JPH1053438A - Fluorescent lamp - Google Patents
Fluorescent lampInfo
- Publication number
- JPH1053438A JPH1053438A JP8207165A JP20716596A JPH1053438A JP H1053438 A JPH1053438 A JP H1053438A JP 8207165 A JP8207165 A JP 8207165A JP 20716596 A JP20716596 A JP 20716596A JP H1053438 A JPH1053438 A JP H1053438A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- sol
- fluorescent lamp
- glass tube
- 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 claims abstract description 83
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000011521 glass Substances 0.000 claims abstract description 40
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000010409 thin film Substances 0.000 claims description 40
- 238000006460 hydrolysis reaction Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000010304 firing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 2
- 238000000034 method Methods 0.000 description 17
- 239000010419 fine particle Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 238000006298 dechlorination reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229920003169 water-soluble polymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- -1 titanium alkoxide Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010998 test method Methods 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 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
- 238000001704 evaporation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 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
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 229920000642 polymer Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 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
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は蛍光ランプに関し、
さらに詳しくは蛍光ランプのガラス管表面に酸化チタン
薄膜を形成し、該酸化チタンの光触媒作用により油煙等
の有機物を分解することによりガラス管表面の汚れを防
止した蛍光ランプに関する。The present invention relates to a fluorescent lamp,
More specifically, the present invention relates to a fluorescent lamp in which a titanium oxide thin film is formed on the surface of a glass tube of a fluorescent lamp, and organic substances such as oily smoke are decomposed by the photocatalytic action of the titanium oxide, thereby preventing the surface of the glass tube from being stained.
【０００２】[0002]
【従来の技術】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。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。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。しかし、透明性の高い薄膜を形成させ
ることが可能であるものは少ない。2. Description of the Related Art 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. As a form of utilization of the thin film, recently, a titanium oxide sol is applied to a glass tube or a cover of a fluorescent lamp, for example, a fluorescent lamp to form a thin film. A method of disassembling the glass tube and the cover to prevent contamination has been proposed. Regarding the method of producing titanium oxide sol, crystalline or amorphous titanium oxide particles are dispersed in a dispersion medium, or a titanium alkoxide, titanium sulfate, titanium tetrachloride or other titanium oxide precursor is mixed into the dispersion medium and neutralized, It is common to form a sol by a method such as hydrolysis. However, few can form a highly transparent thin film.
【０００３】[0003]
【発明が解決しようとする課題】酸化チタン薄膜を蛍光
ランプのガラス管表面（外面）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及び透明性が高いこ
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必要である。透
明性をよくするためにも同様に微粒子であり、かつ単分
散であるものが望ましい。さらに酸化チタン薄膜とガラ
ス管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 the surface (outer surface) of a glass tube of a fluorescent lamp and used as a photocatalyst, the thin film is required to have high catalytic activity and high transparency. Since the photocatalysis is a reaction on the particle surface, it is necessary that the particles are fine particles having a high surface area and have good crystallinity in order to have high activity. Similarly, in order to improve transparency, it is desirable that the particles are fine particles and monodispersed. Further, the adhesion between the titanium oxide thin film and the glass tube must be improved so that the thin film is not easily peeled off.
【０００４】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
発明は蛍光ランプ用のガラス管表面に光触媒作用が大き
く、透明性が高く、かつガラス管との密着性に優れた酸
化チタン薄膜を設け、有機物付着によるガラス管の汚れ
を防止した蛍光ランプ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. The present invention provides a fluorescent lamp in which a titanium oxide thin film having a large photocatalytic action, high transparency, and excellent adhesion to the glass tube is provided on the surface of the glass tube for the fluorescent lamp to prevent the glass tube from being stained by organic substances. The purpose is to provide.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、入手が容
易であり、経済的にも有利な四塩化チタンの加水分解に
着目し、これから光触媒として優れた薄膜を蛍光ランプ
のガラス管に形成する方法について研究した結果、本発
明に到達したものである。即ち、本発明は四塩化チタン
の加水分解により酸化チタン含有ゾルを生成させて、該
ゾルを蛍光ランプ用のガラス管表面に塗布し、焼成して
該表面に薄膜を形成することを特徴とする蛍光ランプで
ある。The present inventors have focused on the hydrolysis of titanium tetrachloride, which is easily available and economically advantageous, and will now provide a thin film excellent as a photocatalyst to a glass tube of a fluorescent lamp. As a result of studying a forming method, the present invention has been achieved. That is, the present invention is characterized in that a titanium oxide-containing sol is generated by hydrolysis of titanium tetrachloride, the sol is applied to the surface of a glass tube for a fluorescent lamp, and baked to form a thin film on the surface. It is a fluorescent lamp.
