WO2012160986A1 - アナターゼ型又はルチル型酸化チタン微粒子分散液の製造方法及び光触媒薄膜を表面に有する部材 - Google Patents
アナターゼ型又はルチル型酸化チタン微粒子分散液の製造方法及び光触媒薄膜を表面に有する部材 Download PDFInfo
- Publication number
- WO2012160986A1 WO2012160986A1 PCT/JP2012/061999 JP2012061999W WO2012160986A1 WO 2012160986 A1 WO2012160986 A1 WO 2012160986A1 JP 2012061999 W JP2012061999 W JP 2012061999W WO 2012160986 A1 WO2012160986 A1 WO 2012160986A1
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- WIPO (PCT)
- Prior art keywords
- titanium oxide
- oxide fine
- fine particle
- particle dispersion
- type titanium
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 60
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 239000010409 thin film Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000006185 dispersion Substances 0.000 claims abstract description 107
- 239000002253 acid Substances 0.000 claims abstract description 65
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 13
- 239000010419 fine particle Substances 0.000 claims description 103
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 9
- 150000003377 silicon compounds Chemical class 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 238000000790 scattering method Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 61
- 239000002994 raw material Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 28
- 238000001816 cooling Methods 0.000 description 22
- 239000002245 particle Substances 0.000 description 19
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 16
- 150000003609 titanium compounds Chemical class 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- -1 inorganic acid salts Chemical class 0.000 description 13
- 239000002612 dispersion medium Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 11
- 239000011941 photocatalyst Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 229910010272 inorganic material Inorganic materials 0.000 description 8
- 239000011147 inorganic material Substances 0.000 description 8
- 239000003125 aqueous solvent Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 150000003606 tin compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
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- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
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- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- JOQGJRQKCIJIDB-UHFFFAOYSA-N tin;hydrochloride Chemical compound Cl.[Sn] JOQGJRQKCIJIDB-UHFFFAOYSA-N 0.000 description 1
- BAKALPNAEUOCDL-UHFFFAOYSA-N titanium hydrochloride Chemical compound Cl.[Ti] BAKALPNAEUOCDL-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
Definitions
- the present invention relates to a method for producing an anatase-type or rutile-type titanium oxide fine particle dispersion and a member having on its surface a photocatalytic thin film formed using the dispersion, and more specifically, excellent dispersion stability of titanium oxide fine particles.
- the present invention also relates to a method for producing an anatase-type or rutile-type titanium oxide fine particle dispersion capable of easily producing a photocatalytic thin film, and a member having a photocatalytic thin film formed on the surface using the dispersion.
- Titanium oxide is used in various applications, such as pigments, ultraviolet shielding agents, catalysts, photocatalysts, catalyst carriers, adsorbents, ion exchangers, fillers, reinforcing agents, raw materials for ceramics, complex oxides such as perovskite complex oxides. Are used as precursors for magnetic tapes, and as a primer for magnetic tape.
- photocatalytic titanium oxide fine particles are based on the photocatalytic coating film formed by coating the dispersion on the surface of various substrates, which decomposes organic substances and makes the film surface hydrophilic by photocatalytic action of titanium oxide. It is widely used for cleaning the surface of materials, deodorizing, antibacterial and so on.
- the primary particle diameter of the particles is required to be 50 nm or less.
- the transparency of the film is also required so as not to lose the design properties of the substrate.
- a fine powder of titanium oxide synthesized by a gas phase method or a liquid phase method is used, and a dispersion medium such as an organic polymer dispersant is used.
- a method of dispersing in the above JP-A-1-003020, JP-A-6-279725, JP-A-7-247119.
- the problem with these production methods is that ultrafine particles having an average particle diameter of 50 nm or less are likely to agglomerate, so that a great deal of labor is required to disperse to the primary particles, and in some cases, even the primary particles may be dispersed. It is impossible.
- a method for producing a long-term stable anatase-type titanium oxide dispersion by hydrothermal treatment of a peroxotitanic acid solution in which titanium hydroxide is dissolved in hydrogen peroxide Japanese Patent Laid-Open No. 10-67516
- coexistence of tin compounds A method for producing a rutile-type titanium oxide dispersion by hydrothermally treating a peroxotitanic acid solution (Japanese Patent Laid-Open No. 1-78928) has also been disclosed.
- a relatively long reaction time of 40 to 2 hours at 85 to 200 ° C. is required, and since it is a batch reaction, a production method with good production efficiency has not been established.
- the present invention has been made in view of the above circumstances, and anatase-type or rutile-type titanium oxide fine particle dispersion that is excellent in dispersion stability of titanium oxide fine particles and can easily produce a highly transparent photocatalytic thin film is continuously produced.
- An object of the present invention is to provide a production method obtained in a short time and a member having a photocatalytic thin film formed on the surface using the dispersion.
- the inventors of the present invention continuously reduced the anatase-type or rutile-type titanium oxide fine particle dispersion by hydrothermal reaction of the peroxotitanic acid solution using a flow reactor. It was found that this titanium oxide fine particle dispersion was excellent in dispersion stability of titanium oxide fine particles, and that a highly transparent photocatalytic thin film can be easily prepared from this titanium oxide fine particle dispersion. Invented the invention.
- the present invention provides a method for producing the following anatase-type or rutile-type titanium oxide fine particle dispersion and a member having a photocatalytic thin film formed on the surface using the dispersion.
- a method for producing anatase-type titanium oxide fine particle dispersion from a peroxotitanic acid solution the peroxotitanic acid solution is continuously supplied to a flow reactor, under conditions of 150 to 250 ° C. and 0.5 to 10 MPa.
- the titanium oxide fine particles in the anatase-type titanium oxide fine particle dispersion are 50 nm or less in a volume-based 50% cumulative distribution diameter (D 50 ) measured by a dynamic scattering method using laser light.
- a method for producing a titanium fine particle dispersion is characterized in that (3) The anatase type oxidation according to (1) or (2), wherein the peroxotitanic acid solution continuously supplied to the flow reactor is heated to a set hydrothermal reaction temperature within 2 minutes.
- a method for producing a rutile-type titanium oxide fine particle dispersion from a tin-containing peroxotitanic acid solution the peroxotitanic acid solution is continuously supplied to a flow reactor, and the temperature is 150 to 250 ° C. and 0.5 to 10 MPa.
- a method for producing a rutile-type titanium oxide fine particle dispersion which is hydrothermally treated under conditions.
- Titanium oxide fine particles in the rutile-type titanium oxide fine particle dispersion are 50 nm or less in a volume-based 50% cumulative distribution diameter (D 50 ) measured by a dynamic scattering method using laser light.
- (12) The peroxotitanic acid solution continuously supplied to the flow reactor is heated to a set hydrothermal reaction temperature within 2 minutes, according to any one of (9) to (11) Process for producing a rutile-type titanium oxide fine particle dispersion.
