JPH1143327A - Titanium oxide particle, its water dispersing sol, coated film and their production - Google Patents
Titanium oxide particle, its water dispersing sol, coated film and their productionInfo
- Publication number
- JPH1143327A JPH1143327A JP9231172A JP23117297A JPH1143327A JP H1143327 A JPH1143327 A JP H1143327A JP 9231172 A JP9231172 A JP 9231172A JP 23117297 A JP23117297 A JP 23117297A JP H1143327 A JPH1143327 A JP H1143327A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- sol
- water
- dispersed
- thin film
- 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 244
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000002245 particle Substances 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000010409 thin film Substances 0.000 claims abstract description 90
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 239000000460 chlorine Substances 0.000 claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- -1 alkyl silicate Chemical compound 0.000 claims description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 25
- 238000006298 dechlorination reaction Methods 0.000 abstract description 5
- 239000010419 fine particle Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 9
- 238000000909 electrodialysis Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000002233 thin-film X-ray diffraction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水分散酸化チタンゾ
ル、該ゾルを用いてセラミックス、プラスチック等の基
材に形成した酸化チタンの薄膜、特定の酸化チタン粒子
及び水分散酸化チタンゾルの製造法に関する。この酸化
チタン薄膜は透明性にして光触媒作用に優れ、また基材
との密着性が良好なものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersed titanium oxide sol, a thin film of titanium oxide formed on a substrate such as a ceramic or plastic using the sol, specific titanium oxide particles, and a method for producing a water-dispersed titanium oxide sol. This titanium oxide thin film is transparent and has excellent photocatalytic action, and has good adhesion to a substrate.
【０００２】[0002]
【従来の技術】二酸化チタン（以下、酸化チタンと称
す）にはアナターゼ、ブルーカイト、ルチル型の３つの
結晶相の存在が知られている。四塩化チタンと酸素等の
混合燃焼方法で製造する気相法の場合において、最も低
温で生成し安定なのがアナターゼ型である。これに熱処
理を施し焼成していくと８１６〜１０４０℃でブルーカ
イト型、それ以上の温度域ではルチル型構造の酸化チタ
ンが得られる（理化学辞典第３版、Ｐ．５１４〜５１
５）。2. Description of the Related Art It is known that titanium dioxide (hereinafter referred to as titanium oxide) has three crystal phases of anatase, brookite and rutile type. In the case of a gas phase method produced by a mixed combustion method of titanium tetrachloride and oxygen or the like, an anatase type is formed and stable at the lowest temperature. By subjecting this to heat treatment and firing, a brookite-type titanium oxide is obtained at 816 to 1040 ° C., and a rutile-type titanium oxide is obtained in a temperature range higher than 816 to 1040 ° C. (Rikken Dictionary, 3rd edition, pp. 514 to 51).
5).
【０００３】また、液相法では例えば、舟木 好右衛
門、工業化学 第５９巻、第１１号、Ｐ．１２９５らに
より四塩化チタン水溶液の加水分解により生成する酸化
チタンの結晶相について詳細に報告している。これによ
ると、主として高濃度液中からはルチル型が、低濃度側
からはアナターゼ型の酸化チタンが生成すると結論づけ
ている。そして液相中ではブルーカイト型でしかも微粒
子の酸化チタンの生成は不可能であったと述べている。
これら報告から今までブルーカイト型の酸化チタンを液
相法で安定的に製造することは困難であった。上記した
ように気相法による酸化チタンを高温で熱処理すればブ
ルーカイト型酸化チタンになるが、熱処理するため粒子
が成長するので、微細な粒子でブルーカイト型結晶のも
のを得ることは従来難しかった。[0003] In the liquid phase method, for example, Yoshiaki Funaki, Kogaku Kagaku, Vol. 59, No. 11, p. 1295 et al. Report in detail the crystal phase of titanium oxide formed by hydrolysis of an aqueous solution of titanium tetrachloride. According to this, it is concluded that rutile-type titanium oxide is produced mainly from a high-concentration solution and anatase-type titanium oxide is produced from a low-concentration side. He states that in the liquid phase, it was impossible to produce brookite-type fine particles of titanium oxide.
From these reports, it has been difficult to stably produce brookite-type titanium oxide by a liquid phase method. If the titanium oxide by the gas phase method is heat-treated at a high temperature as described above, it becomes brookite-type titanium oxide.However, since the particles grow due to the heat treatment, it is conventionally difficult to obtain fine particles of brookite-type crystals. Was.
【０００４】一方、酸化チタンゾルの生成方法に関して
は、結晶性或いはアモルファスの酸化チタン粒子を分散
媒に分散させるか、分散媒中にチタンアルコキシド、硫
酸チタン、四塩化チタンなどの酸化チタンの前駆体を混
入させ中和、加水分解などの方法によりゾルを形成させ
ることが一般的である。酸化チタンゾルは酸化チタン粉
末の製造に用いられたり、あるいはゾルをガラスやプラ
スチック等に塗布し、酸化チタンの薄膜をそれらの表面
に形成したりするのに用いられている。酸化チタンは光
半導体であり、粒子径が小さくなれば透明性が生じ、か
つ光触媒機能が向上することが知られている。酸化チタ
ンの光触媒機能については近年、盛んに研究開発が行わ
れている。この光触媒の利用方法には有害物質の除去に
よる防汚、アンモニアなどの悪臭ガスの脱臭、細菌類の
殺菌などがあるが、その利用目的により酸化チタンの形
態は、バルク粒子、薄膜、ゾルと様々である。この光触
媒機能はさらに透明性を付加しようとする場合はもっぱ
ら薄膜にされる場合が多い。そのために酸化チタンはゾ
ルの形で薄膜生成材料として使用される。On the other hand, regarding the method of producing titanium oxide sol, crystalline or amorphous titanium oxide particles are dispersed in a dispersion medium, or a titanium oxide precursor such as titanium alkoxide, titanium sulfate, titanium tetrachloride is dispersed in the dispersion medium. It is common to mix and form a sol by a method such as neutralization or hydrolysis. Titanium oxide sol is used for producing titanium oxide powder or for applying a sol to glass, plastic, or the like, and forming a thin film of titanium oxide on the surface thereof. Titanium oxide is an optical semiconductor, and it is known that the smaller the particle size, the higher the transparency and the better the photocatalytic function. In recent years, research and development have been actively conducted on the photocatalytic function of titanium oxide. There are various ways to use this photocatalyst, such as antifouling by removing harmful substances, deodorization of odorous gas such as ammonia, and sterilization of bacteria.The form of titanium oxide varies depending on the purpose of use, such as bulk particles, thin films, and sols. It is. This photocatalytic function is often made exclusively as a thin film in order to add transparency. For this purpose, titanium oxide is used as a film-forming material in the form of a sol.
【０００５】酸化チタンの光触媒能力に関しては、ルチ
ル型よりもアナターゼ型の方が能力が大きいことが認め
られている。その理由は、両者のエネルギーギャップに
よるものであり、ルチル型が３．０２ｅＶ、アナターゼ
型が３．２３ｅＶと約０．２ｅＶの差があることによる
（セラミックス３１（１９９６） No.１０、Ｐ．８１
７）。このエネルギー差から高エネルギーギャップを持
つアナターゼ型酸化チタンが光半導体として好んで用い
られている。しかし、ブルーカイト型に関して言えば、
今までに単体物質そのものを取り出した例が少なく、そ
の上光半導体（光触媒）として用いることのできるよう
な高比表面積を持つ微粒子として得ることは従来は高温
での製造のため粒子が焼結してしまい不可能であった。Regarding the photocatalytic ability of titanium oxide, it has been recognized that the anatase type has a higher ability than the rutile type. The reason is due to the difference in energy gap between the two, that is, the difference between the rutile type is 3.02 eV and the anatase type is 3.23 eV, which is about 0.2 eV (Ceramics 31 (1996) No. 10, P. 81).
7). Due to this energy difference, anatase-type titanium oxide having a high energy gap is preferably used as an optical semiconductor. However, regarding the blue kite type,
Until now, there have been few cases in which a single substance itself was taken out. In addition, to obtain fine particles having a high specific surface area that can be used as an optical semiconductor (photocatalyst), conventionally, particles were sintered because of high-temperature production. It was impossible.
【０００６】薄膜の利用形態として最近照明器具、例え
ば蛍光ランプのガラス管やそのカバーに酸化チタンゾル
を塗布して薄膜を形成し、光触媒作用により上記ガラス
管やカバーに油煙等の有機物が付着した場合、それを分
解し、ガラス管やカバーの汚れを防止する方法が提案さ
れている。しかし、前記した方法で得られたゾルを用い
て薄膜を形成した場合、透明性の高い薄膜とすることが
可能であるものは少なく、特にブルーカイト型酸化チタ
ン薄膜を照明器具等の光触媒に用いたものは従来知られ
ていない。Recently, a thin film is formed by applying a titanium oxide sol to a lighting device, for example, a glass tube of a fluorescent lamp or its cover, and an organic substance such as oil smoke adheres to the glass tube or the cover by photocatalysis. There has been proposed a method of disassembling the glass tube and preventing the glass tube and the cover from being stained. However, when a thin film is formed using the sol obtained by the above-described method, there are few cases where a thin film having high transparency can be obtained. In particular, a brookite-type titanium oxide thin film is used as a photocatalyst for lighting equipment and the like. What was previously unknown.
