JPH06298520A - Production of silica gel containing dispersed ultrafine titanium oxide particle - Google Patents
Production of silica gel containing dispersed ultrafine titanium oxide particleInfo
- Publication number
- JPH06298520A JPH06298520A JP10995493A JP10995493A JPH06298520A JP H06298520 A JPH06298520 A JP H06298520A JP 10995493 A JP10995493 A JP 10995493A JP 10995493 A JP10995493 A JP 10995493A JP H06298520 A JPH06298520 A JP H06298520A
- Authority
- JP
- Japan
- Prior art keywords
- colloid
- titanium oxide
- particles
- alkoxide
- silica gel
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸化チタン超微粒子分
散シリカゲルの製造法に関するものである。さらに詳し
くいえば、本発明は、量子閉じ込め効果を示し、かつ透
明性などの光学特性に優れた酸化チタン超微粒子分散シ
リカゲルを、簡単に効率よく製造する方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing silica gel containing titanium oxide ultrafine particles. More specifically, the present invention relates to a method for easily and efficiently producing titanium oxide ultrafine particle-dispersed silica gel exhibiting a quantum confinement effect and excellent in optical properties such as transparency.
【０００２】[0002]
【従来の技術】近年、半導体超微粒子は量子閉じ込め効
果を示すことが知られ、その三次非線形感受率を増大さ
せることが可能になることも指摘されている。半導体超
微粒子が分散したガラスとしては、主にＣｄＳ‐ＣｄＳ
ｅ微粒子分散ガラス、ＣｕＣｌ微粒子分散ガラスが研究
されているが、酸化物半導体超微粒子が分散した材料に
関しては報告例がほとんど見られず、酸化チタン微粒子
の合成に関する報告も数例しかなく、特に酸化チタン微
粒子をガラスマトリックスに分散させたものは未だ知ら
れていない。2. Description of the Related Art In recent years, it has been known that ultrafine semiconductor particles exhibit a quantum confinement effect, and it has been pointed out that it becomes possible to increase the third-order nonlinear susceptibility thereof. CdS-CdS is mainly used as glass in which ultrafine semiconductor particles are dispersed.
Although fine particle-dispersed glass and CuCl fine particle-dispersed glass have been studied, almost no reports have been found on materials in which ultrafine oxide semiconductor particles are dispersed, and there are only a few reports on the synthesis of titanium oxide fine particles, particularly oxidation. A dispersion of titanium fine particles in a glass matrix has not been known yet.
【０００３】このような超微粒子を分散させた材料を製
造するには、例えばＣｄＳ‐ＣｄＳｅ微粒子分散ガラス
の場合、ガラスにあらかじめ微粒子の成分を仕込んでお
き、ガラス形成後に再び熱処理して微粒子を析出させる
方法などが用いられる。In order to produce such a material in which ultrafine particles are dispersed, for example, in the case of CdS-CdSe fine particle-dispersed glass, glass is preliminarily charged with the components of the fine particles and heat-treated again after the glass is formed to precipitate the fine particles. The method of making it etc. are used.
【０００４】しかしながら、同様な方法で酸化物半導体
微粒子をガラス中に分散させるためには、目的とする結
晶が析出するガラス組成から探索する必要があるし、ま
た、マトリックスとしては、紫外領域まで広い範囲に渡
って透明なシリカが光学的に優れた特性を有しており、
マトリックスとして適当であると考えられるが、ガラス
からの結晶析出法を採った場合、ガラスの組成によって
はマトリックスとして不適当となり、利用範囲が制限さ
れるのを免れない。However, in order to disperse the oxide semiconductor fine particles in the glass by the similar method, it is necessary to search from the glass composition in which the desired crystal is deposited, and the matrix is wide in the ultraviolet region. Transparent silica over the range has optically excellent characteristics,
Although it is considered to be suitable as a matrix, when the crystal precipitation method from glass is adopted, it becomes unsuitable as a matrix depending on the composition of glass, and the range of use cannot be avoided.
