WO2006035872A1 - 粘土複合体 - Google Patents
粘土複合体 Download PDFInfo
- Publication number
- WO2006035872A1 WO2006035872A1 PCT/JP2005/017948 JP2005017948W WO2006035872A1 WO 2006035872 A1 WO2006035872 A1 WO 2006035872A1 JP 2005017948 W JP2005017948 W JP 2005017948W WO 2006035872 A1 WO2006035872 A1 WO 2006035872A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- clay
- complex
- water
- titanium
- peroxo
- Prior art date
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- 239000004927 clay Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002734 clay mineral Substances 0.000 claims abstract description 24
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 41
- 239000010936 titanium Substances 0.000 claims description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 33
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 14
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 13
- 150000003609 titanium compounds Chemical class 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 6
- 229910021647 smectite Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- GWPLDXSQJODASE-UHFFFAOYSA-N oxotantalum Chemical compound [Ta]=O GWPLDXSQJODASE-UHFFFAOYSA-N 0.000 claims 1
- 229910052902 vermiculite Inorganic materials 0.000 claims 1
- 239000010455 vermiculite Substances 0.000 claims 1
- 235000019354 vermiculite Nutrition 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 42
- 239000011248 coating agent Substances 0.000 description 39
- 239000007788 liquid Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 4
- 229910000348 titanium sulfate Inorganic materials 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- -1 metal titanium Chemical compound 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910052739 hydrogen Chemical group 0.000 description 2
- 239000001257 hydrogen Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000871495 Heeria argentea Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- B01J21/063—Titanium; 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
Definitions
- the present invention relates to a complex of a metal complex and a clay mineral, which can easily form an inorganic coating, and is useful for a barrier film, a catalyst material utilizing photocatalytic activity, an adsorbent, and the like. Is.
- Clay minerals have a layered crystal structure, and titanium oxide fine particle clay composites in which titanium oxide fine particles are combined between the layers are disclosed (for example, non-patent documents:! To 4, patent documents). 1, see Patent Document 2 etc.).
- the titanium oxide fine particle clay complex obtained by these methods becomes porous due to the gap between layers of the clay mineral used. Utilization of this porous structure for catalysts and adsorbents is considered.
- Non-Patent Document 1 Mater. Chem. Phys., 17, 87-101 (1987)
- Non-Patent Document 2 J. Phys. Chem., 93, 4833-4837 (1989)
- Non-Patent Document 3 Chem. Mater., 14, 5037-5044 (2002)
- Non-Patent Document 4 Chem. Commun., 2687-2679 (2002)
- Patent Document 1 JP 2001-97717 A
- Patent Document 2 Japanese Patent Laid-Open No. 10-245226
- An object of the present invention is to provide a clay composite that can be easily dispersed in water or an organic solvent and can form an inorganic coating having excellent durability.
- the present invention relates to a clay composite comprising (A) a water-soluble metal complex containing a peroxo ligand and (B) a water-swellable clay mineral.
- the present invention also relates to a clay composite composition obtained by dispersing the above clay composite in water and Z or an organic solvent.
- the present invention relates to an inorganic film forming method using the above clay composite composition and an inorganic cover.
- the clay composite of the present invention is obtained by complexing a water-soluble metal complex containing a peroxo ligand with a water-swellable clay mineral and stably exists in water and / or an organic solvent.
- an inorganic coating with excellent durability can be formed without baking at a high temperature, and it is extremely useful for applications such as nourish coatings, photocatalytic materials, and adsorbents. .
- the clay composite of the present invention is a composite of a water-soluble metal complex (A) containing a peroxo ligand and a water-swellable clay mineral (B).
- the metal complex which is the component (A) of the clay complex is a water-soluble metal complex containing a peroxo ligand, and among those capable of using a conventionally known one, a peroxotitanium complex, a peroxomolybdenum complex, It is preferable to use at least one metal complex selected from the group consisting of an oxotungsten complex, a peroxozirconium complex, a peroxodionium complex, a peroxovanadium complex, a peroxotantalum complex, and a peroxomanganese complex.
- a peroxotitanium complex is particularly preferred when used as a photocatalyst.
- the water-soluble metal complex (A) containing a peroxo ligand may contain a ligand other than a peroxo ligand.
- the water-soluble metal complex (A) containing a peroxo ligand As a method for producing the water-soluble metal complex (A) containing a peroxo ligand, a conventionally known method can be used. For example, it can be carried out by reacting a metal or a metal compound with hydrogen peroxide.
- peroxotitanium complex is made by reacting titanium dioxide such as metal titanium, hydrolyzable titanium, hydrolyzable titanium low condensate, titanium hydroxide, titanium hydroxide low condensate, metatitanic acid and hydrogen peroxide solution. Can be manufactured easily.
