JPH09249673A - Aqueous solution for forming silica coating membrane and formation of silica coating membrane - Google Patents
Aqueous solution for forming silica coating membrane and formation of silica coating membraneInfo
- Publication number
- JPH09249673A JPH09249673A JP6089396A JP6089396A JPH09249673A JP H09249673 A JPH09249673 A JP H09249673A JP 6089396 A JP6089396 A JP 6089396A JP 6089396 A JP6089396 A JP 6089396A JP H09249673 A JPH09249673 A JP H09249673A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- forming
- silica coating
- alkali
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液相での堆積法に
よりシリカ被膜を形成する際に用いる、新規なシリカ被
膜形成用水溶液、及び該水溶液によるシリカ被膜の形成
方法に関する。TECHNICAL FIELD The present invention relates to a novel aqueous solution for forming a silica coating used when forming a silica coating by a liquid phase deposition method, and a method for forming a silica coating using the aqueous solution.
【０００２】さらに詳しくは、取扱いが簡単で、基材を
選ぶことなく、簡便な方法でかつ均一なシリカ被膜を形
成することが可能なシリカ被膜形成用水溶液、及び該水
溶液を用いたシリカ被膜の形成方法に関する。本発明の
水溶液を用いて作成したシリカ被膜は、各種絶縁膜、保
護膜等に利用できる。More specifically, an aqueous solution for forming a silica film, which is easy to handle and is capable of forming a uniform silica film by a simple method without selecting a base material, and a silica film using the aqueous solution. It relates to a forming method. The silica coating formed using the aqueous solution of the present invention can be used as various insulating films, protective films, and the like.
【０００３】[0003]
【従来の技術】従来、各種絶縁膜、保護膜などに用いら
れるシリカ被膜を形成する方法として、アルコキシシラ
ンを酸触媒下で加水分解した溶液を塗布乾燥後、焼成す
る方法が一般に行われている（例えば特開昭５６−３８
４７２等）。しかし、この塗布法には、付き回り性、乾
燥収縮による割れの発生、基材との密着性等に問題があ
ると言われている。2. Description of the Related Art Conventionally, as a method for forming a silica film used for various insulating films, protective films, and the like, a method in which a solution obtained by hydrolyzing an alkoxysilane in the presence of an acid catalyst is applied, dried, and fired is generally performed. (For example, Japanese Patent Application Laid-Open No.
472 etc.). However, it is said that this coating method has problems in throwing power, cracking due to drying shrinkage, adhesion to a substrate, and the like.
【０００４】近年、この塗布法の問題点を解決するため
に、液相での堆積法によるシリカ被膜の形成方法が種々
試みられている。例えば、二酸化珪素を過飽和状態ま
で溶解したケイフッ酸水溶液に基材を浸漬し、溶液中で
シリカ被膜を堆積形成する方法（特開昭５７−１９６７
４４等）、疎水性官能基を有するアルコキシシランを
加水分解しシリカ系被膜を形成する方法（特開平７−１
９６３４２）、気化したテトラエトキシシランを炭酸
アンモニウムを溶解した水中に流通し、シリカ被膜を形
成する方法（’９５春期応用物理学会予稿集）等が挙げ
られる。In recent years, in order to solve the problems of the coating method, various methods of forming a silica coating film by a liquid phase deposition method have been tried. For example, a method of dipping a substrate in an aqueous solution of silicofluoric acid in which silicon dioxide is dissolved to a supersaturated state and depositing and forming a silica film in the solution (Japanese Patent Laid-Open No. 1967/1982).
44), and a method of hydrolyzing an alkoxysilane having a hydrophobic functional group to form a silica-based coating (JP-A-7-1).
96342), a method in which vaporized tetraethoxysilane is circulated in water in which ammonium carbonate is dissolved to form a silica film ('95 Spring Applied Physics Society Proceedings).