【０００６】[0006]
【発明の実施の形態】本発明は四塩化チタンを加水分解
して酸化チタン含有ゾルを生成させ、そのゾルの状態で
ガラス管に塗布することが重要である。一般に酸化チタ
ンの微粒子は酸化チタンの前駆体を中和、加水分解して
濾過、乾燥、熱処理等により得られているが、この微粒
子を水などの溶媒に分散させてゾルにしたものは薄膜形
成用には適さない。これは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ためである。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, it is important that titanium tetrachloride is hydrolyzed to form a titanium oxide-containing sol, and the sol is applied to a glass tube. In general, titanium oxide fine particles are obtained by neutralizing and hydrolyzing a precursor of titanium oxide, followed by filtration, drying, heat treatment, and the like.A sol obtained by dispersing these fine particles in a solvent such as water forms a thin film. Not suitable for use. This is because titanium oxide particles have a high surface activity, and the finer the particles, the higher the activity, which makes it extremely difficult to disperse them in water, that is, they become agglomerates, and the thin film made from this is transparent. This is because the photocatalytic action is also reduced.
【０００７】本発明者らは先に粒子径が小さく、結晶性
のよい酸化チタン粒子を製造する方法を特許出願した
（特願平７−２４５４４６）。この方法は四塩化チタン
の加水分解反応を、生成する塩化水素の逸出を抑制しな
がら行う方法である。塩化水素の逸出を抑制する好まし
い方法は、加水分解反応槽に還流冷却器を設置し、蒸発
する塩化水素ガスを凝縮して反応槽に戻す方法である。
上記特許では得られた酸化チタン含有ゾルを濾過、乾
燥、必要により熱処理して酸化チタン粒子としている
が、本発明はこの途中で生成する酸化チタン含有ゾルを
用いて薄膜を形成する。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、
生成する酸化チタン含有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。The present inventors previously filed a patent application for a method for producing titanium oxide particles having a small particle size and good crystallinity (Japanese Patent Application No. Hei 7-245446). In this method, a hydrolysis reaction of titanium tetrachloride is performed while suppressing escape of generated hydrogen chloride. A preferred method of suppressing escape of hydrogen chloride is to install a reflux condenser in the hydrolysis reaction tank, condense the evaporating hydrogen chloride gas and return it to the reaction tank.
In the above-mentioned patent, the obtained titanium oxide-containing sol is filtered, dried and, if necessary, heat-treated to form titanium oxide particles. In the present invention, a thin film is formed using the titanium oxide-containing sol generated during the process. If the concentration of titanium tetrachloride in the titanium tetrachloride aqueous solution to be hydrolyzed is too low, the productivity is poor,
When a thin film is formed from the generated titanium oxide-containing sol, the efficiency is low, and when the concentration is too high, the reaction becomes violent, and the resulting titanium oxide particles are difficult to be fine and the dispersibility is poor, so that a transparent thin film is used. It is not suitable as a forming material.
【０００８】本発明の酸化チタンゾルは生成したまま、
あるいはこれを脱塩素処理や必要により水溶性高分子の
１次結合材を少量加えてガラス管に塗布することが好ま
しく、その場合に酸化チタン濃度があまり薄いと塗布効
率が悪く、また濃度が高いと酸化チタンの透明薄膜形成
が難しくなる。これらのことを考慮して加水分解におけ
る四塩化チタンの濃度は０．０５〜１モル／リットルが
好ましい。この加水分解によって得られるゾルあるいは
これを脱塩素処理等したゾル中の酸化チタンの濃度は、
加水分解の際あるはその後の脱塩素処理等における溶液
の体積変化は少ないので、四塩化チタンの濃度とほぼ同
様０．０５〜１モル／リットル程度である。[0008] The titanium oxide sol of the present invention is produced as
Alternatively, it is preferable to apply a small amount of a primary binder of a water-soluble polymer to the glass tube by applying a small amount of a dechlorination treatment, if necessary. In this case, if the titanium oxide concentration is too low, the coating efficiency is poor and the concentration is high. Thus, it becomes difficult to form a transparent thin film of titanium oxide. Taking these facts into consideration, the concentration of titanium tetrachloride in the hydrolysis is preferably 0.05 to 1 mol / l. The concentration of titanium oxide in the sol obtained by this hydrolysis or in the sol obtained by dechlorinating the sol,
Since the volume change of the solution during the hydrolysis or subsequent dechlorination treatment is small, the concentration is about 0.05 to 1 mol / liter, almost the same as the concentration of titanium tetrachloride.
