JPH08120225A - Composition for forming coating silica film - Google Patents
Composition for forming coating silica filmInfo
- Publication number
- JPH08120225A JPH08120225A JP25379694A JP25379694A JPH08120225A JP H08120225 A JPH08120225 A JP H08120225A JP 25379694 A JP25379694 A JP 25379694A JP 25379694 A JP25379694 A JP 25379694A JP H08120225 A JPH08120225 A JP H08120225A
- Authority
- JP
- Japan
- Prior art keywords
- film
- water
- composition
- tetramethoxysilane
- partial hydrolyzate
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はシリカ系被膜形成用組成
物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silica film-forming composition.
【０００２】[0002]
【従来の技術】各種のシラン化合物、特にシリケート材
料を原料としてゾルゲル法により樹脂、金属、セラミッ
ク等各種基材表面にシリカ被膜を形成することが、これ
ら基盤の傷発生の防止、電気の絶縁、水分や各種薬品に
よる浸食防止などを主な目的として、各分野で行なわれ
ている。これらシラン化合物を含む溶液の基盤上への塗
布・製膜は、含浸法、ディッピング法、スピンコーティ
ング法、スプレー法などで行なわれている。2. Description of the Related Art The formation of silica coatings on the surface of various substrates such as resins, metals and ceramics by the sol-gel method using various silane compounds, especially silicate materials as raw materials prevents the occurrence of scratches on these substrates, insulates electricity, It is used in various fields mainly for the purpose of preventing erosion by water and various chemicals. The coating and film formation of the solution containing these silane compounds on the substrate are performed by an impregnation method, a dipping method, a spin coating method, a spray method or the like.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、一般に
シラン系の塗布液は保存中にゆっくりと反応が進み、形
成される膜は液製造直後とは違った性状を呈するように
なる等、保存安定性に問題がある。また形成される膜の
厚みが十分でなく、厚膜を得ようとすると重ね塗りをす
る必要があり作業性に問題がある。However, in general, a silane-based coating solution slowly reacts during storage, and the formed film exhibits different properties from those immediately after the solution is produced. I have a problem. In addition, the thickness of the formed film is not sufficient, and if a thick film is to be obtained, it is necessary to apply multiple layers, which causes a problem in workability.
【０００４】[0004]
【課題を解決するための手段】そこで本発明者らはこれ
らの従来の問題点に対し鋭意検討した結果、シリカ系被
膜形成用塗布液として下記の成分を必須成分としてなる
組成物が、保存安定性に優れ、さらにこれを用いること
により厚膜であり透明でクラックがなく高温で処理して
も表面疎水性が高いシリカ被膜が得られることを見いだ
し、本願発明に到達した。The inventors of the present invention have made extensive studies as to these conventional problems. As a result, a composition containing the following components as essential components as a coating liquid for forming a silica-based coating film is stable in storage. It has been found that a silica coating having excellent properties, which is a thick film, is transparent, has no cracks, and has high surface hydrophobicity even when treated at a high temperature by using this, and arrived at the present invention.
【０００５】Ａ．テトラメトキシシランとジアルキルジ
メトキシシランとの部分加水分解物 Ｂ．脂肪族一価のアルコール Ｃ．水 Ｄ．ｐＫａが１．０を超えてかつ５．０以下の有機カル
ボン酸 以下に本発明の詳細を説明する。A. Partial hydrolyzate of tetramethoxysilane and dialkyldimethoxysilane B. Aliphatic monohydric alcohol C.I. Water D. Organic Carboxylic Acid Having pKa of More Than 1.0 and 5.0 or Less Hereinafter, the present invention will be described in detail.
