JP4650991B2 - Oxide film mainly composed of SiO2 - Google Patents
Oxide film mainly composed of SiO2 Download PDFInfo
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- JP4650991B2 JP4650991B2 JP2002219386A JP2002219386A JP4650991B2 JP 4650991 B2 JP4650991 B2 JP 4650991B2 JP 2002219386 A JP2002219386 A JP 2002219386A JP 2002219386 A JP2002219386 A JP 2002219386A JP 4650991 B2 JP4650991 B2 JP 4650991B2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title 2
- 229910052681 coesite Inorganic materials 0.000 title 1
- 229910052906 cristobalite Inorganic materials 0.000 title 1
- 239000000377 silicon dioxide Substances 0.000 title 1
- 235000012239 silicon dioxide Nutrition 0.000 title 1
- 229910052682 stishovite Inorganic materials 0.000 title 1
- 229910052905 tridymite Inorganic materials 0.000 title 1
- 239000002245 particle Substances 0.000 claims description 19
- 230000003746 surface roughness Effects 0.000 claims description 19
- 230000002093 peripheral effect Effects 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 125000001165 hydrophobic group Chemical group 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000010408 film Substances 0.000 description 70
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 33
- 239000011521 glass Substances 0.000 description 28
- 229910052782 aluminium Inorganic materials 0.000 description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 108010025899 gelatin film Proteins 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012643 polycondensation polymerization Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Images
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- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Silicon Compounds (AREA)
- Chemically Coating (AREA)
Description
【０００１】
【発明の属する技術分野】
この発明は、金属、ガラス等の種々の材質の基材の表面に形成されるＳｉＯ２を主成分とする酸化物皮膜に関する。
【０００２】
【従来の技術と発明が解決しようとする課題】
金属アルコキシドの加水分解およびその後の縮合重合により得られるゾルを基材に塗布し、ついで乾燥させることにより得られたゲル膜を焼成して酸化物皮膜を形成するゾル−ゲル法によって、表面が平滑で内部が緻密な皮膜や表面に凹凸を持った薄膜が作製できることが知られている。
【０００３】
表面が平滑で内部が緻密な皮膜の場合、基材の腐食や、基材への液体の浸透という問題が生じることは少ないが、皮膜表面にさらにフッ化炭素鎖を持つシランカップリング剤等をコーティングしても超はっ水性を得ることはできず、しかも平滑な皮膜表面に樹脂などの塗装を施す場合、良好な塗膜の密着性が得られないという問題がある。一方、既存のゾル−ゲル法により作製した凹凸を持った薄膜の場合、基材の腐食や、基材への液体の浸透の防止には十分な効果が得られず、また、この皮膜上に表面の凹凸を損なわないように薄くはっ水コーティングを施した場合、比較的耐久性に優れたはっ水膜が得られるものの、超はっ水性が得られるほどの膜表面の凹凸による形状効果はないという問題がある。
【０００４】
この発明の目的は、上記問題を解決し、緻密な皮膜と凹凸を持った皮膜との長所を合わせ持った酸化物皮膜を提供することにある。
【０００５】
【課題を解決するための手段と発明の効果】
この発明による酸化物皮膜は、ＳｉＯ２を主成分とするとともに、ゾル−ゲル法により形成されており、緻密層上に凹凸層が一体に形成され、凹凸層の表面全体に微細な凹凸が形成されて粗面化されているものである。
【０００６】
この発明の酸化物皮膜によれば、ＳｉＯ２を主成分とするとともに、ゾル−ゲル法により形成されており、緻密層上に凹凸層が一体に形成され、凹凸層の表面全体に微細な凹凸が形成されて粗面化されているので、緻密層の働きにより、この酸化物皮膜が形成された基材の腐食や基材への液体の浸透を防止することができる。また、凹凸層の働きにより、皮膜表面に凹凸層の形状を損なわないように薄くはっ水コートすることによって超はっ水性を得ることができ、しかも凹凸皮膜表面に塗膜を施す場合、塗膜の密着性が優れたものとなる。
