JP2001152362A - Photocatalyst-coated metallic sheet - Google Patents
Photocatalyst-coated metallic sheetInfo
- Publication number
- JP2001152362A JP2001152362A JP33893699A JP33893699A JP2001152362A JP 2001152362 A JP2001152362 A JP 2001152362A JP 33893699 A JP33893699 A JP 33893699A JP 33893699 A JP33893699 A JP 33893699A JP 2001152362 A JP2001152362 A JP 2001152362A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- zeolite
- particles
- nox
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 65
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 239000010419 fine particle Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000008119 colloidal silica Substances 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 31
- 239000010457 zeolite Substances 0.000 abstract description 31
- 230000009471 action Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000013032 photocatalytic reaction Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000002987 primer (paints) Substances 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 101150000971 SUS3 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＮＯｘを酸化分解除去
する光触媒反応を損なうことなく光触媒を均一に分散さ
せた構造の塗膜が形成された光触媒被覆金属板に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst-coated metal plate on which a photocatalyst is uniformly dispersed without impairing a photocatalytic reaction for oxidative decomposition and removal of NOx.
【０００２】[0002]
【従来の技術】自動車，工場，発電所等から排出される
ＮＯｘ含有ガスは、環境に重大な悪影響を及ぼす酸性雨
の原因の一つとされている。ＮＯｘは、人体に呼吸器障
害を誘発する物質とも考えられている。このようなこと
から、発生源で排ガス中のＮＯｘを除去する種々の方法
が研究開発されているが、一旦排出されたＮＯｘに対し
ては効果的な除去技術が確立されていないのが現状であ
る。2. Description of the Related Art NOx-containing gas emitted from automobiles, factories, power plants and the like is considered to be one of the causes of acid rain that has a serious adverse effect on the environment. NOx is also considered a substance that induces respiratory disorders in the human body. For this reason, various methods for removing NOx in exhaust gas at the source have been researched and developed. However, at present, no effective removal technology has been established for NOx once discharged. is there.
【０００３】ところで、光触媒を用いた光触媒反応によ
ってＮＯｘを硝酸塩に変換して除去する方法が近年提案
されている。光触媒は、バンドギャップ以上のエネルギ
ーをもつ波長の光が照射されると、光励起によって電子
が伝導体に、正孔が価電子帯に生じる。有機物，水，有
害ガス等は，正孔の強い酸化力で分解される。このよう
な光触媒作用を呈する物質としてＴｉＯ2，ＺｎＯ，Ｚ
ｒＯ2，ＷＯ3，Ｆｅ2Ｏ 3，ＦｅＴｉＯ3，ＳｒＴｉＯ3等
が知られているが、アナターゼ型酸化チタン粉末を光触
媒として利用した例が最も多く報告されている。光触媒
粉末は、実用的な使用に際し、流出や飛散を防ぐため金
属等に被覆し固定される。被覆法としては、たとえば特
開平３−８４４８号公報で紹介されている直接被覆法，
金属板上に塗布した光触媒粒子を４００℃以上の温度で
焼結する方法，加熱分解で光触媒となる前躯体を４００
℃程度の温度に加熱した基板上に吹き付ける方法等が知
られている。[0003] By the way, a photocatalytic reaction using a photocatalyst is performed.
Has recently proposed a method of converting NOx to nitrate and removing it.
Have been. The photocatalyst has an energy above the band gap.
When light of a wavelength with
Are generated in the conductor and holes are generated in the valence band. Organic matter, water, yes
The harmful gas is decomposed by the strong oxidizing power of the holes. like this
TiO as a substance exhibiting a novel photocatalytic actionTwo, ZnO, Z
rOTwo, WOThree, FeTwoO Three, FeTiOThree, SrTiOThreeetc
It is known that anatase type titanium oxide powder
The most frequently used examples are as media. photocatalyst
The powder should be made of gold to prevent spills and
The genus is covered and fixed. As a coating method, for example,
The direct coating method introduced in JP-A-3-8448,
Photocatalyst particles coated on a metal plate at a temperature of 400 ° C or more
Sintering method, 400 mg of precursor that becomes photocatalyst by thermal decomposition
The method of spraying on the substrate heated to about ℃ is known.
Have been.
【０００４】[0004]
【発明が解決しようとする課題】光触媒として酸化チタ
ンを金属板に塗布して光触媒作用を付与するとき、金属
板を酸化チタンで均一に被覆した場合にあっても、酸化
チタンの被覆量は実用上限られているためＮＯｘの酸化
分解能には限界がある。また、光触媒被覆金属板を用い
た光触媒反応では、ＮＯはＮＯ2に、更にＮＯ2はＮＯ3 -
に酸化分解されるが、中間生成物であるＮＯ2の大半は
ＮＯ3 -に酸化分解される前に大気中に放出されてしま
う。そのため、十分なＮＯｘ分解作用が発現されないこ
とがある。When titanium oxide is applied to a metal plate as a photocatalyst to give a photocatalytic effect, even if the metal plate is uniformly coated with titanium oxide, the amount of titanium oxide coated is practical. Because of the upper limit, the oxidation resolution of NOx is limited. In a photocatalytic reaction using a photocatalyst-coated metal plate, NO becomes NO 2 , and NO 2 becomes NO 3 −.
