JP3687594B2 - Base material with antifouling layer and method for producing the same - Google Patents
Base material with antifouling layer and method for producing the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は防汚層付き基材及びその製造方法に関り、特に建築物外壁に施工された場合に長期にわたって汚れが付きにくいセルフクリーニング機能を有した防汚層付き基材及びその製造方法に関する。
【０００２】
【従来の技術】
タイル等の基材表面に超親水性の被膜を形成すると、基材表面に水が付着したときに水が被膜表面に広がり、雨水等と共に汚れが被膜表面に広く広がって流れ落ちるようになり、基材表面に汚れが付きにくくなり、また目立ちにくくなることが知られている。
【０００３】
かかるセルフクリーニング機能を有した超親水性被膜としては酸化チタン（ＴｉＯ２）被膜が広く用いられている。
【０００４】
特開２０００−２９７２７２号には、コロイダルシリカと水ガラスとを含む塗料をタイル等の基材表面に塗布し、１２０℃以上で加熱してシリカ系防汚層を基材表面に形成することが記載されている。
【０００５】
【発明が解決しようとする課題】
建築物の窓にあっては、窓ガラス板と該窓ガラス板を支承する窓フレーム（サッシ）との間にシリコン系シーリング材を充填している。また、タイルの目地間隙にシリコン系シーリング材を充填することもある。
【０００６】
このようなシリコン系シーリング材を用いた外壁面に雨が当ると、シリコン系シーリング材からシリコンオイルが少しずつ溶出し、タイル表面にシリコンオイルが付着する。このシリコンオイルは有機物質との親和性が高いので、シリコンオイルがタイル表面に付着すると有機系の汚れがタイル表面に付き易くなる。また、シリコンオイルは撥水性を有するので、土塵等の無機系の汚れを含んだ水がシリコンオイル付着領域からはじかれ、該シリコンオイル付着領域の外縁に沿って流れ落ちるようになり、この外縁部分に汚れが多量に付着する。この場合、シリコンオイル付着領域ではこの無機系の汚れが少なく、その外縁領域に多量の汚れが付着するので、両者のコントラストが顕著となり、建物外壁面が著しく汚ない外観となる。
【０００７】
本発明者が種々検討を重ねたところ、酸化チタン系の超親水性被膜はこのシリコンオイルとの親和性も高く、それ故に酸化チタン系超親水タイルを施工した建築物外面は、初期段階は光触媒による有機物分解効果が認められ、汚れ防止効果を発揮するものの、長期的には、分解効果が次第に阻害され、通常のタイルと大差がない防汚性能となってしまう。
【０００８】
また、酸化チタン系の超親水性被膜は、ＴｉＯ２の光触媒作用を利用しているため、光の当らない夜間等にあっては本来の親水性による防汚性も発揮されない。
【０００９】
特開２０００−２９７２７２号の防汚層は、防汚特性に優れるが、シリカ質であるためにアルカリ特に温アルカリに対する耐性が低い。
【００１０】
本発明は、防汚特性に優れ、耐薬品性にも優れた防汚層付き基材及びその製造方法を提供することを目的とする。
【００１１】
本発明の防汚層付き基材は、表面に防汚層を有する防汚層付き基材において、該防汚層は、アルミナ、ムライト及びスピネルの少なくとも１種の微粒子の焼結層よりなり、該微粒子の平均粒径が５ｎｍ〜３μｍであることを特徴とするものである。
【００１２】
かかる防汚層付き基材の防汚層は、種々の試験の結果、著しい親水性を有し、防汚性に優れることが認められた。即ち、この防汚層は親水性であるために表面に薄い水膜が形成される。特に、この防汚層は焼結層よりなるので、高い親水性が得られ、それが長期にわたって維持される。これにより汚れがきわめて付きにくいものとなる。
【００１３】
この防汚層は、アルミナ（Ａｌ２Ｏ３）、ムライト（３Ａｌ２Ｏ３・２ＳｉＯ２）及びスピネル（Ａｌ２Ｏ３・ＭｇＯ）の少なくとも１種よりなるものであるため、シリカ質の防汚層に比べて耐薬品性特に耐アルカリ性に優れる。