【０００６】本発明で用いられるＡ成分としては、テト
ラメトキシシランとジアルキルジメトキシシランとを混
合し、これらを部分加水分解して得られる成分を指す。
加水分解反応自体は公知の方法によることができ、例え
ば、上記テトラメトキシシランとジアルキルジメトキシ
シランの混合物に所定量の水を加えて酸触媒等の存在下
で、副生するメタノールを留去しながら通常、室温から
１００℃で反応させる等の方法を採ることができる。こ
れらの反応により、テトラメトキシシランとジアルキル
ジメトキシシランとは加水分解してシラノールとなり、
さらにこれにつづく縮合反応により液状の物質が部分加
水分解物（平均重合度２から８のオリゴマー）として得
られる。加水分解の程度は、使用する水の量により適宜
調節することができるが、本発明においては通常４０〜
９０％程度、さらに好ましくは６０〜８０％程度から選
ばれる。加水分解の程度が４０％より低いと、テトラメ
トキシシランとジアルキルジメトキシシランのモノマー
の割合が大きく、得られる被膜用組成物が保存中に性質
が徐々に変化することがあり得る。逆に加水分解の程度
が９０％より高いと、加水分解時にゲル化等が起こりや
すい。尚、加水分解の程度は、これらアルコキシシラン
の加水分解可能な官能基、すなわちメトキシ基全てを計
算上加水分解し得るモル数、すなわちこれらメトキシ基
のモル数の０．５倍のモル数の水を添加した時を加水分
解１００％とする。こうして得られた部分加水分解物は
モノマーを通常２〜１０％程度含有している。この部分
加水分解物をさらに煮沸し、モノマーを気化させ吹込ん
だ不活性ガスとともにモノマーを除去する、等の方法に
よりモノマー除去を行うことにより、モノマー含量が１
％以下とし、被膜用組成物の安定性を更に向上すること
もできる。本発明で用いることのできるジアルキルジメ
トキシシランのアルキル基としてはメチル基やエチル
基、プロピル基、ブチル基などの１級のアルキル基、イ
ソプロピル基などの２級アルキル基、ターシャリブチル
基などの３級アルキル基、シクロヘキシル基などの環状
アルキル基などが挙げられる。好ましくはメチル基、エ
チル基、プロピル基、ブチル基等の１級のアルキル基、
特に好ましくはメチル基、エチル基等がよい。また、テ
トラメトキシシランとジアルキルジメトキシシランとの
比率は、テトラメトキシシランとジアルキルジメトキシ
シランの合計量１００グラムに対してジアルキルジメト
キシシランは５グラム以上５０グラム以下が望ましい。
５グラムに満たない場合は保存性向上の効果が低く、ま
た５０グラムを越える場合は硬化したときの表面硬度が
低下する傾向にある。The component A used in the present invention refers to a component obtained by mixing tetramethoxysilane and dialkyldimethoxysilane and partially hydrolyzing them.
The hydrolysis reaction itself can be carried out by a known method, for example, by adding a predetermined amount of water to a mixture of the tetramethoxysilane and dialkyldimethoxysilane in the presence of an acid catalyst or the like while distilling off by-produced methanol. Usually, a method such as reaction at room temperature to 100 ° C. can be adopted. By these reactions, tetramethoxysilane and dialkyldimethoxysilane are hydrolyzed to silanol,
Further, by the subsequent condensation reaction, a liquid substance is obtained as a partial hydrolyzate (oligomer having an average degree of polymerization of 2 to 8). The degree of hydrolysis can be appropriately adjusted depending on the amount of water used, but in the present invention, it is usually 40-
It is selected from about 90%, more preferably about 60 to 80%. When the degree of hydrolysis is lower than 40%, the proportion of the monomers of tetramethoxysilane and dialkyldimethoxysilane is large, and the properties of the resulting coating composition may gradually change during storage. On the other hand, if the degree of hydrolysis is higher than 90%, gelation or the like tends to occur during hydrolysis. The degree of hydrolysis is determined by the number of moles that can hydrolyze all the hydrolyzable functional groups of these alkoxysilanes, that is, all methoxy groups, that is, 0.5 times the number of moles of these methoxy groups. When 100% is added, the hydrolysis is 100%. The partial hydrolyzate thus obtained usually contains about 2 to 10% of a monomer. This partial hydrolyzate is further boiled, the monomer is vaporized, and the monomer is removed together with the blown-in inert gas.
