC QR-100) and dried at 150 ° C. for 30 minutes to obtain a photocatalytic sheet.
１．３ 比較例１
蒸留水５００ｇをホットスターラーを用いて攪拌し、温度４０℃の温水を得た。この温水にチタニウムテトライソプロポキシド１００ｇを２０ｇ／ｍｉｎの速度で滴下した。その後、３０ｍｉｎ加熱攪拌し、酸化チタンスラリーを得た。得られた酸化チタンスラリーに、酸化チタンの固形分濃度で１０〜１５ｗｔ％になるように蒸留水を加え、３０ｍｉｎの超音波処理（周波数４５ｋＨｚ）を施し、酸化チタンコーティング液を得た。得られた酸化チタンコーティング液を高純度シリカフィルター（ＡＤＶＡＮＴＥＣ ＱＲ−１００）に塗布し、１５０℃で３０ｍｉｎ乾燥し、光触媒シートを得た。
1.3 Comparative Example 1
500 g of distilled water was stirred using a hot stirrer to obtain hot water having a temperature of 40 ° C. 100 g of titanium tetraisopropoxide was added dropwise to the warm water at a rate of 20 g / min. Thereafter, the mixture was heated and stirred for 30 minutes to obtain a titanium oxide slurry. Distilled water was added to the obtained titanium oxide slurry so that the solid content concentration of titanium oxide was 10 to 15 wt%, and ultrasonic treatment (frequency 45 kHz) was performed for 30 minutes to obtain a titanium oxide coating solution. The obtained titanium oxide coating liquid was applied to a high-purity silica filter (ADVANTEC QR-100) and dried at 150 ° C. for 30 minutes to obtain a photocatalytic sheet.
１．４ 比較例２
１，３−ブタンジオール３５ｇ、水０．４ｇ、硝酸０．５ｇを混合して溶液とし、この溶液にチタンテトライソプロポキシド５ｇを撹拌しながら滴下し、その後４時間常温にて撹拌し、含チタンゾル溶液を得た。この溶液をシリカフィルター上に塗布し、乾燥固化し、熱処理を施すことにより、フィルター上に酸化チタンを形成した。固化は乾燥機中で到達温度１５０℃、保持時間２時間の条件で行った。熱処理は電気炉中で昇温速度１０℃／ｍｉｎ、到達温度５５０℃、保持時間２時間の条件で行った。この方法で得られる酸化チタンは柱状構造を有することとなる。固化は１５０℃で２時間乾燥を行い、熱処理は電気炉中で昇温速度１０℃／１ｍｉｎ、到達温度５５０℃、保持時間１時間の条件で行った。本比較例２による光触媒は、本願出願人らがこれまでに発明した手法によるものである。（参考：特開２００２―２５３９７５号、他）
1.4 Comparative Example 2
35 g of 1,3-butanediol, 0.4 g of water, and 0.5 g of nitric acid were mixed to form a solution. To this solution, 5 g of titanium tetraisopropoxide was added dropwise with stirring, and then stirred at room temperature for 4 hours. A titanium sol solution was obtained. This solution was applied onto a silica filter, dried and solidified, and subjected to heat treatment to form titanium oxide on the filter. Solidification was performed in a dryer under conditions of an ultimate temperature of 150 ° C. and a holding time of 2 hours. The heat treatment was performed in an electric furnace under the conditions of a temperature rising rate of 10 ° C./min, an ultimate temperature of 550 ° C., and a holding time of 2 hours. The titanium oxide obtained by this method has a columnar structure. Solidification was performed at 150 ° C. for 2 hours, and heat treatment was performed in an electric furnace under the conditions of a heating rate of 10 ° C./1 min, an ultimate temperature of 550 ° C., and a holding time of 1 hour. The photocatalyst according to the present comparative example 2 is based on the technique invented by the applicants of the present application. (Reference: JP-A-2002-253975, etc.)
