JP2000351787A - Storage of water-soluble titanium complex aqueous solution - Google Patents
Storage of water-soluble titanium complex aqueous solutionInfo
- Publication number
- JP2000351787A JP2000351787A JP11159813A JP15981399A JP2000351787A JP 2000351787 A JP2000351787 A JP 2000351787A JP 11159813 A JP11159813 A JP 11159813A JP 15981399 A JP15981399 A JP 15981399A JP 2000351787 A JP2000351787 A JP 2000351787A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- titanium
- aqueous solution
- hydroxy
- water
- 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.)
- Pending
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000010936 titanium Substances 0.000 title claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 30
- 238000003860 storage Methods 0.000 title description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 claims abstract description 7
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims abstract description 6
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- NGEWQZIDQIYUNV-UHFFFAOYSA-N L-valinic acid Natural products CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 6
- AFENDNXGAFYKQO-UHFFFAOYSA-N 2-hydroxybutyric acid Chemical compound CCC(O)C(O)=O AFENDNXGAFYKQO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004310 lactic acid Substances 0.000 claims abstract description 4
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims abstract description 3
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 claims abstract description 3
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims abstract description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims abstract description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 3
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 claims abstract description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001630 malic acid Substances 0.000 claims abstract description 3
- 235000011090 malic acid Nutrition 0.000 claims abstract description 3
- 239000011975 tartaric acid Substances 0.000 claims abstract description 3
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 3
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 abstract description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 150000004703 alkoxides Chemical class 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 25
- 239000000758 substrate Substances 0.000 description 13
- 239000010409 thin film Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- -1 titanium alkoxide Chemical class 0.000 description 3
- 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
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BCZYGELZHQODHE-UHFFFAOYSA-N 1,1-diamino-2-methylpropan-1-ol Chemical compound CC(C)C(N)(N)O BCZYGELZHQODHE-UHFFFAOYSA-N 0.000 description 1
- AICJOCBTSVRHRZ-UHFFFAOYSA-J 2-hydroxy-2-methylpropanoate titanium(4+) Chemical compound [Ti+4].CC(C)(O)C([O-])=O.CC(C)(O)C([O-])=O.CC(C)(O)C([O-])=O.CC(C)(O)C([O-])=O AICJOCBTSVRHRZ-UHFFFAOYSA-J 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- DSLZVSRJTYRBFB-LDHWTSMMSA-N D-mannaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-LDHWTSMMSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DSLZVSRJTYRBFB-UHFFFAOYSA-N Galactaric acid Natural products OC(=O)C(O)C(O)C(O)C(O)C(O)=O DSLZVSRJTYRBFB-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 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
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は酸化チタン薄膜製造
の原料となるチタン前駆体とその保存安定化法に関す
る。酸化チタンは光触媒として悪臭や空気中の有害物質
除去あるいは排水処理や浄水処理、抗菌などを行うこと
が出来る。また光触媒酸化チタンの超親水性を利用して
防曇、易清掃、セルフクリーニング材としての用途があ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium precursor used as a raw material for producing a titanium oxide thin film and a method for stabilizing the storage of the titanium precursor. Titanium oxide can be used as a photocatalyst to remove odors and harmful substances in the air, or to perform wastewater treatment, water purification treatment, antibacterial treatment, and the like. In addition, there is a use as an antifogging, easy cleaning, and self-cleaning material utilizing the superhydrophilicity of the photocatalytic titanium oxide.
【０００２】[0002]
【従来の技術】従来、酸化チタン薄膜を基板上に成形す
る技術として、特公平８−２５１７８７４、特公平９−
２６３６１５８、特開平９−２２７１６１に示されるよ
うにチタニアゾルを基材表面にスプレーコーティング
法、デイップコーティング法、フローコーティング法、
スピンコーティング法、ロールコーティング法等の方法
で塗布し、焼成する方法がある。また、有機チタネート
法として、チタンアルコキシド（テトラエトキシチタ
ン、テトラメトキシチタン、テトラプロポキシチタン、
テトラブトキシチタン等）、チタンアセテート、チタン
キレート等の有機チタネートに加水分解抑制剤（塩酸、
エチルアミン等）を添加し、アルコール（エタノール、
プロパノール、ブタノール等）などの非水溶媒で希釈し
た後、部分的に加水分解を進行させながら又は完全に加
水分解を進行させた後、混合物を塗布し、乾燥させる。
乾燥により、有機チタネートの加水分解が完遂して水酸
化チタンが生成し、水酸化チタンの脱水縮重合により無
定型酸化チタンの層が基材表面に形成される。その後、
アナターゼの結晶化温度以上の温度で焼成して、無定型
酸化チタンをアナターゼ型酸化チタンに相転移させる方
法がある。無定型酸化チタンをアナターゼ型酸化チタン
に相転移させる方法としては、焼成という熱的処理以外
に特開平６−１６６５０１、特開平９−１５７８５５に
示されるように水銀灯やレーザーを用いて紫外領域の光
を照射し行う方法もある。しかし、これまで実施されて
きたチタニアゾルや有機チタネートを基板に塗布する方
法では、上述のようにチタニアゾルや有機チタネートの
安定性や透明性を保つため、有機溶媒を使用したり、塩
酸や硝酸のような腐食性の酸を添加する必要があった。
そのため、有機溶媒の有害性が作業安全性から問題とな
ったり、腐食性から製造装置が高価になってしまうなど
の欠点があった。またチタニアゾルや有機チタネートの
安定性や透明性を確保するため溶液に含有されるチタン
元素の重量％を多くすることができず、必要とする膜厚
を得るためには、数度にわたり塗布と焼成などの処理操
作を繰り返す必要があった。そこで、先に本研究者らは
これら上記の欠点を解決する方法として、水溶性チタン
錯体を提案し、特許出願した（特願平１１−６８４０
３）。しかし、本水溶性チタン錯体水溶液は条件によ
り、濁りや白沈を生ずる場合があり、その保存法の確立
が望まれていた。2. Description of the Related Art Conventionally, as a technique for forming a titanium oxide thin film on a substrate, Japanese Patent Publication Nos.
