JP3247857B2 - Method and apparatus for measuring photocatalytic activity - Google Patents
Method and apparatus for measuring photocatalytic activityInfo
- Publication number
- JP3247857B2 JP3247857B2 JP24370397A JP24370397A JP3247857B2 JP 3247857 B2 JP3247857 B2 JP 3247857B2 JP 24370397 A JP24370397 A JP 24370397A JP 24370397 A JP24370397 A JP 24370397A JP 3247857 B2 JP3247857 B2 JP 3247857B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalytically active
- photocatalytic activity
- photocatalytic
- measuring
- light
- 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.)
- Expired - Fee Related
Links
- 230000001699 photocatalysis Effects 0.000 title claims description 122
- 238000000034 method Methods 0.000 title claims description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 100
- 238000012360 testing method Methods 0.000 claims description 70
- 239000004408 titanium dioxide Substances 0.000 claims description 48
- 239000011149 active material Substances 0.000 claims description 35
- 239000010409 thin film Substances 0.000 claims description 33
- 238000000354 decomposition reaction Methods 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 23
- 239000013543 active substance Substances 0.000 claims description 15
- 230000003373 anti-fouling effect Effects 0.000 claims description 13
- 239000011941 photocatalyst Substances 0.000 claims description 13
- 230000001678 irradiating effect Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 5
- 238000011156 evaluation Methods 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 claims description 4
- 238000004611 spectroscopical analysis Methods 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 230000003595 spectral effect Effects 0.000 description 35
- 239000000126 substance Substances 0.000 description 34
- 238000005259 measurement Methods 0.000 description 26
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 240000008415 Lactuca sativa Species 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 238000011002 quantification Methods 0.000 description 7
- 235000012045 salad Nutrition 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000003618 dip coating Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000012937 correction Methods 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 Platinum group metals Chemical class 0.000 description 1
- 229910019897 RuOx Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 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
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒活性の新規
な測定方法およびその装置に関し、さらに詳しくは、光
触媒活性材料の光触媒活性を、正確にかつ感度および再
現性よく、しかも短時間で測定しうる実用的な方法、お
よび光触媒活性測定装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method and apparatus for measuring photocatalytic activity, and more particularly to a method for measuring photocatalytic activity of a photocatalytically active material accurately, with good sensitivity and reproducibility, and in a short time. And a photocatalytic activity measuring device.
【０００２】[0002]
【従来の技術】二酸化チタンなどの半導体を光電極とす
ることにより、水が水素と酸素とに光分解される、いわ
ゆる本多−藤嶋効果［「工業化学雑誌」第７２巻、第１
０８〜１１３ページ（１９６９年）］が見出されて以
来、光触媒の開発や実用化研究が盛んに行われるように
なってきた。この光触媒は、二酸化チタンなどの半導体
粒子を、そのバンドギャップ以上のエネルギーの光で励
起すると、伝導帯に電子が生じ、かつ価電子帯に正孔が
生じ、このエネルギーに富んだ電子−正孔対を利用する
ものである。2. Description of the Related Art When a semiconductor such as titanium dioxide is used as a photoelectrode, water is photodecomposed into hydrogen and oxygen, the so-called Honda-Fujishima effect [Industrial Chemistry Magazine, Vol.
08-113 (1969)], the development of photocatalysts and research for practical use have been actively conducted. When this photocatalyst excites semiconductor particles such as titanium dioxide with light having an energy equal to or greater than the band gap, electrons are generated in the conduction band and holes are generated in the valence band. It uses pairs.
【０００３】このような光触媒を応用して、例えば脱
臭、防汚、抗菌、殺菌、さらには廃水中や廃ガス中の環
境汚染上の問題となっている各種物質の分解・除去など
が検討されている。[0003] Application of such a photocatalyst has been studied for deodorization, antifouling, antibacterial and sterilization, as well as decomposition and removal of various substances which are a problem of environmental pollution in wastewater or waste gas. ing.
【０００４】光触媒としては、これまで種々の半導体的
特性を有する化合物、例えば二酸化チタン、酸化鉄、酸
化タングステン、酸化亜鉛などの金属酸化物、硫化カド
ミウムや硫化亜鉛などの金属硫化物などが知られている
が、これらの中で、特に二酸化チタンは実用的な光触媒
として有用である。この二酸化チタンは、太陽光などの
日常光に含まれる紫外線領域の特定波長の光を吸収する
ことによって優れた光触媒活性を示し、この光触媒作用
に由来する強力な酸化作用によって脱臭、防汚、抗菌、
殺菌作用を発揮するため、各種基材に二酸化チタン薄膜
を設け光触媒作用をもたせることで、脱臭、防汚、抗
菌、殺菌などを有した様々な光触媒活性材料が開発され
ている。As the photocatalyst, compounds having various semiconductor properties such as metal oxides such as titanium dioxide, iron oxide, tungsten oxide and zinc oxide, and metal sulfides such as cadmium sulfide and zinc sulfide have been known. However, among these, titanium dioxide is particularly useful as a practical photocatalyst. This titanium dioxide exhibits excellent photocatalytic activity by absorbing light of a specific wavelength in the ultraviolet region included in daily light such as sunlight, and has a strong oxidizing action derived from this photocatalytic action, thereby deodorizing, antifouling, and antibacterial. ,
Various photocatalytically active materials having deodorization, antifouling, antibacterial, sterilization, and the like have been developed by providing a titanium dioxide thin film on various base materials and exerting a photocatalytic action in order to exert a bactericidal action.
【０００５】ところで、このような光触媒活性材料にお
ける光触媒活性の評価方法としては、これまで、例えば
実際に野外に曝露し、その汚れ具合いを目視観察した
り、あるいはサラダ油などを塗布し、光触媒分解に伴う
重量減少から評価することが試みられてきた。[0005] As an evaluation method for the photocatalytic activity in the photocatalyst active material, heretofore, for example actually exposures outdoors, to observe visually the degree of contamination, or salad oil and the like is applied, photocatalytic degradation Attempts have been made to evaluate from the weight loss associated with.
【０００６】しかしながら、上記目視観察法では、光触
媒活性を量的に評価することが困難である上、再現性に
乏しく、一方、サラダ油塗布法においては、光触媒活性
を量的に評価しうるものの、精度、感度および再現性が
悪く、しかも評価に長時間を要するなどの問題があっ
た。However, in the above-described visual observation method, it is difficult to quantitatively evaluate the photocatalytic activity and the reproducibility is poor. On the other hand, in the salad oil coating method, the photocatalytic activity can be quantitatively evaluated. There are problems such as poor accuracy, sensitivity, and reproducibility, and a long time for evaluation.
【０００７】したがって、光触媒活性材料における光触
媒活性の有無や大小、複数の材料間の光触媒活性の優劣
などを評価することは極めて難しいのが実状である。Therefore, it is actually very difficult to evaluate the presence or absence of photocatalytic activity in a photocatalytic active material, the magnitude of the photocatalytic activity, and the degree of photocatalytic activity among a plurality of materials.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、光触媒活性材料の光触媒活性を、正確に
かつ感度および再現性よく、しかも短時間で測定しうる
実用的な方法を提供することを目的とするものである。Under such circumstances, the present invention provides a practical method capable of measuring the photocatalytic activity of a photocatalytically active material accurately, with good sensitivity and reproducibility, and in a short time. The purpose is to provide.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、光触媒活性材
料の光触媒活性面に有機色素を付着または吸着させ、光
触媒作用に由来する該有機色素の分解速度を、分光光学
的手法などで測定することにより、光触媒活性を求める
ことができ、その目的を達成しうることを見出し、この
知見に基づいて本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, an organic dye has been attached or adsorbed on the photocatalytically active surface of the photocatalytically active material, and the photocatalytic activity has been derived. By measuring the decomposition rate of the organic dye by a spectroscopic method or the like, the photocatalytic activity can be obtained, and it has been found that the object can be achieved, and based on this finding, the present invention has been completed. .
【００１０】すなわち、本発明は、表面に光触媒活性物
質層を有する光触媒活性材料の光触媒活性を測定するに
当たり、該材料の光触媒活性面に有機色素を付着または
吸着させたのち、この有機色素の光触媒作用に基づく分
解速度を測定し、光触媒活性を求めることを特徴とする
光触媒活性の測定方法を提供するものである。That is, in the present invention, when measuring the photocatalytic activity of a photocatalytically active material having a photocatalytically active substance layer on the surface, an organic dye is attached or adsorbed on the photocatalytically active surface of the material, and then the photocatalytic An object of the present invention is to provide a method for measuring photocatalytic activity, which comprises measuring a decomposition rate based on an action to determine photocatalytic activity.
