JP2011167620A - Anatase type titanium oxide dispersion and method for producing the same - Google Patents
Anatase type titanium oxide dispersion and method for producing the same Download PDFInfo
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- JP2011167620A JP2011167620A JP2010032984A JP2010032984A JP2011167620A JP 2011167620 A JP2011167620 A JP 2011167620A JP 2010032984 A JP2010032984 A JP 2010032984A JP 2010032984 A JP2010032984 A JP 2010032984A JP 2011167620 A JP2011167620 A JP 2011167620A
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- Prior art keywords
- dispersion
- titanium oxide
- anatase
- type titanium
- alkoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 97
- 239000007788 liquid Substances 0.000 claims abstract description 64
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- -1 titanium alkoxide Chemical class 0.000 claims abstract description 38
- 239000010955 niobium Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 230000032683 aging Effects 0.000 claims abstract description 31
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 24
- 239000002612 dispersion medium Substances 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 46
- 239000003381 stabilizer Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 230000003466 anti-cipated effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 28
- 238000006460 hydrolysis reaction Methods 0.000 description 25
- 230000007062 hydrolysis Effects 0.000 description 24
- 239000000499 gel Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 239000011521 glass Substances 0.000 description 16
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 5
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- UEFGLENGHNNEBY-UHFFFAOYSA-N 1-methoxyethanol hydrate Chemical compound O.COC(C)O UEFGLENGHNNEBY-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
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- 229920000728 polyester Polymers 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 239000003960 organic solvent Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- DINQVNXOZUORJS-UHFFFAOYSA-N butan-1-olate;niobium(5+) Chemical compound [Nb+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] DINQVNXOZUORJS-UHFFFAOYSA-N 0.000 description 2
- QORWLRPWMJEJKP-UHFFFAOYSA-N butan-1-olate;tantalum(5+) Chemical compound [Ta+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] QORWLRPWMJEJKP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical compound CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CGAFRZVAXRQUEI-UHFFFAOYSA-N niobium(5+);propan-1-olate Chemical compound [Nb+5].CCC[O-].CCC[O-].CCC[O-].CCC[O-].CCC[O-] CGAFRZVAXRQUEI-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- LJTHRDIGXSIYMM-UHFFFAOYSA-N propan-1-olate tantalum(5+) Chemical compound [Ta+5].CCC[O-].CCC[O-].CCC[O-].CCC[O-].CCC[O-] LJTHRDIGXSIYMM-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- KFBXUKHERGLHLG-UHFFFAOYSA-N 2,4-Nonanedione Chemical compound CCCCCC(=O)CC(C)=O KFBXUKHERGLHLG-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- PYNACNWRKVQOMO-UHFFFAOYSA-N 2-methylpropan-2-olate;tantalum(5+) Chemical compound [Ta+5].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] PYNACNWRKVQOMO-UHFFFAOYSA-N 0.000 description 1
- PQCLJXVUAWLNSV-UHFFFAOYSA-N 5-Methyl-2,3-hexanedione Chemical compound CC(C)CC(=O)C(C)=O PQCLJXVUAWLNSV-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HGZSLMTUMOHPBM-UHFFFAOYSA-N [Ta+5].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] Chemical compound [Ta+5].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] HGZSLMTUMOHPBM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 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
- 239000004760 aramid Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- JZIBIUMUMQLPTN-UHFFFAOYSA-N butan-2-olate niobium(5+) Chemical compound [Nb+5].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] JZIBIUMUMQLPTN-UHFFFAOYSA-N 0.000 description 1
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
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- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QPQANCNBWQXGTQ-UHFFFAOYSA-N trihydroxy(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](O)(O)O QPQANCNBWQXGTQ-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、例えば、可視光応答型光触媒材料や電子デバイス材料として好適に用いることができるアナターゼ型酸化チタン分散液およびその製造方法に関する。 The present invention relates to an anatase-type titanium oxide dispersion that can be suitably used as, for example, a visible light responsive photocatalytic material or an electronic device material, and a method for producing the same.
従来から、酸化チタン（チタニア）からなる膜は、光触媒体、保護膜、導電性膜、半導体、紫外線カット被膜、着色コーティング膜など各種用途において利用されており、それら膜性能のさらなる改良も進められている。例えば、光触媒体としては、アナターゼ型酸化チタン膜は、通常、紫外光領域で優れた光触媒活性を発揮するものであるが、膜を形成する酸化チタンに遷移金属であるニオブまたはタンタルをドープさせると、可視光領域における光触媒活性を高めることができる、といった知見が知られている。また、酸化チタンにニオブまたはタンタルの如きドーパントをドープさせることは、導電性膜の比抵抗を下げるうえでも有効であることが知られている。 Conventionally, a film made of titanium oxide (titania) has been used in various applications such as a photocatalyst, a protective film, a conductive film, a semiconductor, an ultraviolet cut film, and a colored coating film, and further improvement of the film performance has been promoted. ing. For example, as a photocatalyst, an anatase-type titanium oxide film usually exhibits excellent photocatalytic activity in the ultraviolet region, but when the titanium oxide forming the film is doped with transition metal niobium or tantalum. The knowledge that the photocatalytic activity in the visible light region can be enhanced is known. It is also known that doping titanium oxide with a dopant such as niobium or tantalum is effective in reducing the specific resistance of the conductive film.
ところで、ドーパントを含む酸化チタン（ドープ酸化チタン）の膜を簡便に形成する方法の一つとして、ドープ酸化チタンの微粒子の分散液あるいはドープ酸化チタンの前駆体の溶液を基材表面に塗布し、その後、乾燥あるいはさらに必要に応じ焼成する、いわゆる塗布法がある。
かかる塗布法において分散液を用いる場合、均質かつ緻密で表面が平滑な膜を形成するためには、用いる分散液の分散安定性が良好であることが望ましい。一般に、分散液中のドープ酸化チタン微粒子の分散安定性を向上させるには、１）アンモニア、分散剤、界面活性剤等を分散安定化剤として含有させるか、あるいは、２）酸化チタンの分散系では等電点がｐＨ７前後であるので、分散液のｐＨを酸性領域もしくはアルカリ性領域に制御することによりゼータ電位の絶対値を大きくし、静電反発作用により微粒子を分散させる手法が採用される。
By the way, as one method for easily forming a titanium oxide film containing a dopant (doped titanium oxide), a dispersion of doped titanium oxide fine particles or a solution of a doped titanium oxide precursor is applied to the substrate surface, Thereafter, there is a so-called coating method in which drying or further firing is performed as necessary.
When a dispersion is used in such a coating method, it is desirable that the dispersion used has good dispersion stability in order to form a uniform, dense, smooth surface film. In general, in order to improve the dispersion stability of the doped titanium oxide fine particles in the dispersion, 1) ammonia or a dispersant, a surfactant or the like is contained as a dispersion stabilizer, or 2) a dispersion system of titanium oxide. Then, since the isoelectric point is around pH 7, a method is adopted in which the absolute value of the zeta potential is increased by controlling the pH of the dispersion to the acidic region or the alkaline region, and the fine particles are dispersed by electrostatic repulsion.
しかし、上記１）の手法によれば、含有させた分散安定化剤が形成される膜中に不純物として残存することになるため、結果として、形成された膜は光触媒体や導電性膜としての性能を損なうこととなる。他方、上記２）の手法には、例えば分散液の液性が酸性であると、成膜プロセスにおいて使用する成膜装置等に酸による腐食が生じる等の問題がある。 However, according to the above method 1), since the contained dispersion stabilizer remains as an impurity in the formed film, as a result, the formed film is used as a photocatalyst or a conductive film. Performance will be impaired. On the other hand, the method 2) has a problem that, for example, if the dispersion liquid is acidic, the film forming apparatus used in the film forming process is corroded by acid.
そこで、酸や塩基および分散安定化剤の非存在下で分散質を安定に分散させる方法として、温度制限のない条件下で金属アルコキシドに対し０．５〜１倍モル未満の水を用いて加水分解するか、−２０℃以下の条件下で金属アルコキシドに対し１．０〜２．０倍モル未満の水を用いて加水分解することにより、有機溶媒中に金属−酸素結合を有する分散質が凝集せず安定に分散してなる金属酸化物ゾルを製造する方法が提案されている（特許文献１）。 Therefore, as a method for stably dispersing the dispersoid in the absence of an acid, a base, and a dispersion stabilizer, water is added in an amount of 0.5 to less than 1 mole relative to the metal alkoxide under a temperature-free condition. The dispersoid having a metal-oxygen bond in an organic solvent is decomposed or hydrolyzed with 1.0 to 2.0 times less water than the metal alkoxide under the condition of −20 ° C. or lower. There has been proposed a method for producing a metal oxide sol which is stably aggregated and dispersed (Patent Document 1).