However, most of the intermediate product NO 2 is released to the atmosphere before being oxidized and decomposed into NO 3 − . Therefore, a sufficient NOx decomposition action may not be exhibited.
【０００５】中間生成物であるＮＯ2の大気への放出
は、金属板表面に形成した塗膜にＮＯ2を一時的に吸着
させることにより抑制できる（特開平６−３１５６１４
号公報）。この方法では、吸着剤としての活性炭と酸化
チタンとの混合物を主成分とする塗膜を形成しているた
め、ＮＯ2の大気への放出は一定時間防止できるもの
の、活性炭がＮＯ2で飽和した段階ではＮＯ2が大気に放
出され始める。また、高い光触媒活性の発現には表面積
の大きなｎｍオーダーの酸化チタン粉末が必要とされる
が、金属板を酸化チタンで被覆する焼結過程で形成され
た酸化チタン皮膜にクラックが入りやすく、皮膜特性が
劣化する傾向がみられる。The release of the intermediate product NO 2 into the atmosphere can be suppressed by temporarily adsorbing NO 2 on the coating film formed on the surface of the metal plate (JP-A-6-315614).
No.). In this method, since a coating film mainly containing a mixture of activated carbon and titanium oxide as an adsorbent is formed, emission of NO 2 to the atmosphere can be prevented for a certain period of time, but activated carbon is saturated with NO 2 . NO 2 begins to be released into the atmosphere in the stage. In addition, titanium oxide powder having a large surface area on the order of nanometers is required for the expression of high photocatalytic activity, but the titanium oxide film formed in the sintering process of coating a metal plate with titanium oxide is apt to crack, There is a tendency for the characteristics to deteriorate.
【０００６】吸着剤としてゼオライトを使用し、酸化チ
タンと複合添加して塗膜を形成することも知られている
（特開平７−１７１４０８号公報）。この塗膜では、ゼ
オライトの吸着機能及び酸化チタンの光触媒機能が得ら
れるものの、ゼオライト及び酸化チタンを単に分散させ
ているため、ゼオライトがＮＯｘで飽和するとＮＯｘの
大気放出が始まる。その結果、長期間にわたるＮＯｘの
除去には改良の余地がある。It is also known to use zeolite as an adsorbent and form a coating film by adding it in combination with titanium oxide (Japanese Patent Application Laid-Open No. 7-171408). In this coating film, the adsorption function of zeolite and the photocatalytic function of titanium oxide are obtained, but since zeolite and titanium oxide are simply dispersed, when the zeolite is saturated with NOx, NOx emission to the atmosphere starts. As a result, there is room for improvement in long term NOx removal.
【０００７】[0007]
【課題を解決するための手段】本発明は、このような問
題を解消すべく案出されたものであり、酸化チタンが表
面に付着したゼオライトを塗膜に分散させることによっ
て、ゼオライトの吸着機能及び酸化チタンの光触媒機能
を相乗的に活用し、長期間に渡りＮＯｘの効果的な除去
が可能な光触媒被覆金属板を提供することを目的とす
る。DISCLOSURE OF THE INVENTION The present invention has been devised in order to solve such a problem, and a zeolite having a titanium oxide adsorbing function is dispersed by dispersing zeolite adhering to the surface into a coating film. Another object of the present invention is to provide a photocatalyst-coated metal plate capable of effectively removing NOx over a long period of time by utilizing the photocatalytic function of titanium oxide synergistically.
【０００８】本発明の光触媒被覆金属板は、その目的を
達成するため、酸化チタン微粒子を付着させたゼオライ
ト粒子が分散され、シリカをバインダーとする塗膜が表
面に形成されていることを特徴とする。この光触媒被覆
金属板をトンネル内壁材として使用するとき、ゼオライ
トの吸着作用が高められ、酸化チタンによるＮＯｘ分解
能が一層向上する。In order to achieve the object, the photocatalyst-coated metal plate of the present invention is characterized in that zeolite particles to which titanium oxide fine particles are adhered are dispersed and a coating film using silica as a binder is formed on the surface. I do. When this photocatalyst-coated metal plate is used as a tunnel inner wall material, the adsorption effect of zeolite is enhanced, and the NOx resolution by titanium oxide is further improved.
【０００９】この光触媒被覆金属板は、酸化チタン微粒
子を付着させたゼオライト粒子が分散している溶剤をコ
ロイド状シリカと混合して塗料を調製し、該塗料を金属
板表面に塗布し、熱処理を施して光触媒層を形成するこ
とにより製造される。酸化チタン微粒子は、予めゼオラ
イト粒子と共に溶剤に添加して攪拌することによりゼオ
ライト粒子の表面に付着させることができる。The photocatalyst-coated metal plate is prepared by mixing a solvent in which zeolite particles having titanium oxide fine particles adhered are mixed with colloidal silica to prepare a coating, applying the coating to the surface of the metal plate, and performing a heat treatment. To form a photocatalyst layer. The titanium oxide fine particles can be attached to the surface of the zeolite particles by adding the titanium oxide particles together with the zeolite particles to a solvent in advance and stirring.