- the titanium oxide fine particle dispersion produced by hydrothermally treating a peroxotitanic acid solution is subsequently cooled to 40 ° C.
- a method for producing an anatase-type or rutile-type titanium oxide fine particle dispersion that is excellent in dispersion stability of titanium oxide fine particles and can easily produce a highly transparent photocatalytic thin film, and the dispersion
- the member which has the photocatalyst thin film formed using on the surface can be provided.
- the production method of the anatase-type titanium oxide fine particle dispersion of the present invention is a production method in which a tin-free peroxotitanic acid solution is hydrothermally reacted in a flow reactor.
- the production method of the rutile type titanium oxide fine particle dispersion of the present invention is a production method in which a tin-containing peroxotitanic acid solution is hydrothermally reacted in a flow reactor.
- tin-free peroxotitanic acid solution a commercially available product (for example, trade name “PTA-85”, manufactured by Sakai Corporation) may be used, or a raw material titanium compound, a basic substance and hydrogen peroxide may be used.
- a peroxotitanic acid solution prepared by reacting in an aqueous dispersion medium may be used.
- As a reaction method there is a method in which a basic substance is added to a raw material titanium compound in an aqueous dispersion medium to form titanium hydroxide, impurity ions contained are removed, and hydrogen peroxide is added to form a peroxotitanic acid solution. .
- a tin-containing peroxotitanic acid solution produced by reacting a raw material titanium compound, tin compound, basic substance and hydrogen peroxide in an aqueous dispersion medium is used.
- a basic substance is added to a mixture of raw material titanium compound and tin compound in an aqueous dispersion medium to form a mixture with tin-containing titanium hydroxide, impurity ions contained are removed, and hydrogen peroxide is added.
- a tin-containing peroxotitanic acid solution is used as a reaction method.
- the tin component is preferably contained in a molar ratio (Ti / Sn) with titanium of 1 to 1,000, particularly preferably 5 to 100, and more preferably 10 to 25.
- Ti / Sn a molar ratio
- the molar ratio exceeds 1,000, the effect is insufficient.
- it is smaller than 1 the content ratio of titanium oxide is lowered, and the photocatalytic effect may not be sufficiently exhibited.
- the titanium oxide becomes an anatase type
- a tin-containing peroxotitanic acid solution is used, the titanium oxide becomes a rutile type.
- the raw material titanium compound examples include inorganic acid salts such as titanium hydrochloride, nitrate and sulfate, organic acid salts such as formic acid, citric acid, oxalic acid, lactic acid and glycolic acid, and water added by adding alkali to these aqueous solutions.
- inorganic acid salts such as titanium hydrochloride, nitrate and sulfate
- organic acid salts such as formic acid, citric acid, oxalic acid, lactic acid and glycolic acid
- water added by adding alkali to these aqueous solutions examples include titanium hydroxide precipitated by decomposition, and one or more of these may be used in combination.
- tin compounds include inorganic acid salts such as tin hydrochloride, nitrate and sulfate, organic acid salts such as formic acid, citric acid, oxalic acid, lactic acid and glycolic acid, and hydrolysis by adding alkali to these aqueous solutions.
- inorganic acid salts such as tin hydrochloride, nitrate and sulfate
- organic acid salts such as formic acid, citric acid, oxalic acid, lactic acid and glycolic acid
- hydrolysis by adding alkali to these aqueous solutions.
- tin hydroxide precipitated can be used, and one or more of these may be used in combination.
- the aqueous dispersion medium is for making the raw material titanium compound or the raw material titanium compound and the tin compound into an aqueous solution, and an aqueous solvent is used.
- the aqueous solvent include a mixed solvent of water and a hydrophilic organic solvent mixed with water at an arbitrary ratio.
- water for example, deionized water, distilled water, pure water and the like are preferable.
- hydrophilic organic solvent for example, alcohols such as methanol, ethanol, and isopropanol are preferable.
- the mixing ratio of the hydrophilic organic solvent is preferably 0 to 50% by mass in the aqueous dispersion medium. Among these, pure water is most preferable from the viewpoint of productivity, cost, and the like.
- the concentration of the raw material titanium compound aqueous solution formed from the raw material titanium compound and the aqueous dispersion medium, or the concentration of the raw material titanium compound aqueous solution formed from the raw material titanium compound, the tin compound, and the aqueous dispersion medium is 60% by mass or less.
- the content is preferably 30% by mass or less.
- concentration is selected suitably, it is preferable that it is 1 mass% or more.
- the basic substance is for making the raw material titanium compound or the tin-containing raw material titanium compound smoothly into titanium hydroxide or tin-containing titanium hydroxide and stabilizing the peroxotitanium component described later in the aqueous dispersion medium
- examples include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as ammonia, alkanolamines and alkylamines.
- the pH of the raw material titanium compound aqueous solution is 7 or more, particularly pH 7 It is added and used in an amount of ⁇ 10.
- the basic substance may be used in the form of an aqueous solution having an appropriate concentration together with the aqueous dispersion medium.
- Hydrogen peroxide is used to convert the above raw material titanium compound or titanium hydroxide into peroxotitanium, that is, a titanium oxide compound containing a Ti—O—O—Ti bond. used.
- the amount of hydrogen peroxide added is preferably 1.5 to 5 times mol of Ti.
- the reaction temperature in the reaction of adding hydrogen peroxide to convert the raw material titanium compound or titanium hydroxide to peroxotitanic acid is preferably 5 to 60 ° C., and the reaction time is 30 minutes to 24 hours. It is preferable.
- the tin-free or tin-containing peroxotitanic acid solution thus obtained may contain an alkaline or acidic substance for pH adjustment and the like.
- the alkaline substance herein include ammonia, sodium hydroxide, and calcium hydroxide.
- the acidic substance include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, phosphoric acid, and hydrogen peroxide. And organic acids such as formic acid, citric acid, succinic acid, lactic acid and glycolic acid.
- the pH of the obtained tin-free or tin-containing peroxotitanic acid solution is preferably 1 to 7, particularly 4 to 7 from the viewpoint of safety in handling.
- a flow reactor for hydrothermally treating a tin-free or tin-containing peroxotitanic acid solution includes a raw material tank, a high-pressure liquid feed pump, a heating unit, a cooling unit, and a recovery unit. An outline of this apparatus is shown in FIG.
- 1a is a raw material tank that contains an aqueous solvent
- 1b is a tank that contains a tin-free or tin-containing peroxotitanic acid solution
- 2 is an aqueous solvent or tin-free material in the raw material tank 1a or 1b.
- a liquid feed pump for feeding a tin-containing peroxotitanic acid solution to the heating unit 3 3 is a heating unit for hydrothermal reaction of tin-free or tin-containing peroxotitanic acid solution, and 4 is the heating unit 3.
- a cooling unit for cooling a titanium oxide fine particle dispersion formed by hydrothermal reaction of a tin-free or tin-containing peroxotitanic acid solution, 5 is a back pressure valve, and 6 is a recovery unit for the obtained titanium oxide fine particle dispersion. It is.
