JPH1129316A - Coating solution composition for forming silica film and formation of silica film - Google Patents
Coating solution composition for forming silica film and formation of silica filmInfo
- Publication number
- JPH1129316A JPH1129316A JP21970297A JP21970297A JPH1129316A JP H1129316 A JPH1129316 A JP H1129316A JP 21970297 A JP21970297 A JP 21970297A JP 21970297 A JP21970297 A JP 21970297A JP H1129316 A JPH1129316 A JP H1129316A
- Authority
- JP
- Japan
- Prior art keywords
- silica film
- sugar
- film
- alkoxysilane
- forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5035—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Surface Treatment Of Glass (AREA)
- Silicon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は無機材料表面例えば金
属、ガラス等の表面にシリカ膜を形成させる塗布液組成
物およびシリカ膜形成方法に関する。シリカ膜を形成さ
せることは、無機材料表面を保護、不動態化、絶縁化す
る目的で産業上広く用いられている方法である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating solution composition for forming a silica film on the surface of an inorganic material such as metal or glass, and a method for forming a silica film. Forming a silica film is a method widely used in industry for the purpose of protecting, passivating, and insulating an inorganic material surface.
【０００２】[0002]
【従来の技術】従来、シリカ薄膜は金属ケイ素表面を酸
素で酸化する基板反応法や、クロロシラン類を気相で分
解して無機材料表面に直接シリカ薄膜を形成させるいわ
ゆるＣＶＤ法や、ＳｉまたはＳｉＯ２をターゲットとし
たスパッター法などによって得られていた。また近年、
アルコキシシラン類の加水分解重縮合物のゾル液または
／およびコロイド分散液を無機材料表面に塗布、乾燥、
焼成して薄膜を形成させるいわゆるゾルーゲル法によっ
て得る研究も盛んに行われている。しかしゾルーゲル法
は薄膜形成法としては簡便な方法ではあるものの薄膜形
成条件を厳密に制御しないと透明で緻密な膜が得られな
いこと、一度形成させた乾燥ゲルは除去するのが難しく
即ち塗り直しが出来ないこと、ゾルーゲル液の安定性が
悪く使用可能な保存期間が短いこと、そしてなによりも
厚膜が得られないことなど実用的には多くの問題点が存
在する。またＣＶＤ法は有害なクロロシラン類を使用す
ること、ＣＶＤ法やスパッター法では薄膜形成条件を厳
密に制御しないと良質な膜が得られないなどの欠点を有
する。さらにＣＶＤ法やスパッター法では、高価な成膜
装置を使用し、スループットが遅いので得られた膜のコ
ストが高い等の欠点を有する。2. Description of the Related Art Conventionally, a silica thin film has a substrate reaction method of oxidizing a metal silicon surface with oxygen, a so-called CVD method of decomposing chlorosilanes in a gas phase to form a silica thin film directly on an inorganic material surface, or Si or SiO. 2 was obtained by a sputtering method or the like. In recent years,
A sol or / and colloidal dispersion of a hydrolyzed polycondensate of an alkoxysilane is applied to the surface of an inorganic material, dried,
Research on obtaining a thin film by baking so-called sol-gel method has also been actively conducted. However, although the sol-gel method is a simple method for forming a thin film, it is difficult to obtain a transparent and dense film unless the conditions for forming the thin film are strictly controlled. Practically, there are many problems such as that the sol-gel liquid is not stable, the usable storage period is short, and above all, a thick film cannot be obtained. Further, the CVD method has disadvantages such as the use of harmful chlorosilanes, and the CVD method and the sputtering method cannot obtain a good-quality film unless the conditions for forming the thin film are strictly controlled. Further, the CVD method and the sputtering method have a drawback that an expensive film forming apparatus is used and the throughput is low, so that the cost of the obtained film is high.