【００１１】また、本発明は、実際に既に施工されてい
る光触媒活性素材について、その施工場所にて、被験物
に有機色素を付着あるいは吸着せしめ、実際の使用環境
下あるいは光量環境下での光触媒防汚活性を評価するこ
とを特徴とする光触媒防汚活性の評価方法を提供するも
のである。Further, the present invention relates to a photocatalytic active material which has already been applied, by adhering or adsorbing an organic dye to a test object at a place where the photocatalytic active material has been applied, to thereby obtain a photocatalytic material in an actual use environment or in a light quantity environment. An object of the present invention is to provide a method for evaluating photocatalyst antifouling activity, which is characterized by evaluating antifouling activity.
【００１２】また、本発明は、光触媒活性材料の光触媒
活性面に光を照射して前処理を施すための手段、この前
処理が施された光触媒活性面に有機色素を付着または吸
着させるための手段、光触媒活性面に光を照射して、光
触媒作用により有機色素を分解させるための手段および
有機色素の分解速度を分光光学的に測定するための手段
を含むことを特徴とする光触媒活性材料の光触媒活性測
定装置をも提供するものである。Further, the present invention provides a means for irradiating a photocatalytically active surface of a photocatalytically active material with light to perform a pretreatment, and for adhering or adsorbing an organic dye on the photocatalytically active surface which has been subjected to the pretreatment. Means, a means for irradiating light to the photocatalytically active surface, means for decomposing the organic dye by photocatalysis, and means for spectroscopically measuring the decomposition rate of the organic dye. A photocatalytic activity measurement device is also provided.
【００１３】[0013]
【発明の実施の形態】本発明の方法が適用される光触媒
活性材料としては、表面に光触媒活性物質層を有するも
のであればよく、特に制限はないが、例えば適当な透光
性または非透光性基材上に、光触媒活性面として、光触
媒活性物質層、具体的には光触媒活性物質からなる薄
膜、微粒子状光触媒活性物質からなる層、光触媒活性物
質を含む塗工層などを有するものを挙げることができ
る。ここで、光触媒活性物質としては、従来公知のも
の、例えば二酸化チタン、酸化亜鉛、チタン酸ストロン
チウム（ＳｒＴｉＯ3）、チタン酸バリウム（ＢａＴｉ4
Ｏ9）、チタン酸ナトリウム（Ｎａ2Ｔｉ6Ｏ13）、二酸
化ジルコニウム、α−Ｆｅ2Ｏ3、Ｋ4Ｎｂ6Ｏ17、Ｒｂ4
Ｎｂ6Ｏ17、Ｋ2Ｒｂ2Ｎｂ6Ｏ17などの金属酸化物、硫化
カドミウム、硫化亜鉛、硫化インジウムなどの金属硫化
物、さらには、これらに助触媒として、白金、パラジウ
ム、ロジウム、ルテニウムなどの白金族金属や、ＮｉＯ
x、ＲｕＯx、ＲｈＯxなどを担持させたものなどが挙げ
られる。これらの中で、光触媒活性および経済性などの
面から、二酸化チタンが好適である。この二酸化チタン
はルチル型やアナターゼ型などがあるが、光触媒活性の
点から、アナターゼ型の方がルチル型よりも好ましい。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The photocatalytic active material to which the method of the present invention is applied is not particularly limited as long as it has a photocatalytic active material layer on its surface. A photocatalytically active material layer, specifically a thin film made of a photocatalytically active material, a layer made of a particulate photocatalytically active material, a layer having a photocatalytically active material-containing coating layer, etc. Can be mentioned. Here, as the photocatalytic active substance, conventionally known substances such as titanium dioxide, zinc oxide, strontium titanate (SrTiO 3 ), barium titanate (BaTi 4)
O 9 ), sodium titanate (Na 2 Ti 6 O 13 ), zirconium dioxide, α-Fe 2 O 3 , K 4 Nb 6 O 17 , Rb 4
Metal oxides such as Nb 6 O 17 and K 2 Rb 2 Nb 6 O 17 , metal sulfides such as cadmium sulfide, zinc sulfide and indium sulfide, and platinum, palladium, rhodium and ruthenium as co-catalysts Platinum group metals, NiO
x, RuOx, RhOx, etc. are supported. Among these, titanium dioxide is preferred from the viewpoint of photocatalytic activity and economic efficiency. This titanium dioxide and the like Le Chi le type or anatase type, from the viewpoint of photocatalytic activity, towards the anatase type is preferable to the rutile type.
【００１４】本発明の方法においては、前記光触媒活性
材料の光触媒活性面に、有機色素を付着または吸着させ
るが、この有機色素としては、（１）それ自体が耐光性
を有すること、具体的には少なくとも３０分以内に、波
長３００ｎｍ〜３８０ｎｍ、光量１ｍＷ／ｃｍ2のＵＶ
光の照射によって分解しない（吸光度が変化しない）こ
と、（２）光触媒活性面と暗所下にて反応しないこと、
具体的には、色素と光触媒活性面とが、少なくとも３０
分以内に、波長３００ｎｍ〜３８０ｎｍ、光量１ｍＷ／
ｃｍ2のＵＶ光の照射なしに反応を起こすことがない
（吸光度が変化しない）こと、（３）光触媒活性物質が
光触媒作用を発現するのに必要な波長域での光の吸収が
少ないこと、具体的には光触媒活性物質が二酸化チタン
である場合は、波長３５０〜４００ｎｍの範囲で光の吸
収が少ないこと、の３条件を満たすものを用いるのが望
ましい。In the method of the present invention, an organic dye is adhered or adsorbed on the photocatalytically active surface of the photocatalytically active material. The organic dye may be (1) itself having light resistance. Is a UV light having a wavelength of 300 nm to 380 nm and a light amount of 1 mW / cm 2 within at least 30 minutes.
Not decomposed by light irradiation (absorbance does not change); (2) not react with the photocatalytically active surface in a dark place;
Specifically, the dye and the photocatalytically active surface are at least 30
Within a minute, the wavelength is 300 nm to 380 nm, and the light amount is 1 mW /
that no reaction occurs (irradiation does not change) without irradiation of UV light of 2 cm 2 , (3) that the photocatalytically active substance has little light absorption in a wavelength range necessary for developing a photocatalytic action, Specifically, when the photocatalytically active substance is titanium dioxide, it is desirable to use a substance that satisfies the three conditions of low light absorption in the wavelength range of 350 to 400 nm.
【００１５】本発明で用いる有機色素としては、上記要
件を満たすものであればよく、特に制限はないが、例え
ばメチレンブルーやマラカイトグリーンなどを好ましく
挙げることができる。The organic dye used in the present invention is not particularly limited as long as it satisfies the above requirements, and examples thereof include methylene blue and malachite green.
【００１６】本発明の方法においては、上記有機色素を
光触媒活性材料の光触媒活性面に付着または吸着させる
前に、予め該光触媒活性面に光を照射して有機物の分
解、除去を行う前処理を施すのが有利である。光触媒活
性面が二酸化チタン薄膜である場合には、この前処理に
より、該二酸化チタン薄膜が親水化され、有機色素水溶
液を用いる場合に、有機色素が極めて均質に付着または
吸着されるので好都合である。この前処理は、例えば波
長３００ｎｍ〜３８０ｎｍ、光量４ｍＷ／ｃｍ2のＵＶ
光を、１〜２４時間程度照射することにより、行うこと
ができる。In the method of the present invention, before the organic dye is attached to or adsorbed on the photocatalytically active surface of the photocatalytically active material, a pretreatment for irradiating the photocatalytically active surface with light to decompose and remove organic substances is performed. It is advantageous to apply. When the photocatalytically active surface is a titanium dioxide thin film, this pretreatment is advantageous because the titanium dioxide thin film is hydrophilized, and when an organic dye aqueous solution is used, the organic dye is very uniformly attached or adsorbed. . This pretreatment is performed, for example, by using a UV light with a wavelength of 300 nm to 380 nm and a light amount of 4 mW / cm 2
Irradiation with light for about 1 to 24 hours can be performed.
【００１７】光触媒活性材料の光触媒活性面に有機色素
を付着または吸着させる方法としては、該有機色素を光
触媒活性面に均質に付着または吸着させうる方法であれ
ばよく、特に制限はないが、例えば以下に示す方法を用
いるのが有利である。The method for adhering or adsorbing the organic dye on the photocatalytically active surface of the photocatalytically active material is not particularly limited as long as the method is capable of uniformly adhering or adsorbing the organic dye on the photocatalytically active surface. It is advantageous to use the method described below.