【０００７】[0007]
【発明が解決しようとする課題】酸化チタン薄膜をガラ
ス、プラスチック、その他の基材に形成して光触媒とし
て利用する場合、その薄膜は触媒活性が高いことが要求
される。光触媒作用は粒子表面での反応であるため高活
性を持たせるには粒子が高い表面積をもつ微粒子である
こと、また結晶性が良いことが好ましい。さらに照明器
具等に薄膜を形成する場合には薄膜は透明性であること
が必要である。透明性をよくするためにも酸化チタンは
触媒活性の場合と同様に微粒子であり、かつ単分散であ
るものが望ましい。こうした問題に対しては、従来はも
っぱらアナターゼ型の酸化チタンを微細化することで対
応していた。また酸化チタン薄膜を基材に形成する場
合、薄膜と基材との密着性をよくし、容易に薄膜が剥離
しないようにしなければならない。When a titanium oxide thin film is formed on glass, plastic, or another substrate and used as a photocatalyst, the thin film is required to have high catalytic activity. Since the photocatalysis is a reaction on the surface of the particles, it is preferable that the particles be fine particles having a high surface area and have good crystallinity in order to have high activity. Further, when a thin film is formed on a lighting device or the like, the thin film needs to be transparent. In order to improve the transparency, the titanium oxide is preferably fine particles and monodispersed as in the case of the catalytic activity. Conventionally, such a problem has been dealt with by making anatase-type titanium oxide finer. When a titanium oxide thin film is formed on a base material, it is necessary to improve the adhesion between the thin film and the base material so that the thin film is not easily peeled off.
【０００８】従来の四塩化チタンを加水分解する方法で
は、粒子径が非常に小さい微粒子で、かつ結晶性がよ
く、薄膜にしたとき透明性がよい酸化チタンゾルをつく
ることが困難であった。チタンアルコシド化合物の加水
分解ではゾル中の酸化チタンは非常に小さい微粒子とな
るなど粉体特性としては優れているが、ゾル中にアルコ
ールが含まれ、薄膜にして焼成する場合爆発などの安全
上の問題がある。また、爆発を防ぐには防爆の大型設備
が必要となり、経済的に不利である。またチタンアルコ
シド化合物は四塩化チタンに比べ非常に高価である。本
発明は水分散酸化チタンゾルを各種の基材に塗布し、基
材表面に酸化チタンの薄膜を形成した場合、薄膜が光触
媒機能及び透明性に優れ、かつ薄膜と基材との密着性が
良好となる酸化チタンゾル及び微細なブルーカイト型酸
化チタン粒子を提供することを目的とする。In the conventional method of hydrolyzing titanium tetrachloride, it has been difficult to produce a titanium oxide sol having fine particles having a very small particle size, good crystallinity, and high transparency when formed into a thin film. Titanium oxide in the sol has excellent powder properties such as very small fine particles in the hydrolysis of the titanium alkoxide compound. There is a problem. Also, large explosion-proof equipment is required to prevent explosions, which is economically disadvantageous. Titanium alkoxide compounds are much more expensive than titanium tetrachloride. In the present invention, when a water-dispersed titanium oxide sol is applied to various substrates and a titanium oxide thin film is formed on the substrate surface, the thin film has excellent photocatalytic function and transparency, and good adhesion between the thin film and the substrate. It is an object to provide a titanium oxide sol and fine brookite-type titanium oxide particles.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、酸化チタ
ンゾルから形成された酸化チタンの薄膜について種々研
究した結果、酸化チタンゾル中に含まれる塩素イオンが
薄膜の透明性、基材と薄膜との密着性等に関与し、特定
の塩素イオン濃度の酸化チタンゾルがこれらの特性をよ
くすること及び酸化チタンの光触媒機能についてエネル
ギーギャップの大きいブルーカイト型が特に優れている
ことを知見し本発明に至った。The present inventors have conducted various studies on titanium oxide thin films formed from titanium oxide sol. As a result, the chlorine ions contained in the titanium oxide sol showed the transparency of the thin film, and showed that the chlorine ion contained in the base material and the thin film did not. In the present invention, it was found that a titanium oxide sol having a specific chlorine ion concentration improves these properties and that a blue kite type having a large energy gap is particularly excellent with respect to the photocatalytic function of titanium oxide. Reached.
【００１０】本発明は基本的には以下の発明からなる。 （１）塩素イオンを塩素元素として５０〜１０，０００
ｐｐｍ含む水分散酸化チタンゾル。 （２）平均粒子径が０．５μｍ以下で比表面積が２０ｍ
2 ／ｇ以上のブルーカイト型酸化チタン粒子が分散した
水分散酸化チタンゾル。 （３）接着剤を含む上記（１）又は（２）記載の水分散
酸化チタンゾル。 （４）平均粒子径が０．５μｍ以下で比表面積が２０ｍ
2 ／ｇ以上であるブルーカイト型酸化チタン粒子。 （５）上記（１）〜（３）の水分散酸化チタンゾルを用
いて基材表面に形成した酸化チタン薄膜。 （６）四塩化チタンの加水分解により水分散酸化チタン
ゾルを生成させ、該ゾル中の塩素イオンを塩素元素とし
て５０〜１０，０００ｐｐｍに調整することを特徴とす
る水分散酸化チタンゾルの製造法。 （７）７５〜１００℃の熱水に四塩化チタンを加え、７
５℃〜溶液の沸点の温度範囲で加水分解することを特徴
とするブルーカイト型酸化チタン粒子の水分散ゾルの製
造法。 （８）上記（７）の酸化チタン粒子の水分散ゾルを濾
過、乾燥することを特徴とするブルーカイト型酸化チタ
ン粒子の製造法。The present invention basically includes the following inventions. (1) 50 to 10,000 using chlorine ion as a chlorine element
Water-dispersed titanium oxide sol containing ppm. (2) The average particle size is 0.5 μm or less and the specific surface area is 20 m
A water-dispersed titanium oxide sol in which 2 / g or more brookite-type titanium oxide particles are dispersed. (3) The water-dispersed titanium oxide sol according to the above (1) or (2), containing an adhesive. (4) The average particle diameter is 0.5 μm or less and the specific surface area is 20 m
A brookite-type titanium oxide particle of 2 / g or more. (5) A titanium oxide thin film formed on a substrate surface using the water-dispersed titanium oxide sol of (1) to (3). (6) A method for producing a water-dispersed titanium oxide sol, which comprises producing a water-dispersed titanium oxide sol by hydrolysis of titanium tetrachloride, and adjusting a chlorine ion in the sol to 50 to 10,000 ppm as a chlorine element. (7) Titanium tetrachloride is added to hot water at 75 to 100 ° C.
A method for producing an aqueous dispersion sol of brookite-type titanium oxide particles, wherein the sol is hydrolyzed in a temperature range of 5 ° C to the boiling point of the solution. (8) A method for producing brookite-type titanium oxide particles, wherein the aqueous dispersion sol of titanium oxide particles according to (7) is filtered and dried.
【００１１】[0011]
【発明の実施の形態】本発明の水分散酸化チタンゾルの
第１は該ゾルから形成した薄膜が光触媒機能に優れるば
かりでなく、特に基材との密着性、透明性を高めたもの
で、その水分散酸化チタンゾルには塩素イオンが塩素元
素として５０〜１０，０００ｐｐｍ、好ましくは１００
〜４，０００ｐｐｍ含まれている。四塩化チタンを加水
分解して水分散酸化チタンゾルを得る方法では反応によ
り塩化水素が生成する。そしてゾル中では殆ど塩素イオ
ンと水素イオンに解離している。一般的にはこの塩化水
素は加熱下の加水分解反応において多くは系外に逸出さ
れる。またゾルに塩化水素が含まれているとゾルから酸
化チタン粉末を得たり、あるいは酸化チタン薄膜を得る
場合にも種々の障害が発生すると考えられ、加水分解反
応でゾル中に塩化水素がある程度以上残留した場合は脱
塩素処理してできるだけゾル中に塩化水素は含まれない
ようにするのが普通であった。しかし、従来はこのゾル
中の塩素イオンが酸化チタンの薄膜特性に及ぼす影響に
ついて考慮されたことはなく、この観点からゾル中の塩
素イオンを制御する技術は存在しなかった。BEST MODE FOR CARRYING OUT THE INVENTION The first aspect of the water-dispersed titanium oxide sol of the present invention is that a thin film formed from the sol not only has excellent photocatalytic function, but also has particularly improved adhesion and transparency to a substrate. In the water-dispersed titanium oxide sol, chlorine ions are contained in an amount of 50 to 10,000 ppm, preferably 100 ppm, as a chlorine element.
4,000 ppm. In the method of obtaining a water-dispersed titanium oxide sol by hydrolyzing titanium tetrachloride, hydrogen chloride is generated by the reaction. And in the sol, it is almost dissociated into chlorine ions and hydrogen ions. Generally, most of this hydrogen chloride escapes out of the system in the hydrolysis reaction under heating. Also, if hydrogen chloride is contained in the sol, various obstacles are considered to occur when obtaining titanium oxide powder from the sol or when obtaining a titanium oxide thin film. When residual, it was common to dechlorinate the sol so that hydrogen chloride was not contained in the sol as much as possible. However, conventionally, no consideration has been given to the effect of chlorine ions in the sol on the thin film properties of titanium oxide, and there has been no technique for controlling the chlorine ions in the sol from this viewpoint.