% Or less, the stability of the coating composition can be further improved. Examples of the alkyl group of dialkyldimethoxysilane that can be used in the present invention include primary alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, secondary alkyl groups such as isopropyl group, and tertiary alkyl groups such as tertiary butyl group. Examples include cyclic alkyl groups such as a primary alkyl group and a cyclohexyl group. Preferably, a primary alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group,
Particularly preferred are methyl group, ethyl group and the like. Further, the ratio of tetramethoxysilane to dialkyldimethoxysilane is preferably 5 g or more and 50 g or less of dialkyldimethoxysilane with respect to 100 g of the total amount of tetramethoxysilane and dialkyldimethoxysilane.
If the amount is less than 5 g, the effect of improving the preservability is low, and if the amount is more than 50 g, the surface hardness when cured tends to decrease.
【０００７】本発明のＢ成分の脂肪族一価のアルコール
は特に限定されるものではなく、Ａ成分のテトラメトキ
シシランとジアルキルジメトキシシランとのオリゴマー
を均一に溶解させうるものであればよい。具体的には、
メタノール、エタノール、イソプロピルアルコール、ブ
タノール、あるいは２−メトキシエタノール、２−エト
キシエタノール、２−（２−エトキシエトキシ）エタノ
ール、２−（２−メトキシエトキシ）エタノール、２−
ブトキシエタノール、２−（２−ブトキシエトキシ）エ
タノール等が挙げられる。The aliphatic monohydric alcohol of the component B of the present invention is not particularly limited as long as it can uniformly dissolve the oligomer of tetramethoxysilane and dialkyldimethoxysilane of the component A. In particular,
Methanol, ethanol, isopropyl alcohol, butanol, or 2-methoxyethanol, 2-ethoxyethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-methoxyethoxy) ethanol, 2-
Examples include butoxyethanol and 2- (2-butoxyethoxy) ethanol.
【０００８】これらのアルコールはＡ成分であるメトキ
シシランおよびその加水分解物の溶解性に優れている。
Ｂ成分として例示した上記の溶媒の中から１種類または
２種類以上を混合して用いる以外に、これらの溶媒に一
般的な他の溶媒を混合して用いてもよい。他の溶媒とし
ては具体的にエチルエーテル、ブチルエーテル等のエー
テル類、エチレングリコール、プロピレングリコール等
の多価アルコール類、アセトン、メチルエチルケトン、
メチルイソブチルケトン等のケトン類、酢酸エチル、ア
セト酢酸エチル等のエステル類が挙げられる。ただし、
脂肪族一価のアルコールに対するこれらの溶媒の使用量
は、得られる膜の均一性の面から脂肪族一価のアルコー
ル１００重量部に対し５０重量部以下とすることが好ま
しい。Ｂ成分のＡ成分に対する好適な量は、Ａ成分１０
０重量部に対し溶媒５０〜１０００重量部が好ましい。
溶媒が５０重量部以下の場合、液の基材への展開性が悪
く、厚みが均一な塗布が困難なものとなる。一方、溶媒
が１０００重量部より多いと、極端に厚みが小さい膜し
か得られず、さらにリコートするなどの必要性が生じる
場合もある。These alcohols are excellent in the solubility of methoxysilane which is the component A and its hydrolyzate.
In addition to using one kind or a mixture of two or more kinds among the above solvents exemplified as the component B, other general solvents may be mixed and used with these solvents. Specific examples of the other solvent include ethers such as ethyl ether and butyl ether, polyhydric alcohols such as ethylene glycol and propylene glycol, acetone, methyl ethyl ketone,
Examples thereof include ketones such as methyl isobutyl ketone, and esters such as ethyl acetate and ethyl acetoacetate. However,
The amount of these solvents used with respect to the aliphatic monohydric alcohol is preferably 50 parts by weight or less with respect to 100 parts by weight of the aliphatic monohydric alcohol from the viewpoint of the uniformity of the obtained film. A suitable amount of B component with respect to A component is A component 10
The solvent is preferably 50 to 1000 parts by weight with respect to 0 parts by weight.