本発明の防汚層付き基材の製造方法は、アルミナ、ムライト及びスピネルの少なくとも１種の微粒子を基材に塗布し、焼成して、平均粒径が５ｎｍ〜３μｍである微粒子の焼結層を形成することを特徴とするものである。
【００１４】
【発明の実施の形態】
以下、本発明についてさらに詳細に説明する。
【００１５】
本発明の防汚層付き基材は、表面にアルミナ、ムライト及びスピネルの少なくとも１種の微粒子の焼結層よりなる防汚層を有するものである。この微粒子の平均粒径は５ｎｍ〜３μｍである。この微粒子の平均粒径が３μｍよりも大きいと、防汚層の防汚特性が悪くなる傾向がある。過度に平均粒径の小さい微粒子はコスト高であると共に、防汚層を緻密化させてその親水性を低下させ、防汚特性を悪くするおそれがある。
【００１６】
この防汚層の量は、１．９〜６．４ｇ／ｍ２が好ましい。６．４ｇ／ｍ２よりも多いと、防汚層の白色が強くなり、基板表面を白っぽくするおそれがある。防汚層の量が１．９ｇ／ｍ２よりも少ないと、防汚特性が不十分になり易い。
【００１７】
この量よりなる防汚層の厚さは、微粒子の粒径にもよるが、略々０．５〜２μｍ程度である。
【００１８】
この防汚層を形成するには、アルミナ、ムライト及びスピネルの少なくとも１種の微粒子を分散させたスラリーを基材表面に例えばロールコーター、スピンコーティング、スプレー、幕掛けなどにより塗布し、必要に応じ乾燥した後、焼成すればよい。
【００１９】
この微粒子は、酸化物の微粒子であってもよく、少なくとも部分的に水和した酸化物微粒子であってもよい。アルミナとしてはαアルミナ、γアルミナが好適である。アルミナゾルとしてはベーマイトが例示される。
【００２０】
このスラリーには、微粒子の分散を安定化させるための分散剤を含有させてもよい。また、防汚層の防汚特性をさほど阻害しない範囲で他の物質を（例えば酸化物）を含有させてもよい。
【００２１】
焼成温度は基材表面が軟化する温度以上とする。
【００２２】
この焼成は、トンネル窯、ローラーハースキルンなどの各種の炉によって行うことができる。
【００２３】
本発明において、基材は建築物の外壁とりわけ窓の下側に施工されるタイルが好適であるが、便器、浴槽、ユニットバスの壁、洗面器、水栓金具、鏡、ガラス製品であってもよい。タイルは施釉されたものであっても良く、施釉されていないものであってもよい。
【００２４】
【実施例】
実施例１
陶磁器質タイル表面に防汚処理用塗料を塗付して本発明の防汚層付き基材（タイル）を製造した。
【００２５】
防汚処理用塗料は、平均粒径３３ｎｍのγアルミナを濃度１０ｗｔ％となるように分散させたスプレーであり、アルミナ重量として６．４ｇ／ｍ２の割合で基材（４５×９５×７ｍｍの施釉タイル）にスプレー掛けした。次いで、乾燥した後、最高温度１３００℃のトンネル窯を用い、３０時間焼成した。これにより、タイル表面に平均厚さ０．９μｍの焼結層よりなり、焼結層を構成する微粒子の平均粒径が６０ｎｍの防汚層が形成された。図１はこの防汚層の表面電子顕微鏡（ＳＥＭ）写真であり、図２はこの防汚層及びその下側のタイル表面を示す断面のＳＥＭ写真である。図２より、この防汚層の厚さは約０．９μｍであることが認められる。
【００２６】
このようにして製造された防汚層付きタイルについて次の親水性試験を行った。
【００２７】
即ち、この防汚層付きタイルの表面にシリコーンオイル含有水（濃度０．１ｐｐｍ）を０．５ｃｃ滴下した後、拭き取り、次いで表面に水を掛けて水膜が形成されるかどうか目視観察する。水膜が形成されなくなるまでの回数をカウントし、１０回以上であれば２重丸、５〜９回であれば１重丸（○）２〜４回であれば△、１回であれば×と判定する。結果を表１示す。
【００２８】
また、このタイルの防汚性を以下のように屋外曝露試験して評価した。
［防汚性能試験法］
４５×９５×７ｍｍのタイル１２枚を約５ｍｍの目地間隔でフレキシブルボードに張り付け、目地部には、シリコン系のシーリングを施した。
このシリコン系シーリング材を目地に施した試料（フレキシブルボード）を屋外に３００日間にわたって曝露試験した。この試験期間中９０日に降雨があった。