しかしながら、特許文献１記載の方法で得られた酸化チタンゾルは、分散液として良好な分散安定性を備えたものではあるが、これを基板に塗布して形成された酸化チタン膜には未だに有機残留物が多い場合があり、その結果、例えば光触媒体として充分な光触媒活性を発揮し得なかったり、導電性膜として導電性が低下するなど、本来期待される膜性能が損なわれることがあった。更に、特許文献１記載の方法で得られた酸化チタンは非晶質であり、高温で焼成してアナターゼ型へと結晶化し、光触媒等の機能が発現するものである。よって、基材が高温焼成に耐えうるものに限定されるといった問題点があった。 However, the titanium oxide sol obtained by the method described in Patent Document 1 has good dispersion stability as a dispersion, but the organic oxide still remains in the titanium oxide film formed by applying this to a substrate. As a result, there are cases in which the originally expected film performance is impaired such that, for example, sufficient photocatalytic activity as a photocatalyst cannot be exhibited, or the conductivity as a conductive film is lowered. Further, the titanium oxide obtained by the method described in Patent Document 1 is amorphous, and is baked at a high temperature to crystallize into an anatase type, and functions such as a photocatalyst are exhibited. Therefore, there is a problem that the base material is limited to those that can withstand high-temperature firing.
そこで、本発明の課題は、良好な分散安定性を有するとともに、有機残留物が少なく光触媒活性や導電性など本来期待される性能を充分に発現しうる膜を焼成することなく比較的低い温度で形成することができるアナターゼ型酸化チタン分散液およびその製造方法を提供することにある。 Therefore, an object of the present invention is to achieve a relatively low temperature without firing a film that has good dispersion stability and has a small amount of organic residue and can sufficiently exhibit the originally expected performance such as photocatalytic activity and conductivity. An object of the present invention is to provide an anatase-type titanium oxide dispersion that can be formed and a method for producing the same.
本発明者は、前記課題を解決するべく鋭意検討を行った。その結果、必須の金属アルコキシドとしてチタンアルコキシドとニオブアルコキシドまたはタンタルアルコキシドとを含む前駆体液を加水分解してニオブまたはタンタルドープ酸化チタンを生成させるにあたり、従来よりも多量の水、具体的には、前駆体液中の金属原子の総モル数（金属アルコキシドの総モル数）に対して２倍モル以上の水の存在下で加水分解を行うとともに、加水分解の後、５０℃以上の温度で酸化チタンの結晶型がアナターゼ型となるまでエージング処理を施し、得られたゲルを分散媒中に分散させるようにすれば、良好な分散安定性を保持しつつ特定のエージング処理において有機残留物を低減できることを見出した。そして、かくして得られた分散液を用いて形成されたアナターゼ型酸化チタン膜が、光触媒活性や導電性などに優れた性能を発揮するものとなることを確認し、本発明を完成した。 The present inventor has intensively studied to solve the above problems. As a result, when a precursor liquid containing titanium alkoxide and niobium alkoxide or tantalum alkoxide as essential metal alkoxides is hydrolyzed to produce niobium or tantalum-doped titanium oxide, more water than before, specifically, precursor Hydrolysis is performed in the presence of water at least twice the total number of metal atoms (total number of metal alkoxides) in the body fluid, and after hydrolysis, the titanium oxide is heated at a temperature of 50 ° C. or higher. If aging treatment is performed until the crystal form becomes anatase type, and the obtained gel is dispersed in a dispersion medium, organic residue can be reduced in a specific aging treatment while maintaining good dispersion stability. I found it. And it confirmed that the anatase type titanium oxide film formed using the dispersion liquid obtained in this way exhibited the performance excellent in photocatalytic activity, electroconductivity, etc., and completed this invention.
すなわち、本発明は、以下の構成からなる。
（１）ニオブまたはタンタルがドープされたアナターゼ型酸化チタンのナノ粒子が分散媒中に分散してなる分散液の製造方法であって、チタンアルコキシドとニオブアルコキシドまたはタンタルアルコキシドとを必須の金属アルコキシドとして含む前駆体液を該前駆体液中の金属原子の総モル数に対し２倍モル以上の水の存在下で加水分解した後、５０℃以上の温度で所定時間エージング処理を施すことにより、ニオブまたはタンタルがドープされたアナターゼ型酸化チタンを含有するゲルを得、このゲルを分散媒中に分散させることを特徴とするアナターゼ型酸化チタン分散液の製造方法。
（２）前記前駆体液中の必須の金属アルコキシドの合計濃度が０．１モル／Ｌ以上である、前記（１）に記載のアナターゼ型酸化チタン分散液の製造方法。
（３）得られる分散液中のアナターゼ型酸化チタンのナノ粒子の平均粒子径が３〜２０ｎｍである、前記（１）または（２）のいずれかに記載のアナターゼ型酸化チタン分散液の製造方法。
（４）得られる分散液の固形分濃度が０．０１〜３０重量％である、前記（１）〜（３）のいずれかに記載のアナターゼ型酸化チタン分散液の製造方法。
（５）得られる分散液は、液性が中性であり、かつ分散安定化剤を含有していない、前記（１）〜（４）のいずれかに記載のアナターゼ型酸化チタン分散液の製造方法。
（６）前記（１）〜（５）のいずれかに記載の製造方法によって得られたアナターゼ型酸化チタン分散液。
That is, this invention consists of the following structures.
(1) A method for producing a dispersion liquid in which nanoparticles of anatase-type titanium oxide doped with niobium or tantalum are dispersed in a dispersion medium, wherein titanium alkoxide and niobium alkoxide or tantalum alkoxide are used as essential metal alkoxides. Niobium or tantalum by hydrolyzing the precursor liquid containing the precursor liquid in the presence of water at least twice the total number of moles of metal atoms in the precursor liquid and then aging treatment at a temperature of 50 ° C. or higher for a predetermined time. A method for producing an anatase-type titanium oxide dispersion characterized by obtaining a gel containing anatase-type titanium oxide doped with an anatase and dispersing the gel in a dispersion medium.
(2) The method for producing an anatase-type titanium oxide dispersion according to (1), wherein the total concentration of essential metal alkoxides in the precursor liquid is 0.1 mol / L or more.
(3) The method for producing an anatase-type titanium oxide dispersion according to (1) or (2) above, wherein the average particle diameter of the anatase-type titanium oxide nanoparticles in the obtained dispersion is 3 to 20 nm. .
(4) The method for producing an anatase-type titanium oxide dispersion according to any one of (1) to (3), wherein a solid content concentration of the obtained dispersion is 0.01 to 30% by weight.
(5) Manufacture of the anatase type titanium oxide dispersion liquid in any one of said (1)-(4) whose liquid dispersion is neutral and does not contain a dispersion stabilizer. Method.
(6) Anatase-type titanium oxide dispersion obtained by the production method according to any one of (1) to (5).
本発明によれば、良好な分散安定性を有するとともに、有機残留物が少なく光触媒活性や導電性など本来期待される性能を充分に発現しうる膜を形成することが可能な、ニオブまたはタンタルがドープされたアナターゼ型酸化チタンの分散液を提供することができる。かかる分散液は、優れた光触媒活性や導電性を発現しうる膜を形成できるので、光触媒材料とりわけ可視光応答型光触媒材料や、電子デバイス材料として好適に用いられる。また、本発明によれば、焼成することなく比較的低い温度で成膜できるので、耐熱性の低い基材に対しても適用可能である。 According to the present invention, there is provided niobium or tantalum that has good dispersion stability and can form a film that has a small amount of organic residue and can sufficiently exhibit the originally expected performance such as photocatalytic activity and conductivity. A dispersion of doped anatase titanium oxide can be provided. Since such a dispersion can form a film capable of exhibiting excellent photocatalytic activity and conductivity, it is suitably used as a photocatalyst material, particularly a visible light responsive photocatalyst material or an electronic device material. In addition, according to the present invention, the film can be formed at a relatively low temperature without firing, and thus can be applied to a substrate having low heat resistance.
本発明のアナターゼ型酸化チタン分散液の製造方法は、ニオブまたはタンタルがドープされたアナターゼ型酸化チタンのナノ粒子（以下、単に「ドープアナターゼ型酸化チタン粒子」と称することもある）が分散媒中に分散してなる分散液を得るものである。かかるドープアナターゼ型酸化チタン粒子は、チタンアルコキシドとニオブアルコキシドまたはタンタルアルコキシドとを必須の金属アルコキシドとし、これら金属アルコキシドの加水分解生成物が縮合することによって得られる粒子である。 In the method for producing an anatase-type titanium oxide dispersion of the present invention, the nanoparticle of anatase-type titanium oxide doped with niobium or tantalum (hereinafter sometimes simply referred to as “doped anatase-type titanium oxide particles”) is contained in the dispersion medium. To obtain a dispersion liquid. Such doped anatase-type titanium oxide particles are particles obtained by using titanium alkoxide and niobium alkoxide or tantalum alkoxide as essential metal alkoxides, and condensing hydrolysis products of these metal alkoxides.
本発明の製造方法においては、まず、チタンアルコキシドとニオブアルコキシドまたはタンタルアルコキシドとを必須の金属アルコキシドとして含む前駆体液を得る。具体的には、前駆体液は、適当な溶媒中に上述した必須の金属アルコキシドを溶解させることによって調製することができる。ここで、ニオブアルコキシドおよびタンタルアルコキシドの両方を必須の金属アルコキシドとしてもよいことは言うまでもない。 In the production method of the present invention, first, a precursor liquid containing titanium alkoxide and niobium alkoxide or tantalum alkoxide as essential metal alkoxide is obtained. Specifically, the precursor liquid can be prepared by dissolving the essential metal alkoxide described above in a suitable solvent. Here, it goes without saying that both niobium alkoxide and tantalum alkoxide may be essential metal alkoxides.