No. 2,636,158 and JP-A-9-227161, a titania sol is spray-coated on a substrate surface, a dip coating method, a flow coating method,
There is a method of applying and baking by a method such as a spin coating method and a roll coating method. As an organic titanate method, titanium alkoxide (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium,
Organic titanates such as tetrabutoxytitanium, titanium acetate, titanium chelate, etc.
Ethylamine) and alcohol (ethanol,
After dilution with a non-aqueous solvent such as propanol, butanol, etc., the mixture is applied and dried with partial or complete hydrolysis.
By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. afterwards,
There is a method in which baking is performed at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from amorphous titanium oxide to anatase titanium oxide. As a method of transforming amorphous titanium oxide into anatase type titanium oxide, besides the thermal treatment of calcination, as described in JP-A-6-166501 and JP-A-9-157855, light in the ultraviolet region is irradiated by using a mercury lamp or laser. Irradiation. However, in the method of applying a titania sol or an organic titanate to a substrate that has been carried out so far, in order to maintain the stability and transparency of the titania sol or the organic titanate as described above, an organic solvent is used, such as hydrochloric acid or nitric acid. It was necessary to add a highly corrosive acid.
Therefore, there are drawbacks such as the harmfulness of the organic solvent becomes a problem from the viewpoint of work safety, and the production equipment becomes expensive due to the corrosiveness. Also, it is not possible to increase the weight percent of the titanium element contained in the solution to ensure the stability and transparency of the titania sol and organic titanate. To obtain the required film thickness, apply and bake several times. It was necessary to repeat such processing operations. Therefore, the present inventors have previously proposed a water-soluble titanium complex as a method for solving the above-mentioned disadvantages, and filed a patent application (Japanese Patent Application No. 11-6840).
3). However, the aqueous solution of the present water-soluble titanium complex may cause turbidity or white precipitation depending on conditions, and establishment of a method for preserving the solution has been desired.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、作業安全性
や腐食性の問題を生じない水溶性チタン錯体水溶液の長
期保存法の提供を目的とするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for long-term storage of an aqueous solution of a water-soluble titanium complex which does not cause problems in working safety and corrosiveness.
【０００４】[0004]
【課題を解決するための手段】本発明者は上記の目的を
達成するため、鋭意研究を重ねた結果、ヒドロキシ（ヒ
ドロキシカルボキシラト）チタンの水溶液にアンモニ
ア、有機アミン、尿素を添加し、溶液のｐＨを２．０〜
８．０に保持することにより水溶性チタン錯体水溶液を
長期にわたり安定に保存できることを見いだし、本研究
を完成させた。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, added ammonia, an organic amine, and urea to an aqueous solution of hydroxy (hydroxycarboxylato) titanium, pH 2.0 ~
It was found that the water-soluble titanium complex aqueous solution can be stably stored for a long period of time by keeping the pH at 8.0, and the present study was completed.
