JP3524342B2 - Titanium dioxide sol and thin film for thin film formation - Google Patents
Titanium dioxide sol and thin film for thin film formationInfo
- Publication number
- JP3524342B2 JP3524342B2 JP23117297A JP23117297A JP3524342B2 JP 3524342 B2 JP3524342 B2 JP 3524342B2 JP 23117297 A JP23117297 A JP 23117297A JP 23117297 A JP23117297 A JP 23117297A JP 3524342 B2 JP3524342 B2 JP 3524342B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- titanium oxide
- sol
- titanium dioxide
- 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.)
- Expired - Lifetime
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 267
- 239000010409 thin film Substances 0.000 title claims description 110
- 239000004408 titanium dioxide Substances 0.000 title claims description 29
- 230000015572 biosynthetic process Effects 0.000 title claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 168
- 239000002245 particle Substances 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000460 chlorine Substances 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 21
- -1 chlorine ions Chemical class 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 20
- 239000000853 adhesive Substances 0.000 claims description 14
- 239000010408 film Substances 0.000 claims description 14
- 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 12
- 239000004033 plastic Substances 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229920003169 water-soluble polymer Polymers 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000123 paper Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 30
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 30
- 238000000034 method Methods 0.000 description 27
- 230000001699 photocatalysis Effects 0.000 description 24
- 238000006460 hydrolysis reaction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010419 fine particle Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 14
- 230000007062 hydrolysis Effects 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000909 electrodialysis Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 238000010304 firing Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000011941 photocatalyst 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
- 238000009835 boiling Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007791 liquid phase 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
- 239000004698 Polyethylene Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 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
- 239000000779 smoke Substances 0.000 description 2
- 238000010998 test method Methods 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
- 239000012808 vapor phase Substances 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
- 229920005479 Lucite® Polymers 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 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
- 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method 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
- 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
- 239000007789 gas Substances 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
- 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
- 239000005416 organic matter Substances 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
- 239000004926 polymethyl methacrylate Substances 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
- 238000011160 research Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 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
- 239000006228 supernatant Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
【０００１】[0001]
【発明の属する技術分野】本発明は薄膜形成用水分散二
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。The present invention relates to the thin film-forming water-dispersible two <br/> titanium oxide sol, ceramics by using the sol, a thin film of titanium oxide formed on a substrate such as plastic.
This titanium oxide thin film is transparent and has excellent photocatalytic action,
It also has good adhesion to the 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 the vapor phase method produced by the mixed combustion method of titanium tetrachloride and oxygen, the anatase type is the one that is produced at the lowest temperature and is stable. By subjecting this to heat treatment and baking, titanium oxide having a blue kite type structure at 816 to 1040 ° C. and a rutile type structure in a temperature range higher than that is obtained (Physical Chemistry Dictionary Third Edition, P. 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。Further, in the liquid phase method, for example, Koemon Funaki, Industrial Chemistry Vol. 59, No. 11, P. 1295 et al. Have reported in detail the crystal phase of titanium oxide produced by hydrolysis of an aqueous solution of titanium tetrachloride. According to this, it is concluded that rutile type titanium oxide is produced mainly from the high concentration liquid and anatase type titanium oxide is produced from the low concentration side. It is stated that in the liquid phase, it was impossible to form a brookite type fine particle titanium oxide.
From these reports, it has been difficult until now to stably produce brookite type titanium oxide by the liquid phase method. As described above, if the vapor-phase titanium oxide is heat-treated at a high temperature, it becomes brookite-type titanium oxide.However, since heat treatment causes the particles to grow, it is conventionally difficult to obtain fine blue-grained crystals. It 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, with respect to the method for producing a 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 or titanium tetrachloride is dispersed in the dispersion medium. It is common to mix them to form a sol by a method such as neutralization or hydrolysis. Titanium oxide sol is used for producing titanium oxide powder, or is used for applying sol to glass, plastic or the like to form a thin film of titanium oxide on the surface thereof. Titanium oxide is an optical semiconductor, and it is known that when the particle size is small, transparency is generated and the photocatalytic function is improved. The photocatalytic function of titanium oxide has been actively researched and developed in recent years. The usage of this photocatalyst includes antifouling by removing harmful substances, deodorization of odorous gases 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. Is. In many cases, this photocatalytic function is formed into a thin film when it is desired to add transparency. Therefore, titanium oxide is used as a thin film forming material in the form of 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 greater ability than the rutile type. The reason for this is due to the energy gap between the two, which is 3.02 eV for the rutile type and 3.23 eV for the anatase type, which is a difference of 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,
Up to now, there have been few examples of taking out simple substances themselves, and in addition to obtaining fine particles with a high specific surface area that can be used as optical semiconductors (photocatalysts), particles have conventionally been sintered because they are manufactured at high temperatures. It was impossible because it happened.