【０００３】[0003]
【本発明が解決しようとする課題】本発明の目的は、無
機材料表面に塗布、乾燥、焼成するという極めて簡便な
方法でシリカ膜を形成させることの出来る組成物および
膜形成方法を提供することである。本発明のもう一つの
目的は、安定性が良く保存期間の長い塗布液組成物を提
供することである。本発明のさらにもう一つの目的はシ
リカの厚膜を形成させることの出来る塗布液組成物を提
供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a composition capable of forming a silica film by a very simple method of coating, drying and firing on the surface of an inorganic material, and a method for forming the film. It is. Another object of the present invention is to provide a coating composition having good stability and a long storage period. Still another object of the present invention is to provide a coating composition capable of forming a thick film of silica.
【０００４】[0004]
【課題を解決するための手段】本発明者は安定性が良
く、厚膜を得ることが出来るシリカ膜形成用塗布液につ
いて研究を行ったところ、テトラアルコキシシランなど
のアルコキシシラン類と糖または糖の誘導体の反応生成
物のアルコール溶液がこの目的を満足させることを発見
した。例えば、テトラエトキシシランをエタノール中Ｄ
−グルコースと酸触媒を加えて加熱還流させると、テト
ラエトキシシランとＤ−グルコースが反応した反応生成
物のエタノール溶液が得られる。この溶液は、室温で３
ケ月保存してもゲル化や性能低下を起こさない。この液
をガラス表面にスピン法、デイップ法、流延法などで塗
布し、低温で乾燥した後、５００℃以上の高温で数分焼
成すると透明なシリカ薄膜が得られる。この方法によっ
て透明な８００ｎｍのシリカ厚膜を得ることが出来た。
テトラアルコキシシランを用いたゾルーゲル法コーテイ
ングでは、一般に、一回のコーテイングと焼成で約３０
０ｎｍ以上のシリカ厚膜を形成させようとすると、膜に
クラックが入ったり、不透明化や剥離が起こったりして
透明膜を得るのが難しい（ゾルーゲル法の科学、アグネ
承風社刊）が、本発明の溶液組成物を用いれば透明な厚
膜が簡便に得られる。このことは産業上の利用範囲を大
きく拡大するものである。The inventors of the present invention have studied a coating solution for forming a silica film which has a good stability and can form a thick film. As a result, an alkoxysilane such as tetraalkoxysilane and a sugar or a sugar have been studied. It has been found that an alcoholic solution of the reaction product of a derivative of the above satisfies this purpose. For example, tetraethoxysilane in ethanol in D
When glucose and an acid catalyst are added and the mixture is heated to reflux, an ethanol solution of a reaction product of the reaction of tetraethoxysilane and D-glucose is obtained. This solution is
Does not cause gelation or performance deterioration even after storage for months. This liquid is applied to a glass surface by a spin method, a dipping method, a casting method, or the like, dried at a low temperature, and then fired at a high temperature of 500 ° C. or more for several minutes to obtain a transparent silica thin film. By this method, a transparent 800 nm thick silica film could be obtained.
In the sol-gel coating method using tetraalkoxysilane, generally, a single coating and baking process requires about 30 times.
When trying to form a silica thick film with a thickness of 0 nm or more, it is difficult to obtain a transparent film due to cracks in the film, opacity and peeling (Sol-gel method science, Agne Shofusha), By using the solution composition of the present invention, a transparent thick film can be easily obtained. This greatly expands the industrial application range.
【０００５】本発明の塗布液はつぎのようにして調製す
ることが出来る。即ちエタノールなどのアルコールにグ
ルコース、グルコノラクトンなどの糖または糖の誘導体
を分散させておき、これにテトラエトキシシランなどの
アルコキシシランと硝酸などの酸触媒を加え数時間加熱
還流させる。糖は次第に反応して溶解し、最終的に透明
な溶液になる。このようにして得られた溶液はそれだけ
でシリカ厚膜形成に充分使用できるのであるが、これに
アミンなどの塩基性物質を加えて中和すると膜の透明性
が向上する。液が塩基性になると安定性が損なわれるの
で中性または酸性側に止めるのがよい。また、膜の透明
性を増すために少量の水（例えばケイ素に対して３倍モ
ル以下）の添加が有効である。[0005] The coating solution of the present invention can be prepared as follows. That is, a sugar or a sugar derivative such as glucose or gluconolactone is dispersed in an alcohol such as ethanol, and an alkoxysilane such as tetraethoxysilane and an acid catalyst such as nitric acid are added thereto, followed by heating under reflux for several hours. The sugar gradually reacts and dissolves, eventually resulting in a clear solution. The solution thus obtained can be used by itself for forming a thick silica film. However, when a basic substance such as an amine is added thereto and neutralized, the transparency of the film is improved. If the solution becomes basic, the stability is impaired. Therefore, it is preferable to stop the solution on the neutral or acidic side. It is effective to add a small amount of water (for example, 3 times or less mol based on silicon) to increase the transparency of the film.