【０００７】
上記酸化物皮膜において、膜厚が０．１〜１０μｍであることが好ましい。
【０００８】
また、上記酸化物皮膜において、凹凸層の表面粗さが最大高さＲmaxで０．０３〜３μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔が０．０３〜１０μｍとなされていることが好ましい。また、上記凹凸層の表面に、微細な凹凸に加え、さらに相当直径０．０３〜１０μｍ、深さ０．０３〜３μｍの孔が形成され、この孔の周面および底面全体にも微細な凹凸が形成されて粗面化されており、孔の周面および底面の表面粗さが最大高さＲmaxで０．０１〜１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔が０．０１〜１μｍとなされていることが好ましい。ここで、相当直径とは、孔の横断面積と等しい面積を有する円の直径を意味する。
【０００９】
この発明による酸化物皮膜の製造方法は、Ｒ１ｎＳｉ（ＯＲ２）４−ｎ（但し式中Ｒ１はアルキル基、フェニル基等の疎水基、あるいはアルキル基等のＣ−Ｈ結合の一部がＣ−Ｆ結合に置換されたものであり、Ｒ２はアルキル基であり、ｎ＝１、２である。）と、溶媒と、水と、酸触媒とよりなる液組成物に、酸化物粒子を混ぜ合わせたものを攪拌することにより得たゾルを基材に塗布して乾燥させることによりゲル膜を作製し、その後焼成することを特徴とするものである。
【００１０】
上記において、アルキル基等のＣ−Ｈ結合の一部がＣ−Ｆ結合に置換されたものの具体例としては、たとえばＣＦ３（ＣＦ２）ｎＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３、ＣＦ３（ＣＦ２）ｎＣＨ２ＣＨ２Ｓｉ（ＣＨ３）（ＯＣＨ３）２（但し両式中ｎ＝０、１、２、３、４…である。）等のフルオロアルキルアルコキシシランが挙げられる。
【００１１】
上記において、溶媒としては、イソプロパノール、エタノール、メタノール等の低級アルコールが単独でもしくは混合して用いられ、またはこれらにブタノールや、ブタノールより炭素数の多いアルコールを適量添加して用いられる。あるいは、これらにエーテル、ケトン、アミド等の有機溶媒が添加される場合もある。
【００１２】
上記において、酸化物粒子としては、ＳｉＯ２、ＴｉＯ２等の表面に−ＯＨ基を有するもの、あるいはカップリング剤で表面修飾したものが用いられ、その粒径は５ｎｍ〜２μｍであることが好ましい。酸化物粒子は、Ｒ１ｎＳｉ（ＯＲ２）４−ｎが加水分解し、縮合重合した生成物と結合し、表面が疎水基で覆われる。
【００１３】
上記において、液組成物には、さらに微量のＳｉ（ＯＲ２）４やＲ３ｎＳｉ（ＯＲ２）４−ｎ（但し式中Ｒ２はアルキル基であり、Ｒ３は末端に親水基を有するＨ２Ｎ（ＣＨ２）３等の置換基であり、ｎ＝１、２である。）を添加しておいてもよい。その添加量は適宜変更されるが、Ｓｉ（ＯＲ２）４がテトラエトキシシランの場合、Ｒ１ｎＳｉ（ＯＲ２）４−ｎがメチルトリエトキシシランであれば、テトラエトキシシランのメチルトリエトキシシランに対する混合比は、モル比でｘ：（１−ｘ）（但し０＜ｘ≦０．３）である。
【００１４】
この発明の酸化物皮膜の製造方法によれば、固体として残る成分、すなわちＲ１ｎＳｉ（ＯＲ２）４−ｎが加水分解し、縮合重合した生成物および表面がＲ１ｎＳｉ（ＯＲ２）４−ｎからの疎水基を持つ生成物で覆われた酸化物粒子と水とが膜乾燥時にはじき合うことにより、ＳｉＯ２を主成分とするとともに、緻密層上に凹凸層が一体に形成されている酸化物皮膜が１回の工程で形成される。
【００１５】
上記方法において、Ｒ１ｎＳｉ（ＯＲ２）４−ｎと、溶媒と、水と、酸触媒との混合比は、好ましくはモル比で１：１〜２０：１〜２０：０．００００１〜０．３である。
【００１６】
また、上記方法において、原料全体中の酸化物粒子の量は４０ｗｔ％以下が好ましい。４０ｗｔ％を越えると、酸化物粒子を液組成物中に分散できなくなるおそれがある。
【００１７】
さらに、上記方法において、酸化物粒子がＳｉＯ２からなることが好ましい。この場合、製造される酸化物皮膜が無色透明となり、この皮膜上に表面の凹凸を損なわないようにさらにフッ化炭素鎖を持つシランカップリング剤等ではっ水コートすることにより、たとえば自動車のフロントガラスに適用した場合、充分な視界を確保した上で、超はっ水性を得ることができ、極めて好都合である。
【００１８】
【発明の実施の形態】
以下、この発明の実施の形態を、図面を参照して説明する。
【００１９】
図１はこの発明による酸化物皮膜の１実施形態を示す。図１において、酸化物皮膜（１）は、ＳｉＯ２を主成分とするとともに、ゾル−ゲル法により形成されており、緻密層（２）上に凹凸層（３）が一体に形成されているものである。凹凸層（３）の表面全体に微細な凹凸が形成されて粗面化されている。
【００２０】
酸化物皮膜（１）の膜厚（Ｔ）は、０．１〜１０μｍである。凹凸層（３）の表面粗さは最大高さＲｍａｘで０．０３〜３μｍであり、凹部（４）から最近接の凹部（４）あるいは凸部（５）から最近接の凸部（５）までの間隔（Ｗ）が０．０３〜１０μｍとなされている。
【００２１】
図２はこの発明による酸化物皮膜の他の実施形態を示す。図２において、酸化物皮膜（１０）は、図１と同様な酸化物皮膜（１）における凹凸層（３）の表面に、微細な凹凸に加え、さらに相当直径（Ｄ）０．０３〜１０μｍ、深さ（Ｓ）０．０３〜３μｍの孔（１１）が形成されたものである。この孔（１１）の周面および底面全体にも微細な凹凸が形成されて粗面化されており、孔（１１）の周面および底面の表面粗さは最大高さＲmaxで０．０１〜１μｍであり、凹部（１２）から最近接の凹部（１２）あるいは凸部（１３）から最近接の凸部（１３）までの間隔（Ｗ1）が０．０１〜１μｍとなされている。
【００２２】
図１および図２に見られる酸化物皮膜（１）（１０）の製造方法は、Ｒ１ｎＳｉ（ＯＲ２）４−ｎ（但し式中Ｒ１はアルキル基、フェニル基等の疎水基、あるいはアルキル基等のＣ−Ｈ結合の一部がＣ−Ｆ結合に置換されたものであり、Ｒ２はアルキル基であり、ｎ＝１、２である。）と、溶媒と、水と、酸触媒とよりなる液組成物に、酸化物粒子を混ぜ合わせたものを攪拌することにより得たゾルを基材に塗布する工程と、基材に塗布したゾルを乾燥させゲル膜を形成する工程と、ゲル膜を焼成する工程とを含む。
