JP3838295B2 - Photocatalytic film production method - Google Patents
Photocatalytic film production method Download PDFInfo
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- JP3838295B2 JP3838295B2 JP22438797A JP22438797A JP3838295B2 JP 3838295 B2 JP3838295 B2 JP 3838295B2 JP 22438797 A JP22438797 A JP 22438797A JP 22438797 A JP22438797 A JP 22438797A JP 3838295 B2 JP3838295 B2 JP 3838295B2
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- fine particles
- metal oxide
- oxide fine
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- 230000001699 photocatalysis Effects 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011230 binding agent Substances 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 16
- 239000011941 photocatalyst Substances 0.000 claims description 15
- 238000009832 plasma treatment Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 208000028659 discharge Diseases 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 239000000758 substrate Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004887 air purification Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- -1 TiO 2 Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、水浄化、空気浄化、消臭、油分の分解等に有効に用いられる光触媒膜の作製方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来より、ＴｉＯ2，ＺｎＯ，ＷＯ3，Ｆｅ2Ｏ3，ＳｒＴｉＯ3等の金属酸化物は光触媒として水浄化、空気浄化、消臭、油分の分解等に広く使用されている。このような光触媒は、通常粉末状で用いられ、例えば浄化、脱臭すべき水などの液体中に撹拌分散させて使用されているが、かかる粉末状の光触媒では使用後に回収することに手間を要し、回収が困難な場合もある。粉末状の光触媒を固定化するために、粉末にバインダーとして樹脂やゴムなどを混ぜて練り、それを基材に塗って数百℃で焼結させる方法もある。しかし、このバインダー固定法の場合、金属酸化物を基材に密着よく担持することが難しく、密着性を上げるためにバインダー量を多くすると触媒効果が弱まり、少ないと密着できない。
【０００３】
本発明は、上記事情に鑑みなされたもので、基材との密着性を損なわず、かつ良好な触媒効果を与える光触媒膜の作製方法を提供することを目的とする。
【０００４】
【課題を解決するための手段及び発明の実施の形態】
本発明者は、上記目的を達成するため鋭意検討を行った結果、酸化チタン等の光触媒活性を有する金属酸化物微粒子をバインダー樹脂に分散させてなる塗料を基材表面に塗布した後、この塗膜表面に放電処理を施して、塗膜表面のバインダー樹脂をエッチング、除去し、金属酸化物微粒子を表面に露出させることにより、バインダー量を多くして基材との密着性を保持する一方、表面部において、バインダーにより被覆された光触媒微粒子を顕出させることでその触媒効果を有効に発揮させることができることを知見し、本発明をなすに至った。
【０００５】
以下、本発明につき更に詳しく説明すると、本発明の光触媒膜の作製方法は、光触媒活性を有する金属酸化物微粒子を、アクリル樹脂、ウレタン樹脂、ポリエステル樹脂、ナイロン樹脂よりなる群から選択された有機系バインダー樹脂に分散させてなる塗料を基材表面に塗布した後、この塗膜表面に放電処理を施して、塗膜表面のバインダー樹脂を除去し、上記金属酸化物微粒子を露出させる光触媒膜の作製方法であって、上記金属酸化物微粒子の平均粒径が１０〜１０００ｎｍであり、上記塗料が上記バインダー樹脂１００重量部当り１０〜１００重量部の上記金属酸化物微粒子が配合されてなると共に、上記放電処理がコロナ放電処理又は低圧プラズマ処理であるものである。
【０００６】
ここで、金属酸化物微粒子としては、ＴｉＯ2，ＺｎＯ，ＷＯ3，Ｆｅ2Ｏ3，ＳｒＴｉＯ3等が挙げられ、中でもＴｉＯ2が好ましい。これら金属酸化物微粒子の平均粒径は適宜選定されるが、１０００ｎｍ以下、特に１０〜５００ｎｍとすることが好ましい。
【０００７】
一方、バインダー樹脂としては、珪素化合物のような無機系バインダー、アクリル樹脂、ウレタン樹脂、ポリエステル樹脂、ナイロン樹脂、エポキシ樹脂のような有機系バインダー等を用いることができる。
【０００８】
このバインダー樹脂に対する上記金属酸化物微粒子の配合量は、バインダー樹脂１００重量部当り１０〜１０００重量部、特に５０〜５００重量部とすることが好ましい。１０重量部より少ないと光触媒活性が低く、また１０００重量部より多いと基材との密着性を損なう場合が生じる。
【０００９】