【０００９】本発明における酸化チタン含有ゾルの好ま
しい製法は、四塩化チタンの加水分解において発生する
塩化水素が反応槽から逸出するのを抑制し、できるだけ
水溶液中に残留させる方法である。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。A preferred method for producing the titanium oxide-containing sol in the present invention is a method in which hydrogen chloride generated in the hydrolysis of titanium tetrachloride is prevented from escaping from the reaction tank and remains in an aqueous solution as much as possible. Hydrogen chloride generated by hydrolysis does not have to be completely prevented from escaping, as long as it is suppressed. The method is not particularly limited as long as the method can be suppressed. For example, pressurization can be performed. However, the easiest and most effective method is to install a reflux condenser in a hydrolysis reaction tank and perform hydrolysis. How to do. 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.
Is installed. 4 is a stirrer, 5 is a thermometer, and 6 is a device for heating the reaction tank. Although water and hydrogen chloride vapor are generated by the hydrolysis reaction, most of them are condensed by the reflux condenser and returned to the reaction tank, so that hydrogen chloride hardly escapes from the reaction tank.
【００１０】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。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。以上はバッ
チ式反応により酸化チタン含有ゾルを得る場合について
説明したが、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。The temperature in the hydrolysis is preferably in the range of 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. The higher the temperature rising rate of the titanium tetrachloride aqueous solution, the finer the particles obtained, so the temperature is preferably 0.2 ° C./min or more, more preferably 0.5 ° C./min or more. The case where a titanium oxide-containing sol is obtained by a batch-type reaction has been described above, but while the reaction vessel is a continuous vessel and titanium tetrachloride and water are continuously charged, the reaction solution is taken out on the opposite side of the charging port, and then dechlorinated. A continuous mode of processing is also possible.
【００１１】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０．０１〜０．０８μｍの範囲の結晶性の
よいものとなる。酸化チタン含有ゾルには塩化水素が含
まれており、ゾルをガラス管に塗布焼成して薄膜を形成
する場合、塩化水素の濃度が高いと薄膜の透明性が下が
り、また焼成中に発生する塩化水素ガスによる装置上の
問題が生じるのでゾルを予め脱塩素処理することが好ま
しい。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、例えばｐＨ０．５
〜５の範囲であり、好ましくはｐＨ２〜３である。According to this method, the titanium oxide particles in the sol have good crystallinity having an average particle size in the range of 0.01 to 0.08 μm. Hydrogen chloride is contained in titanium oxide-containing sol, and when a sol is applied to a glass tube and baked to form a thin film, the concentration of hydrogen chloride is high, the transparency of the thin film is reduced, and the chloride generated during calcination is reduced. It is preferable to subject the sol to a dechlorination treatment in advance because hydrogen gas causes problems on the apparatus. 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, for example, a pH of 0.5
-5, preferably pH 2-3.
【００１２】酸化チタン含有ゾルをガラス管に塗布する
場合、塗膜の成膜性をよくするためゾルに溶解する水溶
性高分子の１次結合材をゾルに添加することが好まし
い。水溶性高分子は、特に制限はないがポリビニルアル
コール、メチルセルロース、エチルセルロース、ニトロ
セルロースなどが好適である。その量はゾル中に含有す
る酸化チタンに対し１０重量％以下が適当である。高分
子の添加時期は脱塩素処理の前でもよいが、処理後がよ
り好ましい。このようにして得られた酸化チタン含有ゾ
ルを蛍光ランプ用のガラス管（蛍光ランプとして製品化
される以前の材料としてのガラス管）に塗布するにはガ
ラス管をゾル中に浸漬する方法、ガラス管にゾルをスプ
レーする方法、ゾルを刷毛でガラス管に塗布するなどの
方法が採用される。ゾルの塗布量は厚さにして０．０１
〜０．２ｍｍが適当である。When the sol containing titanium oxide is applied to a glass tube, it is preferable to add a primary binder of a water-soluble polymer dissolved in the sol to the sol in order to improve the film forming property of the coating film. The water-soluble polymer is not particularly limited, but polyvinyl alcohol, methyl cellulose, ethyl cellulose, nitrocellulose and the like are preferable. The amount is suitably not more than 10% by weight based on the titanium oxide contained in the sol. The polymer may be added before the dechlorination treatment, but after the treatment is more preferred. In order to apply the titanium oxide-containing sol thus obtained to a glass tube for a fluorescent lamp (a glass tube as a material before being commercialized as a fluorescent lamp), a method of immersing the glass tube in the sol, A method of spraying a sol on a tube, a method of applying the sol to a glass tube with a brush, and the like are employed. The applied amount of the sol is 0.01
０．２0.2 mm is appropriate.