【００１０】[0010]
【作用】ゼオライトは、分子径に応じた選択吸着性及び
分子極性に起因する選択吸着性が最も優れた吸着剤であ
り、ＮＯｘの吸着に適している。なかでも、３〜１０Å
の細孔径をもつ合成ゼオライトは、ＮＯ，ＮＯ2等の分
子径が約４Åであることから、ＮＯｘ用として最適な吸
着剤である。しかし、ゼオライトを単独で分散させた塗
膜では、前述したようにゼオライトがＮＯｘで飽和する
と、飽和点を超えるＮＯｘを吸着できず、逆にＮＯｘの
大気放出が始まる。The zeolite is the adsorbent having the best selective adsorptivity according to the molecular diameter and the selective adsorptivity due to the molecular polarity, and is suitable for adsorbing NOx. Above all, 3-10Å
The synthetic zeolite having a pore diameter of about 4 nm is a most suitable adsorbent for NOx, since the molecular diameter of NO, NO 2 and the like is about 4 °. However, in a coating film in which zeolite is dispersed alone, as described above, when the zeolite is saturated with NOx, NOx exceeding the saturation point cannot be adsorbed, and conversely, NOx starts to be released to the atmosphere.
【００１１】この点、本発明に従った光触媒被覆金属板
では、塗膜に分散しているゼオライト粒子の表面に光触
媒機能のある酸化チタン微粒子が付着している。酸化チ
タン微粒子は、ゼオライト粒子の表面に付着した形態で
使用されるため、微粒子相互が凝集することなく、光触
媒反応に必要な表面積を大きくとれ、ゼオライトに吸着
されたＮＯｘとの距離も極めて短くなる。そのため、ゼ
オライトに吸着されたＮＯｘは、至近距離にある酸化チ
タン微粒子の光触媒作用で効果的に分解され、硝酸塩と
して気相から除去される。したがって、長期間にわたっ
て効果的な光触媒反応が維持されると共に、ゼオライト
の吸着能も回復する。In this respect, in the photocatalyst-coated metal plate according to the present invention, titanium oxide fine particles having a photocatalytic function adhere to the surface of zeolite particles dispersed in the coating film. Since the titanium oxide fine particles are used in a form attached to the surface of the zeolite particles, the fine particles do not agglomerate, the surface area required for the photocatalytic reaction can be increased, and the distance from the NOx adsorbed on the zeolite becomes extremely short. . Therefore, the NOx adsorbed on the zeolite is effectively decomposed by the photocatalytic action of the titanium oxide fine particles at a short distance, and is removed from the gas phase as nitrate. Therefore, the effective photocatalytic reaction is maintained over a long period of time, and the adsorption ability of zeolite is restored.
【００１２】本発明に従った光触媒被覆金属板は、特に
自動車，電車等が頻繁に通過するトンネルの内壁材とし
て使用するとき、顕著な効果を発揮する。すなわち、ト
ンネル内では、自動車，電車等の通過時に生じる風圧変
動によってゼオライトの吸着・脱着能が高められ、自動
車，電車等のライトが光源となって光触媒としての酸化
チタンを励起する。その結果、酸化チタンの光触媒作用
によりＮＯｘが効果的に除去され、トンネル内の雰囲気
が浄化される。The photocatalyst-coated metal plate according to the present invention exhibits a remarkable effect particularly when used as an inner wall material of a tunnel through which automobiles, trains and the like frequently pass. That is, in the tunnel, the adsorption / desorption ability of zeolite is enhanced by the wind pressure fluctuation generated when passing through a car, a train, etc., and the light of the car, train, etc. becomes a light source to excite titanium oxide as a photocatalyst. As a result, NOx is effectively removed by the photocatalytic action of titanium oxide, and the atmosphere in the tunnel is purified.
【００１３】[0013]
【実施の形態】ゼオライト粒子に酸化チタン微粒子を付
着させる方法としては、たとえば酸化チタン微粒子及び
ゼオライト粒子を有機溶剤に分散させ、ボールミルで攪
拌する方法が採用される。酸化チタン微粒子としては、
光触媒活性の点からアナターゼ型が好ましく、形状に特
段の制約が加わるものではないが、大きな有効表面積を
得るために平均粒径５０ｎｍ以下の微粒子が好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS As a method for adhering titanium oxide fine particles to zeolite particles, for example, a method in which titanium oxide fine particles and zeolite particles are dispersed in an organic solvent and stirred by a ball mill is employed. As titanium oxide fine particles,
The anatase type is preferred from the viewpoint of photocatalytic activity, and there is no particular restriction on the shape, but fine particles having an average particle size of 50 nm or less are preferred in order to obtain a large effective surface area.