【００２３】
ここで、液組成物におけるＲ１ｎＳｉ（ＯＲ２）４−ｎと、溶媒と、水と、酸触媒との混合比は、モル比で１：１〜２０：１〜２０：０．００００１〜０．３であることが好ましく、原料全体中の酸化物微粒子の量は４０ｗｔ％であることが好ましい。
【００２４】
ゾルの基材への塗布は、ディッピング、スプレーコティング、スピン等により行う。スピンとは、基材表面にゾルを滴下した後、遠心力により塗布する方法である。
【００２５】
ゲル膜の焼成は７０〜８００℃で３０秒〜１０分間加熱することにより行う。
【００２６】
なお、製造された酸化物皮膜に化学的、機械的耐久性を持たせるために、１８０℃以上で熱処理することが好ましい。
【００２７】
【実施例と比較例】
以下、この発明の具体的実施例を比較例とともに説明する。
【００２８】
実施例１
メチルトリエトキシシランと、溶媒であるエタノールおよび２−プロパノールと、水と、塩酸と、２−プロパノールに分散させた粒径０．０１〜０．０２μｍのＳｉＯ２粒子を原料として用意した。なお、ＳｉＯ２粒子を分散させている２−プロパノールは溶媒の一部として用いた。メチルトリエトキシシラン、溶媒（エタノール、２−プロパノールのモル比が１：１）、水、塩酸のモル比が１：５：４：０．００５、粒子濃度が１０ｗｔ％となるように原料を混合し、メチルトリエトキシシランを加水分解、縮合重合させることによりゾルを得た。ついで、このゾル中にアルミニウム板およびガラス板を浸漬し、２ｍｍ／秒の引き上げ速度で引き上げ、乾燥させた後、４００℃で５分間焼成し、アルミニウム板およびガラス板の表面に酸化物皮膜を形成した。
【００２９】
アルミニウム板の表面に形成された酸化物皮膜をＳＥＭにより観察したところ、膜厚は０．８μｍであり、緻密層上に、表面全体に微細な凹凸が形成されて粗面化された凹凸層が一体に形成されていた。凹凸層の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。さらに、凹凸層の表面に、微細な凹凸に加えて相当直径０．０５〜０．１μｍ、深さ０．０５〜０．１μｍの孔が５×１０９個／ｃｍ２以上形成されていた。この孔の周面および底面全体にも微細な凹凸が形成されて粗面化されており、孔の周面および底面の表面粗さは最大高さＲmaxで０．０３〜０．０５μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．０５μｍであった。
【００３０】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、９０〜９２％であった。なお、用いたガラス板自体の透過率は測定波長域４００〜７００ｎｍで９０〜９１％である。
【００３１】
実施例２
ゾル中にアルミニウム板およびガラス板を浸漬した後、アルミニウム板およびガラス板を引き上げるさいの引上げ速度を２０ｍｍ／秒とした他は、上記実施例１と同様にしてアルミニウム板およびガラス板の表面に酸化物皮膜を形成した。
【００３２】
アルミニウム板の表面に形成された酸化物皮膜をＳＥＭにより観察したところ、膜厚は２．６μｍであり、緻密層上に、表面全体に微細な凹凸が形成されて粗面化された凹凸層が一体に形成されていた。凹凸層の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。さらに、凹凸層の表面に、微細な凹凸に加えて相当直径０．２〜０．５μｍ、深さ０．２〜０．５μｍの孔が３．８×１０７個／ｃｍ２、相当直径０．０５〜０．１μｍ、深さ０．０５〜０．１μｍの孔が５×１０９個／ｃｍ２以上形成されていた。これらの孔の周面および底面全体にも微細な凹凸が形成されて粗面化されており、孔の周面および底面の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。
【００３３】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、８３〜９１％であった。
【００３４】
実施例３
液組成物中の溶媒として、２−プロパノールを単独で用いた他は、上記実施例１と同様にしてアルミニウム板およびガラス板の表面に酸化物皮膜を形成した。
【００３５】
アルミニウム板の表面に形成された酸化物皮膜をＳＥＭにより観察したところ、膜厚は０．６μｍであり、緻密層上に、表面全体に微細な凹凸が形成されて粗面化された凹凸層が一体に形成されていた。凹凸層の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。さらに、凹凸層の表面に、微細な凹凸に加えて相当直径０．０５〜０．１μｍ、深さ０．０５〜０．１μｍの孔が５×１０９個／ｃｍ２以上形成されており、この孔の周面および底面全体にも微細な凹凸が形成されて粗面化されており、孔の周面および底面の表面粗さは最大高さＲmaxで０．０３〜０．０５μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．０５μｍであった。
【００３６】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、９１〜９３％であった。
【００３７】
実施例４
ゾル中にアルミニウム板およびガラス板を浸漬した後、アルミニウム板およびガラス板を引き上げるさいの引上げ速度を５ｍｍ／秒とした他は、上記実施例３と同様にしてアルミニウム板およびガラス板の表面に酸化物皮膜を製造した。
【００３８】
アルミニウム板の表面に形成された酸化物皮膜をＳＥＭにより観察したところ、膜厚は１．３μｍであり、緻密層上に、表面全体に微細な凹凸が形成されて粗面化された凹凸層が一体に形成されていた。凹凸層の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。さらに、凹凸層の表面に、微細な凹凸に加えて相当直径０．１〜０．２μｍ、深さ０．１〜０．２μｍの孔が１．８×１０８個／ｃｍ２、相当直径０．０５〜０．１μｍ、深さ０．０５〜０．１μｍの孔が５×１０９個／ｃｍ２以上形成されていた。これら孔の周面および底面全体にも微細な凹凸が形成されて粗面化されており、孔の周面および底面の表面粗さは最大高さＲmaxで０．０３〜０．０７μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．０７μｍであった。