【０００５】本反応に用いられるヒドロキシ（ヒドロキ
シカルボキシラト）チタン水溶液は当該チタン錯体を水
に溶解することにより得られる。本錯体は四塩化チタン
などのチタンのハロゲン化物とヒドロキシカルボン酸を
非水溶媒系で反応させることによっても合成できるが、
チタン酸エステルとヒドロキシカルボン酸から容易に収
率よく合成される。ヒドロキシカルボン酸としてはテト
ラメトキシチタン、テトラエトキシチタン、テトラｎ−
プロポキシチタン、テトライソプロポキシチタン、テト
ラｎ−ブトキシチタンなどが使用できる。また、チタン
酸エステルの４個のアルコキシ基は単一成分でなく２か
ら４種類の成分の組み合わせでもよい。ヒドロキシカル
ボン酸は同一分子内に水酸基とカルボキシル基をもつ化
合物で有れば特に制限はなく、一つの分子内に複数個の
水酸基やカルボキシル基をもつ化合物でも差し使えな
い。また、炭素数についても特に制限はないが、水に対
する錯体の溶解度とチタン含量から適時決められる。こ
の様な化合物としてはグリコール酸、乳酸、α−ヒドロ
キシ酪酸、α−ヒドロキシイソ酪酸、β−ヒドロキシプ
ロピオン酸、β−ヒドロキシ酪酸、β−ヒドロキシイソ
酪酸、γ−ヒドロキシ酪酸、グリセリック酸、タートロ
ニック酸、リンゴ酸、酒石酸、メソ酒石酸、クエン酸が
好適に使用でき、これら単独でも２種以上のヒドロキシ
カルボン酸の混合物でもよい。また、炭素数６の糖類を
酸化して得られるグルコン酸、ガラクタル酸、マンナリ
ック酸なども好適に使用できる。[0005] The aqueous solution of hydroxy (hydroxycarboxylato) titanium used in this reaction is obtained by dissolving the titanium complex in water. This complex can also be synthesized by reacting a titanium halide such as titanium tetrachloride with a hydroxycarboxylic acid in a non-aqueous solvent system.
It is easily synthesized with good yield from titanate and hydroxycarboxylic acid. As hydroxycarboxylic acids, tetramethoxytitanium, tetraethoxytitanium, tetra-n-
Propoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium and the like can be used. Also, the four alkoxy groups of the titanate may be a combination of two to four types of components instead of a single component. The hydroxycarboxylic acid is not particularly limited as long as it is a compound having a hydroxyl group and a carboxyl group in the same molecule, and a compound having a plurality of hydroxyl groups and carboxyl groups in one molecule cannot be used. The number of carbon atoms is not particularly limited, but is determined as appropriate from the solubility of the complex in water and the titanium content. Such compounds include glycolic acid, lactic acid, α-hydroxybutyric acid, α-hydroxyisobutyric acid, β-hydroxypropionic acid, β-hydroxybutyric acid, β-hydroxyisobutyric acid, γ-hydroxybutyric acid, glyceric acid, tertronic acid , Malic acid, tartaric acid, meso-tartaric acid, and citric acid can be suitably used, and they may be used alone or as a mixture of two or more hydroxycarboxylic acids. Further, gluconic acid, galactaric acid, mannaric acid, etc. obtained by oxidizing a saccharide having 6 carbon atoms can also be suitably used.
【０００６】チタン酸エステルとヒドロキシカルボン酸
からヒドロキシ（ヒドロキシカルボキシラト）チタンを
合成する方法としては、それぞれの化合物を溶解する溶
媒を用い、具体的には用いるアルコキシチタンのアルコ
キシ基と同一のアルコキシ基を含むアルコールを使用す
るのが好ましい。例えば、テトライソプロポキシチタン
を用いる場合はイソプロパノールが好適である。これ以
外に各種アルコール、エーテル、エステル、炭化水素、
水などを使用することもできる。As a method for synthesizing hydroxy (hydroxycarboxylato) titanium from a titanate and a hydroxycarboxylic acid, a solvent capable of dissolving each compound is used. Specifically, the same alkoxy group as that of the alkoxytitanium used is used. It is preferred to use an alcohol containing For example, when using tetraisopropoxytitanium, isopropanol is preferred. In addition to this, various alcohols, ethers, esters, hydrocarbons,
Water or the like can also be used.
【０００７】ヒドロキシ（ヒドロキシカルボキシラト）
チタンを製造する条件としては室温から１００℃、好ま
しくは室温から５０℃である。テトラアルコキシチタン
とヒドロキシカルボン酸の混合比は１：０．１から１：
１０、好ましくは１：０．２から１：４である。分子内
に水酸基とカルボキシル基を一つづつ持つヒドロキシカ
ルボン酸、例えばグリコール酸、乳酸、α−ヒドロキシ
酪酸、α−ヒドロキシイソ酪酸からはチタンとヒドロキ
シカルボン酸が１：２の組成比を持つジヒドロキシビス
（ヒドロキシカルボキシラト）チタンが合成される。一
つの分子内に複数個の水酸基やカルボキシル基をもつヒ
ドロキシカルボン酸を用いた場合には、チタンとの混合
比、水酸基やカルボキシル基の数により任意の錯体が合
成されるが、水溶性を保つのであればその構造は限定さ
れない。テトラアルコキシチタンとヒドロキシカルボン
酸の溶液を混合し、溶媒を留出してやることによりヒド
ロキシ（ヒドロキシカルボキシラト）チタンの固体粉末
を容易に得ることができる。Hydroxy (hydroxycarboxylate)
Conditions for producing titanium are room temperature to 100 ° C., preferably room temperature to 50 ° C. The mixing ratio of tetraalkoxytitanium and hydroxycarboxylic acid is from 1: 0.1 to 1:
10, preferably from 1: 0.2 to 1: 4. From hydroxycarboxylic acids having one hydroxyl group and one carboxyl group in the molecule, for example, glycolic acid, lactic acid, α-hydroxybutyric acid, and α-hydroxyisobutyric acid, dihydroxybis having a composition ratio of titanium and hydroxycarboxylic acid of 1: 2 is used. (Hydroxycarboxylato) titanium is synthesized. When a hydroxycarboxylic acid having a plurality of hydroxyl groups or carboxyl groups in one molecule is used, an arbitrary complex is synthesized depending on the mixing ratio with titanium and the number of hydroxyl groups and carboxyl groups, but water solubility is maintained. If so, the structure is not limited. A solid powder of hydroxy (hydroxycarboxylato) titanium can be easily obtained by mixing a solution of tetraalkoxy titanium and hydroxy carboxylic acid and distilling off the solvent.