前記チタンアルコキシドとしては、例えば、テトラメトキシチタン、テトラエトキシチタン、テトラ−ｉ−プロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラ−ｎ−ブトキシチタン、テトラ−ｉ−ブトキシチタン、テトラ−ｓｅｃ−ブトキシチタン、テトラ−ｔ−ブトキシチタン、テトラキス（ジメチルアミノ）チタン、テトラキスジエチルアミノチタン、ジ（イソプロポキシ）ビス（ジピバロイルメタナト）チタン等を用いることができる。チタンアルコキシドは、１種のみを用いてもよいし、２種以上を併用してもよい。 Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-i-butoxy titanium, and tetra-sec-butoxy titanium. , Tetra-t-butoxytitanium, tetrakis (dimethylamino) titanium, tetrakisdiethylaminotitanium, di (isopropoxy) bis (dipivaloylmethanato) titanium and the like can be used. Titanium alkoxide may use only 1 type and may use 2 or more types together.
前記ニオブアルコキシドとしては、例えば、ペンタメトキシニオブ、ペンタエトキシニオブ、ペンタ−ｉ−プロポキシニオブ、ペンタ−ｎ−プロポキシニオブ、ペンタ−ｉ−ブトキシニオブ、ペンタ−ｎ−ブトキシニオブ、ペンタ−ｓｅｃ−ブトキシニオブ等を用いることができる。ニオブアルコキシドは、１種のみを用いてもよいし、２種以上を併用してもよい。
前記タンタルアルコキシドとしては、例えば、ペンタメトキシタンタル、ペンタエトキシタンタル、ペンタ−ｉ−プロポキシタンタル、ペンタ−ｎ−プロポキシタンタル、ペンタ−ｉ−ブトキシタンタル、ペンタ−ｎ−ブトキシタンタル、ペンタ−ｓｅｃ−ブトキシタンタル、ペンタ−ｔ−ブトキシタンタル等を用いることができる。タンタルアルコキシドは、１種のみを用いてもよいし、２種以上を併用してもよい。
Examples of the niobium alkoxide include pentamethoxy niobium, pentaethoxy niobium, penta-i-propoxy niobium, penta-n-propoxy niobium, penta-i-butoxy niobium, penta-n-butoxy niobium, penta-sec-butoxy niobium. Etc. can be used. Niobium alkoxide may use only 1 type and may use 2 or more types together.
Examples of the tantalum alkoxide include pentamethoxy tantalum, pentaethoxy tantalum, penta-i-propoxy tantalum, penta-n-propoxy tantalum, penta-i-butoxy tantalum, penta-n-butoxy tantalum, penta-sec-butoxy tantalum. Penta-t-butoxy tantalum or the like can be used. A tantalum alkoxide may use only 1 type and may use 2 or more types together.
前記チタンアルコキシドと、前記ニオブアルコキシドまたは前記タンタルアルコキシドとの組み合わせとしては、溶媒への溶解性やコスト面から、テトラ−ｉ−プロポキシチタンとペンタエトキシニオブまたはペンタエトキシタンタルとの組み合わせが好ましい。
なお、前記チタンアルコキシド、前記ニオブアルコキシドおよび前記タンタルアルコキシドは、いずれも、水分と接触すると直ちに反応する不安定な物質なので、乾燥（低湿度）雰囲気で扱うことが好ましい。
As a combination of the titanium alkoxide and the niobium alkoxide or the tantalum alkoxide, a combination of tetra-i-propoxytitanium and pentaethoxyniobium or pentaethoxytantalum is preferable from the viewpoint of solubility in a solvent and cost.
The titanium alkoxide, the niobium alkoxide, and the tantalum alkoxide are all unstable substances that react immediately upon contact with moisture, and are therefore preferably handled in a dry (low humidity) atmosphere.
前記前駆体液の調製に用いることのできる溶媒としては、上述した必須の金属アルコキシドを溶解させうるものであれば特に制限されないが、好ましくは、必須の金属アルコキシドの合計濃度を後述する高い濃度範囲に設定しうるだけの高い溶解性を有するものであるのがよい。例えば、アルコール系溶媒（例えば、メタノール、エタノール、イソプロピルアルコール、２−メトキシエタノール、２−エトキシエタノール、メチルカルビトール等）、ケトン系溶媒（メチルエチルケトン、アセトン等）等の有機溶媒を用いることができる。これら溶媒は、１種のみを用いてもよいし、相溶性のある２種以上を併用し混合溶媒として用いてもよい。 The solvent that can be used for the preparation of the precursor liquid is not particularly limited as long as it can dissolve the above-described essential metal alkoxide. Preferably, the total concentration of the essential metal alkoxide is within a high concentration range described later. It should have high solubility that can be set. For example, organic solvents such as alcohol solvents (for example, methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, methyl carbitol, etc.) and ketone solvents (methyl ethyl ketone, acetone, etc.) can be used. These solvents may be used alone, or two or more compatible solvents may be used in combination as a mixed solvent.
前記前駆体液中の必須の金属アルコキシド（チタンアルコキシド、ニオブアルコキシドおよび／またはタンタルアルコキシド）の合計濃度は、０．１モル／Ｌ以上であることが好ましく、より好ましくは０．２モル／Ｌ〜１．５モル／Ｌであるのがよい。このように前駆体液中に含まれる必須の金属アルコキシドの合計濃度を比較的高く設定することにより、後述するエージング処理でアナターゼ型へと結晶化させることができる。必須の金属アルコキシドの合計濃度が０．１モル／未満であると、後述するエージング処理でもアナターゼ型へと結晶化せず非晶質となるおそれがある。
前記前駆体液に含まれるチタンアルコキシドとニオブアルコキシドおよび／またはタンタルアルコキシドとのモル比（すなわち、Ｔｉ：Ｎｂおよび／またはＴａの金属原子比）は、特に制限されないが、例えば、導電性の観点からは、Ｔｉ：Ｎｂおよび／またはＴａ＝９９．９：０．１〜６０：４０であるのがよい。
The total concentration of essential metal alkoxides (titanium alkoxide, niobium alkoxide and / or tantalum alkoxide) in the precursor liquid is preferably 0.1 mol / L or more, more preferably 0.2 mol / L to 1 .5 mol / L is preferable. Thus, by setting the total concentration of essential metal alkoxides contained in the precursor liquid to be relatively high, it can be crystallized into anatase type by an aging treatment described later. If the total concentration of essential metal alkoxides is less than 0.1 mol /, there is a possibility that even an aging treatment described later does not crystallize into anatase type and become amorphous.
The molar ratio of titanium alkoxide and niobium alkoxide and / or tantalum alkoxide contained in the precursor liquid (that is, the metal atomic ratio of Ti: Nb and / or Ta) is not particularly limited. For example, from the viewpoint of conductivity Ti: Nb and / or Ta = 99.9: 0.1-60: 40.
本発明の製造方法においては、上記のようにして得られた前記前駆体液を特定量の水の存在下で加水分解する。この加水分解によって、各々の金属アルコキシドを互いに脱水縮合可能にし、それらが互いに脱水縮合することで酸化物が形成される。
前記前駆体液を加水分解するに際しては、前駆体液中の金属原子の総モル数に対し２倍モル以上、好ましくは３〜５０倍モルの水の存在下で行うことが重要である。水の量が前記範囲よりも少ないと、金属アルコキシドの加水分解・重縮合反応の進行が不十分になり、その結果、得られる分散液を用いて形成された酸化チタン膜に多くの有機残留物が含まれることとなって膜性能の低下を招く。また、水の量が前記範囲よりも少ないと、後述するエージング処理に要する時間が長くなり、生産性に欠けコスト的に不利になるという問題もある。
In the production method of the present invention, the precursor liquid obtained as described above is hydrolyzed in the presence of a specific amount of water. By this hydrolysis, the respective metal alkoxides can be dehydrated and condensed with each other, and they are dehydrated and condensed with each other to form an oxide.
When hydrolyzing the precursor liquid, it is important to carry out the reaction in the presence of 2 times or more, preferably 3 to 50 times moles of water relative to the total number of moles of metal atoms in the precursor liquid. If the amount of water is less than the above range, the hydrolysis / polycondensation reaction of the metal alkoxide becomes insufficient, and as a result, many organic residues are formed on the titanium oxide film formed using the resulting dispersion. As a result, the film performance is degraded. In addition, when the amount of water is less than the above range, there is a problem that the time required for an aging treatment described later becomes long, resulting in a lack of productivity and a disadvantage in cost.