【００１２】水分散酸化チタンゾルにおいて、含有する
塩素イオンが塩素元素として５０ｐｐｍ未満では基材に
形成した酸化チタン薄膜の基材との密着性が十分でな
い。特に薄膜を焼成した場合に塩素イオンが５０ｐｐｍ
以上含むか否かによりこの密着性に差異が現れる。本発
明ではこの密着性は薄膜の基材からの剥離強度及び薄膜
の硬度で表わされる。逆にゾル中の塩素イオンが多くな
り、塩素元素として１０，０００ｐｐｍを越えると薄膜
の透明性が劣る。上記の範囲において特に好ましい範囲
は１００〜４，０００ｐｐｍである。If the chlorine ion contained in the water-dispersed titanium oxide sol is less than 50 ppm as a chlorine element, the adhesion of the titanium oxide thin film formed on the substrate to the substrate is not sufficient. Especially when the thin film is fired, chlorine ion is 50ppm
A difference appears in the adhesion depending on whether or not the above is included. In the present invention, the adhesion is represented by the peel strength of the thin film from the substrate and the hardness of the thin film. Conversely, chlorine ions in the sol increase, and if the chlorine element exceeds 10,000 ppm, the transparency of the thin film deteriorates. A particularly preferred range in the above range is 100 to 4,000 ppm.
【００１３】上記の塩素イオンの作用については定かで
ないが、酸化チタンゾル中において酸化チタン粒子の粒
子間の電気的な反発が多くなるので、粒子の分散性が良
好となることにより透明性と剥離強度等にこのような結
果がもたらされたものと推定される。水分散酸化チタン
ゾルの酸化チタン粒子は細かい方が酸化チタン薄膜の光
触媒作用が高まり、また透明性もよくなる。また触媒作
用の点から結晶質であることが好ましい。しかし、あま
り細かい酸化チタン粒子を得ることは製造上の困難を伴
うので、ゾル中の酸化チタン粒子は平均粒径で０．０１
〜０．１μｍの範囲が好ましい。Although the action of the above-mentioned chlorine ions is not clear, the electric repulsion between the titanium oxide particles in the titanium oxide sol is increased, so that the dispersibility of the particles is improved and the transparency and peel strength are improved. It is presumed that such a result has been brought about. The finer the titanium oxide particles in the water-dispersed titanium oxide sol, the higher the photocatalytic action of the titanium oxide thin film and the better the transparency. It is preferably crystalline from the viewpoint of catalytic action. However, since obtaining fine titanium oxide particles involves difficulty in production, the titanium oxide particles in the sol have an average particle size of 0.01%.
The range is preferably from 0.1 to 0.1 μm.
【００１４】本発明の水分散酸化チタンゾルの第２は、
該ゾルから形成された薄膜の光触媒機能及び透明性を高
めたもので、平均粒子径が０．５μｍ以下、好ましくは
０．０１〜０．１μｍで、比表面積が２０ｍ2 ／ｇ以上
のブルーカイト型酸化チタン粒子が水に分散したゾルで
ある。このブルーカイト型酸化チタン粒子はエネルギー
ギャップが３．２３ｅＶ以上である。酸化チタンの粒子
径に関していえば、酸化チタン薄膜の透明性を高めるた
めゾル中の酸化チタン粒子は平均粒径が０．５μｍ以
下、より好ましくは０．０１〜０．１μｍの単分散であ
ることが好ましい。比表面積が大きくても、ゾル中で１
次粒子が凝集している場合は塗布して薄膜とした時に透
明にはならない。The second aspect of the water-dispersed titanium oxide sol of the present invention is:
A blue kite having a photocatalytic function and transparency of a thin film formed from the sol, having an average particle diameter of 0.5 μm or less, preferably 0.01 to 0.1 μm, and a specific surface area of 20 m 2 / g or more. It is a sol in which type titanium oxide particles are dispersed in water. The brookite-type titanium oxide particles have an energy gap of 3.23 eV or more. Regarding the particle size of titanium oxide, the average particle size of the titanium oxide particles in the sol should be 0.5 μm or less, more preferably 0.01 to 0.1 μm in order to enhance the transparency of the titanium oxide thin film. Is preferred. Even if the specific surface area is large,
When the secondary particles are agglomerated, they do not become transparent when coated to form a thin film.
【００１５】従来はブルーカイト型を得るには、前述し
たようにアナターゼ型酸化チタンの熱処理による方法し
かなく、熱処理により得られたブルーカイト型酸化チタ
ン粒子を薄膜としようとする場合は、粒子径が熱処理に
よる焼結により大きく成長しているので薄膜形成用とし
ては全く使用されなかった。このブルーカイト型酸化チ
タンが水に分散したゾルにも前記同様塩素イオンを塩素
元素として５０〜１０，０００ｐｐｍ含めることができ
る。これによってゾルから形成された薄膜は触媒機能に
優れるばかりでなく、基材との密着性も高まる。上記の
第１及び第２の発明のゾルにおいて、ゾル中の酸化チタ
ン粒子の濃度が高過ぎると粒子が凝集し、ゾルが不安定
になる。また酸化チタン粒子の濃度が低過ぎると、例え
ば薄膜形成の際ゾルの塗布工程に時間がかかるなどの問
題が生じる。これらのことから水分散酸化チタンゾル中
の酸化チタン粒子の濃度（含有量）は０．０５〜１０モ
ル／リットルが特に適する。Conventionally, the brookite type can be obtained only by the heat treatment of the anatase type titanium oxide as described above. When the brookite type titanium oxide particles obtained by the heat treatment are to be formed into a thin film, the particle size is reduced. Was greatly grown by sintering by heat treatment, and was not used at all for thin film formation. The sol in which the brookite-type titanium oxide is dispersed in water can also contain 50 to 10,000 ppm of chlorine ions as a chlorine element as described above. As a result, the thin film formed from the sol not only has an excellent catalytic function, but also has an improved adhesion to the substrate. In the sol of the first and second inventions, if the concentration of the titanium oxide particles in the sol is too high, the particles aggregate and the sol becomes unstable. On the other hand, if the concentration of the titanium oxide particles is too low, there is a problem that, for example, it takes a long time to apply the sol when forming a thin film. From these facts, the concentration (content) of the titanium oxide particles in the water-dispersed titanium oxide sol is particularly suitable from 0.05 to 10 mol / l.
【００１６】本発明の水分散酸化チタンゾルは、これを
濾過、水洗、乾燥することにより酸化チタン粒子を得る
ことができる。ブルーカイト型酸化チタンのゾルから得
られる粒子は平均粒子径が５μｍ以下、好ましくは０．
０１〜０．１μｍで、比表面積が２０ｍ2 ／ｇ以上であ
る。そしてエネルギーギャップは３．２３ｅＶ以上であ
る。また水分散酸化チタンゾルを薄膜形成に用いる場
合、塗膜の成膜性を高めるためにゾルに水溶性高分子を
少量、例えば１０〜１０，０００ｐｐｍ程度添加するこ
とが好ましい。水溶性高分子としてはポリビニルアルコ
ール、メチルセルロース、エチルセルロース、ＣＭＣ、
澱粉などが好適である。The water-dispersed titanium oxide sol of the present invention can be filtered, washed with water and dried to obtain titanium oxide particles. Particles obtained from the brookite-type titanium oxide sol have an average particle diameter of 5 μm or less, preferably 0.1 μm or less.
The specific surface area is 20 m 2 / g or more. And the energy gap is 3.23 eV or more. When a water-dispersed titanium oxide sol is used for forming a thin film, it is preferable to add a small amount of a water-soluble polymer, for example, about 10 to 10,000 ppm to the sol in order to enhance the film forming property of the coating film. Water-soluble polymers include polyvinyl alcohol, methyl cellulose, ethyl cellulose, CMC,
Starch and the like are preferred.
【００１７】本発明の水分散酸化チタンゾルを各種の材
料、成形体等の基材に塗布し、基材の表面に酸化チタン
薄膜を形成することができる。基材としてはセラミック
ス、ガラス、金属、プラスチック、木材、紙等殆ど制限
なく対象とすることができる。基材をアルミナ、ジルコ
ニア等からなる触媒担体とし、これに酸化チタン薄膜の
触媒を担持して触媒として使用することもできる。また
蛍光ランプ等の照明器具のガラスやそのプラスチックカ
バー等を基材としてこれに酸化チタン薄膜を形成すれば
薄膜は透明であり、かつ光触媒作用を有するので光を遮
蔽することなく油煙等の有機物を分解することができ、
ガラスやカバーの汚れを防止するのに有効である。また
建築用ガラスや壁材に酸化チタン薄膜を形成すれば同様
に汚れを防止することが可能になるので、高層ビルなど
の窓材や壁材に用いることができ、清掃作業を必要とし
なくなるためビル管理コスト削減に役立つ。水分散酸化
チタンゾルを基材に塗布するには基材をゾル中に浸漬す
る方法、基材にゾルをスプレーする方法、ゾルを刷毛で
基材に塗布する方法などが採用される。ゾルの塗布量は
液状の厚さにして０．０１〜０．２ｍｍが適当である。
塗布後乾燥して水分を除去すれば薄膜が得られ、このま
までも触媒等の用途に供することができる。The water-dispersed titanium oxide sol of the present invention can be applied to a base material such as various materials and molded articles to form a titanium oxide thin film on the surface of the base material. As the base material, ceramics, glass, metal, plastic, wood, paper, and the like can be used with almost no restrictions. The substrate may be a catalyst carrier made of alumina, zirconia, or the like, and a titanium oxide thin film catalyst may be supported on the carrier and used as a catalyst. Also, if a titanium oxide thin film is formed on a glass of a lighting device such as a fluorescent lamp or a plastic cover thereof as a base material, the thin film is transparent and has a photocatalytic action, so that organic substances such as oily smoke can be removed without shielding light. Can be disassembled,
It is effective in preventing glass and cover from being stained. In addition, if a titanium oxide thin film is formed on architectural glass or wall material, it is possible to prevent dirt similarly, so that it can be used for window materials and wall materials of high-rise buildings, etc., and cleaning work is not required. Helps reduce building management costs. To apply the water-dispersed titanium oxide sol to the substrate, a method of dipping the substrate in the sol, a method of spraying the sol on the substrate, a method of applying the sol to the substrate with a brush, and the like are adopted. The appropriate amount of the sol to be applied is 0.01 to 0.2 mm as a liquid thickness.