When the amount of the solvent is 50 parts by weight or less, the spreadability of the liquid on the substrate is poor, and it becomes difficult to apply the solution having a uniform thickness. On the other hand, if the amount of the solvent is more than 1000 parts by weight, only a film having an extremely small thickness can be obtained, and it may be necessary to recoat the film.
【０００９】本発明のＣ成分の水はＡ成分のメトキシシ
ランの部分加水分解物に残存するメトキシ基の加水分解
反応を進行させるものである。水の添加量は用いるＡ成
分の部分加水分解物に残存するメトキシ基の残存率、す
なわち部分加水分解物の加水分解の程度に応じて異なる
ものであるが、一般にはこれら残存するメトキシ基を計
算上１００％加水分解し得る量に対し、０．５倍量以上
が好ましい。もし、水の量が少ない場合には、塗布後に
高温焼成して得られる膜の極端に厚みが小さくなるばか
りでなく、膜表面の平坦性が著しく損なわれるなどの問
題が生じることがある。The water of the component C of the present invention promotes the hydrolysis reaction of the methoxy group remaining in the partial hydrolyzate of the methoxysilane of the component A. The amount of water added varies depending on the residual ratio of the methoxy groups remaining in the partial hydrolyzate of the component A used, that is, the degree of hydrolysis of the partial hydrolyzate, but in general these residual methoxy groups are calculated. The amount is preferably 0.5 times or more the amount that can be hydrolyzed by 100%. If the amount of water is small, not only the thickness of the film obtained by baking at high temperature after coating but also the film thickness may be extremely reduced, but the flatness of the film surface may be significantly impaired.
【００１０】本発明のＤ成分のｐＫａが１．０を超えて
かつ５．０以下の有機カルボン酸は、Ａ成分のメトキシ
シランに残存するメトキシ基の加水分解反応の進行とそ
れに続く縮合・硬化反応に必要な触媒である。ｐＫａが
１．０を超えてかつ５．０以下の有機カルボン酸でアル
コール／水系溶媒に溶解するものであれば特に限定され
るものではないが、具体的には、マレイン酸、シュウ
酸、トリクロロ酢酸、フマル酸、ギ酸、酢酸、ピバリン
酸等が挙げられる。一般にシリケートオリゴマーの加水
分解および縮合反応の触媒には、有機カルボン酸の以外
の酸または塩基触媒の使用が可能であるが、特にｐＫａ
が１．０を超えてかつ５．０以下の有機カルボン酸は他
の触媒に比べて塗布液の保存安定性からも優れている。
好ましい添加量はＡ成分のテトラメトキシシランとジア
ルキルジメトキシシランの合計１００重量部に対して
０．３重量部以上である。Ｄ成分の量がこれ以下の組成
から被膜を形成すると、得られる膜の厚みは極端に小さ
いものとなることがある。The organic carboxylic acid having a pKa of the component D of more than 1.0 and not more than 5.0 of the present invention is used for the progress of the hydrolysis reaction of the methoxy group remaining in the methoxysilane of the component A and the subsequent condensation / curing. It is a catalyst required for the reaction. The organic carboxylic acid having a pKa of more than 1.0 and 5.0 or less is not particularly limited as long as it is soluble in an alcohol / water-based solvent, but specifically, maleic acid, oxalic acid, trichloro Examples thereof include acetic acid, fumaric acid, formic acid, acetic acid, pivalic acid and the like. In general, as a catalyst for the hydrolysis and condensation reaction of the silicate oligomer, an acid or base catalyst other than the organic carboxylic acid can be used, but in particular pKa
The organic carboxylic acid having a ratio of more than 1.0 and 5.0 or less is superior to other catalysts in terms of storage stability of the coating solution.
