JP5578609B2 - High-strength composite nanosheet film, transparent super water-repellent film using the same, and method for producing the same - Google Patents
High-strength composite nanosheet film, transparent super water-repellent film using the same, and method for producing the same Download PDFInfo
- Publication number
- JP5578609B2 JP5578609B2 JP2010081712A JP2010081712A JP5578609B2 JP 5578609 B2 JP5578609 B2 JP 5578609B2 JP 2010081712 A JP2010081712 A JP 2010081712A JP 2010081712 A JP2010081712 A JP 2010081712A JP 5578609 B2 JP5578609 B2 JP 5578609B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- nanosheet
- compound
- nanosheet film
- microstructure
- 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.)
- Active
Links
Images
Landscapes
- Laminated Bodies (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、高強度複合ナノシート膜、それを用いた水との接触角が、１４０〜１７５°である透明且つ機械強度がある超撥水性材料及びその製造方法に関する。 The present invention relates to a high-strength composite nanosheet film, a transparent and mechanical strength superhydrophobic material having a contact angle with water of 140 to 175 ° and a method for producing the same.
透明なガラスの撥水は、自動車、建物などの窓ガラス、メガネ等、様々な応用が期待されている。多くは、低分極率化合物をガラス表面上にコーティングする方法であるが、150度以上の超撥水と呼ばれるような高い撥水性は得られていない。低分極率化合物を用いた化学的な手法では、理論上、実験上において超撥水の実現は不可能であり、Cassieの式を用いた空気を利用する技術が必要である。このため、表面の微細な構造を制御し、超撥水を得る技術が必要とされている。（非特許文献１，２）
現状では、リソグラフィーなどのトップダウンプロセス、プラズマ処理によって凹凸構造を作製しているが、光の散乱による透明性劣化の問題がある（特許文献１〜２参照）。高分子の自己集合を利用してガラス上に微細構造を形成させる方法もあるが、安定な無機材料による微細構造の制御が望ましい。
しかし、これらの微細構造は機械的強度に問題があり、実用のために、膜の強度あるいは膜の撥水耐久性を向上する必要がある。ナノ微細構造を成長させるボトムアッププロセスを用いて、Al化合物ナノシート微細構造を作製することにより、超撥水性表面を作りだす手法は、既に成功し、特許も出願済みである（特許文献３〜４参照）。図１と図２aには、それぞれ、撥水加工する前の石英基板と上記ボトムアッププロセスから成長させたAl化合物ナノシートを1000℃で40分熱処理した膜の撥水性能を示している。しかし、このナノシート微細構造は比較的強度に優れず(図２ｂ参照)、1000℃で空気中40分加熱によっても、５０回のワイパー駆動実験で撥水性能は低下した。
The water repellent property of transparent glass is expected to be used in various applications such as window glass and glasses for automobiles and buildings. In many cases, a low polarizability compound is coated on the glass surface, but high water repellency called super water repellency of 150 degrees or more has not been obtained. The chemical method using a low polarizability compound is theoretically impossible to realize super water repellency experimentally, and requires a technique using air using Cassie's formula. For this reason, a technique for controlling the fine structure of the surface and obtaining super water repellency is required. (Non-Patent Documents 1 and 2)
At present, the concavo-convex structure is produced by a top-down process such as lithography or plasma treatment, but there is a problem of transparency deterioration due to light scattering (see Patent Documents 1 and 2). Although there is a method of forming a microstructure on a glass by utilizing self-assembly of a polymer, it is desirable to control the microstructure with a stable inorganic material.
However, these fine structures have a problem in mechanical strength, and it is necessary to improve the strength of the film or the water repellency of the film for practical use. A technique for creating a super water-repellent surface by producing an Al compound nanosheet microstructure by using a bottom-up process for growing the nanostructure has already been successful, and patents have been filed (see Patent Documents 3 to 4). ). FIGS. 1 and 2a show the water repellency performance of a quartz substrate before water repellency processing and a film obtained by heat-treating an Al compound nanosheet grown from the bottom-up process at 1000 ° C. for 40 minutes, respectively. However, this nanosheet microstructure was not relatively excellent in strength (see FIG. 2b), and the water repellency was lowered in 50 wiper driving experiments even when heated in air at 1000 ° C. for 40 minutes.