【０００５】他方、Ｓｉ微粒子分散シリカガラスを気相
法で製造することも知られているが、シランガスなどの
取り扱いに注意が必要なガスを用いざるを得ないため、
特殊な装置や煩雑な操作を要する。On the other hand, it is also known to produce a silica fine particle-dispersed silica glass by a vapor phase method, but since a gas such as silane gas which requires careful handling must be used,
Requires special equipment and complicated operations.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、このような
従来の量子閉じ込め効果を示す酸化チタン超微粒子の製
造法のもつ欠点を克服し、量子閉じ込め効果を示し、か
つ透明性などの光学特性に優れた酸化チタン超微粒子分
散シリカゲルを簡単に効率よく製造する方法を提供する
ことを目的としてなされたものである。DISCLOSURE OF THE INVENTION The present invention overcomes the disadvantages of the conventional method for producing titanium oxide ultrafine particles exhibiting the quantum confinement effect, exhibits the quantum confinement effect, and has optical characteristics such as transparency. The object of the present invention is to provide a method for easily and efficiently producing excellent titanium oxide ultrafine particle-dispersed silica gel.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、前記した
好ましい特徴を有する酸化チタン超微粒子分散シリカゲ
ルの製造法を開発するために種々研究を重ねた結果、酸
化チタン超微粒子をシリカコロイドに分散し、ゲル化し
たのち、焼成することにより、その目的を達成しうるこ
とを見出し、この知見に基づいて本発明を完成するに至
った。[Means for Solving the Problems] The inventors of the present invention have conducted various studies in order to develop a method for producing silica gel containing titanium oxide ultrafine particles having the above-mentioned preferable characteristics. It was found that the object can be achieved by dispersing, gelling, and then firing, and the present invention has been completed based on this finding.
【０００８】すなわち、本発明は、酸化チタン超微粒子
をシリカコロイドに分散したのち、コロイドをゲル化
し、次いで焼成することを特徴とする酸化チタン超微粒
子分散シリカゲルの製造方法を提供するものである。That is, the present invention provides a method for producing a titanium oxide ultrafine particle-dispersed silica gel, which comprises dispersing the titanium oxide ultrafine particles in a silica colloid, gelling the colloid, and then firing.
【０００９】本発明において用いる酸化チタン超微粒子
は、量子閉じ込め効果を示す程度に微細であればどのよ
うなものでもよい。The titanium oxide ultrafine particles used in the present invention may be any particles as long as they are fine enough to exhibit a quantum confinement effect.
【００１０】このようなものとしては、例えばアルコー
ルで希釈したチタンアルコキシドを強酸性水に少量ずつ
添加する方法で得られる酸化チタンコロイドなどが適当
である。As such a material, for example, a titanium oxide colloid obtained by a method of adding titanium alkoxide diluted with alcohol to strongly acidic water little by little is suitable.
【００１１】このコロイドはｐＨが高くなると凝集しや
すくなるので、コロイド中の水素イオン濃度を１ｍｏｌ
／ｌ以上すなわちｐＨ１以下に調整するのが好ましい。This colloid easily aggregates as the pH increases, so the hydrogen ion concentration in the colloid should be 1 mol.
/ L or more, that is, the pH is preferably adjusted to 1 or less.
【００１２】前記の例示した方法について、さらに説明
する。この方法において用いるアルコールで希釈したチ
タンアルコキシド（以下希釈チタンアルコキシドとい
う）は、通常チタンアルコキシドをその１モルに対し５
〜５０モルのアルコールで希釈することにより調製され
る。このチタンアルコキシドに対するアルコールのモル
比が５未満になると沈殿が生成するし、５０を超えると
コロイド粒子がチタニルイオンに分解する傾向が顕著に
なる。The above exemplified method will be further described. Titanium alkoxide diluted with alcohol (hereinafter referred to as diluted titanium alkoxide) used in this method is usually titanium alkoxide in an amount of 5 mol / mol.
Prepared by diluting with ~ 50 moles alcohol. When the molar ratio of the alcohol to the titanium alkoxide is less than 5, precipitation is generated, and when it exceeds 50, the colloidal particles have a remarkable tendency to decompose into titanyl ions.