The preferable addition amount is 0.3 parts by weight or more based on 100 parts by weight of the total of the component A tetramethoxysilane and dialkyldimethoxysilane. When a film is formed from a composition having an amount of component D of less than this, the thickness of the film obtained may be extremely small.
【００１１】本発明は上記４成分を主成分とするが、そ
の配合方法は室温でアルコールを含む溶媒にＡ成分のテ
トラメトキシシランとジアルキルジメトキシシランとの
部分加水分解物を溶解した後、次いで水、有機カルボン
酸を添加するのが一般的である。こうして得られた本発
明の組成物を各種塗布法にてセラミック、金属等の基材
に製膜し、次いで、溶媒を揮発後に４００℃以上で加熱
硬化することで、表面疎水性の高いシリカ系被膜を得る
ことができる。In the present invention, the above-mentioned four components are the main components. The mixing method is to dissolve the partial hydrolyzate of tetramethoxysilane and dialkyldimethoxysilane of the component A in a solvent containing alcohol at room temperature, and then add water. Generally, an organic carboxylic acid is added. The composition of the present invention thus obtained is formed into a film on a substrate such as a ceramic or a metal by various coating methods, and then the solvent is volatilized and then heat-cured at 400 ° C. or higher to obtain a silica-based material having a high surface hydrophobicity. A coating can be obtained.
【００１２】[0012]
【実施例】以下、実施例により本発明をさらに詳細に説
明する。 合成例１ テトラメトキシシラン９０グラム、ジメチルジメトキシ
シラン１０グラム、メタノール３２．４グラム、水８．
９８グラム、１規定塩酸０．１４グラムを液温６５℃で
２時間加熱しそののち１００℃、１５０℃と加熱して蒸
留して、部分加水分解物Ａを得た。The present invention will be described in more detail with reference to the following examples. Synthesis Example 1 Tetramethoxysilane 90 g, dimethyldimethoxysilane 10 g, methanol 32.4 g, water 8.
98 g of 1N hydrochloric acid (0.14 g) was heated at a liquid temperature of 65 ° C. for 2 hours, then heated to 100 ° C. and 150 ° C. and distilled to obtain a partial hydrolyzate A.
【００１３】合成例２ 合成例１と同様にテトラメトキシシラン８０グラム、ジ
エチルジメトキシシラン２０グラム、メタノール３３．
２グラム、水９．２グラム、１規定塩酸０．１４グラム
を使用して部分加水分解物Ｂを得た。 合成例３ 合成例１と同様にテトラメトキシシラン５０グラム、ジ
メチルジメトキシシラン５０グラム、メタノール３５．
８グラム、水９．９２グラム、１規定塩酸０．１５グラ
ムを使用して部分加水分解物Ｃを得た。Synthesis Example 2 As in Synthesis Example 1, 80 g of tetramethoxysilane, 20 g of diethyldimethoxysilane, 33.
A partial hydrolyzate B was obtained by using 2 g, 9.2 g of water and 0.14 g of 1N hydrochloric acid. Synthesis Example 3 As in Synthesis Example 1, 50 grams of tetramethoxysilane, 50 grams of dimethyldimethoxysilane, 35.
A partial hydrolyzate C was obtained using 8 grams, 9.92 grams of water, and 0.15 grams of 1N hydrochloric acid.
【００１４】合成例４ テトラメトキシシラン１００グラム、メタノール３１．
６グラム、水８．８グラム、１規定塩酸０．１３グラム
を液温６５℃で２時間加熱しそののち１００℃、１５０
℃と加熱して蒸留した。そののち内容物を室温まで冷却
して減圧下で３０分間攪拌してモノマーを取り除き部分
加水分解物Ｄを得た。Synthesis Example 4 Tetramethoxysilane 100 g, methanol 31.