なお、ここで「柱状構造」の光触媒とは、結晶核から成長させた柱状構造、または柱状中空構造を有する光触媒材料であり、柱状中空の酸化チタン結晶がその典型である。すなわち、結晶核上に一つ以上の柱状結晶を成長させ、結晶核とその上に成長させる柱状結晶が同一方位に成長し、典型的なものでは柱状結晶の内部は中空構造を有している。 Here, the “columnar structure” photocatalyst is a photocatalytic material having a columnar structure grown from a crystal nucleus or a columnar hollow structure, and a columnar hollow titanium oxide crystal is typical. That is, one or more columnar crystals are grown on the crystal nucleus, and the crystal nucleus and the columnar crystal grown on the crystal nucleus grow in the same orientation. Typically, the inside of the columnar crystal has a hollow structure. .
また、光触媒結晶の形状が柱状とは、角柱状のものを始めとして、円柱状、棒状、その他柱状の立体構造をとるものをすべて含み、また該柱状結晶は鉛直方向に真っ直ぐに伸びるもの、傾斜状に伸びるもの、湾曲しながら伸びるもの、枝状に分岐して伸びるもの、柱状結晶が複数本成長し途中で融合したもの等を含む。また、結晶核はスパッタリング法、ＰＶＤ法、またはＣＶＤ法で作製した結晶核のみならず、その種類は単結晶、多結晶体、その他を広く用いることができる。また結晶核としては、通常の化学反応に見られる様に明らかには核と認められないようなもの、たとえば基板上の傷等を核の代替物とすることも可能である。 In addition, the shape of the photocatalytic crystal is a columnar shape, including a prismatic shape, a columnar shape, a rod shape, and other shapes having a columnar structure, and the columnar crystal extends straight in the vertical direction. And those that extend in a curved shape, those that extend while curving, those that branch and extend, and those in which a plurality of columnar crystals are grown and fused in the middle. Further, the crystal nucleus is not limited to a crystal nucleus produced by a sputtering method, a PVD method, or a CVD method, and a single crystal, a polycrystal, or the like can be widely used. Further, as a crystal nucleus, it is possible to substitute a nucleus that is not clearly recognized as a nucleus as seen in a normal chemical reaction, such as a scratch on a substrate.
１．５ 比較例３
市販の光触媒コーティング液（石原産業株式会社 ＳＴＳ−０１）を比較例３とした。これを、高純度シリカフィルター（ＡＤＶＡＮＴＥＣ ＱＲ−１００）に塗布し、１５０℃で３０ｍｉｎ乾燥した。その後、蒸留水に含浸させて表面に吸着している酸性イオンを洗浄し、再度１５０℃で３０ｍｉｎ乾燥し、光触媒シートを得た。
1.5 Comparative Example 3
A commercially available photocatalyst coating liquid (Ishihara Sangyo Co., Ltd. STS-01) was used as Comparative Example 3. This was applied to a high purity silica filter (ADVANTEC QR-100) and dried at 150 ° C. for 30 min. Then, the acidic ion which was made to impregnate in distilled water and was adsorb | sucked on the surface was wash | cleaned, and it dried for 30 minutes again at 150 degreeC, and obtained the photocatalyst sheet.
１．６ 比較例４
市販の光触媒粉体（日本アエロジル製 Ｐ−２５）を比較例４とした。蒸留水にＰ−２５を固形分濃度で１０ｗｔ％になるように添加、調製し、高純度シリカフィルター（ＡＤＶＡＮＴＥＣ ＱＲ−１００）に塗布した。その後１５０℃で３０ｍｉｎ乾燥して光触媒シートを得た。
1.6 Comparative Example 4
A commercially available photocatalyst powder (Nippon Aerosil P-25) was used as Comparative Example 4. P-25 was added to distilled water so as to have a solid content concentration of 10 wt%, prepared, and applied to a high-purity silica filter (ADVANTEC QR-100). Thereafter, it was dried at 150 ° C. for 30 minutes to obtain a photocatalyst sheet.