【００１８】すなわち、まず、有機色素を水などの適当
な溶媒に溶解して有機色素溶液を調製し、この溶液中
に、光触媒活性を測定しようとする光触媒活性材料（被
験物）を浸漬処理する。二酸化チタン薄膜などの光触媒
活性面に色素を付着または吸着させる場合、色素溶液が
十分濃い濃度であれば、色素は複層吸着されるものと考
えられる。しかしながら光触媒による酸化・有機物分解
反応は光触媒活性物質表面でしか起こりえず、光触媒活
性に伴う色素の分解速度は、複層の層数に依らず一定で
ある。したがって、均質に付着または吸着できるのであ
れば、色素の付着または吸着量は一定以上であればよ
い。That is, first, an organic dye solution is prepared by dissolving an organic dye in an appropriate solvent such as water, and a photocatalytically active material (test substance) whose photocatalytic activity is to be measured is immersed in this solution. . When attaching or adsorbing a dye on a photocatalytically active surface such as a titanium dioxide thin film, it is considered that the dye is adsorbed in multiple layers if the concentration of the dye solution is sufficiently high. However, photocatalytic oxidation / organic substance decomposition reaction can occur only on the surface of the photocatalytic active substance, and the decomposition rate of the dye accompanying the photocatalytic activity is constant irrespective of the number of layers. Therefore, as long as the dye can be uniformly attached or adsorbed, the amount of adhering or adsorbing the dye may be a certain level or more.
【００１９】色素溶液への被験物の浸漬時間は３０分以
上が好ましく、１〜３時間程度がより好ましい。色素の
二酸化チタン薄膜などの光触媒活性面（測定面）への吸
着には化学的吸着も含まれるものと思われる。したがっ
て光触媒活性面（測定面）を色素溶液中に十分な時間浸
漬させ、化学的吸着平衡の状態にするのが好ましい。浸
漬処理後、光触媒活性材料を取り出し、余剰の色素溶液
を除去後、乾燥させることにより、光触媒活性面に、十
分な量の有機色素が均質に付着または吸着した光触媒活
性材料が得られる。なお、後述の定量法において、吸光
度法（ＡＢＳ法）を用いる場合には、被験物の非測定面
に付着または吸着した色素を溶媒で完全に除去すること
が望ましい。The immersion time of the test substance in the dye solution is preferably 30 minutes or more, more preferably about 1 to 3 hours. It is considered that the adsorption of the dye on the photocatalytically active surface (measurement surface) such as a titanium dioxide thin film includes chemical adsorption. Therefore, it is preferable that the photocatalytically active surface (measurement surface) is immersed in the dye solution for a sufficient time to bring about a state of chemical adsorption equilibrium. After the immersion treatment, the photocatalytically active material is taken out, excess dye solution is removed, and then dried, whereby a photocatalytically active material having a sufficient amount of organic dye uniformly adhered or adsorbed on the photocatalytically active surface is obtained. When the absorbance method (ABS method) is used in the quantification method described below, it is desirable to completely remove the dye adhering or adsorbing to the non-measurement surface of the test object with a solvent.
【００２０】次に、このようにして光触媒活性面に付着
または吸着した色素の光触媒作用による分解速度を測定
するが、この場合、色素の定量は測定感度のよい分光光
学的手法が好ましい。この分光光学的手法としては、例
えば吸光度法（ＡＢＳ法）、反射率法、Ｌａｂ表色系法
などを用いることができる。例えば光触媒活性ガラスの
ような透光性の良好な被験物の場合、ＡＢＳ測定が好ま
しい。光触媒活性面に吸着した色素が有する最大吸収波
長でのＡＢＳ測定を行うことで、色素の定量が高感度で
可能である。ＡＢＳ測定に用いられる測定機器は一般に
広く用いられている紫外・可視分光光度計でよい。また
光触媒活性タイルのような透光性の不良な被験物の場合
は、分光反射率法、あるいはＬａｂ表色系法の明度Ｌの
測定が好ましい。分光反射率を測定する場合は、光触媒
活性面に吸着した色素が有する最大吸収波長での反射率
でよい。これらの測定に用いられる測定機器は該評価が
可能な色差計でよい。しかしながら、同色の光触媒活性
タイルを評価する場合はいずれの測定でも問題ないが、
異色の光触媒活性タイルを評価する場合は、分光反射率
を測定することが可能な色差計でなければならない。Next, the decomposition rate of the dye adhering or adsorbed on the photocatalytically active surface in this way is measured by the photocatalytic action. In this case, the dye is preferably quantified by a spectroscopic method having high measurement sensitivity. As the spectroscopic method, for example, an absorbance method (ABS method), a reflectance method, a Lab color system method, or the like can be used. For example, in the case of an object having good light transmission such as a photocatalytically active glass, ABS measurement is preferable. By performing the ABS measurement at the maximum absorption wavelength of the dye adsorbed on the photocatalytically active surface, the dye can be quantitatively determined with high sensitivity. The measuring device used for the ABS measurement may be a generally used ultraviolet / visible spectrophotometer. In the case of a specimen having poor light transmission such as a photocatalytically active tile, it is preferable to measure the lightness L by the spectral reflectance method or the Lab color system method. When measuring the spectral reflectance, the reflectance at the maximum absorption wavelength of the dye adsorbed on the photocatalytically active surface may be used. A measuring instrument used for these measurements may be a color difference meter capable of performing the evaluation. However, when evaluating photocatalytically active tiles of the same color, there is no problem with either measurement,
When evaluating photocatalytically active tiles of different colors, the color difference meter must be capable of measuring spectral reflectance.
【００２１】ＡＢＳ測定や分光反射率測定の場合は、色
素として、例えばメチレンブルーを用いた場合、該色素
は光触媒活性面（測定面）に付着または吸着させた状態
で、図１に示すように、波長５８０ｎｍ付近に大きな光
吸収を有しているので、最大吸収波長として、この波長
を利用すればよい。In the case of ABS measurement or spectral reflectance measurement, for example, when methylene blue is used as a dye, the dye is adhered or adsorbed on a photocatalytically active surface (measurement surface) as shown in FIG. Since it has a large light absorption near the wavelength of 580 nm, this wavelength may be used as the maximum absorption wavelength.
【００２２】次に、被験物のブラックライト照射時間に
対する、ＡＢＳ、分光反射率、明度Ｌの測定値の変化量
をプロットすれば、被験物の光触媒活性に伴う有機色素
の分解速度がプロットの傾きから得られる。有機色素の
分解に伴う難分解物の発生などの要因により該プロット
が直線にならない場合があるが、その場合は、該プロッ
ト曲線の初期の傾きを求めればよい。この傾きが色素の
光触媒活性による分解速度であり、すなわち光触媒活性
を表すこととなる。Next, plotting the variation of measured values of ABS, spectral reflectance, and lightness L with respect to the black light irradiation time of the test object, the decomposition rate of the organic dye accompanying the photocatalytic activity of the test object is plotted. Obtained from The plot may not be a straight line due to factors such as the generation of hardly decomposable substances accompanying the decomposition of the organic dye. In such a case, the initial slope of the plot curve may be obtained. This slope is the decomposition rate due to the photocatalytic activity of the dye, that is, represents the photocatalytic activity.
【００２３】分光光学的手法にて色素の定量を行う場合
は、具体的には以下に示す手順で行う。When the dye is quantified by a spectroscopic technique, the procedure is specifically described below.
【００２４】まず、ＡＢＳによる測定法は、被験物が透
光性に優れる場合にのみ限られる。予め色素未吸着の状
態の被験物にてベースライン補正を行い、色素を吸着さ
せた被験物の紫外・可視光スペクトルを得る。得られた
スペクトルの最大吸光度をＡ1とする。First, the method of measurement using ABS is limited only to the case where the test object is excellent in light transmittance. Baseline correction is performed on the test substance in a state where the dye is not adsorbed in advance, and an ultraviolet / visible light spectrum of the test substance on which the dye is adsorbed is obtained. The maximum absorbance of the obtained spectrum and A 1.
【００２５】次に反射率法による色素の定量において
は、被験物が透光性に優れる場合、被験物の非測定面に
白色紙などの可視光領域の反射率が高くかつ反射率が既
知であるものをあてて測定を行う。分光反射率の測定可
能な色差計を用いて吸着色素がもつ最大吸収波長での分
光反射率を測定する。例えば色素にメチレンブルーを用
いた場合、５８０ｎｍでの反射率を測定すればよい。得
られた特定波長での反射率をＴ1とする。Next, in the determination of the dye by the reflectivity method, when the test object has excellent translucency, the non-measurement surface of the test object has a high reflectance in a visible light region such as white paper and the reflectance is known. A measurement is applied to a certain object. The spectral reflectance at the maximum absorption wavelength of the adsorbed dye is measured using a color difference meter capable of measuring the spectral reflectance. For example, when methylene blue is used as the dye, the reflectance at 580 nm may be measured. The reflectance obtained in a specific wavelength and T 1.
