JP4863471B2 - A method for producing a super water-repellent glass substrate. - Google Patents
A method for producing a super water-repellent glass substrate. Download PDFInfo
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- JP4863471B2 JP4863471B2 JP2006289386A JP2006289386A JP4863471B2 JP 4863471 B2 JP4863471 B2 JP 4863471B2 JP 2006289386 A JP2006289386 A JP 2006289386A JP 2006289386 A JP2006289386 A JP 2006289386A JP 4863471 B2 JP4863471 B2 JP 4863471B2
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本発明は、超撥水ガラス基板及びその製造方法に関する。 The present invention relates to a super water-repellent glass substrate and a method for producing the same.
従来の技術では、エッチングによるナノ構造制御は、プラスチックでのみ実現されており（非特許文献１参照）、無機物質であるガラスでは、エッチングによるナノ構造制御は報告されていない。
有機化合物であるプラスチックでは、耐熱性、構造の強度などは低く、耐熱性に優れ、高強度であり安価なガラス材料を用いた簡易なナノ構造作製プロセスが必要とされてきた。
また、従来の技術では、基板上に酸化アルミニウムをゾル-ゲル法によって作製した後、温水処理によって、花弁状組織を作製し、これにシラン化合物をコーティングして、超撥水性（接触角）165度を得ている（特許文献１参照）。
Plastics that are organic compounds have low heat resistance, structural strength, and the like, and a simple nanostructure fabrication process using a glass material that is excellent in heat resistance, high strength, and inexpensive has been required.
In the conventional technique, after aluminum oxide is produced on a substrate by a sol-gel method, a petal-like structure is produced by hot water treatment, and this is coated with a silane compound to produce a super-water-repellent (contact angle) of 165 (See Patent Document 1).
本発明は、ガラス基板の表面を微細加工することにより、ガラス表面に微細な凹凸を作り出し、その上にシラン化合物の縮合物による被膜を形成させることにより、超撥水ガラス基板を製造する。 The present invention produces a super-water-repellent glass substrate by finely processing the surface of the glass substrate to create fine irregularities on the glass surface and forming a film of the silane compound condensate thereon.
上記目的を達成するために本発明者は、鋭意研究を続け、ガラス基板をアルカリで処理することにより、ガラス表面に微細な凹凸を作り出し、その上に特殊なシラン化合物の縮合物による被膜を形成させることにより、超撥水ガラス基板を製造することを見出した。
すなわち、本発明は、石英ガラス以外のガラス基板を、ＬｉＯＨ，ＮａＯＨ，ＫＯＨ、ＮＨ ４ ＯＨ、尿素から選ばれるアルカリのｐＨ８以上水溶液で、温度が９０〜２５０℃であるアルカリ溶液に０．５〜４８時間浸漬処理することにより得られるナノサイズの微細構造を有するガラス基板表面に、直接、撥水剤の被膜を設ける超撥水ガラス基板の製造方法である。
また、本発明の超撥水性ガラス基板の製造方法においては、撥水剤が、フッ素を含まないヘキシルトリメトキシシランの縮合物、若しくはフッ素を含むヘプタデカフルオロデシルトリメトキシシラン、トリデカフルオロオクチルメトキシシラン、２−（パーフルオロオクチル）エチルトリクロロシランから選ばれるシランカップリング剤、パーフルオロラウリン酸、ポリ（パーフルオロデシルエチルアクリレート）から選ばれる長鎖パーフルオロアルキル基を有する高分子、ビニル末端ポリジメチルシロキサンからなる群れより選ばれる１種とすることができる。
In order to achieve the above-mentioned object, the present inventor continued earnest research and treated the glass substrate with alkali to create fine irregularities on the glass surface and to form a coating with a special silane compound condensate thereon. It has been found that a super water-repellent glass substrate can be produced by making it.
That is, according to the present invention, a glass substrate other than quartz glass is added to an alkaline solution having a temperature of 90 to 250 ° C. with an alkaline aqueous solution of pH 8 or higher selected from LiOH, NaOH, KOH, NH 4 OH, and urea. This is a method for producing a super water-repellent glass substrate in which a coating of a water repellent is directly provided on the surface of a glass substrate having a nano-sized fine structure obtained by immersion for 48 hours.