【００３９】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、９２〜９３％であった。
【００４０】
実施例５
ゾル中にアルミニウム板およびガラス板を浸漬した後、アルミニウム板およびガラス板を引き上げるさいの引上げ速度を２０ｍｍ／秒とした他は、上記実施例３と同様にしてアルミニウム板およびガラス板の表面に酸化物皮膜を形成した。
【００４１】
アルミニウム板の表面に形成された酸化物皮膜をＳＥＭにより観察したところ、膜厚は２．８μｍであり、緻密層上に、表面全体に微細な凹凸が形成されて粗面化された凹凸層が一体に形成されていた。凹凸層の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。さらに、凹凸層の表面に、微細な凹凸に加えて相当直径０．２〜０．５μｍ、深さ０．２〜０．５μｍの孔が１．１×１０８個／ｃｍ２、相当直径０．０５〜０．１μｍ、深さ０．０５〜０．１μｍの孔が５×１０９個／ｃｍ２以上形成されていた。これら孔の周面および底面全体にも微細な凹凸が形成されて粗面化されており、孔の周面および底面の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。
【００４２】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、８６〜９１％であった。
【００４３】
実施例６
液組成物中の溶媒として、１−ブタノールと２−プロパノールとをモル比で４８：５２となるように混合したものを用いた他は、上記実施例１と同様にしてアルミニウム板およびガラス板の表面に酸化物皮膜を製造した。
【００４４】
アルミニウム板の表面に形成された金属酸化物皮膜をＳＥＭにより観察したところ、膜厚は０．８μｍであり、緻密層上に、表面全体に微細な凹凸が形成されて粗面化された凹凸層が一体に形成されていた。凹凸層の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。
【００４５】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、９０〜９３％であった。
【００４６】
実施例７
ゾル中にアルミニウム板およびガラス板を浸漬した後、アルミニウム板およびガラス板を引き上げるさいの引上げ速度を２０ｍｍ／秒とした他は、上記実施例６と同様にしてアルミニウム板およびガラス板の表面に酸化物皮膜を製造した。
【００４７】
アルミニウム板の表面に形成された金属酸化物皮膜をＳＥＭにより観察したところ、膜厚は２．４μｍであり、緻密層上に、表面全体に微細な凹凸が形成されて粗面化された凹凸層が一体に形成されていた。凹凸層の表面粗さは最大高さＲmaxで０．０３〜０．１μｍであり、凹部から最近接の凹部あるいは凸部から最近接の凸部までの間隔は０．０３〜０．１μｍであった。
【００４８】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、９２〜９３％であった。
【００４９】
比較例１
メチルトリエトキシシランと、テトラエトキシシランと、２−プロパノールと、水と、塩酸と、２−プロパノールに分散させた粒径０．０１〜０．０２μｍのＳｉＯ２粒子を原料として用意した。なお、ＳｉＯ２粒子を分散させている２−プロパノールは溶媒の一部として用いた。メチルトリエトキシシラン、テトラエトキシシラン、２−プロパノール、水、塩酸のモル比が０．５：０．５：５：４：０．００５、粒子濃度が１０ｗｔ％となるように原料を混合し、メチルトリエトキシシランおよびテトラエトキシシランを加水分解、縮合重合させることによりゾルを得た。ついで、このゾル中にアルミニウム板およびガラス板を浸漬し、５ｍｍ／秒の引き上げ速度で引き上げ、乾燥させた後、４００℃で５分間焼成し、アルミニウム板およびガラス板の表面に酸化物皮膜を形成した。
【００５０】
アルミニウム板の表面に形成された酸化物皮膜をＳＥＭにより観察したところ、膜厚は１．５μｍであった。皮膜表面には相当直径０．０５〜０．１５μｍ、深さ０．０５〜０．１５μｍの孔が２．８×１０７個／ｃｍ２形成されていたが、実施例１〜７に見られるような微細な凹凸は存在しなかった。
【００５１】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、９１〜９３％であった。
【００５２】
比較例２
メチルトリエトキシシランと、２−プロパノールと、水と、塩酸とよりなり、かつ各成分の量がモル比で１：５：４：０．００５である液組成物を用意した。そして、この液組成物を混合し、メチルトリエトキシシランの加水分解、縮合重合によりゾルを得た。ついで、このゾル中にアルミニウム板およびガラス板を浸漬し、５ｍｍ／秒の引き上げ速度で引き上げ、乾燥させた後、４００℃で５分間焼成し、アルミニウム板およびガラス板の表面に酸化物皮膜を形成した。
【００５３】
アルミニウム板の表面に形成された酸化物皮膜を観察したところ、膜厚は０．７μｍであった。また、皮膜全体が緻密であって、表面は全体に平滑であった。
【００５４】
また、表面に酸化物皮膜が形成されたガラス板の透過率を、測定波長域４００〜７００ｎｍで測定したところ、９１〜９３％であった。
【図面の簡単な説明】
【図１】 この発明による酸化物皮膜の１実施形態を示す一部切欠き拡大斜視図である。
【図２】 この発明による酸化物皮膜の他の実施形態を示す一部切欠き拡大斜視図である。
【符号の説明】
（１）（１０）：酸化物皮膜
（２）：緻密層
（３）：凹凸層[0001]
BACKGROUND OF THE INVENTION
The present invention, metal, relates to an oxide skin film composed mainly of SiO 2 formed on the surface of various materials of the base material such as glass.