３００日経過後のタイル表面の汚なさを次の３段階に評価した。
○：汚れは殆ど目立たない
△：汚れが少し目立つ
×：汚れが多く目立つ
結果を表１に示す。
【００２９】
実施例２，３
γアルミナの塗布量を３．２ｇ／ｍ２（実施例２）又は１．９ｇ／ｍ２（実施例３）としたこと以外は実施例１と同様にして防汚層付きタイルを製造し、同様にして特性を評価した。結果を表１に示す。
【００３０】
実施例４，５
γアルミナの代わりに平均粒径６６ｎｍのムライト（実施例４）又は平均粒径３０ｎｍのスピネル（実施例５）を用いたこと以外は実施例１と同様にして防汚層付きタイルを製造し、特性を評価した。結果を表１に示す。
【００３１】
比較例１〜４
γアルミナの代わりにシリカ（比較例１）、酸化セリウム（比較例２）、酸化錫（比較例３）、又は酸化チタン（比較例４）を用いたこと以外は実施例１と同様にして防汚層付きタイルを製造し、特性を評価した。結果を表１に示す。
【００３２】
比較例５
防汚層を設けないタイルについて同様の特性評価を行った。
【００３３】
比較例６
最高温度１３００℃のトンネル窯を用いた３０時間の焼成の代わりに、最高温度５００℃のトンネル窯を用い、１時間の焼成を行ったこと以外は実施例５と同様にして防汚層付きタイルを製造し、特性を評価した。比較例６のタイルは、スピネルの微粒子が焼結されていないことが確認された。結果を表１に示す。表１に示される通り、防汚層が焼結されていない比較例６のタイルは、屋外曝露試験の結果、汚れが多く目立つものであり、防汚特性を維持できるものではなかった。この理由は比較例６のタイルの防汚層が焼成されているが焼結されていないので、防汚層を形成する微粒子が経時的にタイルから剥離することによるものと思われる。
【００３４】
【表１】
表１より、本発明によると著しく防汚特性に優れたタイルが提供されることが明らかである。本発明のタイルは、高い親水性を示し、長期にわたり屋外曝露されても優れた防汚特性を示すことが認められた。
【００３６】
【発明の効果】
以上の実施例及び比較例からも明らかな通り、本発明によると、屋外曝露した場合でも長期にわたり著しく防汚性に優れたタイル等の基材が提供される。
【図面の簡単な説明】
【図１】実施例１の防汚層付きタイルの表面の粒子構造を示すＳＥＭ写真である。
【図２】実施例１の防汚層付きタイルの表面付近の断面の粒子構造を示すＳＥＭ写真である。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a substrate with an antifouling layer and a method for producing the same , and more particularly to a substrate with an antifouling layer having a self-cleaning function that is difficult to get dirty for a long time when constructed on an outer wall of a building and a method for producing the same. .
[0002]
[Prior art]
When a super-hydrophilic film is formed on the surface of a substrate such as a tile, when water adheres to the surface of the substrate, the water spreads on the surface of the film, and the dirt spreads along the surface of the film together with rainwater and flows down. It is known that the surface of the material is less likely to get dirty and less noticeable.