【００２６】一方、Ｌａｂ表色系法による色素の定量に
おいては、上記反射率法と同様に被験物が透光性に優れ
る場合、被験物の非測定面に白色紙などの可視光領域の
反射率が高いものをあてて測定を行う。ＣＩＥＬａｂ表
色系（ＣＩＥ １９７６）あるいはハンターＬａｂ表色
系など一般に用いられているＬａｂ表色系が測定可能な
色差計を用いて色素を付着または吸着させた被験物の明
度Ｌを測定する。得られた明度をＬ1とする。On the other hand, in the quantification of the dye by the Lab color system method, when the test object is excellent in translucency similarly to the reflectance method, the reflection of visible light such as white paper on the non-measurement surface of the test object is determined. Measure with a high rate. Using a colorimeter capable of measuring a commonly used Lab color system such as the CIELab color system (CIE 1976) or the Hunter Lab color system, the lightness L of the test substance to which the dye is attached or adsorbed is measured. The resulting lightness and L 1.
【００２７】光触媒活性面（測定面）に付着または吸着
した色素の定量が終了した被験物を、実際の使用用途に
合わせて図２、図３のいずれかの形で光照射する。この
際の光源としてはブラックライト灯が好適である。例え
ば光触媒タイルなどの光触媒活性を測定する場合では、
光触媒活性物質層に吸収される光は光触媒活性面から照
射されることを考慮して図３の装置で一定時間光照射す
る。また光触媒電灯カバーなどの光触媒活性を測定する
場合では、光触媒活性物質層に吸収される光は光触媒活
性面の反対側の面から照射されることが多いことを考慮
して図２の装置で一定時間光照射する。なお、図中符号
１はブラックライト灯、２は光触媒活性物質層、３はシ
リカガラスである。The test object, for which the amount of the dye adhering or adsorbed on the photocatalytically active surface (measurement surface) has been quantified, is irradiated with light in one of the forms shown in FIGS. In this case, a black light lamp is suitable as a light source. For example, when measuring photocatalytic activity of a photocatalytic tile,
The light absorbed by the photocatalytic active material layer is irradiated for a certain period of time by the apparatus shown in FIG. 3 in consideration of the fact that the light is irradiated from the photocatalytic active surface. When measuring the photocatalytic activity of a photocatalytic light cover or the like, the light absorbed by the photocatalytic active material layer is often applied from the surface opposite to the photocatalytic active surface. Irradiate for hours. In the drawings, reference numeral 1 denotes a black light lamp, 2 denotes a photocatalytic active material layer, and 3 denotes silica glass.
【００２８】光の光量は各測定で統一されていれば何れ
の光量でもよく、好ましくは０．５〜３．０ｍＷ／ｃｍ
2、より好ましくは１．０ｍＷ／ｃｍ2程度の光量がよ
い。照射時間も各測定で統一されていれば何れの照射時
間でもよく、好ましくは１〜３０分、より好ましくは５
〜１０分の照射時間がよい。The light quantity of the light may be any quantity as long as it is unified in each measurement, and is preferably 0.5 to 3.0 mW / cm.
2 , more preferably about 1.0 mW / cm 2 . The irradiation time may be any irradiation time as long as it is unified for each measurement, preferably 1 to 30 minutes, more preferably 5 to 30 minutes.
An irradiation time of 10 minutes to 10 minutes is good.
【００２９】被験物に光照射後、残存した色素の定量を
行う。定量方法は光触媒活性面（測定面）に付着または
吸着した色素の定量を行った方法と同じである。ここで
得られた結果を、最大吸光度の場合でＡ2、分光反射率
の場合でＴ2、Ｌａｂ表色系の明度Ｌの場合でＬ2とす
る。After irradiating the test substance with light, the remaining dye is quantified. The quantification method is the same as the method of quantifying the dye adhering or adsorbed on the photocatalytically active surface (measurement surface). The results obtained here are A 2 for the maximum absorbance, T 2 for the spectral reflectance, and L 2 for the lightness L of the Lab color system.
【００３０】次に、定量した結果得られた色素の変化量
を、光照射時間でプロットする。定量を最大吸光度で行
った場合、その変化量ΔＡは「Ａ1−Ａ2」で定義され
る。また定量を分光反射率で行った場合は、その変化量
ΔＴを「Ｔ2−Ｔ1」で定義する。また定量をＬａｂ表色
系の明度Ｌで行った場合は、その変化量ΔＬを「Ｌ2−
Ｌ1」で定義する。得られたグラフの傾きは光触媒反応
による被験物に付着または吸着した色素の分解速度であ
り、すなわち被験物の光触媒活性を表している。したが
って該グラフの初期の傾きから得た被験物の光触媒活性
に伴う色素の分解速度を該被験物の光触媒活性とする。Next, the amount of change in the dye obtained as a result of the quantification is plotted with the light irradiation time. When quantification is performed at the maximum absorbance, the variation ΔA is defined as “A 1 −A 2 ”. When the quantification is performed based on the spectral reflectance, the amount of change ΔT is defined as “T 2 −T 1 ”. When the quantification is performed using the lightness L of the Lab color system, the change amount ΔL is expressed as “L 2 −
L 1 . The slope of the obtained graph is the rate of decomposition of the dye attached or adsorbed to the test substance by the photocatalytic reaction, that is, represents the photocatalytic activity of the test substance. Therefore, the decomposition rate of the dye accompanying the photocatalytic activity of the test substance obtained from the initial slope of the graph is defined as the photocatalytic activity of the test substance.
【００３１】あるいは光触媒活性の簡便な評価法として
以下の手法を用いてもよい。すなわち、該被験物のブラ
ックライト灯の照射時間を、好ましくは１〜３０分、よ
り好ましくは５〜１０分のいずれかの照射時間で固定
し、そのときのΔＡ、ΔＴあるいはΔＬを被験物の光触
媒活性としてもよい。Alternatively, the following method may be used as a simple method for evaluating the photocatalytic activity. That is, the irradiation time of the black light lamp of the test object is preferably fixed at any one of 1 to 30 minutes, more preferably 5 to 10 minutes, and ΔA, ΔT or ΔL at that time is set to the test object. Photocatalytic activity may be used.
【００３２】また複数の被験物のいずれか１点を基準と
し、その他の被験物の光触媒活性を基準被験物の光触媒
活性との比で表すと有用である。It is also useful to express the photocatalytic activity of the other test substances in terms of the ratio to the photocatalytic activity of the reference test substance, based on any one of the plurality of test substances.
【００３３】また、本発明は光触媒防汚活性の評価方法
を提供するものであり、この方法は、実際に既に施工さ
れている光触媒活性素材について、その施工場所にて、
被験物に色素を付着あるいは吸着せしめ、実際の使用環
境下あるいは光量環境下での光触媒防汚活性を評価する
ことを特徴とし、これにより光触媒防汚活性を正確にか
つ感度および再現性よく、しかも短時間で測定すること
ができる。The present invention also provides a method for evaluating the photocatalyst antifouling activity. This method comprises the steps of:
The dye is attached or adsorbed to the test object, and the photocatalyst antifouling activity is evaluated under the actual use environment or the light amount environment, whereby the photocatalyst antifouling activity is accurately, sensitively and reproducibly, and It can be measured in a short time.
【００３４】本発明はまた、光触媒活性材料の光触媒活
性測定装置をも提供する。本発明の装置は、光触媒活性
材料の光触媒活性面に光を照射して前処理を施すための
手段、この前処理が施された光触媒活性面に有機色素を
付着または吸着させるための手段、光触媒活性面に光を
照射して、光触媒作用により有機色素を分解させるため
の手段および有機色素の分解速度を分光光学的に測定す
るための手段を含む。The present invention also provides an apparatus for measuring the photocatalytic activity of a photocatalytically active material. The apparatus of the present invention comprises a means for irradiating a photocatalytically active surface of a photocatalytically active material with light to perform a pretreatment, a means for attaching or adsorbing an organic dye to the photocatalytically active surface which has been subjected to the pretreatment, Includes means for irradiating the active surface with light to decompose the organic dye by photocatalysis and means for spectroscopically measuring the decomposition rate of the organic dye.
【００３５】このような装置を用いることにより、光触
媒活性材料の光触媒活性を、正確にかつ感度および再現
性よく、しかも短時間で測定することができる。By using such an apparatus, the photocatalytic activity of the photocatalytically active material can be measured accurately, with good sensitivity and reproducibility, and in a short time.