【０００８】得られた固形粉末を水に溶解することによ
り、ヒドロキシ（ヒドロキシカルボキシラト）チタン水
溶液が得られる。水に対する溶解度は合成に用いたヒド
ロキシカルボン酸の種類により決まるが、水溶液にアン
モニア、有機アミン、尿素を添加し溶液のｐＨをコント
ロールすることにより、溶解度を著しく向上させること
が出来る。また、ヒドロキシ（ヒドロキシカルボキシラ
ト）チタン水溶液は透明な溶液であるが、空気中に室温
で放置した場合、経時的に用いたヒドロキシカルボン酸
の種類や濃度により濁りや沈殿を生じる場合がある。水
溶液にアンモニア、有機アミン、尿素を添加し溶液のｐ
Ｈをコントロールすることによりこの濁りや沈殿は発生
しなくなり、水溶液の安定性が確保できる。通常ヒドロ
キシビス（ヒドロキシカルボキシラト）チタン水溶液の
ｐＨは２．０以下であるがアンモニア、有機アミン、尿
素を添加することにより、ｐＨを２．０に以上にするこ
とで水溶液の安定性が向上してくる。しかし、アンモニ
ア、有機アミン、尿素を添加しすぎてｐＨを８．０より
大きくした場合、再び水溶液の安定性が低下して濁りや
沈殿を発生するようになる。水溶液のｐＨコントロール
としては２．０〜８．０が好ましい。By dissolving the obtained solid powder in water, an aqueous hydroxy (hydroxycarboxylato) titanium solution is obtained. The solubility in water is determined by the type of hydroxycarboxylic acid used in the synthesis, but the solubility can be significantly improved by adding ammonia, organic amine, and urea to the aqueous solution and controlling the pH of the solution. The hydroxy (hydroxycarboxylato) titanium aqueous solution is a transparent solution, but when left in the air at room temperature, turbidity or precipitation may occur depending on the type and concentration of the hydroxycarboxylic acid used over time. Add ammonia, organic amine, urea to the aqueous solution
By controlling H, this turbidity or precipitation does not occur, and the stability of the aqueous solution can be ensured. Usually, the pH of the aqueous solution of hydroxybis (hydroxycarboxylato) titanium is 2.0 or less, but the stability of the aqueous solution is improved by adding ammonia, organic amine, and urea to adjust the pH to 2.0 or more. Come. However, when the pH is increased to more than 8.0 by adding ammonia, organic amine, and urea excessively, the stability of the aqueous solution is again reduced, and turbidity and precipitation occur. As the pH control of the aqueous solution, 2.0 to 8.0 is preferable.
【０００９】アンモニア、尿素は水溶性でありこのま
ま、または水溶液として添加可能である。有機アミンは
特に制限はないが水に可溶な化合物が好ましい。そのよ
うな化合物としてはモノエタノールアミン、ジエタノー
ルアミン、トリエタノールアミン、Ｎ−メチルジエタノ
ールアミン、Ｎ−エチルジエタノールアミン、Ｎ，Ｎ−
ジメチルジアミノエタノール、ジイソプロパノールアミ
ンなどのアルコールアミン類やモノメチルアミン、ジメ
チルアミン、トリメチルアミン、エチルアミンなとの炭
素数の比較的少ないアルキルアミン類、エチレンジアミ
ン等のキレート性アミン類などがある。また、これら以
外にポリビニールアルコール、ポリエチレングリコー
ル、ポリアクリルアミドやカルボキシメチルセルロース
などの水溶性有機高分子化合物を添加し溶液の粘度を調
整することもなんら問題にならない。Ammonia and urea are water-soluble and can be added as such or as an aqueous solution. The organic amine is not particularly limited, but is preferably a water-soluble compound. Such compounds include monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-
Examples thereof include alcohol amines such as dimethyldiaminoethanol and diisopropanolamine, alkylamines having a relatively small number of carbon atoms such as monomethylamine, dimethylamine, trimethylamine and ethylamine, and chelating amines such as ethylenediamine. In addition, there is no problem in adjusting the viscosity of the solution by adding a water-soluble organic polymer compound such as polyvinyl alcohol, polyethylene glycol, polyacrylamide or carboxymethyl cellulose.