- Reference numerals 7 and 8 are valves.
- the anatase type or rutile type titanium oxide fine particle dispersion is produced from the tin-free or tin-containing peroxotitanic acid solution using the above flow reactor, first, an aqueous solution such as pure water in the raw material tank 1a is used.
- the solvent is sent to the heating section by the feed pump 2 and the aqueous solvent is raised to a predetermined temperature of 150 to 250 ° C., then the feeding of the aqueous solvent is stopped, and then the tin-free or tin-containing peroxotitanic acid solution is added.
- the solution is fed and hydrothermally reacted.
- the liquid feed pump 2 is preferably a high-pressure liquid feed pump.
- a metal tube such as stainless steel is used, and tin-free or tin-containing peroxotitanium is contained therein. It is preferable to distribute an acid solution or the like.
- High-pressure liquid feed pump The suction part side is connected to a tank 1a containing an aqueous solvent and a tank 1b containing a tin-free or tin-containing peroxotitanic acid solution via valves 7 and 8, respectively, and the discharge part side. Is connected to a stainless steel tube that continues to the heating unit 3 and the cooling unit 4. It is preferable to use a high-pressure liquid feed pump that can discharge the raw material solution at a high pressure.
- Heating unit A stainless steel tube wound in a coil shape is connected to the discharge side of the high-pressure liquid feeding pump, and tin-free or tin-containing peroxotitanic acid raw material solution is passed through the tube.
- This tube is heated from the outside, and the raw material solution passing through the inside is hydrothermally treated.
- the raw material solution is converted into an anatase type or rutile type titanium oxide fine particle dispersion with hydrothermal treatment.
- the back pressure valve 5 is installed on the outlet side of the cooling unit, and the pressure in the tube is maintained at the saturated vapor pressure or higher of the heating temperature.
- the heating method from the outside is not particularly limited as long as the raw material solution in the tube can be heated to a set temperature.
- a steam heating, an electric furnace, an oil bath, a sand bath, or the like can be used.
- the inner diameter of the coiled stainless steel tube is suitably 20 mm or less, preferably 10 mm or less, more preferably 5 mm or less from the viewpoint of heat conduction to the fluid passing through the inside, but the inner diameter is 1 mm or more, particularly 2 mm or more.
- the hydrothermal treatment temperature is suitably 150 to 250 ° C., preferably 180 to 250 ° C. from the viewpoint of reaction efficiency and reaction controllability.
- the pressure in the tube is appropriately 0.5 to 10 MPa, preferably 2 to 10 MPa, in order to allow the temperature of the raw material solution to be raised to 150 ° C. or higher.
- the reaction time is suitably 0.5 to 20 minutes and preferably 1 to 10 minutes in order to control the raw material conversion.
- the heating time up to the hydrothermal treatment temperature is suitably 2 minutes or less, preferably 1 minute or less, from the viewpoint of the uniformity of the titanium oxide fine particles to be produced and the particle diameter.
- the said reaction time is time after temperature rising and reaching
- the back pressure valve is not particularly limited as long as the pressure in the tube can be kept constant.
- Cooling unit A stainless steel tube for cooling is connected to the outlet side tube of the heating unit, this tube is cooled from the outside, the anatase type or rutile type titanium oxide dispersion passing through the tube is cooled, and the reaction is stopped. .
- the cooling method from the outside is not particularly limited as long as the anatase-type or rutile-type titanium oxide dispersion in the tube can be cooled to a set temperature. For example, a water bath, an ice bath, or the like can be used.
- the inner diameter of the stainless steel tube for cooling is suitably 20 mm or less from the viewpoint of heat conduction to the fluid passing through the inside, preferably 10 mm or less, more preferably 5 mm or less, but the inner diameter is 1 mm or more, particularly 2 mm or more.
- the cooling temperature is suitably 40 ° C. or less, preferably 30 ° C. or less, from the viewpoint of stopping the reaction.
- the lower limit of the cooling temperature is not particularly limited, but is usually 0 ° C. or higher.
- the time required for cooling is suitably within 3 minutes, preferably within 2 minutes, from the viewpoint of the uniformity of the titanium oxide produced and the particle size.
- an anatase type or rutile type titanium oxide fine particle dispersion liquid is obtained.
- the titanium oxide fine particles in the dispersion liquid have a volume-based 50% cumulative distribution diameter measured by a dynamic scattering method using laser light ( D 50 ) (hereinafter referred to as “average particle diameter”) is preferably 50 nm or less, and more preferably 20 nm or less.
- the lower limit is not particularly limited, but is preferably 5 nm or more.
- the concentration of the titanium oxide fine particles is preferably 0.01 to 20% by mass, and particularly preferably 0.5 to 10% by mass in the dispersion from the viewpoint that a photocatalytic thin film having a required thickness can be easily produced.
- the conversion rate from the peroxotitanic acid solution to the titanium oxide fine particle dispersion is suitably 95 to 99.5%, more preferably 98 to 99.5%.
- the conversion is less than 95%, the photocatalytic effect of the photocatalytic thin film obtained from the dispersion may be insufficient.
- the conversion exceeds 99.5%, the titanium oxide fine particles in the dispersion It may become easy to aggregate.
- the anatase-type or rutile-type titanium oxide fine particle dispersion thus obtained can be used for forming a photocatalytic film on the surface of various members.
- the various members are not particularly limited, but examples of the material of the members include organic materials and inorganic materials, and the inorganic materials include, for example, non-metallic inorganic materials and metallic inorganic materials. These can have various shapes according to their respective purposes and applications.
- organic materials examples include vinyl chloride resin (PVC), polyethylene (PE), polypropylene (PP), polycarbonate (PC), acrylic resin, polyacetal, fluororesin, silicone resin, and ethylene-vinyl acetate copolymer (EVA).
- PVC vinyl chloride resin
- PE polyethylene
- PP polypropylene
- PC polycarbonate
- acrylic resin acrylic resin
- polyacetal polyacetal
- fluororesin silicone resin
- silicone resin ethylene-vinyl acetate copolymer
- EVA ethylene-vinyl acetate copolymer
- NBR Acrylonitrile-butadiene rubber
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PVB polyvinyl butyral
- EVOH ethylene-vinyl alcohol copolymer
- PPS polyphenylene sulfide
- PEI polyether Imide
- PEEI polyetheretherimide
- PEEK polyetheretherketone
- ABS acrylonitrile-butadiene-styrene
- Synthetic resin material natural materials such as natural rubber, or semi-synthetic materials include the above-mentioned synthetic resin material and natural material. These may be commercialized into a required shape and configuration such as a film, a sheet, a fiber material, a fiber product, other molded products, and a laminate.
- non-metallic inorganic materials include glass, ceramics, stones and the like. These may be commercialized in various forms such as tiles, glass, mirrors, walls, and design materials.