上記金属酸化物微粒子及びバインダー樹脂を主成分とする塗料中には、更に必要に応じて補強剤、架橋剤、架橋補助剤、安定剤等を添加することができる。
【００１０】
なお、この塗料は、上記バインダー樹脂を溶解可能な溶剤、例えばアルコール系、ケトン系、トルエン、キシレン等の芳香族系有機溶媒等に該バインダー樹脂を溶解又はエマルジョン化して用いることができる。
【００１１】
基材は特に限定されないが、金属板、ガラス板等の無機系板材、プラスチック板、プラスチックフィルム等を用いることができ、この基材に上記塗料を塗布して上記バインダー樹脂中に金属酸化物微粒子が分散した塗膜を形成する。この場合、塗膜厚さは適宜選定されるが、通常０．１〜１０００μｍ、より好ましくは１〜５０μｍである。
【００１２】
上記塗膜は、乾燥後、或いはバインダー樹脂が硬化を必要とする場合は硬化前又は硬化後、これに放電処理を施して、塗膜表面のバインダー樹脂をエッチング、除去すると共に、上記金属酸化物微粒子を表面に露出させる。
【００１３】
この場合、放電処理としては、コロナ放電処理、低圧プラズマ処理、エキシマ光照射、レーザー加工等、表面部のバインダー樹脂をエッチング、除去可能ないずれの処理であってもよく、その条件も公知の樹脂エッチング条件とすることができるが、特には酸素プラズマ処理が好適に採用される。酸素プラズマ処理の条件としては、特に制限されるものではないが、０．０００１〜１００Ｔｏｒｒ、特に０．０１〜１０Ｔｏｒｒの真空もしくは減圧下、酸素ガスを０．１〜１０００ｃｃ／ｍｉｎ、特に１０〜３００ｃｃ／ｍｉｎ供給し、パワー１〜１０００Ｗ、特に１０〜５００Ｗ、３０秒〜３０分間程度の処理を行うという条件を採用し得る。
【００１４】
以上のようにして得られる光触媒膜は、公知の光触媒膜と同様にして使用することができ、例えばこの光触媒膜に光を照射することによって光触媒が励起し、殺菌、脱臭等の作用を発揮するもので、水浄化、空気浄化、消臭、油分の分解などに用いることができる。
【００１５】
【発明の効果】
本発明によれば、高い触媒活性を有する光触媒膜を基材との密着性を損なうことなく作製することができる。
【００１６】
【実施例】
以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００１７】
〔実施例、比較例〕
下記組成の塗料を調製した。
バインダー樹脂（アクリル系） １００重量部
酸化チタン（平均粒径１００ｎｍ） １００重量部
溶剤（メチルイソブチルエーテル） １００重量部
次に、上記塗料をガラス板上に塗膜の厚みが２０μｍになるように塗布し、乾燥後、得られた塗膜を酸素プラズマエッチング処理した。この場合、酸素プラズマエッチング処理は、１Ｔｏｒｒの真空下、酸素ガス１００ｃｃ／ｍｉｎを供給し、１００Ｗで５分間処理することによって行った。
【００１８】
比較例は酸素プラズマエッチング処理を行わないものとした。
次に、上記光触媒膜の表面に機械油を０．１ｍｇ／ｃｍ2塗布した後、４００Ｗ低圧水銀ランプ下１５ｃｍの位置に置き、３時間照射した後の機械油の重量減少量を測定し、光触媒硬化を評価した。
【００１９】
結果は、プラズマ処理を施した実施例の光触媒膜は９９％の分解率であり、プラズマ処理を施さなかった比較例の光触媒膜は３０％の分解率であり、本発明の効果が立証された。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a photocatalytic film that is effectively used for water purification, air purification, deodorization, oil decomposition, and the like.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, metal oxides such as TiO 2 , ZnO, WO 3 , Fe 2 O 3 , and SrTiO 3 have been widely used as photocatalysts for water purification, air purification, deodorization, oil decomposition, and the like. Such a photocatalyst is usually used in the form of a powder, and is used, for example, by stirring and dispersing in a liquid such as water to be purified and deodorized. However, such a powdery photocatalyst requires time and effort to recover after use. However, it may be difficult to collect. In order to immobilize the powdery photocatalyst, there is a method in which a powder is mixed with a resin or rubber as a binder and kneaded, and then applied to a substrate and sintered at several hundred degrees Celsius. However, in the case of this binder fixing method, it is difficult to carry the metal oxide on the substrate with good adhesion, and if the amount of the binder is increased in order to increase the adhesion, the catalytic effect is weakened, and if it is small, the adhesion cannot be achieved.