＜２．特性評価方法＞
２．１ トルエン分解性能評価
２０Ｌの反応容器内にトルエン約２０ｐｐｍを注入し、濃度が安定した後、ブラックライトを照射し、トルエンの濃度減少を測定、評価した。トルエン濃度が２０ｐｐｍから１ｐｐｍ以下になるまでにかかる時間を測定し、光触媒性能として評価した。評価に供するＴｉＯ２量は約０．１ｇとした。
<2. Characteristic evaluation method>
2.1 Toluene decomposition performance evaluation About 20 ppm of toluene was injected into a 20 L reaction vessel, and after the concentration was stabilized, black light was irradiated to measure and evaluate the decrease in toluene concentration. The time taken for the toluene concentration to fall from 20 ppm to 1 ppm or less was measured and evaluated as photocatalytic performance. The amount of TiO 2 used for evaluation was about 0.1 g.
２．２ 結晶相の同定および比表面積の測定
結晶相の同定および比表面積の測定には下記の装置を用いた。
表面積（ＢＥＴ法）：日本ベル株式会社 ＢＥＬＳＯＲＰ−ｍｉｎｉ高精度ガス吸着装置
ＸＲＤ：日本電子株式会社 ＪＤＸ−３５３０ 粉末Ｘ線回折装置
2.2 Identification of crystal phase and measurement of specific surface area The following apparatus was used for identification of crystal phase and measurement of specific surface area.
Surface area (BET method): Nippon Bell Co., Ltd. BELSORP-mini high-precision gas adsorption device XRD: JEOL Ltd. JDX-3530 Powder X-ray diffractometer
＜３．特性評価結果＞
３．１ トルエン分解性能
表１は、各実施例および比較例によって得られた光触媒シートについて、トルエン分解性能測定結果をまとめたものである。表より、市販物である比較例３、比較例４では、トルエン分解時間は８０〜１１０ｍｉｎであり、１時間以上の分解速度であるのに対し、本発明製法による実施例１、２では、３５〜４０ｍｉｎであった。特に、水−アルコール混合溶液を加水分解用の媒体として用いた実施例２では、比較例３と比べると分解時間を１／２以下に、また比較例４と比べると分解時間を１／３以下にまでも短縮できており、これら市販のものよりも約２〜３倍あるいはそれ以上もの優れた分解速度を備えていることが明らかとなった。
<3. Characterization results>
3.1 Toluene decomposition performance Table 1 summarizes the toluene decomposition performance measurement results for the photocatalyst sheets obtained in each of Examples and Comparative Examples. From the table, in Comparative Examples 3 and 4 which are commercially available products, the toluene decomposition time is 80 to 110 min, which is a decomposition rate of 1 hour or more, while in Examples 1 and 2 according to the production method of the present invention, 35 ~ 40 min. In particular, in Example 2 using a water-alcohol mixed solution as a medium for hydrolysis, the decomposition time was ½ or less compared to Comparative Example 3, and the decomposition time was を or less compared to Comparative Example 4. It has been clarified that the decomposition rate is about 2-3 times or more superior to those on the market.
また、本製法による実施例１、２の光触媒は、本願出願人がこれまで発明し開示してきた製法による比較例２のものと比べても、高い分解性能を示した。 In addition, the photocatalysts of Examples 1 and 2 according to the present production method showed high decomposition performance as compared with that of Comparative Example 2 according to the production method that the present applicant has invented and disclosed so far.
一方、加水分解用の媒体を水とし、加水分解の温度を４０℃として調製した比較例１では、トルエンの濃度減少が認められず、触媒活性は示されなかった。なお、本製法においては、加水分解用の媒体として特に水、アルコール、水とアルコールの適宜容量比による混合溶液を好適に用いることができるが、比較例１の結果、エタノールの沸点が常圧にて約７８℃であることなどから、これらの加水分解用の媒体を用いる場合に特にその反応温度を７０℃以上１０５℃以下の範囲とすることが、より望ましい。 On the other hand, in Comparative Example 1 prepared by setting the hydrolysis medium to water and the hydrolysis temperature to 40 ° C., no decrease in toluene concentration was observed and no catalytic activity was shown. In this production method, water, alcohol, and a mixed solution with an appropriate volume ratio of water and alcohol can be suitably used as the hydrolysis medium. However, as a result of Comparative Example 1, the boiling point of ethanol is at normal pressure. Therefore, it is more desirable to set the reaction temperature in the range of 70 ° C. or more and 105 ° C. or less particularly when these hydrolysis media are used.