【００３６】[0036]
【作用】二酸化チタンに代表される光触媒活性物質は半
導体特性を有し、そのバンドギャップ以上のエネルギー
をもつ波長の光を吸収・励起すると、内部に電子・正孔
対が生成する。二酸化チタンの場合では、そのバンドギ
ャップが約３．２ｅＶであるため、ブラックライト灯な
どに含まれる約３８０ｎｍ以下の波長の紫外線を吸収す
ることで該現象が起こりうる。次に、この光触媒活性物
質表面に存在する吸着水が正孔によって酸化され、非常
に反応性の高い水酸ラジカル（ＯＨ・）が生成する。ま
た対となる励起電子は水中あるいは空気中に存在する酸
素を還元し、スーパーオキサイドアニオン（・Ｏ2 -）が
生成する。これらの活性酸素種が光触媒活性物質表面に
付着または吸着した色素と反応する。また付着または吸
着有機色素が正孔により直接酸化を受ける場合もある。The photocatalytically active substance represented by titanium dioxide has semiconductor properties. When light of a wavelength having energy equal to or greater than the band gap is absorbed and excited, an electron-hole pair is generated inside. In the case of titanium dioxide, since its band gap is about 3.2 eV, the phenomenon can occur by absorbing ultraviolet light having a wavelength of about 380 nm or less included in a black light lamp or the like. Next, the water adsorbed on the surface of the photocatalytic active substance is oxidized by the holes, and a highly reactive hydroxyl radical (OH.) Is generated. Excited electrons forming a pair reduce oxygen existing in water or air to generate a superoxide anion (· O 2 − ). These active oxygen species react with the dye attached or adsorbed on the photocatalytically active material surface. In some cases, the attached or adsorbed organic dye is directly oxidized by holes.
【００３７】光触媒活性とは、これら活性酸素種による
有機物の分解速度を意味する。したがって有機色素の分
解速度を調べることで、光触媒活性を評価することが可
能になる。The photocatalytic activity means the rate of decomposition of organic substances by these active oxygen species. Therefore, it is possible to evaluate the photocatalytic activity by examining the decomposition rate of the organic dye.
【００３８】[0038]
【実施例】次に、本発明を実施例によりさらに詳細に説
明するが、本発明は、これらの例によってなんら限定さ
れるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００３９】実施例１ まず、光触媒活性の異なる被験物を以下のようにして作
成した。すなわち、良く洗浄したパイレックス・ガラス
板（７０ｍｍ×７０ｍｍ×１．０ｍｍ）にディップ・コ
ーティング法を用いてシリカガラス層をコートした。コ
ート剤にはＮＤＨ−５００Ａ（日本曹達（株）製）を用
い、膜厚が０．２μｍになるようにした。次に該ガラス
板の片面をマスキングし、片面のみに同じディップ・コ
ーティング法を用いて二酸化チタン層をコートしたの
ち、焼成した。コート剤にはＮＤＨ−５１０Ｃ（日本曹
達（株）製）を用い、膜厚は、一方が０．１μｍ（低光
触媒活性）、もう一方が０．４μｍ（高光触媒活性）と
なるようにした。なお二酸化チタン薄膜を設けた面を表
面、マスキングした面を裏面とする。また各二酸化チタ
ン層の焼成条件は、１２０℃にて３０分間乾燥させたの
ち、昇温速度１００℃／ｈｒで５００℃まで昇温し、そ
の温度で１時間焼成した。Example 1 First, test substances having different photocatalytic activities were prepared as follows. That is, a well-cleaned Pyrex glass plate (70 mm × 70 mm × 1.0 mm) was coated with a silica glass layer using a dip coating method. NDH-500A (manufactured by Nippon Soda Co., Ltd.) was used as a coating agent so that the film thickness was 0.2 μm. Next, one side of the glass plate was masked, and only one side was coated with a titanium dioxide layer using the same dip coating method, and then fired. NDH-510C (manufactured by Nippon Soda Co., Ltd.) was used as the coating agent, and the film thickness of one was 0.1 μm (low photocatalytic activity) and the other was 0.4 μm (high photocatalytic activity). The surface provided with the titanium dioxide thin film is referred to as the front surface, and the masked surface is referred to as the back surface. The firing conditions of each titanium dioxide layer were as follows: after drying at 120 ° C. for 30 minutes, the temperature was raised to 500 ° C. at a heating rate of 100 ° C./hr, and firing was performed at that temperature for 1 hour.
【００４０】このようにして作成した被験物をブラック
ライト照射下（約４．０ｍＷ／ｃｍ2）に２４時間さら
し、付着有機物を除去すると同時に、二酸化チタン薄膜
表面を親水化させた（前処理）。The test article thus prepared was exposed to black light irradiation (about 4.0 mW / cm 2 ) for 24 hours to remove the attached organic substances and at the same time hydrophilize the surface of the titanium dioxide thin film (pretreatment). .
【００４１】１．０×１０-3ｍｏｌ／リットル濃度のメ
チレンブルー水溶液を調製し、前処理した被験物を完全
に浸漬させ二酸化チタン薄膜上にメチレンブルーを吸着
させた。浸漬時間は１時間とした。被験物をゆっくりと
取り出し、立て掛けた状態でデシケーター中に入れ、暗
所にて３０分間乾燥させた。また裏面に付着した色素を
湿らせた布などで拭き取った。An aqueous solution of methylene blue having a concentration of 1.0 × 10 −3 mol / liter was prepared, and the pretreated test article was completely immersed to adsorb methylene blue on the titanium dioxide thin film. The immersion time was 1 hour. The test article was slowly removed, placed upright in a desiccator, and dried in the dark for 30 minutes. The dye adhering to the back surface was wiped off with a damp cloth or the like.
【００４２】被験物のＡＢＳスペクトルを任意１０ヶ所
で測定し、その最大ＡＢＳの平均値を初期ＡＢＳ
（Ａ1）とした。The ABS spectrum of the test object was measured at any 10 points, and the average of the maximum ABS was calculated as the initial ABS.
(A 1 ).
【００４３】次に、図２に示すように、被験物の裏面か
らブラックライト灯を照射した（１．０ｍＷ／ｃ
ｍ2）。所定時間ブラックライト灯下に曝したのち、再
度被験物のＡＢＳスペクトルを任意１０ヶ所で測定し、
その最大ＡＢＳの平均値を分解後ＡＢＳ（Ａ2）とし
た。Next, as shown in FIG. 2, a black light lamp was irradiated from the back of the test object (1.0 mW / c).
m 2 ). After being exposed to a black light for a predetermined time, the ABS spectrum of the test object is measured again at any 10 places,
The average value of the maximum ABS was defined as ABS (A 2 ) after decomposition.
【００４４】光触媒活性による色素の分解に伴うＡＢＳ
の変化量ΔＡ（＝Ａ1−Ａ2）の光照射時間に対する変化
を図４に示すようにプロットし、そのＡＢＳの初期変化
速度を求めた。０．１μｍの二酸化チタン薄膜（低光触
媒活性）の初期変化速度を度数１とした場合の、０．４
μｍの二酸化チタン薄膜（高光触媒活性）の度数を初期
変化速度から求め、この度数を光触媒活性とした。この
結果、０．４μｍの二酸化チタン薄膜（高光触媒活性）
の光触媒活性度数は３．１であった。ABS accompanying dye decomposition by photocatalytic activity
The change of the change ΔA (= A 1 −A 2 ) with respect to the light irradiation time was plotted as shown in FIG. 4, and the initial change speed of the ABS was obtained. When the initial change rate of the titanium dioxide thin film of 0.1 μm (low photocatalytic activity) is set to frequency 1, 0.4
The frequency of the μm titanium dioxide thin film (high photocatalytic activity) was determined from the initial change rate, and this frequency was defined as the photocatalytic activity. As a result, a 0.4 μm titanium dioxide thin film (high photocatalytic activity)
Had a photocatalytic activity of 3.1.
【００４５】実施例２ まず、光触媒活性の異なる被験物を以下のようにして作
成した。すなわち、良く洗浄した陶器製タイル（７０ｍ
ｍ×７０ｍｍ、白色）にディップ・コーティング法を用
いてシリカガラス層をコートした。コート剤にはＮＤＨ
−５００Ａ（日本曹達（株）製）を用い、膜厚が０．２
μｍになるようにした。次に該タイルの片面をマスキン
グし、片面のみに同じディップ・コーティング法を用い
て二酸化チタン層をコートしたのち、焼成した。コート
剤にはＮＤＨ−５１０Ｃ（日本曹達（株）製）を用い、
膜厚は、一方が０．１μｍ（低光触媒活性）、もう一方
が０．４μｍ（高光触媒活性）となるようにした。なお
二酸化チタン薄膜を設けた面を表面、マスキングした面
を裏面とする。また二酸化チタン層の焼成条件は、１２
０℃にて３０分間乾燥させたのち、昇温速度１００℃／
ｈｒで５００℃まで昇温し、その温度で１時間焼成し
た。Example 2 First, test substances having different photocatalytic activities were prepared as follows. That is, a well-washed ceramic tile (70 m
m × 70 mm, white) was coated with a silica glass layer using a dip coating method. NDH for coating agent
-500A (manufactured by Nippon Soda Co., Ltd.) with a film thickness of 0.2
μm. Next, one side of the tile was masked, and only one side was coated with a titanium dioxide layer using the same dip coating method, and then fired. NDH-510C (Nippon Soda Co., Ltd.) was used as a coating agent.