【００１３】この際に用いるチタンアルコキシドについ
ては特に制限はないが、例えばチタンイソプロポキシ
ド、チタンプロポキシド、チタンエトキシド、チタンメ
トキシド、チタンブトキシドなど公知のものの中から任
意に選んで使用することができる。There are no particular restrictions on the titanium alkoxide used at this time, but any known one such as titanium isopropoxide, titanium propoxide, titanium ethoxide, titanium methoxide, titanium butoxide may be used. You can
【００１４】また、アルコールについては特に制限はな
いが、例えばエタノール、メタノール、プロパノール、
イソプロパノール、ブタノールなどを用いることができ
る。The alcohol is not particularly limited, but for example, ethanol, methanol, propanol,
Isopropanol, butanol, etc. can be used.
【００１５】また、チタンアルコキシドの希釈度あるい
はチタンアルコキシドの濃度を変えるなどして調整する
ことにより、得られる酸化チタンコロイドの粒子の大き
さを制御することが可能になる。通常、一定の強酸性水
に対し、前記希釈度を小さくするかあるいは前記濃度を
高めると、前記コロイド粒子の粒径を大きくすることが
できる。By adjusting the dilution degree of titanium alkoxide or the concentration of titanium alkoxide, the size of the obtained titanium oxide colloid particles can be controlled. Generally, the particle size of the colloidal particles can be increased by decreasing the dilution degree or increasing the concentration with respect to a certain strongly acidic water.
【００１６】次いで、前記希釈チタンアルコキシドを、
強酸性水に、少量ずつ添加する、すなわち滴下するか、
あるいはゆっくり添加する。この操作によりアルコキシ
ドは加水分解を受け、チタンの水和酸化物が分散した所
望の酸化チタンコロイドが生成する。Next, the diluted titanium alkoxide is added,
Add to the strongly acidic water little by little, i.e. drop by drop,
Or add slowly. By this operation, the alkoxide is hydrolyzed, and a desired titanium oxide colloid in which a hydrated oxide of titanium is dispersed is produced.
【００１７】この際に用いる強酸性水については、その
酸性度は前記希釈チタンアルコキシドの希釈度、希釈に
用いるアルコールの種類、強酸性水に用いる強酸の種類
などにより適宜調整されるが、通常、ｐＨ１以下が選ば
れる。この範囲内では透明性の良好なコロイドが得られ
るが、この範囲を逸脱するとコロイドの透明性が低下し
たり、沈殿を生じる。The acidity of the strongly acidic water used at this time is appropriately adjusted depending on the dilution of the diluted titanium alkoxide, the type of alcohol used for dilution, the type of strong acid used for the strongly acidic water, etc. A pH of 1 or less is selected. Within this range, a colloid with good transparency can be obtained, but if it deviates from this range, the transparency of the colloid will decrease, or precipitation will occur.
【００１８】特に有利には得られるコロイド液のｐＨが
酸化チタンの零電荷点よりも低くなるように調整され
る。Particularly preferably, the pH of the colloidal solution obtained is adjusted to be below the zero charge point of titanium oxide.
【００１９】強酸性水に用いる強酸については特に制限
はないが、通常塩酸、硫酸、硝酸、リン酸などの無機
酸、各種スルホン酸やカルボン酸などの有機酸が挙げら
れる。The strong acid used in the strongly acidic water is not particularly limited, but examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as various sulfonic acids and carboxylic acids.
【００２０】前記希釈チタンアルコキシドの強酸性水へ
の添加速度は、希釈度や酸性度などにより変動するが、
通常、１ｍｌ／分、好ましくは０．８ｍｌ／分の範囲で
選ばれる。Although the rate of addition of the diluted titanium alkoxide to the strongly acidic water varies depending on the degree of dilution and acidity,
Usually, it is selected in the range of 1 ml / min, preferably 0.8 ml / min.
【００２１】本発明に用いるシリカコロイドについては
特に制限はなく、例えばシリコンアルコキシドの加水分
解によって合成したものや、市販のコロイド状シリカな
どが挙げられる。The silica colloid used in the present invention is not particularly limited, and examples thereof include those synthesized by hydrolysis of silicon alkoxide and commercially available colloidal silica.