A thin film can be obtained by drying after application to remove water, and can be used for a catalyst or the like as it is.
【００１８】基材が金属やセラミックス、例えばガラス
等の耐熱性である場合は酸化チタン薄膜を形成後焼成す
ることができ、これによって薄膜は一層強く基材に密着
し、薄膜の硬度も上る。この焼成温度は２００℃以上が
好ましい。焼成温度の上限には特に制限はなく、基材の
耐熱性に応じて定めればよいが、あまり温度を高くして
も薄膜の硬度や基材との密着性は増さないので８００℃
位迄が適当である。また、ブルーカイト型酸化チタンの
場合は、その結晶形を維持するには７００℃以下の温度
で焼結するのがよい。焼成の雰囲気は特に制限されず、
大気中でよい。焼成時間は特に制限はなく、例えば１〜
６０分の範囲で行えばよい。焼成によって得られる酸化
チタン薄膜の厚さは、前記の塗布量の場合０．０５〜
１．０μｍ位である。また、本発明の透明薄膜をより強
固で基材に対する接着力を高めるために、適当な接着剤
を水分散酸化チタンゾルに添加することもできる。例え
ば、アルキルシリケートなどの有機シリカ化合物が好適
である。添加量は本発明の酸化チタンゾル中の酸化チタ
ンに対しＳｉＯ2 換算にして１〜５０重量％程度でよ
い。添加量が１重量％未満であると、接着剤の添加効果
が低い。また、５０重量％を越えると、基材に対する接
着強度は非常に強固になるが、酸化チタン粒子が接着剤
に完全にくるまれてしまい光触媒能が消失してしまうの
で好ましくない。この場合の接着剤は、接着剤の性質に
より成膜直前に混入するかあらかじめゾルに混合した状
態にするか選択すればよく、どちらでも本発明の効果に
は何ら問題はない。この接着剤を含む薄膜は焼成しなく
てもよいが焼成することもできる。When the substrate is heat-resistant such as metal or ceramics, for example, glass, it can be fired after forming a titanium oxide thin film, whereby the thin film adheres more strongly to the substrate and the hardness of the thin film increases. The firing temperature is preferably 200 ° C. or higher. The upper limit of the sintering temperature is not particularly limited and may be determined according to the heat resistance of the base material. However, if the temperature is too high, the hardness of the thin film and the adhesion to the base material do not increase, so that the temperature is 800 ° C.
The order is appropriate. In the case of brookite-type titanium oxide, it is preferable to sinter at a temperature of 700 ° C. or less in order to maintain the crystal form. The firing atmosphere is not particularly limited,
Good in the atmosphere. The firing time is not particularly limited.
It may be performed within a range of 60 minutes. The thickness of the titanium oxide thin film obtained by firing is 0.05 to
It is about 1.0 μm. Further, in order to make the transparent thin film of the present invention stronger and to enhance the adhesive strength to the substrate, a suitable adhesive may be added to the water-dispersed titanium oxide sol. For example, an organic silica compound such as an alkyl silicate is suitable. The addition amount may be about 1 to 50% by weight in terms of SiO 2 with respect to the titanium oxide in the titanium oxide sol of the present invention. If the addition amount is less than 1% by weight, the effect of adding the adhesive is low. On the other hand, if it exceeds 50% by weight, the adhesive strength to the substrate becomes very strong, but the titanium oxide particles are completely wrapped in the adhesive and the photocatalytic activity is lost, which is not preferable. The adhesive in this case may be selected to be mixed immediately before film formation or to be mixed with the sol in advance depending on the properties of the adhesive, and there is no problem in the effect of the present invention. The thin film containing the adhesive may not be fired, but may be fired.
【００１９】本発明による酸化チタンゾルを用いて製造
される酸化チタン薄膜は共通して結晶性であること、酸
化チタン微粒子が非常に微細な粒子であること、不純物
を含んでいないこと、さらにこの酸化チタン微粒子が１
次粒子に限りなく近く分散していることから光触媒能力
及び透明性が高く、特に酸化チタンがブルーカイト型で
ある場合一層触媒能力が高い。The titanium oxide thin films produced by using the titanium oxide sol according to the present invention are commonly crystalline, the titanium oxide fine particles are very fine particles, do not contain impurities, and 1 titanium fine particles
Since the particles are dispersed as close as possible to the next particles, the photocatalytic ability and the transparency are high. In particular, when the titanium oxide is a brookite type, the catalytic ability is even higher.
【００２０】次にゾルの製造法の発明について説明す
る。本発明の第１の水分散酸化チタンゾルは前記した量
の塩素イオンが含まれていればよく、その製法は特に限
定されない。例えばチタンのアルコキシド化合物を加水
分解し、アルコールを少量含む水分散酸化チタンゾルを
得、これにＨＣｌ等を加え、塩素イオン濃度を前記の範
囲とすることも可能である。しかし、加水分解により塩
化水素が生成する四塩化チタンを用いることが好まし
い。第２の発明は四塩化チタンを特定の条件で加水分解
することにより得られる。これらの加水分解において生
成する塩化水素は反応槽からの逸出を防止し、できるだ
けゾル中に残留させることが好ましい。発生する塩化水
素を逸出させながら四塩化チタンの加水分解を行なうと
ゾル中の酸化チタンは粒子径が小さくなりにくく、また
結晶性もよくない。Next, the invention of a method for producing a sol will be described. The first water-dispersed titanium oxide sol of the present invention only needs to contain the above-mentioned amount of chloride ions, and its production method is not particularly limited. For example, an alkoxide compound of titanium is hydrolyzed to obtain a water-dispersed titanium oxide sol containing a small amount of alcohol, and HCl or the like is added to the sol to adjust the chlorine ion concentration to the above range. However, it is preferable to use titanium tetrachloride which produces hydrogen chloride by hydrolysis. The second invention is obtained by hydrolyzing titanium tetrachloride under specific conditions. It is preferable that hydrogen chloride generated in these hydrolysis prevent escape from the reaction tank and remain as much as possible in the sol. If titanium tetrachloride is hydrolyzed while allowing the generated hydrogen chloride to escape, the titanium oxide in the sol is less likely to have a small particle size and poor crystallinity.
【００２１】加水分解により発生する塩化水素は完全に
逸出が防止されていなくても抑制されておればよい。ま
たその方法も抑制できるものであれば特に限定されず、
例えば加圧することによっても可能であるが、最も容易
にして効果的な方法は加水分解の反応槽に還流冷却器を
設置して加水分解を行う方法である。この装置を図１に
示す。図において１が四塩化チタンの水溶液２を充填し
た反応槽で、これに還流冷却器３が設置されている。４
は撹拌機、５は温度計、６は反応槽を加熱するための装
置である。加水分解反応によって水及び塩化水素の蒸気
が発生するが、その大部分は還流冷却器により凝縮し、
反応槽に戻されるので反応槽から外に塩化水素が逸出す
ることは殆どない。[0021] Hydrogen chloride generated by hydrolysis may be suppressed even if the escape is not completely prevented. The method is not particularly limited as long as the method can be suppressed.
For example, pressurization is possible, but the easiest and most effective method is to install a reflux condenser in the hydrolysis reaction tank to carry out hydrolysis. This device is shown in FIG. In the figure, reference numeral 1 denotes a reaction tank filled with an aqueous solution 2 of titanium tetrachloride, in which a reflux condenser 3 is installed. 4
Is a stirrer, 5 is a thermometer, and 6 is a device for heating the reaction tank. The hydrolysis reaction produces water and hydrogen chloride vapor, most of which are condensed by the reflux condenser,
Since it is returned to the reaction tank, hydrogen chloride hardly escapes from the reaction tank.
【００２２】加水分解する四塩化チタン水溶液中の四塩
化チタンの濃度は低過ぎると生産性が悪く、生成する水
分散酸化チタンゾルから薄膜を形成する際に効率が低
く、また濃度が高過ぎると反応が激しくなり、得られる
酸化チタンの粒子が微細になりにくく、かつ分散性も悪
くなるために透明薄膜形成材としては適さない。従って
加水分解により酸化チタンの濃度の高いゾルを生成さ
せ、これを多量の水で希釈して前記したような酸化チタ
ンの濃度０．０５〜１０モル／リットルに調整する方法
は好ましくない。ゾルの生成時において酸化チタンの濃
度が前記の範囲にするのがよく、そのためには加水分解
される四塩化チタン水溶液中の四塩化チタンの濃度は前
記した生成する酸化チタンの濃度と大差ない値、即ちほ
ぼ０．０５〜１０モル／リットルとすればよく、必要な
らば以後の工程で少量の水の添加もしくは濃縮すること
で濃度を０．０５〜１０モル／リットルに調整してもよ
い。If the concentration of titanium tetrachloride in the aqueous solution of titanium tetrachloride to be hydrolyzed is too low, the productivity is poor, and the efficiency of forming a thin film from the resulting water-dispersed titanium oxide sol is low. And the resulting titanium oxide particles are hardly finely divided and have poor dispersibility, so that they are not suitable as a material for forming a transparent thin film. Therefore, a method of producing a sol having a high concentration of titanium oxide by hydrolysis and diluting the sol with a large amount of water to adjust the concentration of the titanium oxide to 0.05 to 10 mol / l as described above is not preferable. During the production of the sol, the concentration of titanium oxide is preferably within the above range. For this purpose, the concentration of titanium tetrachloride in the aqueous solution of titanium tetrachloride to be hydrolyzed is a value that is not much different from the concentration of titanium oxide to be produced. That is, the concentration may be approximately 0.05 to 10 mol / l, and if necessary, the concentration may be adjusted to 0.05 to 10 mol / l by adding or concentrating a small amount of water in a subsequent step.