前記加水分解は、例えば、前記前駆体液に上述した量の水を含む加水分解液を添加することにより行うことができる。ここで、加水分解液は、水そのものであってもよいし、無機酸または有機酸に上述した量の水を含有させた酸水溶液であってもよいし、水酸化物または有機アミン類などのアルカリに上述した量の水を含有させたアルカリ水溶液であってもよい。なお、加水分解液を添加する際の添加方法は、特に限定されるものではなく、例えば、全量を一括して投入してもよいし、分割して投入してもよく、また、連続して滴下してもよいし、間歇的に滴下してもよい。
一般的に金属アルコキシドは室温では加水分解液と共存すると瞬時に加水分解・重縮合反応が進行する。よって、本発明では、前記前駆体液中の金属アルコキシドの加水分解反応開始温度以下の温度で加水分解液を添加し、攪拌して均一に混合した後に加水分解開始反応温度以上に昇温し、加水分解・重縮合反応を進行させることが推奨される。
前記加水分解液を添加する際の前記前駆体液の温度は、上記条件を満たす場合には特に制限されないが、通常−１９６〜０℃、好ましくは−３０〜−１０℃の範囲であるのがよい。加水分解を行う際の温度が前記範囲よりも高いと、前記加水分解液を添加した瞬間に添加部近傍のみで不均一に金属アルコキシドの加水分解・重合反応が起こり、その結果、得られる粒子の粒径分布が広くなるおそれがあり、一方、前記範囲よりも低いと、冷却するのに時間とコストがかかり、生産性の低下を招くおそれがある。
The hydrolysis can be performed, for example, by adding a hydrolysis liquid containing the above-mentioned amount of water to the precursor liquid. Here, the hydrolyzed solution may be water itself, an acid aqueous solution containing the above-mentioned amount of water in an inorganic acid or an organic acid, or a hydroxide or an organic amine. An alkaline aqueous solution in which the above-described amount of water is contained in an alkali may be used. In addition, the addition method at the time of adding a hydrolysis liquid is not specifically limited, For example, you may throw in the whole quantity collectively, may be divided | segmented, and may be added continuously. It may be dropped or may be dropped intermittently.
In general, when a metal alkoxide coexists with a hydrolyzed liquid at room temperature, a hydrolysis / polycondensation reaction proceeds instantaneously. Therefore, in the present invention, the hydrolysis liquid is added at a temperature not higher than the hydrolysis reaction start temperature of the metal alkoxide in the precursor liquid, and after stirring and mixing uniformly, the temperature is raised to the hydrolysis start reaction temperature or higher. It is recommended that the decomposition / polycondensation reaction proceed.
The temperature of the precursor liquid at the time of adding the hydrolyzed liquid is not particularly limited when the above conditions are satisfied, but is usually in the range of −196 to 0 ° C., preferably −30 to −10 ° C. . If the temperature during the hydrolysis is higher than the above range, the metal alkoxide hydrolysis / polymerization reaction occurs non-uniformly only in the vicinity of the addition portion at the moment when the hydrolysis liquid is added. On the other hand, when the particle size distribution is lower than the above range, it takes time and cost to cool, and the productivity may be reduced.
なお、前記加水分解の際に存在させる水の量（前記加水分解液中の水の量）を上述した範囲内で適宜調整することにより、得られる分散液中のドープアナターゼ型酸化チタン粒子の粒子径を所望の大きさに制御することが可能である。具体的には、粒子径の大きいドープアナターゼ型酸化チタン粒子を所望する場合には、加水分解時の水の量を多くすればよく、逆に、粒子径の小さいドープアナターゼ型酸化チタン粒子を所望する場合には、加水分解時の水の量を少なくすればよい。 In addition, the particle | grains of dope anatase type titanium oxide particle in the dispersion liquid obtained by adjusting suitably the quantity (the quantity of the water in the said hydrolysis liquid) which exists in the said hydrolysis within the range mentioned above It is possible to control the diameter to a desired size. Specifically, when a dope anatase type titanium oxide particle having a large particle size is desired, the amount of water during hydrolysis may be increased, and conversely, a dope anatase type titanium oxide particle having a small particle size is desired. If so, the amount of water during hydrolysis may be reduced.
本発明の製造方法においては、上記のようにして前記前駆体液を加水分解した後、５０℃以上の温度で所定時間エージング処理を施す。これにより、ドープアナターゼ型酸化チタン粒子を含有するゲルが得られる。ここで、エージング処理とは、５０℃以上の温度で、ニオブまたはタンタルがドープされた酸化チタンの結晶型がアナターゼ型になるまでの時間、ガラス容器等の密閉容器中で放置することである。
前記エージング処理の処理温度は、５０℃以上であればよいが、好ましくは６０℃以上であるのがよい。エージング処理の処理温度が５０℃未満であると、アナターゼ型へと結晶化するのに時間がかかり、生産性の低下を招く。また、エージング処理の処理温度があまりに高すぎると、特殊な装置が必要となったり電気代等のランニングコストが高くなるおそれがあるので、エージング処理の処理温度の上限は、好ましくは２００℃以下、より好ましくは１５０℃以下であるのがよい。
前記エージング処理は、上述したように、酸化チタンの結晶型がアナターゼ型になるまで行えばよいが、好ましくは、アナターゼ型結晶粒子が生成し、充分に成長するまで行うのが望ましい。具体的な処理時間は、処理温度等に応じて適宜設定されるものであるが、通常、１時間〜６０日間、好ましくは６時間〜２０日間の範囲で設定される。
なお、前記エージング処理を施すにあたり、加水分解直後の液温をエージング処理の処理温度まで昇温する際には、０．５℃／分程度の昇温速度で行うのがよい。
In the production method of the present invention, the precursor liquid is hydrolyzed as described above, and then subjected to aging treatment at a temperature of 50 ° C. or higher for a predetermined time. Thereby, the gel containing dope anatase type titanium oxide particle is obtained. Here, the aging treatment is to stand in a closed container such as a glass container at a temperature of 50 ° C. or higher until the crystal form of titanium oxide doped with niobium or tantalum becomes an anatase type.
The treatment temperature of the aging treatment may be 50 ° C. or higher, but preferably 60 ° C. or higher. If the treatment temperature of the aging treatment is less than 50 ° C., it takes time to crystallize into an anatase type, resulting in a decrease in productivity. Further, if the treatment temperature of the aging treatment is too high, a special device may be required or the running cost such as electricity bill may increase. Therefore, the upper limit of the treatment temperature of the aging treatment is preferably 200 ° C. or less, More preferably, it is good at 150 degrees C or less.
As described above, the aging treatment may be performed until the crystal form of titanium oxide becomes anatase type, but it is preferable to perform the aging process until the anatase type crystal particles are generated and sufficiently grown. The specific treatment time is appropriately set according to the treatment temperature and the like, but is usually set in the range of 1 hour to 60 days, preferably 6 hours to 20 days.
In addition, when performing the said aging process, when raising the liquid temperature just after a hydrolysis to the process temperature of an aging process, it is good to carry out at the temperature increase rate of about 0.5 degree-C / min.
前記エージング処理の際には、超音波照射処理をも施すことが好ましい。超音波を照射しながらエージング処理を施すことにより、結晶化が促進され、生産性を向上させることができる。なお、超音波照射処理は、エージング処理の開始から終了まで常時行ってもよいし、エージング処理の開始から終了までの間に一時行うだけであってもよい。 In the aging process, an ultrasonic irradiation process is also preferably performed. By performing an aging treatment while irradiating ultrasonic waves, crystallization is promoted and productivity can be improved. The ultrasonic irradiation process may be performed all the time from the start to the end of the aging process, or may be performed only temporarily during the period from the start to the end of the aging process.
本発明の製造方法においては、上記のようにして得られたゲルを分散媒中に分散させて、アナターゼ型酸化チタン分散液を得る。
前記ゲルを分散させる分散媒としては、ゲルの種類や得られる分散液の用途等に応じて適宜選択すればよく、特に制限されないが、例えば、アルコール系溶媒（例えば、メタノール、エタノール、イソプロピルアルコール、２−メトキシエタノール、２−エトキシエタノール等）、ケトン系溶媒（メチルエチルケトン、アセトン等）等の有機溶媒や、水を用いることができる。これら分散媒は、１種のみを用いてもよいし、相溶性のある２種以上を併用してもよい。
In the production method of the present invention, the gel obtained as described above is dispersed in a dispersion medium to obtain an anatase-type titanium oxide dispersion.
The dispersion medium for dispersing the gel may be appropriately selected according to the type of gel and the use of the resulting dispersion, and is not particularly limited. For example, alcohol solvents (for example, methanol, ethanol, isopropyl alcohol, Organic solvents such as 2-methoxyethanol and 2-ethoxyethanol) and ketone solvents (methyl ethyl ketone, acetone and the like) and water can be used. These dispersion media may use only 1 type and may use 2 or more types compatible.
前記ゲルを分散媒に分散させる際の方法は、特に制限されるものではなく、従来公知の分散手法を適宜採用すればよい。例えば、前記加水分解および前記エージング処理の条件によっては、得られたゲルがスラリー状または塊状となる場合があるが、そのような場合には、生成したゲルを分散媒中に投入し、必要に応じて、機械的粉砕あるいは超音波を使用した粉砕を行いながら、分散媒中に分散させればよい。 The method for dispersing the gel in the dispersion medium is not particularly limited, and a conventionally known dispersion method may be appropriately employed. For example, depending on the conditions of the hydrolysis and the aging treatment, the obtained gel may be in the form of a slurry or a lump. In such a case, the generated gel is put into a dispersion medium and necessary. Accordingly, it may be dispersed in the dispersion medium while performing mechanical pulverization or pulverization using ultrasonic waves.