In the method for producing a super water-repellent glass substrate of the present invention, the water repellent is a condensate of hexyltrimethoxysilane containing no fluorine, or heptadecafluorodecyltrimethoxysilane or tridecafluorooctylmethoxy containing fluorine. Silane, a silane coupling agent selected from 2- (perfluorooctyl) ethyltrichlorosilane, a polymer having a long-chain perfluoroalkyl group selected from perfluorolauric acid and poly (perfluorodecylethyl acrylate), vinyl-terminated poly It can be one selected from the group consisting of dimethylsiloxane .
本発明の超撥水ガラス基板は、いずれも接触角150°以上の超撥水を示し、比較的簡単な製造方法により手軽に超撥水ガラス基板を作成することができる。 All of the super water-repellent glass substrates of the present invention exhibit super water repellency with a contact angle of 150 ° or more, and a super water-repellent glass substrate can be easily produced by a relatively simple manufacturing method.
本発明で用いるガラス基板のガラスは、石英ガラス以外なら何でも良く、市販の各種ガラス板を利用することができる。
本発明で用いるアルカリとしては、ＬｉＯＨ，NaOH，ＫＯＨからなる群れより選ばれる１種であり、NaOHが好ましく用いられる。
アルカリの濃度は、ｐＨは８以上であり、好ましくは、ｐＨ８．５〜１３であり、より好ましくはｐＨ９〜１１である。
本発明におけるアルカリ水溶液の温度は、９０〜２５０℃の温度であり、好ましくは、９０〜１２０℃である。
また、本発明における浸漬時間は、温度によっても異なるが通常０．５〜４８時間であり、好ましくは１〜２４時間である。
本発明について実施例を用いてさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
The glass of the glass substrate used in the present invention may be anything other than quartz glass, and various commercially available glass plates can be used.
The alkali used in the present invention is one selected from the group consisting of LiOH, NaOH and KOH, and NaOH is preferably used.
As for the alkali concentration, the pH is 8 or more, preferably pH 8.5 to 13, more preferably pH 9 to 11.
The temperature of the aqueous alkali solution in the present invention is 90 to 250 ° C, preferably 90 to 120 ° C.
Moreover, although the immersion time in this invention changes also with temperature, it is 0.5 to 48 hours normally, Preferably it is 1 to 24 hours.
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
ガラス基板を1MのNaOH水溶液に浸し、100-200℃で数時間保持し、その後取り出して洗浄し、乾燥させた。
これにシラン化合物のフッ素を含まないヘキシルトリメトキシシランもしくはフッ素を含むヘプタデカフルオロデシルトリメトキシシランをコーティングした。
コーティングはヘキサン中にシランを溶解させ、６０℃にて24時間静置し、取り出し、室温で乾燥させた。
図１に 1MのNaOH 水溶液中、100℃ 5hの処理をしたガラス基板のSEM写真を示す。ナノスケールの凹凸が確認できる。
図2は、1MのNaOH 水溶液中、100℃ 5hの処理をした基板に、ヘキシルトリメトキシシランをコーティングした超撥水の写真である。
図3は1MのNaOH 水溶液中、100℃ 5hの処理をした基板に、）ヘプタデカフルオロデシルトリメトキシシランをコーティングした超撥水の写真である。いずれも接触角150°以上の超撥水を示していることが分かる。
図４は平滑なガラス基板上にヘプタデカフルオロデシルトリメトキシシランをコートしたガラス基板（比較例）の撥水の写真であり、接触角は約113度と、150度以上の超撥水は示さない。
図5には1MのNaOH 水溶液中、100℃ 5hで処理したガラスを示す。良好な透明性が得られていることが分かる。
The glass substrate was immersed in 1M NaOH aqueous solution and kept at 100-200 ° C. for several hours, then taken out, washed and dried.
This was coated with hexyltrimethoxysilane containing no fluorine or heptadecafluorodecyltrimethoxysilane containing fluorine.
For coating, silane was dissolved in hexane, left at 60 ° C. for 24 hours, taken out, and dried at room temperature.
Fig. 1 shows an SEM photograph of a glass substrate that was treated in a 1M NaOH aqueous solution for 5 hours at 100 ° C. Nanoscale irregularities can be confirmed.
FIG. 2 is a super-water-repellent photograph in which hexyltrimethoxysilane is coated on a substrate that has been treated at 100 ° C. for 5 hours in a 1M NaOH aqueous solution.
Fig. 3 is a photograph of super-water-repellent material in which heptadecafluorodecyltrimethoxysilane was coated on a substrate that had been treated at 100 ° C for 5 hours in 1M NaOH aqueous solution. It can be seen that both show super water repellency with a contact angle of 150 ° or more.