【００２３】加水分解における温度は５０℃以上、四塩
化チタン水溶液の沸点迄の範囲が好ましい。５０℃未満
では加水分解反応に長時間を要する。加水分解は上記の
温度に昇温し、１０分から１２時間程度保持して行われ
る。この保持時間は加水分解の温度が高温側にある程短
くてよい。四塩化チタン水溶液の加水分解は四塩化チタ
ンと水との混合溶液を反応槽中で所定の温度に加熱して
もよく、また水を反応槽中で予め加熱しておき、これに
四塩化チタンを添加し、所定の温度にしてもよい。この
加水分解により一般的にはブルーカイト型にアナターゼ
型及び／又はブルーカイト型が混合した酸化チタンが得
られる。その中でブルーカイト型の酸化チタンの含有率
を高めるには水を反応槽で予め７５〜１００℃に加熱し
ておき、これに四塩化チタンを添加し、７５℃〜溶液の
沸点の温度範囲で加水分解する方法が適する。その方法
によって生成する全酸化チタンのうちブルーカイト型の
酸化チタンを７０重量％以上とすることが可能である。The temperature in the hydrolysis is preferably 50 ° C. or higher and up to the boiling point of the aqueous solution of titanium tetrachloride. If the temperature is lower than 50 ° C., a long time is required for the hydrolysis reaction. The hydrolysis is carried out by raising the temperature to the above-mentioned temperature and holding for about 10 minutes to 12 hours. This holding time may be shorter as the hydrolysis temperature is higher. For the hydrolysis of the aqueous solution of titanium tetrachloride, a mixed solution of titanium tetrachloride and water may be heated to a predetermined temperature in a reaction vessel, or water may be heated in advance in the reaction vessel, To a predetermined temperature. By this hydrolysis, titanium oxide in which an anatase type and / or a brookite type are generally mixed with a brookite type is obtained. In order to increase the content of brookite-type titanium oxide therein, water is previously heated to 75 to 100 ° C in a reaction vessel, and titanium tetrachloride is added thereto, and the temperature range is from 75 ° C to the boiling point of the solution. Is suitable. The brookite-type titanium oxide can be 70% by weight or more of the total titanium oxide produced by the method.
【００２４】加水分解における四塩化チタン水溶液の昇
温速度は早い方が得られる粒子が細かくなるので、好ま
しくは０．２℃／ｍｉｎ以上、さらに好ましくは０．５
℃／ｍｉｎ以上である。この方法によってゾル中の酸化
チタン粒子は平均粒径が０．５μｍ以下、好ましくは
０．０１〜０．１μｍの範囲の結晶性のよいものとな
る。本発明の水分散酸化チタンゾルの製造方法はバッチ
式に限らず、反応槽を連続槽にして四塩化チタンと水を
連続投入しながら、投入口の反対側で反応液を取り出
し、引き続き脱塩素処理するような連続方式も可能であ
る。生成したゾルは第１の発明においては脱塩素処理や
あるいは支障ない範囲で水の添加、脱水等により塩素イ
オンが５０〜１０，０００ｐｐｍになるように調整す
る。また第２発明においても必要により前記同様塩素イ
オンを５０〜１０，０００ｐｐｍに調整することができ
る。The higher the temperature rising rate of the titanium tetrachloride aqueous solution in the hydrolysis, the finer the particles obtained, so that the temperature is preferably 0.2 ° C./min or more, more preferably 0.5 ° C./min.
C / min or more. According to this method, the titanium oxide particles in the sol have good crystallinity with an average particle size of 0.5 μm or less, preferably in the range of 0.01 to 0.1 μm. The method for producing the water-dispersed titanium oxide sol of the present invention is not limited to the batch method, and while the reaction vessel is a continuous vessel and titanium tetrachloride and water are continuously charged, the reaction liquid is taken out on the opposite side of the charging port, and then dechlorination treatment is performed. A continuous system is also possible. In the first invention, the produced sol is adjusted so as to have a chlorine ion of 50 to 10,000 ppm by dechlorination treatment or addition or dehydration of water within a range that does not interfere. Also, in the second invention, the chlorine ion can be adjusted to 50 to 10,000 ppm as described above, if necessary.
【００２５】脱塩素処理は一般の公知手段でよく電気透
析、イオン交換樹脂、電気分解などが可能である。脱塩
素の程度はゾルのｐＨを目安にすればよく、塩素イオン
が５０〜１０，０００ｐｐｍの場合、ｐＨは約５〜０．
５、好ましい範囲である１００〜４，０００ｐｐｍの場
合、ｐＨは約４〜１である。本発明の水分散ゾルに有機
溶媒を加え、水と有機溶媒の混合物に酸化チタン粒子を
分散させることもできる。本発明の水分散酸化チタンゾ
ルから酸化チタンの薄膜を形成する場合、加水分解反応
で生成したゾルをそのまま用いるのが好ましく、このゾ
ルから酸化チタンの粉末を製造し、これを水に分散し、
ゾルにして用いることは好ましい方法ではない。酸化チ
タンの粒子は表面活性が高く、微粒子になればなるほど
活性度が上昇するため水への分散は非常に困難になる、
すなわち凝集体となってしまい、これからつくられた薄
膜は透明性に劣り、光触媒作用も低下するからである。The dechlorination treatment can be performed by a commonly known means, such as electrodialysis, ion exchange resin, or electrolysis. The degree of dechlorination may be based on the pH of the sol. When the chlorine ion is 50 to 10,000 ppm, the pH is about 5 to 0.5 ppm.
5. In the preferred range of 100 to 4,000 ppm, the pH is about 4-1. An organic solvent may be added to the water-dispersed sol of the present invention to disperse the titanium oxide particles in a mixture of water and the organic solvent. When forming a thin film of titanium oxide from the water-dispersed titanium oxide sol of the present invention, it is preferable to use the sol generated by the hydrolysis reaction as it is, to produce a titanium oxide powder from this sol, disperse this in water,
Use as a sol is not a preferred method. Titanium oxide particles have a high surface activity, and the finer the particles, the higher the activity becomes, so dispersion in water becomes extremely difficult.
That is, it becomes an agglomerate, and the thin film formed therefrom is inferior in transparency and has a reduced photocatalytic action.
【００２６】[0026]
【実施例】以下、実施例により具体的に説明するが、本
発明は実施例に限定されるものではない。 （実施例１〜６）四塩化チタン（純度９９．９％）に水
を加え、四塩化チタン濃度が０．２５モル／リットル
（酸化チタン換算２重量％）となるように溶液を調整し
た。この時、水溶液の液温が５０℃以上に上昇しないよ
うに氷冷など適当な冷却装置を設けた。次に、この水溶
液１リットルを図１に示す還流冷却器付きの反応槽に装
入し、沸点付近（１０４℃）まで加熱し、６０分間保持
して加水分解した。得られたゾルを冷却後、反応で生成
した残留塩素を電気透析により取り除き、表１に示す塩
素イオン濃度とした。電気透析は旭化成工業（株）製電
気透析装置Ｇ３型を用いゾル液のｐＨを監視しながら実
施した。塩素イオンを調整した夫々の水分散酸化チタン
ゾルに、成膜用助剤として水溶性高分子であるポリビニ
ルアルコールをゾル液重量に対して１，０００ｐｐｍ添
加した。このゾルは塩素イオンが５０〜１０，０００ｐ
ｐｍのものは安定であり、１日以上経過しても生成した
酸化チタン微粒子の沈降は認められなかった。しかし、
塩素イオンが３０ｐｐｍのものはゾル中の酸化チタンの
凝集がみられ、また１５，０００ｐｐｍのものはそれを
用いた薄膜が薄い白色を呈した。透過型電子顕微鏡でゾ
ル中の粒子を観察したところ粒子の平均粒子径は０．０
１５〜０．０１８μｍであり、Ｘ線回折装置から前記粒
子の同定を行ったところ結晶性の酸化チタンであった。EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to the examples. (Examples 1 to 6) Water was added to titanium tetrachloride (purity 99.9%), and the solution was adjusted so that the titanium tetrachloride concentration was 0.25 mol / liter (2% by weight in terms of titanium oxide). At this time, an appropriate cooling device such as ice cooling was provided so that the liquid temperature of the aqueous solution did not rise to 50 ° C. or higher. Next, 1 liter of this aqueous solution was charged into a reaction vessel equipped with a reflux condenser shown in FIG. 1, heated to near the boiling point (104 ° C.), and held for 60 minutes to hydrolyze. After cooling the obtained sol, residual chlorine generated by the reaction was removed by electrodialysis to obtain a chlorine ion concentration shown in Table 1. The electrodialysis was performed using an electrodialyzer G3 manufactured by Asahi Kasei Corporation while monitoring the pH of the sol solution. To each of the water-dispersed titanium oxide sols in which chlorine ions were adjusted, a water-soluble polymer, polyvinyl alcohol, as a film-forming auxiliary, was added in an amount of 1,000 ppm based on the weight of the sol. This sol contains 50 to 10,000p of chloride ions.
pm was stable, and no sedimentation of the generated titanium oxide fine particles was observed even after one day or more. But,
When the chlorine ion was 30 ppm, aggregation of titanium oxide in the sol was observed, and when it was 15,000 ppm, the thin film using the same exhibited a thin white color. When the particles in the sol were observed with a transmission electron microscope, the average particle diameter of the particles was 0.0
The particle size was 15 to 0.018 μm, and the particle was identified by an X-ray diffractometer. As a result, the particle was crystalline titanium oxide.