本発明では、ナノ微細構造を成長させるボトムアッププロセスを用いて、Al化合物ナノシート微細構造を作製することにより、超撥水性表面を作りだす方法をさらに改良し、高強度複合ナノシート膜とすることにより、ナノシート微細構造を更に制御および強化することにより、超撥水性と透明性を保つとともに耐久性にもこたえる超撥水性膜、及びその製造方法を提供することを目的とする。 In the present invention, by using a bottom-up process for growing a nano-fine structure, by making an Al compound nano-sheet fine structure, the method of creating a super water-repellent surface is further improved, and a high-strength composite nano-sheet film is obtained. An object of the present invention is to provide a super water-repellent film that maintains super water repellency and transparency as well as durability by further controlling and strengthening the nanosheet microstructure, and a method for producing the same.
高強度複合ナノシート膜とし、これを超撥水性透明膜とするためは、超撥水透明膜に耐摩耗性能を付与するには、一般にはナノシートと基板そしてナノシートと低分極率化合物コーティング材の間の界面の結合を強める必要があると考えられる。さらに界面の結合強度に加え、ナノシート微細構造自身の弱さが膜の超撥水性を失効してしまう最も重要な原因であると実験より確認した。それに基づく、上記目的を達成するために本発明は、特殊なプロセスでAl化合物ナノシート微細構造を強化する高強度複合ナノシート膜の製造方法である。
In order to make a high-strength composite nanosheet film and a super-water-repellent transparent film, in order to impart wear resistance to the super-water-repellent transparent film, it is generally between the nanosheet and the substrate and between the nanosheet and the low polarizability compound coating material It is considered necessary to strengthen the bond at the interface. Furthermore, in addition to the bond strength at the interface, the weakness of the nanosheet microstructure itself was confirmed by experiments to be the most important cause of losing the superhydrophobicity of the film. In order to achieve the above object, the present invention is a method for manufacturing a high-strength composite nanosheet film that reinforces the Al compound nanosheet microstructure by a special process .
すなわち、本発明は、石英ガラス基板に金属Alをスパッタし、90℃温水バスに浸漬し、Al化合物ナノシート膜を成長させ、当該Al化合物ナノシート膜を洗浄して室温乾燥させてから、 AlThat is, the present invention sputters metal Al on a quartz glass substrate, immerses it in a 90 ° C. hot water bath, grows an Al compound nanosheet film, cleans the Al compound nanosheet film, and dries it at room temperature.
22
OO
3Three
微粒子層をスパッタし、二層複合構造ナノシート膜を作り、この二層複合構造ナノシート膜を空気中９００〜１１００℃で焼結させる高強度複合ナノシート膜の製造方法である。This is a method for producing a high-strength composite nanosheet film in which a fine particle layer is sputtered to form a double-layer composite structure nanosheet film, and this double-layer composite structure nanosheet film is sintered at 900 to 1100 ° C. in air.
また、本発明は、石英ガラス基板に金属Alをスパッタし、90℃温水バスに浸漬し、Al化合物ナノシート膜を成長させ、当該Al化合物ナノシート膜を洗浄して室温乾燥させて、空気中９００〜１１００℃で５〜２０分加熱した後、AlFurther, the present invention sputters metal Al on a quartz glass substrate, immerses it in a 90 ° C. hot water bath, grows an Al compound nanosheet film, cleans the Al compound nanosheet film, and dries it at room temperature. After heating at 1100 ° C. for 5-20 minutes, Al
22
OO
3Three
微粒子層40 nmをスパッタし、９００〜１１００℃で焼結させ二層複合微細構造の高強度複合ナノシート膜の製造方法である。This is a method for producing a high-strength composite nanosheet film having a two-layer composite microstructure by sputtering a fine particle layer of 40 nm and sintering at 900 to 1100 ° C.
さらに、本発明は、石英ガラス基板に金属Alをスパッタし、90℃温水バスに浸漬し、Al化合物ナノシート膜を成長させ、当該Al化合物ナノシート膜を洗浄して室温乾燥させてから、 AlFurthermore, the present invention sputters metal Al on a quartz glass substrate, immerses it in a 90 ° C. hot water bath, grows an Al compound nanosheet film, cleans the Al compound nanosheet film, and dries it at room temperature.