- metal inorganic material examples include cast iron, steel, iron, iron alloy, aluminum, aluminum alloy, nickel, nickel alloy, and zinc die cast. These may be plated with the metal inorganic material, may be coated with the organic material, or may be plated on the surface of the organic material or non-metallic inorganic material.
- the anatase-type or rutile-type titanium oxide fine particle dispersion is applied to the surface of the member by, for example, a known coating method such as spray coating or dip coating.
- a known coating method such as spray coating or dip coating.
- What is necessary is just to dry by the well-known drying methods, such as infrared rays drying, IH drying, hot air drying, and the thickness of a photocatalyst film
- membrane can also be selected variously, However, Usually, the range of 50 nm-10 micrometers is preferable.
- the anatase-type or rutile-type titanium oxide fine particle dispersion has a binder, particularly a silicon compound binder, for the purpose of facilitating application of the dispersion to the surfaces of the various members and adhesion of the fine particles. Is added in the range of 1:99 to 99: 1, more preferably 10:90 to 90:10, still more preferably 30:70 to 70:30. May be.
- the silicon compound binder is a colloidal dispersion, solution or emulsion of a silicon compound comprising a solid or liquid silicon compound in an aqueous dispersion medium, specifically, colloidal silica; Silicate solution such as silicate; Silane, siloxane hydrolyzate emulsion; Silicone resin emulsion; Emulsion of copolymer of silicone resin such as silicone-acrylic resin copolymer and silicone-urethane resin copolymer with other resin Etc.
- the photocatalyst film thus formed is transparent and gives a good photocatalytic action in the ultraviolet region as in the past.
- Various members formed with the photocatalyst film are made of organic substances by photocatalytic action of titanium oxide. Since the film surface is made hydrophilic, the surface of the member can be cleaned, deodorized, and antibacterial.
- Average particle diameter of fine titanium oxide particles in the dispersion (D 50 ) The average particle size (D 50 ) of the titanium oxide fine particles in the dispersion was measured using a particle size distribution analyzer (trade name “Nanotrack particle size analyzer UPA-EX”, manufactured by Nikkiso Co., Ltd.).
- the HAZE value (%) of the glass plate as the substrate was measured.
- the photocatalyst thin film was produced by applying the dispersion liquid on the glass and drying, and the HAZE value of the glass plate in the state of producing the thin film was measured. From the difference, the HAZE value of the photocatalytic thin film was obtained.
- the HAZE value was measured using a HAZE meter (trade name “Digital Haze Meter NDH-200”, manufactured by Nippon Denshoku Industries Co., Ltd.).
- the transparency of the photocatalytic thin film was evaluated according to the following criteria from the difference in the HAZE value obtained.
- Acetaldehyde gas decomposition performance test of photocatalytic thin film (under UV irradiation) The activity of the photocatalyst thin film produced by applying and drying the dispersion was evaluated by the decomposition reaction of acetaldehyde gas. The evaluation was performed by a flow-type gas decomposition performance evaluation method. Specifically, a sample for evaluation in which a photocatalytic thin film is formed on a substrate made of glass of 5 cm ⁇ 10 cm is placed in a quartz glass cell having a volume of 100 cm 3 , and the concentration is adjusted to 50% in the cell at a concentration of 100 ppm.
- acetaldehyde gas was circulated at a flow rate of 30 mL ⁇ s ⁇ 1 , light was irradiated with a black light installed at the top of the cell to 1 mW ⁇ cm ⁇ 2 .
- the concentration of acetaldehyde gas in the gas flowing out from the cell decreased. Therefore, the amount of acetaldehyde gas decomposition could be determined by measuring the concentration.
- the acetaldehyde gas concentration was measured using a gas chromatograph (trade name “GC-8A”, manufactured by Shimadzu Corporation).
- the suction part side of the high-pressure liquid pump is connected to the raw material tank, and the discharge part side is connected to a stainless steel tube heating reactor with an outer diameter of 3 mm, an inner diameter of 2 mm, and a diameter of 50 m installed in a steam heating furnace. did.
- the outlet side of the heating reactor was connected to a stainless steel tube cooling part having an outer diameter of 3 mm, an inner diameter of 2 mm, and 50 m installed in a water bath, and a back pressure valve was further provided on the outlet side of the cooling part, so The reaction apparatus shown in FIG. 1 in which the reaction product can be recovered.
- Example 1 A 36 mass% titanium chloride (IV) aqueous solution was diluted 10 times with pure water, and 10 mass% ammonia water was gradually added to the aqueous solution to neutralize and hydrolyze, thereby precipitating titanium hydroxide. Got. The pH of the solution at this time was 9. The resulting titanium hydroxide precipitate was deionized by repeatedly adding pure water and decanting. 30% by mass hydrogen peroxide solution was added to the titanium hydroxide precipitate after the deionization treatment so that the hydrogen peroxide / titanium hydroxide (molar ratio) was 2.5 or more, and the mixture was sufficiently stirred at room temperature all day and night. To react. Thereafter, pure water was added to adjust the concentration, thereby obtaining a yellow transparent peroxotitanic acid solution (solid content concentration: 1% by mass).
- a raw material tank (1a) charged with 20 L of pure water and a raw material tank (1b) charged with 20 L of peroxotitanic acid solution for a suction tube of a high-pressure water pump (trade name “general-purpose high-pressure liquid pump 8832 type” manufactured by AQUATH) ).
- pure water was fed from the raw material tank (1a) into the device tube with a high-pressure water pump, and after the tube was filled with pure water, the pressure in the tube was maintained at 2 MPa or more by a back pressure valve.
- the average particle diameter of the titanium oxide fine particles in the obtained dispersion was 13.7 nm, and the conversion rate of the peroxotitanic acid solution to titanium oxide particles was 99.3%.
- the hydrothermal reaction time in a heating part was 3 minutes, the time required for temperature rising was 20 seconds, and the time required for cooling was 1 minute.
- Example 2 Hydrothermal treatment was performed in a batch reactor. Specifically, 400 mL of the peroxotitanic acid solution obtained as in Example 1 was charged into a 500 mL volume autoclave and hydrothermally treated for 90 minutes at 190 ° C. and 1.4 MPa. Thereafter, the reaction mixture in the autoclave was discharged into a container held in a 25 ° C. water bath via a sampling tube, and the reaction was stopped by rapidly cooling to obtain a titanium oxide fine particle dispersion.
- a silica-based binder (colloidal silica, trade name: Snowtex 20 (manufactured by Nissan Chemical Industries, Ltd.)) was added to the dispersions produced in Example 1 and Comparative Examples 1 and 2 in a TiO 2 / SiO 2 mass ratio of 1.5. After being added, the glass plate was coated with a dip coater and dried to form a photocatalytic thin film having a film thickness of 300 nm to obtain a sample for evaluation.