なお、前記分散に際しては、別々に調製した２種以上のゲルを用い、これらを一つの分散媒中に投入するようにしてもよいし、あるいは、得られた１種類のゲルを二以上に分け、各々を別の分散媒中に投入して異なる手法や条件で分散させた後、それらを合わせるようにしてもよい。例えばこれらの方法によって、最終的に得られる分散液に含まれるドープアナターゼ型酸化チタン粒子の粒度分布が二つ以上のピークを持つ（換言すれば、最終的に得られる分散液に粒子径の異なる粒子が存在する）ことになるようにすると、該分散液を用いて形成された膜は、粒子径の大きな粒子によって形成される空隙に粒子径の小さい粒子が充填された充填密度が高い膜となるので、好ましい。
かくして分散させた分散液中のドープアナターゼ型酸化チタン粒子は、分散液の保管時に凝集が起きなければ、単分散している状態でもよいし、一次粒子が凝集している二次粒子の状態でもよい。
In the dispersion, two or more kinds of gels prepared separately may be used, and these may be put in one dispersion medium, or the obtained one kind of gel is divided into two or more. Each may be put into a different dispersion medium and dispersed by different methods and conditions, and then combined. For example, by these methods, the particle size distribution of the doped anatase-type titanium oxide particles contained in the finally obtained dispersion has two or more peaks (in other words, the finally obtained dispersion has different particle diameters). A film formed using the dispersion liquid is a film having a high packing density in which voids formed by particles having a large particle diameter are filled with particles having a small particle diameter; Therefore, it is preferable.
The doped anatase-type titanium oxide particles in the dispersion thus dispersed may be in a monodispersed state or in a secondary particle state in which primary particles are aggregated as long as aggregation does not occur during storage of the dispersion. Good.
本発明のアナターゼ型酸化チタン分散液は、上記のような製造方法によって得られるものである。
本発明の製造方法により得られる分散液は、固形分濃度が０．０１〜３０重量％であることが好ましい。分散液の固形分濃度が０．０１重量％未満であると、該分散液を塗布して膜を形成する際に１回の塗装で形成できる膜厚が小さくなるので、生産性の点で不利となり、一方、３０重量％を超えると、流動性が低下する傾向があり、該分散液を均一に塗布することが困難になるおそれがある。
The anatase-type titanium oxide dispersion of the present invention is obtained by the production method as described above.
The dispersion obtained by the production method of the present invention preferably has a solid concentration of 0.01 to 30% by weight. When the solid content concentration of the dispersion is less than 0.01% by weight, the film thickness that can be formed by one coating is reduced when the dispersion is applied to form a film, which is disadvantageous in terms of productivity. On the other hand, if it exceeds 30% by weight, the fluidity tends to decrease, and it may be difficult to uniformly apply the dispersion.
本発明の製造方法により得られる分散液中のドープアナターゼ型酸化チタン粒子は、一次粒子の平均粒子径が３〜２０ｎｍであることが好ましい。ここで、分散液中の一次粒子の平均粒子径は、Ｘ線回折測定の結果からシェラーの式で算出される結晶子径を意味する。また、一次粒子を含む分散液中の二次粒子の平均粒子径は、１０〜２００ｎｍであるのが好ましい。一次粒子を含む二次粒子の平均粒子径は、動的光散乱法により求めるか、あるいはＴＥＭ等で直接観察することができる。 The doped anatase-type titanium oxide particles in the dispersion obtained by the production method of the present invention preferably have an average primary particle diameter of 3 to 20 nm. Here, the average particle diameter of the primary particles in the dispersion means a crystallite diameter calculated by the Scherrer equation from the result of X-ray diffraction measurement. Moreover, it is preferable that the average particle diameter of the secondary particle in the dispersion liquid containing a primary particle is 10-200 nm. The average particle diameter of the secondary particles including the primary particles can be obtained by a dynamic light scattering method or directly observed by TEM or the like.
本発明の製造方法により得られる分散液は、好ましくは、液性が中性であり、かつ分散安定化剤を含有していないものである。本発明の製造方法では、詳細なメカニズムは未だ不明であるが、おそらく、粒子合成時に使用した２−メトキシエタノールが粒子表面に一部残存し、分散剤として作用していること、ならびに、本発明の製造方法では得られる分散液中でのゼータ電位の絶対値が１０〜４０ｍＶと比較的高いことから、得られた分散液は、ｐＨを酸性領域もしくはアルカリ性領域に制御したり、分散安定化剤を添加したりすることなく、良好な分散安定性を備えたものとなるのである。分散液の液性が中性であることにより、成膜プロセスにおける装置の腐食等の問題を回避することができ、分散安定化剤を含有していないことにより、分散安定化剤由来の不純物が膜中に残存することを懸念する必要がなくなる。 The dispersion obtained by the production method of the present invention is preferably neutral in liquidity and does not contain a dispersion stabilizer. In the production method of the present invention, although the detailed mechanism is still unclear, it is likely that 2-methoxyethanol used at the time of particle synthesis partially remains on the particle surface and acts as a dispersant. Since the absolute value of the zeta potential in the obtained dispersion is relatively high at 10 to 40 mV, the obtained dispersion can be controlled in the acidic region or alkaline region, or the dispersion stabilizer Thus, it is possible to provide a good dispersion stability without adding. Due to the neutrality of the dispersion liquid, problems such as corrosion of the apparatus in the film forming process can be avoided, and by not containing the dispersion stabilizer, impurities derived from the dispersion stabilizer can be prevented. There is no need to worry about remaining in the film.
なお、前記分散安定化剤とは、ドープアナターゼ型酸化チタン粒子を分散媒中になるべく安定に分散させるために添加させる成分をいい、解膠剤、保護コロイド、界面活性剤等の凝結防止剤等を意味する。具体的には、キレート性の化合物等を例示することができ、例えば、グリコール酸、グルコン酸、乳酸、酒石酸、クエン酸、リンゴ酸、コハク酸等の多価カルボン酸もしくはヒドロキシカルボン酸；ピロ燐酸、トリポリ燐酸；等が挙げられる。また、アセチルアセトン、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸−ｎ−プロピル、アセト酢酸−ｉ−プロピル、アセト酢酸−ｎ−ブチル、アセト酢酸−ｓｅｃ−ブチル、アセト酢酸−ｔ−ブチル、２，４−ヘキサン−ジオン、２，４−ヘプタン−ジオン、３，５−ヘプタン−ジオン、２，４−オクタン−ジオン、２，４−ノナン−ジオン、５−メチル−ヘキサン−ジオン等の如き、金属原子に対して強いキレート能力を有する多座配位子化合物も、分散安定化剤として挙げられる。さらに、市販の各種分散安定化剤（脂肪族アミン系、ハイドロステアリン酸系、ポリエステルアミン）として、スルパース３０００、９０００、１７０００、２００００、２４０００（以上、ゼネカ社製）、Ｄｉｓｐｅｒｂｙｋ−１６１、−１６２、−１６３、−１６４（以上、ビックケミー社製）等を例示することができる。さらに、例えば、特開平９−２０８４３８号公報、特開平２０００−５３４２１号公報等に記載されているジメチルポリシロキサン・メチル（ポリシロキシアルキレン）シロキサン共重合体、トリメチルシロキシケイ酸、カルボキシ変性シリコーンオイル、アミン変性シリコーン等のシリコーン化合物等も、分散安定化剤として挙げられる。 The dispersion stabilizer is a component to be added in order to disperse the doped anatase-type titanium oxide particles as stably as possible in the dispersion medium, such as a flocculating agent, a protective colloid, a coagulation inhibitor such as a surfactant, etc. Means. Specific examples include chelating compounds such as glycolic acid, gluconic acid, lactic acid, tartaric acid, citric acid, malic acid, succinic acid and other polycarboxylic acids or hydroxycarboxylic acids; pyrophosphoric acid , Tripolyphosphoric acid; and the like. Also, acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4 Metal atoms such as hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methyl-hexane-dione, etc. A polydentate ligand compound having a strong chelating ability against the above can also be mentioned as a dispersion stabilizer. Furthermore, as various commercially available dispersion stabilizers (aliphatic amine type, hydrostearic acid type, polyester amine), Sulperus 3000, 9000, 17000, 20000, 24000 (above, manufactured by Zeneca), Disperbyk-161, -162, -163, -164 (above, manufactured by Big Chemie) and the like can be exemplified. Furthermore, for example, dimethylpolysiloxane methyl (polysiloxyalkylene) siloxane copolymer, trimethylsiloxysilicic acid, carboxy-modified silicone oil described in JP-A-9-208438, JP-A-2000-53421 and the like, Silicone compounds such as amine-modified silicones are also exemplified as dispersion stabilizers.