Fig. 4 is a photograph of water repellency of a glass substrate (comparative example) in which heptadecafluorodecyltrimethoxysilane is coated on a smooth glass substrate. The contact angle is about 113 degrees, indicating super-water repellency of 150 degrees or more. Absent.
Figure 5 shows a glass treated at 100 ° C for 5 hours in 1M NaOH aqueous solution. It turns out that favorable transparency is acquired.
ナノスケールの凹凸が確認できる。図６は、NaOHを用いてpHを9.14に制御した水溶液中、200℃ 24hの処理をした基板に、ヘプタデカフルオロデシルトリメトキシシランをコーティングした超撥水の写真である。150°以上の超撥水を示していることが分かる。図７はNaOHを用いてpHを9.14に制御した水溶液中、200℃ 24hの処理をしたガラスへ、ヘプタデカフルオロデシルトリメトキシシランをコートした膜上に油であるヘキサデカンを滴下した撥油の写真である。接触角が約105度と、撥油膜であることが分かる。図８にはNaOHを用いてpHを9.14に制御した水溶液中、200℃ 2hの処理をしたガラス基板を示す。良好な透明性が得られていることが分かる。 Nanoscale irregularities can be confirmed. FIG. 6 is a super water-repellent photograph in which heptadecafluorodecyltrimethoxysilane is coated on a substrate that has been treated at 200 ° C. for 24 hours in an aqueous solution with a pH controlled to 9.14 using NaOH. It can be seen that it exhibits super water repellency of 150 ° or more. Fig. 7 is a photograph of oil repellency in which hexadecane, an oil, is dropped onto a glass coated with heptadecafluorodecyltrimethoxysilane on glass treated at 200 ° C for 24 hours in an aqueous solution controlled to pH 9.14 using NaOH. It is. It can be seen that the contact angle is about 105 degrees, which is an oil repellent film. FIG. 8 shows a glass substrate treated at 200 ° C. for 2 hours in an aqueous solution whose pH is controlled to 9.14 using NaOH. It turns out that favorable transparency is acquired.
図９は、NaOHを用いてpHを9.14に制御した水溶液中、200℃ 24hの処理をしたガラス基板に、ヘプタデカフルオロデシルトリメトキシシランをコーティングした超撥水の写真である。150°以上の超撥水を示していることが分かる。図１０はNaOHを用いてpHを9.14に制御した水溶液中、200℃ 24hの処理をしたガラス基板へ、ヘプタデカフルオロデシルトリメトキシシランをコートした膜上に油であるヘキサデカンを滴下した撥油の写真である。接触角が約1４５度と、非常に良好な撥油膜であることが分かる。 FIG. 9 is a photograph of super-water-repellency in which heptadecafluorodecyltrimethoxysilane is coated on a glass substrate treated at 200 ° C. for 24 hours in an aqueous solution whose pH is controlled to 9.14 using NaOH. It can be seen that it exhibits super water repellency of 150 ° or more. FIG. 10 shows an oil-repellent solution in which hexadecane as an oil is dropped onto a glass substrate coated with heptadecafluorodecyltrimethoxysilane on a glass substrate treated at 200 ° C. for 24 hours in an aqueous solution whose pH is controlled to 9.14 using NaOH. It is a photograph. It can be seen that the contact angle is about 145 degrees, which is a very good oil repellent film.
本発明の超撥水ガラス基板は、大量生産に向いており、自動車やビルの窓ガラス等に利用することが期待できる。 The super water-repellent glass substrate of the present invention is suitable for mass production, and can be expected to be used for window glass of automobiles and buildings.
Claims (2)
The water repellent is a condensate of hexyltrimethoxysilane containing no fluorine, or a silane selected from fluorine-containing heptadecafluorodecyltrimethoxysilane, tridecafluorooctylmethoxysilane, 2- (perfluorooctyl) ethyltrichlorosilane 2. It is one kind selected from the group consisting of a coupling agent, perfluorolauric acid, a polymer having a long-chain perfluoroalkyl group selected from poly (perfluorodecylethyl acrylate), and vinyl-terminated polydimethylsiloxane. A method for producing the described super water-repellent glass substrate .
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| JPH0597478A (en) * | 1991-10-04 | 1993-04-20 | Nippon Sheet Glass Co Ltd | Water repellent glass article and its production |
| JPH09309745A (en) * | 1996-05-24 | 1997-12-02 | Central Glass Co Ltd | Water-repellent and oil-repellent article and its production |
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