[0003]
A titanium oxide (TiO 2 ) film is widely used as such a superhydrophilic film having a self-cleaning function.
[0004]
In JP 2000-297272 A, a paint containing colloidal silica and water glass is applied to the surface of a substrate such as a tile and heated at 120 ° C. or higher to form a silica-based antifouling layer on the surface of the substrate. Has been described.
[0005]
[Problems to be solved by the invention]
In a building window, a silicon-based sealing material is filled between a window glass plate and a window frame (sash) that supports the window glass plate. In addition, the silicon sealing material may be filled in the joints between the tiles.
[0006]
When rain hits the outer wall surface using such a silicon-based sealing material, the silicon oil is gradually eluted from the silicon-based sealing material, and the silicon oil adheres to the tile surface. Since this silicone oil has a high affinity with organic substances, if the silicone oil adheres to the tile surface, organic stains are likely to adhere to the tile surface. In addition, since silicon oil has water repellency, water containing inorganic dirt such as dirt is repelled from the silicon oil adhesion area and flows down along the outer edge of the silicon oil adhesion area. A large amount of dirt adheres to the surface. In this case, there is little inorganic dirt in the silicon oil adhesion area, and a large amount of dirt adheres to the outer edge area, so that the contrast between the two becomes remarkable, and the outer wall surface of the building becomes not very dirty.
[0007]
As a result of various studies by the present inventor, the titanium oxide-based superhydrophilic coating has a high affinity with the silicon oil. Therefore, the outer surface of the building on which the titanium oxide-based superhydrophilic tile is constructed is a photocatalyst in the initial stage. Although the organic matter decomposing effect is recognized and the anti-staining effect is exhibited, the decomposing effect is gradually hindered in the long term, and the anti-staining performance is not significantly different from that of ordinary tiles.
[0008]
In addition, since the titanium oxide-based superhydrophilic film utilizes the photocatalytic action of TiO 2 , the antifouling property due to the original hydrophilicity is not exhibited at night when light is not applied.
[0009]
The antifouling layer of Japanese Patent Application Laid-Open No. 2000-297272 is excellent in antifouling properties, but since it is siliceous, it has low resistance to alkali, especially warm alkali.
[0010]
An object of this invention is to provide the base material with an antifouling layer which was excellent in the antifouling property and was excellent also in chemical resistance, and its manufacturing method .
[0011]
Antifouling layer-substrate of the present invention, the substrate with an antifouling layer having an antifouling layer on the surface, antifouling layer, alumina, Ri name from sintered layer of at least one particulate mullite and spinel The average particle size of the fine particles is 5 nm to 3 μm .
[0012]
As a result of various tests, the antifouling layer of the substrate with the antifouling layer was found to have remarkable hydrophilicity and excellent antifouling properties. That is, since this antifouling layer is hydrophilic, a thin water film is formed on the surface. In particular, since the antifouling layer is composed of a sintered layer, high hydrophilicity is obtained and maintained for a long time. This makes it very difficult to get dirt.
[0013]
Since this antifouling layer is composed of at least one of alumina (Al 2 O 3 ), mullite (3Al 2 O 3 .2SiO 2 ) and spinel (Al 2 O 3 .MgO), it is siliceous antifouling. Excellent chemical resistance, especially alkali resistance compared to the layer.
The method for producing a base material with an antifouling layer according to the present invention comprises applying a fine particle of at least one kind of alumina, mullite and spinel to a base material, followed by firing, and sintering a fine particle having an average particle size of 5 nm to 3 μm. It is characterized by forming.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0015]
The substrate with an antifouling layer of the present invention has an antifouling layer comprising a sintered layer of at least one kind of fine particles of alumina, mullite and spinel on the surface. The average particle diameter of the microparticles is 5 nm~3μm. When the average particle size of the fine particles is larger than 3 μm, the antifouling property of the antifouling layer tends to deteriorate. Fine particles having an excessively small average particle diameter are expensive and may cause the antifouling layer to be densified to lower its hydrophilicity and deteriorate the antifouling properties.