6 g of water, 8.8 g of water, and 0.13 g of 1N hydrochloric acid were heated at a liquid temperature of 65 ° C. for 2 hours, and then heated at 100 ° C., 150
Distilled by heating at ℃. Then, the content was cooled to room temperature and stirred under reduced pressure for 30 minutes to remove the monomer, and thus a partial hydrolyzate D was obtained.
【００１５】合成例５ ジメチルジメトキシシラン１００グラム、メタノール４
０．０グラム、水１１．１グラム、１規定塩酸０．１７
グラムを液温６５℃で２時間加熱しそののち１００℃、
１５０℃と加熱して蒸留した。そののち内容物を室温ま
で冷却して減圧下で３０分間攪拌してモノマーを取り除
き部分加水分解物Ｅを得た。Synthesis Example 5 100 g of dimethyldimethoxysilane, 4 of methanol
0.0 g, water 11.1 g, 1N hydrochloric acid 0.17
Gram is heated at a liquid temperature of 65 ° C. for 2 hours, and then 100 ° C.,
It was heated to 150 ° C. and distilled. Then, the content was cooled to room temperature and stirred under reduced pressure for 30 minutes to remove the monomer, and thus a partial hydrolyzate E was obtained.
【００１６】実施例１ エタノール６４．９ｇに上記合成例により得られた部分
加水分解物Ａ３１．０ｇを混合し、室温下で攪拌し均一
に溶解させた。これに水３．８ｇとマレイン酸（ｐＫａ
＝１．９２）０．３ｇをこの順序で加え、マレイン酸が
溶解するまでさらに攪拌してシリカ系被膜形成用塗布液
の組成物を得た。この溶液は２３℃で１００日放置して
もゲル化することはなかった。この組成物にガラスを漬
けた後、２３℃、相対湿度５５％でガラスを３００ｍｍ
／ｍｉｎで引き上げ１２０℃の熱風オーブンにて２分間
溶媒を揮発させた後、さらに熱風オーブンにて４５０
℃、３０分加熱硬化した。膜は透明でクラックは見あた
らなかった。得られた膜の特性について表２に示す。Example 1 64.9 g of ethanol was mixed with 31.0 g of the partial hydrolyzate A obtained according to the above-mentioned synthesis example, and the mixture was stirred at room temperature and uniformly dissolved. To this, 3.8 g of water and maleic acid (pKa
= 1.92) 0.3 g was added in this order, and the mixture was further stirred until maleic acid was dissolved to obtain a composition of a silica-based coating film forming coating liquid. This solution did not gel even when left at 23 ° C. for 100 days. After soaking the glass in this composition, the glass is 300 mm at 23 ° C. and 55% relative humidity.
/ Min to evaporate the solvent for 2 minutes in a hot air oven at 120 ° C, and then 450 in a hot air oven
It was cured by heating at 30 ° C. for 30 minutes. The film was transparent and no cracks were found. The characteristics of the obtained film are shown in Table 2.
【００１７】水との接触角の測定方法 シリンジにて直径２ｍｍの水の球を作製し、これに下か
らゆっくり浸漬したガラス基材を上昇させて接触させた
後、再度基材をさげて液滴を作り、基材との接触角を測
定する。 保存性の測定方法 各溶液を密栓した透明ガラス容器に入れ、これを室温に
て静置し溶液の流動性が全く無くなった時点を寿命とし
た。Method for measuring contact angle with water A water ball having a diameter of 2 mm was prepared with a syringe, and a glass base material slowly dipped from below was raised to make contact with the ball, and then the base material was again lowered to remove the liquid. Make a drop and measure the contact angle with the substrate. Method for measuring storability Each solution was placed in a transparent glass container tightly stoppered and allowed to stand at room temperature, and the time when the fluidity of the solution completely disappeared was defined as the life.