The thickness of one film was 0.1 μm (low photocatalytic activity) and the other was 0.4 μm (high photocatalytic activity). The surface provided with the titanium dioxide thin film is referred to as the front surface, and the masked surface is referred to as the back surface. The firing conditions for the titanium dioxide layer are 12
After drying at 0 ° C. for 30 minutes, the temperature was raised at a rate of 100 ° C. /
The temperature was raised to 500 ° C. for one hour, and calcination was performed at that temperature for one hour.
【００４６】このようにして得られた被験物をブラック
ライト照射下（約４．０ｍＷ／ｃｍ2）に２４時間さら
し、付着有機物を除去すると同時に、二酸化チタン薄膜
表面を親水化させた（前処理）。The test sample thus obtained was exposed to black light irradiation (about 4.0 mW / cm 2 ) for 24 hours to remove attached organic substances and at the same time hydrophilize the surface of the titanium dioxide thin film (pretreatment). ).
【００４７】１．０×１０-3ｍｏｌ／リットル濃度のメ
チレンブルー水溶液を調製し、前処理した被験物を完全
に浸漬させ二酸化チタン薄膜上にメチレンブルーを吸着
させた。浸漬時間は１時間とした。被験物をゆっくりと
取り出し、立て掛けた状態でデシケーター中に入れ、暗
所にて３０分間乾燥させた。An aqueous solution of methylene blue having a concentration of 1.0 × 10 −3 mol / liter was prepared, and the pretreated test article was completely immersed to adsorb methylene blue on the titanium dioxide thin film. The immersion time was 1 hour. The test article was slowly removed, placed upright in a desiccator, and dried in the dark for 30 minutes.
【００４８】被験物の５８０ｎｍの分光反射率を任意１
０ヶ所で測定し、その分光反射率の平均値を初期分光反
射率（Ｔ1）とした。The spectral reflectance of the test object at 580 nm
The measurement was performed at 0 points, and the average value of the spectral reflectance was defined as the initial spectral reflectance (T 1 ).
【００４９】次に、図３に示すように、被験物の表面に
ブラックライト灯を照射した（１．０ｍＷ／ｃｍ2）。
所定時間ブラックライト灯下に曝したのち、再度被験物
の５８０ｎｍの分光反射率を任意１０ヶ所で測定し、そ
の分光反射率の平均値を分解後分光反射率（Ｔ2）とし
た。Next, as shown in FIG. 3, the surface of the test object was irradiated with a black light lamp (1.0 mW / cm 2 ).
After being exposed to a black light lamp for a predetermined time, the spectral reflectance of the test object at 580 nm was measured again at arbitrary 10 positions, and the average value of the spectral reflectance was taken as the spectral reflectance after decomposition (T 2 ).
【００５０】光触媒活性による色素の分解に伴う分光反
射率の変化量ΔＴ（＝Ｔ2−Ｔ1）の光照射時間に対する
変化を図５に示すようにプロットし、その分光反射率の
初期変化速度を求めた。０．１μｍの二酸化チタン薄膜
（低光触媒活性）の初期変化速度を度数１とした場合
の、０．４μｍの二酸化チタン薄膜（高光触媒活性）の
度数を初期変化速度から求め、この度数を光触媒活性と
した。この結果、０．４μｍの二酸化チタン薄膜（高光
触媒活性）の光触媒活性度数は３．１であった。The change of the spectral reflectance change ΔT (= T 2 −T 1 ) with the light irradiation time accompanying the decomposition of the dye due to the photocatalytic activity is plotted as shown in FIG. 5, and the initial change rate of the spectral reflectance is shown in FIG. I asked. When the initial change rate of the 0.1 μm titanium dioxide thin film (low photocatalytic activity) is set to frequency 1, the frequency of the 0.4 μm titanium dioxide thin film (high photocatalytic activity) is determined from the initial change rate, and this frequency is determined by the photocatalytic activity. And As a result, the photocatalytic activity number of the 0.4 μm titanium dioxide thin film (high photocatalytic activity) was 3.1.
【００５１】実施例３ まず、光触媒活性の異なる被験物を実施例２と同様にし
て作成した。Example 3 First, test substances having different photocatalytic activities were prepared in the same manner as in Example 2.
【００５２】この被験物をブラックライト照射下（約
４．０ｍＷ／ｃｍ2）に２４時間さらし、付着有機物を
除去すると同時に、二酸化チタン薄膜表面を親水化させ
た（前処理）。The specimen was exposed to black light irradiation (about 4.0 mW / cm 2 ) for 24 hours to remove organic substances adhering and at the same time hydrophilize the surface of the titanium dioxide thin film (pretreatment).
【００５３】１．０×１０-3ｍｏｌ／リットル濃度のメ
チレンブルー水溶液を調製し、前処理した被験物を完全
に浸漬させ二酸化チタン薄膜上にメチレンブルーを吸着
させた。浸漬時間は１時間とした。被験物をゆっくりと
取り出し、立て掛けた状態でデシケーター中に入れ、暗
所にて３０分間乾燥させた。An aqueous solution of methylene blue having a concentration of 1.0 × 10 −3 mol / liter was prepared, and the pretreated test object was completely immersed to adsorb methylene blue on the titanium dioxide thin film. The immersion time was 1 hour. The test article was slowly removed, placed upright in a desiccator, and dried in the dark for 30 minutes.
【００５４】被験物の明度Ｌを任意１０ヶ所で測定し、
その測定値の平均値を初期分光反射率（Ｌ1）とした。The lightness L of the test object was measured at any 10 places,
The average of the measured values was defined as the initial spectral reflectance (L 1 ).
【００５５】次に、図３に示すように、被験物の表面に
ブラックライト灯を照射した（１．０ｍＷ／ｃｍ2）。
所定時間ブラックライト灯下に曝したのち、再度被験物
の明度Ｌを任意１０ヶ所で測定し、その測定値の平均値
を分解後明度（Ｌ2）とした。Next, as shown in FIG. 3, the surface of the test object was irradiated with a black light lamp (1.0 mW / cm 2 ).
After being exposed to a black light for a predetermined time, the lightness L of the test object was measured again at any 10 points, and the average of the measured values was taken as the lightness after decomposition (L 2 ).
【００５６】光触媒活性による色素の分解に伴う明度Ｌ
の変化量ΔＬ（＝Ｌ2−Ｌ1）の光照射時間に対する変化
を図６に示すようにプロットし、その明度の初期変化速
度を求めた。０．１μｍの二酸化チタン薄膜（低光触媒
活性）の初期変化速度を度数１とした場合の、０．４μ
ｍの二酸化チタン薄膜（高光触媒活性）の度数を初期変
化速度から求め、この度数を光触媒活性とした。この結
果、０．４μｍの二酸化チタン薄膜（高光触媒活性）の
光触媒活性度数は２．９であった。Lightness L associated with the decomposition of dye due to photocatalytic activity
The change in the amount of change ΔL (= L 2 −L 1 ) with respect to the light irradiation time was plotted as shown in FIG. 6, and the initial change speed of the brightness was obtained. 0.4 μm when the initial change rate of the 0.1 μm titanium dioxide thin film (low photocatalytic activity) is 1 degree.
The frequency of the titanium dioxide thin film (high photocatalytic activity) of m was determined from the initial change rate, and this frequency was defined as the photocatalytic activity. As a result, the photocatalytic activity number of the 0.4 μm titanium dioxide thin film (high photocatalytic activity) was 2.9.
【００５７】実施例４ まず、背色は異なるが同じ光触媒活性の被験物を以下の
ようにして作成した。すなわち、良く洗浄した陶器製タ
イル（７０ｍｍ×７０ｍｍ）にディップ・コーティング
法を用いてシリカガラス層をコートした。コート剤には
ＮＤＨ−５００Ａ（日本曹達（株）製）を用い、膜厚が
０．２μｍになるようにした。次に該タイルの片面をマ
スキングし、片面のみに同じディップ・コーティング法
を用いて二酸化チタン層をコートしたのち、焼成した。
コート剤にはＮＤＨ−５１０Ｃ（日本曹達（株）製）を
用い、膜厚は０．４μｍ（高光触媒活性）となるように
した。なお二酸化チタン薄膜を塗布した面を表面、マス
キングした面を裏面とする。また二酸化チタン層の焼成
条件は、１２０℃にて３０分間乾燥させたのち、昇温速
度１００℃／ｈｒで５００℃まで昇温し、その温度で１
時間焼成した。Example 4 First, test articles having different background colors but the same photocatalytic activity were prepared as follows. That is, a well-washed ceramic tile (70 mm × 70 mm) was coated with a silica glass layer using a dip coating method. NDH-500A (manufactured by Nippon Soda Co., Ltd.) was used as a coating agent so that the film thickness was 0.2 μm. Next, one side of the tile was masked, and only one side was coated with a titanium dioxide layer using the same dip coating method, and then fired.