【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。As a form of using the thin film, when a thin film is formed by applying titanium oxide sol to a glass tube of a lighting fixture, for example, a fluorescent lamp or its cover, and a thin film is formed by photocatalytic action, organic substances such as oil smoke adhere to the glass tube or the cover. , A method of disassembling it to prevent the glass tube and the cover from being soiled has been proposed. However, when a thin film is formed using the sol obtained by the above-mentioned method, there are few that can be made into a highly transparent thin film, and in particular, a blue kite type titanium oxide thin film is used for a photocatalyst such as a lighting fixture. What was there was not known in the past.
【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 photocatalytic action is a reaction on the surface of the particles, it is preferable that the particles are 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 transparency, titanium oxide is preferably fine particles and monodispersed as in the case of catalytic activity. Conventionally, such problems have been dealt with mainly by miniaturizing anatase-type titanium oxide. Further, 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 does not easily peel 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 was difficult to prepare a titanium oxide sol which is fine particles having a very small particle size, good crystallinity, and good transparency when formed into a thin film. Titanium oxide in the sol is very small particles when hydrolyzed with titanium alcoside compound, but it has excellent powder characteristics, but alcohol is contained in the sol, and when it is burned into a thin film, it is safe for explosion and other reasons. I have a problem. Also, large explosion-proof equipment is required to prevent explosion, which is economically disadvantageous. Further, the titanium alcoside compound is 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 the adhesion between the thin film and the substrate is good. It is an object of the present invention to provide a titanium oxide sol and fine brookite type titanium oxide particles to be the following.
【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二酸化チタンの薄膜について種々
研究した結果、二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二酸化チタンゾルがこれらの特
性をよくすることを知見し本発明に至った。また、本発
明者らは、二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
とも見出し、ブルーカイト型酸化チタンゾルを好ましい
態様として開示する。 Means for Solving the Problems The present inventors have found, as a result of various studies on a thin film of titanium dioxide formed from titanium oxide sol, the transparency of the chlorine ions is a thin film contained in the dioxide sol, and the substrate Involved in adhesion with thin film,
Are two oxide sol particular chlorine ion concentration led to the finding by the present invention to improve the these properties. Also,
The authors have been studying the energy of titanium dioxide's photocatalytic function.
-The blue kite type with a large gap is especially good.
It is also found that the blue kite type titanium oxide sol is preferable.
It is disclosed as an aspect.
【００１０】本発明は、以下の発明からなる。 （１）二酸化チタンが結晶質であり、塩素イオンを塩素
元素として１，０００〜１０，０００ｐｐｍ含む薄膜形
成用水分散二酸化チタンゾル。 （２）二酸化チタンが平均粒径０．０１〜０．１μｍの
結晶質である上記（１）に記載の薄膜形成用水分散二酸
化チタンゾル。 （３）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
上記（１）記載の薄膜形成用水分散二酸化チタンゾル。 （４）酸化チタン含有量が０．０５〜１０モル／リット
ルである上記（１）〜（３）に記載の薄膜形成用水分散
二酸化チタンゾル。 （５）水溶性高分子を１０〜１０，０００ｐｐｍ含む上
記（１）〜（４）に記載の薄膜形成用水分散二酸化チタ
ンゾル。 （６）接着剤を二酸化チタンに対し酸化珪素換算で１〜
５０重量％含む上記（１）〜（５）に記載の薄膜形成用
水分散二酸化チタンゾル。 （７）接着剤がアルキルシリケートである上記（６）記
載の薄膜形成用水分散二酸化チタンゾル。 （８）上記（１）〜（７）に記載の薄膜形成用水分散二
酸化チタンゾルを用いて基材表面に形成した二酸化チタ
ン薄膜。 （９）基材がセラミックス、金属、ガラス、プラスチッ
ク、紙、木材のいずれかである上記（８）に記載の二酸
化チタン薄膜。 （１０）基材がセラミックス、金属、ガラス等の耐熱性
物質であり、酸化チタン薄膜が焼成したものである上記
（８）に記載の二酸化チタン薄膜。 The present invention comprises the following inventions. (1) Titanium dioxide is crystalline and chloride ion is chlorine
Thin film type containing 1,000 to 10,000 ppm as an element
Water dispersion titanium dioxide sol for production. (2) Titanium dioxide having an average particle size of 0.01 to 0.1 μm
Water-dispersed diacid for thin film formation according to the above (1), which is crystalline
Titanium oxide sol. (3) Average particle size of 0.5 μm or less and specific surface area of 20 m
2 / G or more of blue kite type titanium oxide particles dispersed
The water-dispersed titanium dioxide sol for forming a thin film according to (1) above. (4) Titanium oxide content is 0.05 to 10 mol / lit.
Water dispersion for forming a thin film according to the above (1) to (3)
Titanium dioxide sol. (5) Including 10 to 10,000 ppm of water-soluble polymer
Water-dispersed titanium dioxide for thin film formation according to the above (1) to (4)
Sol. (6) The adhesive is 1 to 1 in terms of silicon oxide with respect to titanium dioxide.
For forming a thin film according to (1) to (5) above, containing 50% by weight.