【０００５】しかし、これらの方法にはそれぞれ以下に
示すような問題がある。の方法は溶液にフッ酸が含ま
れるため、溶液の取扱いが難しく、また、フッ酸の腐食
性の点で基材が極めて限定される。の方法は、堆積膜
中に炭素やフッ素が混入し、これらを除去するためには
高温での焼成が必要となる。の方法は、液中に沈澱が
生ずる条件でのみ、被膜の形成が行われる事が示されて
いる。しかし、液中に沈澱が存在すると、堆積した膜中
にその粒子が取り込まれて膜の均一性が損なわれたりす
る等の問題が生じる。However, each of these methods has the following problems. In the method (1), since the solution contains hydrofluoric acid, it is difficult to handle the solution, and the base material is extremely limited in terms of corrosiveness of hydrofluoric acid. In the method (1), carbon and fluorine are mixed in the deposited film, and baking at high temperature is required to remove them. It has been shown that the method of (1) forms a film only under the condition that precipitation occurs in the liquid. However, the presence of precipitates in the liquid causes problems such as the inclusion of particles in the deposited film, impairing the uniformity of the film.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記のよう
なシリカ被膜の形成法の種々の問題点を解決することを
目的とするものである。すなわち、腐食性がなく、取扱
いが簡単で、基材を選ぶことなく、焼成することなしに
簡便な方法でかつ均一なシリカ被膜を形成することが可
能な、新規なシリカ被膜形成用水溶液、及び該水溶液を
用いたシリカ被膜の形成方法を提供することを目的とす
るものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the various problems of the above-mentioned method for forming a silica coating. That is, a novel aqueous solution for forming a silica film, which is not corrosive, is easy to handle, can form a uniform silica film by a simple method without selecting a substrate and without firing, and It is an object of the present invention to provide a method for forming a silica coating film using the aqueous solution.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の目
的を達成するために、鋭意検討した結果、特定のシリカ
源、及びアルカリを含むことを特徴とする、新規なシリ
カ被膜形成用水溶液を見い出し、発明の完成に至った。DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, have a specific silica source and an alkali for forming a novel silica coating film. He found an aqueous solution and completed the invention.
【０００８】すなわち、シリカ源としてテトラエトキシ
シラン、及びアルカリとしてアンモニア、有機アルカ
リ、無機酸及び／または有機酸のアンモニウム塩、また
は有機酸及び／または無機酸の有機アルカリ塩の中から
選ばれる、少なくとも１種類以上のものを含むことを特
徴とする、新規なシリカ被膜形成用水溶液である。That is, at least one selected from tetraethoxysilane as a silica source, ammonia as an alkali, an organic alkali, an ammonium salt of an inorganic acid and / or an organic acid, or an organic alkali salt of an organic acid and / or an inorganic acid. It is a novel aqueous solution for forming a silica film, which contains one or more kinds of substances.
【０００９】本発明による、新規なシリカ被膜形成用水
溶液は、その液中に沈殿を生じることなくシリカ被膜の
形成が可能であることから、粒子の付着により膜の均一
性が損なわれることがない。さらに、フッ酸を含まない
ことから腐食性もなく、従って取扱いが簡単で基材を選
ぶこともない。Since the novel aqueous solution for forming a silica film according to the present invention can form a silica film without causing precipitation in the solution, the adhesion of particles does not impair the uniformity of the film. . Furthermore, since it does not contain hydrofluoric acid, it is not corrosive, and therefore it is easy to handle and there is no need to select a substrate.
【００１０】以下、本発明のシリカ被膜形成用水溶液に
関して説明する。本発明の水溶液に用いられるシリカ源
としてのテトラエトキシシランには、特に制限はなく、
工業用、あるいは試薬として広く一般に用いられている
ものでよいが、好ましくはより高純度のものが適してい
る。The aqueous silica film-forming solution of the present invention will be described below. The tetraethoxysilane as a silica source used in the aqueous solution of the present invention is not particularly limited,
Although it may be one that is widely used in industry or as a reagent, one having a higher purity is preferable.
【００１１】添加するテトラエトキシシランの量に特に
制限はないが、好ましくはケイ素濃度として０．００２
〜０．０２モル／リットル、さらに好ましくは０．００
５〜０．０１モル／リットルの範囲である。ケイ素濃度
が、０．００２モル／リットル未満ではシリカ被膜の堆
積速度がきわめて遅く実用的ではない。また、０．０２
モル／リットル以上では溶液中に沈殿が生成する場合が
ある。The amount of tetraethoxysilane to be added is not particularly limited, but preferably 0.002 as the silicon concentration.