【００１８】実施例２ 部分加水分解物Ｂを使用した以外は実施例１、表２に従
って組成物を得、成膜、加熱硬化した。膜は透明でクラ
ックは見あたらなかった。得られた膜の特性について表
２に示す。 実施例３ 部分加水分解物Ｃを使用した以外は実施例１、表２に従
って組成物を得、成膜、加熱硬化した。膜は透明でクラ
ックは見あたらなかった。得られた膜の特性について表
２に示す。Example 2 A composition was obtained according to Example 1 and Table 2 except that the partial hydrolyzate B was used, and a film was formed and heat-cured. The film was transparent and no cracks were found. The characteristics of the obtained film are shown in Table 2. Example 3 A composition was obtained according to Example 1 and Table 2 except that the partial hydrolyzate C was used, and a film was formed and heat-cured. The film was transparent and no cracks were found. The characteristics of the obtained film are shown in Table 2.
【００１９】実施例４ マレイン酸の代わりに酢酸し使用した以外は実施例１、
表２に従って組成物を得、成膜、加熱硬化した。膜は透
明でクラックは見あたらなかった。得られた膜の特性に
ついて表２に示す。 比較例１ 部分加水分解物Ｄを使用した以外は実施例１、表２に従
って組成物を得、成膜、加熱硬化した。膜は透明でクラ
ックは見あたらなかった。得られた膜の特性について表
２に示す。水との接触角は実施例のものに比べて低く、
疎水性が低い。Example 4 Example 1 except that acetic acid was used instead of maleic acid.
A composition was obtained according to Table 2, and a film was formed and heat-cured. The film was transparent and no cracks were found. The characteristics of the obtained film are shown in Table 2. Comparative Example 1 A composition was obtained according to Example 1 and Table 2 except that the partial hydrolyzate D was used, and a film was formed and heat-cured. The film was transparent and no cracks were found. The characteristics of the obtained film are shown in Table 2. The contact angle with water is lower than that of the example,
Low hydrophobicity.
【００２０】比較例２ 部分加水分解物Ｅを使用した以外は実施例１、表２に従
って組成物を得、成膜、加熱硬化した。膜は透明でクラ
ックは見あたらなかった。得られた膜の特性について表
２に示す。加熱後膜の一部が消失していた。 比較例３ エタノール６６．５ｇに部分加水分解物Ａ３３．２ｇグ
ラムを溶解し、水を加えずにマレイン酸０．３ｇを加え
組成物を得た。実施例１と同様に被膜を形成した。得ら
れた膜の特性について表２に示す。膜は全体的に薄く加
熱後膜の一部が消失していた。 比較例４ 実施例１でマレイン酸の代わりにヒドラジン（ｐＫａ＝
７．９７）を同量用いた以外は実施例１と同条件で調液
したところ、４成分混合後１時間で組成物は増粘、白濁
した。その結果透明で均一な厚みの膜は得られなかっ
た。Comparative Example 2 A composition was obtained according to Example 1 and Table 2 except that the partial hydrolyzate E was used, and a film was formed and heat cured. The film was transparent and no cracks were found. The characteristics of the obtained film are shown in Table 2. After heating, part of the film had disappeared. Comparative Example 3 36.2 g of the partial hydrolyzate A was dissolved in 66.5 g of ethanol, and 0.3 g of maleic acid was added without adding water to obtain a composition. A film was formed in the same manner as in Example 1. The characteristics of the obtained film are shown in Table 2. The film was thin as a whole and part of the film disappeared after heating. Comparative Example 4 Instead of maleic acid in Example 1, hydrazine (pKa =
When a solution was prepared under the same conditions as in Example 1 except that the same amount of 7.97) was used, the composition thickened and became cloudy one hour after mixing the four components. As a result, a transparent film having a uniform thickness could not be obtained.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】表からも明らかなように本発明の組成物を
用いることにより、厚膜であり透明でクラックがなく水
との接触角の大きい、疎水性の高いシリカ系被膜が得ら
れる。As is clear from the table, by using the composition of the present invention, a highly hydrophobic silica coating which is a thick film, is transparent, has no crack, and has a large contact angle with water can be obtained.