Water dispersed titanium dioxide sol. (7) The above (6), wherein the adhesive is an alkyl silicate
Water-dispersed titanium dioxide sol for thin film formation. (8) The thin film-forming aqueous dispersion described in (1) to (7) above.
Titanium dioxide formed on the surface of a substrate using titanium oxide sol
Thin film. (9) Base material is ceramics, metal, glass, plastic
Diacid according to the above (8), which is one of black, paper and wood.
Titanium oxide thin film. (10) Heat resistance of base material such as ceramics, metal, glass
It is a substance, and the titanium oxide thin film is fired.
The titanium dioxide thin film according to (8).
【００１１】[0011]
【発明の実施の形態】本発明の水分散酸化チタンゾルは
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１，０００〜１０，０００ｐｐｍ、好ましくは１，０
００〜４，０００ｐｐｍ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。Aqueous dispersion of titanium oxide sol DETAILED DESCRIPTION OF THE INVENTION The present invention is not only thin film formed from <br/> the sol has excellent photocatalytic function, in particular with improved adhesion to the substrate, transparency In the water-dispersed titanium oxide sol, chlorine ions as a chlorine element are 1,000 to 10,000 ppm, preferably 1,0.
It is contained in the range of 00 to 4,000 ppm. In the method of hydrolyzing titanium tetrachloride to obtain a water-dispersed titanium oxide sol, hydrogen chloride is produced by the reaction. And in the sol, it is almost dissociated into chlorine ions and hydrogen ions. In general, most of this hydrogen chloride escapes out of the system in the hydrolysis reaction under heating. In addition, if hydrogen chloride is contained in the sol, various obstacles are considered to occur when titanium oxide powder is obtained from the sol or when a titanium oxide thin film is obtained. When it remained, it was usual to dechlorinate so that hydrogen chloride was not contained in the sol as much as possible. However, heretofore, no consideration has been given to the influence of chlorine ions in the sol on the thin film properties of titanium oxide, and from this point of view, there is no technique for controlling the chlorine ions in the sol.
【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１，０００ｐｐｍ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１，０
００ｐｐｍ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。In the water-dispersed titanium oxide sol, if the chlorine ion contained is less than 1,000 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 baked, chlorine ions are 1,0
A difference appears in this adhesion depending on whether or not the content is more than 00 ppm. In the present invention, this adhesion is represented by the peel strength of the thin film from the substrate and the hardness of the thin film. On the contrary, if the chlorine ions in the sol increase and the chlorine element content exceeds 10,000 ppm, the transparency of the thin film becomes poor. A particularly preferable 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 electrical repulsion between the particles of titanium oxide particles in the titanium oxide sol increases, so that the dispersibility of the particles is improved, resulting in transparency and peel strength. It is presumed that such a result has been brought about. The smaller the titanium oxide particles of 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 it is difficult to produce titanium oxide particles that are too fine, the titanium oxide particles in the sol have an average particle size of 0.01
The range of 0.1 μm is preferable.
【００１４】本発明の好ましい水分散酸化チタンゾル
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。Of the present inventionPreferred water-dispersed titanium oxide sol
Is a photocatalytic function and transparency of a thin film formed from the sol.
The average particle size is 0.5 μm or less, which is preferable.
Or 0.01-0.1 μm with a specific surface area of 20 m2 / G
The above-mentioned brookite type titanium oxide particles are dispersed in water.
It is Le. The blue kite type titanium oxide particles are
The gie gap is 3.23 eV or more. Of titanium oxide
In terms of particle size, increase the transparency of titanium oxide thin film
Therefore, the titanium oxide particles in the sol have an average particle size of 0.5 μm.
Or less, more preferably in a monodispersion of 0.01 to 0.1 μm.
Preferably there is. Even if the specific surface area is large, in the sol
When the primary particles are agglomerated, when they are applied to form a thin film
It does not become transparent.
【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１，０００〜１０，０００ｐｐｍ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 only method for obtaining a brookite type is the heat treatment of anatase type titanium oxide as described above, and when the brookite type titanium oxide particles obtained by the heat treatment are to be formed into a thin film, the particle diameter is However, it has not been used for thin film formation at all because it has grown greatly by sintering due to heat treatment. This brookite type titanium oxide-dispersed sol can also contain chlorine ions as a chlorine element in the range of 1,000 to 10,000 ppm as described above. As a result, not only the thin film formed from the sol has an excellent catalytic function, but also the adhesion to the substrate is enhanced.
In the above sol , if the concentration of titanium oxide particles in the sol is too high, the particles agglomerate and the sol becomes unstable. Further, if the concentration of titanium oxide particles is too low, there arises a problem that, for example, the step of applying the sol takes a long time when forming a thin film. From these facts, the concentration (content) of titanium oxide particles in the water-dispersed titanium oxide sol is particularly preferably 0.05 to 10 mol / liter.
【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。In the water-dispersed titanium oxide sol of the present invention, titanium oxide particles can be obtained by filtering, washing with water and drying. Particles obtained from a brookite-type titanium oxide sol have an average particle diameter of 5 μm or less, preferably 0.1.