３．２ ＸＲＤパターン
図２は、実施例１、２および比較例１、２のＸＲＤパターンを示すグラフである。図に示されるように、実施例１、実施例２および比較例２では、アナタ−ゼの回折パターンが得られ、１００℃以下の温度で結晶化していることが認められた。一方、反応温度４０℃で製造した比較例１はアモルファスであり、基材のシリカフィルターのハローピークのみが認められた。
3.2 XRD Pattern FIG. 2 is a graph showing XRD patterns of Examples 1 and 2 and Comparative Examples 1 and 2. As shown in the figure, in Example 1, Example 2 and Comparative Example 2, an anatase diffraction pattern was obtained, and it was observed that crystallization occurred at a temperature of 100 ° C. or lower. On the other hand, Comparative Example 1 produced at a reaction temperature of 40 ° C. was amorphous, and only the halo peak of the silica filter of the substrate was observed.
表２は、実施例１、２および比較例１、２のＸＲＤパターンからシェラー式を用いて得られた結晶子サイズをそれぞれ示したものである。表の通り、実施例１、２共にその結晶子サイズは、１０ｎｍ以下の微粒子であることが示された。特に実施例２では、加水分解用の媒体として水を用いた実施例１と比較して、反応場にアルコールを混在させることで原料の加水分解速度が制御され、微細な酸化チタン結晶粒子を生成させ、それによって表面積を増加させ、分解速度の向上が得られていることが示唆された。このように、加水分解の際、反応場環境を変えることで結晶子のサイズもコントロールすることが可能であることが明らかとなった。 Table 2 shows crystallite sizes obtained from the XRD patterns of Examples 1 and 2 and Comparative Examples 1 and 2 using the Scherrer equation. As shown in the table, in both Examples 1 and 2, the crystallite size was shown to be fine particles of 10 nm or less. Especially in Example 2, compared with Example 1 using water as a medium for hydrolysis, the hydrolysis rate of the raw material is controlled by mixing alcohol in the reaction field, and fine titanium oxide crystal particles are generated. It was suggested that the surface area was increased thereby improving the decomposition rate. Thus, it became clear that the size of the crystallites can be controlled by changing the reaction field environment during hydrolysis.
＜４．本方法による酸化亜鉛微粒子の作製＞
４．１ 実施例３
硝酸亜鉛九和物を蒸留水に溶解し、硝酸亜鉛九水和物濃度１０ｗｔ％の溶液を得た。この溶液をホットスターラーを用いて加熱攪拌し、８５〜９５℃の加熱状態とした。これに２％のアンモニア水を、自動滴下装置を用いて１００ｍｌ／ｈｒの速度で滴下した。加水分解用の媒体たる該アンモニア水滴下終了後、攪拌状態で温度８５〜９５℃で３０ｍｉｎ維持し、白色スラリーを得た。得られたスラリーをろ過・洗浄し、蒸留水に分散させ、全量の３０ｗｔ％となるようにイソプロパノールを加え、酸化亜鉛コーティング液とした。この際、コーティング液に沈殿は認められず、薄い白色の解膠状態を呈していた。
<4. Preparation of fine zinc oxide particles by this method>
4.1 Example 3
Zinc nitrate nonahydrate was dissolved in distilled water to obtain a solution having a zinc nitrate nonahydrate concentration of 10 wt%. This solution was heated and stirred using a hot stirrer to obtain a heated state of 85 to 95 ° C. 2% aqueous ammonia was added dropwise thereto at a rate of 100 ml / hr using an automatic dropping device. After completion of the dropwise addition of the aqueous ammonia as a hydrolysis medium, the mixture was maintained at a temperature of 85 to 95 ° C. for 30 minutes with stirring to obtain a white slurry. The obtained slurry was filtered and washed, dispersed in distilled water, and isopropanol was added so as to be 30 wt% of the total amount to obtain a zinc oxide coating solution. At this time, no precipitation was observed in the coating solution, and a thin white peptized state was exhibited.