【００１４】ゼオライト粒子には天然ゼオライト，合成
ゼオライトの何れも使用可能であるが、ＮＯｘの選択吸
着性を考慮すると３〜１０Åの細孔径をもつ合成ゼオラ
イトが好ましい。合成ゼオライトとしては、陽イオンと
してＫ，Ｎａ，Ｍｇ，Ｃｕ，Ａｇ等の１種又は２種以上
を含むＸ型，Ｙ型等の結晶構造をもつものが使用され
る。ゼオライト粒子は、形状に特段の制約が加わるもの
ではないが、均一な塗膜を金属板表面に形成させるため
１０μｍ以下の平均粒径をもつものが好ましい。平均粒
径が１０μｍを超えると、塗膜の平滑度が低下する傾向
がみられる。Either a natural zeolite or a synthetic zeolite can be used for the zeolite particles, but a synthetic zeolite having a pore diameter of 3 to 10 ° is preferable in consideration of the selective adsorption of NOx. As the synthetic zeolite, those having an X-type or Y-type crystal structure containing one or more of cations such as K, Na, Mg, Cu, Ag and the like are used. The shape of the zeolite particles is not particularly limited, but preferably has an average particle size of 10 μm or less in order to form a uniform coating film on the surface of the metal plate. When the average particle size exceeds 10 μm, the smoothness of the coating film tends to decrease.
【００１５】酸化チタン微粒子及びゼオライト粒子が分
散される有機溶剤としては、ブチルセルソルブ，エチル
セルソルブ等のエーテル類やイソプロパノール，エタノ
ール等のアルコール類，或いはそれらの混合溶剤が使用
される。たとえば、ブチルセルソルブとイソプロパノー
ルの混合溶剤（１：３）は、分散能が高く、酸化チタン
微粒子及びゼオライト粒子を凝集なく安定した懸濁状態
に維持する。有機溶剤に酸化チタン微粒子及びゼオライ
ト粒子を添加した後、ボールミル等を用いた攪拌により
ゼオライト粒子の表面に酸化チタン微粒子を付着させ
る。攪拌では、酸化チタン微粒子及びゼオライト粒子が
破砕されることなく、酸化チタン微粒子とゼオライト粒
子との間に機械的な付着状態が得られるようにボール重
量，攪拌速度，攪拌時間等の攪拌条件が設定される。As the organic solvent in which the titanium oxide fine particles and zeolite particles are dispersed, ethers such as butyl cellosolve and ethyl cellosolve, alcohols such as isopropanol and ethanol, or a mixed solvent thereof are used. For example, a mixed solvent (1: 3) of butyl cellosolve and isopropanol has a high dispersibility and maintains the titanium oxide fine particles and zeolite particles in a stable suspension state without aggregation. After adding the titanium oxide fine particles and the zeolite particles to the organic solvent, the titanium oxide fine particles are adhered to the surface of the zeolite particles by stirring using a ball mill or the like. In the stirring, the stirring conditions such as ball weight, stirring speed, and stirring time are set so that the titanium oxide fine particles and the zeolite particles are not crushed and a mechanical adhesion state is obtained between the titanium oxide fine particles and the zeolite particles. Is done.
【００１６】攪拌によりゼオライト粒子に酸化チタン微
粒子を付着させた後、ゼオライト粒子及び酸化チタン微
粒子を含む有機溶剤は、コロイド状シリカと混合され
る。コロイド状シリカとしては、たとえば平均粒径５〜
１５０μｍのシリカ粒子を１０〜５０質量％含む分散液
が使用される。この種のコロイド状シリカ混合分散液と
しては、固形成分を１０〜８０質量％分散させた分散液
が特許第２５８４２１６号明細書で紹介されている。After the titanium oxide particles are adhered to the zeolite particles by stirring, the organic solvent containing the zeolite particles and the titanium oxide particles is mixed with colloidal silica. As the colloidal silica, for example, an average particle size of 5 to 5
A dispersion containing 10 to 50% by mass of 150 μm silica particles is used. As a colloidal silica mixed dispersion of this type, a dispersion in which a solid component is dispersed in an amount of 10 to 80% by mass is introduced in Japanese Patent No. 2584216.
【００１７】ゼオライト粒子及び酸化チタン微粒子を含
む有機溶剤をコロイド状シリカと混合することにより、
光触媒機能を付与した塗膜の形成に必要な塗料が調製さ
れる。この塗料は、好ましくは酸化チタン：２０〜４０
質量％，ゼオライト：１〜６０質量％，シリカ：２０質
量％以上の組成に調整される。塗膜の光触媒作用は、２
０質量％以上の酸化チタンで顕著になるが、４０質量％
を超える過剰量の酸化チタンが含まれると塗膜にクラッ
クが入りやすくなる。塗膜のＮＯｘ吸着能は、１質量％
以上のゼオライトで顕著になるが、６０質量％を超える
過剰量のゼオライトが含まれると相対的にシリカの配合
量が低下し、形成された塗膜の金属板表面に対する密着
性が低下する。塗膜の密着性を確保する上から、２０質
量％以上のシリカが必要とされる。By mixing an organic solvent containing zeolite particles and titanium oxide fine particles with colloidal silica,
A paint necessary for forming a coating film having a photocatalytic function is prepared. The paint is preferably titanium oxide: 20-40.
The composition is adjusted to have a composition of 1% to 60% by mass, zeolite: 1 to 60% by mass, and silica: 20% by mass or more. The photocatalytic action of the coating is 2
It becomes remarkable with 0% by mass or more of titanium oxide, but is increased by 40% by mass.
If an excessive amount of titanium oxide is contained, the coating film tends to crack. NOx adsorption capacity of coating film is 1% by mass
The above-mentioned zeolite becomes remarkable, but if the zeolite contains an excessive amount of more than 60% by mass, the amount of silica is relatively reduced, and the adhesion of the formed coating film to the metal plate surface is reduced. In order to ensure the adhesion of the coating film, 20% by mass or more of silica is required.