[0016]
The amount of the antifouling layer is preferably 1.9 to 6.4 g / m 2 . When it is more than 6.4 g / m 2 , the antifouling layer becomes white and the substrate surface may become whitish. When the amount of the antifouling layer is less than 1.9 g / m 2 , the antifouling property tends to be insufficient.
[0017]
The thickness of the antifouling layer comprising this amount is about 0.5 to 2 μm, although it depends on the particle size of the fine particles.
[0018]
In order to form this antifouling layer, a slurry in which at least one kind of fine particles of alumina, mullite and spinel is dispersed is applied to the substrate surface by, for example, a roll coater, spin coating, spraying, curtaining, etc. After drying, baking may be performed.
[0019]
The fine particles may be oxide fine particles, or may be at least partially hydrated oxide fine particles. As alumina, α-alumina and γ-alumina are suitable. Boehmite is exemplified as the alumina sol.
[0020]
This slurry may contain a dispersant for stabilizing the dispersion of fine particles. Moreover, you may contain another substance (for example, oxide) in the range which does not inhibit the antifouling property of an antifouling layer so much.
[0021]
The firing temperature is equal to or higher than the temperature at which the substrate surface is softened.
[0022]
This firing can be performed in various furnaces such as a tunnel kiln and a roller hearth kiln.
[0023]
In the present invention, the base material is preferably a tile constructed on the outer wall of the building, particularly the lower side of the window, but is a toilet bowl, bathtub, unit bath wall, basin, faucet fitting, mirror, glassware, Also good. The tiles may be glazed or unglazed.
[0024]
【Example】
Example 1
An antifouling coating was applied to the ceramic tile surface to produce a substrate (tile) with an antifouling layer of the present invention.
[0025]
The antifouling coating is a spray in which γ-alumina having an average particle size of 33 nm is dispersed so as to have a concentration of 10 wt%, and the base material (45 × 95 × 7 mm with an alumina weight of 6.4 g / m 2 ). (Glazed tile) was sprayed. Next, after drying, firing was performed for 30 hours using a tunnel kiln having a maximum temperature of 1300 ° C. Thus, an antifouling layer having an average thickness of 0.9 μm and a fine particle constituting the sintered layer having an average particle diameter of 60 nm was formed on the tile surface. FIG. 1 is a surface electron microscope (SEM) photograph of the antifouling layer, and FIG. 2 is a cross-sectional SEM photograph showing the antifouling layer and the tile surface below the antifouling layer. From FIG. 2, it is recognized that the thickness of the antifouling layer is about 0.9 μm.
[0026]
The following hydrophilicity test was performed on the tile with the antifouling layer thus produced.
[0027]
That is, 0.5 cc of silicone oil-containing water (concentration 0.1 ppm) is dropped on the surface of the tile with the antifouling layer, wiped off, and then water is applied to the surface to visually observe whether a water film is formed. Count the number of times until no water film is formed. If it is 10 times or more, double circle, if it is 5-9 times, single circle (○) if it is 2-4 times, Δ if it is 1 time X is determined. The results are shown in Table 1.
[0028]
Further, the antifouling property of the tile was evaluated by an outdoor exposure test as follows.
[Anti-fouling performance test method]
Twelve 45 × 95 × 7 mm tiles were pasted on a flexible board with a joint spacing of about 5 mm, and the joints were subjected to silicone sealing.
A sample (flexible board) with the silicone sealant applied to the joint was subjected to an exposure test outdoors for 300 days. There was rainfall for 90 days during this test period.
The dirtyness of the tile surface after the elapse of 300 days was evaluated in the following three stages.
○: Dirt is hardly noticeable Δ: Dirt is slightly conspicuous ×: The result in which much dirt is conspicuous is shown in Table 1.
[0029]
Examples 2 and 3
A tile with an antifouling layer was produced in the same manner as in Example 1 except that the coating amount of γ-alumina was 3.2 g / m 2 (Example 2) or 1.9 g / m 2 (Example 3). The characteristics were evaluated in the same manner. The results are shown in Table 1.