22
OO
3Three
微粒子層をスパッタし、二層複合構造ナノシート膜を作り、この二層複合構造ナノシート膜を空気中９００〜１１００℃で焼結させる高強度複合ナノシート膜の製造方法（請求項１に記載した製造方法）又は石英ガラス基板に金属Alをスパッタし、90℃温水バスに浸漬し、Al化合物ナノシート膜を成長させ、当該Al化合物ナノシート膜を洗浄して室温乾燥させて、空気中９００〜１１００℃で５〜２０分加熱した後、AlA method for producing a high-strength composite nanosheet film by sputtering a fine particle layer to form a double-layer composite structure nanosheet film, and sintering the double-layer composite structure nanosheet film at 900 to 1100 ° C. in air (the manufacturing method according to claim 1) ) Or sputtered metal Al on a quartz glass substrate, immersed in a 90 ° C. hot water bath to grow an Al compound nanosheet film, washed the Al compound nanosheet film and dried at room temperature, and in air at 900 to 1100 ° C. 5 After heating for ~ 20 minutes, Al
22
OO
3Three
微粒子層40 nmをスパッタし、９００〜１１００℃で焼結させ二層複合微細構造の高強度複合ナノシート膜の製造方法（請求項２に記載した製造方法）により得られる高強度複合ナノシート膜の表面を、溶剤中にヘプタデカフルオロデシルトリメトキシシラン（FAS）を溶解させた溶液中に１２〜３６時間静置した後、取り出し、洗浄して室温乾燥させる超撥水性透明膜の製造方法である。The surface of a high-strength composite nanosheet film obtained by sputtering a fine particle layer of 40 nm and sintering at 900 to 1100 ° C. to produce a high-strength composite nanosheet film having a two-layer composite microstructure (production method according to claim 2) Is a method for producing a super water-repellent transparent film in which heptadecafluorodecyltrimethoxysilane (FAS) is dissolved in a solvent for 12 to 36 hours, taken out, washed and dried at room temperature.
またさらに、本発明は、石英ガラス基板に金属Alをスパッタし、90℃温水バスに浸漬し、Al化合物ナノシート膜を成長させ、当該Al化合物ナノシート膜を洗浄して室温乾燥させてから、 AlFurthermore, the present invention sputters metal Al on a quartz glass substrate, immerses in a 90 ° C. hot water bath, grows an Al compound nanosheet film, cleans the Al compound nanosheet film, and dries it at room temperature.
22
OO
3Three
微粒子層をスパッタし、二層複合構造ナノシート膜を作り、この二層複合構造ナノシート膜を空気中９００〜１１００℃で焼結させる高強度複合ナノシート膜の製造方法（請求項１に記載した製造方法）又は石英ガラス基板に金属Alをスパッタし、90℃温水バスに浸漬し、Al化合物ナノシート膜を成長させ、当該Al化合物ナノシート膜を洗浄して室温乾燥させて、空気中９００〜１１００℃で５〜２０分加熱した後、AlA method for producing a high-strength composite nanosheet film by sputtering a fine particle layer to form a double-layer composite structure nanosheet film, and sintering the double-layer composite structure nanosheet film at 900 to 1100 ° C. in air (the manufacturing method according to claim 1) ) Or sputtered metal Al on a quartz glass substrate, immersed in a 90 ° C. hot water bath to grow an Al compound nanosheet film, washed the Al compound nanosheet film and dried at room temperature, and in air at 900 to 1100 ° C. 5 After heating for ~ 20 minutes, Al
22
OO
3Three
微粒子層40 nmをスパッタし、９００〜１１００℃で焼結させ二層複合微細構造の高強度複合ナノシート膜の製造方法（請求項２に記載した製造方法）により得られる高強度複合ナノシート膜の表面にヘプタデカフルオロデシルトリメトキシシラン（FAS）を蒸着させる超撥水性透明膜の製造方法である。The surface of a high-strength composite nanosheet film obtained by sputtering a fine particle layer of 40 nm and sintering at 900 to 1100 ° C. to produce a high-strength composite nanosheet film having a two-layer composite microstructure (production method according to claim 2) Is a method for producing a super water-repellent transparent film in which heptadecafluorodecyltrimethoxysilane (FAS) is vapor-deposited.
Al化合物またはAl2O3へ変化した単層ナノシート微細構造にAl2O3微粒子層を再スパッタし、空気中1000℃で数十分から数時間熱処理することにより、強度の高い二層複合ナノシート微細構造が作製される。この複合Al2O3ナノシート微細構造の表面に低分極率化合物をコーティングすることにより、耐久性かつ透明性を有する超撥水膜を得ることができる。作製された超撥水膜は、水との接触角が初期値として160以上°であり、ワイパー50回往復摺動後150°以上、150回往復摺動後おいても145°以上を持つことが可能である。すなわち、機械摩耗性に優れた耐久性をもつ超撥水膜である。このような機械摩耗性に優れた耐久性をもつ透明な超撥水膜は自動車、建物などの窓ガラス、メガネ等、様々な応用が期待される。 Re sputtered Al 2 O 3 fine particle layer in a single layer nanosheet microstructure changed to Al compound or Al 2 O 3, by heat treatment several tens of minutes to several hours at 1000 ° C. in air, high strength two-layer composite nanosheet A microstructure is created. By coating the surface of this composite Al 2 O 3 nanosheet microstructure with a low polarizability compound, a superhydrophobic film having durability and transparency can be obtained. The manufactured super water-repellent film has an initial contact angle with water of 160 ° or more, and has a wiper of 150 ° or more after 50 reciprocating slides and 145 ° or more after 150 reciprocating slides. Is possible. That is, it is a super water-repellent film having excellent mechanical wear resistance and durability. Such a transparent super water-repellent film having excellent mechanical wear resistance is expected to be used in various applications such as automobiles, window glass for buildings, and glasses.