NDH-510C (manufactured by Nippon Soda Co., Ltd.) was used as a coating agent, and the film thickness was adjusted to 0.4 μm (high photocatalytic activity). The surface coated with the titanium dioxide thin film is referred to as the front surface, and the masked surface is referred to as the back surface. The firing conditions for the titanium dioxide layer were as follows: after drying at 120 ° C. for 30 minutes, the temperature was raised to 500 ° C. at a rate of 100 ° C./hr,
Fired for hours.
【００５８】このようにして得られた被験物をブラック
ライト灯照射下（約４．０ｍＷ／ｃｍ2）に２４時間さ
らし、付着有機物を除去すると同時に、二酸化チタン薄
膜表面を親水化させた（前処理）。The specimen thus obtained was exposed to a black light lamp (approximately 4.0 mW / cm 2 ) for 24 hours to remove adhering organic substances and at the same time hydrophilize the surface of the titanium dioxide thin film. processing).
【００５９】１．０×１０-3ｍｏｌ／リットル濃度のメ
チレンブルー水溶液を調製し、前処理した被験物を完全
に浸漬させ二酸化チタン薄膜上にメチレンブルーを吸着
させた。浸漬時間は１時間とした。被験物をゆっくりと
取り出し、立て掛けた状態でデシケーター中に入れ、暗
所にて３０分間乾燥させた。An aqueous solution of methylene blue having a concentration of 1.0 × 10 −3 mol / liter was prepared, and the pretreated test article was completely immersed to adsorb methylene blue on the titanium dioxide thin film. The immersion time was 1 hour. The test article was slowly removed, placed upright in a desiccator, and dried in the dark for 30 minutes.
【００６０】被験物の５８０ｎｍの分光反射率を任意１
０ヶ所で測定し、その分光反射率の平均値を初期分光反
射率（Ｔ1）とした。The spectral reflectance of the test object at 580 nm
The measurement was performed at 0 points, and the average value of the spectral reflectance was defined as the initial spectral reflectance (T 1 ).
【００６１】次に、図３に示すように、被験物の表面に
ブラックライト灯を照射した（１．０ｍＷ／ｃｍ2）。
５分間ブラックライト灯下に曝したのち、再度被験物の
５８０ｎｍの分光反射率を任意１０ヶ所で測定し、その
分光反射率の平均値を分解後分光反射率（Ｔ2）とし
た。Next, as shown in FIG. 3, the surface of the test object was irradiated with a black light lamp (1.0 mW / cm 2 ).
After being exposed to a black light lamp for 5 minutes, the spectral reflectance of the test object at 580 nm was measured again at arbitrary 10 points, and the average value of the spectral reflectance was taken as the spectral reflectance after decomposition (T 2 ).
【００６２】光触媒活性による色素の分解に伴う分光反
射率の変化量ΔＴ（＝Ｔ2−Ｔ1）と背色自体の５８０ｎ
ｍの分光反射率Ｔ0を求めた。次に式 補正ΔＴ＝ΔＴ／Ｔ0 に従ってΔＴをＴ0で補正した。また補正ΔＴを用いて
基準（０．１μｍの二酸化チタン薄膜のブラックライト
照射５分後の補正ΔＴ）からその光触媒活性度数を算出
した。その結果、いずれも活性度数がほぼ３．１となっ
た。結果を表１に示す。The amount of change ΔT (= T 2 −T 1 ) in the spectral reflectance due to the decomposition of the dye due to the photocatalytic activity and 580 n of the back color itself
m was determined as the spectral reflectance T 0 . Next, [Delta] T was corrected by T 0 according to the equation corrected [Delta] T = [Delta] T / T 0. The photocatalytic activity was calculated from the reference (correction ΔT 5 minutes after black light irradiation of the 0.1 μm titanium dioxide thin film) using the correction ΔT. As a result, in each case, the activity frequency was almost 3.1. Table 1 shows the results.
【００６３】[0063]
【表１】 [Table 1]
【００６４】比較例１ まず、光触媒活性の異なる被験物を実施例１と同様にし
て作成した。Comparative Example 1 First, test articles having different photocatalytic activities were prepared in the same manner as in Example 1.
【００６５】この被験物をブラックライト照射下（約
４．０ｍＷ／ｃｍ2）に２４時間さらし、付着有機物を
除去すると同時に、二酸化チタン薄膜表面を親水化させ
た（前処理）。The specimen was exposed to black light irradiation (about 4.0 mW / cm 2 ) for 24 hours to remove organic substances adhering thereto and, at the same time, hydrophilize the surface of the titanium dioxide thin film (pretreatment).
【００６６】次に、二酸化チタン薄膜表面に市販サラダ
油を約０．１ｍｇ／ｃｍ2塗布し、被験物の重量を測定
した（Ｗ1）。次いで、図２に示すように被験物の裏面
からブラックライト灯を照射した（３．０ｍＷ／ｃ
ｍ2）。所定時間ブラックライト照射下に曝したのち、
再度被験物の重量を測定した（Ｗ2）。Next, about 0.1 mg / cm 2 of commercially available salad oil was applied to the surface of the titanium dioxide thin film, and the weight of the test substance was measured (W 1 ). Next, as shown in FIG. 2, a black light lamp was irradiated from the back surface of the test object (3.0 mW / c).
m 2 ). After exposure under black light irradiation for a predetermined time,
The weight of the test object was measured again (W 2 ).
【００６７】光触媒活性によるサラダ油の分解に伴う被
験物の重量の変化量ΔＷ（＝Ｗ1−Ｗ2）の光照射時間に
対する変化を図７に示すようにプロットし、その重量の
初期変化速度を求めた。この結果、０．１μｍの二酸化
チタン薄膜（低光触媒活性）の光触媒活性によるサラダ
油の分解速度し、０．４μｍの二酸化チタン薄膜（高光
触媒活性）の光触媒活性によるサラダ油の分解速度に、
明確な差が認められた。The change of the weight change ΔW (= W 1 -W 2 ) of the test substance with the light irradiation time accompanying the decomposition of the salad oil due to the photocatalytic activity is plotted as shown in FIG. I asked. As a result, the decomposition rate of salad oil by the photocatalytic activity of the 0.1 μm titanium dioxide thin film (low photocatalytic activity) and the decomposition rate of the salad oil by the photocatalytic activity of 0.4 μm titanium dioxide thin film (high photocatalytic activity)
A clear difference was observed.
【００６８】しかしながら、測定による誤差も大きく、
正確な重量減少曲線が得られにくいため、両被験物の光
触媒活性を見積ることは困難であった。However, the error due to the measurement is large,
Since it was difficult to obtain an accurate weight loss curve, it was difficult to estimate the photocatalytic activity of both test substances.
【００６９】実施例５ 電灯設備に設置されているガラス製光触媒電灯カバー
（被験物）を数個取り出し、洗浄した後、ブラックライ
ト照射下（約４．０ｍＷ／ｃｍ2）２４時間さらし、付
着有機物を除去すると同時に、酸化チタン表面を親水化
させた（前処理）。Example 5 Several glass photocatalytic lamp covers (test objects) installed in a lamp unit were taken out, washed, exposed to black light irradiation (approximately 4.0 mW / cm 2 ) for 24 hours, and adhered organic matter was removed. And at the same time, the surface of the titanium oxide was made hydrophilic (pretreatment).
【００７０】１．０×１０-3ｍｏｌ／リットル濃度のメ
チレンブルー水溶液を作成し、前処理した被験物を完全
に浸漬させ光触媒活性面（測定面）上にメチレンブルー
を吸着させた。浸漬時間は１時間とした。An aqueous solution of methylene blue having a concentration of 1.0 × 10 −3 mol / liter was prepared, and the pretreated test article was completely immersed to adsorb methylene blue on the photocatalytically active surface (measurement surface). The immersion time was 1 hour.
【００７１】被験物をゆっくりと取り出し、立て掛けた
状態でデシケーター中に入れ、暗所にて３０分間乾燥さ
せた。なお、裏面に付着した色素を湿らせた布などで拭
き取った。The test object was slowly taken out, placed in a desiccator in a standing state, and dried in a dark place for 30 minutes. The dye adhering to the back surface was wiped off with a damp cloth or the like.
【００７２】被験物の裏面に、白色紙を隙間なく当て、
被験物の５８０ｎｍの分光反射率を任意１０カ所で測定
し、その分光透過率の平均値を初期分光反射率（Ｔ1)と
した。A white paper was applied to the back of the test object without any gap,
The spectral reflectance at 580 nm of the test object was measured at any 10 points, and the average value of the spectral transmittance was defined as the initial spectral reflectance (T 1 ).
【００７３】次に、被験物を元の場所に再度設置し、１
０分間電灯を点灯させた。この時の被験物への光照射光
量は０．３ｍＷ／ｃｍ2であった。Next, the test object is placed again in the original place,
The light was turned on for 0 minutes. At this time, the amount of light irradiation on the test object was 0.3 mW / cm 2 .