[0003]
This invention is made | formed in view of the said situation, and it aims at providing the preparation method of the photocatalyst film | membrane which does not impair adhesiveness with a base material and gives the favorable catalytic effect.
[0004]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive investigations to achieve the above object, the present inventor applied a paint obtained by dispersing metal oxide fine particles having photocatalytic activity such as titanium oxide in a binder resin, and then applied this coating. While performing discharge treatment on the film surface, etching and removing the binder resin on the surface of the coating film, and exposing the metal oxide fine particles to the surface, the amount of the binder is increased and the adhesion with the substrate is maintained, It has been found that the catalytic effect can be effectively exhibited by revealing the photocatalyst fine particles coated with the binder on the surface portion, and the present invention has been made.
[0005]
Hereinafter, the present invention will be described in more detail. The photocatalytic film production method of the present invention is an organic system in which metal oxide fine particles having photocatalytic activity are selected from the group consisting of acrylic resins, urethane resins, polyester resins, and nylon resins. After the coating material dispersed in the binder resin is applied to the substrate surface, the coating film surface is subjected to a discharge treatment to remove the binder resin on the coating film surface, thereby producing a photocatalytic film that exposes the metal oxide fine particles. The average particle diameter of the metal oxide fine particles is 10 to 1000 nm, and the paint is blended with 10 to 100 parts by weight of the metal oxide fine particles per 100 parts by weight of the binder resin. The discharge treatment is a corona discharge treatment or a low-pressure plasma treatment.
[0006]
Here, examples of the metal oxide fine particles include TiO 2 , ZnO, WO 3 , Fe 2 O 3 , SrTiO 3 and the like, and among them, TiO 2 is preferable. Although the average particle diameter of these metal oxide fine particles is appropriately selected, it is preferably 1000 nm or less, particularly preferably 10 to 500 nm.
[0007]
On the other hand, as the binder resin, an inorganic binder such as a silicon compound, an organic binder such as an acrylic resin, a urethane resin, a polyester resin, a nylon resin, and an epoxy resin can be used.
[0008]
The blending amount of the metal oxide fine particles with respect to the binder resin is preferably 10 to 1000 parts by weight, particularly 50 to 500 parts by weight per 100 parts by weight of the binder resin. When the amount is less than 10 parts by weight, the photocatalytic activity is low. When the amount is more than 1000 parts by weight, the adhesion to the substrate may be impaired.
[0009]
A reinforcing agent, a cross-linking agent, a cross-linking auxiliary agent, a stabilizer, and the like can be further added to the coating material containing the metal oxide fine particles and the binder resin as main components as necessary.
[0010]
In addition, this coating material can be used by dissolving or emulsifying the binder resin in a solvent capable of dissolving the binder resin, for example, an aromatic organic solvent such as alcohol, ketone, toluene or xylene.
[0011]
The base material is not particularly limited, but an inorganic plate material such as a metal plate or a glass plate, a plastic plate, a plastic film, or the like can be used. Forms a coated film. In this case, the coating thickness is appropriately selected, but is usually 0.1 to 1000 μm, more preferably 1 to 50 μm.
[0012]
The coating film is dried or, if the binder resin needs to be cured, before or after curing, it is subjected to discharge treatment to etch and remove the binder resin on the surface of the coating film, and the metal oxide. Fine particles are exposed on the surface.
[0013]
In this case, the discharge treatment may be any treatment capable of etching and removing the binder resin on the surface, such as corona discharge treatment, low-pressure plasma treatment, excimer light irradiation, laser processing, etc. Although etching conditions can be set, oxygen plasma treatment is particularly preferably employed. Conditions for the oxygen plasma treatment are not particularly limited, but oxygen gas is 0.1 to 1000 cc / min, particularly 10 to 300 cc under a vacuum or reduced pressure of 0.0001 to 100 Torr, particularly 0.01 to 10 Torr. / Min supply and power 1 to 1000 W, particularly 10 to 500 W, 30 seconds to 30 minutes may be used.
[0014]
The photocatalyst film obtained as described above can be used in the same manner as a known photocatalyst film. For example, when the photocatalyst film is irradiated with light, the photocatalyst is excited to exhibit actions such as sterilization and deodorization. It can be used for water purification, air purification, deodorization, oil decomposition, and the like.
[0015]
【The invention's effect】
According to the present invention, a photocatalytic film having high catalytic activity can be produced without impairing adhesion with a substrate.
[0016]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0017]
Examples and comparative examples
A paint having the following composition was prepared.
Binder resin (acrylic) 100 parts by weight Titanium oxide (average particle size 100 nm) 100 parts by weight Solvent (methyl isobutyl ether) 100 parts by weight Next, the above coating is applied on a glass plate so that the thickness of the coating film becomes 20 μm. Then, after drying, the obtained coating film was subjected to an oxygen plasma etching treatment. In this case, the oxygen plasma etching treatment was performed by supplying oxygen gas at 100 cc / min under a vacuum of 1 Torr and treating at 100 W for 5 minutes.
[0018]
In the comparative example, oxygen plasma etching was not performed.
Next, after applying 0.1 mg / cm 2 of machine oil to the surface of the photocatalyst film, it was placed at a position of 15 cm under a 400 W low-pressure mercury lamp, and the weight loss of the machine oil after irradiation for 3 hours was measured. Curing was evaluated.
[0019]
As a result, the photocatalyst film of the example subjected to the plasma treatment had a decomposition rate of 99%, and the photocatalyst film of the comparative example not subjected to the plasma treatment had a decomposition rate of 30%, thus demonstrating the effect of the present invention. .
Claims (3)
上記金属酸化物微粒子の平均粒径が１０〜１０００ｎｍであり、上記塗料が上記バインダー樹脂１００重量部当り１０〜１００重量部の上記金属酸化物微粒子が配合されてなると共に、上記放電処理がコロナ放電処理又は低圧プラズマ処理であることを特徴とする光触媒膜の作製方法。After coating the base material surface with a paint in which metal oxide fine particles having photocatalytic activity are dispersed in an organic binder resin selected from the group consisting of acrylic resin, urethane resin, polyester resin, and nylon resin, this coating film It is a method for producing a photocatalyst film by performing discharge treatment on the surface, removing the binder resin on the surface of the coating film, and exposing the metal oxide fine particles,
The metal oxide fine particles have an average particle size of 10 to 1000 nm, and the paint is mixed with 10 to 100 parts by weight of the metal oxide fine particles per 100 parts by weight of the binder resin. A method for producing a photocatalyst film, which is a treatment or a low-pressure plasma treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22438797A JP3838295B2 (en) | 1997-08-06 | 1997-08-06 | Photocatalytic film production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22438797A JP3838295B2 (en) | 1997-08-06 | 1997-08-06 | Photocatalytic film production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1147614A JPH1147614A (en) | 1999-02-23 |
| JP3838295B2 true JP3838295B2 (en) | 2006-10-25 |
Family
ID=16812957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22438797A Expired - Fee Related JP3838295B2 (en) | 1997-08-06 | 1997-08-06 | Photocatalytic film production method |
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| JP2007039270A (en) * | 2005-08-02 | 2007-02-15 | Bridgestone Corp | Method for crystallizing metal-doped tio2 thin film, and laminate having metal-doped tio2 thin film |
| JP2009155202A (en) * | 2009-04-06 | 2009-07-16 | Saruta Shiki Nosan Kk | Highly dispersive titanium dioxide powder |
| CN106861389B (en) * | 2017-04-08 | 2020-06-23 | 苏州鱼翔环境工程有限公司 | VOC waste gas purification equipment and purification method |
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