【０００６】アルコキシシランと糖または糖の誘導体の
量は、単糖類の場合、糖または糖の誘導体１分子に対し
てアルコキシシラン２分子が反応すると考えられるの
で、この比率を基準に適宜選択できる。二糖類の場合は
糖または糖の誘導体１分子に対してアルコキシシラン４
分子が反応すると考えて良い。このモル比を大幅に越え
た糖を用いると反応に時間がかかるかまたは最終的に糖
がすべて溶解せず透明液が得られない。等モル量より大
幅に少ない糖を用いると未反応のアルコキシシランが残
留し安定性の良い液を得ることが難しい。[0006] The amount of the alkoxysilane and the sugar or sugar derivative can be appropriately selected on the basis of this ratio since it is considered that two molecules of the alkoxysilane react with one molecule of the sugar or sugar derivative in the case of a monosaccharide. In the case of disaccharides, one molecule of a sugar or a derivative of a sugar is alkoxysilane 4 per molecule.
You can think of the molecules as reacting. When a saccharide having a molar ratio greatly exceeding this ratio is used, the reaction takes a long time, or the saccharide is not completely dissolved and a clear liquid cannot be obtained. If a sugar much less than the equimolar amount is used, unreacted alkoxysilane remains, and it is difficult to obtain a liquid having good stability.
【０００７】本発明に使用されるアルコキシシランは、
一般式Ｓｉ（ＯＲ）４（Ｒは炭素数１〜４の低級アルキ
ル基を示す）で示されるアルコキシシランのモノマーま
たはオリゴマーが使用可能であるが、反応速度、液安定
性の点から、テトラメトキシシラン、テトラエトキシシ
ラン、テトライソプロポキシシラン、テトラ−ｎ−プロ
ポキシシラン、テトラ−ｎ−ブトキシシランのモノマー
またはオリゴマーが推奨出来るがこれらに限定されるも
のではない。また、２種以上のアルコキシシランの混合
物を用いることも可能である。アルキル基の炭素数が５
以上のアルコキシシランでは反応性に乏しく取り扱いが
困難である。The alkoxysilane used in the present invention is
An alkoxysilane monomer or oligomer represented by the general formula Si (OR) 4 (R represents a lower alkyl group having 1 to 4 carbon atoms) can be used. However, from the viewpoint of reaction rate and liquid stability, tetramethoxy Monomers or oligomers of silane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, and tetra-n-butoxysilane can be recommended, but are not limited thereto. It is also possible to use a mixture of two or more alkoxysilanes. 5 carbon atoms in the alkyl group
The above alkoxysilanes have poor reactivity and are difficult to handle.
【０００８】本発明で反応溶媒として使用される溶媒は
メタノール、エタノール、ｎ−プロパノール、イソプロ
パノール、ｎ−ブタノール、イソブタノール、ｔ−ブタ
ノールなどの比較的沸点の低い低級アルコールが成膜し
やすさの点から適している。必要に応じてこれらのアル
コールと混和する極性溶媒を併用することは何ら差し支
えない。また、本発明の塗布液の製造に用いられる触媒
は、塩酸、硝酸、硫酸などの無機酸が適している。[0008] The solvent used as a reaction solvent in the present invention is a lower alcohol having a relatively low boiling point such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and t-butanol. Suitable from the point of view. If necessary, a polar solvent miscible with these alcohols may be used in combination. As the catalyst used for producing the coating solution of the present invention, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid are suitable.