【００１３】酸化チタンゾルを塗布したガラス管は次に
焼成する。焼成により生成する酸化チタン薄膜の強度が
向上し、またガラス管と薄膜との密着性が向上する。焼
成温度は１００℃以上で効果があるが、好ましくは２０
０℃以上である。焼成温度の上限には特に制限はなく、
ガラス管が変形しない範囲であればよい。一般的には焼
成の上限温度は８００℃位、好ましくは６００℃位であ
る。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。本発明による酸化チタンゾルを用いて製造される酸
化チタン薄膜が高い光触媒能力を示し、かつ透明性も高
いのは、酸化チタンが結晶性であること、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状態であることによると考えら
れる。本発明の蛍光ランプはそのガラス管が前記した特
定の酸化チタン薄膜を有するものである以外は従来のと
変わりはなく、すべての蛍光ランプを対象とすることが
できる。The glass tube coated with the titanium oxide sol is then fired. The strength of the titanium oxide thin film formed by firing is improved, and the adhesion between the glass tube and the thin film is improved. The sintering temperature is effective at 100 ° C. or higher, but is preferably 20 ° C.
0 ° C. or higher. There is no particular upper limit for the firing temperature,
What is necessary is just a range which does not deform | transform a glass tube. Generally, the upper limit temperature of firing is about 800 ° C., preferably about 600 ° C. The firing atmosphere is not particularly limited, and may be in the air. The firing time is not particularly limited, and may be, for example, in the range of 1 to 60 minutes. The thickness of the titanium oxide thin film obtained by firing is about 0.05 to 1.0 μm in the case of the above-mentioned coating amount. The titanium oxide thin film produced by using the titanium oxide sol according to the present invention exhibits high photocatalytic ability and high transparency because the titanium oxide is crystalline and the titanium oxide fine particles are very fine particles. This is considered to be due to the fact that they do not contain impurities and that the titanium oxide fine particles are dispersed as close as possible to the primary particles. The fluorescent lamp of the present invention is the same as the conventional fluorescent lamp except that the glass tube has the above-mentioned specific titanium oxide thin film, and can be applied to all fluorescent lamps.
【００１４】[0014]
【実施例】以下、実施例により具体的に説明する。 実施例１ 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。
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、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。透過型電子顕微鏡
でこの粒子を観察したところ平均粒子径は０．０１５ｎ
ｍ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。このゾルを用いてデ
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。The present invention will be specifically described below with reference to examples. Example 1 Water was added to titanium tetrachloride (purity: 99.9%), and the titanium tetrachloride concentration was 0.25 mol / liter (2 in terms of titanium oxide).
(% By weight). 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 is
Into a reactor equipped with a reflux condenser shown in
(0.4 ° C.) and held for 60 minutes to hydrolyze.
After cooling, residual chlorine generated by the reaction was removed by electrodialysis, and the pH was adjusted to 2. Then, polyvinyl alcohol as a water-soluble polymer was added as a film-forming auxiliary at 0.1% with respect to the content of titanium oxide. Thus, a titanium oxide sol was obtained. This sol was stable, and no sedimentation of the generated titanium oxide fine particles was observed even after one day or more. Observation of these particles using a transmission electron microscope revealed that the average particle size was 0.015 n.
m, and the particles were identified by an X-ray diffractometer. As a result, the particles were crystalline titanium oxide. This sol is applied on a glass plate by dip coating and dried.