- the hydrolyzable titanium described above is a titanium compound having a hydrolyzable group that directly binds to titanium, and generates titanium hydroxide by reacting with water such as water or water vapor. is there.
- all of the groups bonded to titanium may be hydrolyzable groups, or one part thereof may be a hydrolyzed hydroxyl group.
- the hydrolyzable group is not particularly limited as long as it produces titanium hydroxide by reacting with moisture as described above.
- Hydrolyzable titanium containing a lower alkoxy group as a hydrolyzable group includes General formula Ti ( ⁇ R) (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.
- the tetraalkoxytitanium represented by Examples of the alkyl group having 1 to 5 carbon atoms include a methylol group, an ethyl group, an n-propyl group, an iso_propyl group, an n_butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned.
- Typical examples of the hydrolyzable titanium having a group capable of forming a salt with titanium as the hydrolyzable group include salt and titanium sulfate.
- the hydrolyzable titanium low condensate is a low condensate of the above hydrolyzable titanium.
- the degree of condensation in the hydrolyzable titanium low condensate or the titanium hydroxide low condensate is preferably about 2 to 30, and it is particularly preferable to use a condensation degree within the range of 2 to 10:
- the form of the water-soluble metal complex (A) may be either powdered or liquid, and it is particularly preferable that the water-soluble metal complex (A) is in a solution state since it can be easily combined with (B).
- specific examples of a method for producing a peroxotitanium complex solution include the following.
- a liquid for forming a titania film obtained by synthesizing a titanium hydroxide gel produced from a salty titanium or titanium sulfate aqueous solution and a basic solution with the action of a hydrogen peroxide solution (Japanese Patent Laid-Open No. 9-71418) Gazette and JP-A-10-67516).
- titanium hydroxide gel called orthotitanic acid is obtained by reacting a salty titanium or titanium sulfate aqueous solution having a salt forming group with titanium and an alkaline solution such as ammonia or caustic soda. To precipitate.
- the titanium hydroxide gel is separated by decantation using water, washed thoroughly with water, further added with hydrogen peroxide water to decompose and remove excess hydrogen peroxide, thereby obtaining a yellow transparent viscous liquid. .
- the precipitated orthotitanic acid is in a gel state polymerized by polymerization of OH groups or hydrogen bonds, and cannot be used as an aqueous liquid containing titanium as it is.
- hydrogen peroxide solution is added to this gel, some of the OH groups become peroxidized and become peroxotitanate. It is dissolved as ON, or it becomes a kind of zonole state in which the polymer chain is divided into low molecules, and excess hydrogen peroxide is decomposed into water and oxygen and used as an aqueous liquid containing titanium for inorganic film formation become able to.
- this sol contains oxygen atoms and hydrogen atoms in addition to titanium atoms and does not contain any forces, when it is changed to titanium oxide by drying or baking, substantially only water and oxygen are generated, so it is not necessary to remove organic components. Therefore, it is possible to produce a crystalline titanium oxide film having a relatively high density even at a lower temperature than in the past.
- the peroxotitanium complex solution it is particularly preferable to use a solution prepared by adding a titanium compound to hydrogen peroxide water.
- the titanium compound is particularly represented by the general formula Ti (OR) (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms).
- hydrolyzable titanium containing a group that is hydrolyzed to become a hydroxyl group and its hydrolyzable titanium low condensate It is preferable to use hydrolyzable titanium containing a group that is hydrolyzed to become a hydroxyl group and its hydrolyzable titanium low condensate.
- hydrolyzable titanium a The mixing ratio of hydrolyzable titanium and / or a low condensate thereof (hereinafter simply referred to as "hydrolyzable titanium a") and hydrogen peroxide solution is the hydrolytic titanium alO parts by weight.
- the hydrogen peroxide solution is preferably in the range of 0.:! To 100 parts by weight, particularly :! to 20 parts by weight in terms of hydrogen peroxide. If the amount is less than 0.1 parts by weight in terms of hydrogen peroxide, chelate formation is not sufficient and white turbid precipitation occurs. On the other hand, if it exceeds 100 parts by weight, unreacted hydrogen peroxide tends to remain, and dangerous active oxygen is released during storage.
- the hydrogen peroxide concentration of the hydrogen peroxide solution is not particularly limited, but is preferably in the range of 3 to 30% by weight from the viewpoint of ease of handling and the solid content of the generated liquid related to coating workability. Yes.
- peroxotitanium complex solution using hydrolyzable titanium a is hydrolyzable. It can be produced by reacting titanium a with hydrogen peroxide within a reaction temperature range of 1 to 70 ° C for about 10 minutes to 20 hours.