【０００９】本発明に用いることの出来る糖は、単糖
類、二糖類から適宜選択して使用出来る。単糖類として
は、グリセロース、エリトロース、トレオース、アラビ
ノース、リボース、リキソース、キシロース、グルコー
ス、マンノース、アロース、アルトロース、タロース、
ガラクトース、イドース、グロースなどのアルドース、
エリツルロース、リブロース、キシルロース、フルクト
ース、プシコース、タガトース、ソルボースなどのケト
ースまたはこれらの環状構造体であるピラノース、フラ
ノース類が挙げられるがこれらに限定されるものではな
い。単糖類の誘導体としては、グルコン酸、グルコノラ
クトン、糖酸、糖酸モノラクトン、グルクロン酸、グル
シトールなどが挙げられるがこれらに限定されるもので
はない。二糖類としてはスクロース、ラクトース、マル
トースなどが挙げられるがこれらに限定されるものでは
ない。三糖類以上の多糖類は加水分解条件下では最終的
に単糖類まで分解されるので使用可能であるが、加水分
解条件を整えるために多量の水を必要とし、また反応時
間が長くなるので多糖類の使用は望ましいことではな
い。例示したこれらの糖類は２種以上の混合物として用
いることが出来る。The saccharide that can be used in the present invention can be appropriately selected from monosaccharides and disaccharides. Monosaccharides include glycerose, erythrose, threose, arabinose, ribose, lyxose, xylose, glucose, mannose, allose, altrose, talose,
Aldose such as galactose, idose, and growth,
Ketoses such as erythrulose, ribulose, xylulose, fructose, psicose, tagatose, and sorbose, or pyranose and furanoses, which are cyclic structures thereof, include, but are not limited to. Monosaccharide derivatives include, but are not limited to, gluconic acid, gluconolactone, sugar acids, sugar acid monolactone, glucuronic acid, glucitol and the like. Examples of the disaccharide include, but are not limited to, sucrose, lactose, and maltose. Polysaccharides higher than trisaccharides can be used because they are finally decomposed to monosaccharides under hydrolysis conditions, but they require a large amount of water to adjust the hydrolysis conditions, and the reaction time is long, so many polysaccharides can be used. The use of sugars is not desirable. These exemplified saccharides can be used as a mixture of two or more.
【００１０】本発明のシリカ膜はつぎのようにして作成
できる。アルコキシシランと糖の反応生成物のアルコー
ル溶液をガラスなどの任意の基板上にスピン法、デイッ
プ法、流延法などの方法で塗布する。用いる基板として
は任意のガラス基板、ＳＵＳ等の金属基板、アルミナ等
のセラミックス基板等が好適である。塗布した後、室温
または１００℃以下の比較的低温で溶媒を蒸発させ透明
膜を得る。これを更に５００℃以上の高温で焼成すると
透明なシリカ膜が得られる。焼成は室温から徐々に昇温
していく焼成法や高温炉に投入する方法あるいはこれら
の組み合わせによる方法があるが、液の組成に応じて任
意の方法を組み合わせることができる。この方法で形成
させたシリカ膜上に更に同様の方法で塗布、乾燥、焼成
し、複数回重ね塗りをすることも出来るが、本発明の大
きな特徴は１回の塗布で厚膜が形成出来ることである。
このようにして得られたシリカ膜は、無機材料表面のア
ンダーコート膜としての不動態膜、トップコート膜とし
ての保護膜として有用なものである。The silica film of the present invention can be prepared as follows. An alcohol solution of a reaction product of an alkoxysilane and a sugar is applied to an arbitrary substrate such as glass by a method such as spinning, dipping, or casting. As a substrate to be used, an arbitrary glass substrate, a metal substrate such as SUS, and a ceramic substrate such as alumina are suitable. After coating, the solvent is evaporated at room temperature or at a relatively low temperature of 100 ° C. or less to obtain a transparent film. When this is further fired at a high temperature of 500 ° C. or more, a transparent silica film is obtained. There is a firing method in which the temperature is gradually raised from room temperature, a method in which the material is put into a high-temperature furnace, or a method based on a combination of these methods. An arbitrary method can be combined according to the composition of the liquid. On the silica film formed by this method, coating, drying and baking can be further performed in the same manner as above, and multiple coatings can be performed. However, a major feature of the present invention is that a thick film can be formed by one coating. It is.