【００２２】酸化チタン超微粒子のシリカコロイドに対
する使用割合は、通常固形分に基づき、１〜１０重量％
の範囲で選ばれるが、有利には、混合分散させた酸化チ
タンコロイドなどの酸化チタン超微粒子を安定に保つた
めに、シリカコロイドの水素イオン濃度を１ｍｏｌ／ｌ
以上すなわちｐＨ１以下に保つのがよい。The use ratio of titanium oxide ultrafine particles to silica colloid is usually 1 to 10% by weight based on the solid content.
However, in order to keep the titanium oxide ultrafine particles such as titanium oxide colloid mixed and dispersed stably, the hydrogen ion concentration of the silica colloid is preferably 1 mol / l.
It is preferable to keep the pH above 1 or below.
【００２３】本発明においては、このようにして得た分
散物に対し、そのコロイドをゲル化処理する。この処理
は、４０〜６０℃の温度で行うのが好ましい。この温度
が低すぎるとゲル化に時間がかかりすぎるために用いる
酸化チタンコロイドなどの酸化チタン超微粒子によって
はコロイド粒子が成長し過ぎるし、また、高すぎても酸
化チタンコロイドなどの酸化チタン超微粒子が成長しす
ぎてゲルを白濁させるので不適当である。In the present invention, the colloid of the dispersion thus obtained is subjected to gelation treatment. This treatment is preferably performed at a temperature of 40 to 60 ° C. If the temperature is too low, the gelation takes too long, so the colloid particles grow too much depending on the titanium oxide ultrafine particles such as titanium oxide colloid used, and if it is too high, the titanium oxide ultrafine particles such as titanium oxide colloid. Is unsuitable because it grows too much and makes the gel cloudy.
【００２４】本発明においては、次いでゲル化処理物を
通常５００〜１０００℃、好ましくは７５０〜１０００
℃の温度で焼成する。焼成時間は通常３０分〜２時間、
好ましくは３０分〜１時間の範囲で選ばれる。In the present invention, the gelled product is then usually treated at 500 to 1000 ° C., preferably 750 to 1000.
Bake at a temperature of ° C. The firing time is usually 30 minutes to 2 hours,
It is preferably selected in the range of 30 minutes to 1 hour.
【００２５】[0025]
【発明の効果】本発明方法によれば、量子閉じ込め効果
を示し、かつ透明性などの光学特性に優れた酸化チタン
超微粒子分散シリカゲルを、入手容易な原料と電気炉程
度の簡単な設備だけでそれ以上の原料や特殊な装置を必
要とすることなく、簡単に効率よく製造でき、また、酸
化チタン超微粒子を光学的に優れた特性をもつシリカマ
トリックス中に分散しうるという顕著な効果を奏する。According to the method of the present invention, titanium oxide ultrafine particle-dispersed silica gel exhibiting a quantum confinement effect and excellent optical properties such as transparency can be obtained by using easily available raw materials and simple equipment such as an electric furnace. It has a remarkable effect that it can be easily and efficiently produced without the need for further raw materials or special equipment, and that ultrafine titanium oxide particles can be dispersed in a silica matrix having optically excellent characteristics. .
【００２６】本発明方法で得られる酸化チタン超微粒子
分散シリカゲルは、良好な三次非線形感受率を示すと予
想されるので、光メモリや非線形光学材料などのオプト
エレクトロニクス素子用材料としての利用や、また、量
子閉じ込め効果を利用して、例えば光触媒として用いる
と量子効率を増大させうるので、種々の光学材料、電子
材料、化学材料へ応用することができる。Since the titanium oxide ultrafine particle-dispersed silica gel obtained by the method of the present invention is expected to exhibit a good third-order nonlinear susceptibility, it can be used as a material for optoelectronic devices such as optical memories and nonlinear optical materials, and Utilizing the quantum confinement effect, for example, when used as a photocatalyst, the quantum efficiency can be increased, so that it can be applied to various optical materials, electronic materials, and chemical materials.
【００２７】[0027]
【実施例】次に実施例によって本発明をさらに詳細に説
明する。The present invention will be described in more detail with reference to Examples.
【００２８】実施例１ チタンイソプロポキシド４容量部を脱水したエタノール
２０容量部で希釈し、これを２規定の塩酸５０容量部中
に微量定量ポンプで１容量部／分の速度でかきまぜなが
ら滴下して透明な酸化チタンコロイドを得た。Example 1 4 parts by volume of titanium isopropoxide was diluted with 20 parts by volume of dehydrated ethanol, and this was added dropwise to 50 parts by volume of 2N hydrochloric acid while stirring at a rate of 1 part by volume / min with a microvolume metering pump. Thus, a transparent titanium oxide colloid was obtained.