【００１０】本発明の酸化チタン薄膜光触媒はこうして
得られたヒドロキシ（ヒドロキシカルボキシラト）チタ
ンの水溶液をディップコーティング法やスピンコーティ
ング法、塗布法、スプレー法などにより基板にコーティ
ングした後、室温から徐々に加熱昇温することで部分的
に加水分解を進行させながら乾燥させる。乾燥により加
水分解が完遂して水酸化チタンが生成し、水酸化チタン
の脱水縮重合により無定型酸化チタン層が基材表面に成
形される。この際、水溶性チタン錯体を用いる本発明で
は、アルコールや炭化水素などの有機溶媒を用いないた
め、有機溶媒蒸気の発生がなく作業環境性が著しく向上
される。また、加水分解抑制剤として塩酸や硝酸などの
腐食性の高い鉱酸を用いないため、装置の腐食がなく、
安価な設備投資ですむ利点がある。その後、アナターゼ
の結晶化温度以上の温度で焼成し、無定型酸化チタンを
アナターゼ型酸化チタンに相転移させる。この時の昇温
の最終温度、焼成温度は６００〜７００℃が好ましい。
直接６００〜７００℃の温度で焼成したり、焼成温度が
６００℃より低かったり、７００℃より高かった場合、
光触媒として低活性なルチル型酸化チタンや非晶質の混
じった酸化チタン薄膜しか得られない。The titanium oxide thin film photocatalyst of the present invention is obtained by coating the aqueous solution of hydroxy (hydroxycarboxylato) titanium thus obtained on a substrate by a dip coating method, a spin coating method, a coating method, a spraying method or the like, and then gradually from room temperature. By heating and raising the temperature, drying is performed while partially promoting hydrolysis. The hydrolysis is completed by drying to produce titanium hydroxide, and an amorphous titanium oxide layer is formed on the surface of the base material by dehydration-condensation polymerization of titanium hydroxide. In this case, in the present invention using a water-soluble titanium complex, an organic solvent such as an alcohol or a hydrocarbon is not used, so that no organic solvent vapor is generated and the work environment is remarkably improved. In addition, since a highly corrosive mineral acid such as hydrochloric acid or nitric acid is not used as a hydrolysis inhibitor, there is no corrosion of the device,
It has the advantage of requiring low capital investment. Then, it is calcined at a temperature equal to or higher than the crystallization temperature of anatase, and the amorphous titanium oxide undergoes a phase transition to the anatase titanium oxide. The final temperature of the heating and the firing temperature at this time are preferably from 600 to 700 ° C.
When firing directly at a temperature of 600 to 700 ° C, or when the firing temperature is lower than 600 ° C or higher than 700 ° C,
As a photocatalyst, only low-activity rutile-type titanium oxide or amorphous titanium oxide thin film can be obtained.
【００１１】また、チタニアゾル法や有機チタネート法
では、ゾルの安定性や有機チタネートの溶解度などの関
係からチタン含量の割合の低いものしか調製できなかっ
たが、本発明のチタン錯体の水溶液ではチタン含量を多
くすることができる。そこで従来、丈夫で高性能の酸化
チタン薄膜を得るには、チタニアゾルや有機チタネート
を薄く塗布し加熱焼成し、この作業を繰り返し、厚くて
丈夫な酸化チタン膜を得ていた。これに対してチタン錯
体の水溶液ではこの繰り返し操作回数を低減できる利点
がある。In the titania sol method and the organic titanate method, only a titanium compound having a low titanium content can be prepared due to the stability of the sol and the solubility of the organic titanate. Can be more. Therefore, conventionally, in order to obtain a durable and high-performance titanium oxide thin film, a titania sol or an organic titanate is applied thinly and fired, and this operation is repeated to obtain a thick and durable titanium oxide film. On the other hand, an aqueous solution of a titanium complex has the advantage that the number of repetitive operations can be reduced.
【００１２】本発明の酸化チタン薄膜光触媒を製造する
際に使用される基板はガラスやセラミックス、コンクリ
ート、金属など６００〜７００℃の温度での焼成に耐え
られるものであれば、どの様な材質であっても良い。ま
たこれら基板の表面にシリカやアルミナなどの層を塗布
したり成形したものであってもなんら問題はない。その
形状も限定されない。The substrate used for producing the titanium oxide thin film photocatalyst of the present invention is made of any material such as glass, ceramics, concrete, and metal, as long as it can withstand firing at a temperature of 600 to 700 ° C. There may be. There is no problem even if a layer such as silica or alumina is applied or molded on the surface of these substrates. The shape is not limited.