- Table 1 shows the reaction conditions and average particle diameter of Example 1, Comparative Examples 1 and 2, crystal phase, raw material conversion, transparency evaluation of photocatalytic thin film, and gas decomposition rate after 90 minutes of black light irradiation in the acetaldehyde gas decomposition test. Are shown together.
- Example 1 As can be seen from the results of Example 1 and Comparative Example 2, it can be seen that when the time to reach the reaction temperature is early, the particle diameter of the titanium oxide fine particles obtained is reduced and the gas decomposition performance as a photocatalyst is improved.
- Example 2 After diluting 36 mass% titanium chloride (IV) aqueous solution and 5 mol% tin chloride (IV) with pure water 10 times with pure water, 10 mass% ammonia water was gradually added to this aqueous solution. A precipitate of titanium hydroxide was obtained by neutralization and hydrolysis. The pH of the solution at this time was 9. The resulting titanium hydroxide precipitate was deionized by repeatedly adding pure water and decanting. 30% by mass hydrogen peroxide solution was added to the titanium hydroxide precipitate after the deionization treatment so that the hydrogen peroxide / titanium hydroxide (molar ratio) was 2.5 or more, and the mixture was sufficiently stirred at room temperature all day and night. To react. Thereafter, pure water was added to adjust the concentration, thereby obtaining a yellow transparent tin-containing peroxotitanic acid solution (solid content concentration 1 mass%).
- a high-pressure water pump trade name “General-purpose high-pressure liquid pump 8832 type” manufactured by AQUATH Co., Ltd.
- the average particle diameter of the titanium oxide fine particles in the obtained dispersion was 10.5 nm, and the conversion rate of the peroxotitanic acid solution to titanium oxide particles was 98.9%.
- the hydrothermal reaction time in a heating part was 3 minutes, the time required for temperature rising was 20 seconds, and the time required for cooling was 1 minute.
- a silica-based binder (colloidal silica, trade name: Snowtex 20 (manufactured by Nissan Chemical Industries, Ltd.)) was added to the dispersions produced in Example 2 and Comparative Examples 3 and 4 in a TiO 2 / SiO 2 mass ratio of 1.5. After being added, the glass plate was coated with a dip coater and dried to form a photocatalytic thin film having a film thickness of 300 nm to obtain a sample for evaluation.
- Table 2 shows the reaction conditions and average particle diameter of Example 2, Comparative Examples 3 and 4, crystal phase, raw material conversion rate, transparency evaluation of the photocatalytic thin film, and gas decomposition rate after 90 minutes of black light irradiation in the acetaldehyde gas decomposition test. Are shown together.
- Example 2 As can be seen from the results of Example 2 and Comparative Example 4, it can be seen that when the time to reach the reaction temperature is early, the particle diameter of the titanium oxide fine particles obtained is reduced and the gas decomposition performance as a photocatalyst is improved.
- the anatase-type or rutile-type titanium oxide fine particle dispersion of the present invention is applied to various substrates composed of inorganic substances such as glass and metal, and organic substances such as polymer films (PET film, etc.) to form a photocatalytic thin film. It is useful for producing, and particularly useful for producing a transparent photocatalytic thin film on a polymer film.