The silica film thus obtained is useful as a passivation film as an undercoat film on the surface of an inorganic material and a protective film as a topcoat film.
【００１１】実施例１ Ｄ−グルコース２１．６ｇをエタノール６４ｇに分散さ
せこれにテトラエトキシシラン２５ｇを加えた。６０％
硝酸２．７６ｇを加え撹拌しながら湯浴上加熱還流し
た。加熱開始後約３時間で殆ど透明になり、更に２時間
加熱還流して透明な液を得た。この液を一夜放置した後
ジ−ｎ−ブチルアミン３．４ｇ（硝酸と等モル）を加え
１時間加熱還流して淡黄色の透明液を得た。得られた液
に水１．２７ｇを加えて更に３時間還流させた。得られ
た液を、洗浄した５ｃｍ角のソーダライムガラスに、５
００ｒｐｍ、６０秒の条件でスピンコートし、１００℃
で３０分乾燥した後５５０℃の電気炉に投入し３０分焼
成した。膜厚８００ｎｍの透明膜が得られた。膜の屈折
率は１．３９であった。Example 1 21.6 g of D-glucose was dispersed in 64 g of ethanol, and 25 g of tetraethoxysilane was added thereto. 60%
2.76 g of nitric acid was added, and the mixture was heated and refluxed on a hot water bath with stirring. It became almost transparent about 3 hours after the start of heating, and was further heated under reflux for 2 hours to obtain a transparent liquid. After leaving this solution to stand overnight, 3.4 g (equimolar to nitric acid) of di-n-butylamine was added, and the mixture was heated under reflux for 1 hour to obtain a pale yellow transparent liquid. 1.27 g of water was added to the obtained liquid, and the mixture was further refluxed for 3 hours. The obtained liquid was added to a washed 5 cm square soda lime glass
Spin coating under the conditions of 00 rpm and 60 seconds, 100 ° C.
After drying for 30 minutes in an electric furnace at 550 ° C., firing was performed for 30 minutes. A transparent film having a thickness of 800 nm was obtained. The refractive index of the film was 1.39.
【００１２】実施例２ Ｄ−グルコース２１．６ｇをエタノール６４ｇに分散さ
せ、これにテトラメトキシシランオリゴマー（重合度約
５）１４ｇを加えた。６０％硝酸２．７６ｇを加え攪拌
しながら湯浴上加熱還流した。加熱開始後約２時間で殆
ど透明になり、更に４時間加熱還流して透明な液を得
た。冷却したのち、この液の半量にジ−ｎ−ブチルアミ
ン１．７ｇを加え約３０分還流させた。得られた液をエ
タノールで２倍に希釈し実施例１と同様に洗浄した５ｃ
ｍ角のソーダライムガラスに、５００ｒｐｍで５秒、２
０００ｒｐｍで６０秒の条件でスピンコートし、１００
℃で３０分プリベークした後５５０℃の電気炉に投入し
３０分焼成した。無色透明なシリカ膜が得られた。膜厚
は約１２０ｎｍで、膜の屈折率は１．４０であった。Example 2 21.6 g of D-glucose was dispersed in 64 g of ethanol, and 14 g of a tetramethoxysilane oligomer (degree of polymerization: about 5) was added thereto. 2.76 g of 60% nitric acid was added, and the mixture was heated and refluxed on a hot water bath with stirring. It became almost transparent about 2 hours after the start of heating, and was further heated under reflux for 4 hours to obtain a transparent liquid. After cooling, 1.7 g of di-n-butylamine was added to half of the liquid, and the mixture was refluxed for about 30 minutes. The obtained liquid was diluted 2-fold with ethanol and washed as in Example 1 5c
For 5 seconds at 500 rpm on soda lime glass
Spin coating at 000 rpm for 60 seconds, 100
After prebaking at 30 ° C. for 30 minutes, it was put into an electric furnace at 550 ° C. and baked for 30 minutes. A colorless and transparent silica film was obtained. The thickness was about 120 nm, and the refractive index of the film was 1.40.