Heat treatment was performed at 0 ° C. for 1 hour in the air to obtain a titanium oxide thin film. The thickness of the titanium oxide thin film after the heat treatment was 0.15 μm.
【００１５】実施例２ 水溶性高分子をメチルセルロースに変えた以外は実施例
１と同様にして酸化チタンゾルを作成し、同様に酸化チ
タン薄膜を得た。Example 2 A titanium oxide sol was prepared in the same manner as in Example 1 except that the water-soluble polymer was changed to methyl cellulose, and a titanium oxide thin film was similarly obtained.
【００１６】比較例１ １次粒子径が０．０１μｍであるアモルファスの酸化チ
タン粒子を用い、実施例１と同じ酸化チタン濃度を２重
量％として水に超音波分散器を用いて分散させた。この
際、塩酸を添加してｐＨを実施例１と同じ値にし、さら
に実施例１と同様の操作をして酸化チタンゾルとした。
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は
光触媒能力が認められなかったため、ゾルを再び超音波
分散器で分散させてから実施例１と同じ方法でガラス板
上に成膜し、光触媒能力の評価を行った。Comparative Example 1 Amorphous titanium oxide particles having a primary particle diameter of 0.01 μm were used, and the same titanium oxide concentration as in Example 1 was used at 2% by weight and dispersed in water using an ultrasonic disperser. At this time, hydrochloric acid was added to adjust the pH to the same value as in Example 1, and the same operation as in Example 1 was performed to obtain a titanium oxide sol.
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 again dispersed with an ultrasonic disperser, and then formed on a glass plate in the same manner as in Example 1. An evaluation was performed.
【００１７】比較例２ １次粒子径が０．０５μｍである結晶性の酸化チタン粒
子を用いた以外は比較例１と同様にして酸化チタンゾル
を得た。このゾルも比較例１と同様酸化チタン微粒子の
沈降が認められたので再分散させて成膜した。 成膜の評価 実施例、比較例それぞれの酸化チタンゾルから得た酸化
チタン薄膜の光透過率、光触媒能力及びガラス板との密
着性を測定した。Comparative Example 2 A titanium oxide sol was obtained in the same manner as in Comparative Example 1, except that crystalline titanium oxide particles having a primary particle size of 0.05 μm were used. This sol was redispersed to form a film because precipitation of titanium oxide fine particles was observed as in Comparative Example 1. Evaluation of film formation Light transmittance, photocatalytic ability, and adhesion to a glass plate of a titanium oxide thin film obtained from each of the titanium oxide sols of Examples and Comparative Examples were measured.
【００１８】光透過率の測定方法は、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２に示す。また焼成後
の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３に示す。The light transmittance is measured by setting a titanium oxide thin film formed on a glass plate in a spectrophotometer manufactured by JASCO Corporation and continuously changing the wavelength from 700 to 200 nm. The rate was measured. Then, the light transmittance at 550 nm was represented as the light transmittance in the present invention. Table 1 shows the results. The decomposition method of oxalic acid is to prepare a reaction vessel with a glass plate with a titanium oxide thin film formed,
5 mmol / l oxalic acid was added thereto, and a 100 W mercury lamp was irradiated while blowing oxygen, and the decomposition amount of oxalic acid after 4 hours was determined by redox titration of potassium permanganate. Table 2 shows the results. The adhesion between the fired glass plate and the thin film was determined by a pencil hardness test method and a peeling test method (JIS K5400). Table 3 shows the results.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
【００２１】比較例１においては、酸化チタンの凝集体
がガラス板上に形成され表面が不均一であった。比較例
２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 1, an aggregate of titanium oxide was formed on the glass plate and the surface was uneven. In Comparative Example 2, the evaluation of the photocatalytic ability was not performed because a transparent titanium oxide thin film was not obtained.