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Abstract
Description
(1) ペルオキソチタン酸溶液からアナターゼ型酸化チタン微粒子分散液を製造する方法において、ペルオキソチタン酸溶液を流通式反応器に連続的に供給し、150~250℃、0.5~10MPaの条件下で水熱処理することを特徴とするアナターゼ型酸化チタン微粒子分散液の製造方法。
(2) 前記アナターゼ型酸化チタン微粒子分散液中の酸化チタン微粒子が、レーザー光を用いた動的散乱法により測定される体積基準の50%累積分布径(D50)で50nm以下であることを特徴とする(1)記載のアナターゼ型酸化チタン微粒子分散液の製造方法。
(3) 流通式反応器に連続的に供給されるペルオキソチタン酸溶液が設定した水熱反応温度まで2分間以内に加熱されることを特徴とする(1)又は(2)記載のアナターゼ型酸化チタン微粒子分散液の製造方法。
(4) ペルオキソチタン酸溶液を水熱処理して製造された酸化チタン微粒子分散液が、続いて2分間以内に40℃以下まで冷却されることを特徴とする(1)~(3)のいずれかに記載のアナターゼ型酸化チタン微粒子分散液の製造方法。
(5) 流通式反応器でのペルオキソチタン酸溶液から酸化チタン微粒子分散液への転化率が95~99.5%であるように反応時間を調整することを特徴とする(1)~(4)のいずれかに記載のアナターゼ型酸化チタン微粒子分散液の製造方法。
(6) (1)~(5)のいずれかに記載の製造方法によって得られるアナターゼ型酸化チタン微粒子分散液に更にバインダーを添加したことを特徴とするアナターゼ型酸化チタン微粒子分散液の製造方法。
(7) (6)に記載のバインダーがケイ素化合物系バインダーであることを特徴とするアナターゼ型酸化チタン微粒子分散液の製造方法。
(8) (1)~(7)のいずれかに記載の製造方法によって得られるアナターゼ型酸化チタン微粒子分散液を用いて形成される光触媒薄膜を表面に有することを特徴とする部材。
(9) スズ含有ペルオキソチタン酸溶液からルチル型酸化チタン微粒子分散液を製造する方法において、ペルオキソチタン酸溶液を流通式反応器に連続的に供給し、150~250℃、0.5~10MPaの条件下で水熱処理することを特徴とするルチル型酸化チタン微粒子分散液の製造方法。
(10) スズ成分の含有量が、酸化チタンとのモル比(Ti/Sn)で1~1,000であることを特徴とする(9)記載のルチル型酸化チタン微粒子分散液の製造方法。
(11) 前記ルチル型酸化チタン微粒子分散液中の酸化チタン微粒子が、レーザー光を用いた動的散乱法により測定される体積基準の50%累積分布径(D50)で50nm以下であることを特徴とする(9)又は(10)記載のルチル型酸化チタン微粒子分散液の製造方法。
(12) 流通式反応器に連続的に供給されるペルオキソチタン酸溶液が設定した水熱反応温度まで2分間以内に加熱されることを特徴とする(9)~(11)のいずれかに記載のルチル型酸化チタン微粒子分散液の製造方法。
(13) ペルオキソチタン酸溶液を水熱処理して製造された酸化チタン微粒子分散液が、続いて2分間以内に40℃以下まで冷却されることを特徴とする(9)~(12)のいずれかに記載のルチル型酸化チタン微粒子分散液の製造方法。
(14) 流通式反応器でのペルオキソチタン酸溶液から酸化チタン微粒子分散液への転化率が95~99.5%であるように反応時間を調整することを特徴とする(9)~(13)のいずれかに記載のルチル型酸化チタン微粒子分散液の製造方法。
(15) (9)~(14)のいずれかに記載の製造方法によって得られるルチル型酸化チタン微粒子分散液に更にバインダーを添加したことを特徴とするルチル型酸化チタン微粒子分散液の製造方法。
(16) (15)に記載のバインダーがケイ素化合物系バインダーであることを特徴とするルチル型酸化チタン微粒子分散液の製造方法。
(17) (9)~(16)のいずれかに記載の製造方法によって得られるルチル型酸化チタン微粒子分散液を用いて形成される光触媒薄膜を表面に有することを特徴とする部材。
<アナターゼ型又はルチル型酸化チタン微粒子分散液の製造方法>
本発明のアナターゼ型酸化チタン微粒子分散液の製造方法は、スズ非含有のペルオキソチタン酸溶液を流通式反応器にて水熱反応させる製造方法である。
本発明のルチル型酸化チタン微粒子分散液の製造方法は、スズ含有ペルオキソチタン酸溶液を流通式反応器にて水熱反応させる製造方法である。
スズ非含有のペルオキソチタン酸溶液は、市販の製品(例えば商品名“PTA-85”、(株)鯤コーポレーション製)を使用してもよいし、原料チタン化合物、塩基性物質及び過酸化水素を水性分散媒中で反応させることにより製造したペルオキソチタン酸溶液を使用してもよい。
反応方法としては、水性分散媒中の原料チタン化合物に塩基性物質を添加して水酸化チタンとし、含有する不純物イオンを除去し、過酸化水素を添加してペルオキソチタン酸溶液とする方法がある。
・スズ含有ペルオキソチタン酸溶液:
原料チタン化合物、スズ化合物、塩基性物質及び過酸化水素を水性分散媒中で反応させることにより製造したスズ含有ペルオキソチタン酸溶液を使用する。
反応方法としては、水性分散媒中の原料チタン化合物とスズ化合物の混合物に塩基性物質を添加してスズ含有水酸化チタンとの混合物とし、含有する不純物イオンを除去し、過酸化水素を添加してスズ含有ペルオキソチタン酸溶液とする方法がある。
このように、スズ非含有のペルオキソチタン酸溶液を使用すると、酸化チタンはアナターゼ型となり、一方、スズ含有のペルオキソチタン酸溶液を使用すると、酸化チタンはルチル型となる。
塩基性物質は、上記水性分散媒と共に適当な濃度の水溶液にして使用してもよい。
過酸化水素の添加量は、Tiの1.5~5倍モルとすることが好ましい。また、この過酸化水素を添加して原料チタン化合物又は水酸化チタンをペルオキソチタン酸にする反応における反応温度は、5~60℃とすることが好ましく、反応時間は、30分~24時間とすることが好ましい。
ここでいう、アルカリ性物質としては、例えば、アンモニア、水酸化ナトリウム、水酸化カルシウム等が挙げられ、酸性物質としては、例えば、硫酸、硝酸、塩酸、炭酸、リン酸、過酸化水素等の無機酸及び蟻酸、クエン酸、蓚酸、乳酸、グリコール酸等の有機酸が挙げられる。
この場合、得られたスズ非含有又はスズ含有のペルオキソチタン酸溶液のpHは1~7、特に4~7であることが取り扱いの安全性の点で好ましい。
スズ非含有又はスズ含有のペルオキソチタン酸溶液を水熱処理する流通式反応器は、原料タンク、高圧送液ポンプ、加熱部、冷却部、回収部から構成される。本装置の概要を図1に示す。
図1において、1aは水性溶媒が収容される原料タンク、1bはスズ非含有又はスズ含有のペルオキソチタン酸溶液が収容されるタンク、2は上記原料タンク1a又は1b内の水性溶媒又はスズ非含有若しくはスズ含有のペルオキソチタン酸溶液を加熱部3に送液する送液ポンプ、3はスズ非含有又はスズ含有のペルオキソチタン酸溶液を水熱反応させるための加熱部、4は上記加熱部3でスズ非含有又はスズ含有のペルオキソチタン酸溶液を水熱反応させることにより形成された酸化チタン微粒子分散液を冷却する冷却部、5は背圧弁、6は得られた酸化チタン微粒子分散液の回収部である。なお、7,8はバルブである。