【００１８】光触媒機能が付与された塗膜を金属板表面
に形成するためには、塗膜面に酸化チタン微粒子及びゼ
オライトが露出していることが重要である。このような
塗膜を形成する方法としては、スプレー法，ゾル−ゲル
法，物理蒸着法，粉体塗装法，浸漬法等がある。なかで
も、スプレー法は、樹脂等に混合する必要がなく揮発性
の高い有機溶剤のみで塗装可能なため、酸化チタン微粒
子及びゼオライトを露出させた塗膜の形成が容易で、塗
装コストも安価である。In order to form a coating film provided with a photocatalytic function on the surface of a metal plate, it is important that titanium oxide fine particles and zeolite are exposed on the coating film surface. As a method of forming such a coating film, there are a spray method, a sol-gel method, a physical vapor deposition method, a powder coating method, an immersion method and the like. Above all, the spray method does not need to be mixed with a resin or the like, and can be coated with only a highly volatile organic solvent, so that it is easy to form a coating film exposing titanium oxide fine particles and zeolite, and the coating cost is low. is there.
【００１９】塗膜が形成される金属板は、特に材質が制
限されるものではないが、普通鋼板，ステンレス鋼板，
めっき鋼板，アルミニウム板，銅板等が使用される。塗
装に先立って、塗膜密着性を改善するため脱脂，洗浄，
酸洗，クロメート処理，リン酸塩処理等の前処理が必要
に応じて施される。更には、プライマー層を予め形成し
てもよい。プライマー層は、光触媒層の密着性を向上
し、下地金属板の色調を隠蔽する作用を呈する。この金
属板の表面に、乾燥膜厚で０．５μｍ以上となる塗布量
で酸化チタン微粒子，ゼオライト粒子を含む塗料が塗布
される。０．５μｍ未満の膜厚では、十分なＮＯｘ分解
等の光触媒作用が発現されない場合がある。The material of the metal plate on which the coating film is formed is not particularly limited.
Plated steel plates, aluminum plates, copper plates, etc. are used. Prior to painting, degreasing, washing,
Pretreatment such as pickling, chromate treatment, and phosphate treatment is performed as necessary. Further, a primer layer may be formed in advance. The primer layer has the function of improving the adhesion of the photocatalyst layer and hiding the color tone of the underlying metal plate. A coating containing titanium oxide fine particles and zeolite particles is applied to the surface of the metal plate at an application amount of 0.5 μm or more in dry film thickness. If the film thickness is less than 0.5 μm, a sufficient photocatalytic action such as NOx decomposition may not be exhibited.
【００２０】金属板表面に塗布された塗料は、熱処理に
よって溶剤が除去される。熱処理温度を１５０〜４００
℃に設定すると、塗膜から溶剤が完全に除去されると共
に、光触媒，ゼオライトとシリカが強固に結合した塗膜
が形成される。低すぎる熱処理温度や短時間の熱処理で
は、酸化チタン微粒子やゼオライト粒子の間に一部の溶
剤が残存し、光触媒反応や吸着作用に悪影響を及ぼす傾
向がみられる。また、コロイド状シリカの縮重合が不十
分で、塗膜の密着性が不足しやすくなる。しかし、４０
０℃を超える熱処理温度では、塗膜に割れが発生しやす
くなる。The solvent is removed from the paint applied to the metal plate surface by heat treatment. Heat treatment temperature 150-400
When the temperature is set to ° C., the solvent is completely removed from the coating film, and a coating film in which the photocatalyst, zeolite and silica are strongly bonded is formed. If the heat treatment temperature is too low or if the heat treatment is performed for a short time, a part of the solvent remains between the titanium oxide fine particles and the zeolite particles, which tends to adversely affect the photocatalytic reaction and the adsorption action. Further, the condensation polymerization of the colloidal silica is insufficient, and the adhesion of the coating film tends to be insufficient. But 40
If the heat treatment temperature exceeds 0 ° C., cracks are likely to occur in the coating film.
【００２１】[0021]
【実施例】塗装原板として、板厚１．５ｍｍのＳＵＳ３
０４ステンレス鋼板を用いた。塗装原板を脱脂，酸洗し
た後、シリカ系プライマー塗料を塗布し、１４０℃×２
０分で焼き付けた。使用したプライマー塗料は、ブチル
セルソルブ／イソプロパノールの混合溶剤にメチルトリ
シリケートを溶解し，水を添加して加水分解反応を進行
させることによりオルガノシリカゾルを生成させ、得ら
れたオルガノシリカゾルにＡｌ2Ｏ3処理酸化チタン粉末
（白色顔料）を分散させることにより調製した。[Example] SUS3 with a thickness of 1.5 mm as a coating original plate
A 04 stainless steel plate was used. After degreasing and pickling the coated base plate, apply a silica-based primer coating, and apply 140 ° C x 2
Bake in 0 minutes. Primer coating used can be prepared by dissolving the methyl trisilicate in a mixed solvent of butyl cellosolve / isopropanol, the addition of water to produce a organosilica sol by advancing the hydrolysis reaction, the organosilica sol obtained Al 2 O It was prepared by dispersing 3 treated titanium oxide powder (white pigment).