- the water-swellable clay mineral that is the component (B) of the clay composite is a clay mineral that swells with water.
- smectite clay minerals such as montmorillonite, hectorite, and saponite
- the force S that can be mentioned, among which smectite clay minerals are preferred.
- the amount of water-swellable clay mineral (B) used is 0.:!
- the clay composite of the present invention is a composite of a water-soluble metal complex (A) containing a peroxo ligand and a water-swellable clay mineral (B).
- Swellable clay mineral (B), water-soluble metal complex (A) containing a peroxo ligand, and optionally water and Z or an organic solvent can be mixed and heat-treated.
- the amount of peroxo group in the clay composite was measured by weighing the sample solution (w [g]) into a 100 ml beaker, adding 10 ml of 15% potassium iodide aqueous solution and 10 ml of 0.1N sulfuric acid aqueous solution for several hours. Stir. Next, add 1 ml of saturated aqueous starch solution, and use 0.1N aqueous sodium thiosulfate solution as the titrant, and the titration end point is the volume (X [ml]) at which the color changed from brown to colorless. The amount of peroxo group in the sample is given by 0.05 XX ⁇ w.
- the peroxo group content in the clay composite varies depending on the heat treatment conditions. For example, when heat treatment performed at a temperature of 100 ° C or higher is used as the heat treatment, a water-soluble metal complex containing a peroxo ligand is used. Since most or all of the peroxometal complex component in (A) is decomposed and the precursor is converted into coarse particles, the resulting clay composite dispersion becomes non-uniform, film-forming properties and Painting workability may be reduced.
- the heating temperature in the heat treatment is preferably 50 ° C or higher and lower than 100 ° C, and more preferably in the range of 80 to 98 ° C. If the heating temperature is too low, both the water-soluble metal complex (A) containing the peroxo ligand and the water-swellable clay mineral (B) will not be sufficiently complexed, and the resulting clay complex dispersion will not be It becomes uniform and paintability deteriorates.
- the heat treatment time is preferably in the range of 1 to 12 hours, particularly 3 to 8 hours. If the heating time is too short, the water-soluble metal complex (A) containing a peroxo ligand (A) and the swellable clay mineral (B) are insufficiently complexed. On the other hand, if the heating time is too long, the water-solubility becomes insufficient. In either case, the clay composite dispersion becomes non-uniform, and the adhesion to the base material and the workability of the coating deteriorate.
- the clay composite dispersion obtained by the above method can be used as it is as a clay composite composition for forming an inorganic film
- inorganic fine particles may be further blended if necessary.
- the inorganic fine particles include silica, zeolite, alumina, zinc oxide, and titanium oxide.
- titanium oxide There are no particular restrictions on the blending amount as long as the smoothness and water resistance of the coating film are not lowered. Titanium oxide having photocatalytic activity may be selected.
- the clay composite composition of the present invention is coated or impregnated on various substrates and then dried to form an inorganic coating containing the metal oxide fine particle-clay composite.
- This inorganic coating is durable and can be applied to various uses such as a barrier film, and has a photocatalytic activity if a peroxotitanium complex is used as the water-soluble metal complex (A) containing a peroxo ligand.
- Materials can also be formed and used for environmental purification and pollutant removal can do. For example, a spray method, a roller method, a brush coating method, a bar coater method, a spin coating method and the like can be appropriately selected as a method for applying the clay composite composition for forming the inorganic coating. Nare ,.
- the film thickness is preferably within the range of 0.1 to 3 xm, and more preferably within the range of 0.3 to lxm. If the film thickness is too low, the durability of the coating will be reduced, making it difficult to maintain photocatalytic activity over a long period of time. On the other hand, if the film thickness is too high, the adhesion of the base material, the smoothness of the coated surface, etc. may be reduced, or the coating film may be distorted.
- the drying temperature of the coating is preferably in the range of 20 to 200 ° C, but is preferably in the range of 50 to 140 ° C from the viewpoint of the finish of the coated surface.
- Example 1 a clay composite composition was obtained in the same manner as in Example 1 except that smectite-based “Lapolite RD” (trade name, manufactured by Rockwood) was used in place of “Nole 1 Centite SWN”. It was. The peroxo group content was 5.6 mmol per lg solids.
- Example 3 In Example 1, instead of 1.5 g of “Lucentite SWN”, the same as Example 1 except that 1.5 g of “Lucentite SWN” and 0.6 g of fine zinc white (manufactured by Zhiyogaku Kogyo Co., Ltd.) were used. Thus, a clay composite composition was obtained. The peroxo group content was 2. lmmol per lg solids.
- Example 1 1.5 g of “Lucentite SWN” and 1.5 g of titanium oxide for photocatalyst “P-25” (trade name, manufactured by Degassa) are used instead of 1.5 g of “Lucentite SWN”.