本発明においては、超撥水膜の耐摩耗性能を向上するには、一般にはナノシートと基板そしてナノシートと低分極率化合物コーティング材の間の界面の結合を強める必要があると考えられる。さらに界面の結合強度に加え、ナノシート微細構造自身の弱さが膜の超撥水性を失効してしまう最も重要な原因であると実験より確認した。
上記目的を達成するために本発明は、二通りのプロセスでAl化合物ナノシート微細構造を強化した。（１）単層Al化合物ナノシート微細構造を熱処理なしにAl2O3微粒子層をスパッタし、二層を焼結させ、強い複合ナノ微細構造を作り出す；（２）単層Al化合物ナノシートを1000℃で短時間熱処理し、Al化合物はもとのナノシートの形状を保ちながらAl2O3への変化を行った上で、更にAl2O3微粒子層をスパッタして、二層を焼結させ、強い複合ナノ微細構造を作り出す。
In the present invention, in order to improve the wear resistance performance of the super water-repellent film, it is generally considered necessary to strengthen the interface bond between the nanosheet and the substrate and between the nanosheet and the low polarizability compound coating material. Furthermore, in addition to the bond strength at the interface, the weakness of the nanosheet microstructure itself was confirmed by experiments to be the most important cause of losing the superhydrophobicity of the film.
In order to achieve the above object, the present invention reinforces the Al compound nanosheet microstructure by two processes. (1) Sputtering Al 2 O 3 fine particle layer without heat treatment of single layer Al compound nanosheet microstructure without sintering, creating strong composite nanostructure; (2) 1000 ° C single layer Al compound nanosheet After heat-treating for a short time, the Al compound changed to Al 2 O 3 while maintaining the original nanosheet shape, and further sputtered the Al 2 O 3 fine particle layer to sinter the two layers, Create strong composite nanostructures.
具体な作り方は、下記の通りである。
（１）石英基板にAl金属膜5-150 nmをスパッタし、70-100℃の温水バスに0.5-3時間浸して、Al化合物ナノシート微細構造を成長させる。
（２）上記（１）から成長したAl化合物ナノシート微細構造に直接適当な厚みのAl2O3微粒子層（例えば、20〜100 nm）をスパッタし、二層複合構造をつくる。この二層複合構造を空気中1000℃で数十分熱処理し、焼結させ、強度の高い複合ナノシート微細構造を作製する。
（３）上記（１）から成長したAl化合物ナノシート微細構造を空気中1000℃で数分から数十分熱処理することで、Al化合物はもとのナノシート微細構造を保ちながらAl2O3への変化と結晶成長を先に行う。その後、単層Al2O3ナノシート微細構造の上に適当な厚みのAl2O3微粒子層（例えば、20〜100 nm）をスパッタし、二層複合構造をつくる。この二層複合構造を空気中1000℃で数十分から数時間熱処理し、焼結させ、強度の高い複合ナノシート微細構造を作製する。
（４）上記（２）と（３）による作製した複合Al2O3ナノシート微細構造の表面に低分極率化合物（例えば、フッ素を含むシラン化合物のヘプタデカフルオロデシルトリメトキシシラン（FAS））をコーティングすれば、超撥水性かつ耐熱、耐摩損性を持つ透明な膜が仕上がる。コーティング法としては、溶液浸漬法（60℃、24時間）または化学蒸着（CVD）法（180℃、1時間）等を挙げられる。
The specific method is as follows.
(1) Sputter an Al metal film of 5-150 nm on a quartz substrate and immerse in a hot water bath at 70-100 ° C. for 0.5-3 hours to grow an Al compound nanosheet microstructure.
(2) An Al 2 O 3 fine particle layer (for example, 20 to 100 nm) having an appropriate thickness is sputtered directly on the Al compound nanosheet microstructure grown from (1) to form a two-layer composite structure. This two-layer composite structure is heat-treated at 1000 ° C. for several tens of minutes in air and sintered to produce a high-strength composite nanosheet microstructure.