【００２７】（比較例１，２）水分散酸化チタンゾル中
の塩素イオン濃度を３０ｐｐｍ（比較例１）及び１５，
０００ｐｐｍ（比較例２）とした以外は実施例と同様に
してゾルを得た。(Comparative Examples 1 and 2) The chlorine ion concentration in the water-dispersed titanium oxide sol was 30 ppm (Comparative Example 1) and
A sol was obtained in the same manner as in Example except that the amount was set to 000 ppm (Comparative Example 2).
【００２８】実施例、比較例のゾルを用いてディップコ
ートによりガラス板上に塗布して乾燥後、５００℃で１
時間空気中で熱処理して酸化チタン薄膜を得た。熱処理
後の酸化チタン薄膜の厚さは０．１５μｍであった。酸
化チタンの結晶形を粉末Ｘ線回折パターンのリートベル
ト解析により調べた結果、熱処理前のものはアナターゼ
型約５０重量％と、ブルーカイト型約５０重量％の混合
物であり、８００℃以上に加熱するとルチル型単独とな
った。The sols of Examples and Comparative Examples were applied on a glass plate by dip coating and dried.
Heat treatment was performed in the air for a time to obtain a titanium oxide thin film. The thickness of the titanium oxide thin film after the heat treatment was 0.15 μm. As a result of examining the crystal form of titanium oxide by Rietveld analysis of powder X-ray diffraction pattern, the one before the heat treatment was a mixture of about 50% by weight of anatase type and about 50% by weight of brookite type, and heated to 800 ° C. or more. Then it became a rutile type alone.
【００２９】成膜の評価 実施例、比較例それぞれの水分散酸化チタンゾルから得
た酸化チタン薄膜の光透過率、光触媒能力及び石英ガラ
ス板との密着性を測定した。光透過率の測定方法は、石
英ガラス板上に成膜した酸化チタン薄膜を日本分光
（株）製分光光度計にセットして７００〜２００ｎｍま
で波長を連続的に変化させることで光透過率を測定し
た。そして５５０ｎｍにおける光透過率を本発明におけ
る光透過率として表わした。その結果を表１に示す。シ
ュウ酸の分解方法は、成膜した酸化チタン薄膜付石英ガ
ラス板で反応容器を作製し、これに５ミリモル／リット
ルのシュウ酸を入れ、酸素を吹込みながら１００Ｗの水
銀ランプを照射し、４時間後のシュウ酸の分解量を過マ
ンガン酸カリウムの酸化還元滴定により求めた。その結
果を表１に示す。また焼成後の石英ガラス板と薄膜との
密着性は鉛筆硬度試験法ならびにごばん目剥離試験法
（ＪＩＳ Ｋ５４００）により求めた。その結果を表１
に示す。Evaluation of Film Formation The light transmittance, photocatalytic ability and adhesion to the quartz glass plate of the titanium oxide thin films obtained from the water-dispersed titanium oxide sol of each of the examples and comparative examples were measured. The light transmittance is measured by setting a titanium oxide thin film formed on a quartz glass plate in a spectrophotometer manufactured by JASCO Corporation, and continuously changing the wavelength from 700 to 200 nm to reduce the light transmittance. It was measured. Then, the light transmittance at 550 nm was represented as the light transmittance in the present invention. Table 1 shows the results. Oxalic acid can be decomposed by preparing a reaction vessel from a quartz glass plate with a thin film of titanium oxide formed thereon, adding 5 mmol / l oxalic acid thereto, and irradiating it with a 100 W mercury lamp while blowing oxygen. After a lapse of time, the amount of oxalic acid decomposed was determined by redox titration of potassium permanganate. Table 1 shows the results. Further, the adhesion between the quartz glass plate and the thin film after firing was determined by a pencil hardness test method and a grain separation test method (JIS K5400). Table 1 shows the results.
Shown in
【００３０】[0030]
【表１】 [Table 1]
【００３１】（実施例７，８、比較例３，４）実施例１
〜６、比較例１，２と同じく水分散酸化チタンゾルを用
い、基材としてプラスチック（ポリエチレンテレフタレ
ート（ＰＥＴ））板を用い、その上に前記酸化チタンゾ
ルの塗膜を形成し、焼成の代りに１００℃で乾燥した以
外は前記実施例、比較例と同様にして酸化チタン薄膜を
形成し、その薄膜の特性を評価した。その結果を表２に
示す。(Examples 7 and 8, Comparative Examples 3 and 4) Example 1
6, a water-dispersed titanium oxide sol was used as in Comparative Examples 1 and 2, a plastic (polyethylene terephthalate (PET)) plate was used as a substrate, and a coating film of the titanium oxide sol was formed thereon. A titanium oxide thin film was formed in the same manner as in the above Examples and Comparative Examples except that the titanium oxide film was dried at ℃, and the characteristics of the thin film were evaluated. Table 2 shows the results.
【００３２】[0032]
【表２】 [Table 2]
【００３３】（実施例９）蒸留水９５４ｍｌを図１に示
す還流冷却器付きの反応槽に装入し、９５℃に加温す
る。撹拌速度を約２００ｒｐｍに保ちながら、ここに四
塩化チタン（Ｔｉ含有量：１６．３％、比重１．５９、
純度９９．９％）水溶液４６ｍｌを約５ｍｌ／ｍｉｎの
速度で反応槽に滴下した。この時、反応液の温度が下が
らないように注意した。その結果、四塩化チタン濃度が
０．２５ｍｏｌ／ｌ（酸化チタン換算２重量％）であっ
た。反応槽中では反応液が滴下直後から、白濁し始めた
がそのままの温度で保持を続け、滴下終了後さらに昇温
し沸点付近（１０４℃）まで加熱し、この状態で６０分
間保持して完全に反応を終了した。冷却後、反応で生成
した残留塩素を電気透析により取り除き、ｐＨ＝２（塩
素イオン６００ｐｐｍ）とした後、成膜用助剤として水
溶性高分子であるポリビニルアルコールを酸化チタン含
有量に対して０．１％添加して、酸化チタンゾルとし
た。このゾルは安定であり、３０日以上経過しても生成
した酸化チタン微粒子の沈降は認められなかった。Example 9 954 ml of distilled water was charged into a reactor equipped with a reflux condenser shown in FIG. 1 and heated to 95 ° C. While maintaining the stirring speed at about 200 rpm, titanium tetrachloride (Ti content: 16.3%, specific gravity 1.59,
46 ml of an aqueous solution (purity: 99.9%) was dropped into the reaction vessel at a rate of about 5 ml / min. At this time, care was taken not to lower the temperature of the reaction solution. As a result, the concentration of titanium tetrachloride was 0.25 mol / l (2% by weight in terms of titanium oxide). In the reaction tank, the reaction solution began to become cloudy immediately after the dropwise addition, but the temperature was maintained at the same temperature, and after the completion of the dropwise addition, the temperature was further increased and heated to around the boiling point (104 ° C.). The reaction was terminated. After cooling, residual chlorine generated by the reaction was removed by electrodialysis, and the pH was adjusted to 2 (chlorine ion: 600 ppm). Then, polyvinyl alcohol, which is a water-soluble polymer, was used as a film-forming auxiliary in an amount of 0 to titanium oxide content. .1% to obtain a titanium oxide sol. This sol was stable, and no precipitation of the generated titanium oxide fine particles was observed even after 30 days or more.
【００３４】前記ゾルを濾過後６０℃の真空乾燥器を用
いて粉末として取り出し、前記したＸ線回折法により同
定した結果、酸化チタンはブルーカイト型が９６．７重
量％、ルチル型が０．９重量％、アナターゼ型が２．４
重量％であった。また、透過型電子顕微鏡でこの微粒子
を観察したところ、１次粒子の平均粒子径は１５ｎｍで
あった。さらにＢＥＴ法によりこの微粒子比表面積は１
００ｍ2 ／ｇであった。一方、前記ゾルをスピンコータ
ーを用いて石英ガラス基板に均一に塗布して、１００℃
乾燥器で乾燥し透明膜を得た。この薄膜付き石英ガラス
基板の透過率は可視部では９５％以上を示し完全に透明
であった。さらに、紫外部において吸収が認められ、基
礎吸収端から求めたエネルギーギャップは３．７５ｅＶ
であった。この時のエネルギーギャップを求める式は
（１）式に示す。 λ＝１２３９／Ｅｇ （１） λ：基礎吸収端（ｎｍ） Ｅｇ：エネルギーギャ
ップ（ｅＶ）After the sol was filtered, it was taken out as a powder using a vacuum dryer at 60 ° C. and identified by the X-ray diffraction method. As a result, 96.7% by weight of brookite type titanium oxide and 0.1% of rutile type titanium oxide were obtained. 9% by weight, 2.4 of anatase type
% By weight. When the fine particles were observed with a transmission electron microscope, the average primary particle diameter was 15 nm. Further, the specific surface area of the fine particles is 1 according to the BET method.