【００１３】６００〜７００℃の温度での焼成に耐えら
れない基板、例えばプラスティック表面に酸化チタン薄
膜光触媒を製造する場合や、焼成を行わずにガラスやセ
ラミックス表面に酸化チタン薄膜光触媒を成形したい場
合は３５０ｎｍ以下の光を、エネルギー密度５０〜１０
０ｍＪ／ｃｍ2 で照射することにより可能となる。When a titanium oxide thin film photocatalyst is manufactured on a substrate that cannot withstand firing at a temperature of 600 to 700 ° C., for example, on a plastic surface, or when a titanium oxide thin film photocatalyst is formed on a glass or ceramic surface without firing. Emits light of 350 nm or less at an energy density of 50 to 10
Irradiation at 0 mJ / cm 2 is possible.
【００１４】操作方法としては焼成法と同様に、まず無
定型酸化チタン層を基材表面に成形する。この際、耐熱
温度の低いプラスティックを基板として用いる場合は、
使用するプラスティックのガラス転移温度以下で実施す
るのが好ましい。ガラスやセラミックス、コンクリート
などの基板では特に問題はない。基板に水溶性チタン錯
体水溶液を塗布し、溶媒である水を乾燥させながら加水
分解し、水に不溶のゲル膜、無定型酸化チタン層を形成
させる。その際、残存している有機物であるヒドロキシ
カルボン酸を水洗して除去することもできる。As an operation method, first, an amorphous titanium oxide layer is formed on the surface of the base material, similarly to the firing method. At this time, if a plastic with a low heat-resistant temperature is used as the substrate,
It is preferably carried out below the glass transition temperature of the plastic used. There is no particular problem with substrates such as glass, ceramics, and concrete. An aqueous solution of a water-soluble titanium complex is applied to a substrate and hydrolyzed while drying water as a solvent to form a water-insoluble gel film and an amorphous titanium oxide layer. At this time, the remaining organic hydroxycarboxylic acid can be removed by washing with water.
【００１５】基板表面に無定型酸化チタン層が形成され
ると、その薄膜に対して波長が３５０ｎｍ以下である紫
外線を照射する。紫外線の光源としては、波長が３５０
ｎｍ以下である紫外光を照射可能であれば、その種類は
問わない。例えば、高圧水銀ランプ、低圧水銀ランプ、
エキシマランプ、ＡｒＦエキシマレーザー、ＫｒＦエキ
シマレーザー、ＹＡＧレーザー４倍波、シンクロトロン
放射光などが使用される。また、これらの光源のうち２
つもしくはそれ以上のものを組み合わせて使用すること
も可能である。この薄膜への紫外線照射の際に、基板を
加熱したり、基板を減圧下に置いたり、酸化雰囲気、還
元雰囲気に置いたりすることも可能である。紫外光の照
射強度やショット数は金属酸化物ゲルの薄膜の種類や組
成などに応じて適時選択されるが、酸化チタン薄膜光触
媒を製造する場合、照射強度は光触媒に高活性なアナタ
ーゼ型酸化チタンを生成するエネルギー密度５０〜１０
０ｍＪ／ｃｍ2 が好ましい。５０ｍＪ／ｃｍ2 より低い
エネルギー密度ではアナターゼ相の生成は認められず、
また１００ｍＪ／ｃｍ2 より高いエネルギー密度では光
活性の低いルチル相の生成が多くなってしまう。When the amorphous titanium oxide layer is formed on the surface of the substrate, the thin film is irradiated with ultraviolet light having a wavelength of 350 nm or less. The wavelength of the light source is 350
Any type can be used as long as it can be irradiated with ultraviolet light of nm or less. For example, high-pressure mercury lamp, low-pressure mercury lamp,
An excimer lamp, an ArF excimer laser, a KrF excimer laser, a fourth harmonic of a YAG laser, synchrotron radiation, and the like are used. Also, two of these light sources
It is also possible to use one or more of them in combination. When irradiating the thin film with ultraviolet light, the substrate may be heated, the substrate may be placed under reduced pressure, or may be placed in an oxidizing atmosphere or a reducing atmosphere. The irradiation intensity and the number of shots of ultraviolet light are selected as appropriate according to the type and composition of the thin film of the metal oxide gel.However, when manufacturing a titanium oxide thin film photocatalyst, the irradiation intensity is anatase-type titanium oxide which is highly active on the photocatalyst. Energy density to produce 50 to 10
0 mJ / cm 2 is preferred. At an energy density lower than 50 mJ / cm 2 , no anatase phase is formed,
If the energy density is higher than 100 mJ / cm 2, the generation of a rutile phase having low photoactivity increases.