本発明の製造方法により得られる分散液を用いれば、低温で、光触媒活性や導電性を発現する膜を形成することができる。すなわち、一般に、ドープ酸化チタンからなる膜において光触媒活性や導電性を発現させるためには、その結晶性がアモルファスではなくアナターゼ型になっていることが重要であり、アモルファスからアナターゼ型に結晶化させるには、通常４００℃以上の高温での熱処理が必要である。本発明の製造方法により得られる分散液によれば、含まれるドープ酸化チタンの粒子は既にアナターゼ型になっているので、例えば該分散液を基材上に塗布して分散媒を乾燥（除去）させるだけで、結晶化のための加熱を行うことなく、アナターゼ型のドープ酸化チタン膜を形成することができるのである。これにより、耐熱性が低い基材に対しても光触媒活性や導電性を発現する膜を形成することが可能になる。
なお、本発明の製造方法により得られる分散液を用いて成膜する場合にも、分散媒を乾燥（除去）する目的で、分散液を基材に塗布した後にホットプレートやオーブンなどの加熱装置を用いて加熱を行うことはあるが、ここでの加熱は、分散媒とした溶剤を揮散させうる程度の温度で行えばよく、結晶化のための加熱に比べるとはるかに低温でよい。勿論、本発明の製造方法により得られる分散液を基材に塗布した後、自然乾燥によって分散媒を除去してもよい。
If the dispersion obtained by the production method of the present invention is used, a film exhibiting photocatalytic activity and conductivity can be formed at a low temperature. That is, in general, in order to exhibit photocatalytic activity and conductivity in a film made of doped titanium oxide, it is important that the crystallinity is not an amorphous but anatase type, and crystallizes from amorphous to anatase type. Usually requires heat treatment at a high temperature of 400 ° C. or higher. According to the dispersion obtained by the production method of the present invention, the contained doped titanium oxide particles are already in the anatase type. Therefore, for example, the dispersion is applied onto a substrate and the dispersion medium is dried (removed). Thus, an anatase-type doped titanium oxide film can be formed without heating for crystallization. This makes it possible to form a film that exhibits photocatalytic activity and conductivity even on a substrate having low heat resistance.
In the case of forming a film using the dispersion obtained by the production method of the present invention, a heating device such as a hot plate or oven is applied after the dispersion is applied to the substrate for the purpose of drying (removing) the dispersion medium. However, the heating here may be performed at a temperature that can volatilize the solvent used as the dispersion medium, and may be much lower than the heating for crystallization. Of course, the dispersion medium obtained by the production method of the present invention may be applied to a substrate, and then the dispersion medium may be removed by natural drying.
本発明の製造方法により得られる分散液を用いて成膜する場合、その膜厚は用途に応じて設定すればよく特に制限されないが、乾燥膜厚で、通常０．０１〜２．０μｍ、好ましくは０．１〜１．０μｍである。また、成膜方法としては、分散液を均一にウェットコーティングできる方法であれば特に制限はなく、例えば、スプレーコート法、スピンコート法、ロールコート法、シルク印刷法、スクリーン印刷法、ブレードコーター法、バーコーター法、キャピラリコート法、スリットダイコート法、ディップコート法、フレキソ印刷法等の従来公知の方法を採用することができる。 In the case of forming a film using the dispersion obtained by the production method of the present invention, the film thickness is not particularly limited as long as it is set according to the application, but is usually 0.01 to 2.0 μm, preferably a dry film thickness. Is 0.1 to 1.0 μm. The film forming method is not particularly limited as long as the dispersion can be uniformly wet coated. For example, spray coating method, spin coating method, roll coating method, silk printing method, screen printing method, blade coater method. Conventionally known methods such as a bar coater method, a capillary coating method, a slit die coating method, a dip coating method, and a flexographic printing method can be employed.
本発明の製造方法により得られる分散液を用いて膜を形成する際の基材は、用途に応じて適宜選択すればよく、特に制限されない。例えば、光触媒材料の用途においては、板ガラス、金属板、強化ガラス、タイルなどの無機系基材や、ポリカーボネート、アクリル板の如き有機高分子シート等の有機系基材が挙げられる。より具体的には、各種金属板（ステンレス板、アルミ板等）、建材用ガラス、自動車用ガラス、各種鏡（浴室、洗面室、道路、反射鏡等）、機器防護用ガラス（信号、センサー等）、ガラス食器、冷蔵・冷凍ショーケースガラス、展示用ガラス、医療・歯科用ミラー、内視鏡等医療用カメラ、熱交換用金属フィン等が挙げられ、中でも特に、化粧性や透明性が求められる基材に適用するのが好ましい。また、例えば、電子デバイス用材料の用途においては、紙・フェノール銅張積層板、紙・エポキシ銅張積層板、紙・ポリエステル銅張積層板などの紙基材銅張積層板；ガラス布・エポキシ銅張積層板、ガラス布・ポリイミド銅張積層板、ガラス布・テフロン（登録商標）銅張積層板などのガラス基材銅張積層板；紙・ガラス布・エポキシ銅張積層板、ガラス不織布・エポキシ銅張積層板などのコンポジット銅張積層板；ポリエーテルイミド基板、ポリエーテルケトン基板、ポリサルフォン系樹脂基板、ポリカーボネート基板、ポリイミド基板、ポリエステルなどの樹脂基板；ポリエステルフィルム、ポリエステル銅張フィルム基板、ポリイミドフィルム、アラミドフィルム、ポリイミド銅張フィルム基板、各種液晶ポリマーフィルムなどのフレキシブル基板；等の有機系基板や、アルミナ基板、窒化アルミニウム基板、炭化ケイ素基板などのセラミック基板；アルミニウムベース基板、鉄ベース基板などの金属系基板；ガラス基板；シリコン基板；石英基板；等の無機系基板のほか、これらの基板に回路の構成材料が配置されたものが挙げられる。
なお、光触媒材料の用途において有機系基材を用いる場合には、分散液により形成される膜と基材との間に、光触媒ブロック層としてプライマー層を設けることが望ましい。
The substrate for forming a film using the dispersion obtained by the production method of the present invention may be appropriately selected depending on the application, and is not particularly limited. For example, in the use of the photocatalytic material, inorganic base materials such as plate glass, metal plate, tempered glass, and tile, and organic base materials such as organic polymer sheets such as polycarbonate and acrylic plates can be used. More specifically, various metal plates (stainless steel plates, aluminum plates, etc.), glass for building materials, glass for automobiles, various mirrors (bathrooms, washrooms, roads, reflectors, etc.), glass for equipment protection (signals, sensors, etc.) ), Glass tableware, refrigerated / frozen showcase glass, display glass, medical / dental mirrors, medical cameras such as endoscopes, metal fins for heat exchange, etc. It is preferable to apply to a substrate to be formed. Also, for example, in the use of electronic device materials, paper-based copper-clad laminates such as paper / phenolic copper-clad laminates, paper / epoxy copper-clad laminates, paper / polyester copper-clad laminates; glass cloth / epoxy Glass-based copper-clad laminates such as copper-clad laminates, glass cloth / polyimide copper-clad laminates, glass cloth / Teflon (registered trademark) copper-clad laminates; paper / glass cloth / epoxy copper-clad laminates, glass nonwoven fabrics / Composite copper-clad laminates such as epoxy copper-clad laminates; polyetherimide substrates, polyetherketone substrates, polysulfone resin substrates, polycarbonate substrates, polyimide substrates, polyester and other resin substrates; polyester films, polyester copper-clad film substrates, polyimides Film, aramid film, polyimide copper-clad film substrate, various liquid crystal polymer films, etc. Organic substrates such as Kibible substrates; Ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates; Metal substrates such as aluminum base substrates and iron base substrates; Glass substrates; Silicon substrates; Quartz substrates; In addition to the system substrate, those in which circuit constituent materials are arranged on these substrates can be mentioned.
In addition, when using an organic base material in the use of a photocatalyst material, it is desirable to provide a primer layer as a photocatalyst block layer between the film | membrane formed with a dispersion liquid and a base material.
本発明の製造方法により得られる分散液は、上述したように、それ自体を基材上に塗布するなどして膜形成に利用できることは勿論、ペイント等の塗装材や有機高分子含有左官材など既存の各種素材組成物に配合して利用することもできる。 As described above, the dispersion obtained by the production method of the present invention can be used for film formation by, for example, coating itself on a base material, as well as a coating material such as paint, a plastering material containing an organic polymer, etc. It can also be used by blending with existing various material compositions.