[0002]
[Prior art and problems to be solved by the invention]
A sol obtained by hydrolysis of metal alkoxide and subsequent condensation polymerization is applied to a substrate, and then dried to form a oxide film by firing the gel film obtained by drying, thereby smoothing the surface. It is known that a thin film with a dense inside and a thin film with irregularities on the surface can be produced.
[0003]
In the case of a coating with a smooth surface and a dense interior, there is little problem of corrosion of the substrate or penetration of liquid into the substrate, but a silane coupling agent having a fluorocarbon chain on the surface of the coating, etc. Even if it is coated, it is not possible to obtain super water repellency, and there is a problem that good coating film adhesion cannot be obtained when a coating such as resin is applied to the smooth film surface. On the other hand, in the case of an uneven thin film produced by an existing sol-gel method, sufficient effects cannot be obtained for corrosion of the base material and prevention of liquid penetration into the base material. When a thin water-repellent coating is applied so as not to impair the surface irregularities, a water-repellent film with relatively high durability can be obtained, but the shape effect due to the film surface irregularities enough to obtain super water-repellency There is no problem.
[0004]
The purpose of this invention is to solve the above problems, provides with the combined advantages of a film having a dense film and uneven oxide skin film.
[0005]
[Means for Solving the Problems and Effects of the Invention]
The oxide film according to the present invention has SiO 2 as a main component and is formed by a sol-gel method. The uneven layer is integrally formed on the dense layer, and fine unevenness is formed on the entire surface of the uneven layer. And roughened.
[0006]
According to the oxide film of the present invention, SiO 2 is the main component and is formed by a sol-gel method. The uneven layer is integrally formed on the dense layer, and fine unevenness is formed on the entire surface of the uneven layer. Is formed and roughened, the corrosion of the base material on which the oxide film is formed and the penetration of liquid into the base material can be prevented by the action of the dense layer. In addition, due to the function of the concavo-convex layer, it is possible to obtain super water repellency by thinly water-repellent coating so as not to impair the shape of the concavo-convex layer on the surface of the film, The film adhesion is excellent.
[0007]
In the oxide film, the film thickness is preferably 0.1 to 10 μm.
[0008]
Further, in the above oxide film, the surface roughness of the uneven layer is 0.03 to 3 μm at the maximum height Rmax, and the distance from the recessed portion to the nearest recessed portion or the protruding portion to the nearest protruding portion is 0.03. It is preferable that the thickness is 10 μm. Further, in addition to the fine unevenness, a hole having an equivalent diameter of 0.03 to 10 μm and a depth of 0.03 to 3 μm is formed on the surface of the uneven layer, and fine unevenness is also formed on the entire peripheral surface and bottom surface of the hole. Is formed, and the surface roughness of the peripheral surface and bottom surface of the hole is 0.01 to 1 μm at the maximum height Rmax, and the concave portion closest to the concave portion or the convex portion closest to the convex portion. It is preferable that the space | interval is set to 0.01-1 micrometer. Here, the equivalent diameter means the diameter of a circle having an area equal to the cross-sectional area of the hole.
[0009]
The method for producing an oxide film according to the present invention comprises: R 1 nSi (OR 2 ) 4-n (wherein R 1 is a hydrophobic group such as an alkyl group, a phenyl group, or a part of a C—H bond such as an alkyl group) Is substituted with a C—F bond, R 2 is an alkyl group, and n = 1 and 2), a liquid composition comprising a solvent, water, and an acid catalyst. A sol obtained by stirring the mixture of particles is applied to a substrate and dried to prepare a gel film and then fired.
[0010]
In the above, as a specific example of a part in which a C—H bond such as an alkyl group is substituted with a C—F bond, for example, CF 3 (CF 2 ) n CH 2 CH 2 Si (OCH 3 ) 3 , CF 3 Fluoroalkylalkoxysilanes such as (CF 2 ) n CH 2 CH 2 Si (CH 3 ) (OCH 3 ) 2 (where n = 0, 1, 2, 3, 4...) Are mentioned.
[0011]
In the above, as the solvent, lower alcohols such as isopropanol, ethanol, methanol and the like are used alone or in combination, or butanol and an alcohol having a higher carbon number than butanol are added in an appropriate amount. Alternatively, an organic solvent such as ether, ketone or amide may be added to these.
[0012]
In the above, as the oxide particles, those having a —OH group on the surface of SiO 2 , TiO 2 or the like, or those modified with a coupling agent are used, and the particle diameter is preferably 5 nm to 2 μm. . In the oxide particles, R 1 nSi (OR 2 ) 4-n is hydrolyzed and bonded to the condensation polymerized product, and the surface is covered with a hydrophobic group.