ここで、上記流通式反応器を用いてスズ非含有又はスズ含有のペルオキソチタン酸溶液からアナターゼ型又はルチル型酸化チタン微粒子分散液を製造するに際しては、まず原料タンク1a内の純水等の水性溶媒を送液ポンプ2により加熱部に送り、水性溶媒を150~250℃の所定温度に上昇させた後、水性溶媒の送液を停止し、次いでスズ非含有又はスズ含有のペルオキソチタン酸溶液を送液し、水熱反応させるものである。
この場合、送液ポンプ2としては、高圧送液ポンプが好ましい。また、スズ非含有又はスズ含有のペルオキソチタン酸溶液等を加熱部3、冷却部4に流通させる手段としてはステンレススチール等の金属製チューブを用い、この内部にスズ非含有又はスズ含有のペルオキソチタン酸溶液等を流通させるようにすることが好ましい。
吸引部側を水性溶媒の入ったタンク1a及びスズ非含有又はスズ含有のペルオキソチタン酸溶液の入ったタンク1bにそれぞれバルブ7,8を介して接続し、吐出部側を加熱部3、冷却部4へと続く、ステンレス製チューブに接続する。ポンプは原料溶液が高圧で吐出可能な高圧送液ポンプを使用することが好ましい。
コイル状に巻いたステンレス製チューブを高圧送液ポンプの吐出側に接続し、チューブ内にスズ非含有又はスズ含有のペルオキソチタン酸原料溶液を通液する。このチューブを外部から加熱し、内部を通る原料溶液を水熱処理する。原料溶液は水熱処理に伴いアナターゼ型又はルチル型酸化チタン微粒子分散液に変換されていく。また、チューブ内温度を150℃以上に昇温するため、冷却部出口側に背圧弁5を設置し、チューブ内圧力を加熱温度の飽和蒸気圧以上に維持する。外部からの加熱方法は、チューブ内の原料溶液を設定温度に加熱可能であれば特に限定されないが、例えばスチーム加熱、電気炉、オイルバス、サンドバス等を使用することができる。
コイル状ステンレス製チューブの内径は内部を通過する流体への熱伝導の観点から20mm以下が適切であり、好ましくは10mm以下、より好ましくは5mm以下であるが、内径は1mm以上、特に2mm以上であることが好ましい。
水熱処理温度は反応効率と反応制御性の観点から150~250℃が適切であり、好ましくは180~250℃である。
チューブ内圧力は原料溶液の150℃以上への昇温を可能にするため、0.5~10MPaが適切であり、好ましくは2~10MPaである。
反応時間は原料転化率を制御するため、0.5~20分間が適切であり、好ましくは1~10分間である。
水熱処理温度までの昇温時間は、生成する酸化チタン微粒子の均一性、及び粒子径の観点から2分間以内が適切であり、好ましくは1分間以内である。なお、上記反応時間は、この水熱処理温度に昇温、到達してからの時間であり、上記昇温時間は含まない。
背圧弁はチューブ内圧力を一定に保圧できるものならば特に限定されない。
加熱部の出口側チューブに冷却用ステンレス製チューブを接続し、このチューブを外部から冷却してチューブ内を通るアナターゼ型又はルチル型酸化チタン分散液を冷却し、反応を停止させる。外部からの冷却方法は、チューブ内のアナターゼ型又はルチル型酸化チタン分散液を設定温度に冷却可能であれば特に限定されないが、例えば水浴、氷浴等を使用することができる。
冷却用ステンレス製チューブの内径は内部を通過する流体への熱伝導の観点から20mm以下が適切であり、好ましくは10mm以下、より好ましくは5mm以下であるが、内径は1mm以上、特に2mm以上であることが好ましい。
冷却温度は反応を停止させる観点から40℃以下が適切であり、好ましくは30℃以下である。なお、冷却温度の下限は特に制限されるものではないが、通常0℃以上である。
冷却に要する時間は、生成する酸化チタンの均一性、及び粒子径の観点から3分間以内が適切であり、好ましくは2分間以内である。
冷却部出口側のチューブから回収容器にアナターゼ型又はルチル型酸化チタン微粒子分散液を回収する。
また、酸化チタン微粒子の濃度は、所要の厚さの光触媒薄膜を作製し易い点で、該分散液中、0.01~20質量%が好ましく、特に0.5~10質量%が好ましい。
このようにして得られるアナターゼ型又はルチル型酸化チタン微粒子分散液は、各種部材の表面に光触媒膜を形成させるために使用することができる。
ここで、各種部材は、特に制限されないが、部材の材料としては、例えば、有機材料、無機材料が挙げられ、無機材料には、例えば、非金属無機材料、金属無機材料が包含される。これらは、それぞれの目的、用途に応じた様々な形状を有することができる。
これらは、フィルム、シート、繊維材料、繊維製品、その他の成型品、積層体等の所要の形状、構成に製品化されていてもよい。
なお、上記アナターゼ型又はルチル型酸化チタン微粒子分散液には、上記各種部材表面に該分散液を塗布し易くすると共に該微粒子を接着し易いようにする目的で、バインダー、特にはケイ素化合物系バインダーを配合比(ケイ素化合物と酸化チタンの質量比)1:99~99:1、より好ましくは10:90~90:10、更に好ましくは30:70~70:30の範囲で添加して使用してもよい。
ここで、ケイ素化合物系バインダーとは、固体状又は液体状のケイ素化合物を水性分散媒中に含んでなるケイ素化合物の、コロイド分散液、溶液又はエマルジョンであって、具体的には、コロイダルシリカ;シリケート等のケイ酸塩類溶液;シラン、シロキサン加水分解物エマルジョン;シリコーン樹脂エマルジョン;シリコーン-アクリル樹脂共重合体、シリコーン-ウレタン樹脂共重合体等のシリコーン樹脂と他の樹脂との共重合体のエマルジョン等を挙げることができる。
このようにして形成される光触媒膜は、透明であり、従来のように紫外領域において良好な光触媒作用を与えるものであり、該光触媒膜が形成された各種部材は、酸化チタンの光触媒作用により有機物を分解し膜表面を親水性にすることから、該部材表面の清浄化、脱臭、抗菌等の効果を発揮することができるものである。
分散液中の酸化チタン微粒子の平均粒子径(D50)は、粒度分布測定装置(商品名“ナノトラック粒度分析計UPA-EX”、日機装(株)製)を用いて測定した。
得られた酸化チタンの微粒子の結晶相は、粉末X線回折装置(商品名“MultiFlex”,(株)Rigaku製)を用いて測定した。
ペルオキソチタン酸水溶液の酸化チタン微粒子分散液への転化率は、反応混合物中のチタン量を過酸化水素吸光光度法によって測定することで算出した。吸光度は、反応混合物の一部を抜き出し、硫酸酸性とした上で過酸化水素と反応、呈色させた後、紫外可視分光光度計(商品名“UVmini1240”、(株)島津製作所製)を用いて測定した。
基材であるガラス板のHAZE値(%)を測定した。次に、分散液を該ガラス上に塗布、乾燥することで光触媒薄膜を作製し、該薄膜を作製した状態のガラス板のHAZE値を測定した。その差から光触媒薄膜のHAZE値を求めた。HAZE値の測定はHAZEメーター(商品名“デジタルヘイズメーターNDH-200”、日本電色工業(株)製)を用いた。光触媒薄膜の透明性を求められたHAZE値の差から次の基準で評価した。
良好(○と表示) ・・・・ 差が+1%以下
やや不良(△と表示)・・・・ 差が+1%を超え、+3%以下
不良(×と表示) ・・・・ 差が+3%を超える
分散液を塗布、乾燥することで作製した光触媒薄膜の活性を、アセトアルデヒドガスの分解反応により評価した。評価は流通式ガス分解性能評価法により行った。具体的には、容積100cm3の石英ガラス製セル内に5cm×10cmのガラスからなる基板上に光触媒薄膜を形成した評価用サンプルを設置し、該セルに湿度50%に調湿した濃度100ppmのアセトアルデヒドガスを流量30mL・s-1で流通させながら、セル上部に設置したブラックライトで1mW・cm-2になるように光を照射した。薄膜上の光触媒によりアセトアルデヒドガスが分解すると、該セルから流出するガス中のアセトアルデヒドガス濃度が低下した。そこで、その濃度を測定することで、アセトアルデヒドガス分解量を求めることができた。アセトアルデヒドガス濃度はガスクロマトグラフ(商品名“GC-8A”、(株)島津製作所製)を用いて測定した。