【００７４】１０分間電灯を点灯させた後、再度被験物
の５８０ｎｍの分光反射率を任意１０カ所で測定し、そ
の分光反射率の平均値を分解後分光反射率（Ｔ2)とし
た。After turning on the electric lamp for 10 minutes, the spectral reflectance of the test object at 580 nm was measured again at arbitrary 10 points, and the average value of the spectral reflectance was taken as the spectral reflectance after decomposition (T 2 ).
【００７５】光触媒活性による色素の分解に伴う分光反
射率の変化量ΔＴ（＝Ｔ2−Ｔ1）を求め、０．１化チタ
ン薄膜（低光触媒活性）の分光反射率の変化量を度数１
としたときの、各被験物の度数を分光反射率の変化量Δ
Ｔから求めた。この度数を光触媒防汚活性度数とした。
この結果得られた各々の被験物の内、いくつかは光触媒
活性度数は１．９〜２．４であった。また被験物の一つ
は光触媒活性がほとんど失われていることがわかった。
結果を表２に示す。The change ΔT (= T 2 −T 1 ) in the spectral reflectance due to the decomposition of the dye due to the photocatalytic activity was determined, and the change in the spectral reflectance of the 0.1-thin titanium thin film (low photocatalytic activity) was calculated as frequency 1
And the frequency of each test object, the change in spectral reflectance Δ
It was determined from T. This frequency was defined as the photocatalyst antifouling activity frequency.
Some of the test articles obtained as a result had photocatalytic activity numbers of 1.9 to 2.4. It was also found that one of the test items had almost lost photocatalytic activity.
Table 2 shows the results.
【００７６】[0076]
【表２】 [Table 2]
【００７７】[0077]
【発明の効果】本発明によれば、脱臭、防汚、抗菌、殺
菌などの作用を有する光触媒活性材料の光触媒活性を、
正確にかつ感度および再現性よく、しかも短時間で測定
することができる。According to the present invention, the photocatalytic activity of a photocatalytically active material having actions such as deodorization, antifouling, antibacterial, and sterilization is improved.
Measurement can be performed accurately, with good sensitivity and reproducibility, and in a short time.
【図１】メチレンブルーの吸収スペクトル図である。FIG. 1 is an absorption spectrum diagram of methylene blue.
【図２】光触媒活性面にブラックライト灯で光を照射す
る一例を示す説明図である。FIG. 2 is an explanatory view showing an example of irradiating a photocatalytically active surface with a black light lamp.
【図３】光触媒活性面にブラックライト灯で光を照射す
る別の例を示す説明図である。FIG. 3 is an explanatory view showing another example of irradiating a photocatalytically active surface with light from a black light lamp.
【図４】実施例１における光照射時間と色素の吸光度変
化量との関係を示すグラフである。FIG. 4 is a graph showing the relationship between the light irradiation time and the amount of change in absorbance of a dye in Example 1.
【図５】実施例２における光照射時間と色素の反射率変
化量との関係を示すグラフである。FIG. 5 is a graph showing the relationship between the light irradiation time and the amount of change in the reflectance of the dye in Example 2.
【図６】実施例３における光照射時間と色素の明度変化
量との関係を示すグラフである。FIG. 6 is a graph showing the relationship between the light irradiation time and the amount of change in lightness of a dye in Example 3.
【図７】比較例１における光照射時間とサラダ油の重量
減少量との関係を示すグラフである。FIG. 7 is a graph showing the relationship between the light irradiation time and the weight loss of salad oil in Comparative Example 1.
１ ブラックライト灯 ２ 光触媒活性物質層 ３ シリカガラス DESCRIPTION OF SYMBOLS 1 Black light lamp 2 Photocatalytic substance layer 3 Silica glass
───────────────────────────────────────────────────── フロントページの続き (72)発明者 橋本 和仁 神奈川県横浜市栄区飯島町2073番地２ ニューシティ本郷台 Ｄ棟 213号 (72)発明者 藤嶋 昭 神奈川県川崎市中原区中丸子710−５ (56)参考文献 特開 平８−338808（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 31/10 B01D 53/86 B01J 21/06 G01N 21/75 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuhito Hashimoto 2073-2 Iijimacho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture New City Hongodai D Building No. 213 (72) Inventor Akira Fujishima 710-5 Nakamaruko Nakahara-ku, Kawasaki City, Kanagawa Prefecture (56 References JP-A-8-338808 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) G01N 31/10 B01D 53/86 B01J 21/06 G01N 21/75
Claims (9)
活性材料の光触媒活性を測定するに当たり、該材料の光
触媒活性面に有機色素を付着または吸着させたのち、こ
の有機色素の光触媒作用に基づく分解速度を測定し、光
触媒活性を求めることを特徴とする光触媒活性の測定方
法。When measuring the photocatalytic activity of a photocatalytically active material having a photocatalytically active substance layer on its surface, an organic dye is attached to or adsorbed on the photocatalytically active surface of the material, and then the organic dye is decomposed based on the photocatalytic activity. A method for measuring photocatalytic activity, comprising measuring speed and determining photocatalytic activity.
よって測定する請求項１に記載の光触媒活性の測定方
法。2. The method for measuring photocatalytic activity according to claim 1, wherein the decomposition rate of the organic dye is measured by a spectroscopic method.
内に、波長３００ｎｍ〜３８０ｎｍ、光量１ｍＷ／ｃｍ
2のＵＶ光の照射によって分解しないこと、（２）色素
と光触媒活性面とが、少なくとも３０分以内にブラック
ライト灯による照射なしに反応を起こすことがないこ
と、および（３）光触媒活性物質が光触媒作用を発現す
るのに必要な波長域での光の吸収が少ないこと、の３条
件を満たすものである請求項１または２に記載の光触媒
活性の測定方法。3. The method according to claim 1, wherein the organic dye is (1) a wavelength of 300 nm to 380 nm and a light amount of 1 mW / cm within at least 30 minutes.
It does not decompose by the irradiation of the second UV light, (2) the dye and the photocatalyst active surface, it is not to cause reaction without irradiation with a black light lamp within at least 30 min, and (3) the photocatalytic active substance The method for measuring photocatalytic activity according to claim 1 or 2, wherein the photocatalytic activity satisfies three conditions: low light absorption in a wavelength range necessary for exhibiting a photocatalytic action.
らなる薄膜、微粒子状光触媒活性物質からなる層または
光触媒活性物質を含む塗工層である請求項１、２または
３に記載の光触媒活性の測定方法。4. The photocatalytically active substance layer according to claim 1, 2 or 3, wherein the photocatalytically active substance layer is a thin film made of a photocatalytically active substance, a layer made of a particulate photocatalytically active substance, or a coating layer containing a photocatalytically active substance. Measuring method.
求項１〜４のいずれかに記載の光触媒活性の測定方法。5. The method for measuring photocatalytic activity according to claim 1, wherein the photocatalytically active substance is titanium dioxide.
光触媒活性面に光を照射して前処理を施す請求項１〜５
のいずれかに記載の光触媒活性の測定方法。6. The method for adhering or adsorbing an organic dye,
The pretreatment is performed by irradiating the photocatalytically active surface with light.
The method for measuring photocatalytic activity according to any one of the above.
項１〜６のいずれかに記載の光触媒活性の測定方法。7. The method for measuring photocatalytic activity according to claim 1, wherein the photocatalytic activity is photocatalytic antifouling activity.
材について、その施工場所にて、被験物に有機色素を付
着あるいは吸着せしめ、実際の使用環境下あるいは光量
環境下での光触媒防汚活性を評価することを特徴とする
光触媒防汚活性の評価方法。8. The photocatalytically active material that has already been applied is made to adhere or adsorb an organic dye to a test object at the place where the photocatalytically active material is applied, so that the photocatalytic antifouling activity in an actual use environment or a light amount environment is improved. An evaluation method for photocatalyst antifouling activity, which is characterized by being evaluated.
射して前処理を施すための手段、この前処理が施された
光触媒活性面に有機色素を付着または吸着させるための
手段、光触媒活性面に光を照射して、光触媒作用により
有機色素を分解させるための手段および有機色素の分解
速度を分光光学的に測定するための手段を含むことを特
徴とする光触媒活性材料の光触媒活性測定装置。9. A means for irradiating a photocatalytically active surface of a photocatalytically active material with light to perform a pretreatment, a means for attaching or adsorbing an organic dye to the photocatalytically active surface which has been subjected to the pretreatment, A photocatalytic activity measuring device for a photocatalytically active material, comprising: means for irradiating a surface with light to decompose an organic dye by photocatalysis and means for spectroscopically measuring the decomposition rate of the organic dye. .
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| DE102004027118B4 (en) * | 2004-06-03 | 2006-05-11 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for detecting the photocatalytic degradation of organic dyes by fluorescence analysis |
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