It is from 01 to 0.1 μm and has a specific surface area of 20 m 2 / g or more. 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 to the sol, for example, about 10 to 10,000 ppm 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 preferable.
【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 bodies 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 without any limitation. The base material may be a catalyst carrier made of alumina, zirconia or the like, and a titanium oxide thin film catalyst may be supported on the base material to be used as a catalyst. In addition, if a titanium oxide thin film is formed on a glass of a lighting fixture such as a fluorescent lamp or its plastic cover as a base material, the thin film is transparent and has a photocatalytic effect, so that organic matter such as oil smoke can be protected without blocking light. Can be disassembled,
It is effective in preventing stains on the glass and cover. Also, by forming a thin film of titanium oxide on architectural glass and wall materials, it is possible to prevent dirt in the same way, so it can be used for window materials and wall materials in 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 base material, a method of immersing the base material in the sol, a method of spraying the sol on the base material, a method of applying the sol to the base material with a brush, or the like is adopted. The appropriate amount of sol applied is 0.01 to 0.2 mm in terms of liquid thickness.
A thin film can be obtained by drying after application to remove water, and the film can be used as it is for a catalyst or the like.
【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 base material is heat-resistant, such as metal or ceramics, such as glass, the titanium oxide thin film can be formed and fired, so that the thin film is more strongly adhered to the base material and the hardness of the thin film is increased. The firing temperature is preferably 200 ° C. or higher. The upper limit of the firing temperature is not particularly limited and may be determined according to the heat resistance of the base material, but if the temperature is raised too much, the hardness of the thin film and the adhesion to the base material will not increase, so 800 ° C.
Up to the place is appropriate. Further, in the case of brookite type titanium oxide, it is preferable to sinter at a temperature of 700 ° C. or lower in order to maintain its crystal form. The firing atmosphere is not particularly limited,
Good in the atmosphere. The firing time is not particularly limited, for example, 1 to
It may be performed within the range of 60 minutes. The thickness of the titanium oxide thin film obtained by firing is 0.05-
It is about 1.0 μm. Further, in order to make the transparent thin film of the present invention stronger and increase the adhesive force to the substrate, an appropriate 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 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. In this case, the adhesive may be selected depending on the nature of the adhesive, either to be mixed immediately before film formation or in a state of being mixed in the sol in advance, and there is no problem in the effect of the present invention in either case. The thin film containing the adhesive does not have to be fired, but can 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 film produced by using the titanium oxide sol according to the present invention has a common crystallinity, the fine particles of titanium oxide are very fine particles, and they do not contain impurities. 1 titanium fine particle
Since it is dispersed as close as possible to the secondary particles, the photocatalytic ability and the transparency are high, and particularly when the titanium oxide is a brookite type, the catalytic ability is 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。ブ
ルーカイト型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 the method for producing a sol will be described. The water-dispersed titanium oxide sol of the present invention need only contain the above-mentioned amount of chlorine ions, and the production method thereof is not particularly limited. For example, hydrolyzing a titanium alkoxide compound to obtain a water-dispersed titanium oxide sol containing a small amount of alcohol,
It is also possible to add HCl or the like to this so that the chlorine ion concentration is within the above range. However, it is preferable to use titanium tetrachloride, which produces hydrogen chloride by hydrolysis. Bu
The lucite type is obtained by hydrolyzing titanium tetrachloride under specific conditions. It is preferable that hydrogen chloride produced in these hydrolysis prevent escape from the reaction tank and remain in the sol as much as possible. When titanium tetrachloride is hydrolyzed while allowing the generated hydrogen chloride to escape, the titanium oxide in the sol is unlikely to have a small particle size and also has 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。Hydrogen chloride generated by hydrolysis may be suppressed even if escape is not completely prevented. Also, the method is not particularly limited as long as it can be suppressed,
Although it is possible to apply pressure, for example, the easiest and most effective method is to carry out hydrolysis by installing a reflux condenser in the hydrolysis reaction tank. This device is shown in FIG. In the figure, 1 is a reaction tank filled with an aqueous solution 2 of titanium tetrachloride, in which a reflux condenser 3 is installed. Four
Is a stirrer, 5 is a thermometer, and 6 is a device for heating the reaction tank. Water and hydrogen chloride vapor are generated by the hydrolysis reaction, most of which is 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 hydrolyzed titanium tetrachloride aqueous solution is too low, the productivity will be poor, and the efficiency will be low when forming a thin film from the water-dispersed titanium oxide sol produced, and if the concentration is too high, the reaction will occur. Is not suitable as a material for forming a transparent thin film, because the obtained titanium oxide particles are less likely to be fine and the dispersibility is poor. 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 titanium oxide to 0.05 to 10 mol / liter as described above is not preferable. The concentration of titanium oxide during the formation of the sol is preferably in the above range, for which the concentration of titanium tetrachloride in the aqueous solution of titanium tetrachloride to be hydrolyzed is a value that is not significantly different from the concentration of titanium oxide produced above. That is, the concentration may be approximately 0.05 to 10 mol / liter, and if necessary, the concentration may be adjusted to 0.05 to 10 mol / liter by adding or concentrating a small amount of water in the subsequent steps.