なお、実施例は以下に述べる反応装置を用いて行った。
(反応装置)
高圧送液ポンプの吸引部側を原料タンクに接続し、吐出部側を、スチーム加熱炉内に設置されたコイル状に巻いた外径3mm、内径2mm、50mのステンレス製チューブ加熱反応器に接続した。続いて加熱反応器出口側を、水浴中に設置された外径3mm、内径2mm、50mのステンレス製チューブ冷却部に接続し、更に冷却部出口側に背圧弁を設け、常圧で回収容器に反応生成物を回収できるようにした図1に示す反応装置。
36質量%の塩化チタン(IV)水溶液を純水で10倍に希釈した後、この水溶液に10質量%のアンモニア水を徐々に添加して中和、加水分解することにより水酸化チタンの沈殿物を得た。このときの溶液のpHは9であった。得られた水酸化チタンの沈殿物を、純水の添加とデカンテーションを繰り返して脱イオン処理した。この脱イオン処理後の水酸化チタン沈殿物に過酸化水素/水酸化チタン(モル比)が2.5以上となるように30質量%過酸化水素水を添加し、室温で一昼夜撹拌して十分に反応させた。その後、純水を添加して濃度調整を行うことにより、黄色透明のペルオキソチタン酸溶液(固形分濃度1質量%)を得た。
得られた分散液中の酸化チタン微粒子の平均粒子径を測定したところ、13.7nm、ペルオキソチタン酸溶液の酸化チタン粒子への転化率を測定したところ99.3%であった。
なお、加熱部での水熱反応時間は3分間、昇温に要した時間は20秒間、冷却に要した時間は1分間であった。
加熱部の加熱温度を130℃にした以外は実施例1と同様にして水熱処理を行った。
回分式反応器により水熱処理を行った。具体的には、実施例1のようにして得たペルオキソチタン酸溶液を容積500mLのオートクレーブに400mL仕込み、これを190℃、1.4MPaの条件下、90分間水熱処理した。その後、オートクレーブ内の反応混合物を、サンプリング管を経由して、25℃の水浴中に保持した容器に排出し、急速に冷却することで反応を停止させ、酸化チタン微粒子分散液を得た。
36質量%の塩化チタン(IV)水溶液とTiに対して5mol%量の塩化スズ(IV)を純水で10倍に希釈した後、この水溶液に10質量%のアンモニア水を徐々に添加して中和、加水分解することにより水酸化チタンの沈殿物を得た。このときの溶液のpHは9であった。得られた水酸化チタンの沈殿物を、純水の添加とデカンテーションを繰り返して脱イオン処理した。この脱イオン処理後の水酸化チタン沈殿物に過酸化水素/水酸化チタン(モル比)が2.5以上となるように30質量%過酸化水素水を添加し、室温で一昼夜撹拌して十分に反応させた。その後、純水を添加して濃度調整を行うことにより、黄色透明のスズ含有ペルオキソチタン酸溶液(固形分濃度1質量%)を得た。
得られた分散液中の酸化チタン微粒子の平均粒子径を測定したところ、10.5nm、ペルオキソチタン酸溶液の酸化チタン粒子への転化率を測定したところ98.9%であった。
なお、加熱部での水熱反応時間は3分間、昇温に要した時間は20秒間、冷却に要した時間は1分間であった。
加熱部の加熱温度を130℃にした以外は実施例2と同様にして水熱処理を行った。
回分式反応器により水熱処理を行った。具体的には、実施例2のようにして得たスズ含有ペルオキソチタン酸溶液を容積500mLのオートクレーブに400mL仕込み、これを190℃、1.4MPaの条件下、90分間水熱処理した。その後、オートクレーブ内の反応混合物を、サンプリング管を経由して、25℃の水浴中に保持した容器に排出し、急速に冷却することで反応を停止させ、酸化チタン微粒子分散液を得た。
Claims (17)
- ペルオキソチタン酸溶液からアナターゼ型酸化チタン微粒子分散液を製造する方法において、ペルオキソチタン酸溶液を流通式反応器に連続的に供給し、150~250℃、0.5~10MPaの条件下で水熱処理することを特徴とするアナターゼ型酸化チタン微粒子分散液の製造方法。
- 前記アナターゼ型酸化チタン微粒子分散液中の酸化チタン微粒子が、レーザー光を用いた動的散乱法により測定される体積基準の50%累積分布径(D50)で50nm以下であることを特徴とする請求項1記載のアナターゼ型酸化チタン微粒子分散液の製造方法。
- 流通式反応器に連続的に供給されるペルオキソチタン酸溶液が設定した水熱反応温度まで2分間以内に加熱されることを特徴とする請求項1又は2記載のアナターゼ型酸化チタン微粒子分散液の製造方法。
- ペルオキソチタン酸溶液を水熱処理して製造された酸化チタン微粒子分散液が、続いて2分間以内に40℃以下まで冷却されることを特徴とする請求項1~3のいずれか1項記載のアナターゼ型酸化チタン微粒子分散液の製造方法。
- 流通式反応器でのペルオキソチタン酸溶液から酸化チタン微粒子分散液への転化率が95~99.5%であるように反応時間を調整することを特徴とする請求項1~4のいずれか1項記載のアナターゼ型酸化チタン微粒子分散液の製造方法。
- 請求項1~5のいずれか1項記載の製造方法によって得られるアナターゼ型酸化チタン微粒子分散液に更にバインダーを添加したことを特徴とするアナターゼ型酸化チタン微粒子分散液の製造方法。
- 請求項6に記載のバインダーがケイ素化合物系バインダーであることを特徴とするアナターゼ型酸化チタン微粒子分散液の製造方法。
- 請求項1~7のいずれか1項記載の製造方法によって得られるアナターゼ型酸化チタン微粒子分散液を用いて形成される光触媒薄膜を表面に有することを特徴とする部材。
- スズ含有ペルオキソチタン酸溶液からルチル型酸化チタン微粒子分散液を製造する方法において、ペルオキソチタン酸溶液を流通式反応器に連続的に供給し、150~250℃、0.5~10MPaの条件下で水熱処理することを特徴とするルチル型酸化チタン微粒子分散液の製造方法。
- スズ成分の含有量が、酸化チタンとのモル比(Ti/Sn)で1~1,000であることを特徴とする請求項9記載のルチル型酸化チタン微粒子分散液の製造方法。
- 前記ルチル型酸化チタン微粒子分散液中の酸化チタン微粒子が、レーザー光を用いた動的散乱法により測定される体積基準の50%累積分布径(D50)で50nm以下であることを特徴とする請求項9又は10記載のルチル型酸化チタン微粒子分散液の製造方法。
- 流通式反応器に連続的に供給されるペルオキソチタン酸溶液が設定した水熱反応温度まで2分間以内に加熱されることを特徴とする請求項9~11のいずれか1項記載のルチル型酸化チタン微粒子分散液の製造方法。
- ペルオキソチタン酸溶液を水熱処理して製造された酸化チタン微粒子分散液が、続いて2分間以内に40℃以下まで冷却されることを特徴とする請求項9~12のいずれか1項記載のルチル型酸化チタン微粒子分散液の製造方法。
- 流通式反応器でのペルオキソチタン酸溶液から酸化チタン微粒子分散液への転化率が95~99.5%であるように反応時間を調整することを特徴とする請求項9~13のいずれか1項記載のルチル型酸化チタン微粒子分散液の製造方法。
- 請求項9~14のいずれか1項記載の製造方法によって得られるルチル型酸化チタン微粒子分散液に更にバインダーを添加したことを特徴とするルチル型酸化チタン微粒子分散液の製造方法。
- 請求項15に記載のバインダーがケイ素化合物系バインダーであることを特徴とするルチル型酸化チタン微粒子分散液の製造方法。
- 請求項9~16のいずれか1項記載の製造方法によって得られるルチル型酸化チタン微粒子分散液を用いて形成される光触媒薄膜を表面に有することを特徴とする部材。
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