~ 0.02 mol / liter, more preferably 0.00
It is in the range of 5 to 0.01 mol / liter. When the silicon concentration is less than 0.002 mol / liter, the deposition rate of the silica coating is very slow and not practical. Also, 0.02
If it is more than mol / liter, a precipitate may be formed in the solution.
【００１２】ケイ素濃度は、テトラエトキシシランの添
加量より算出できるが、水溶液を原子吸光分析により測
定することもできる。測定は、ケイ素の波長251.6nm の
スペクトルを分析線とし、フレームは、アセチレン／亜
酸化窒素によるものを用いるとよい。The silicon concentration can be calculated from the amount of tetraethoxysilane added, but it can also be measured by atomic absorption spectrometry of the aqueous solution. For the measurement, it is advisable to use a spectrum of silicon at a wavelength of 251.6 nm as an analysis line and use a frame of acetylene / nitrous oxide as a frame.
【００１３】本発明の水溶液に用いられるアルカリに
は、アンモニア、有機アルカリ、無機酸及び／または有
機酸のアンモニウム塩、または無機酸及び／または有機
酸の有機アルカリ塩等が挙げられる。Examples of the alkali used in the aqueous solution of the present invention include ammonia, organic alkalis, ammonium salts of inorganic acids and / or organic acids, organic alkali salts of inorganic acids and / or organic acids, and the like.
【００１４】アルカリの具体例としては、アンモニアの
他に、有機アルカリとしては、モノメチルアミン、ジメ
チルアミン、トリメチルアミン、モノエチルアミン、ジ
エチルアミン、トリエチルアミン、ピリジン、アニリ
ン、コリン、テトラメチルアンモニウムハイドロオキサ
イド、グアニジン等が挙げられる。Specific examples of alkali include, in addition to ammonia, organic alkalis such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, pyridine, aniline, choline, tetramethylammonium hydroxide and guanidine. Can be mentioned.
【００１５】また、無機酸のアンモニウム塩としては、
炭酸アンモニウム、炭酸水素アンモニウム、ホウ酸アン
モニウム、リン酸アンモニウム等が、有機酸のアンモニ
ウム塩としては、ギ酸アンモニウム、酢酸アンモニウ
ム、プロピオン酸アンモニウム、乳酸アンモニウム、安
息香酸アンモニウム、シュウ酸アンモニウム、コハク酸
アンモニウム、酒石酸アンモニウム、フタル酸アンモニ
ウム等が挙げられる。As the ammonium salt of inorganic acid,
Ammonium carbonate, ammonium hydrogen carbonate, ammonium borate, ammonium phosphate and the like, ammonium salts of organic acids, ammonium formate, ammonium acetate, ammonium propionate, ammonium lactate, ammonium benzoate, ammonium oxalate, ammonium succinate, Examples thereof include ammonium tartrate and ammonium phthalate.
【００１６】さらに、有機酸の有機アルカリ塩として
は、ギ酸モノメチルアミン、酢酸ジメチルアミン、乳酸
ピリジン、グアニジノ酢酸、酢酸アニリンなどが挙げら
れる。Examples of the organic alkali salts of organic acids include monomethylamine formate, dimethylamine acetate, pyridine lactate, guanidinoacetic acid, aniline acetate and the like.
【００１７】アルカリは、これらの内一種を単独でも、
また二種以上を組み合わせて用いても良い。Alkali may be one of these alone,
Moreover, you may use it in combination of 2 or more type.
【００１８】アルカリの添加量に特に制限はないが、水
溶液のｐＨが７．１〜１０．０の範囲にすることが好ま
しい。さらに好ましくは、ｐＨ７．５〜９．５の範囲で
ある。この範囲外では、被膜が形成されないか、または
成膜速度が極めて低く実用的でない。ｐＨの測定は、ｐ
Ｈメーターを用いると、簡便に、精度が高い測定ができ
る。例えば、メトラー社製ＤＥＬＴＡ３５０型ｐＨメー
ター（内部電極：Ａｇ／ＡｇＣｌ、内部電解液ＫＯＨ）
を用いる。測定は、水溶液の温度を２０℃で行う。The amount of alkali added is not particularly limited, but the pH of the aqueous solution is preferably in the range of 7.1 to 10.0. More preferably, it is in the range of pH 7.5 to 9.5. Outside this range, no film is formed or the film formation rate is extremely low, which is not practical. pH is measured by p
The use of the H meter enables simple and highly accurate measurement. For example, METTLER DELTA350 pH meter (internal electrode: Ag / AgCl, internal electrolyte KOH)
Is used. The measurement is performed at a temperature of the aqueous solution of 20 ° C.