(3) The Al compound nanosheet microstructure grown from (1) above is heat-treated in air at 1000 ° C for several minutes to several tens of minutes, so that the Al compound changes to Al 2 O 3 while maintaining the original nanosheet microstructure. And crystal growth first. Thereafter, an Al 2 O 3 fine particle layer (for example, 20 to 100 nm) having an appropriate thickness is sputtered on the single layer Al 2 O 3 nanosheet microstructure to form a two-layer composite structure. This two-layer composite structure is heat-treated in air at 1000 ° C. for several tens of minutes to several hours and sintered to produce a composite nanosheet microstructure with high strength.
(4) A low polarizability compound (for example, heptadecafluorodecyltrimethoxysilane (FAS), which is a silane compound containing fluorine) is applied to the surface of the composite Al 2 O 3 nanosheet microstructure prepared according to (2) and (3) above. When coated, a transparent film with super water repellency, heat resistance, and abrasion resistance is finished. Examples of the coating method include a solution immersion method (60 ° C., 24 hours) or a chemical vapor deposition (CVD) method (180 ° C., 1 hour).
本発明では耐熱透明石英ガラス基板を用いる。金属Alをスパッタする前に、基板のクリーニングをすることが望ましい。金属Al膜の厚みは5-150 nm で透明かつ耐久性を有する超撥水膜が作製できるが20-70 nm にすることが望ましい。また、温水バスは85〜90℃、1〜1.5時間であるとすることが望ましい。
二層複合構造をつくるには、アモルファスAl化合物ナノシート膜に直接Al2O3微粒子層をスパッタする手法や、900-1000℃で10分程度熱処理後にスパッタする手法があるが、熱処理する時間は20分超えないことが望ましい。Al2O3微粒子層の厚みは20-100 nmで透明かつ耐久性を有する超撥水膜が作製できるが40-70nmが望ましい。この二層複合構造を空気中1000℃で焼結させ、強度の高い複合ナノシート微細構造が作製される。焼結時間は10分から数時間で透明かつ耐久性を有する超撥水膜が作製できるが、30〜60分が好ましい。
強化したナノシート微細構造の表面にコーティングする低分極率化合物シラン化合物とは、市販されているフッ素を含まないへキシルトリメトキシシラン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（FAS）などが挙げられる。
コーティング法としては、溶液浸漬法（60℃、24時間）またはCVD法（180℃、1時間）等を挙げられる。大量にまたは大面積を作製する場合は、CVD法が簡単でコーティング材の節約も可能である。
In the present invention, a heat-resistant transparent quartz glass substrate is used. It is desirable to clean the substrate before sputtering the metal Al. The metal Al film has a thickness of 5 to 150 nm, and a transparent and durable super water-repellent film can be produced. The hot water bath is desirably 85 to 90 ° C. and 1 to 1.5 hours.
To create a two-layer composite structure, there are a method of sputtering an Al 2 O 3 fine particle layer directly on an amorphous Al compound nanosheet film and a method of sputtering after heat treatment at 900-1000 ° C. for about 10 minutes, but the heat treatment time is 20 It is desirable not to exceed a minute. The Al 2 O 3 fine particle layer has a thickness of 20-100 nm, and a transparent and durable super water-repellent film can be produced, but 40-70 nm is desirable. This two-layer composite structure is sintered in air at 1000 ° C. to produce a high-strength composite nanosheet microstructure. The sintering time is 10 minutes to several hours, and a transparent and durable super water-repellent film can be produced, but 30 to 60 minutes is preferable.
Examples of the low polarizability compound silane compound that coats the surface of the reinforced nanosheet microstructure include commercially available fluorine-free hexyltrimethoxysilane or fluorine-containing heptadecafluorodecyltrimethoxysilane (FAS). .
Examples of the coating method include a solution immersion method (60 ° C., 24 hours) or a CVD method (180 ° C., 1 hour). When producing a large amount or a large area, the CVD method is simple and the coating material can be saved.