【００１６】[0016]
【実施例】以下にこの発明を具体的に適用した実施例に
ついて説明する。 実施例１水溶性チタン錯体の合成法 ヒドロキシカルボン酸としてα−ヒドロキシイソ酪酸を
用いた場合の水溶性チタン錯体合成法の一例を述べる
が、以下の方法は他のヒドロキシカルボン酸を用いた場
合にも適用可能である。イソプロパノール１００ｇにα
−ヒドロキシイソ酪酸７４ｇを溶解させ、そこにテトラ
イソプロポキシチタン１００ｇをゆっくりと滴下してい
った。加えたα−ヒドロキシイソ酪酸とテトライソプロ
ポキシチタンとの比率はモル比で２：１である。滴下終
了後室温でそのまま攪拌し、白色懸濁液になったところ
で攪拌をやめ、ロータリーエバポレーターで溶媒を留去
した。得られた白色粉末は１２６ｇであった。ＩＣＰに
よりＴｉの重量存在量をはかったところ１７．３％であ
った。また、元素分析からＣ：３３．０％，Ｈ：５．４
％であった（理論値 Ｔｉ：１６．６％，Ｃ：３３．３
％，Ｈ：５．６％）。このことから得られた白色粉末は
ジヒドロキシビス（ヒドロキシイソブチラート）チタン
と同定された。この化合物を２６．５ｇ採取し、水１０
０ｇを添加し攪拌したところ無色透明な水溶性チタン水
溶液が得られた。Embodiments of the present invention will be described below. Example 1 Synthesis Method of Water-Soluble Titanium Complex An example of a method of synthesizing a water-soluble titanium complex using α-hydroxyisobutyric acid as a hydroxycarboxylic acid will be described. The following method is applied to a case where another hydroxycarboxylic acid is used. Is also applicable. Α to 100 g of isopropanol
74 g of hydroxyisobutyric acid was dissolved, and 100 g of tetraisopropoxytitanium was slowly added dropwise thereto. The ratio between the added α-hydroxyisobutyric acid and tetraisopropoxytitanium is 2: 1 in molar ratio. After completion of the dropwise addition, the mixture was stirred as it was at room temperature. When a white suspension was formed, the stirring was stopped, and the solvent was distilled off using a rotary evaporator. The amount of the obtained white powder was 126 g. The weight abundance of Ti measured by ICP was 17.3%. From elemental analysis, C: 33.0%, H: 5.4.
% (Theoretical values: Ti: 16.6%, C: 33.3)
%, H: 5.6%). The white powder obtained from this was identified as dihydroxybis (hydroxyisobutyrate) titanium. 26.5 g of this compound was collected, and 10
When 0 g was added and stirred, a colorless and transparent water-soluble titanium aqueous solution was obtained.
【００１７】実施例２〜１７および比較例１〜４ 種々のヒドロキシカルボン酸を用いヒドロキシ（ヒドロ
キシカルボキシラト）チタンを合成し、水溶液を調製
後、溶液のpHを測定し、２５℃における保存安定性を調
べた。また、アンモニア、有機アミン、尿素を添加した
場合についても溶液のpHを測定し、保存安定性を調べ
た。結果を表１にまとめた。ヒドロキシ（ヒドロキシカ
ルボキシラト）チタン単独水溶液で溶液のｐＨが２．０
より低い場合、完全に溶液にならないものや、経時的に
濁りや沈殿を生じたりするものがあった。また、アンモ
ニア、有機アミン、尿素を添加しすぎ溶液のｐＨが８．
０より大きくなった場合も経時的に濁りや沈殿を生じ
た。溶液のｐＨを２．０〜８．０に調製することにより
このような問題は起こらなくなり保存安定性が向上し
た。Examples 2 to 17 and Comparative Examples 1 to 4 Hydroxy (hydroxycarboxylato) titanium was synthesized using various hydroxycarboxylic acids, an aqueous solution was prepared, the pH of the solution was measured, and the storage stability at 25 ° C. Was examined. In addition, when ammonia, organic amine, and urea were added, the pH of the solution was measured to examine the storage stability. The results are summarized in Table 1. The aqueous solution of hydroxy (hydroxycarboxylato) titanium alone has a pH of 2.0
At lower levels, there were some that did not completely turn into a solution, and those that became turbid or precipitated over time. In addition, ammonia, organic amine, and urea are added too much, and the pH of the solution becomes 8.
When it was larger than 0, turbidity and precipitation occurred over time. By adjusting the pH of the solution to 2.0 to 8.0, such a problem did not occur and the storage stability was improved.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【発明の効果】従来問題であった水溶性チタン錯体水溶
液の長期安定性も良好な保存法が確立された。According to the present invention, a method for preserving a long-term stability of a water-soluble titanium complex aqueous solution, which has been a problem, has been established.