【００２４】[0024]
【発明の効果】本発明により、塗布液としての保存安定
性が良好で、さらにこれを用いることにより厚膜であり
透明でクラックがなく疎水性の高いシリカ系被膜が得ら
れる。According to the present invention, the storage stability as a coating solution is good, and by using this, a thick, transparent, crack-free silica-based coating having a high hydrophobicity can be obtained.
Claims (1)
ジメトキシシランとの部分加水分解物 Ｂ．脂肪族一価のアルコール Ｃ．水 Ｄ．ｐＫａが１．０を超えてかつ５．０以下の有機カル
ボン酸を必須成分とするシリカ系被膜形成用組成物。1. A. First Embodiment Partial hydrolyzate of tetramethoxysilane and dialkyldimethoxysilane B. Aliphatic monohydric alcohol C.I. Water D. A silica-based coating film-forming composition containing an organic carboxylic acid having a pKa of more than 1.0 and 5.0 or less as an essential component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25379694A JPH08120225A (en) | 1994-10-19 | 1994-10-19 | Composition for forming coating silica film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25379694A JPH08120225A (en) | 1994-10-19 | 1994-10-19 | Composition for forming coating silica film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08120225A true JPH08120225A (en) | 1996-05-14 |
Family
ID=17256276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25379694A Pending JPH08120225A (en) | 1994-10-19 | 1994-10-19 | Composition for forming coating silica film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08120225A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1008571A3 (en) * | 1998-12-11 | 2000-11-02 | The Morgan Crucible Company Plc | Method of treating ceramic surfaces |
| WO2005049757A1 (en) * | 2003-11-21 | 2005-06-02 | The University Of Queensland | Silica films and method of production thereof |
| US7642199B2 (en) | 2004-11-22 | 2010-01-05 | Xerocoat Inc. | Silica and silica-like films and method of production |
| KR101379479B1 (en) * | 2013-01-07 | 2014-04-01 | 주식회사 동성화학 | Open cell foam composition, hydrophobic open cell foam and a method for preparing them using the same |
| US8734906B2 (en) | 2003-11-21 | 2014-05-27 | Brismat Inc. | Films and method of production thereof |
| CN111454626A (en) * | 2020-04-14 | 2020-07-28 | 三河方元绿洲节能科技有限公司 | Concrete deformation-preventing nano ceramic thermal insulation material under large temperature difference and preparation method thereof |
-
1994
- 1994-10-19 JP JP25379694A patent/JPH08120225A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1008571A3 (en) * | 1998-12-11 | 2000-11-02 | The Morgan Crucible Company Plc | Method of treating ceramic surfaces |
| US6652918B1 (en) | 1998-12-11 | 2003-11-25 | The Morgan Crucible Company Plc | Method of treating ceramic surfaces |
| WO2005049757A1 (en) * | 2003-11-21 | 2005-06-02 | The University Of Queensland | Silica films and method of production thereof |
| US7919145B2 (en) | 2003-11-21 | 2011-04-05 | Xerocoat Inc. | Silica films and method of production thereof |
| US8734906B2 (en) | 2003-11-21 | 2014-05-27 | Brismat Inc. | Films and method of production thereof |
| US7642199B2 (en) | 2004-11-22 | 2010-01-05 | Xerocoat Inc. | Silica and silica-like films and method of production |
| KR101379479B1 (en) * | 2013-01-07 | 2014-04-01 | 주식회사 동성화학 | Open cell foam composition, hydrophobic open cell foam and a method for preparing them using the same |
| CN111454626A (en) * | 2020-04-14 | 2020-07-28 | 三河方元绿洲节能科技有限公司 | Concrete deformation-preventing nano ceramic thermal insulation material under large temperature difference and preparation method thereof |
| CN111454626B (en) * | 2020-04-14 | 2021-09-28 | 三河方元绿洲节能科技有限公司 | Concrete deformation-preventing nano ceramic thermal insulation material under large temperature difference and preparation method thereof |
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