00 m 2 / g. On the other hand, the sol was uniformly coated on a quartz glass substrate using a spin coater,
It was dried in a dryer to obtain a transparent film. The transmittance of this quartz glass substrate with a thin film was 95% or more in the visible region, and was completely transparent. Further, absorption was observed in the ultraviolet, and the energy gap determined from the basic absorption edge was 3.75 eV.
Met. The equation for calculating the energy gap at this time is shown in equation (1). λ = 1239 / Eg (1) λ: Basic absorption edge (nm) Eg: Energy gap (eV)
【００３５】（実施例１０）実施例９において、四塩化
チタン水溶液の滴下する反応温度を７５℃とした以外
は、実施例９と同様にして酸化チタンを析出させた。こ
の粒子を同様にＸ線回折装置で同定したところブルーカ
イト型酸化チタンが７５重量％、ルチル型酸化チタンが
２５重量％であった。また、透過型電子顕微鏡でこの微
粒子を観察したところ、１次粒子の平均粒子径は１０ｎ
ｍであった。さらにＢＥＴ法によりこの微粒子比表面積
は１２０ｍ2 ／ｇであった。電気透析により、ｐＨ＝１
（塩素イオン３０００ｐｐｍ）とした酸化チタンゾルを
用いてガラス基板に塗布して、５００℃に焼成すること
で透明薄膜を作製した。この薄膜を薄膜Ｘ線回折で測定
したところ、前記同様ブルーカイト型とルチル型の混合
酸化チタンであった。また、この薄膜付きガラス基板の
透過スペクトルから可視部では９５％以上の透過率を示
し完全に透明であった。さらに、紫外部による基礎吸収
端から求めたエネルギーギャップは３．３０ｅＶであっ
た。Example 10 Titanium oxide was precipitated in the same manner as in Example 9 except that the reaction temperature for dropping the aqueous solution of titanium tetrachloride was changed to 75 ° C. When the particles were similarly identified by an X-ray diffractometer, brookite-type titanium oxide was 75% by weight and rutile-type titanium oxide was 25% by weight. When the fine particles were observed with a transmission electron microscope, the average primary particle diameter was 10 n.
m. Further, the specific surface area of the fine particles was 120 m 2 / g by the BET method. PH = 1 by electrodialysis
A titanium oxide sol (chloride ion: 3000 ppm) was applied to a glass substrate and baked at 500 ° C. to form a transparent thin film. When this thin film was measured by thin film X-ray diffraction, it was a mixed brookite-type and rutile-type titanium oxide as described above. Further, from the transmission spectrum of this glass substrate with a thin film, it showed a transmittance of 95% or more in the visible region, and was completely transparent. Further, the energy gap determined from the fundamental absorption edge by ultraviolet light was 3.30 eV.
【００３６】（実施例１１）実施例９において、水と四
塩化チタン水溶液の量をそれぞれ８６２ｍｌ、１３８ｍ
ｌとした以外は同様にした。電気透析でｐＨを２とした
後、このゾルに対してエチルアルコールを等量添加して
有機溶媒混合ゾルとした。これをポリエチレンシート上
に塗布して乾燥することで酸化チタン薄膜を得た。解析
の結果、結晶形はブルーカイト型８５重量％、ルチル型
１５重量％の混合物で、粒子径は１５ｎｍであった。可
視部の透過率は８０％以上であり、エネルギーギャップ
は３．５１ｅＶであった。(Example 11) In Example 9, the amounts of water and an aqueous solution of titanium tetrachloride were 862 ml and 138 m, respectively.
The procedure was the same except that it was 1. After adjusting the pH to 2 by electrodialysis, an equal amount of ethyl alcohol was added to this sol to obtain an organic solvent mixed sol. This was applied on a polyethylene sheet and dried to obtain a titanium oxide thin film. As a result of the analysis, the crystal form was a mixture of 85% by weight of brookite type and 15% by weight of rutile type, and the particle size was 15 nm. The transmittance of the visible portion was 80% or more, and the energy gap was 3.51 eV.
【００３７】（比較例５）１次粒子径が７ｎｍであるア
ナターゼ型酸化チタン粒子を用い、実施例９と同じよう
に酸化チタン濃度が２％水溶液となるように水に超音波
分散器を用いて分散させた。この際、解膠剤として塩酸
を添加してｐＨ１とし、以下同様の操作をして酸化チタ
ンゾルとした。また、同様にガラス基板上に塗布、１０
０℃での乾燥により透明薄膜を作成した。(Comparative Example 5) An anatase type titanium oxide particle having a primary particle diameter of 7 nm was used, and an ultrasonic disperser was used in water so that the titanium oxide concentration became a 2% aqueous solution as in Example 9. And dispersed. At this time, hydrochloric acid was added as a deflocculant to adjust the pH to 1, and the same operation was performed to obtain a titanium oxide sol. In addition, similarly, apply on a glass substrate.
A transparent thin film was formed by drying at 0 ° C.
【００３８】（比較例６）１次粒子径が５０ｎｍである
ルチル型の酸化チタン粒子を用いた以外は比較例５と同
様にして酸化チタンゾルを得た。このゾルも比較例５と
同様酸化チタン微粒子の沈降が認められたので解膠剤と
して塩酸を用いて再分散させて成膜した。この酸化チタ
ンのゾルは時間の経過と共に酸化チタンの微粒子が沈降
した。沈降後の上澄み液で成膜した膜に光触媒能力が認
められなかったため、ゾルを作成直後に超音波分散器で
分散させてから実施例９と同じ方法でガラス基板上に成
膜し、光触媒能力の評価を行った。Comparative Example 6 A titanium oxide sol was obtained in the same manner as in Comparative Example 5, except that rutile type titanium oxide particles having a primary particle diameter of 50 nm were used. Since precipitation of titanium oxide fine particles was observed in the same manner as in Comparative Example 5, this sol was redispersed using hydrochloric acid as a deflocculant to form a film. In this titanium oxide sol, fine particles of titanium oxide settled with the passage of time. Since the film formed from the supernatant liquid after sedimentation did not show photocatalytic ability, the sol was dispersed with an ultrasonic disperser immediately after preparation, and then formed on a glass substrate in the same manner as in Example 9, and the photocatalytic ability was obtained. Was evaluated.
【００３９】成膜した薄膜の評価結果 実施例９〜１１、比較例５，６のそれぞれの酸化チタン
ゾルから得た酸化チタン薄膜の光触媒能力を前記したシ
ュウ酸分解法で求めた。その結果を表３に示す。Evaluation Results of the Formed Thin Films The photocatalytic ability of the titanium oxide thin films obtained from the titanium oxide sols of Examples 9 to 11 and Comparative Examples 5 and 6 was determined by the oxalic acid decomposition method described above. Table 3 shows the results.
【００４０】[0040]
【表３】 [Table 3]
【００４１】比較例５においては、酸化チタンの凝集体
がガラス基板上に形成され表面が不均一であった。比較
例６においては、透明な酸化チタン薄膜が得られなかっ
たため、光触媒能力の評価は実施しなかった。In Comparative Example 5, an aggregate of titanium oxide was formed on the glass substrate and the surface was uneven. In Comparative Example 6, the evaluation of the photocatalytic ability was not performed because a transparent titanium oxide thin film was not obtained.
【００４２】（実施例１２）実施例９と同様の反応を行
い、濃度が０．２５ｍｏｌ／ｌの四塩化チタン（酸化チ
タン換算２重量％）を加水分解させた。次にこの反応液
を濃縮し酸化チタン濃度を１０重量％とし、電気透析で
残留塩素を取り除き、ｐＨ＝２（塩素イオン濃度約６０
０ｐｐｍ）とした後、接着剤としてテトラメチルオルソ
シリケートＳｉ（ＯＣＨ3 ）4 を酸化チタンに対してＳ
ｉＯ2 換算で５重量％となるように添加して、酸化チタ
ンゾルとした。Example 12 The same reaction as in Example 9 was carried out, and titanium tetrachloride having a concentration of 0.25 mol / l (2% by weight in terms of titanium oxide) was hydrolyzed. Next, this reaction solution was concentrated to a titanium oxide concentration of 10% by weight, residual chlorine was removed by electrodialysis, and pH = 2 (chlorine ion concentration of about 60%).
0 ppm), and then tetramethyl orthosilicate Si (OCH 3 ) 4 was used as an adhesive with respect to titanium oxide.
Titanium oxide sol was added by adding so as to be 5% by weight in terms of iO 2 .
【００４３】（実施例１３）実施例１２と濃縮、電気透
析まで同様な操作を行った後、イソプロピルアルコール
で５倍に希釈した後、接着剤としてテトラエチルオルソ
シリケートＳｉ（ＯＣ2 Ｈ5 ）4 を酸化チタンに対して
ＳｉＯ2 換算で２０重量％となるように添加して、有機
溶媒混合の酸化チタンゾルとした。(Example 13) The same operation as in Example 12 was performed up to concentration and electrodialysis. After diluting 5-fold with isopropyl alcohol, tetraethylorthosilicate Si (OC 2 H 5 ) 4 was used as an adhesive. It was added to titanium oxide in an amount of 20% by weight in terms of SiO 2 to obtain a titanium oxide sol mixed with an organic solvent.
【００４４】（実施例１４）実施例１２において、テト
ラエチルオルソシリケートの代りにテトラプロピルオル
ソシリケートＳｉ（ＯＣ3 Ｈ7 ）4 を酸化チタンに対し
てＳｉＯ2 換算で３５重量％となるように添加して、酸
化チタンゾルとした。Example 14 In Example 12, tetrapropyl orthosilicate Si (OC 3 H 7 ) 4 was added in place of tetraethyl orthosilicate so as to be 35% by weight in terms of SiO 2 with respect to titanium oxide. Thus, a titanium oxide sol was obtained.