４．２ 比較例５
硝酸亜鉛九和物を蒸留水に溶解し、硝酸亜鉛九水和物濃度１０ｗｔ％の溶液を得た。この溶液をホットスターラーを用いて加熱攪拌し、３０〜４５℃の加熱状態とした。これに２％のアンモニア水を、自動滴下装置を用いて１００ｍｌ／ｈｒの速度で滴下した。アンモニア水滴下終了後、攪拌状態で温度３０〜４５℃で３０ｍｉｎ維持し、白色スラリーを得た。得られたスラリーをろ過・洗浄し、蒸留水に分散させ、全量の３０ｗｔ％となるようにイソプロパノールを加え、酸化亜鉛コーティング液とした。
4.2 Comparative Example 5
Zinc nitrate nonahydrate was dissolved in distilled water to obtain a solution having a zinc nitrate nonahydrate concentration of 10 wt%. This solution was heated and stirred using a hot stirrer to obtain a heated state of 30 to 45 ° C. 2% aqueous ammonia was added dropwise thereto at a rate of 100 ml / hr using an automatic dropping device. After completion of the dropwise addition of aqueous ammonia, the mixture was maintained at a temperature of 30 to 45 ° C. for 30 minutes with stirring to obtain a white slurry. The obtained slurry was filtered and washed, dispersed in distilled water, and isopropanol was added so as to be 30 wt% of the total amount to obtain a zinc oxide coating solution.
４．３ ＸＲＤ
実施例３、比較例５により得られた酸化亜鉛コーティング液を、高純度シリカフィルター（ＡＤＶＡＮＴＥＣ ＱＲ−１００）に塗布し、１５０℃で３０ｍｉｎ乾燥し、ＸＲＤに供した。
4.3 XRD
The zinc oxide coating solution obtained in Example 3 and Comparative Example 5 was applied to a high-purity silica filter (ADVANTEC QR-100), dried at 150 ° C. for 30 minutes, and subjected to XRD.
図３は、実施例３および比較例５のＸＲＤパターンを示すグラフである。図に示されるように、実施例３では明瞭な酸化亜鉛のピークが認められているのに対し、３０〜４５℃で反応させた比較例５では酸化亜鉛に対応するピークは認められなかった。 FIG. 3 is a graph showing XRD patterns of Example 3 and Comparative Example 5. As shown in the figure, a clear zinc oxide peak was observed in Example 3, whereas no peak corresponding to zinc oxide was observed in Comparative Example 5 reacted at 30 to 45 ° C.
本発明によれば、比較的安価でかつ簡単に結晶性の良い金属酸化物微粒子を製造することができる。高温での加熱焼成工程を必要としないことから、表面積の低下を抑えることができ、触媒および触媒担体の製造方法として極めて有効である。
According to the present invention, metal oxide fine particles having relatively good crystallinity can be produced at a relatively low cost. Since a high-temperature heat-firing step is not required, a reduction in surface area can be suppressed, which is extremely effective as a method for producing a catalyst and a catalyst carrier.
得られる金属酸化物は超微粒子であるため、水やアルコール等の分散剤と併用することで薄膜材料を作製することができ、しかも低温で合成、製造可能であるため、プラスチック等の非耐熱性基材への応用も可能である。したがって、金属酸化物を用いた機能材料の合成方法として、極めて利用価値が高い発明である。 Since the resulting metal oxides are ultrafine particles, they can be used in combination with dispersants such as water and alcohol to produce thin film materials and can be synthesized and manufactured at low temperatures. Application to a substrate is also possible. Therefore, it is an invention with extremely high utility value as a method for synthesizing a functional material using a metal oxide.