【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 titanium tetrachloride aqueous solution. If the temperature is lower than 50 ° C, it takes a long time for the hydrolysis reaction. The hydrolysis is carried out by raising the temperature to the above temperature and holding it for about 10 minutes to 12 hours. This holding time may be shorter as the hydrolysis temperature is higher. To hydrolyze the aqueous solution of titanium tetrachloride, a mixed solution of titanium tetrachloride and water may be heated to a predetermined temperature in the reaction tank, or water may be preheated in the reaction tank and titanium tetrachloride may be added thereto. May be added to bring the mixture to a predetermined temperature. By this hydrolysis, titanium oxide in which anatase type and / or brookite type are mixed with brookite type is generally obtained. In order to increase the content of brookite-type titanium oxide in it, water is preheated to 75 to 100 ° C in a reaction tank, titanium tetrachloride is added thereto, and the temperature range of 75 ° C to the boiling point of the solution is reached. The method of hydrolysis with is suitable. It is possible to make the brookite type titanium oxide 70% by weight or more in 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１，０００〜１
０，０００ｐｐｍになるように調整する。 The higher the rate of temperature rise of the aqueous solution of titanium tetrachloride in the hydrolysis, the finer the particles obtained, so it is preferably 0.2 ° C./min or more, more preferably 0.5.
℃ / min or more. By this method, the titanium oxide particles in the sol have a good crystallinity with an average particle size of 0.5 μm or less, preferably 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 type, and while the reaction tank is a continuous tank and titanium tetrachloride and water are continuously charged, the reaction liquid is taken out on the opposite side of the charging port, and subsequently dechlorination treatment is performed. A continuous method is also possible. The generated sol has a chlorine ion of 1,000 to 1 due to dechlorination or addition of water or dehydration within a range that does not hinder.
Adjust so that it will be 0000 ppm .
【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１，０００〜１０，０００ｐｐｍの場合、ｐＨは約
１．７〜０．５、好ましい範囲である１，０００〜４，
０００ｐｐｍの場合、ｐＨは約１．７〜１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 may be carried out by a generally known method, such as electrodialysis, ion exchange resin, electrolysis, etc. The degree of dechlorination may be determined by using the pH of the sol as a guide. When chlorine ion is 1,000 to 10,000 ppm, the pH is about
1.7 to 0.5, which is a preferable range of 1,000 to 4,
For 000 ppm, pH of about 1.7 to 1. It is also possible to add an organic solvent 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 produced by the hydrolysis reaction as it is, to prepare a powder of titanium oxide from this sol, disperse this in water, sol Is not the preferred method. Titanium oxide particles have high surface activity,
This is because the finer the particles are, the higher the activity becomes, so that it becomes very difficult to disperse them in water, that is, they become agglomerates, and the thin film made from this is inferior in transparency and the photocatalytic action is also lowered.
【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。
（参考例１〜２、実施例１〜４）
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（１
０４℃）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５０〜１０，０００ｐｐｍ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３０
ｐｐｍ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。後述のように、塩素イオンが５０ｐｐｍ
から１，０００ｐｐｍへ増加すると、薄膜の硬度、シュ
ウ酸の分解率がより向上する。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０．０１
５〜０．０１８μｍ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 specifically described below with reference to examples, but the present invention is not limited to the examples. ( Reference Examples 1 and 2 and Examples 1 to 4 ) Water was added to titanium tetrachloride (purity 99.9%) to give a titanium tetrachloride concentration of 0.25 mol / liter (titanium oxide conversion 2
The solution was adjusted so as to be (% by weight). At this time, an appropriate cooling device such as ice cooling was provided so that the liquid temperature of the aqueous solution would not rise above 50 ° C. Next, 1 liter of this aqueous solution is shown in FIG.
It was charged in a reaction tank equipped with a reflux condenser as shown in Fig.
(04 ° C.) and held for 60 minutes for hydrolysis.
After cooling the obtained sol, residual chlorine produced in the reaction was removed by electrodialysis to obtain chlorine ion concentrations shown in Table 1. The electrodialysis was performed using an electrodialysis device G3 type manufactured by Asahi Kasei Kogyo Co., Ltd. while monitoring the pH of the sol solution. To each water-dispersed titanium oxide sol in which chlorine ions were adjusted, 1,000 ppm of polyvinyl alcohol, which is a water-soluble polymer, was added as a film forming aid, based on the weight of the sol liquid. This sol is stable when the chlorine ion content is 50 to 10,000 ppm, and no precipitation of titanium oxide fine particles formed was observed even after one day or more. However, chlorine ion is 30
In the case of ppm, the aggregation of titanium oxide in the sol was observed, and in the case of 15,000 ppm, the thin film using it exhibited a pale white color. As described below, chlorine ion is 50ppm
From 1,000 ppm to 1,000 ppm,
The decomposition rate of uric acid is further improved. When the particles in the sol were observed with a transmission electron microscope, the average particle diameter of the particles was 0.01.