Claims (2)
ト）チタンの水溶液に、アンモニア、有機アミン及び尿
素からなる群より選ばれる少なくとも一種類を添加し、
水溶液のｐＨを２．０〜８．０に保持することを特徴と
する水溶性チタン錯体水溶液の保存法。1. An aqueous solution of hydroxy (hydroxycarboxylato) titanium is added with at least one selected from the group consisting of ammonia, organic amines and urea,
A method for storing an aqueous solution of a water-soluble titanium complex, wherein the pH of the aqueous solution is maintained at 2.0 to 8.0.
ト）チタンがテトラアルコキシチタンとヒドロキシカル
ボン酸から製造され、ヒドロキシカルボン酸がグリコー
ル酸、乳酸、α−ヒドロキシ酪酸、α−ヒドロキシイソ
酪酸、β−ヒドロキシプロピオン酸、β−ヒドロキシ酪
酸、β−ヒドロキシイソ酪酸、γ−ヒドロキシ酪酸、グ
リセリック酸、タートロニック酸、リンゴ酸、酒石酸、
メソ酒石酸又はクエン酸である請求項１記載の水溶性チ
タン錯体水溶液の保存法。2. Hydroxy (hydroxycarboxylato) titanium is produced from tetraalkoxytitanium and hydroxycarboxylic acid, wherein the hydroxycarboxylic acid is glycolic acid, lactic acid, α-hydroxybutyric acid, α-hydroxyisobutyric acid, β-hydroxypropionic acid, β-hydroxybutyric acid, β-hydroxyisobutyric acid, γ-hydroxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid,
The method for preserving an aqueous solution of a water-soluble titanium complex according to claim 1, which is mesotartaric acid or citric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11159813A JP2000351787A (en) | 1999-06-07 | 1999-06-07 | Storage of water-soluble titanium complex aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11159813A JP2000351787A (en) | 1999-06-07 | 1999-06-07 | Storage of water-soluble titanium complex aqueous solution |
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| Publication Number | Publication Date |
|---|---|
| JP2000351787A true JP2000351787A (en) | 2000-12-19 |
Family
ID=15701820
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11159813A Pending JP2000351787A (en) | 1999-06-07 | 1999-06-07 | Storage of water-soluble titanium complex aqueous solution |
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| Country | Link |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003082883A1 (en) * | 2002-04-01 | 2003-10-09 | Daiso Co., Ltd. | Titanium salts, process for preparation thereof, and process for preparing epoxides with the same |
| JP2007277360A (en) * | 2006-04-04 | 2007-10-25 | Kao Corp | Resin composition |
| JPWO2008001764A1 (en) * | 2006-06-30 | 2009-11-26 | 有限会社フォアロードリサーチ | Latex composition containing a crosslinking agent and crosslinked molded article thereof |
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1999
- 1999-06-07 JP JP11159813A patent/JP2000351787A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003082883A1 (en) * | 2002-04-01 | 2003-10-09 | Daiso Co., Ltd. | Titanium salts, process for preparation thereof, and process for preparing epoxides with the same |
| JP2007277360A (en) * | 2006-04-04 | 2007-10-25 | Kao Corp | Resin composition |
| JPWO2008001764A1 (en) * | 2006-06-30 | 2009-11-26 | 有限会社フォアロードリサーチ | Latex composition containing a crosslinking agent and crosslinked molded article thereof |
| JP2010059441A (en) * | 2006-06-30 | 2010-03-18 | Four Road Research Ltd | Latex composition containing crosslinking agent and crosslinked molded body thereof |
| JP4647026B2 (en) * | 2006-06-30 | 2011-03-09 | 有限会社フォアロードリサーチ | Latex composition containing a crosslinking agent and crosslinked molded article thereof |
| US8389620B2 (en) | 2006-06-30 | 2013-03-05 | Four Road Research Ltd. | Dip forming latex composition containing crosslinking agent and dip formed article obtained therefrom |
| JP2011236203A (en) * | 2010-04-12 | 2011-11-24 | Nitto Denko Corp | Titanium complex, titanium oxide particle and production method therefor |
| US9847544B2 (en) | 2010-04-12 | 2017-12-19 | Nitto Denko Corporation | Ion conductive organic-inorganic composite particles, particle-containing resin composition and ion conductive molded article |
| US10265693B2 (en) | 2010-04-12 | 2019-04-23 | Nitto Denko Corporation | Particles, particle dispersion, particle-dispersed resin composition, producing method therefor, resin molded article, producing method therefor, catalyst particles, catalyst solution, catalyst composition, catalyst molded article, titanium complex, titanium oxide particles and producing method therefor |
| WO2022004786A1 (en) | 2020-07-03 | 2022-01-06 | コスモ石油株式会社 | Hydrogenation treatment catalyst for hydrocarbon oil, method for producing hydrogenation treatment catalyst for hydrocarbon oil, and hydrogenation treatment method for hydrocarbon oil |
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