[0030]
Examples 4 and 5
A tile with an antifouling layer was produced in the same manner as in Example 1 except that mullite having an average particle diameter of 66 nm (Example 4) or spinel having an average particle diameter of 30 nm (Example 5) was used instead of γ-alumina, Characteristics were evaluated. The results are shown in Table 1.
[0031]
Comparative Examples 1-4
Prevention was conducted in the same manner as in Example 1 except that silica (Comparative Example 1), cerium oxide (Comparative Example 2), tin oxide (Comparative Example 3), or titanium oxide (Comparative Example 4) was used instead of γ-alumina. Soiled tiles were manufactured and evaluated for properties. The results are shown in Table 1.
[0032]
Comparative Example 5
Similar characteristics were evaluated for tiles without an antifouling layer.
[0033]
Comparative Example 6
A tile with an antifouling layer in the same manner as in Example 5 except that instead of firing for 30 hours using a tunnel kiln having a maximum temperature of 1300 ° C., firing was performed for 1 hour using a tunnel kiln having a maximum temperature of 500 ° C. Were manufactured and the characteristics were evaluated. The tile of Comparative Example 6 was confirmed to have no sintered spinel particles. The results are shown in Table 1. As shown in Table 1, the tile of Comparative Example 6 in which the antifouling layer was not sintered was conspicuous with many stains as a result of the outdoor exposure test, and the antifouling property could not be maintained. This is probably because the antifouling layer of the tile of Comparative Example 6 was fired but not sintered, so that the fine particles forming the antifouling layer peeled off from the tile over time.
[0034]
[Table 1]
From Table 1, it is clear that according to the present invention, a tile excellent in antifouling property is provided. The tiles of the present invention were found to exhibit high hydrophilicity and excellent antifouling properties even when exposed outdoors for long periods.
[0036]
【The invention's effect】
As is clear from the above Examples and Comparative Examples, according to the present invention, a substrate such as a tile that is remarkably excellent in antifouling properties over a long period of time even when exposed outdoors is provided.
[Brief description of the drawings]
1 is a SEM photograph showing the particle structure of the surface of a tile with an antifouling layer of Example 1. FIG.
2 is a SEM photograph showing the particle structure of a cross section near the surface of a tile with an antifouling layer of Example 1. FIG.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001353826A JP3687594B2 (en) | 2000-11-20 | 2001-11-19 | Base material with antifouling layer and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000-353098 | 2000-11-20 | ||
| JP2000353098 | 2000-11-20 | ||
| JP2001353826A JP3687594B2 (en) | 2000-11-20 | 2001-11-19 | Base material with antifouling layer and method for producing the same |
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| Publication Number | Publication Date |
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| JP2002234106A JP2002234106A (en) | 2002-08-20 |
| JP3687594B2 true JP3687594B2 (en) | 2005-08-24 |
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| JP2001353826A Expired - Fee Related JP3687594B2 (en) | 2000-11-20 | 2001-11-19 | Base material with antifouling layer and method for producing the same |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08133823A (en) * | 1994-11-04 | 1996-05-28 | Minnesota Mining & Mfg Co <3M> | Alumina composition |
| JPH0940479A (en) * | 1995-07-26 | 1997-02-10 | Riboole:Kk | Foamed ceramic molded plate |
| JPH10338566A (en) * | 1997-06-04 | 1998-12-22 | Isuzu Ceramics Kenkyusho:Kk | Ceramic sliding member with high hydrophilicity and low friction |
| JP4165014B2 (en) * | 1999-03-09 | 2008-10-15 | Ｔｏｔｏ株式会社 | Hydrophilic member, method for producing the same, coating agent and apparatus for the production |
| JP3879313B2 (en) * | 1999-04-13 | 2007-02-14 | 株式会社Ｉｎａｘ | Base material with antifouling layer |
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2001
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