[0013]
In the above, the liquid composition further contains a trace amount of Si (OR 2 ) 4 or R 3 nSi (OR 2 ) 4-n (where R 2 is an alkyl group, and R 3 has a hydrophilic group at the terminal). A substituent such as H 2 N (CH 2 ) 3 and n = 1, 2) may be added. The amount of addition is appropriately changed, but when Si (OR 2 ) 4 is tetraethoxysilane, if R 1 nSi (OR 2 ) 4-n is methyltriethoxysilane, methyltriethoxysilane of tetraethoxysilane The mixing ratio with respect to is x: (1-x) (where 0 <x ≦ 0.3) in molar ratio.
[0014]
According to the method for producing an oxide film of the present invention, a component remaining as a solid, that is, a product obtained by hydrolysis and condensation polymerization of R 1 nSi (OR 2 ) 4-n and the surface thereof are R 1 nSi (OR 2 ) 4. -Oxide particles covered with a product having a hydrophobic group from n and water repel each other at the time of film drying, so that SiO 2 is the main component and an uneven layer is integrally formed on the dense layer. The oxide film is formed in one step.
[0015]
In the above method, the mixing ratio of R 1 nSi (OR 2 ) 4-n , solvent, water, and acid catalyst is preferably 1: 1 to 20: 1 to 20: 0.00001 to 0 in molar ratio. .3.
[0016]
In the above method, the amount of oxide particles in the entire raw material is preferably 40 wt% or less. If it exceeds 40 wt%, the oxide particles may not be dispersed in the liquid composition.
[0017]
Furthermore, in the above method, the oxide particles are preferably made of SiO 2 . In this case, the manufactured oxide film is colorless and transparent, and is coated with a silane coupling agent or the like having a fluorocarbon chain so as not to impair the surface irregularities. When applied to glass, it is extremely advantageous because it can obtain a super water repellency while securing a sufficient field of view.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below with reference to the drawings.
[0019]
FIG. 1 shows an embodiment of an oxide film according to the present invention. In FIG. 1, the oxide film (1) has SiO 2 as a main component and is formed by a sol-gel method, and an uneven layer (3) is integrally formed on the dense layer (2). Is. Fine irregularities are formed and roughened on the entire surface of the irregular layer (3).
[0020]
The film thickness (T) of the oxide film (1) is 0.1 to 10 μm. The surface roughness of the concavo-convex layer (3) is 0.03 to 3 μm at the maximum height Rmax, and the concave portion (4) closest to the concave portion (4) or the convex portion closest to the convex portion (5) (5). (W) is 0.03 to 10 μm.
[0021]
FIG. 2 shows another embodiment of the oxide film according to the present invention. In FIG. 2, the oxide film (10) has an equivalent diameter (D) of 0.03 to 10 μm in addition to the fine unevenness on the surface of the uneven layer (3) in the oxide film (1) similar to FIG. , A hole (11) having a depth (S) of 0.03 to 3 μm is formed. Fine irregularities are also formed on the entire peripheral surface and bottom surface of the hole (11) to roughen the surface, and the surface roughness of the peripheral surface and bottom surface of the hole (11) is 0.01 to maximum height Rmax. The distance (W1) from the concave portion (12) to the nearest concave portion (12) or the convex portion (13) to the nearest convex portion (13) is set to 0.01 to 1 µm.
[0022]
The manufacturing method of the oxide film (1) (10) seen in FIG. 1 and FIG. 2 is R 1 nSi (OR 2 ) 4-n (where R 1 is a hydrophobic group such as an alkyl group or a phenyl group, or A part of the C—H bond such as an alkyl group is substituted with a C—F bond, R 2 is an alkyl group, and n = 1, 2), a solvent, water, an acid to become more liquid composition and the catalyst, a step of applying a sol obtained by stirring those mixed oxide particles to a substrate, forming a gel film is dried the sol applied to the substrate And a step of firing the gel film.
[0023]
Here, the mixing ratio of R 1 nSi (OR 2 ) 4-n , solvent, water, and acid catalyst in the liquid composition is 1: 1 to 20: 1 to 20: 0.00001 to a molar ratio. 0.3 is preferable, and the amount of oxide fine particles in the entire raw material is preferably 40 wt%.
[0024]
Application of the sol to the substrate is performed by dipping, spray coating, spinning, or the like. Spin is a method in which a sol is dropped onto a substrate surface and then applied by centrifugal force.
[0025]
The gel film is baked by heating at 70 to 800 ° C. for 30 seconds to 10 minutes.
[0026]
In addition, in order to give chemical and mechanical durability to the manufactured oxide film, it is preferable to heat-process at 180 degreeC or more.
[0027]
[Examples and comparative examples]
Hereinafter, specific examples of the present invention will be described together with comparative examples.
[0028]
Example 1
Methyltriethoxysilane, ethanol and 2-propanol as solvents, water, hydrochloric acid, and SiO 2 particles having a particle diameter of 0.01 to 0.02 μm dispersed in 2-propanol were prepared as raw materials. In addition, 2 -propanol in which SiO 2 particles are dispersed was used as a part of the solvent. The raw materials are mixed so that the molar ratio of methyltriethoxysilane, solvent (ethanol, 2-propanol molar ratio is 1: 1), water, hydrochloric acid is 1: 5: 4: 0.005, and the particle concentration is 10 wt%. A sol was obtained by hydrolysis and condensation polymerization of methyltriethoxysilane. Next, an aluminum plate and a glass plate are immersed in this sol, pulled up at a pulling rate of 2 mm / second, dried, and then fired at 400 ° C. for 5 minutes to form an oxide film on the surfaces of the aluminum plate and the glass plate. did.