石英ガラス基板に金属Alを70 nmスパッタし、90℃温水バスに60分浸し、Al化合物ナノシート膜を成長させる。取り出した膜をエタノールで洗浄して室温乾燥させてから、厚み40 nmの Al2O3微粒子層をスパッタし、二層複合構造をつくる。この二層複合構造を空気中1000℃で40分熱処理し、焼結させ、強化複合ナノシート微細構造が出来上がる。その後、この微細構造の表面に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（FAS）をコーティングした。コーティングはへキサン中にシラン（FAS）を溶解させ、60℃にて24時間静置し、取り出し、エタノールで洗浄して室温乾燥させた。図３に、この強化複合ナノシート膜のワイパーテスト前後の微細構造および撥水性能を示している。Al化合物ナノシート及びそれを1000℃で熱処理したもの(図２)と比べると、Al2O3微粒子層をスパッタにより作製した二層複合構造は、1000℃で40分熱処理後、初期撥水性能が若干落ちるが機械摩耗に対する耐久性が高くなっていると分かる。ワイパー50回後でも、水との接触角が約143°を示す。 Sputtering 70 nm of metal Al on a quartz glass substrate and immersing in a 90 ° C hot water bath for 60 minutes to grow an Al compound nanosheet film. The extracted film is washed with ethanol and dried at room temperature, and then a 40 nm thick Al 2 O 3 fine particle layer is sputtered to form a two-layer composite structure. This two-layer composite structure is heat-treated in air at 1000 ° C. for 40 minutes and sintered to produce a reinforced composite nanosheet microstructure. Thereafter, heptadecafluorodecyltrimethoxysilane (FAS) containing fluorine was coated on the surface of this fine structure. In the coating, silane (FAS) was dissolved in hexane, allowed to stand at 60 ° C. for 24 hours, taken out, washed with ethanol, and dried at room temperature. FIG. 3 shows the microstructure and water repellency of the reinforced composite nanosheet film before and after the wiper test. Compared with Al compound nanosheets and those heat-treated at 1000 ° C (Fig. 2), the two-layer composite structure in which the Al 2 O 3 fine particle layer was sputtered has an initial water-repellent performance after heat treatment at 1000 ° C for 40 minutes. Although it falls a little, it turns out that the durability with respect to mechanical wear is high. Even after 50 wipers, the contact angle with water shows about 143 °.
実施例１と同様に、Al化合物ナノシート膜を成長させ、エタノール洗浄し、室温で乾燥させる。それを1000℃で10分加熱してから、Al2O3微粒子層40 nmをスパッタし、1000℃で40分焼結させ、二層複合微細構造を持つAl2O3膜を作製した。次に、実施例１と同様にFASをコーティングした。得られた膜のワイパーテスト前後の微細構造および撥水性能を図４に示している。Al2O3微粒子層をスパッタする前に１０分間熱処理することで、アモルファス膜をナノシート膜のAl2O3への変化に加えある程度の結晶成長をさせると、膜の初期撥水性が高くなり、50回ワイパー後でも、水との接触角が144°を示す。 Similarly to Example 1, an Al compound nanosheet film is grown, washed with ethanol, and dried at room temperature. After heating it at 1000 ° C. for 10 minutes, an Al 2 O 3 fine particle layer of 40 nm was sputtered and sintered at 1000 ° C. for 40 minutes to produce an Al 2 O 3 film having a two-layer composite microstructure. Next, FAS was coated in the same manner as in Example 1. FIG. 4 shows the microstructure and water repellency performance of the obtained film before and after the wiper test. By heat-treating the Al 2 O 3 fine particle layer for 10 minutes before sputtering, the amorphous film is changed to the Al 2 O 3 of the nanosheet film, and when the crystal grows to some extent, the initial water repellency of the film increases. Even after 50 wipers, the contact angle with water shows 144 °.
石英ガラス基板に金属Alを20 nmスパッタし、90℃温水バスに60分浸し、Al化合物ナノシート成長させる。取り出した膜をエタノールで洗浄して室温乾燥させてから、厚み70 nmの Al2O3微粒子層をスパッタし、二層複合構造をつくる。この二層複合構造を空気中1000℃で40分熱処理し、焼結させ、強化複合ナノシート微細構造が出来上がる。その後、上記実施例１と２と同様にFASをコーティングした。得られた膜のワイパーテスト前後の微細構造および撥水性能を図５に示している。この例から、スパッタする金属AlとAl2O3微粒子層の厚みを適切に組み合わせることで、機械摩耗に対する耐久性の優れた撥水膜ができると分かる。例としてAl-20nmとAl2O3-70nmをスパッタした場合、作製された膜は、水との接触角が初期において約155°、ワイパー50回後約150°を示している。更に、 ワイパー100回、150回にした後でも、水との接触角がそれぞれ約148°と147°を示した。
また、例として、この膜の透明性を図６に示した。
Sputtering 20 nm of metal Al on a quartz glass substrate and immersing in a 90 ° C hot water bath for 60 minutes to grow Al compound nanosheets. The extracted film is washed with ethanol and dried at room temperature, and then a 70 nm thick Al 2 O 3 fine particle layer is sputtered to form a two-layer composite structure. This two-layer composite structure is heat-treated in air at 1000 ° C. for 40 minutes and sintered to produce a reinforced composite nanosheet microstructure. Thereafter, FAS was coated in the same manner as in Examples 1 and 2 above. FIG. 5 shows the microstructure and water repellency of the obtained film before and after the wiper test. From this example, it can be seen that a water-repellent film having excellent durability against mechanical wear can be obtained by appropriately combining the thicknesses of the sputtered metal Al and Al 2 O 3 fine particle layer. As an example, when Al-20 nm and Al 2 O 3 -70 nm are sputtered, the produced film shows an initial contact angle with water of about 155 ° and about 150 ° after 50 wipers. Furthermore, the contact angle with water showed about 148 ° and 147 °, respectively, even after 100 and 150 wipers.