【００１９】前記のテトラエトキシシランとアルカリを
水溶液中で混合すると、テトラエトキシシランの一部は
加水分解され、Ｓｉ−ＯＨ結合を持つ化合物になる。こ
の、Ｓｉ−ＯＨ結合を持つ化合物は、更に反応し、Ｓｉ
−Ｏ−Ｓｉ結合を持つ縮重合体が生成する。本発明のシ
リカ被膜形成用水溶液には、原料であるテトラエトキシ
シランとアルカリ以外に、これらの反応生成物も含む。When the above-mentioned tetraethoxysilane and alkali are mixed in an aqueous solution, a part of the tetraethoxysilane is hydrolyzed to be a compound having a Si-OH bond. This compound having a Si-OH bond is further reacted to produce Si.
A condensation polymer having an —O—Si bond is formed. The aqueous solution for forming a silica film of the present invention contains not only tetraethoxysilane as a raw material and an alkali but also a reaction product of these.
【００２０】本発明に用いる水は、特に限定しないが、
好ましくは濾過等により粒子を除去した水、さらに好ま
しくは、粒子除去に加え、イオン樹脂で処理する等し
て、金属イオンを除去した水を用いると良い。The water used in the present invention is not particularly limited, but
It is preferable to use water from which particles have been removed by filtration or the like, and more preferably water from which metal ions have been removed by treating with an ionic resin in addition to removing particles.
【００２１】本発明のシリカ被膜形成用水溶液の調製
は、一般的な水溶液調製法で出来る。例えば、所定のｐ
Ｈ値を示すよう水にアルカリを溶解し、テトラエトキシ
シランを添加する、等が挙げられるが、これらの混合の
順番は何れが先でも、被膜形成が可能である。The silica coating film forming aqueous solution of the present invention can be prepared by a general aqueous solution preparation method. For example, given p
It is possible to dissolve an alkali in water and add tetraethoxysilane so as to show an H value, and the like, but the coating can be formed regardless of the order of mixing these.
【００２２】次いで、本発明のシリカ被膜形成用水溶液
を用いた、シリカ被膜の形成法について説明する。Next, a method for forming a silica coating using the aqueous solution for forming a silica coating of the present invention will be described.
【００２３】シリカ被膜形成用水溶液をあらかじめ調製
しておき、その中に基材を投入してシリカ被膜を形成す
る方法、基材を容器に入れておき、シリカ被膜形成用水
溶液をそこで調製する方法、等が挙げられるが、シリカ
被膜形成用水溶液の原料、基材を投入する順番は、いず
れが先でも被膜形成が可能である。A method of preparing an aqueous solution for forming a silica coating in advance and then adding a substrate therein to form a silica coating, or placing the substrate in a container and preparing an aqueous solution for forming a silica coating therein. , Etc., but the order of adding the raw material of the aqueous solution for forming a silica coating and the base material can be such that the coating can be formed first.
【００２４】シリカ被膜は堆積により成長するので、基
本的には、成膜時間を長くすれば膜厚を厚くできる。し
かし、シリカ被膜形成用水溶液中のテトラエトキシシラ
ン及びその反応生成物が、被膜の形成により大部分消費
された場合には、成膜速度は著しく低下する。連続した
被膜堆積は、テトラエトキシシランを、前記ケイ素濃度
範囲になるように、経時的に添加することにより達成で
きる。Since the silica coating grows by deposition, basically the film thickness can be increased by increasing the film formation time. However, when the tetraethoxysilane and its reaction product in the aqueous silica film-forming solution are mostly consumed by the film formation, the film formation rate is significantly reduced. Continuous film deposition can be achieved by adding tetraethoxysilane over time so that the above silicon concentration range is achieved.