【００２２】[0022]
【表３】 [Table 3]
【００２３】[0023]
【発明の効果】本発明の酸化チタンゾルは有機溶媒を全
く含まず溶媒が水であり、これに結晶性の酸化チタン微
粒子を効率よく分散させている。さらに、触媒活性を低
下させるような不純物の含有量も少ないために、成膜し
て得られる酸化チタン薄膜は紫外線吸収による光触媒能
力を有する透明薄膜材料として好適である。また、酸化
チタン薄膜は透明性がよく、かつガラス管との密着性が
よい。従って、この薄膜を蛍光ランプのガラス管に形成
させることによりガラス管の透明性を損なうことなく、
しかも耐久性がよいので長期に亘って光触媒作用により
有機物を分解し汚れを防止することができる。本発明に
おけるゾル組成が基本的に水系であるために成膜時に防
爆設備等の有機成分の除外設備を必要としないために装
置的、経済的に有利である。The titanium oxide sol of the present invention contains no organic solvent and the solvent is water, in which crystalline titanium oxide fine particles are efficiently dispersed. Further, the titanium oxide thin film obtained by forming the film is suitable as a transparent thin film material having a photocatalytic ability by absorbing ultraviolet light because the content of impurities which lowers the catalytic activity is small. Further, the titanium oxide thin film has good transparency and good adhesion to a glass tube. Therefore, by forming this thin film on the glass tube of the fluorescent lamp, without impairing the transparency of the glass tube,
In addition, since it has good durability, organic substances can be decomposed by photocatalysis for a long period of time to prevent contamination. Since the sol composition in the present invention is basically water-based, equipment for eliminating organic components such as explosion-proof equipment is not required at the time of film formation, which is advantageous in terms of equipment and economy.
【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
Claims (7)
ン含有ゾルを生成させて、該ゾルを蛍光ランプ用のガラ
ス管表面に塗布し、焼成して該表面に酸化チタン薄膜を
形成したガラス管を使用することを特徴とする蛍光ラン
プ。1. A method for producing a titanium oxide-containing sol by hydrolysis of titanium tetrachloride, applying the sol to the surface of a glass tube for a fluorescent lamp, and firing the glass tube to form a titanium oxide thin film on the surface. A fluorescent lamp characterized by being used.
ガラス管表面に塗布する請求項１記載の蛍光ランプ。2. The fluorescent lamp according to claim 1, wherein the titanium oxide sol is generated and then dechlorinated and applied to the surface of the glass tube.
である請求項２記載の蛍光ランプ。3. The pH of the sol containing titanium oxide is 0.5 to 5
The fluorescent lamp according to claim 2, wherein
０．０１〜０．０８μｍである請求項１〜３のいずれか
に記載の蛍光ランプ。4. The fluorescent lamp according to claim 1, wherein the titanium oxide particles in the sol have an average particle size of 0.01 to 0.08 μm.
チタン水溶液中の四塩化チタンの濃度が０．０５〜１モ
ル／ｌである請求項１〜４のいずれかに記載の蛍光ラン
プ。5. The fluorescent lamp according to claim 1, wherein the concentration of titanium tetrachloride in the titanium tetrachloride aqueous solution in the hydrolysis of titanium tetrachloride is 0.05 to 1 mol / l.
て行う請求項１〜５のいずれかに記載の蛍光ランプ。6. The fluorescent lamp according to claim 1, wherein the hydrolysis is performed by installing a reflux condenser in the reaction tank.
項１〜６のいずれかに記載の蛍光ランプ。7. The fluorescent lamp according to claim 1, wherein a firing temperature is 100 to 800 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20716596A JP3726366B2 (en) | 1996-08-06 | 1996-08-06 | Fluorescent lamp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20716596A JP3726366B2 (en) | 1996-08-06 | 1996-08-06 | Fluorescent lamp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1053438A true JPH1053438A (en) | 1998-02-24 |
| JP3726366B2 JP3726366B2 (en) | 2005-12-14 |
Family
ID=16535312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20716596A Expired - Fee Related JP3726366B2 (en) | 1996-08-06 | 1996-08-06 | Fluorescent lamp |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3726366B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006506302A (en) * | 2002-09-13 | 2006-02-23 | ショイテン グラースグループ | Fireproof glass unit |
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| JPH01169866A (en) * | 1987-12-25 | 1989-07-05 | Hitachi Ltd | Discharge lamp |
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| JPH0899041A (en) * | 1993-12-09 | 1996-04-16 | Agency Of Ind Science & Technol | Photocatalyst of titanium oxide porous thin film and preparation of the same |
| JPH07232080A (en) * | 1993-12-28 | 1995-09-05 | Toto Ltd | Multifunctional material with photocatalyst function and its preparation |
| JPH08173512A (en) * | 1994-12-27 | 1996-07-09 | Sharp Corp | Deodorizing element |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006506302A (en) * | 2002-09-13 | 2006-02-23 | ショイテン グラースグループ | Fireproof glass unit |
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