実施例として説明した酸化チタン光触媒や、酸化亜鉛による紫外線遮断性の塗膜のみならず、他にもたとえば、触媒、触媒担体、吸着材、保護膜、熱線反射材、ガスセンサー、発光素子、圧電素子、調光材、導電膜、電磁波吸収材等にも用いることができ、広範な産業分野において優れた利用価値を有する発明である。 In addition to the titanium oxide photocatalysts described as examples and UV-blocking coating films with zinc oxide, other examples include catalysts, catalyst carriers, adsorbents, protective films, heat ray reflective materials, gas sensors, light emitting elements, piezoelectrics, etc. The invention can be used for elements, light control materials, conductive films, electromagnetic wave absorbers, and the like, and has excellent utility value in a wide range of industrial fields.
Ｍ…一次金属化合物
Ｐ１…金属酸化物粉体
Ｐ２…金属酸化物コーティング液
Ｐ３…金属酸化物薄膜
Ｒ…原料または原料溶液
Ｓ１…加水分解工程
Ｓ２…分離工程
Ｓ３…粉体化工程
Ｓ４…分散工程
Ｓ５…コーティング工程
M ... primary metal compound P1 ... metal oxide powder P2 ... metal oxide coating solution P3 ... metal oxide thin film R ... raw material or raw material solution S1 ... hydrolysis step S2 ... separation step S3 ... powdering step S4 ... dispersion step S5 ... Coating process
Claims (6)
（Ａ）触媒、触媒担体、吸着材、保護膜、熱線反射材、ガスセンサー、発光素子、圧電素子、調光材、導電膜、電磁波吸収材
The product according to any one of the following (A), wherein the metal oxide film obtained by the method for producing a metal oxide film according to any one of claims 1 to 5 is used.
(A) Catalyst, catalyst carrier, adsorbent, protective film, heat ray reflective material, gas sensor, light emitting element, piezoelectric element, light modulating material, conductive film, electromagnetic wave absorbing material
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006325012A JP4800914B2 (en) | 2006-11-30 | 2006-11-30 | Method for producing metal oxide film |
| PCT/JP2007/073011 WO2008066095A1 (en) | 2006-11-30 | 2007-11-29 | Process for production of metal oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006325012A JP4800914B2 (en) | 2006-11-30 | 2006-11-30 | Method for producing metal oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008137843A JP2008137843A (en) | 2008-06-19 |
| JP4800914B2 true JP4800914B2 (en) | 2011-10-26 |
Family
ID=39467885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006325012A Active JP4800914B2 (en) | 2006-11-30 | 2006-11-30 | Method for producing metal oxide film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4800914B2 (en) |
| WO (1) | WO2008066095A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5421293B2 (en) * | 2008-02-11 | 2014-02-19 | ダウニア ソラー セル エッセ・エッレ・エッレ | Method for producing titanium dioxide having nanometer size and controlled shape |
| CN102974356A (en) * | 2012-12-11 | 2013-03-20 | 常州大学 | Titanium-zinc-iron composite photocatalyst and preparation method thereof |
| JP6143640B2 (en) * | 2013-10-21 | 2017-06-07 | 大東化成工業株式会社 | Acicular zinc oxide particles, production method thereof, and cosmetics |
| JP6926433B2 (en) * | 2016-09-30 | 2021-08-25 | 三菱ケミカル株式会社 | Laminated film and its manufacturing method |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5542282A (en) * | 1978-09-22 | 1980-03-25 | Dowa Mining Co Ltd | Wet forming method for fine zinc oxide |
| JP2821357B2 (en) * | 1994-02-22 | 1998-11-05 | 株式会社日本触媒 | Manufacturing method of zinc oxide fine particles |
| JP4250332B2 (en) * | 2000-12-30 | 2009-04-08 | 芳樹 山下 | Visible light reactive titanium oxide, method for producing the same, and method for removing contaminants |
| JP2002275390A (en) * | 2001-03-15 | 2002-09-25 | Fukuoka Prefecture | Crystalline gel dispersing coating solution, and method for forming thin film using crystalline gel dispersing coating solution |
| US6919029B2 (en) * | 2002-02-14 | 2005-07-19 | Trustees Of Stevens Institute Of Technology | Methods of preparing a surface-activated titanium oxide product and of using same in water treatment processes |
| WO2003070348A1 (en) * | 2002-02-21 | 2003-08-28 | Shell Internationale Research Maatschappij B.V. | Apparatus and method for treating a fluid |
| JP2003253157A (en) * | 2002-02-28 | 2003-09-10 | Furukawa Co Ltd | Coating solution of titania or titania-containing composite oxide excellent in storage stability |