【００２５】被膜形成中の水溶液の温度は、特に限定し
ないが、好ましくは１０〜９０℃の範囲、より好ましく
は、２０〜６０℃の範囲で成膜を行う。成膜温度が高い
ほど、成膜速度が上昇するが、温度が高すぎると水溶液
の組成を一定に保つことが困難になる。The temperature of the aqueous solution during film formation is not particularly limited, but film formation is preferably carried out in the range of 10 to 90 ° C, more preferably 20 to 60 ° C. The higher the film forming temperature, the higher the film forming rate, but if the temperature is too high, it becomes difficult to keep the composition of the aqueous solution constant.
【００２６】シリカ被膜の成膜に用いることのできる基
材としては、金属、セラミックス、プラスチック、炭素
等が挙げられる。これらの基材は、必要に応じて事前に
表面を処理することもできる。Examples of the base material that can be used for forming the silica coating film include metals, ceramics, plastics and carbon. The surface of these substrates can be treated in advance if necessary.
【００２７】本発明により形成したシリカ被膜は、特に
焼成の必要はない。もちろん、焼成して用いることも可
能である。The silica coating formed according to the present invention does not need to be fired. Of course, it is also possible to use it after firing.
【００２８】[0028]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明を限定するものではない。The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.
【００２９】（実施例１）100CC ビーカーに水50ミリリ
ットルを入れ、マグネチックスターラーで撹拌しなが
ら、テトラエトキシシラン（ナカライテスク製）を0.00
045 モル加え、アルカリとして炭酸水素アンモニウム0.
032 モルを加え、均一に溶解し水溶液１を調製した。調
製は20℃にて行い、調製後の水溶液１のｐＨは8.0 であ
った。また、溶液状態は、目視で確認した。水溶液１
に、基材としてシリコンウエハー（20℃にてアセトン中
で5 分間超音波洗浄し、膜厚測定用に部分的にマスクし
たもの）を浸漬し、組成物温度20℃にて、17時間保持
し、成膜を行った。成膜中溶液は透明で沈澱の生成は観
察されなかった。その後、基材を取り出し、流水で5 分
間洗浄した後、乾燥空気を吹き付け乾燥した。生成した
膜の膜厚を段差計（SLOAN 製DEKTAK3030）により測定し
たところ30nmであった。(Example 1) 50 ml of water was put into a 100 CC beaker and 0.004 of tetraethoxysilane (manufactured by Nacalai Tesque) was added while stirring with a magnetic stirrer.
Add 045 mol and add ammonium hydrogen carbonate as an alkali.
Aqueous solution 1 was prepared by adding 032 mol and uniformly dissolving it. The preparation was carried out at 20 ° C., and the pH of the aqueous solution 1 after preparation was 8.0. The solution state was visually confirmed. Aqueous solution 1
A silicon wafer (which was ultrasonically cleaned in acetone at 20 ° C for 5 minutes and partially masked for film thickness measurement) was immersed in the substrate, and the composition was kept at 20 ° C for 17 hours. Then, a film was formed. During the film formation, the solution was transparent and no precipitation was observed. Then, the substrate was taken out, washed with running water for 5 minutes, and then dried by blowing dry air. The thickness of the formed film was 30 nm when measured with a step meter (DEKTAK3030 manufactured by SLOAN).
【００３０】（実施例２〜７）実施例１と同様に、表１
に記載したアルカリを用いて、水溶液２〜７を調製し
た。次いで、水溶液１と同様に、前処理した基材を浸漬
し、成膜を行った。膜厚の測定結果を表２に記載する。(Examples 2 to 7) As in Example 1, Table 1
Aqueous solutions 2 to 7 were prepared using the alkali described in 1. Then, as in the case of the aqueous solution 1, the pretreated substrate was dipped to form a film. Table 2 shows the measurement results of the film thickness.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】（比較例１）実施例１のテトラエトキシシ
ランに変えて、テトラメトキシシランを用い、水溶液８
を調製した。しかし、水溶液８は沈殿が発生したため、
成膜は行わなかった。Comparative Example 1 Tetramethoxysilane was used in place of the tetraethoxysilane of Example 1, and an aqueous solution 8
Was prepared. However, since the aqueous solution 8 has precipitated,
No film was formed.