以下、実施例により本発明をより詳細に説明するが、本発明はかかる実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
（実施例１〜１７）
ペンタエトキシニオブ（Ｎｂ（ＯＣ2Ｈ5）5）と、溶媒である２−メトキシエタノール（メチルセロソルブ）とを乾燥窒素雰囲気中にて混合し、次いで、得られた混合物にテトラ−ｉ−プロポキシチタン（Ｔｉ（ＯＣＨ（ＣＨ3）2）4）を加えて攪拌することにより、前駆体液を調製した。このとき、ペンタエトキシニオブ、テトラ−ｉ−プロポキシチタンおよび２−メトキシエタノールの使用量は、前駆体液中のＴｉとＮｂとの金属原子比（モル比）が表１に示す比率になり、かつ金属アルコキシド濃度（ペンタエトキシニオブとテトラ−ｉ−プロポキシチタンとの合計濃度）が表１に示す値になるように、決定した。
(Examples 1-17)
Pentaethoxyniobium (Nb (OC 2 H 5 ) 5 ) and 2-methoxyethanol (methyl cellosolve) as a solvent are mixed in a dry nitrogen atmosphere, and tetra-i-propoxytitanium is then added to the resulting mixture. by stirred with (Ti (OCH (CH 3) 2) 4), was prepared precursor liquid. At this time, the amount of pentaethoxyniobium, tetra-i-propoxytitanium and 2-methoxyethanol used is such that the metal atomic ratio (molar ratio) between Ti and Nb in the precursor liquid is the ratio shown in Table 1, and the metal The alkoxide concentration (the total concentration of pentaethoxyniobium and tetra-i-propoxytitanium) was determined to be the value shown in Table 1.
次に、得られた前駆体液を−３０℃に保持し、その中に、水と２−メトキシエタノールとの等体積混合溶液を所定量滴下し、加水分解を行った。このとき、水と２−メトキシエタノールとの等体積混合溶液の滴下量は、該混合溶液中の水の量が、前駆体液中の金属原子（ＮｂおよびＴｉ）の総モル数に対して表１に示す水のモル数になるように、決定した。 Next, the obtained precursor liquid was kept at −30 ° C., and a predetermined amount of an equal volume mixed solution of water and 2-methoxyethanol was dropped therein to perform hydrolysis. At this time, the dropping amount of the equal volume mixed solution of water and 2-methoxyethanol is such that the amount of water in the mixed solution is as shown in Table 1 with respect to the total number of moles of metal atoms (Nb and Ti) in the precursor liquid. It determined so that it might become the mole number of water shown in.
次いで、上記加水分解後、引き続き、密閉したガラス容器中、表１に示す条件（温度及び時間）でエージング処理を施し、ゲルを得た。なお、エージング処理を施している間、適宜、Ｘ線回折測定を行ったところ、エージング処理の初期（処理開始から凡そ２日後）には、Ｘ線回折パターン中に回折ピークが認められなかったが、エージング処理が進むと（処理開始から凡そ３日後）、アナターゼ型酸化チタンに由来する回折パターンが現れるようになり、さらにエージング処理が進むと（処理開始から凡そ４日後）、アナターゼ型酸化チタン由来の回折ピークが大きくなることが確認できた（図１）。
また、エージング処理後のゲル中の粒子の結晶構造を、エネルギー分散型Ｘ線マイクロアナライザー（ＴＥＭ−ＥＤＸ）および電界放射型電子顕微鏡（ＦＥ−ＳＥＭ−ＥＤＸ）により観察したところ、Ｎｂがドープされた酸化チタンの多結晶体であった。これらのことから、得られたゲルは、ニオブドープアナターゼ型酸化チタン粒子が凝集したものであることが分かった。
次いで、上記で得られたゲルを表１に示す分散媒中に、表１に示す固形分濃度となるように投入し、超音波照射することにより分散させて、本発明の分散液を得た。
Subsequently, after the hydrolysis, an aging treatment was performed in the sealed glass container under the conditions (temperature and time) shown in Table 1 to obtain a gel. In addition, when X-ray diffraction measurement was appropriately performed during the aging treatment, no diffraction peak was observed in the X-ray diffraction pattern at the initial stage of the aging treatment (approximately 2 days after the start of the aging treatment). When the aging process proceeds (approximately 3 days after the start of treatment), a diffraction pattern derived from anatase-type titanium oxide appears, and when the aging process proceeds further (approximately 4 days after the start of treatment), it originates from anatase-type titanium oxide. It was confirmed that the diffraction peak of was increased (FIG. 1).
Moreover, when the crystal structure of the particles in the gel after the aging treatment was observed with an energy dispersive X-ray microanalyzer (TEM-EDX) and a field emission electron microscope (FE-SEM-EDX), Nb was doped. It was a polycrystal of titanium oxide. From these facts, it was found that the obtained gel was an aggregate of niobium-doped anatase-type titanium oxide particles.
Next, the gel obtained above was put into the dispersion medium shown in Table 1 so as to have the solid content concentration shown in Table 1, and dispersed by irradiating with ultrasonic waves to obtain the dispersion of the present invention. .
得られた分散液中のニオブドープアナターゼ型酸化チタン粒子の粒径分布を、分散液を作製した直後に、ダイナミック光散乱光度計（大塚電子（株）製「ＤＬＳ−８０００」）を用いて動的光散乱法により測定し、平均粒子径を算出した。結果を表１に示す。実施例９の分散液中の粒子のＴＥＭ像を図２に示す。実施例１４の分散液中の粒子のＴＥＭ像を図３と図４にそれぞれ示す。図２、図３では、粒径１０ｎｍ前後の粒子形状が見られ、拡大した図４では粒子内にアナターゼ構造に由来すると考えられる格子縞が見られた。更に、実施例１４の分散液中の粒子の電子線回折図形を図５に示す。粒子が重なっているために複数の粒子の電子線回折図形となっているが、回折点がはっきりと確認できた。 The particle size distribution of the niobium-doped anatase-type titanium oxide particles in the obtained dispersion was measured using a dynamic light scattering photometer (“DLS-8000” manufactured by Otsuka Electronics Co., Ltd.) immediately after the dispersion was prepared. The average particle size was calculated by measuring with an automatic light scattering method. The results are shown in Table 1. A TEM image of the particles in the dispersion of Example 9 is shown in FIG. TEM images of the particles in the dispersion liquid of Example 14 are shown in FIGS. 3 and 4, respectively. In FIGS. 2 and 3, a particle shape with a particle diameter of about 10 nm was observed, and in FIG. 4 that was enlarged, lattice fringes thought to be derived from the anatase structure were observed in the particles. Furthermore, the electron diffraction pattern of the particles in the dispersion liquid of Example 14 is shown in FIG. Since the particles overlap, the electron diffraction pattern of a plurality of particles is obtained, but the diffraction points can be clearly confirmed.
さらに、本発明の分散液の分散安定性を調べるため、実施例１〜１７で得られた分散液を、温度約２０℃、湿度約６０％の雰囲気下で３０日間静置した。そして、静置後の分散液について、上記と同様にして再び平均粒子径を測定した。その結果を表１に示すが、いずれも分散粒子径は変化しておらず、保存安定性は良好であった。
これらの結果から、本発明の分散液は良好な分散安定性を有していることが分かった。
Furthermore, in order to investigate the dispersion stability of the dispersion liquid of the present invention, the dispersion liquids obtained in Examples 1 to 17 were allowed to stand for 30 days in an atmosphere at a temperature of about 20 ° C. and a humidity of about 60%. And the average particle diameter was again measured similarly to the above about the dispersion liquid after stationary. The results are shown in Table 1. In all cases, the dispersed particle size did not change, and the storage stability was good.
From these results, it was found that the dispersion of the present invention has good dispersion stability.
上記各実施例で得られた分散液を用いて形成した膜の光触媒活性を調べた。
まず、光触媒活性測定用の試料を作製した。すなわち、得られた分散液をドライ膜厚２００ｎｍとなるように透明基材（無アルカリガラス「コーニング社製１７３７」、厚さ０．７ｍｍ）上にスピンコータで１回塗布し、５０℃にて１０分間乾燥することにより溶媒を揮散させて膜を形成した後、紫外線強度が２ｍＷ／ｃｍ2となるようにブラックライトからの紫外線を１６時間照射して、光触媒活性測定用試料とした。
The photocatalytic activity of the film formed using the dispersion obtained in each of the above examples was examined.
First, a sample for measuring photocatalytic activity was prepared. That is, the obtained dispersion was applied once on a transparent substrate (non-alkali glass “Corning Corporation 1737”, thickness 0.7 mm) to a dry film thickness of 200 nm by a spin coater, and 10 times at 50 ° C. After the solvent was stripped by drying for a minute, a film was formed, and then UV light from black light was irradiated for 16 hours so that the UV intensity was 2 mW / cm 2 to obtain a sample for photocatalytic activity measurement.