The particle size was 5 to 0.018 μm, and when the particles were identified by an X-ray diffractometer, it was found to be 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 15,
A sol was obtained in the same manner as in the example except that the concentration was changed to 000 ppm (Comparative example 2).
【００２８】参考例、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、５０
０℃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 sol of Reference Examples, Examples and Comparative Examples was applied on a glass plate by dip coating and dried, and then 50
It heat-processed at 0 degreeC in air for 1 hour, and obtained the titanium oxide thin film. The thickness of the titanium oxide thin film after the heat treatment was 0.15 μm. As a result of investigating the crystalline form of titanium oxide by Rietveld analysis of the powder X-ray diffraction pattern, the one before heat treatment was a mixture of about 50% by weight of anatase type and about 50% by weight of brookite type, which was heated to 800 ° C or higher. Then it became a rutile type alone.
【００２９】成膜の評価参考例、
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７００〜２００ｎ
ｍ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 a quartz glass plate of titanium oxide thin films obtained from the water-dispersed titanium oxide sol of each of Reference Example, Example and Comparative Example were measured. The light transmittance was measured by setting a titanium oxide thin film formed on a quartz glass plate in a spectrophotometer manufactured by JASCO Corporation to measure 700 to 200n.
The light transmittance was measured by continuously changing the wavelength up to m. The light transmittance at 550 nm was expressed as the light transmittance in the present invention. The results are shown in Table 1.
The method of decomposing oxalic acid is to prepare a reaction vessel from a quartz glass plate with a titanium oxide thin film formed thereon, add 5 mmol / l of oxalic acid into the reaction vessel, and irradiate it with a 100 W mercury lamp while blowing oxygen. The amount of oxalic acid decomposed after the lapse of time was determined by redox titration of potassium permanganate. The results are shown in Table 1. Further, the adhesion between the quartz glass plate and the thin film after firing was determined by a pencil hardness test method and an eye peel test method (JIS K5400). The results are shown in Table 1.
Shown in.
【００３０】[0030]
【表１】 [Table 1]
【００３１】（参考例３、実施例５、比較例３，４）参考例１〜２、
実施例１〜４、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。( Reference Example 3, Example 5 , Comparative Examples 3 and 4) As in Reference Examples 1 and 2, Examples 1 to 4 and Comparative Examples 1 and 2, water-dispersed titanium oxide sol was used, and a plastic (polyethylene) was used as a substrate. Using a terephthalate (PET) plate,
A titanium oxide thin film was formed in the same manner as in the above-mentioned Examples and Comparative Examples except that a coating film of the above-mentioned titanium oxide sol was formed thereon and dried at 100 ° C. instead of firing, and the characteristics of the thin film were evaluated. The results are shown in Table 2.
【００３２】[0032]
【表２】 [Table 2]
【００３３】（参考例４）
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２００ｒｐ
ｍに保ちながら、ここに四塩化チタン（Ｔｉ含有量：１
６．３％、比重１．５９、純度９９．９％）水溶液４６
ｍｌ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、３
０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。 Reference Example 4 954 ml of distilled water is charged into the reaction tank with a reflux condenser shown in FIG. 1 and heated to 95 ° C. Stir speed is about 200 rp
Titanium tetrachloride (Ti content: 1
6.3%, specific gravity 1.59, purity 99.9%) aqueous solution 46
ml was added dropwise to the reaction tank 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 titanium tetrachloride concentration 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 dropping, but continued to be maintained at the same temperature, and after the completion of the dropping, the temperature was further raised and heated to near the boiling point (104 ° C), and kept in this state for 60 minutes to complete the reaction. The reaction was completed. After cooling, residual chlorine produced by the reaction was removed by electrodialysis to adjust the pH to 2 (chlorine ion 600 ppm), and then polyvinyl alcohol, which is a water-soluble polymer as a film forming aid, was added to the titanium oxide content to 0. 0.1% was added to obtain a titanium oxide sol. This sol is stable, 3
No sedimentation of the produced titanium oxide fine particles was observed even after 0 day 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 filtering the sol, 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, titanium oxide was found to be 96.7% by weight in the brookite type and 0.1% in the rutile type. 9% by weight, anatase type 2.4
% By weight. When the fine particles were observed with a transmission electron microscope, the average particle diameter of the primary particles was 15 nm. Furthermore, the specific surface area of the fine particles is 1 by the BET method.
It was 00 m 2 / g. Meanwhile, the sol was uniformly coated on a quartz glass substrate using a spin coater, and the temperature was 100 ° C.
It was dried in a drier 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 it was completely transparent. Furthermore, absorption was observed in the ultraviolet, and the energy gap calculated from the basic absorption edge was 3.75 eV.