[0029]
When the oxide film formed on the surface of the aluminum plate was observed with an SEM, the film thickness was 0.8 μm, and the uneven layer roughened by forming fine unevenness on the entire surface on the dense layer. It was integrally formed. The surface roughness of the concavo-convex layer is 0.03 to 0.1 μm at the maximum height Rmax, and the distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion is 0.03 to 0.1 μm. It was. Furthermore, 5 × 10 9 holes / cm 2 or more of an equivalent diameter of 0.05 to 0.1 μm and a depth of 0.05 to 0.1 μm were formed on the surface of the uneven layer in addition to fine unevenness. Fine irregularities are also formed on the entire peripheral surface and bottom surface of the hole to be roughened, and the surface roughness of the peripheral surface and bottom surface of the hole is 0.03 to 0.05 μm at the maximum height Rmax, The distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion was 0.03 to 0.05 μm.
[0030]
Moreover, it was 90 to 92% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm. In addition, the transmittance | permeability of the used glass plate itself is 90 to 91% in a measurement wavelength range 400-700 nm.
[0031]
Example 2
The surface of the aluminum plate and the glass plate was oxidized in the same manner as in Example 1 except that the aluminum plate and the glass plate were immersed in the sol, and then the pulling speed was 20 mm / sec. A physical film was formed.
[0032]
When the oxide film formed on the surface of the aluminum plate was observed by SEM, the film thickness was 2.6 μm, and the uneven layer roughened by forming fine unevenness on the entire surface on the dense layer. It was integrally formed. The surface roughness of the concavo-convex layer is 0.03 to 0.1 μm at the maximum height Rmax, and the distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion is 0.03 to 0.1 μm. It was. Further, on the surface of the uneven layer, in addition to fine unevenness, there are 3.8 × 10 7 holes / cm 2 with an equivalent diameter of 0.2 to 0.5 μm and a depth of 0.2 to 0.5 μm, and an equivalent diameter of 0. There were formed 5 × 10 9 holes / cm 2 or more of holes having a thickness of 0.05 to 0.1 μm and a depth of 0.05 to 0.1 μm. Fine irregularities are also formed on the entire peripheral surface and bottom surface of these holes to roughen the surface, and the surface roughness of the peripheral surface and bottom surface of the holes is 0.03-0.1 μm at the maximum height Rmax. The distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion was 0.03 to 0.1 μm.
[0033]
Moreover, it was 83 to 91% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm.
[0034]
Example 3
An oxide film was formed on the surfaces of the aluminum plate and the glass plate in the same manner as in Example 1 except that 2-propanol was used alone as the solvent in the liquid composition.
[0035]
When the oxide film formed on the surface of the aluminum plate was observed by SEM, the film thickness was 0.6 μm, and the uneven layer roughened by forming fine unevenness on the entire surface on the dense layer. It was integrally formed. The surface roughness of the concavo-convex layer is 0.03 to 0.1 μm at the maximum height Rmax, and the distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion is 0.03 to 0.1 μm. It was. Furthermore, 5 × 10 9 holes / cm 2 or more of an equivalent diameter of 0.05 to 0.1 μm and a depth of 0.05 to 0.1 μm are formed on the surface of the uneven layer in addition to fine unevenness, Fine irregularities are also formed on the entire peripheral surface and bottom surface of the hole to be roughened, and the surface roughness of the peripheral surface and bottom surface of the hole is 0.03 to 0.05 μm at the maximum height Rmax, The distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion was 0.03 to 0.05 μm.
[0036]
Moreover, it was 91 to 93% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm.
[0037]
Example 4
The surface of the aluminum plate and the glass plate was oxidized in the same manner as in Example 3 except that the aluminum plate and the glass plate were immersed in the sol, and then the pulling rate was 5 mm / sec. A physical coating was produced.
[0038]
When the oxide film formed on the surface of the aluminum plate was observed by SEM, the film thickness was 1.3 μm, and on the dense layer, there was an uneven layer roughened by forming fine unevenness on the entire surface. It was integrally formed. The surface roughness of the concavo-convex layer is 0.03 to 0.1 μm at the maximum height Rmax, and the distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion is 0.03 to 0.1 μm. It was. Further, on the surface of the concavo-convex layer, in addition to the fine concavo-convex, 1.8 × 10 8 holes / cm 2 with an equivalent diameter of 0.1 to 0.2 μm and a depth of 0.1 to 0.2 μm and an equivalent diameter of 0 There were formed 5 × 10 9 holes / cm 2 or more of holes having a thickness of 0.05 to 0.1 μm and a depth of 0.05 to 0.1 μm. Fine irregularities are also formed on the entire peripheral surface and bottom surface of these holes to be roughened, and the surface roughness of the peripheral surface and bottom surface of the holes is 0.03 to 0.07 μm at the maximum height Rmax, The distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion was 0.03 to 0.07 μm.
[0039]
Moreover, it was 92 to 93% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm.
[0040]
Example 5
The surface of the aluminum plate and the glass plate was oxidized in the same manner as in Example 3 except that the aluminum plate and the glass plate were immersed in the sol, and then the pulling speed was 20 mm / sec. A physical film was formed.