【００２９】別に、テトラエトキシシラン１８ｍｌを特
級エタノール１０ｍｌで希釈し、１規定の硝酸１０ｍｌ
を加えて加水分解し、シリカコロイドを得た。このシリ
カコロイドに、固形分として酸化チタンを１重量％、５
重量％及び１０重量％含むように前記酸化チタンコロイ
ドを混合分散したのち、適当な（蓋付き）容器に流し込
み５０℃に保った恒温槽中に静置してゲル化させ、その
まま乾燥させた。Separately, 18 ml of tetraethoxysilane was diluted with 10 ml of special grade ethanol to obtain 10 ml of 1N nitric acid.
Was added and hydrolyzed to obtain a silica colloid. 1% by weight of titanium oxide was added to this silica colloid as a solid content.
The titanium oxide colloid was mixed and dispersed so as to be contained in an amount of 10% by weight and 10% by weight, poured into an appropriate (with a lid) container, allowed to stand in a thermostat kept at 50 ° C. for gelation, and dried as it was.
【００３０】このようにして得られた透明な乾燥ゲルを
５００〜１０００℃で１時間焼成した。得られた焼成物
を透過電子顕微鏡で観察して直径５ｎｍ程度の酸化チタ
ン微粒子が分散しているのを確認した。また、その可視
紫外吸収スペクトルを測定した結果、その吸収端は３７
０ｎｍ付近にあり、バルクの吸収端が３９０ｎｍにある
のと比べると短波長側に移動していることから、量子閉
じ込め効果が確認された。The transparent dry gel thus obtained was calcined at 500 to 1000 ° C. for 1 hour. The obtained fired product was observed with a transmission electron microscope, and it was confirmed that titanium oxide fine particles having a diameter of about 5 nm were dispersed. In addition, as a result of measuring the visible ultraviolet absorption spectrum, the absorption edge was 37
The quantum confinement effect was confirmed because the absorption edge of the bulk is near 0 nm and the absorption edge of the bulk is moved to the shorter wavelength side compared to that at 390 nm.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安江 和夫 愛知県一宮市荻原町串作1372番地 (72)発明者 宇敷 建一 愛知県名古屋市千種区北千種３丁目２番地 千種東住宅13棟23号 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Yasue 1372, Kushisaku, Ogiwara-cho, Ichinomiya-shi, Aichi (72) Inventor Kenichi Ushiki 3-chome, Chikusa-ku, Nagoya, Aichi 13 13 Chikusa East Housing 13 issue
Claims (4)
分散したのち、コロイドをゲル化し、次いで焼成するこ
とを特徴とする酸化チタン超微粒子分散シリカゲルの製
造方法。1. A method for producing silica gel containing titanium oxide ultrafine particles, which comprises dispersing the titanium oxide ultrafine particles in a silica colloid, gelling the colloid, and then calcining.
求項１記載の製造方法。2. The production method according to claim 1, wherein the pH of the silica colloid is 1 or less.
で行う請求項１又は２記載の製造方法。3. The production method according to claim 1, wherein the gelling of the colloid is performed at a temperature of 40 to 60 ° C.