Met. The formula for obtaining the energy gap at this time is shown in formula (1). λ = 1239 / Eg (1) λ: Fundamental absorption edge (nm) Eg: Energy gap (eV)
【００３５】（実施例６）参考例４
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、参考例４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１０ｎｍ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３０００ｐｐ
ｍ）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。[0035] (Example 6) Reference Example 4, except that the reaction temperature of dropping of the aqueous titanium tetrachloride solution and 75 ° C., to precipitate titanium oxide in the same manner as in Reference Example 4. When the particles were similarly identified by an X-ray diffractometer, they were 75% by weight of brookite type titanium oxide and 25% by weight of rutile type titanium oxide. Also,
When the fine particles were observed with a transmission electron microscope, the average particle size of the primary particles was 10 nm. Furthermore, the specific surface area of the fine particles was 120 m 2 / g by the BET method.
By electrodialysis, pH = 1 (chlorine ion 3000 pp
A transparent thin film was prepared by applying the titanium oxide sol described in (m) above to a glass substrate and baking at 500 ° C. When this thin film was measured by thin film X-ray diffraction, it was a mixed titanium oxide of brookite type and rutile type as described above. Further, from the transmission spectrum of this glass substrate with a thin film, the visible region showed a transmittance of 95% or more and was completely transparent.
Furthermore, the energy gap obtained from the basic absorption edge due to ultraviolet was 3.30 eV.
【００３６】（参考例５）参考例４
において、水と四塩化チタン水溶液の量をそれ
ぞれ８６２ｍｌ、１３８ｍｌ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。 Reference Example 5 The procedure of Reference Example 4 was repeated except that the amounts of water and titanium tetrachloride aqueous solution were 862 ml and 138 ml, respectively.
After the pH was adjusted to 2 by electrodialysis, an equal amount of ethyl alcohol was added to this sol to give 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 diameter was 15 nm. The visible part had a transmittance of 80% or more and an energy gap of 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) Anatase type titanium oxide particles having a primary particle diameter of 7 nm were used, and an ultrasonic disperser was used for water so that the titanium oxide concentration became a 2% aqueous solution as in Example 9. Dispersed. At this time, hydrochloric acid was added as a deflocculating agent to adjust the pH to 1, and the same operation was performed to obtain a titanium oxide sol. In addition, similarly, coating on a glass substrate, 10
A transparent thin film was prepared 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参考例４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 size of 50 nm were used. As in the case of Comparative Example 5, the precipitation of titanium oxide fine particles was observed in this sol. In this titanium oxide sol, fine particles of titanium oxide settled with the passage of time. Since the photocatalytic ability was not recognized in the film formed by the supernatant liquid after the sedimentation, the sol was dispersed by the ultrasonic disperser immediately after the formation, or the film was formed on the glass substrate by the same method as in Reference Example 4, and the photocatalytic ability was obtained. Was evaluated.
【００３９】成膜した薄膜の評価結果参考例４〜５、
実施例６、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 Formed Thin Film The photocatalytic ability of the titanium oxide thin films obtained from the titanium oxide sols of Reference Examples 4 to 5, Example 6 , and Comparative Examples 5 and 6 was determined by the oxalic acid decomposition method described above. The results are shown in Table 3.
【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, titanium oxide aggregates were formed on the glass substrate and the surface was non-uniform. In Comparative Example 6, since the transparent titanium oxide thin film was not obtained, the evaluation of the photocatalytic ability was not performed.
【００４２】（参考例６）参考例４
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１
０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６００ｐｐｍ）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ＳｉＯ2 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。 Reference Example 6 The same reaction as in Reference Example 4 was performed, and the concentration was 0.25 mol /
l of titanium tetrachloride (2% by weight in terms of titanium oxide) was hydrolyzed. Next, this reaction solution is concentrated to a titanium oxide concentration of 1
0% by weight, electrodialysis to remove residual chlorine, pH =
2 (chlorine ion concentration of about 600ppm), then tetramethylorthosilicate Si (OCH 3 ) as an adhesive
4 was added to titanium oxide in an amount of 5% by weight in terms of SiO 2 to obtain a titanium oxide sol.
【００４３】（参考例７）参考例６
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。 Reference Example 7 After the same operations as in Reference Example 6 up to concentration and electrodialysis were performed,
After diluting 5 times with isopropyl alcohol, tetraethyl orthosilicate Si (OC 2 H 5 ) was used as an adhesive.
4 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】（参考例８）参考例６
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 Ｈ
7 ）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。 Reference Example 8 In Reference Example 6 , tetrapropyl orthosilicate Si (OC 3 H) was used instead of tetraethyl orthosilicate.
7) 4 35 wt% in terms of SiO 2 with respect to titanium oxide
To obtain a titanium oxide sol.
【００４５】（比較例７）参考例８
において、テトラプロピルオルソシリケートＳ
ｉ（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 Reference Example 8 , tetrapropyl orthosilicate S
i (OC 3 H 7 ) 4 was added to titanium oxide in an amount of 55% by weight in terms of SiO 2 to obtain a titanium oxide sol.