次に、この光触媒活性測定用試料を内容積１Ｌのガスバッグ内の底面に入れて密閉し、次いで、このガスバッグ内部を真空にした後、酸素と窒素との体積比が１：４である混合ガス６００ｍＬを封入し、さらにその中に、アセトアルデヒドを１体積％の濃度で含む窒素ガス６ｍＬを封入して、暗所で室温下１時間保持した。その後、白色蛍光灯を光源とし、試料近傍での照度が６０００ルクスとなるようにガスバッグの外から蛍光灯の光を照射し、アセトアルデヒドの分解反応を行った。このとき、試料近傍における紫外線強度は４０μＷ／ｃｍ2（トプコン社製紫外線強度計「ＵＶＲ−２」に、同社製受光部「ＵＤ−３６」を装着して測定）であった。蛍光灯の光照射を開始してから１．５時間毎にガスバッグ内のガスをサンプリングし、アセトアルデヒドの濃度をガスクロマトグラフ（島津製作所社製「ＧＣ−１４Ａ」）にて測定した。 Next, this photocatalytic activity measurement sample is put in the bottom of a gas bag having an internal volume of 1 L and sealed, and then the inside of the gas bag is evacuated, and then the volume ratio of oxygen and nitrogen is 1: 4. A mixed gas (600 mL) was sealed, and nitrogen gas (6 mL) containing acetaldehyde at a concentration of 1% by volume was sealed therein, and kept in the dark at room temperature for 1 hour. Thereafter, a white fluorescent lamp was used as a light source, and light from the fluorescent lamp was irradiated from the outside of the gas bag so that the illuminance in the vicinity of the sample was 6000 lux. At this time, the ultraviolet intensity in the vicinity of the sample was 40 μW / cm 2 (measured by attaching a UV receiver “UD-36” manufactured by the company to a UV intensity meter “UVR-2” manufactured by Topcon Corporation). The gas in the gas bag was sampled every 1.5 hours after the light irradiation of the fluorescent lamp was started, and the concentration of acetaldehyde was measured with a gas chromatograph (“GC-14A” manufactured by Shimadzu Corporation).
その結果、いずれの実施例で得られた分散液を用いた場合も、照射時間が長くなるに従い、アセトアルデヒド濃度が大幅に減少し、高い光触媒活性が発揮されていることが分かった。このように低温（５０℃）で成膜したにも拘わらず高い光触媒活性が認められたことは、得られた分散液中の酸化チタンナノ粒子が高いアナターゼ型結晶性を有するとともに、有機残留物が少ないことを示している。 As a result, it was found that even when the dispersion liquid obtained in any of the examples was used, the acetaldehyde concentration was significantly reduced and the high photocatalytic activity was exhibited as the irradiation time became longer. The fact that high photocatalytic activity was observed despite the film formation at a low temperature (50 ° C.) in this way is that the titanium oxide nanoparticles in the obtained dispersion have high anatase-type crystallinity and the organic residue is It shows that there are few.
（比較例１）
ペンタエトキシニオブ（Ｎｂ（ＯＣ2Ｈ5）5）と、溶媒である２−メトキシエタノール（メチルセロソルブ）とを乾燥窒素雰囲気中にて混合し、次いで、得られた混合物にテトラ−ｉ−プロポキシチタン（Ｔｉ（ＯＣＨ（ＣＨ3）2）4）を加えて攪拌することにより、前駆体液を調製した。このとき、ペンタエトキシニオブ、テトラ−ｉ−プロポキシチタンおよび２−メトキシエタノールの使用量は、前駆体液中のＴｉとＮｂとの金属原子比（モル比）がＴｉ：Ｎｂ（モル比）＝９４：６になり、かつ金属アルコキシド濃度（ペンタエトキシニオブとテトラ−ｉ−プロポキシチタンとの合計濃度）が２０重量％になるようにした。
(Comparative Example 1)
Pentaethoxyniobium (Nb (OC 2 H 5 ) 5 ) and 2-methoxyethanol (methyl cellosolve) as a solvent are mixed in a dry nitrogen atmosphere, and tetra-i-propoxytitanium is then added to the resulting mixture. by stirred with (Ti (OCH (CH 3) 2) 4), was prepared precursor liquid. At this time, the amount of pentaethoxyniobium, tetra-i-propoxytitanium and 2-methoxyethanol used is such that the metal atom ratio (molar ratio) between Ti and Nb in the precursor liquid is Ti: Nb (molar ratio) = 94: 6 and the metal alkoxide concentration (total concentration of pentaethoxyniobium and tetra-i-propoxytitanium) was 20% by weight.
次に、得られた前駆体液を−３０℃に保持し、その中に、水と２−メトキシエタノールとの等体積混合溶液を所定量滴下し、加水分解を行った。このとき、水と２−メトキシエタノールとの等体積混合溶液の滴下量は、前駆体液中の金属原子（ＮｂおよびＴｉ）の総モル数に対する混合溶液中の水のモル数（Ｈ2Ｏ／（Ｔｉ＋Ｎｂ））が１．６になるようにした。加水分解後、室温（２０℃）まで昇温して、比較用の分散液とした。この分散液の粘度を 山一電機製振動式粘度計ＶＭ−１００Ａで測定したところ、９．５ｃＰであった。
得られた比較用の分散液を、室温（約２０℃）、湿度約６０％の雰囲気下で静置したところ、２７時間後には粘度が１１．８ｃＰで少し白濁した状態になり、３４時間後には粘度が１８．２ｃＰで少し白濁した状態になり、５日後には完全にゲル化して流動性がなくなった。
Next, the obtained precursor liquid was kept at −30 ° C., and a predetermined amount of an equal volume mixed solution of water and 2-methoxyethanol was dropped therein to perform hydrolysis. At this time, the dropping amount of the equal volume mixed solution of water and 2-methoxyethanol is the number of moles of water in the mixed solution (H 2 O / () with respect to the total number of moles of metal atoms (Nb and Ti) in the precursor liquid. Ti + Nb)) was adjusted to 1.6. After hydrolysis, the temperature was raised to room temperature (20 ° C.) to obtain a comparative dispersion. It was 9.5 cP when the viscosity of this dispersion liquid was measured with Yamaichi Denki's vibration viscometer VM-100A.
The obtained comparative dispersion was allowed to stand in an atmosphere of room temperature (about 20 ° C.) and humidity of about 60%. After 27 hours, the viscosity became 11.8 cP and the solution became slightly cloudy, and after 34 hours. Became a little cloudy at a viscosity of 18.2 cP, completely gelled after 5 days, and lost its fluidity.
上記で得られたゲルについて、実施例と同様にしてＸ線回析を行ったところ、アモルファスであることがわかった。このゲルを分散媒中に分散させて分散液を得、これを透明基材に塗布し、５０℃で１０分間乾燥させて膜を形成した。この膜には光触媒活性は全く示さなかった。 When the gel obtained above was subjected to X-ray diffraction in the same manner as in Example, it was found to be amorphous. This gel was dispersed in a dispersion medium to obtain a dispersion, which was applied to a transparent substrate and dried at 50 ° C. for 10 minutes to form a film. This film did not show any photocatalytic activity.
Claims (6)
チタンアルコキシドとニオブアルコキシドまたはタンタルアルコキシドとを必須の金属アルコキシドとして含む前駆体液を該前駆体液中の金属原子の総モル数に対し２倍モル以上の水の存在下で加水分解した後、５０℃以上の温度で所定時間エージング処理を施すことにより、ニオブまたはタンタルがドープされたアナターゼ型酸化チタンを含有するゲルを得、このゲルを分散媒中に分散させることを特徴とするアナターゼ型酸化チタン分散液の製造方法。 A method for producing a dispersion in which nanoparticles of anatase-type titanium oxide doped with niobium or tantalum are dispersed in a dispersion medium,
After hydrolyzing a precursor liquid containing titanium alkoxide and niobium alkoxide or tantalum alkoxide as an essential metal alkoxide in the presence of water at least twice the total number of moles of metal atoms in the precursor liquid, 50 ° C. or higher An anatase-type titanium oxide dispersion characterized in that a gel containing anatase-type titanium oxide doped with niobium or tantalum is obtained by performing an aging treatment at a temperature of 5 ° C., and the gel is dispersed in a dispersion medium Manufacturing method.
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| JP2001049131A (en) * | 1999-08-10 | 2001-02-20 | Toppan Printing Co Ltd | High-refractive composition |
| JP2001262008A (en) * | 2000-03-17 | 2001-09-26 | Mitsubishi Gas Chem Co Inc | Titania coating liquid and its production method, and titania film and its formation method |
| JP2002030416A (en) * | 2000-07-14 | 2002-01-31 | Japan Atom Energy Res Inst | Method for manufacturing visible ray response type titanium oxide thin film |
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| WO2005094978A1 (en) * | 2004-03-18 | 2005-10-13 | Gifu University | Composition for dispersing of particle, composition having particle dispersed therein, process for producing the same, and sintered compact of anatase titanium oxide |
| JP2005313055A (en) * | 2004-04-28 | 2005-11-10 | Toagosei Co Ltd | Functional dispersion |
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| JP2001049131A (en) * | 1999-08-10 | 2001-02-20 | Toppan Printing Co Ltd | High-refractive composition |
| JP2001262008A (en) * | 2000-03-17 | 2001-09-26 | Mitsubishi Gas Chem Co Inc | Titania coating liquid and its production method, and titania film and its formation method |
| JP2002030416A (en) * | 2000-07-14 | 2002-01-31 | Japan Atom Energy Res Inst | Method for manufacturing visible ray response type titanium oxide thin film |
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| JP2007044657A (en) * | 2005-08-11 | 2007-02-22 | Mie Prefecture | Manufacturing method of titania paste, manufacturing method of titania porous layer, and photocatalyst layer |
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| RU2733521C1 (en) * | 2019-12-25 | 2020-10-02 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "КОМИ научный центр Уральского отделения Российской академии наук" | Aqueous dispersion based on nanoparticles of tantalum oxide, method of producing and use thereof as contrast agent for in vivo diagnosis |
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