請求項１、２又は３記載の製造方法。4. The production method according to claim 1, 2 or 3, wherein the firing is performed at a temperature of 500 to 1000 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10995493A JPH085660B2 (en) | 1993-04-13 | 1993-04-13 | Method for producing silica gel containing titanium oxide ultrafine particles dispersed therein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10995493A JPH085660B2 (en) | 1993-04-13 | 1993-04-13 | Method for producing silica gel containing titanium oxide ultrafine particles dispersed therein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06298520A true JPH06298520A (en) | 1994-10-25 |
| JPH085660B2 JPH085660B2 (en) | 1996-01-24 |
Family
ID=14523349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10995493A Expired - Lifetime JPH085660B2 (en) | 1993-04-13 | 1993-04-13 | Method for producing silica gel containing titanium oxide ultrafine particles dispersed therein |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085660B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09227829A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Photocatalytic, hydrophilic coating composition, method for forming hydrophilic coating, and coated article |
| JPH09231821A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Luminaire and method for maintaining illuminance |
| US6013372A (en) * | 1995-03-20 | 2000-01-11 | Toto, Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with superhydrophilic photocatalytic surface, and method of making thereof |
| US6090489A (en) * | 1995-12-22 | 2000-07-18 | Toto, Ltd. | Method for photocatalytically hydrophilifying surface and composite material with photocatalytically hydrophilifiable surface |
| US6165256A (en) * | 1996-07-19 | 2000-12-26 | Toto Ltd. | Photocatalytically hydrophilifiable coating composition |
| EP1070679A1 (en) * | 1999-07-23 | 2001-01-24 | Asahi Glass Company Ltd. | Fine particulate silica gel and fine particulate silical gel internally containing microparticles of a metal compound |
| US6337129B1 (en) | 1997-06-02 | 2002-01-08 | Toto Ltd. | Antifouling member and antifouling coating composition |
| US6524664B1 (en) | 1996-03-21 | 2003-02-25 | Toto Ltd. | Photocatalytically hydrophilifying and hydrophobifying material |
| US6830785B1 (en) | 1995-03-20 | 2004-12-14 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
| JP2005224698A (en) * | 2004-02-12 | 2005-08-25 | Asahi Kasei Chemicals Corp | Photocatalyst member |
| JP2006167594A (en) * | 2004-12-15 | 2006-06-29 | National Institute Of Advanced Industrial & Technology | Crystal structure having periodic structure |
| JP2019048753A (en) * | 2017-09-12 | 2019-03-28 | 富士ゼロックス株式会社 | Silica-titania composite aerogel particle, method for producing silica-titania composite aerogel particle, photocatalyst-forming composition, photocatalyst and structure |
-
1993
- 1993-04-13 JP JP10995493A patent/JPH085660B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6013372A (en) * | 1995-03-20 | 2000-01-11 | Toto, Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with superhydrophilic photocatalytic surface, and method of making thereof |
| US6830785B1 (en) | 1995-03-20 | 2004-12-14 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
| US6090489A (en) * | 1995-12-22 | 2000-07-18 | Toto, Ltd. | Method for photocatalytically hydrophilifying surface and composite material with photocatalytically hydrophilifiable surface |
| JPH09227829A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Photocatalytic, hydrophilic coating composition, method for forming hydrophilic coating, and coated article |
| JPH09231821A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Luminaire and method for maintaining illuminance |
| US6524664B1 (en) | 1996-03-21 | 2003-02-25 | Toto Ltd. | Photocatalytically hydrophilifying and hydrophobifying material |
| US6165256A (en) * | 1996-07-19 | 2000-12-26 | Toto Ltd. | Photocatalytically hydrophilifiable coating composition |
| US6337129B1 (en) | 1997-06-02 | 2002-01-08 | Toto Ltd. | Antifouling member and antifouling coating composition |
| EP1070679A1 (en) * | 1999-07-23 | 2001-01-24 | Asahi Glass Company Ltd. | Fine particulate silica gel and fine particulate silical gel internally containing microparticles of a metal compound |
| US6495257B1 (en) | 1999-07-23 | 2002-12-17 | Asahi Glass Company, Limited | Fine particulate silica gel and fine particulate silica gel internally containing microparticles of a metal compound |
| JP2005224698A (en) * | 2004-02-12 | 2005-08-25 | Asahi Kasei Chemicals Corp | Photocatalyst member |
| JP4520175B2 (en) * | 2004-02-12 | 2010-08-04 | 旭化成ケミカルズ株式会社 | Photocatalyst |
| JP2006167594A (en) * | 2004-12-15 | 2006-06-29 | National Institute Of Advanced Industrial & Technology | Crystal structure having periodic structure |
| JP2019048753A (en) * | 2017-09-12 | 2019-03-28 | 富士ゼロックス株式会社 | Silica-titania composite aerogel particle, method for producing silica-titania composite aerogel particle, photocatalyst-forming composition, photocatalyst and structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH085660B2 (en) | 1996-01-24 |
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