【００３４】（実施例８）実施例１の水溶液１と全く同
様の組成の水溶液を、調製及び基板浸漬中の温度を60℃
として、成膜を行った。膜厚の測定結果を表２に記載す
る。Example 8 An aqueous solution having exactly the same composition as the aqueous solution 1 of Example 1 was prepared and the temperature during the substrate immersion was 60 ° C.
Then, a film was formed. Table 2 shows the measurement results of the film thickness.
【００３５】被膜評価 実施例１〜８で得られた、基材上の被膜を透過法赤外吸
収スペクトル（日本分光製FT-IR-8000）を測定したとこ
ろ、1000〜1100ｃｍ-1にＳｉ−Ｏ−Ｓｉ伸縮振動由来の
吸収が観測され、2800〜3000ｃｍ-1にＣ−Ｈ伸縮振動由
来の吸収は観測されず、生成した被膜はシリカに同定さ
れた。 Coating Evaluation The coatings on the substrates obtained in Examples 1 to 8 were measured by a transmission infrared absorption spectrum (FT-IR-8000 manufactured by JASCO Corporation) to find that Si-at 1000 to 1100 cm -1 . Absorption due to O—Si stretching vibration was observed, absorption due to C—H stretching vibration was not observed at 2800 to 3000 cm −1 , and the formed film was identified as silica.
【００３６】[0036]
【発明の効果】本発明により、腐食性がなく、取扱いが
簡単で、基材を選ぶことなく、焼成することなしに簡便
な方法で、かつ均一なシリカ被膜を形成することが可能
な、新規なシリカ被膜形成用水溶液、及び該水溶液を用
いたシリカ被膜の形成方法を提供できる。これにより、
従来からのシリカ被膜の形成方法の問題点が解決でき
る。Industrial Applicability According to the present invention, it is possible to form a uniform silica coating without corrosiveness, easy handling, a simple method without selecting a substrate and without firing. An aqueous solution for forming a silica coating and a method for forming a silica coating using the aqueous solution can be provided. This allows
It is possible to solve the problems of conventional methods for forming a silica coating.
Claims (4)
含むことを特徴とするシリカ被膜形成用水溶液。1. An aqueous solution for forming a silica coating, which contains tetraethoxysilane and an alkali.
イ素濃度が０．００２〜０．０２モル／リットルである
請求項１記載のシリカ被膜形成用水溶液。2. The aqueous solution for forming a silica film according to claim 1, which has a pH of 7.1 to 10.0 and a silicon concentration of 0.002 to 0.02 mol / liter.
リ、無機酸及び／または有機酸のアンモニウム塩、また
は無機酸及び／または有機酸の有機アルカリ塩の中から
選ばれる、少なくとも１種類以上のものである事を特徴
とする、請求項１または２記載のシリカ被膜形成用水溶
液。3. The alkali is at least one selected from ammonia, organic alkalis, ammonium salts of inorganic acids and / or organic acids, or organic alkali salts of inorganic acids and / or organic acids. The aqueous solution for forming a silica film according to claim 1 or 2, characterized in that.