As an example, the transparency of this film is shown in FIG.
本発明の高強度複合ナノシート膜は、超撥水透明膜のみならず、超撥水不透明膜やその他の機能性膜としても利用でき、また、本発明の超撥水透明膜は、ワイーパーなどを作動させない省エネルギーの乗り物の窓など、きわめて利用価値が高く、産業上の利用可能性が高いものである。 The high-strength composite nanosheet film of the present invention can be used not only as a super-water-repellent transparent film, but also as a super-water-repellent opaque film and other functional films. The super-water-repellent transparent film of the present invention uses a wiper and the like. The window of energy-saving vehicles that cannot be operated is extremely valuable and has high industrial applicability.
Claims (4)
石英ガラス基板に金属Alをスパッタし、90℃温水バスに浸漬し、Al化合物ナノシート膜を成長させ、当該Al化合物ナノシート膜を洗浄して室温乾燥させてから、 Al2O3微粒子層をスパッタし、二層複合構造ナノシート膜を作り、この二層複合構造ナノシート膜を空気中９００〜１１００℃で焼結させる高強度複合ナノシート膜の製造方法。
Sputtered metal Al on a quartz glass substrate, immersed in a 90 ° C hot water bath, grown Al compound nanosheet film, washed the Al compound nanosheet film and dried at room temperature, then sputtered Al 2 O 3 fine particle layer The manufacturing method of the high intensity | strength composite nanosheet film | membrane which makes a double layer composite structure nanosheet film | membrane and sinters this double layer composite structure nanosheet film | membrane at 900-1100 degreeC in the air.
石英ガラス基板に金属Alをスパッタし、90℃温水バスに浸漬し、Al化合物ナノシート膜を成長させ、当該Al化合物ナノシート膜を洗浄して室温乾燥させて、空気中９００〜１１００℃で５〜２０分加熱した後、Al2O3微粒子層40 nmをスパッタし、９００〜１１００℃で焼結させ二層複合微細構造の高強度複合ナノシート膜の製造方法。
Sputtering metal Al on a quartz glass substrate, immersing in a 90 ° C. hot water bath, growing an Al compound nanosheet film, washing the Al compound nanosheet film and drying at room temperature, and in air at 900-1100 ° C. for 5-20 A method for producing a high-strength composite nanosheet film having a two-layer composite microstructure by sputtering the Al 2 O 3 fine particle layer of 40 nm after the partial heating and sintering at 900 to 1100 ° C.
請求項１または請求項２に記載した製造方法により得られる高強度複合ナノシート膜の表面を、溶剤中にヘプタデカフルオロデシルトリメトキシシラン（FAS）を溶解させた溶液中に１２〜３６時間静置した後、取り出し、洗浄して室温乾燥させる超撥水性透明膜の製造方法。
The surface of the high-strength composite nanosheet film obtained by the production method according to claim 1 or 2 is allowed to stand for 12 to 36 hours in a solution in which heptadecafluorodecyltrimethoxysilane (FAS) is dissolved in a solvent. Then, it is taken out, washed, and dried at room temperature.