【００２２】プライマー層の上に更にトップ塗料を塗布
し、２４０℃×２０分の熱処理によってアナターゼ型酸
化チタン微粒子，ゼオライト粒子，シリカ粒子を含む混
合酸化物のトップ層（光触媒層）を形成した。使用した
トップ塗料は、平均粒径７ｎｍのアナターゼ型酸化チタ
ン微粒子及び平均粒径２μｍの合成ゼオライト粒子をブ
チルセルソルブ／イソプロパノールの混合溶剤（１：
３）に加え、ボールミルで３０分間攪拌した後、オルガ
ノシリカゾルと混合することにより調製した。比較のた
め、アナターゼ型酸化チタン微粒子及び合成ゼオライト
を同じ配合量でオルガノシリカゾルに直接混合した塗料
を用い、他は同じ条件下でトップ層を形成した。A top coating was further applied on the primer layer, and a heat treatment at 240 ° C. for 20 minutes was performed to form a mixed oxide top layer (photocatalytic layer) containing anatase type titanium oxide fine particles, zeolite particles and silica particles. The top paint used was an anatase type titanium oxide fine particle having an average particle diameter of 7 nm and a synthetic zeolite particle having an average particle diameter of 2 μm, and a mixed solvent of butyl cellosolve / isopropanol (1:
In addition to 3), the mixture was stirred by a ball mill for 30 minutes and then mixed with an organosilica sol. For comparison, a top layer was formed under the same conditions except that anatase-type titanium oxide fine particles and a synthetic zeolite were directly mixed in the same amount in an organosilica sol.
【００２３】得られた塗装金属板から試験片を切り出
し、ＮＯｘ分解能試験及び塗膜密着性試験に供した。Ｎ
Ｏｘ分解能試験では、３００ｍｍ×２１０ｍｍの試験片
を石英ガラス製反応容器に入れ、ＮＯ：１ｐｐｍを含む
精製空気を反応容器に導入すると共に、反応容器の外側
から光化学用ブラックライト（２０Ｗ，３本）で波長３
００〜４００ｎｍの近紫外線を４０時間照射した。この
条件下で、反応容器から流出する精製空気に含まれてい
るＮＯ，ＮＯ2等のＮＯｘ濃度を測定し、試験前後のＮ
Ｏｘ濃度の変化から次式に従ってＮＯｘ濃度低下率を算
出した。 ＮＯx濃度低下率（％）＝（試験前のＮＯx濃度−試験後
のＮＯx濃度）／（試験前のＮＯx濃度）×１００ ＮＯ濃度低下率及びＮＯ2濃度低下率が共に９５％以上
をＮＯｘ分解能が優れているもの（○），ＮＯ濃度低下
率が９５％以上であるがＮＯ2濃度低下率が９５％未満
をＮＯｘ分解特性に改善がないもの（△），ＮＯ濃度低
下率及びＮＯ2濃度低下率共に９５％未満を特性が劣化
したもの（×）として，ＮＯｘ分解能を評価した。A test piece was cut out from the obtained coated metal plate and subjected to a NOx resolution test and a coating film adhesion test. N
In the Ox resolution test, a test piece of 300 mm × 210 mm was placed in a reaction vessel made of quartz glass, purified air containing NO: 1 ppm was introduced into the reaction vessel, and a black light for photochemistry (20 W, 3 pieces) was introduced from outside the reaction vessel. Wavelength 3
Irradiation with near-ultraviolet light of 00 to 400 nm was performed for 40 hours. In this condition, NO contained in the purified air flowing out of the reaction vessel, measuring the NOx concentration of such NO 2, before and after the test N
The NOx concentration reduction rate was calculated from the change in the Ox concentration according to the following equation. Concentration of NO x reduction rate (%) = (NO x concentration before test - concentration of NO x after test) / (concentration of NO x before test) × 100 NO concentration reduction rate and NO 2 concentration reduction rate are both 95% When the NOx resolution is excellent (分解 能), when the NO concentration reduction rate is 95% or more but the NO 2 concentration reduction rate is less than 95%, the NOx decomposition characteristics are not improved (△), the NO concentration reduction rate and The NOx resolving power was evaluated when the characteristics were deteriorated (x) when both of the NO 2 concentration reduction rates were less than 95%.
【００２４】塗膜密着性試験では、碁盤目状テープ剥離
試験によって塗膜の剥離状況を計測し、全く剥離しなか
った塗膜を密着性良好，少しでも剥離が観察された塗膜
を密着性不良として塗膜密着性を評価した。表１に掲げ
た組成比をもつ塗膜は、本発明例及び比較例共に良好な
塗膜密着性を示した。更に、金属板表面に形成された塗
膜を走査型電子顕微鏡で観察したところ、表１に掲げた
組成比をもつ塗膜では本発明例及び比較例共に割れが検
出されず、緻密な塗膜であることが確認された。In the coating film adhesion test, the peeling state of the coating film was measured by a cross-cut tape peeling test. The coating film adhesion was evaluated as poor. The coating films having the composition ratios shown in Table 1 exhibited good coating film adhesion in both the present invention examples and comparative examples. Further, when the coating film formed on the surface of the metal plate was observed with a scanning electron microscope, no crack was detected in the coating films having the composition ratios listed in Table 1 in both the present invention example and the comparative example. Was confirmed.