【００１３】実施例３ デルターグルコノラクトン２１．４ｇをエタノール６４
ｇに分散させ、テトラエトキシシラン２５ｇを加えた。
６０％硝酸２．７６ｇを加え撹拌しながら湯浴上加熱還
流した。加熱開始後約３０分で殆ど透明になり、更に５
時間加熱還流して透明な液を得た。この液を一夜放置し
た後ジ−ｎ−ブチルアミン３．４ｇ（硝酸と等モル）、
水１．３ｇを加えさらに３時間還流して淡黄色の透明液
を得た。得られた液について実施例１と同様にスピンコ
ート、プリベーク、焼成したところ欠陥の無い透明膜が
得られた。膜厚は約７２０ｎｍで膜の屈折率は１．３９
であった。Example 3 21.4 g of delta-gluconolactone was added to ethanol 64
g, and 25 g of tetraethoxysilane was added.
2.76 g of 60% nitric acid was added, and the mixture was heated and refluxed on a hot water bath with stirring. Almost 30 minutes after the start of heating, it became almost transparent,
After heating under reflux for a period of time, a clear liquid was obtained. After allowing this solution to stand overnight, 3.4 g of di-n-butylamine (equimolar to nitric acid),
1.3 g of water was added, and the mixture was further refluxed for 3 hours to obtain a pale yellow transparent liquid. The obtained liquid was subjected to spin coating, pre-baking and baking in the same manner as in Example 1 to obtain a transparent film having no defect. The film thickness is about 720 nm and the refractive index of the film is 1.39.
Met.
【００１３】実施例４ エタノール６４ｇ、サッカロース２０．５４ｇ、テトラ
エトキシシラン２５ｇ、６０％硝酸２．７６ｇの混合物
を約６時間加熱還流して透明液を得た。この液にジ−ｎ
−ブチルアミン０．３ｇと水１．３ｇを加えさらに３時
間還流させた。この液をエタノールで２倍に希釈し、流
延法によりガラス上に塗布し、５０℃で１時間乾燥した
後、電気炉に投入し、室温より昇温速度１０℃／１分で
加熱し、５００℃で３０分焼成したところ、膜厚２６０
ｎｍ、屈折率１．３９の透明シリカ膜が得られた。Example 4 A mixture of 64 g of ethanol, 20.54 g of saccharose, 25 g of tetraethoxysilane and 2.76 g of 60% nitric acid was heated under reflux for about 6 hours to obtain a transparent liquid. This solution contains di-n
0.3 g of -butylamine and 1.3 g of water were added, and the mixture was further refluxed for 3 hours. This solution was diluted twice with ethanol, applied to glass by a casting method, dried at 50 ° C. for 1 hour, then put into an electric furnace, and heated from room temperature at a rate of 10 ° C./1 minute, When baked at 500 ° C. for 30 minutes, the film thickness becomes 260
As a result, a transparent silica film having a refractive index of 1.39 nm was obtained.
【００１４】実施例５ エタノール６４ｇにＤ−フルクトース２１．６ｇを分散
させ、テトラエトキシシラン２５ｇ、６０％硝酸２．７
６を加えて約３時間還流させ淡黄色の透明液を得た。ジ
−ｎ−ブチルアミン３ｇと水１．３ｇを加えて、さらに
３時間還流させた。この液をエタノールで２倍に希釈し
て、実施例４と同様にしてガラス基板上にスピンコート
し、乾燥、プリベーク、焼成したところ膜厚約１１０ｎ
ｍ、屈折率１．３７のシリカ膜が得られた。Example 5 21.6 g of D-fructose was dispersed in 64 g of ethanol, 25 g of tetraethoxysilane and 2.7% of 60% nitric acid.
6 was added and refluxed for about 3 hours to obtain a pale yellow transparent liquid. 3 g of di-n-butylamine and 1.3 g of water were added, and the mixture was further refluxed for 3 hours. This solution was diluted twice with ethanol, spin-coated on a glass substrate in the same manner as in Example 4, dried, pre-baked, and baked.
m, and a silica film having a refractive index of 1.37 was obtained.