形成用水溶液に、基材を接触させることを特徴とするシ
リカ被膜の形成方法。4. A method for forming a silica coating, which comprises bringing a substrate into contact with the aqueous solution for forming a silica coating according to claim 1, 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6089396A JPH09249673A (en) | 1996-03-18 | 1996-03-18 | Aqueous solution for forming silica coating membrane and formation of silica coating membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6089396A JPH09249673A (en) | 1996-03-18 | 1996-03-18 | Aqueous solution for forming silica coating membrane and formation of silica coating membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09249673A true JPH09249673A (en) | 1997-09-22 |
Family
ID=13155501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6089396A Pending JPH09249673A (en) | 1996-03-18 | 1996-03-18 | Aqueous solution for forming silica coating membrane and formation of silica coating membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09249673A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039903A1 (en) * | 2002-10-31 | 2004-05-13 | Catalysts & Chemicals Industries Co., Ltd. | Coating liquid for forming amorphous silica coating film of low dielectric constant and process for producing the coating liquid |
| US6875262B1 (en) | 1998-05-26 | 2005-04-05 | Tokyo Ohka Kogyo Co., Ltd. | Silica-based coating film on substrate and coating solution therefor |
| JP2007070494A (en) * | 2005-09-07 | 2007-03-22 | Neos Co Ltd | Silicon-containing transparent aqueous liquid |
| WO2013001975A1 (en) * | 2011-06-29 | 2013-01-03 | 信越化学工業株式会社 | Inorganic hydrophilic coating solution, hydrophilic coating film obtained therefrom, and member using same |
-
1996
- 1996-03-18 JP JP6089396A patent/JPH09249673A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6875262B1 (en) | 1998-05-26 | 2005-04-05 | Tokyo Ohka Kogyo Co., Ltd. | Silica-based coating film on substrate and coating solution therefor |
| US7135064B2 (en) | 1998-05-26 | 2006-11-14 | Tokyo Ohka Kogyo Co., Ltd. | Silica-based coating film on substrate and coating solution therefor |
| WO2004039903A1 (en) * | 2002-10-31 | 2004-05-13 | Catalysts & Chemicals Industries Co., Ltd. | Coating liquid for forming amorphous silica coating film of low dielectric constant and process for producing the coating liquid |
| JP2007070494A (en) * | 2005-09-07 | 2007-03-22 | Neos Co Ltd | Silicon-containing transparent aqueous liquid |
| WO2013001975A1 (en) * | 2011-06-29 | 2013-01-03 | 信越化学工業株式会社 | Inorganic hydrophilic coating solution, hydrophilic coating film obtained therefrom, and member using same |
| CN103635543A (en) * | 2011-06-29 | 2014-03-12 | 信越化学工业株式会社 | Inorganic hydrophilic coating solution, hydrophilic coating film obtained therefrom, and member using same |
| JPWO2013001975A1 (en) * | 2011-06-29 | 2015-02-23 | 信越化学工業株式会社 | Inorganic hydrophilic coating liquid, hydrophilic coating obtained therefrom and member using the same |
| US10377904B2 (en) | 2011-06-29 | 2019-08-13 | Shin-Etsu Chemical Co., Ltd. | Inorganic hydrophilic coating solution, hydrophilic coating film obtained therefrom, and member using same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0128697B1 (en) | Indium tin oxide sol compositions | |
| US5132140A (en) | Process for depositing silicon dioxide films | |
| EP0410564A2 (en) | Metastable silane hydrolyzate solutions and process for their preparation | |
| US5871558A (en) | Process for producing silica glass | |
| JP3320440B2 (en) | Coating liquid for film formation and method for producing the same | |
| JP3163579B2 (en) | Coating liquid for film formation | |
| JPH01301514A (en) | Production of oxide thin film | |
| Ohya et al. | Preparation and characterization of titania thin films from aqueous solutions | |
| JPH09249673A (en) | Aqueous solution for forming silica coating membrane and formation of silica coating membrane | |
| US6099911A (en) | Process for forming silica film | |
| JP4960595B2 (en) | Sol-gel method for producing a glassy film having high adhesion and a stable colloidal solution suitable for carrying out said method | |
| JP3694900B2 (en) | Method for producing silica-based coating | |
| JPH03285821A (en) | Production of titanium oxide coating film | |
| Tsukuma et al. | Liquid phase deposition of a film of silica with an organic functional group | |
| JP2872826B2 (en) | Manufacturing method of oxide thin film | |
| JPS59141441A (en) | Method for producing glass coated with titanium oxide film | |
| EP0150530B1 (en) | Method of providing a metal layer | |
| JPH04280812A (en) | Formation of porous coating film of silica on substrate | |
| JP3824517B2 (en) | Method for forming metal oxide thin film on semiconductor substrate | |
| JPH09308833A (en) | Manufacture of fiber composite containing photocatalyst | |
| JPH0762087B2 (en) | Method for producing molded body of silicon dioxide-coated polycarbonate | |
| JPH02251585A (en) | Coating composition | |
| CA1185056A (en) | Method for formation of coating film of silicon oxide | |
| JPH10297921A (en) | Production of titanium oxide film | |
| JPH062155A (en) | Formation of silicon dioxide coating film on metal body |