[0041]
When the oxide film formed on the surface of the aluminum plate was observed by SEM, the film thickness was 2.8 μm, and the uneven layer roughened by forming fine unevenness on the entire surface on the dense layer. It was integrally formed. The surface roughness of the concavo-convex layer is 0.03 to 0.1 μm at the maximum height Rmax, and the distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion is 0.03 to 0.1 μm. It was. Furthermore, 1.1 × 10 8 holes / cm 2 with an equivalent diameter of 0.2 to 0.5 μm and a depth of 0.2 to 0.5 μm in addition to the fine unevenness on the surface of the uneven layer, the equivalent diameter of 0 There were formed 5 × 10 9 holes / cm 2 or more of holes having a thickness of 0.05 to 0.1 μm and a depth of 0.05 to 0.1 μm. Fine irregularities are also formed on the entire peripheral surface and bottom surface of these holes to be roughened, and the surface roughness of the peripheral surface and bottom surface of the hole is 0.03-0.1 μm at the maximum height Rmax, The distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion was 0.03 to 0.1 μm.
[0042]
Moreover, it was 86 to 91% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm.
[0043]
Example 6
As the solvent in the liquid composition, aluminum plates and glass plates were formed in the same manner as in Example 1 except that 1-butanol and 2-propanol were mixed in a molar ratio of 48:52. An oxide film was produced on the surface.
[0044]
When the metal oxide film formed on the surface of the aluminum plate was observed by SEM, the film thickness was 0.8 μm, and the uneven layer was roughened by forming fine unevenness on the entire surface on the dense layer. Was integrally formed. The surface roughness of the concavo-convex layer is 0.03 to 0.1 μm at the maximum height Rmax, and the distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion is 0.03 to 0.1 μm. It was.
[0045]
Moreover, it was 90 to 93% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm.
[0046]
Example 7
The surface of the aluminum plate and the glass plate was oxidized in the same manner as in Example 6 except that the aluminum plate and the glass plate were immersed in the sol, and then the pulling rate was 20 mm / sec. A physical coating was produced.
[0047]
When the metal oxide film formed on the surface of the aluminum plate was observed by SEM, the film thickness was 2.4 μm, and the uneven layer was roughened by forming fine unevenness on the entire surface on the dense layer. Was integrally formed. The surface roughness of the concavo-convex layer is 0.03 to 0.1 μm at the maximum height Rmax, and the distance from the concave portion to the nearest concave portion or from the convex portion to the nearest convex portion is 0.03 to 0.1 μm. It was.
[0048]
Moreover, it was 92 to 93% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm.
[0049]
Comparative Example 1
Methyltriethoxysilane, tetraethoxysilane, 2-propanol, water, hydrochloric acid, and SiO 2 particles having a particle diameter of 0.01 to 0.02 μm dispersed in 2-propanol were prepared as raw materials. In addition, 2 -propanol in which SiO 2 particles are dispersed was used as a part of the solvent. The raw materials are mixed so that the molar ratio of methyltriethoxysilane, tetraethoxysilane, 2-propanol, water, hydrochloric acid is 0.5: 0.5: 5: 4: 0.005, and the particle concentration is 10 wt%. A sol was obtained by hydrolysis and condensation polymerization of methyltriethoxysilane and tetraethoxysilane. Next, an aluminum plate and a glass plate are immersed in this sol, pulled up at a pulling rate of 5 mm / second, dried, and then fired at 400 ° C. for 5 minutes to form an oxide film on the surfaces of the aluminum plate and the glass plate. did.
[0050]
When the oxide film formed on the surface of the aluminum plate was observed by SEM, the film thickness was 1.5 μm. Although 2.8 × 10 7 holes / cm 2 having an equivalent diameter of 0.05 to 0.15 μm and a depth of 0.05 to 0.15 μm were formed on the surface of the film, it can be seen in Examples 1 to 7. There were no such fine irregularities.
[0051]
Moreover, it was 91 to 93% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm.
[0052]
Comparative Example 2
A liquid composition comprising methyltriethoxysilane, 2-propanol, water, and hydrochloric acid, and the amount of each component in a molar ratio of 1: 5: 4: 0.005 was prepared. Then, this liquid composition was mixed, and a sol was obtained by hydrolysis and condensation polymerization of methyltriethoxysilane. Next, an aluminum plate and a glass plate are immersed in this sol, pulled up at a pulling rate of 5 mm / second, dried, and then fired at 400 ° C. for 5 minutes to form an oxide film on the surfaces of the aluminum plate and the glass plate. did.
[0053]
When the oxide film formed on the surface of the aluminum plate was observed, the film thickness was 0.7 μm. Further, the entire film was dense and the surface was smooth overall.
[0054]
Moreover, it was 91 to 93% when the transmittance | permeability of the glass plate in which the oxide film was formed on the surface was measured in the measurement wavelength range 400-700 nm.
[Brief description of the drawings]
FIG. 1 is a partially cutaway enlarged perspective view showing an embodiment of an oxide film according to the present invention.
FIG. 2 is a partially cutaway enlarged perspective view showing another embodiment of the oxide film according to the present invention.
[Explanation of symbols]
(1) (10): Oxide film (2): Dense layer (3): Concavity and convexity layer
Claims (3)
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| JP2002219386A JP4650991B2 (en) | 2002-07-29 | 2002-07-29 | Oxide film mainly composed of SiO2 |
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| JP00834497A Division JP3364672B2 (en) | 1997-01-21 | 1997-01-21 | Method for producing oxide film containing SiO2 as a main component |
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