【００１５】実施例６ 実施例１で得られた塗布液について、洗浄した５ｃｍ角
の石英ガラスに、５００ｒｐｍで５秒、１０００ｒｐｍ
で６０秒の条件でスピンコートし、風乾した後、室温よ
り昇温速度１０℃／１分で加熱し、５００℃に到達した
ところで３０分保持したところ、膜厚１８８ｎｍ、屈折
率１．３９の透明シリカ膜が得られた。到達温度を変え
て同様の実験を行い、下記の物性を持つ焼成膜を得た。 到達温度（℃） 膜厚（ｎｍ） 屈折率 ６００ １８６ １．３９ ７００ １７８ １．３９ ８００ １８０ １．４０ ９００ １８０ １．４０Example 6 The coating solution obtained in Example 1 was applied to a washed 5 cm square quartz glass at 500 rpm for 5 seconds at 1000 rpm.
After spin-coating at 60 ° C. for 60 seconds and air-drying, the substrate was heated from room temperature at a heating rate of 10 ° C./1 minute, and when the temperature reached 500 ° C., it was kept for 30 minutes. A transparent silica film was obtained. The same experiment was performed by changing the ultimate temperature to obtain a fired film having the following physical properties. Ultimate temperature (° C) Film thickness (nm) Refractive index 600 186 1.39 700 178 1.39 800 180 1.40 900 180 1.40
Claims (5)
との反応生成物を成分とし、低級アルコールを主とする
溶媒を用いたシリカ膜作成用塗布液組成物1. A coating liquid composition for forming a silica film, comprising a reaction product of an alkoxysilane and a sugar or a sugar derivative as a component, and using a solvent mainly composed of a lower alcohol.
（Ｒは炭素数１〜４の低級アルキル基を示す）で示され
るアルコキシシランのモノマーまたはオリゴマーである
請求項１記載の塗布液組成物2. An alkoxysilane having the general formula Si (OR) 4
The coating liquid composition according to claim 1, wherein R is a monomer or oligomer of an alkoxysilane represented by the formula (1), wherein R represents a lower alkyl group having 1 to 4 carbon atoms.
導体、二糖類またはその誘導体から選ばれる一種以上で
ある請求項１記載の塗布液組成物3. The coating composition according to claim 1, wherein the sugar or the sugar derivative is at least one selected from a monosaccharide or a derivative thereof, and a disaccharide or a derivative thereof.
ル、アセタール、グルコシド、酸またはラクトンである
請求項１乃至請求項３に係わる塗布液組成物4. The coating liquid composition according to claim 1, wherein the sugar derivative is a sugar alcohol, acetal, glucoside, acid or lactone derived from sugar.
の反応生成物の溶液を主成分とするシリカ膜作成用塗布
液組成物を基板上に塗布した後、乾燥、焼成することに
よるシリカ膜作成方法5. A method for preparing a silica film by applying a coating solution composition for preparing a silica film mainly comprising a solution of a reaction product of an alkoxysilane and a sugar or a sugar derivative on a substrate, followed by drying and firing. Method
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21970297A JPH1129316A (en) | 1997-07-09 | 1997-07-09 | Coating solution composition for forming silica film and formation of silica film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21970297A JPH1129316A (en) | 1997-07-09 | 1997-07-09 | Coating solution composition for forming silica film and formation of silica film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1129316A true JPH1129316A (en) | 1999-02-02 |
Family
ID=16739635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21970297A Pending JPH1129316A (en) | 1997-07-09 | 1997-07-09 | Coating solution composition for forming silica film and formation of silica film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1129316A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004085313A1 (en) * | 2003-03-25 | 2004-10-07 | Organization Of Shinshu University | Silicon dioxide thin-film and method of manufacturing the same |
| JP2013505195A (en) * | 2009-09-23 | 2013-02-14 | エフエエフ ケミカルズ アクティーゼルスカブ | Preparation of mesoporous and macroporous silica gel |
-
1997
- 1997-07-09 JP JP21970297A patent/JPH1129316A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004085313A1 (en) * | 2003-03-25 | 2004-10-07 | Organization Of Shinshu University | Silicon dioxide thin-film and method of manufacturing the same |
| JP2013505195A (en) * | 2009-09-23 | 2013-02-14 | エフエエフ ケミカルズ アクティーゼルスカブ | Preparation of mesoporous and macroporous silica gel |
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