【００２５】しかし、ＮＯｘ分解能についてみると、表
１の調査結果にみられるように、本発明に従った光触媒
被覆金属板は何れも優れたＮＯｘ分解能を示したが、比
較例の光触媒被覆金属板では近紫外線４０時間照射後の
ＮＯｘ分解能が劣っていた。このようにＮＯｘ分解能に
生じた差は、酸化チタン微粒子及びゼオライトの分散形
態のみで本発明例と比較例とが異なることから、酸化チ
タニア微粒子を付着させたゼオライトを塗膜に分散させ
た有意性を示すものである。However, as for the NOx resolution, as can be seen from the investigation results in Table 1, the photocatalyst-coated metal plates according to the present invention all exhibited excellent NOx resolution, but the photocatalyst-coated metal plates of Comparative Examples In this case, the NOx resolution after irradiation with near ultraviolet rays for 40 hours was inferior. As described above, the difference in NOx resolution is different only in the dispersion form of the titanium oxide fine particles and the zeolite from the present invention and the comparative example. It shows.
【００２６】 [0026]
【００２７】[0027]
【発明の効果】以上に説明したように、本発明の光触媒
被覆金属板は、酸化チタン微粒子を予め付着させたゼオ
ライト粒子が分散した塗膜構造をもっているため、ゼオ
ライト粒子に吸着されたＮＯｘが酸化チタン微粒子と至
近距離に確保され、酸化チタン微粒子の光触媒作用が効
果的にＮＯｘの分解除去に使用される。また、光触媒反
応によって吸着されたＮＯｘが分解除去されるため、ゼ
オライト粒子がＮＯｘで飽和することもなく、ゼオライ
ト粒子の吸着能も長期間に渡って維持される。その結
果、ＮＯｘの吸着及び光触媒反応による分解除去が効率
よく行われ、環境浄化に役立つ塗装金属板として使用さ
れる。なかでも、トンネル内壁材として使用するとき、
自動車，電車等の通過時に生じる風圧変動によってゼオ
ライトへのＮＯｘ吸着が促進され、ＮＯｘ分解除去機能
が一層向上する。As described above, since the photocatalyst-coated metal plate of the present invention has a coating structure in which zeolite particles having titanium oxide fine particles adhered in advance are dispersed, NOx adsorbed on the zeolite particles is oxidized. The titanium oxide particles are secured at a close distance to the titanium particles, and the photocatalytic action of the titanium oxide particles is effectively used for decomposing and removing NOx. Further, since the adsorbed NOx is decomposed and removed by the photocatalytic reaction, the zeolite particles do not saturate with NOx, and the adsorption ability of the zeolite particles is maintained for a long time. As a result, NOx is adsorbed and decomposed and removed by a photocatalytic reaction, which is performed efficiently, and is used as a coated metal plate useful for environmental purification. Above all, when used as a tunnel inner wall material,
The adsorption of NOx to zeolite is promoted by the wind pressure fluctuation generated when passing through a car, a train, or the like, and the function of decomposing and removing NOx is further improved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２３Ｃ 18/12 Ｂ０１Ｄ 53/36 Ｊ Ｆターム(参考） 4D048 AA06 AB01 AB03 BA03X BA06X BA07X BA11X BA13X BA41X BA42X BB03 CA06 EA01 4F100 AA20B AA21B AB01A AC04B BA02 BA10A BA10B CC00B DE01B EH462 EJ082 EJ422 GB07 GB90 JL08B 4G069 AA01 AA04 AA08 AA09 AA11 BA01B BA01C BA02A BA02B BA02C BA04A BA04B BA04C BA07A BA07B BA17 BA18 BA48A BA48C BB04A BB04B BB04C BB06A BB06B BB06C CA02 CA03 CA07 CA10 CA13 DA06 EA08 EC22Y FA02 FA03 FA04 FA06 FB23 ZA02A ZA03B 4K022 AA02 AA11 AA41 BA15 BA20 BA22 BA33 CA09 DA06 EA01 4K044 AA03 BA12 BA13 BA14 BA21 BB03 CA24 CA53 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C23C 18/12 B01D 53/36 J F term (Reference) 4D048 AA06 AB01 AB03 BA03X BA06X BA07X BA11X BA13X BA41X BA42X BB03 CA06 EA01 4F100 AA20B AA21B AB01A AC04B BA02 BA10A BA10B CC00B DE01B EH462 EJ082 EJ422 GB07 GB90 JL08B 4G069 AA01 AA04 AA08 AA09 AA11 BA01B BA01C BA02A BA02B BA02C BA04A BA04B BA04C BA07A BA07B BA17 BA18 BA48A BA48C BB04A BB04B BB04C BB06A BB06B BB06C CA02 CA03 CA07 CA10 CA13 DA06 EA08 EC22Y FA02 FA03 FA04 FA06 FB23 ZA02A ZA03B 4K022 AA02 AA11 AA41 BA15 BA20 BA22 BA33 CA09 DA06 EA01 4K044 AA03 BA12 BA13 BA14 BA21 BB03 CA24 CA53
Claims (3)
ト粒子が分散され、シリカをバインダーとする塗膜が金
属板の表面に直接、又はプライマー層を介して形成され
ていることを特徴とする光触媒被覆金属板。1. A photocatalytic coating, wherein zeolite particles to which titanium oxide fine particles are adhered are dispersed, and a coating film using silica as a binder is formed directly on the surface of a metal plate or via a primer layer. Metal plate.