- a clay composite composition was obtained in the same manner as in Example 1 except for the above.
- the peroxo group content was 2.5 mmol per lg of solid content.
- the So-group content was 20 mmol per lg solids.
- the aqueous liquid (1.5% by weight in terms of Nb 2 O) containing the peroxobiobium complex obtained during the production of the clay composite composition in Example 4 was used as the coating liquid for inorganic film formation.
- the peroxo group content was 25 mmol / g solids.
- the ruxo group content was 32 mmol / g solids.
- It can be used as a barrier film, a catalyst material having a photocatalytic activity, an adsorbent and the like.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP2006537801A JP4807851B2 (ja) | 2004-09-29 | 2005-09-29 | 粘土複合体 |
EP05788179A EP1813575A1 (en) | 2004-09-29 | 2005-09-29 | Clay composite material |
US11/664,160 US20080090011A1 (en) | 2004-09-29 | 2005-10-29 | Clay Composite |
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JP2004284994 | 2004-09-29 | ||
JP2004-284994 | 2004-09-29 | ||
JP2005071598 | 2005-03-14 | ||
JP2005-071598 | 2005-03-14 |
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WO2006035872A1 true WO2006035872A1 (ja) | 2006-04-06 |
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PCT/JP2005/017948 WO2006035872A1 (ja) | 2004-09-29 | 2005-09-29 | 粘土複合体 |
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US (1) | US20080090011A1 (ja) |
EP (1) | EP1813575A1 (ja) |
JP (1) | JP4807851B2 (ja) |
WO (1) | WO2006035872A1 (ja) |
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JP7241632B2 (ja) * | 2018-08-27 | 2023-03-17 | シャープ株式会社 | 光触媒組成物 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62167215A (ja) * | 1986-01-16 | 1987-07-23 | Fuji Kagaku Kogyo Kk | 多孔質構造を有する粘土誘導体の製造法 |
JP2001097717A (ja) * | 1999-10-01 | 2001-04-10 | Sadenko Co Inc | 酸化チタン/粘土複合体の製造方法 |
JP2002137915A (ja) * | 2000-10-25 | 2002-05-14 | Mizusawa Ind Chem Ltd | チタン含有合成スメクタイトおよびその製法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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DE4121352A1 (de) * | 1991-06-28 | 1993-01-07 | Merck Patent Gmbh | Oberflaechenmodifizierte plaettchenfoermige pigmente |
DE4327620A1 (de) * | 1993-08-17 | 1995-02-23 | Merck Patent Gmbh | Stabilisiertes, leitfähiges Pigment |
AU2001267910A1 (en) * | 2000-07-03 | 2002-01-14 | Kansai Paint Co. Ltd. | Gas-barrier film |
US6736890B2 (en) * | 2000-07-25 | 2004-05-18 | Kansai Paint Co., Ltd. | Coating material for forming titanium oxide film, method for forming titanium oxide film and use of said coating material |
TW575523B (en) * | 2001-05-22 | 2004-02-11 | Kansai Paint Co Ltd | Inorganic film-forming coating composition and inorganic film-forming method by use of the same |
US7077895B2 (en) * | 2001-10-30 | 2006-07-18 | Kansai Paint Co., Ltd. | Coating compound for forming titanium oxide film, method for forming titanium oxide film and metal susbstrate coated with titanium oxide film |
US7205049B2 (en) * | 2004-04-16 | 2007-04-17 | Tioxoclean Inc. | Metal peroxide films |
-
2005
- 2005-09-29 WO PCT/JP2005/017948 patent/WO2006035872A1/ja active Application Filing
- 2005-09-29 EP EP05788179A patent/EP1813575A1/en not_active Withdrawn
- 2005-09-29 JP JP2006537801A patent/JP4807851B2/ja not_active Expired - Fee Related
- 2005-10-29 US US11/664,160 patent/US20080090011A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62167215A (ja) * | 1986-01-16 | 1987-07-23 | Fuji Kagaku Kogyo Kk | 多孔質構造を有する粘土誘導体の製造法 |
JP2001097717A (ja) * | 1999-10-01 | 2001-04-10 | Sadenko Co Inc | 酸化チタン/粘土複合体の製造方法 |
JP2002137915A (ja) * | 2000-10-25 | 2002-05-14 | Mizusawa Ind Chem Ltd | チタン含有合成スメクタイトおよびその製法 |
Also Published As
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JPWO2006035872A1 (ja) | 2008-05-15 |
JP4807851B2 (ja) | 2011-11-02 |
EP1813575A1 (en) | 2007-08-01 |
US20080090011A1 (en) | 2008-04-17 |
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