【００４６】成膜した薄膜の評価結果参考例６〜８
、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 Formed Thin Film Each of the titanium oxide sols of Reference Examples 6 to 8 and Comparative Example 7 was uniformly applied to a quartz glass plate using a spin coater, allowed to stand at room temperature and dried to obtain a transparent film. It was The transmittance of this quartz glass plate with a film was 95% or more in the visible part and was completely transparent. Further, the pencil hardness test and the adhesion test of the quartz glass plate with the transparent film were evaluated by the above-mentioned methods. The results are shown in Table 4.
【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。When the water-dispersed titanium oxide sol of the present invention is applied to various base materials to form a titanium oxide thin film, the thin film is transparent and has excellent photocatalytic action. In particular, when titanium oxide is of the blue kite type, the photocatalytic action is high. Further, the thin film has high hardness and excellent adhesion to the base material. Therefore, the thin film on the base material is durable, and if this thin film is used for, for example, a glass tube of a luminaire or a cover of a luminaire, 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 cross-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 1 reaction tank 2 Titanium tetrachloride aqueous solution 3 reflux condenser 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 (56)参考文献 特開 昭62−283817（ＪＰ，Ａ) 特開 昭61−283629（ＪＰ，Ａ) 特開 昭62−229139（ＪＰ，Ａ) 特開 平７−251081（ＪＰ，Ａ) 特開 平６−246165（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 23/00 - 23/08 B01J 21/00 - 38/74 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriko Murase 1-1-1, Onodai, Midori-ku, Chiba-shi, Chiba Showa Denko KK Research Institute (56) Reference JP-A-62-283817 (JP, A) JP-A-61-283629 (JP, A) JP-A-62-229139 (JP, A) JP-A-7-251081 (JP, A) JP-A-6-246165 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C01G 23/00-23/08 B01J 21/00-38/74
Claims (10)
ンを塩素元素として１，０００〜１０，０００ｐｐｍ含
む薄膜形成用水分散二酸化チタンゾル。1. A is titanium dioxide crystalline, 1,000～10,000Ppm including thin film forming water-dispersible titanium dioxide sol chlorine ions as elemental chlorine.
１μｍの結晶質である請求項１に記載の薄膜形成用水分
散二酸化チタンゾル。2. A titanium dioxide an average particle diameter of 0.01 to 0.
Film forming water dispersible titanium dioxide sol of claim 1 which is crystalline 1 [mu] m.
が２０ｍ2 ／ｇ以上のブルーカイト型酸化チタン粒子が
分散した請求項１記載の薄膜形成用水分散二酸化チタン
ゾル。Wherein an average particle diameter of 0.5μm or less in specific surface area of 20 m 2 / g or more brookite titanium oxide particles are dispersed claim 1 for forming a thin film aqueous dispersion titanium dioxide sol according.
／リットルである請求項１〜３のいずれかに記載の薄膜
形成用水分散二酸化チタンゾル。4. The titanium oxide content is 0.05 to 10 mol.
/ Liter, The thin film according to claim 1.
Water-dispersed titanium dioxide sol for forming .
ｍ含む請求項１〜４のいずれかに記載の薄膜形成用水分
散二酸化チタンゾル。5. A water-soluble polymer of 10 to 10,000 pp
Water for forming a thin film according to any one of claims 1 to 4, which contains m.
Titanium dioxide sol .
算で１〜５０重量％含む請求項１〜５のいずれかに記載
の薄膜形成用水分散二酸化チタンゾル。6. An adhesive agent for converting titanium dioxide to silicon oxide.
The amount of 1 to 50% by weight is included in the calculation.
Water-dispersed titanium dioxide sol for thin film formation .
項６記載の薄膜形成用水分散二酸化チタンゾル。7. The adhesive is an alkyl silicate.
Item 7. A water-dispersed titanium dioxide sol for forming a thin film according to item 6 .
成用水分散二酸化チタンゾルを用いて基材表面に形成し
た二酸化チタン薄膜。8. A thin film type according to claim 1.
Formed on the surface of the substrate using a water-dispersed titanium dioxide sol
Titanium dioxide thin film .
ラスチック、紙、木材のいずれかである請求項８に記載
の二酸化チタン薄膜。9. The base material is ceramics, metal, glass, plastic
9. The plastic according to claim 8, which is any of plastic, paper and wood.
Titanium dioxide thin film .
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８に記載の二酸化チタン薄膜。10. A base material is ceramics, metal, glass, or the like.
It is a heat-resistant substance of
The titanium dioxide thin film according to claim 8 .
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1143327A JPH1143327A (en) | 1999-02-16 |
| JP3524342B2 true JP3524342B2 (en) | 2004-05-10 |
Family
ID=27317424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23117297A Expired - Lifetime JP3524342B2 (en) | 1996-08-30 | 1997-08-27 | Titanium dioxide sol and thin film for thin film formation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3524342B2 (en) |
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| JPH1143327A (en) | 1999-02-16 |
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