ト粒子が分散している溶剤をコロイド状シリカと混合し
て塗料を調製し、該塗料を金属板表面に直接、又はプラ
イマー層を介して塗布し、熱処理を施して光触媒層を形
成することを特徴とする光触媒被覆金属板の製造方法。2. A coating material is prepared by mixing a solvent in which zeolite particles having titanium oxide fine particles adhered are dispersed with colloidal silica, and applying the coating material directly to a metal plate surface or via a primer layer. Forming a photocatalyst layer by heat treatment.
溶剤に添加して攪拌することによりゼオライト粒子の表
面に酸化チタン微粒子を付着させる請求項２記載の光触
媒被覆金属板の製造方法。3. The method for producing a photocatalyst-coated metal plate according to claim 2, wherein the titanium oxide fine particles are adhered to the surface of the zeolite particles by adding the zeolite particles and the titanium oxide fine particles to a solvent and stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33893699A JP2001152362A (en) | 1999-11-30 | 1999-11-30 | Photocatalyst-coated metallic sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33893699A JP2001152362A (en) | 1999-11-30 | 1999-11-30 | Photocatalyst-coated metallic sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001152362A true JP2001152362A (en) | 2001-06-05 |
Family
ID=18322729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33893699A Withdrawn JP2001152362A (en) | 1999-11-30 | 1999-11-30 | Photocatalyst-coated metallic sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001152362A (en) |
Cited By (8)
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|---|---|---|---|---|
| JP2003080034A (en) * | 2001-09-10 | 2003-03-18 | Mitsubishi Heavy Ind Ltd | Oxidation apparatus and method for maintaining the same |
| KR100449341B1 (en) * | 2002-01-15 | 2004-09-22 | 이종황 | Photo catalytic powder combined with carrier and water paint using the same |
| JP2006515388A (en) * | 2003-01-03 | 2006-05-25 | セミカ エス アー | Viscosity-adjustable photosensitive dispersion for metal deposition on insulating substrates and use thereof |
| JP2008148726A (en) * | 2006-12-14 | 2008-07-03 | Catalysts & Chem Ind Co Ltd | Deodorizing and antibacterial composition |
| EP1990378A1 (en) * | 2007-05-10 | 2008-11-12 | SigmaKalon B.V. | A primer composition |
| JP2012005914A (en) * | 2010-06-22 | 2012-01-12 | Fujita Corp | Photocatalyst-coated material for cleaning of atmosphere, pavement method for cleaning of atmosphere which uses the photocatalyst-coated material, and method for forming atmosphere-cleaning wall surface |
| JP2012515644A (en) * | 2009-01-23 | 2012-07-12 | エフェエメセ フォレト，ソシエダ アノニマ | Photocatalytic mixture for the decomposition of nitrogen oxides |
| RU2482912C1 (en) * | 2011-09-30 | 2013-05-27 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Method of producing filtering-sorbing material with photo catalytic properties |
-
1999
- 1999-11-30 JP JP33893699A patent/JP2001152362A/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003080034A (en) * | 2001-09-10 | 2003-03-18 | Mitsubishi Heavy Ind Ltd | Oxidation apparatus and method for maintaining the same |
| KR100449341B1 (en) * | 2002-01-15 | 2004-09-22 | 이종황 | Photo catalytic powder combined with carrier and water paint using the same |
| JP2006515388A (en) * | 2003-01-03 | 2006-05-25 | セミカ エス アー | Viscosity-adjustable photosensitive dispersion for metal deposition on insulating substrates and use thereof |
| JP2008148726A (en) * | 2006-12-14 | 2008-07-03 | Catalysts & Chem Ind Co Ltd | Deodorizing and antibacterial composition |
| EP1990378A1 (en) * | 2007-05-10 | 2008-11-12 | SigmaKalon B.V. | A primer composition |
| WO2008138895A1 (en) * | 2007-05-10 | 2008-11-20 | Ppg B.V. | A primer composition |
| CN101679785B (en) * | 2007-05-10 | 2013-08-21 | Ppg有限责任公司 | A primer composition |
| US9085701B2 (en) | 2007-05-10 | 2015-07-21 | Ppg B.V. | Primer composition |
| JP2012515644A (en) * | 2009-01-23 | 2012-07-12 | エフェエメセ フォレト，ソシエダ アノニマ | Photocatalytic mixture for the decomposition of nitrogen oxides |
| JP2012005914A (en) * | 2010-06-22 | 2012-01-12 | Fujita Corp | Photocatalyst-coated material for cleaning of atmosphere, pavement method for cleaning of atmosphere which uses the photocatalyst-coated material, and method for forming atmosphere-cleaning wall surface |
| RU2482912C1 (en) * | 2011-09-30 | 2013-05-27 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Method of producing filtering-sorbing material with photo catalytic properties |
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