請求項１又は請求項２に記載した製造方法により得られる高強度複合ナノシート膜の表面にヘプタデカフルオロデシルトリメトキシシラン（FAS）を蒸着させる超撥水性透明膜の製造方法。
A method for producing a super water-repellent transparent film in which heptadecafluorodecyltrimethoxysilane (FAS) is vapor-deposited on the surface of a high-strength composite nanosheet film obtained by the production method according to claim 1 or 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010081712A JP5578609B2 (en) | 2010-03-31 | 2010-03-31 | High-strength composite nanosheet film, transparent super water-repellent film using the same, and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010081712A JP5578609B2 (en) | 2010-03-31 | 2010-03-31 | High-strength composite nanosheet film, transparent super water-repellent film using the same, and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011213511A JP2011213511A (en) | 2011-10-27 |
| JP5578609B2 true JP5578609B2 (en) | 2014-08-27 |
Family
ID=44943657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010081712A Active JP5578609B2 (en) | 2010-03-31 | 2010-03-31 | High-strength composite nanosheet film, transparent super water-repellent film using the same, and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5578609B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107073899B (en) * | 2014-08-11 | 2019-06-28 | 株式会社Lg化学 | Alumina composition, substrate comprising the same, and method for producing the same |
| KR101814859B1 (en) | 2014-08-14 | 2018-01-04 | 주식회사 엘지화학 | Hydrophobic substrate and method for manufacturing the same |
| CN106623901B (en) * | 2016-12-19 | 2021-01-19 | 北京化工大学 | A kind of aluminum nanosheet, its preparation method and use |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2865065B2 (en) * | 1995-06-14 | 1999-03-08 | 東陶機器株式会社 | Composite with hydrophilic surface |
| JP4247354B2 (en) * | 1999-07-08 | 2009-04-02 | 財団法人大阪産業振興機構 | Low temperature formation method of surface fine uneven structure and substrate having the structure |
| JP2006205558A (en) * | 2005-01-28 | 2006-08-10 | Gunma Prefecture | Alumina coating structure and its manufacturing method |
| JP5062507B2 (en) * | 2006-02-08 | 2012-10-31 | 学校法人早稲田大学 | Alumina film, method for producing the same, and optical apparatus |
| JP2008104936A (en) * | 2006-10-25 | 2008-05-08 | National Institute Of Advanced Industrial & Technology | Super water-repellent aluminum foil and manufacturing method thereof |
| US8393478B2 (en) * | 2007-02-27 | 2013-03-12 | Corning Incorporated | Inorganic membranes and method of making |
| JP5392737B2 (en) * | 2007-05-22 | 2014-01-22 | 独立行政法人産業技術総合研究所 | Brittle material film structure |
-
2010
- 2010-03-31 JP JP2010081712A patent/JP5578609B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011213511A (en) | 2011-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Manca et al. | Durable superhydrophobic and antireflective surfaces by trimethylsilanized silica nanoparticles-based sol− gel processing | |
| Ebert et al. | Transparent, superhydrophobic, and wear-resistant coatings on glass and polymer substrates using SiO2, ZnO, and ITO nanoparticles | |
| JP5470628B2 (en) | Substrate surface treatment method that makes the surface of the substrate highly hydrophobic | |
| CN103993320B (en) | A kind of surface treatment method obtaining super-hydrophobicity aluminum or aluminum alloy surface | |
| US10450225B2 (en) | Low reflective and superhydrophobic or super water-repellent glasses and method of fabricating the same | |
| TW201119966A (en) | Super non-wetting, anti fingerprint coatings for glass | |
| TWI386297B (en) | Method of manufacturing plastic surface with superhydrophobicity and high transparency | |
| CN102463714B (en) | Covered element with fingerprint resistance and manufacture method thereof | |
| CN101215683A (en) | A Method for Improving the Bonding Strength of Plasma Sprayed Ceramic Coating and Substrate | |
| JP5578609B2 (en) | High-strength composite nanosheet film, transparent super water-repellent film using the same, and method for producing the same | |
| CN102843888A (en) | Casing and preparation method thereof | |
| TWI503430B (en) | Coated article and method for making the same | |
| TWI496917B (en) | Housing and method for making same | |
| CN103108979B (en) | Method for improving hydrophilicity of coating film by surface morphology treatment and superhydrophilic glass coating prepared by the method | |
| TWI536036B (en) | Methods for fabricating optical film | |
| Yasuda et al. | Fabrication of Superhydrophobic Nanostructures on Glass Surfaces Using Hydrogen Fluoride Gas | |
| KR101335705B1 (en) | A surface structure of metal having an Superhydrophobic property coatings and Method for fabricating of the same | |
| JP2012140670A (en) | Method of manufacturing metal oxide layer coating resin product and resin product thereof | |
| TWI668320B (en) | Method for enhancing adhesion of anti-fouling film | |
| Yang et al. | Ultrahydrophobicity of ZnO modified CVD diamond films | |
| CN111139478A (en) | Application and method of MoS2-ZnO heterostructure as reversible light-controlled wetting material | |
| CN107283955B (en) | A screen protector and method of making the same | |
| KR102851947B1 (en) | HIGH TRANSMITTANCE ZnS LENS COATED WITH ANTIREFLECTION IN THE INTRARED REGION AND MANUFACTURING METHOD THEREOF | |
| CN102400138B (en) | Film plating member and its manufacturing method | |
| TWI480400B (en) | Coated articles and method for making the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130326 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130325 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131211 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140207 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140605 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140703 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5578609 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |