JP4522886B2 - Photocatalyst paint, steel sheet coated with the paint, and tent - Google Patents
Photocatalyst paint, steel sheet coated with the paint, and tent Download PDFInfo
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- 239000003973 paint Substances 0.000 title claims description 33
- 239000011941 photocatalyst Substances 0.000 title claims description 32
- 229910000831 Steel Inorganic materials 0.000 title claims description 18
- 239000010959 steel Substances 0.000 title claims description 18
- 238000000576 coating method Methods 0.000 claims description 82
- 239000011248 coating agent Substances 0.000 claims description 79
- 230000001699 photocatalysis Effects 0.000 claims description 54
- 239000011230 binding agent Substances 0.000 claims description 39
- 229910044991 metal oxide Inorganic materials 0.000 claims description 28
- 150000004706 metal oxides Chemical class 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 229920000557 Nafion® Polymers 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 238000010559 graft polymerization reaction Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 description 22
- 230000001877 deodorizing effect Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000003373 anti-fouling effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920001477 hydrophilic polymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は、光触媒機能を有する金属酸化物を配合した光触媒塗料、該塗料を塗布した鋼板およびテント地に関するものである。 The present invention relates to a photocatalyst coating containing a metal oxide having a photocatalytic function, a steel plate coated with the coating, and a tent.
最近では、耐汚染性や抗菌性に優れた光触媒機能を有する金属酸化物を配合した光触媒塗料が注目されている。 Recently, a photocatalyst coating containing a metal oxide having a photocatalytic function excellent in stain resistance and antibacterial properties has attracted attention.
また、建築物外壁や車体鋼板やテント地等の塗装に使用される塗料には、外観が良好で、雨筋汚れ等の汚れが付着し難い性質、つまり耐汚染性（環境汚染）を有していることが望まれている。 In addition, the paint used for the coating of building exterior walls, body steel plates, tents, etc. has a good appearance and is resistant to dirt such as rain-stain stains, that is, contamination resistance (environmental pollution). It is hoped that
そのために、耐汚染性や抗菌性を発現すると共に親水性に優れた光触媒機能を有する塗装材や表面処理材（以後まとめて塗料と称する）を有効に利用する方法が模索されている。一般に、光触媒機能を有する金属酸化物を塗料として配合する際には、環境汚れに対する光触媒機能を十分発揮するために、通常、親水性の樹脂バインダ（親水性ポリマー）が用いられている。 Therefore, a method for effectively using a coating material or a surface treatment material (hereinafter collectively referred to as a paint) having a photocatalytic function that exhibits stain resistance and antibacterial properties and is excellent in hydrophilicity is being sought. Generally, when a metal oxide having a photocatalytic function is blended as a paint, a hydrophilic resin binder (hydrophilic polymer) is usually used in order to sufficiently exhibit a photocatalytic function against environmental dirt.
また、光触媒機能は、激烈な酸化還元反応を励起して有機物を分解するために、塗料として配合する有機樹脂バインダをも分解し、塗膜が劣化して耐久性が劣るという問題があった。 Further, the photocatalytic function has a problem that the organic resin binder to be blended as a paint is also decomposed to excite a severe oxidation-reduction reaction and the coating film is deteriorated and durability is inferior.
そのために、光触媒塗料を配合する際には、シリカゾルと称されるガラス質の無機バインダが専ら用いられている。 Therefore, when blending a photocatalyst paint, a vitreous inorganic binder called silica sol is exclusively used.
また、シリカゾルを含むと共に分散安定性に優れた光触媒塗料が既に出願されている（例えば、特許文献１参照）。 A photocatalyst coating material containing silica sol and having excellent dispersion stability has already been filed (for example, see Patent Document 1).
さらに、シリカゾルを結着剤として使用して、結着剤が光触媒作用により劣化しない酸化チタン塗料組成物が既に出願されている（例えば、特許文献２参照）。
光触媒機能を有する金属酸化物を配合すると共に、劣化しないバインダとしてシリカゾルを用いた塗料では、硬化するのに長時間を要するという問題がある。 A paint using a silica sol as a binder that does not deteriorate while blending a metal oxide having a photocatalytic function has a problem that it takes a long time to cure.
また、硬化したあとの塗膜に柔軟性が全くなく、塗装後に曲げ加工を行うカラー鋼板に適用することはできない。さらに、組み立てと折り畳みを繰り返すことの多いテント地の塗料として使用することも不適当である。 In addition, the cured coating film has no flexibility and cannot be applied to a color steel sheet that is bent after coating. Furthermore, it is also unsuitable for use as a tent place paint that is frequently assembled and folded.
本発明の目的は、上記問題点を解消するために、所定の光触媒機能を備えると共に、塗布した後の硬化時間を短縮し、さらに硬化した塗膜が光触媒作用により分解されず、さらに柔軟性を有する光触媒塗料の塗膜（いいかえれば塗布方法）を提供し、光触媒塗料を塗布したあとで屈曲しても塗膜が剥離しない鋼板およびテント地等をも提供することである。 An object of the present invention is to provide a predetermined photocatalytic function in order to eliminate the above-mentioned problems, shorten the curing time after coating, and further prevent the cured coating film from being decomposed by the photocatalytic action, further improving flexibility. providing a coating (in other words coating method) of the photocatalyst coating material having, even when bent after the photocatalytic coating material is applied is that the coating film also provides a non steel and canvas like peeling.
上記の目的を達成するために請求項１に係る発明は、被塗布物表面に対し、Ｃ−Ｆ結合を有する有機樹脂バインダとしてのスルホン酸基がグラフト重合されたポリ４フッ化エチレンであるナフィオン（登録商標）に光触媒機能を有する金属酸化物を配合した塗料を塗布して乾燥することにより厚みが５μｍ以上の塗膜を形成することを特徴としている。 In order to achieve the above object, the invention according to claim 1 is a Nafion which is polytetrafluoroethylene in which a sulfonic acid group as an organic resin binder having a C—F bond is graft-polymerized on the surface of an object to be coated. It is characterized in that a coating film having a thickness of 5 μm or more is formed by applying a paint containing a metal oxide having a photocatalytic function to (registered trademark) and drying it.
上記の構成を有する請求項１に係る発明によれば、樹脂バインダが分解されないので、塗膜が劣化せず長寿命となり、長期間光触媒機能を発揮することができる。また、乾燥硬化後に柔軟性を有するので、塗装した後で屈曲させても、塗膜が割れたり剥離したりしない光触媒塗料からなる塗膜を得ることができる。 According to the invention according to claim 1 having the above-described configuration, since the resin binder is not decomposed, the coating film is not deteriorated and has a long life and can exhibit a photocatalytic function for a long time. Moreover, since it has flexibility after drying and curing, it is possible to obtain a coating film made of a photocatalyst coating material that does not crack or peel even if it is bent after coating .
請求項１に係る発明は、前記樹脂バインダとしての、スルホン酸基がグラフト重合されたポリ４フッ化エチレンであるナフィオン（Ｎａｆｉｏｎ：デュポン社の登録商標）は光触媒機能により分解されないだけでなく、乾燥硬化後に超親水性も発揮するので、環境汚染に対して非常に有効な光触媒塗料とすることができる。 According to the first aspect of the present invention, Nafion (registered trademark of DuPont), which is polytetrafluoroethylene having grafted sulfonic acid groups as the resin binder , is not decomposed by the photocatalytic function but also dried. Since it exhibits super hydrophilicity after curing, it can be a photocatalyst coating that is very effective against environmental pollution.
請求項２に係る発明は、前記金属酸化物が多孔質の酸化チタンであることを特徴としている。 The invention according to claim 2 is characterized in that the metal oxide is porous titanium oxide.
上記の構成を有する請求項２に係る発明によれば、酸化チタンが多孔質であるため、耐汚染機能だけでなく、消臭機能も十分発揮可能な塗膜を形成することができる。 According to the invention concerning Claim 2 which has said structure, since the titanium oxide is porous, the coating film which can fully exhibit not only a pollution-resistant function but a deodorizing function can be formed.
請求項３に係る発明は、鋼板表面に対し、Ｃ−Ｆ結合を有する有機樹脂バインダとしてのスルホン酸基がグラフト重合されたポリ４フッ化エチレンであるナフィオンに光触媒機能を有する金属酸化物を配合した塗料を塗布して乾燥することにより厚み５μｍ以上の塗膜が設けられたことを特徴とする鋼板である。また請求項４に係る発明は、テント地表面に対し、Ｃ−Ｆ結合を有する有機樹脂バインダとしてのスルホン酸基がグラフト重合されたポリ４フッ化エチレンであるナフィオンに光触媒機能を有する金属酸化物を配合した塗料を塗布して乾燥することにより厚み５μｍ以上の塗膜が設けられたことを特徴とするテント地である。さらに請求項５に係る発明は、ガラス表面に対し、Ｃ−Ｆ結合を有する有機樹脂バインダとしてのスルホン酸基がグラフト重合されたポリ４フッ化エチレンであるナフィオンに光触媒機能を有する金属酸化物を配合した塗料を塗布して乾燥することにより厚み５μｍ以上の塗膜が設けられたことを特徴とするガラスで、請求項６に係る発明は、車体表面に対し、Ｃ−Ｆ結合を有する有機樹脂バインダとしてのスルホン酸基がグラフト重合されたポリ４フッ化エチレンであるナフィオンに光触媒機能を有する金属酸化物を配合した塗料を塗布して乾燥することにより厚み５μｍ以上の塗膜が設けられたことを特徴とする自動車車体である。 In the invention according to claim 3, a metal oxide having a photocatalytic function is blended with Nafion , which is polytetrafluoroethylene obtained by graft polymerization of a sulfonic acid group as an organic resin binder having a C—F bond, on the steel sheet surface. The steel sheet is characterized in that a coating film having a thickness of 5 μm or more is provided by applying and drying the applied paint. The invention according to claim 4 is a metal oxide having a photocatalytic function in Nafion , which is polytetrafluoroethylene obtained by graft polymerization of a sulfonic acid group as an organic resin binder having a C—F bond to the tent ground surface. A tent is characterized in that a coating film having a thickness of 5 μm or more is provided by applying and drying a paint blended with No. 1. Furthermore, the invention according to claim 5 is a method for forming a metal oxide having a photocatalytic function on Nafion , which is polytetrafluoroethylene obtained by graft polymerization of a sulfonic acid group as an organic resin binder having a C—F bond to a glass surface. The glass according to claim 6 is provided with a coating having a thickness of 5 μm or more by applying and drying the blended paint, and the invention according to claim 6 is an organic resin having a C—F bond to the surface of the vehicle body. A coating having a thickness of 5 μm or more was formed by applying a coating containing a metal oxide having a photocatalytic function to Nafion, a polytetrafluoroethylene graft-polymerized with sulfonic acid groups as a binder, and drying. It is a car body characterized by.
上記の構成を有する請求項３〜６に係る各発明によれば、硬化した塗膜が柔軟性を有しているので、例えば請求項３の発明では、塗装後の曲げ加工が可能な鋼板とすることができる。また、５μｍ以上の厚みの光触媒塗料を塗布したので、耐汚染機能や消臭機能と抗菌機能を十分発揮可能な塗膜を形成することができる。 According to each of the inventions according to claims 3 to 6 having the above configuration, since the cured coating film has flexibility, for example, in the invention of claim 3, a steel plate capable of bending after coating and can do. In addition, since the photocatalyst coating having a thickness of 5 μm or more is applied, a coating film that can sufficiently exhibit the stain resistance function, the deodorizing function, and the antibacterial function can be formed.
上記したように本発明によれば、光触媒機能により劣化されないだけでなく、乾燥硬化後の塗膜が柔軟性を有していると共に超親水性も発揮して、環境汚染に対して非常に有効な光触媒塗料の塗膜とすることができる。さらに、光触媒塗料を塗装した基材を屈曲しても剥離しない塗膜を有しており、塗装後に曲げ加工可能な鋼板や折り畳みと組み立てを繰り返し可能なテント地を得ることができる。 As described above, according to the present invention, not only is it not deteriorated by the photocatalytic function, but also the coating film after drying and curing has flexibility and super hydrophilicity, and is very effective against environmental pollution. it can be a coating of a photocatalytic coating. Furthermore, it has a coating film that does not peel off even if the substrate coated with the photocatalyst paint is bent, and it is possible to obtain a steel plate that can be bent after coating and a tent place that can be repeatedly folded and assembled.
以下、本発明に係る光触媒塗料の実施の形態について詳細に説明する。 Hereinafter, embodiments of the photocatalyst coating material according to the present invention will be described in detail.
本発明に係る光触媒塗料は、スルホン酸基がグラフト重合されたポリ４フッ化エチレンであるナフィオン（Ｎａｆｉｏｎ：デュポン社の登録商標）を樹脂バインダとして、光触媒金属酸化物を配合した塗料である。 The photocatalyst coating material according to the present invention is a coating material in which a photocatalytic metal oxide is blended using Nafion (registered trademark of DuPont), which is polytetrafluoroethylene in which sulfonic acid groups are graft-polymerized, as a resin binder.
上記ナフィオン（デュポン社の登録商標）は高分子固体型燃料電池の固体電解質として一般的に使用されている有機ポリマーであって、電気化学反応に対して高度に安定している樹脂である。 The Nafion (registered trademark of DuPont) is an organic polymer that is generally used as a solid electrolyte of a polymer solid fuel cell, and is a resin that is highly stable to electrochemical reactions.
また、そのために、電気化学反応の一種である光触媒反応に対しても、非常に安定していることが本発明者により確認された。 For this reason, the present inventor has confirmed that the photocatalytic reaction, which is a kind of electrochemical reaction, is very stable.
光触媒機能を有する金属酸化物としては、酸化チタンや酸化亜鉛や酸化錫等が存在しているが、特に光触媒機能が安定し、さらに、簡単に入手可能な酸化チタンが好適に使用される。前記酸化チタンは微細な粒子状のものが市販されており、これを適当な樹脂バインダと有機溶剤や水などに所定量配合し攪拌混合して、所定の光触媒塗料を製造する。 As the metal oxide having a photocatalytic function, titanium oxide, zinc oxide, tin oxide, and the like are present. In particular, titanium oxide that has a stable photocatalytic function and is easily available is preferably used. The titanium oxide is in the form of fine particles, and a predetermined amount of the titanium oxide is mixed in an appropriate resin binder, an organic solvent, water, and the like, and stirred to produce a predetermined photocatalyst paint.
また、一般に酸化チタン等の光触媒金属酸化物を分散させる樹脂バインダとしては、光触媒の反応を促進するため、また、光触媒特性の一つである超親水性を活用して塗布表面を清浄化するために、親水性樹脂バインダが採用されている。 In general, as a resin binder that disperses photocatalytic metal oxides such as titanium oxide, in order to promote the reaction of the photocatalyst, and to clean the coating surface by utilizing superhydrophilicity, which is one of the photocatalytic properties. In addition, a hydrophilic resin binder is employed.
しかし、親水性樹脂バインダに光触媒金属酸化物を配合すると、光触媒作用による激烈な酸化還元反応でバインダ分解（バインダの自己崩壊）が生じて、耐久性が短くなるという問題がある。 However, when a photocatalytic metal oxide is blended with a hydrophilic resin binder, there is a problem that durability is shortened because binder decomposition (self-collapse of the binder) occurs due to an intense redox reaction due to photocatalytic action.
そのために、現在はシリカゾルと称されるガラス質の無機バインダが用いられている。このシリカゾルはガラスと略同じ性質を示すため、光触媒作用に対しては安定であるが、柔軟性が全くなく、また、硬化反応に長時間を要するという二つの致命的な欠陥を持っている。 Therefore, a glassy inorganic binder called silica sol is currently used. Since this silica sol exhibits almost the same properties as glass, it is stable to photocatalysis but has no flexibility and has two fatal defects that require a long time for the curing reaction.
そして、柔軟性がないために、一旦塗装した部材を折り曲げると、塗膜に亀裂が発生したり、剥離が生じたりする。また、硬化反応に長時間要するために、カラー鋼板等の高速連続生産には不適であった。 And since there is no softness | flexibility, if the member once painted is bent, a crack will generate | occur | produce in a coating film or peeling will arise. In addition, since the curing reaction takes a long time, it is unsuitable for high-speed continuous production of colored steel sheets.
しかし、本発明者が、高分子固体型燃料電池の固体電解質として一般的に使用されている有機ポリマーである前記ナフィオン（デュポン社の登録商標）をバインダとして、光触媒金属酸化物である酸化チタンを配合した組成物を生成したところ、この組成物を構成するバインダは親水性は発揮するが、光触媒作用を受けずに劣化しないことが明らかとなった。 However, the present inventor uses the above-mentioned Nafion (registered trademark of DuPont), which is an organic polymer generally used as a solid electrolyte of a polymer solid fuel cell, as a binder, and uses titanium oxide, which is a photocatalytic metal oxide, as a binder. When the blended composition was generated, it was revealed that the binder constituting the composition exhibits hydrophilicity but does not deteriorate without receiving a photocatalytic action.
また、上記の組成物に溶剤（例えばエタノール）を配合して生成した塗料は、塗装後の乾燥時間が非常に短いことが明らかとなった。 Moreover, it became clear that the coating material produced | generated by mix | blending a solvent (for example, ethanol) with said composition was very short in the drying time after coating.
そのために、前記ナフィオン（デュポン社の登録商標）と酸化チタンとエタノールや水等の適当な溶剤を所定量配合して攪拌混合して得られる光触媒塗料は、従来の光触媒機能や超親水性を発現すると共に、樹脂バインダが劣化せず乾燥時間も短い塗料となる。 Therefore, the photocatalyst paint obtained by mixing a predetermined amount of Nafion (registered trademark of DuPont), titanium oxide and a suitable solvent such as ethanol and water and mixing them, exhibits the conventional photocatalytic function and super hydrophilicity. In addition, the resin binder does not deteriorate and the paint has a short drying time.
また、前記ナフィオン（デュポン社の登録商標）をバインダとした光触媒塗料は、塗装した後の塗膜が非常に柔軟であることも明らかとなった。 It was also revealed that the photocatalyst paint using Nafion (registered trademark of DuPont) as a binder has a very flexible coating film.
そのために、前記塗料は、塗装品の高速連続生産にも適合し、塗装した後で曲げ加工を行うカラー鋼板にも適用可能となる。さらには、折り畳みと組み立てを繰り返すテント地にも塗布可能な光触媒塗料となることが判った。 Therefore, the coating material is also suitable for high-speed continuous production of coated products, and can be applied to a color steel plate that is bent after coating. Furthermore, it has been found that the photocatalyst paint can be applied to tents that are repeatedly folded and assembled.
また、バインダの自己崩壊が生じないので、配合する光触媒金属酸化物の配合量を大きくしても、バインダが劣化しない。そのために、塗料として塗布可能な範囲まで金属酸化物の濃度を大きくすることが可能である。 Further, since the binder does not self-destruct, the binder does not deteriorate even if the blending amount of the photocatalytic metal oxide to be blended is increased. Therefore, it is possible to increase the concentration of the metal oxide to the extent that it can be applied as a paint.
光触媒金属酸化物を含む塗料であれば、超親水性を発揮して環境汚染を受け難くなる。さらに、その他の光触媒機能である消臭機能や抗菌機能を発揮することも可能である。 If it is a coating material containing a photocatalytic metal oxide, it exhibits super hydrophilicity and is less susceptible to environmental pollution. Furthermore, it is also possible to exert other deodorizing functions and antibacterial functions, which are other photocatalytic functions.
前述した消臭機能や抗菌機能を十分発揮するには、塗膜自体に十分なガス吸着能力が必要であるが、そのためには塗膜の吸着表面積を大きくしてやればよい。また、塗膜の吸着表面積を大きくするには、塗料に配合する酸化チタン等の金属酸化物の比表面積が大きなものを採用すればよく、例えば、石原産業（株）製の多孔質な酸化チタンＳＴ−０１を用いることができる。 In order to sufficiently exhibit the deodorizing function and antibacterial function described above, the coating film itself needs to have a sufficient gas adsorption capacity. To that end, the adsorption surface area of the coating film may be increased. Further, in order to increase the adsorption surface area of the coating film, a metal oxide such as titanium oxide blended in the coating material having a large specific surface area may be employed. For example, porous titanium oxide manufactured by Ishihara Sangyo Co., Ltd. ST-01 can be used.
さらには、所定の厚み以上の塗膜（例えば５μｍ以上）とすることで、塗布した表面だけでなく、塗膜の厚み方向の内部にも吸着機能を担持させることができる。また、そのために、内部に吸着するガスや液体に対しても消臭機能を十分発揮可能となる。 Furthermore, by setting it as the coating film more than predetermined thickness (for example, 5 micrometers or more), an adsorption | suction function can be carry | supported not only on the apply | coated surface but the inside of the coating film thickness direction. For this reason, the deodorizing function can be sufficiently exerted even on the gas or liquid adsorbed inside.
次に具体的な光触媒塗料例について説明する。 Next, a specific example of a photocatalyst paint will be described.
実施例Ａ：酸化チタンＳＴ−０１（石原産業（株）製：吸着表面積３００ｍ2／ｇ）１０重量部とナフィオンＤＥ２０２１（デュポン社製品２０％溶液）５０重量部とエタノール４０重量部とを配合して調製された本発明に係わる光触媒塗料。 Example A: Titanium oxide ST-01 (manufactured by Ishihara Sangyo Co., Ltd .: adsorption surface area of 300 m 2 / g), 50 parts by weight of Nafion DE2021 (DuPont product 20% solution) and 40 parts by weight of ethanol were blended. A photocatalyst coating material according to the present invention prepared in the above manner.
比較例Ｂ：前記ナフィオンＤＥ２０２１に代えて親水性ポリマーであるスノーテックス２０（日産化学工業（株）製）を用い、エタノールに代えて水を用いた光触媒塗料。 Comparative Example B: Photocatalyst paint using Snowtex 20 (manufactured by Nissan Chemical Industries, Ltd.), which is a hydrophilic polymer, instead of Nafion DE2021, and water instead of ethanol.
前記の実施例Ａと比較例Ｂとを用いて、ＰＥＴフィルムを基材とし、その表面に光触媒塗料をそれぞれ５０ｇ／ｍ2塗布し、硬化に至る時間と、光触媒効果の有無と、折り曲げた時の塗膜の状況を調べた結果を表１に示す。尚、光触媒効果は防汚染効果と消臭効果で確認した。 Using Example A and Comparative Example B, using PET film as a base material and applying 50 g / m 2 of photocatalyst paint on the surface, curing time, presence or absence of photocatalytic effect, and bending Table 1 shows the results of examining the state of the coating film. The photocatalytic effect was confirmed by the antifouling effect and the deodorizing effect.
防汚染効果は、屋外にて２ヶ月の自然暴露で、光触媒施工部と非施工部の汚染状態を目視検査した。また、消臭実験は、２０Ｗ蛍光灯を５０ｃｍの距離から照射して３時間後のアンモニアの濃度変化にて測定した。 The antifouling effect was visually inspected for the contamination state of the photocatalyst construction part and the non-construction part by natural exposure outdoors for two months. Further, in the deodorization experiment, measurement was performed by changing the concentration of ammonia 3 hours after irradiation with a 20 W fluorescent lamp from a distance of 50 cm.
つまり、スルホン酸基がグラフト重合されたポリ４フッ化エチレンであるナフィオン（Ｎａｆｉｏｎ：デュポン社の登録商標）をバインダとして、金属酸化物である酸化チタンを配合した光触媒塗料は、防汚染機能や消臭機能等の光触媒機能を発揮して所定の光触媒効果を有するだけでなく、塗装した後の乾燥硬化時間が非常に短くてよく、塗布した塗膜が柔軟性を備えており、基材を折り曲げても塗膜が剥離しない効果を有していることが判った。 In other words, photocatalyst paints containing titanium oxide, which is a metal oxide, using Nafion (registered trademark of DuPont), which is polytetrafluoroethylene graft-polymerized with sulfonic acid groups, as a binder, have antifouling and anti-fouling properties. It not only has a predetermined photocatalytic effect by exerting a photocatalytic function such as an odor function, but the drying and curing time after coating may be very short, the applied coating film has flexibility, and the substrate is bent. However, it was found that the coating film had an effect of not peeling off.
その理由としては、フッ素樹脂を構成するＣ−Ｆ結合の結合エネルギーが大きくて、非常に緻密で安定した分子鎖を形成しているために、結晶化度が高く、耐薬品性、耐候性を示し、電気化学反応に対して高度に安定であり、さらには、Ｆ原子のもつ小さな原子半径と低い分極性から、分子間凝集力が低くなり、低表面張力、低摩擦係数という性質を示し外からの力に変形しやすくなるためと考えられる。（プラスチック・機能性高分子材料事典：産業調査会事典出版センター発行（２００４年）の３０６ページ目参照）。 The reason is that the bond energy of the C—F bond constituting the fluororesin is large, and a very dense and stable molecular chain is formed. Therefore, the crystallinity is high, and the chemical resistance and weather resistance are high. It is highly stable to electrochemical reactions, and further, due to the small atomic radius and low polarizability of F atoms, intermolecular cohesion is reduced, and the properties of low surface tension and low coefficient of friction are not shown. It is thought that it becomes easy to be deformed by the force from. (Refer to page 306 of Encyclopedia of Plastics / Functional Polymer Materials: Issued by Industry Research Association Encyclopedia Publishing Center (2004)).
上記したように、本発明に係わる光触媒塗料は、光触媒機能を有する金属酸化物（例えば酸化チタン）を、光触媒機能により分解されないと共に乾燥後に柔軟性を有する有機樹脂バインダに配合したものである。 As described above, the photocatalyst coating material according to the present invention is obtained by blending a metal oxide (for example, titanium oxide) having a photocatalytic function into an organic resin binder that is not decomposed by the photocatalytic function and has flexibility after drying.
そのために、樹脂バインダとして、上記の性質（光触媒作用により劣化しない、塗膜が柔軟性を有する）を備えるものを用いればよい。しかし、通常の樹脂バインダは、炭素と水素との結合Ｃ−Ｈ結合のために、光触媒作用を受けて分解されるので、Ｃ−Ｈ結合を有しておらず、前述した結合エネルギーの大きいＣ−Ｆ結合を有するナフィオン（デュポン社の登録商標）を用いている。 Therefore, what has the above-mentioned property (it does not deteriorate by a photocatalytic action and a coat has flexibility) should just be used as a resin binder. However, a normal resin binder is decomposed by photocatalysis because of the bond C—H bond between carbon and hydrogen, and therefore does not have a C—H bond, and has a large bond energy as described above. Iteiru use Nafion (DuPont registered trademark) having a -F bonds.
前記ナフィオン（Ｎａｆｉｏｎ：デュポン社の登録商標）の化学式を下記に示す。 The chemical formula of Nafion (registered trademark of DuPont) is shown below.
上記したように、本発明に係わる光触媒塗料（実施例Ａ）は、光触媒作用を受け難く分解されないと共に乾燥後に柔軟性を有する有機樹脂バインダを用いて、光触媒機能を有する金属酸化物である酸化チタンを配合した塗料としたので、塗装後の塗膜が劣化せず長寿命となり、長期間光触媒機能を発揮することができる。また、乾燥後に柔軟性を有するので、塗装した後で屈曲しても塗膜が剥離せず、安定した塗膜状態を維持可能な光触媒塗料を得ることができる。 As described above, the photocatalyst coating material according to the present invention (Example A) is a titanium oxide which is a metal oxide having a photocatalytic function by using an organic resin binder which is not easily decomposed due to photocatalysis and has flexibility after drying. Thus, the coating film after coating does not deteriorate and has a long life, and can exhibit a photocatalytic function for a long time. Moreover, since it has flexibility after drying, a photocatalyst coating material that can maintain a stable coating film state can be obtained without peeling off the coating film even if it is bent after coating.
そのために、塗装した後で曲げ加工を行うカラー鋼板の表面処理材にも、折り畳みと組み立てを繰り返すテント地の表面処理材にも適用可能であることが判った。 For this reason, it has been found that the present invention can be applied to a surface treatment material for a colored steel plate that is bent after coating, and a surface treatment material for a tent that is repeatedly folded and assembled.
さらに、多孔質の酸化チタンを用いると共に所定の厚み以上の塗膜（消臭実験によれば５μｍ以上）とすることで、ガスの吸着能力が高くなり、外気に対する消臭機能と抗菌機能の光触媒活性を向上させることができる。 Furthermore, by using porous titanium oxide and making it a coating film with a predetermined thickness or more (according to a deodorization experiment, 5 μm or more), the gas adsorption ability is enhanced, and the photocatalyst has a deodorizing function and an antibacterial function against outside air The activity can be improved.
また、カラー鋼板やテント地以外にも、もちろん適用可能であり、外壁や門柱やロッカー等の汚染防止の塗料として、また、自動車の車体やガラス面の汚染防止や消臭効果のためにも使用可能である。 In addition to colored steel plates and tents, it is of course applicable and can be used as anti-contamination paint for exterior walls, gate pillars, lockers, etc., and for anti-contamination and deodorizing effects on automobile bodies and glass surfaces. Is possible.
また、車内のソファー等の内装備品等に対しても、防汚染効果と消臭効果のための表面処理材に用いることもできる。 It can also be used as a surface treatment material for antifouling and deodorizing effects on interior equipment such as a sofa in a vehicle.
上記したように、本発明によれば、光触媒作用により劣化されないだけでなく、乾燥硬化後の塗膜が柔軟性を有していると共に超親水性も発揮して、環境汚染に対して非常に有効な防汚染効果を有すると共に高寿命な光触媒塗料とすることができる。さらに、乾燥硬化時間を非常に短くすることができるので、高速焼付けを行いながら連続生産するカラー鋼板の生産ラインにも適用することができる。 As described above, according to the present invention, not only is it not deteriorated by the photocatalytic action, but also the coating film after drying and curing has flexibility and also exhibits super hydrophilicity, which is extremely resistant to environmental pollution. A photocatalyst paint having an effective antifouling effect and having a long life can be obtained. Furthermore, since the drying and curing time can be very short, it can also be applied to a color steel plate production line that is continuously produced while performing high-speed baking.
また、塗装後に曲げ加工を行う薄板鋼板や、折り畳みと組み立てを繰り返すテント地等にも塗布可能な光触媒塗料を得ることができる。 Moreover, the photocatalyst coating material which can be apply | coated also to the thin plate steel plate which performs a bending process after coating, the tent place which repeats folding and an assembly, etc. can be obtained.
そのために、防汚染機能や消臭機能を備えると共に寿命の長い塗膜が塗布された、折り曲げ可能な鋼板やテント地を得ることができる。 Therefore, it is possible to obtain a foldable steel sheet or tent that has a contamination prevention function and a deodorization function and is coated with a long-life coating film.
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| JP2009208470A (en) * | 2008-02-04 | 2009-09-17 | Metal Tech:Kk | Coated steel sheet |
| JP2009185107A (en) * | 2008-02-04 | 2009-08-20 | Pialex Technologies Corp | Hydrophilic coating material and hydrophilic coated object |
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| WO2011128968A1 (en) | 2010-04-12 | 2011-10-20 | 株式会社メタルテック | Photocatalytic coating material |
| JP5721753B2 (en) * | 2013-01-28 | 2015-05-20 | 株式会社ピアレックス・テクノロジーズ | Hydrophilic paint and hydrophilic coated body |
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| WO2014017535A1 (en) | 2012-07-27 | 2014-01-30 | 株式会社ダイセル | Photoelectric conversion layer composition and photoelectric conversion element |
| WO2014017536A1 (en) | 2012-07-27 | 2014-01-30 | 株式会社ダイセル | Photoelectric conversion layer composition and photoelectric conversion element |
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