【００４５】（比較例７）実施例１４において、テトラ
プロピルオルソシリケートＳｉ（ＯＣ3 Ｈ7 ）4を酸化
チタンに対してＳｉＯ2 換算で５５重量％となるように
添加して、酸化チタンゾルとした。Comparative Example 7 In Example 14, a titanium oxide sol was prepared by adding tetrapropyl orthosilicate Si (OC 3 H 7 ) 4 to titanium oxide so as to be 55% by weight in terms of SiO 2 . .
【００４６】成膜した薄膜の評価結果 実施例１２〜１４、比較例７のそれぞれの酸化チタンゾ
ルをスピンコーターを用いて石英ガラス板に均一に塗布
して室温に放置・乾燥して透明膜を得た。この膜付き石
英ガラス板の透過率は可視部では９５％以上の透過率を
示し完全に透明であった。また、透明膜付きの石英ガラ
ス板の鉛筆硬度試験と密着性の試験を前述の方法で評価
した。その結果を表４に示す。Evaluation results of the formed thin films The titanium oxide sols of Examples 12 to 14 and Comparative Example 7 were evenly applied to a quartz glass plate using a spin coater, left at room temperature and dried to obtain a transparent film. Was. The transmittance of the quartz glass plate with the film was 95% or more in the visible region, and was completely transparent. Further, the pencil hardness test and the adhesion test of the quartz glass plate provided with the transparent film were evaluated by the methods described above. Table 4 shows the results.
【００４７】[0047]
【表４】 [Table 4]
【００４８】[0048]
【発明の効果】本発明の水分散酸化チタンゾルはこれを
各種の基材に塗布して酸化チタンの薄膜を形成した場
合、薄膜は透明にして光触媒作用に優れる。特に酸化チ
タンがブルーカイト型の場合、光触媒作用が高い。また
薄膜は硬度が高く、かつ基材との密着性に優れたものと
なる。従って基材上の薄膜は耐久性があり、この薄膜を
例えば照明器具のガラス管や照明器具のカバー等に使用
すれば光を遮断することなく長期に亘って光触媒作用が
維持される。本発明の水分散酸化チタンゾルは四塩化チ
タンを原料とする水系で製造することが可能であるの
で、原料は安価であり、またゾルが容易に薄膜を形成で
き、経済的にも有利である。The water-dispersed titanium oxide sol of the present invention is applied to various substrates to form a titanium oxide thin film, and the thin film is transparent and has excellent photocatalytic action. In particular, when the titanium oxide is a brookite type, the photocatalytic action is high. Further, the thin film has high hardness and excellent adhesion to the substrate. Therefore, the thin film on the base material is durable, and if this thin film is used, for example, for a glass tube of a lighting fixture or a cover of a lighting fixture, the photocatalytic action is maintained for a long time without blocking light. Since the water-dispersed titanium oxide sol of the present invention can be produced in an aqueous system using titanium tetrachloride as a raw material, the raw material is inexpensive, and the sol can easily form a thin film, which is economically advantageous.
【図１】本発明の方法に用いられる反応槽の概略断面図
である。FIG. 1 is a schematic sectional view of a reaction tank used in the method of the present invention.
１ 反応槽 ２ 四塩化チタン水溶液 ３ 還流冷却器 ４ 撹拌機 ５ 温度計 ６ 加熱装置 DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Titanium tetrachloride aqueous solution 3 Reflux cooler 4 Stirrer 5 Thermometer 6 Heating device
───────────────────────────────────────────────────── フロントページの続き (72)発明者 村瀬 典子 千葉県千葉市緑区大野台１丁目１番１号 昭和電工株式会社総合研究所内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Noriko Murase 1-1-1 Ohnodai, Midori-ku, Chiba-shi, Chiba Pref. Showa Denko KK
Claims (17)
０，０００ｐｐｍ含む水分散酸化チタンゾル。(1) a chlorine element having a chlorine element of 50 to 1;
Water-dispersed titanium oxide sol containing 0000 ppm.
μｍの結晶質である請求項１に記載の水分散酸化チタン
ゾル。2. The titanium oxide has an average particle diameter of 0.01 to 0.1.
The water-dispersed titanium oxide sol according to claim 1, which is crystalline with a particle size of μm.
が２０ｍ2 ／ｇ以上のブルーカイト型酸化チタン粒子が
分散した水分散酸化チタンゾル。3. A water-dispersed titanium oxide sol in which brookite-type titanium oxide particles having an average particle diameter of 0.5 μm or less and a specific surface area of 20 m 2 / g or more are dispersed.
０，０００ｐｐｍ含む請求項３に記載の水分散酸化チタ
ンゾル。4. A chlorine ion having a chlorine element of 50 to 1
The water-dispersed titanium oxide sol according to claim 3, which contains 0000 ppm.
／リットルである請求項１〜４に記載の水分散酸化チタ
ンゾル。5. The water-dispersed titanium oxide sol according to claim 1, wherein the content of titanium oxide is 0.05 to 10 mol / l.
ｍ含む請求項１〜５に記載の水分散酸化チタンゾル。6. The water-soluble polymer is used in an amount of 10 to 10,000 pp.
The water-dispersed titanium oxide sol according to any one of claims 1 to 5, which contains m.
で１〜５０重量％含む請求項１〜６記載の水分散酸化チ
タンゾル。7. The water-dispersed titanium oxide sol according to claim 1, wherein the adhesive contains 1 to 50% by weight of titanium oxide in terms of silicon oxide with respect to titanium oxide.
項７記載の水分散酸化チタンゾル。8. The water-dispersed titanium oxide sol according to claim 7, wherein the adhesive is an alkyl silicate.
が２０ｍ2 ／ｇ以上であるブルーカイト型酸化チタン粒
子。9. Blue brookite type titanium oxide particles having an average particle diameter of 0.5 μm or less and a specific surface area of 20 m 2 / g or more.
ーギャップが３．２３ｅＶ以上である請求項３〜９に記
載の水分散酸化チタンゾル又は酸化チタン粒子。10. The water-dispersed titanium oxide sol or titanium oxide particles according to claim 3, wherein the energy gap of the brookite-type titanium oxide is 3.23 eV or more.
用いて基材表面に形成した酸化チタン薄膜。11. A titanium oxide thin film formed on the surface of a substrate using the sol according to claim 1.
プラスチック、紙、木材のいずれかである請求項１１に
記載の酸化チタン薄膜。12. The base material is made of ceramics, metal, glass,
The titanium oxide thin film according to claim 11, which is any one of plastic, paper, and wood.
の耐熱性物質であり、酸化チタン薄膜が焼成したもので
ある請求項１１に記載の酸化チタン薄膜。13. The titanium oxide thin film according to claim 11, wherein the base material is a heat-resistant substance such as ceramics, metal, glass or the like, and the titanium oxide thin film is fired.
酸化チタンゾルを生成させ、該ゾル中の塩素イオンを塩
素元素として５０〜１０，０００ｐｐｍに調整すること
を特徴とする水分散酸化チタンゾルの製造法。14. A method for producing a water-dispersed titanium oxide sol, which comprises producing a water-dispersed titanium oxide sol by hydrolysis of titanium tetrachloride, and adjusting a chlorine ion in the sol to 50 to 10,000 ppm as a chlorine element. .
を加え、７５℃〜溶液の沸点の温度範囲で加水分解する
ことを特徴とするブルーカイト型酸化チタン粒子の水分
散ゾルの製造法。15. A process for producing an aqueous dispersion sol of brookite-type titanium oxide particles, comprising adding titanium tetrachloride to hot water at 75 to 100 ° C. and hydrolyzing at a temperature ranging from 75 ° C. to the boiling point of the solution. .
ゾルを濾過、乾燥することを特徴とするブルーカイト型
酸化チタン粒子の製造法。16. A method for producing brookite-type titanium oxide particles, wherein the aqueous dispersion sol of titanium oxide particles according to claim 15 is filtered and dried.
流冷却器を設置して行なう請求項１４又は１５に記載の
水分散酸化チタンゾルの製造法。17. The method for producing a water-dispersed titanium oxide sol according to claim 14, wherein the hydrolysis of titanium tetrachloride is carried out by installing a reflux condenser in the reaction tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23117297A JP3524342B2 (en) | 1996-08-30 | 1997-08-27 | Titanium dioxide sol and thin film for thin film formation |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-230776 | 1996-08-30 | ||
| JP23077696 | 1996-08-30 | ||
| JP9-137192 | 1997-05-27 | ||
| JP13719297 | 1997-05-27 | ||
| JP23117297A JP3524342B2 (en) | 1996-08-30 | 1997-08-27 | Titanium dioxide sol and thin film for thin film formation |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002350159A Division JP4010934B2 (en) | 1996-08-30 | 2002-12-02 | Titanium oxide particles, water-dispersed sols, thin films thereof, and production methods thereof |
| JP2003382714A Division JP4187632B2 (en) | 1996-08-30 | 2003-11-12 | Method for forming titanium dioxide thin film and catalyst having the titanium dioxide thin film |
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| Publication Number | Publication Date |
|---|---|
| JPH1143327A true JPH1143327A (en) | 1999-02-16 |
| JP3524342B2 JP3524342B2 (en) | 2004-05-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP23117297A Expired - Lifetime JP3524342B2 (en) | 1996-08-30 | 1997-08-27 | Titanium dioxide sol and thin film for thin film formation |
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