| JP3612546B2 (en) * | 2002-05-27 | 2005-01-19 | 関西ティー・エル・オー株式会社 | Method for producing metal oxide fine particles |
| JP4047243B2 (en) * | 2003-08-07 | 2008-02-13 | 株式会社日立製作所 | Organic / inorganic oxide mixed thin film, electronic substrate with built-in passive element using the same, and method for producing organic / inorganic oxide mixed thin film |
| JP2005289674A (en) * | 2004-03-31 | 2005-10-20 | Murata Mfg Co Ltd | Method for manufacturing anatase-type titanium dioxide powder |
| US7482382B2 (en) * | 2004-05-19 | 2009-01-27 | The Texas A&M University System | Process for preparing nano-sized metal oxide particles |
-
2006
- 2006-11-30 JP JP2006325012A patent/JP4800914B2/en active Active
-
2007
- 2007-11-29 WO PCT/JP2007/073011 patent/WO2008066095A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008137843A (en) | 2008-06-19 |
| WO2008066095A1 (en) | 2008-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6607407B2 (en) | Fine particle titanium oxide and method for producing the same | |
| JP3524342B2 (en) | Titanium dioxide sol and thin film for thin film formation | |
| Goutailler et al. | Low temperature and aqueous sol–gel deposit of photocatalytic active nanoparticulate TiO 2 | |
| EP2969957B1 (en) | Rutile titanium dioxide nanoparticles and ordered acicular aggregates of same | |
| JP4093744B2 (en) | Method for producing tubular titanium oxide particles and tubular titanium oxide particles | |
| EP2780287B1 (en) | Mesoporous titanium dioxide nanoparticles and process for their production | |
| JPH1095617A (en) | Plate-shaped titanium oxide, production thereof, and anti-sunburn cosmetic material, resin composition, coating material, adsorbent, ion exchanging resin, complex oxide precursor containing the same | |
| KR100444892B1 (en) | Synthesis of highly active photocatalytic TiO2-sol containing active metals | |
| Lakbita et al. | Influence of the crystal structure of Ag2CO3 on the photocatalytic activity under visible light of Ag2CO3-Palygorskite nanocomposite material | |
| JP4800914B2 (en) | Method for producing metal oxide film | |
| WO2010030098A2 (en) | Method for the manufacture of uniform anatase titanium dioxide nanoparticles | |
| AU2016275742B2 (en) | A photocatalytic particle comprising TiO2 and its manufacture | |
| Yamabi et al. | Fabrication of rutile TiO2 foils with high specific surface area via heterogeneous nucleation in aqueous solutions | |
| TWI794460B (en) | Titanium oxide particles and method for producing same | |
| CN104194403A (en) | Preparation method of rutile titanium oxide/diatomite composite material | |
| JP4187632B2 (en) | Method for forming titanium dioxide thin film and catalyst having the titanium dioxide thin film | |
| CN102838159A (en) | Method for synthesizing nano-zinc oxide by micro-emulsion carbon black adsorption precipitation method | |
| JP4010934B2 (en) | Titanium oxide particles, water-dispersed sols, thin films thereof, and production methods thereof | |
| JP2004097989A (en) | Method for producing photocatalyst, photocatalyst by using the method, photocatalyst carrier by using the method | |
| KR20140144509A (en) | Nano TiO2 using precipitation method for high temperature and Its Manufacturing Method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091214 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100212 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110214 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110415 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110512 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110705 |
|
| 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: 20110729 |
|
| 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: 20110804 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140812 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4800914 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |