JP2001322816A - Titanium oxide, photocatalyst body made thereof and photocatalyst body coatong agent - Google Patents
Titanium oxide, photocatalyst body made thereof and photocatalyst body coatong agentInfo
- Publication number
- JP2001322816A JP2001322816A JP2000330202A JP2000330202A JP2001322816A JP 2001322816 A JP2001322816 A JP 2001322816A JP 2000330202 A JP2000330202 A JP 2000330202A JP 2000330202 A JP2000330202 A JP 2000330202A JP 2001322816 A JP2001322816 A JP 2001322816A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- spectrum
- index
- formula
- time
- 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.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 title 1
- 238000001228 spectrum Methods 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 238000004458 analytical method Methods 0.000 claims abstract description 12
- 238000002835 absorbance Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 230000001186 cumulative effect Effects 0.000 abstract description 6
- 230000001678 irradiating effect Effects 0.000 abstract description 4
- 238000000985 reflectance spectrum Methods 0.000 abstract 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 230000003595 spectral effect Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000004566 building material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229910001040 Beta-titanium Inorganic materials 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
- 241000195493 Cryptophyta Species 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は酸化チタン、それを
用いてなる光触媒体及び光触媒体コーティング剤に関す
るものである。The present invention relates to a titanium oxide, a photocatalyst using the same, and a photocatalyst coating agent.
【０００２】[0002]
【従来の技術】半導体に紫外線を照射すると強い還元作
用を持つ電子と強い酸化作用を持つ正孔が生成し、半導
体に接触した分子種を酸化還元作用により分解する。こ
のような作用を光触媒作用と呼び、この光触媒作用を利
用することによって、居住空間や作業空間での悪臭物質
の分解除去、あるいは水中の有機溶剤や農薬、界面活性
剤等の分解除去を行うことができる。光触媒作用を示す
物質として酸化チタンが注目され、酸化チタンからなる
光触媒体が市販されている。2. Description of the Related Art When a semiconductor is irradiated with ultraviolet rays, electrons having a strong reducing action and holes having a strong oxidizing action are generated, and molecular species in contact with the semiconductor are decomposed by the redox action. Such action is called photocatalysis, and by using this photocatalysis, it is possible to decompose and remove odorous substances in living and working spaces, or to decompose and remove organic solvents, pesticides, surfactants, etc. in water. Can be. Attention has been paid to titanium oxide as a substance having a photocatalytic action, and a photocatalyst made of titanium oxide is commercially available.
【０００３】しかしながら、現在市販されている酸化チ
タンからなる光触媒体は、可視光線を照射する場合には
十分な光触媒作用を示すものではなかった。[0003] However, currently available photocatalysts made of titanium oxide do not show a sufficient photocatalytic action when irradiated with visible light.
【０００４】[0004]
【発明が解決しようとする課題】本発明の課題は、可視
光線を照射することにより高い光触媒作用を示す光触媒
体、その触媒成分としての酸化チタン、及びコーティン
グ剤としての光触媒体コーティング剤を提供することに
ある。SUMMARY OF THE INVENTION An object of the present invention is to provide a photocatalyst which exhibits a high photocatalytic activity upon irradiation with visible light, titanium oxide as a catalyst component thereof, and a photocatalyst coating agent as a coating agent. It is in.
【０００５】[0005]
【課題を解決するための手段】本発明者等は上記課題を
解決すべく鋭意検討を行った結果、可視光線を照射する
ことにより高い光触媒作用を示す光触媒体に適する触媒
成分としての酸化チタンを見出し、本発明を完成するに
至った。Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that titanium oxide as a catalyst component suitable for a photocatalyst that exhibits a high photocatalytic action by irradiating visible light. As a result, the present invention has been completed.
【０００６】本発明は、Ｘ線光電子分光法により８回分
析し、チタンの電子状態について、１回目と２回目の分
析の積算スペクトル及び７回目と８回目の分析の積算ス
ペクトルを求め、それぞれの積算スペクトルのうち結合
エネルギー４５８ｅＶ〜４６０ｅＶにあるピークを求
め、１回目と２回目の分析の積算スペクトルにあるピー
クの半価幅をＡ1とし、７回目と８回目の分析の積算ス
ペクトルにあるピークの半価幅をＢ1としたとき、式
（I） Ｘ1＝Ｂ1／Ａ1 （I） により算出される指数Ｘ1が０．９以下であり、かつ、
紫外可視拡散反射スペクトルを測定して、波長２５０ｎ
ｍ〜５５０ｎｍの吸光度の積分値をＣ1とし、波長４０
０ｎｍ〜５５０ｎｍの吸光度の積分値をＤ1としたと
き、式（II） Ｙ1＝Ｄ1／Ｃ1 （II） により算出される指数Ｙ1が０．０７５以上であること
を特徴とする酸化チタンを提供するものである。According to the present invention, analysis is performed eight times by X-ray photoelectron spectroscopy, and the integrated spectrum of the first and second analyzes and the integrated spectrum of the seventh and eighth analyzes are obtained for the electronic state of titanium. the peak in the binding energy 458eV~460eV of integrated spectrum, the half width of a peak in the accumulated spectra of the first and second analysis and a 1, peak at the integrated spectrum of the seventh and eighth analyzes Is defined as B 1 , the index X 1 calculated by the formula (I) X 1 = B 1 / A 1 (I) is 0.9 or less, and
The UV-visible diffuse reflection spectrum is measured, and the wavelength is 250 n.
The integrated value of absorbance m~550nm and C 1, wavelength 40
When the integrated value of absorbance of 0nm~550nm was D 1, oxidation index Y 1 calculated by the equation (II) Y 1 = D 1 / C 1 (II) is characterized in that 0.075 or more It is intended to provide titanium.
【０００７】また、本発明は、前記酸化チタンを含む光
触媒体を提供するものである。[0007] The present invention also provides a photocatalyst containing the titanium oxide.
【０００８】さらに、本発明は、前記酸化チタンと溶媒
とを含む光触媒体コーティング剤を提供するものであ
る。Further, the present invention provides a photocatalyst coating agent containing the titanium oxide and a solvent.
【０００９】[0009]
【発明の実施の形態】酸化チタンはＴｉＯ2なる組成式
を有し、その化学組成自体はもちろん公知であるが、本
発明では、その中のチタン原子の特定の電子状態にある
ものが見出されたのである。すなわち、酸化チタンをＸ
線光電子分光法（以下、ＸＰＳという。）により８回分
析して、チタンの電子状態についての１回目と２回目の
積算スペクトル及び７回目と８回目の積算スペクトルの
うち、結合エネルギー４５８ｅＶ〜４６０ｅＶにあるそ
れぞれのピークを求め、１回目と２回目の積算スペクト
ルにあるピークの半価幅Ａ1及び７回目と８回目の積算
スペクトルにあるピークの半価幅Ｂ1から、前記式（I）
により算出される指数Ｘ1を酸化チタン中のチタン原子
の電子状態を示す指標とする。チタン原子の電子状態は
結合エネルギーで示すことができ、一般には、指数Ｘ1
が小さいほど、結合エネルギーの高い電子をもつチタン
原子と結合エネルギーの低い電子をもつチタン原子とか
ら構成され、Ｘ線の繰り返し照射により結合エネルギー
の高い電子をもつチタン原子が減少することになり、一
方、指数Ｘ1が大きければ、結合エネルギーの高い電子
をもたないチタン原子から構成されていることになる。
そこで本発明では、指数Ｘ1が０．９以下であることを
一つの要件とする。DESCRIPTION OF THE PREFERRED EMBODIMENTS Titanium oxide has a composition formula of TiO 2 , and its chemical composition itself is, of course, known. However, in the present invention, titanium oxide in which titanium atom has a specific electronic state is found. It was done. That is, titanium oxide is converted to X
Analysis was performed eight times by linear photoelectron spectroscopy (hereinafter referred to as XPS). Of the first and second integrated spectra and the seventh and eighth integrated spectra of the electronic state of titanium, the binding energy was 458 eV to 460 eV. seeking certain respective peaks, from the half width B 1 of the peak in the first time and the half width a 1 and 7 th and 8 th cumulative spectral peaks in the second integrated spectrum, the formula (I)
An index indicating the electronic state of titanium atoms in the titanium oxide index X 1 calculated by. The electronic state of a titanium atom can be represented by a binding energy, and generally, an index X 1
Is smaller, the titanium atom having an electron having a higher binding energy and the titanium atom having an electron having a lower binding energy are included, and the titanium atom having an electron having a higher binding energy is reduced by repeated irradiation of X-rays. On the other hand, if the index X 1 is large, it is composed of titanium atoms having no electrons with high binding energy.
In this invention, as one of requirements that index X 1 is 0.9 or less.
【００１０】積算スペクトルは、光電子分光測定装置
（ピーク位置を決めるための基準には炭素を使用す
る。）を用い、酸化チタンについて、チタンの電子状態
を１回あたり６０秒で２回分析（１回目、２回目）、酸
素の電子状態を１回あたり５６秒で２回分析、炭素の電
子状態を１回あたり８０秒で２回分析、チタンの電子状
態を１回あたり６０秒で２回分析（３回目、４回目）、
酸素の電子状態を１回あたり５６秒で２回分析、炭素の
電子状態を１回あたり８０秒で２回分析、チタンの電子
状態を１回あたり６０秒で２回分析（５回目、６回
目）、酸素の電子状態を１回あたり５６秒で２回分析、
炭素の電子状態を１回あたり８０秒で２回分析、チタン
の電子状態を１回あたり６０秒で２回分析（７回目、８
回目）、酸素の電子状態を１回あたり５６秒で２回分
析、炭素の電子状態を１回あたり８０秒で２回分析、を
順に行って各々ＸＰＳスペクトルを求めた後、チタンの
電子状態についての１回目のＸＰＳスペクトルと２回目
のＸＰＳスペクトルとを積算して、及び７回目のＸＰＳ
スペクトルと８回目のＸＰＳスペクトルとを積算して求
めることができる。前記の一連の分析は、分析時及び分
析と分析との間、酸化チタンを大気中に暴露させること
なく行い、開始から終了迄の時間が３０分以内となるよ
うに行う。The integrated spectrum is analyzed twice using a photoelectron spectrometer (carbon is used as a criterion for determining the peak position) at 60 seconds per time for titanium oxide (1 time). The second and second), the electronic state of oxygen is analyzed twice at 56 seconds per time, the electronic state of carbon is analyzed twice at 80 seconds per time, and the electronic state of titanium is analyzed twice at 60 seconds per time (3rd, 4th),
The electronic state of oxygen is analyzed twice at 56 seconds per time, the electronic state of carbon is analyzed twice at 80 seconds per time, and the electronic state of titanium is analyzed twice at 60 seconds per time (5th and 6th times) ), Analyzing the electronic state of oxygen twice in 56 seconds each time,
The electronic state of carbon was analyzed twice at 80 seconds per time, and the electronic state of titanium was analyzed twice at 60 seconds per time (7th time, 8 times)
Second), the electronic state of oxygen was analyzed twice at 56 seconds per time, and the electronic state of carbon was analyzed twice at 80 seconds per time, and the XPS spectra were obtained. Of the first XPS spectrum and the second XPS spectrum, and the seventh XPS
The spectrum can be obtained by integrating the spectrum and the eighth XPS spectrum. The above series of analyzes is performed without exposing the titanium oxide to the atmosphere at the time of analysis and between analyses, so that the time from the start to the end is within 30 minutes.
【００１１】半価幅は、得られた積算スペクトルのピー
クから求めることができる。詳細には、積算スペクトル
のピークの中で、結合エネルギー４５８ｅＶ〜４６０ｅ
Ｖにあるチタンのピークから求めることができる。結合
エネルギー４５８ｅＶ〜４６０ｅＶにチタンのピークが
２つ以上ある場合、それらピークの中で最も高いピーク
から求めることができる。The half width can be determined from the peak of the obtained integrated spectrum. Specifically, in the peak of the integrated spectrum, the binding energy is 458 eV to 460 eV.
It can be determined from the peak of titanium at V. When there are two or more peaks of titanium at a binding energy of 458 eV to 460 eV, the peak can be determined from the highest peak among the peaks.
【００１２】本発明の酸化チタンを特定するもう一つの
要件は、紫外可視拡散反射スペクトルを測定して、波長
２５０ｎｍ〜５５０ｎｍの吸光度の積分値及び波長４０
０ｎｍ〜５５０ｎｍの吸光度の積分値を求め、前者の積
分値をＣ1とし、後者の積分値をＤ1としたとき、前記式
（II）により算出される指数Ｙ1である。この指数Ｙ 1は
可視光線に対する酸化チタンの吸収能力を示す指標とな
る。そこで本発明では、指数Ｙ1が０．０７５以上であ
ることをもう一つの要件とする。この指数Ｙ1は、好ま
しくは０．１１０以上、より好ましくは０．１４５以上
である。Another one of the titanium oxides of the present invention is specified.
The requirements are to measure the UV-visible diffuse reflection spectrum and
Integrated value of absorbance from 250 nm to 550 nm and wavelength 40
The integrated value of the absorbance from 0 nm to 550 nm is obtained, and the product of the former is obtained.
Minute value C1And the latter integral value is D1And the above equation
Index Y calculated by (II)1It is. This index Y 1Is
It is an indicator of the absorption capacity of titanium oxide for visible light.
You. Therefore, in the present invention, the index Y1Is 0.075 or more
Is another requirement. This index Y1Is preferred
0.110 or more, more preferably 0.145 or more
It is.
【００１３】吸光度の積分値とは、縦軸を吸光度とし、
横軸を波長とした紫外可視拡散反射スペクトルにおい
て、指定された波長の範囲内で横軸と拡散反射スペクト
ルとで囲まれた領域の面積を示す。紫外可視拡散反射ス
ペクトルは、例えば、紫外可視分光光度計を用い、硫酸
バリウムを標準白板として測定することができる。[0013] The integrated value of the absorbance is the absorbance on the vertical axis,
In the ultraviolet-visible diffuse reflection spectrum with the horizontal axis as the wavelength, the area of the region surrounded by the horizontal axis and the diffuse reflection spectrum within the designated wavelength range is shown. The ultraviolet-visible diffuse reflection spectrum can be measured, for example, using an ultraviolet-visible spectrophotometer using barium sulfate as a standard white plate.
【００１４】本発明の酸化チタンは、結晶子の大きさを
Ｅ1としたとき、式（III） Ｚ1＝Ｙ1×Ｅ1 （III） 〔式（III）中、Ｙ1は式（II）により算出される指数を
表す。〕により算出される指数Ｚ1が０．７５以上であ
ることが好ましい。また、指数Ｚ1は１．５以上、さら
には１．８以上であることがより好ましい。結晶子の大
きさＥ1は、例えば、Ｘ線回折装置を用い、酸化チタン
の最強干渉線（面指数１０１）のピークの半価幅とピー
ク位置（ブラッグ角）を求め、Ｓｃｈｅｒｒｅｒの式に
より算出することができる。[0014] Titanium oxide of the present invention, when the size of crystallite and E 1, wherein (III) Z 1 = Y 1 × E 1 (III) [Formula (III), Y 1 is the formula (II ). It is preferred index Z 1 calculated is 0.75 or more by]. Also, index Z 1 is 1.5 or more, more further preferably 1.8 or more. The crystallite size E 1 is calculated, for example, by using an X-ray diffractometer to determine the half width and peak position (Bragg angle) of the peak of the strongest interference line (plane index 101) of titanium oxide, and calculating by the Scherrer's formula. can do.
【００１５】本発明の酸化チタンは、結晶子の大きさを
Ｅ1とし、アナターゼ化率をＦ1としたとき、式（IV） Ｗ1＝Ｙ1×Ｅ1×Ｆ1 （IV） 〔式（IV）中、Ｙ1は前記式（II）により算出される指
数を表す。〕により算出される指数Ｗ1が０．４以上で
あることが好ましい。また、指数Ｗ1は１．３以上、さ
らには１．８以上であることがより好ましい。アナター
ゼ化率Ｆ 1は、例えば、Ｘ線回折装置を用い、酸化チタ
ンの最強干渉線（面指数１０１）のピーク面積を求め、
算出することができる。The titanium oxide of the present invention has a large crystallite size.
E1And the anatase conversion rate is F1Then, the formula (IV) W1= Y1× E1× F1 (IV) [In formula (IV), Y1Is the finger calculated by the above formula (II)
Represents a number. Exponent W calculated by1Is 0.4 or more
Preferably, there is. Also, the index W1Is 1.3 or more
More preferably, it is 1.8 or more. Anata
Z conversion rate F 1For example, using an X-ray diffractometer,
The peak area of the strongest interference line (plane index 101)
Can be calculated.
【００１６】本発明の酸化チタンの形状は、使用方法に
より異なり一義的ではないが、例えば、粒子状、繊維状
等が挙げられる。また、酸化チタンには、可視光線の照
射による光触媒活性を損なわせない範囲で他の無機化合
物を混合してもよいし、又は混合した後、熱処理等して
混合物を複合化してもよい。他の無機化合物としては、
例えばシリカ（ＳｉＯ2）、アルミナ（Ａｌ2Ｏ3）、ジ
ルコニア（ＺｒＯ2）、マグネシア（ＭｇＯ）、酸化亜
鉛（ＺｎＯ）、酸化鉄（Ｆｅ2Ｏ3、Ｆｅ3Ｏ4）等が挙げ
られる。The shape of the titanium oxide of the present invention varies depending on the method of use and is not unique, but examples include a particle shape and a fiber shape. In addition, other inorganic compounds may be mixed with the titanium oxide within a range that does not impair the photocatalytic activity by irradiation with visible light, or the mixture may be mixed and then heat treated to form a composite. As other inorganic compounds,
Examples include silica (SiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ), magnesia (MgO), zinc oxide (ZnO), iron oxide (Fe 2 O 3 , Fe 3 O 4 ).
【００１７】本発明による特定のＸＰＳスペクトル特性
及び紫外可視拡散反射スペクトル特性を示す酸化チタン
は、例えば、オキシ硫酸チタンを水に溶解し、冷却しな
がらその水溶液に塩基を添加して固形物を沈澱させ、得
られた固形物を焼成する方法によって製造することがで
きる。Titanium oxide having specific XPS spectral characteristics and ultraviolet-visible diffuse reflection spectral characteristics according to the present invention can be prepared, for example, by dissolving titanium oxysulfate in water and adding a base to the aqueous solution while cooling to precipitate solids. Then, the obtained solid can be manufactured by a method of firing.
【００１８】本発明の光触媒体は、触媒成分として、前
述した特定のＸＰＳスペクトル特性及び紫外可視拡散反
射スペクトル特性を示す酸化チタンを含む。The photocatalyst of the present invention contains, as a catalyst component, titanium oxide exhibiting the specific XPS spectral characteristics and the ultraviolet-visible diffuse reflection spectral characteristics described above.
【００１９】この光触媒体としては、例えば、粒子状酸
化チタンに成形助剤を添加した後、押出成形して得られ
たシート状光触媒体、繊維状酸化チタンと有機繊維とを
交絡させて得られたシート状光触媒体、金属製又は樹脂
製の支持体に酸化チタンを塗布又は被覆して得られたも
の等が挙げられる。また、この光触媒体は、高分子樹
脂、成形助剤、結合剤、帯電防止剤、吸着剤等を添加し
て用いてもよく、また紫外線の照射に対し光触媒活性を
有する他の酸化チタン等と併用してもよい。As the photocatalyst, for example, a sheet-shaped photocatalyst obtained by adding a molding aid to particulate titanium oxide and then extruding the same, or obtained by entanglement of fibrous titanium oxide and organic fibers. And a sheet-shaped photocatalyst obtained by coating or coating titanium oxide on a metal or resin support. The photocatalyst may be used by adding a polymer resin, a molding aid, a binder, an antistatic agent, an adsorbent, or the like, and may be used together with another titanium oxide having photocatalytic activity against ultraviolet irradiation. You may use together.
【００２０】この光触媒体の使用に際しては、例えば、
可視光線を透過するガラス製容器に光触媒体と被処理液
又は被処理気体等とを入れ、光源を用いて光触媒体に波
長が４３０ｎｍ以上である可視光線を照射すればよい。
照射時間は、光源の光線の強度、及び被処理液等の中の
被処理物質の種類や量により適宜選択すればよい。In using the photocatalyst, for example,
A photocatalyst, a liquid to be treated, a gas to be treated, and the like are placed in a glass container that transmits visible light, and the photocatalyst is irradiated with visible light having a wavelength of 430 nm or more using a light source.
The irradiation time may be appropriately selected depending on the intensity of the light beam from the light source and the type and amount of the substance to be treated in the liquid to be treated and the like.
【００２１】用いる光源としては、波長が４３０ｎｍ以
上である可視光線を含む光線を照射できるものであれば
制限されるものではなく、例えば太陽光線、蛍光灯、ハ
ロゲンランプ、ブラックライト、キセノンランプ、水銀
灯、ナトリウムランプ等が適用できる。また、光源には
必要に応じて紫外線カットフィルター及び／又は赤外線
カットフィルターを装着してもよい。The light source used is not limited as long as it can emit light including visible light having a wavelength of 430 nm or more. For example, sunlight, fluorescent light, halogen lamp, black light, xenon lamp, mercury lamp , A sodium lamp or the like can be applied. Further, the light source may be provided with an ultraviolet cut filter and / or an infrared cut filter as necessary.
【００２２】本発明の光触媒体コーティング剤は、前述
した特定のＸＰＳスペクトル特性及び紫外可視拡散反射
スペクトル特性を示す酸化チタンと溶媒とを含む。The photocatalyst coating agent of the present invention contains titanium oxide and a solvent, which exhibit the specific XPS spectral characteristics and ultraviolet-visible diffuse reflection spectral characteristics described above.
【００２３】この光触媒体コーティング剤は、建築材
料、自動車材料等に酸化チタンを塗布すること、又は建
築材料、自動車材料等を酸化チタンで被覆することを容
易にし、かつ建築材料、自動車材料等に高い光触媒活性
を付与することを可能とする。溶媒としては、塗布後又
は被覆後に蒸発して酸化チタンに残存しない溶媒が好ま
しく、例えば、水、塩酸、アルコール類、ケトン類等が
挙げられる。The photocatalyst coating agent makes it easy to apply titanium oxide to building materials, automobile materials, etc., or to coat building materials, automobile materials, etc. with titanium oxide, and to apply them to building materials, automobile materials, etc. High photocatalytic activity can be provided. As the solvent, a solvent that evaporates after coating or coating and does not remain in titanium oxide is preferable, and examples thereof include water, hydrochloric acid, alcohols, and ketones.
【００２４】この光触媒体コーティング剤は、例えば、
酸化チタンを水に分散させてスラリー化する方法、酸化
チタンを酸等で解膠させる方法等によって製造すること
ができる。分散に際しては、必要に応じて分散剤を添加
してもよい。The photocatalyst coating agent is, for example,
It can be produced by a method of dispersing titanium oxide in water to form a slurry, a method of peptizing titanium oxide with an acid or the like, or the like. At the time of dispersion, a dispersant may be added as necessary.
【００２５】[0025]
【実施例】以下、実施例により本発明をさらに詳細に説
明する。これら実施例では、アセトアルデヒドの光分解
作用で光触媒活性を評価しているが、本発明は本実施例
に限定されるものではない。尚、酸化チタンのＸ線光電
子分光スペクトル、紫外可視拡散反射スペクトル、結晶
子の大きさ及びアナターゼ化率の測定は以下の方法で行
った。The present invention will be described in more detail with reference to the following examples. In these examples, the photocatalytic activity was evaluated by the photodecomposition action of acetaldehyde, but the present invention is not limited to these examples. The X-ray photoelectron spectroscopy spectrum, ultraviolet-visible diffuse reflection spectrum, crystallite size and anatase conversion of titanium oxide were measured by the following methods.
【００２６】Ｘ線光電子分光スペクトル：光電子分光測
定装置（理学電機製、商品名：ＸＰＳ−７０００、Ｘ線
源：ＭｇＫα ８ｋＶ ３０ｍＡ、ナロースキャン、ｐ
ａｓｓ Ｅ＝１０ｅＶ、ｓｔｅｐＥ＝０．０４ｅＶ）を
用いて行った。X-ray photoelectron spectroscopy spectrum: photoelectron spectrometer (trade name: XPS-7000, manufactured by Rigaku Denki), X-ray source: MgKα 8 kV 30 mA, narrow scan, p
(ass E = 10 eV, step E = 0.04 eV).
【００２７】紫外可視拡散反射スペクトル：紫外可視分
光光度計（島津製作所製、商品名：ＵＶ−２５００Ｐ
Ｃ）を用いて行った。UV-visible diffuse reflection spectrum: UV-visible spectrophotometer (manufactured by Shimadzu Corporation, trade name: UV-2500P)
C).
【００２８】結晶子の大きさ：Ｘ線回折装置（理学電機
製、商品名：ＲＡＤ−ＩＩＡ）を用い、所定の条件（Ｘ
線管球：Ｃｕ、管電圧：４０ｋＶ、管電流：３５ｍＡ、
発散スリット：１度、散乱スリット：１度、受光スリッ
ト：０．３０ｍｍ、サンプリング幅：０．０２０度、走
査速度：２．００度／分，測定積算回数：１回）で測定
して、酸化チタンの最強干渉線（面指数１０１）のピー
クの半価幅β（ラジアン）とピーク位置２θ（ラジア
ン）を求め、Ｓｃｈｅｒｒｅｒの式（V）により結晶子
の大きさＥ1を算出した。 Ｅ1（ｎｍ）＝Ｋ・λ／（βｃｏｓθ） （V） 〔式（V）中、Ｋは定数０．９４、λ（ｎｍ）は測定Ｘ
線波長（ＣｕＫα線：０．１５４０５６ｎｍ）を表
す。〕Crystallite size: Using an X-ray diffractometer (trade name: RAD-IIA, manufactured by Rigaku Denki) under predetermined conditions (X
Line tube: Cu, tube voltage: 40 kV, tube current: 35 mA,
Divergence slit: 1 degree, scattering slit: 1 degree, light receiving slit: 0.30 mm, sampling width: 0.020 degree, scanning speed: 2.00 degree / min, measurement integration frequency: 1), and oxidation The half width β (radian) and the peak position 2θ (radian) of the peak of the strongest interference line (plane index 101) of titanium were determined, and the crystallite size E 1 was calculated by Scherrer's formula (V). E 1 (nm) = K · λ / (βcosθ) (V) [In the formula (V), K is a constant 0.94, and λ (nm) is the measurement X.
Represents the linear wavelength (CuKα ray: 0.154056 nm). ]
【００２９】アナターゼ化率：Ｘ線回折装置（理学電機
製、商品名：ＲＡＤ−ＩＩＡ）を用い、結晶子の大きさ
を求めるときと同じ条件で測定して、酸化チタンの最強
干渉線（面指数１０１）のピーク面積を求め、アナター
ゼ化率を算出した。尚、標準試料には、アナターゼ型酸
化チタン（チタン工業製、商品名：ＳＴＴ−６５Ｃ―
Ｓ）を用い、そのアナターゼ化率を１（１００％）とし
た。Anatase conversion rate: Measured using an X-ray diffractometer (trade name: RAD-IIA, manufactured by Rigaku Denki) under the same conditions as those used to determine the size of crystallites. The peak area of the index 101) was obtained, and the anatase conversion was calculated. In addition, an anatase type titanium oxide (manufactured by Titanium Industry, trade name: STT-65C-
S), and the anatase conversion was set to 1 (100%).
【００３０】また、酸化チタンの光触媒活性を評価する
ための可視光線の照射には、図１に示す分光特性を有す
る紫外線カットフィルター（東芝硝子製、商品名Ｙ−４
５）と図２に示す分光特性を有する赤外線カットフィル
ター（ウシオ電機製、商品名スーパーコールドフィルタ
ー）とを装着した５００Ｗキセノンランプ（ウシオ電機
製、商品名オプティカルモジュレックスＳＸ−ＵＩ５０
０ＸＱ、ランプＵＸＬ−５００ＳＸ）を光源として用い
た。For the irradiation of visible light for evaluating the photocatalytic activity of titanium oxide, an ultraviolet cut filter (trade name: Y-4, manufactured by Toshiba Glass Co., Ltd.) having the spectral characteristics shown in FIG.
5) and a 500 W xenon lamp (manufactured by Ushio Inc., trade name: Optical Modlex SX-UI50) equipped with an infrared cut filter (manufactured by Ushio Inc., trade name: super cold filter) having the spectral characteristics shown in FIG.
0XQ, lamp UXL-500SX) was used as the light source.
【００３１】実施例１ １Ｌフラスコに水３６０ｇを入れた後、攪拌下でオキシ
硫酸チタン（添川理化学製、商品名：オキシ硫酸チタ
ン）９０ｇを混合し溶解した。次いで、氷水で冷却しな
がら２５％アンモニア水（和光純薬製、特級）１０１ｇ
を２２分で滴下して固形物を沈澱させ、固形物を濾過、
乾燥した。次いで、得られた乾燥物を３５０℃の空気中
で１時間焼成して、粒子状酸化チタンを得た。得られた
酸化チタンの結晶構造はアナターゼ型であった。この酸
化チタンの物性を表１に、ＸＰＳスペクトルを図３に示
す。Example 1 After placing 360 g of water in a 1 L flask, 90 g of titanium oxysulfate (trade name: Titanium oxysulfate, manufactured by Soegawa Rikagaku) was mixed and dissolved with stirring. Next, 101 g of 25% aqueous ammonia (special grade, manufactured by Wako Pure Chemical Industries) while cooling with ice water.
Was added dropwise in 22 minutes to precipitate a solid, and the solid was filtered,
Dried. Next, the obtained dried product was fired in the air at 350 ° C. for 1 hour to obtain particulate titanium oxide. The crystal structure of the obtained titanium oxide was an anatase type. The physical properties of this titanium oxide are shown in Table 1, and the XPS spectrum is shown in FIG.
【００３２】次いで、密閉式のパイレックスガラス（商
標）製反応容器（直径８ｃｍ×高さ１０ｃｍ、容量約
０．５リットル）内に、直径５ｃｍのガラス製シャーレ
を設置し、そのシャーレ上に、粒子状酸化チタンだけか
らなる光触媒体０．３ｇを置いた。反応容器内を混合ガ
ス（酸素と窒素との体積比が１：４である。）で満た
し、アセトアルデヒド４．５μｍｏｌを封入し、波長が
４３０ｎｍ以上である可視光線の照射を行った。光触媒
体のアセトアルデヒドに対する光分解作用を、照射によ
り生成したアセトアルデヒドの酸化分解生成物である二
酸化炭素の濃度を光音響マルチガスモニタ（ＩＮＮＯＶ
Ａ製、１３１２型）を用いて測定することによって、評
価した。二酸化炭素の生成速度は触媒１ｇあたり１９．
３６μｍｏｌ／ｈであった。Next, a glass Petri dish having a diameter of 5 cm was placed in a sealed Pyrex glass (trademark) reaction vessel (diameter 8 cm × height 10 cm, capacity about 0.5 liter), and particles were placed on the Petri dish. 0.3 g of a photocatalyst consisting solely of titanium oxide was placed. The inside of the reaction vessel was filled with a mixed gas (the volume ratio of oxygen and nitrogen was 1: 4), 4.5 μmol of acetaldehyde was sealed, and irradiation with visible light having a wavelength of 430 nm or more was performed. The photodecomposition effect of the photocatalyst on acetaldehyde is measured by measuring the concentration of carbon dioxide, which is an oxidative decomposition product of acetaldehyde generated by irradiation, using a photoacoustic multi-gas monitor (INNOV).
A, 1312 type). The rate of carbon dioxide production was 19.
It was 36 μmol / h.
【００３３】実施例２ ５００ｍＬナス型フラスコに水７０ｇを入れた後、攪拌
下でオキシ硫酸チタン（添川理化学製、商品名：オキシ
硫酸チタン）３０ｇを混合し溶解した。次いで、エバポ
レーター（６０℃）にてオキシ硫酸チタン換算で８６．
９ｗｔ％まで濃縮し、冷凍庫で−２５℃に冷却しながら
２５％アンモニア水（和光純薬製：特級）１３７ｇを５
秒間で滴下し固形物を沈澱させ、固形物を濾過、乾燥し
た。次いで、得られた乾燥物を４００℃の空気中で１時
間焼成して、粒子状酸化チタンを得た。得られた酸化チ
タンの結晶構造はアナターゼ型であった。この酸化チタ
ンの物性を表１に、ＸＰＳスペクトルを図４に示す。Example 2 After placing 70 g of water in a 500 mL eggplant-shaped flask, 30 g of titanium oxysulfate (trade name: titanium oxysulfate, manufactured by Soegawa Rika Kagaku) was mixed and dissolved with stirring. Then, at 86.degree.
The solution was concentrated to 9 wt%, and 137 g of 25% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) was added to 5% while cooling to −25 ° C. in a freezer.
The solid was precipitated by dropping for 2 seconds, and the solid was filtered and dried. Next, the obtained dried product was fired in the air at 400 ° C. for 1 hour to obtain particulate titanium oxide. The crystal structure of the obtained titanium oxide was an anatase type. Table 1 shows the physical properties of this titanium oxide, and FIG. 4 shows the XPS spectrum.
【００３４】次いで、実施例１と同様にしてアセトアル
デヒドに対する光分解作用を評価した。二酸化炭素の生
成速度は触媒１ｇあたり４３．１５μｍｏｌ／ｈであっ
た。Next, the photolytic action on acetaldehyde was evaluated in the same manner as in Example 1. The generation rate of carbon dioxide was 43.15 μmol / h per gram of the catalyst.
【００３５】比較例１ β−水酸化チタン（キシダ化学製）を４００℃の空気中
で１時間焼成して、酸化チタンを得た。得られた酸化チ
タンの結晶構造はアナターゼ型であった。この酸化チタ
ンの物性を表１に、ＸＰＳスペクトルを図５に示す。Comparative Example 1 β-titanium hydroxide (manufactured by Kishida Chemical) was calcined in air at 400 ° C. for 1 hour to obtain titanium oxide. The crystal structure of the obtained titanium oxide was an anatase type. Table 1 shows the physical properties of the titanium oxide, and FIG. 5 shows the XPS spectrum.
【００３６】次いで、実施例１と同様にしてアセトアル
デヒドに対する光分解作用を評価した。二酸化炭素の生
成速度は触媒１ｇあたり０．９３μｍｏｌ／ｈであっ
た。Next, the photolytic action on acetaldehyde was evaluated in the same manner as in Example 1. The rate of carbon dioxide generation was 0.93 μmol / h per gram of catalyst.
【００３７】比較例２ 実施例１において、市販の酸化チタン（デグッサ製、商
品名Ｐ−２５）だけからなる光触媒体を用いた以外は、
実施例１と同様にして行った。二酸化炭素の生成速度は
触媒１ｇあたり０．０μｍｏｌ／ｈであった。この酸化
チタンの物性を表１に、ＸＰＳスペクトルを図６に示
す。Comparative Example 2 In Example 1, except that a photocatalyst composed of only commercially available titanium oxide (manufactured by Degussa, trade name: P-25) was used.
Performed in the same manner as in Example 1. The rate of carbon dioxide generation was 0.0 μmol / h per gram of catalyst. Table 1 shows the physical properties of the titanium oxide, and FIG. 6 shows the XPS spectrum.
【００３８】[0038]
【表１】 [Table 1]
【００３９】実施例３ 水に実施例１で得られた粒子状酸化チタンを分散させて
光触媒体コーティング剤を調製した。得られた光触媒体
コーティング剤を自動車用ガラスに塗布し、乾燥するこ
とによって自動車ガラス表面に均一に酸化チタンの層が
形成された。Example 3 The particulate titanium oxide obtained in Example 1 was dispersed in water to prepare a photocatalyst coating agent. The obtained photocatalyst coating agent was applied to automotive glass and dried to form a titanium oxide layer uniformly on the automotive glass surface.
【００４０】本発明の光触媒体は、波長が４３０ｎｍ以
上である可視光線を照射したときのアセトアルデヒドに
対する酸化分解について、市販の酸化チタンだけからな
る光触媒体に比べてその酸化分解作用（光触媒作用）に
優れる。The photocatalyst of the present invention has a smaller oxidative decomposition effect (photocatalysis) than a commercially available photocatalyst consisting of only titanium oxide with respect to oxidative decomposition of acetaldehyde when irradiated with visible light having a wavelength of 430 nm or more. Excellent.
【００４１】[0041]
【発明の効果】本発明の酸化チタンは、波長が４３０ｎ
ｍ以上である可視光線の照射により高い光触媒作用を示
す。本発明の光触媒体（酸化チタンだけからなる光触媒
体を含む。）は、酸化チタンの高い光触媒作用により、
アセトアルデヒド等のアルデヒド類をはじめ各種有機物
を分解する。本発明の光触媒体コーティング剤は、建築
材料、自動車材料等に酸化チタンを塗布すること、又は
建築材料、自動車材料等を酸化チタンで被覆することを
容易にし、建築材料、自動車材料等に高い光触媒作用を
付与することを可能とする。The titanium oxide of the present invention has a wavelength of 430n.
m shows a high photocatalytic action by irradiation with visible light of m or more. The photocatalyst of the present invention (including a photocatalyst consisting only of titanium oxide) has a high photocatalytic action of titanium oxide.
Decomposes various organic substances including aldehydes such as acetaldehyde. The photocatalyst coating agent of the present invention makes it easy to apply titanium oxide to building materials, automobile materials, etc., or to coat building materials, automobile materials, etc. with titanium oxide. It is possible to give an effect.
【００４２】また、本発明の光触媒体（酸化チタンだけ
からなる光触媒体を含む。）や光触媒体コーティング剤
を塗布等した自動車材料等は、大気中のＮＯｘを分解し
たり、居住空間や作業空間での悪臭物質（例えば煙草
臭）等を分解したり、水中の有機溶剤、農薬、界面活性
剤等を分解したり、又は細菌（例えば放射菌）、藻類、
黴類等の増殖を抑制することに適用可能である。Further, the photocatalyst (including a photocatalyst consisting only of titanium oxide) of the present invention and an automobile material coated with a photocatalyst coating agent can decompose NOx in the atmosphere, and can be used in living and working spaces. Decompose odorous substances (eg, tobacco odor) in water, decompose organic solvents, pesticides, surfactants, etc. in water, or germs (eg, radioactive bacteria), algae,
It is applicable to suppressing the growth of molds and the like.
【図1】 実施例における光触媒体の光分解作用評価の
ための可視光線照射の際、光源に装着した紫外線カット
フィルターの分光特性を示す波長−透過率線図。FIG. 1 is a wavelength-transmittance diagram showing spectral characteristics of an ultraviolet cut filter attached to a light source when irradiating visible light for evaluating a photodecomposition action of a photocatalyst body in an example.
【図2】 実施例における光触媒体の光分解作用評価の
ための可視光線照射の際、光源に装着した赤外線カット
フィルターの分光特性を示す波長−透過率線図。FIG. 2 is a wavelength-transmittance diagram showing spectral characteristics of an infrared cut filter attached to a light source when irradiating visible light for evaluating photodecomposition action of a photocatalyst body in Examples.
【図3】 実施例１で用いた酸化チタンのＸＰＳによる
１回目と２回目との積算スペクトル及び７回目と８回目
との積算スペクトル。FIG. 3 shows the first and second integrated spectra and the seventh and eighth integrated spectra of the titanium oxide used in Example 1 by XPS.
【図4】 実施例２で用いた酸化チタンのＸＰＳによる
１回目と２回目との積算スペクトル及び７回目と８回目
との積算スペクトル。FIG. 4 shows the first and second integrated spectra and the seventh and eighth integrated spectra of the titanium oxide used in Example 2 by XPS.
【図5】 比較例１で用いた酸化チタンのＸＰＳによる
１回目と２回目との積算スペクトル及び７回目と８回目
との積算スペクトル。FIG. 5 shows the first and second integrated spectra and the seventh and eighth integrated spectra of the titanium oxide used in Comparative Example 1 by XPS.
【図6】 比較例２で用いた酸化チタンのＸＰＳによる
１回目と２回目との積算スペクトル及び７回目と８回目
との積算スペクトル。FIG. 6 shows the first and second integrated spectra and the seventh and eighth integrated spectra of the titanium oxide used in Comparative Example 2 by XPS.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 竹内 美明 愛媛県新居浜市惣開町５番１号 住友化学 工業株式会社内 Ｆターム(参考） 4G047 CA02 CB05 CC03 CD03 CD07 4G069 AA02 AA03 AA08 AA09 BA04A BA04B BA04C BA48A BB10C CA01 CA07 CA10 CA13 CA17 EA01Y EA08 EC22Y EC25 EC27 FB08 FB23 4J038 HA096 HA156 HA216 JA17 JA32 KA04 KA06 MA07 MA08 MA10 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Miaki Takeuchi 5-1 Sokai-cho, Niihama-shi, Ehime F-term (reference) in Sumitomo Chemical Co., Ltd. 4G047 CA02 CB05 CC03 CD03 CD07 4G069 AA02 AA03 AA08 AA09 BA04A BA04B BA04C BA48A BB10C CA01 CA07 CA10 CA13 CA17 EA01Y EA08 EC22Y EC25 EC27 FB08 FB23 4J038 HA096 HA156 HA216 JA17 JA32 KA04 KA06 MA07 MA08 MA10
Claims (5)
タンの電子状態について、１回目と２回目の分析の積算
スペクトル及び７回目と８回目の分析の積算スペクトル
を求め、それぞれの積算スペクトルのうち結合エネルギ
ー４５８ｅＶ〜４６０ｅＶにあるピークを求め、１回目
と２回目の分析の積算スペクトルにあるピークの半価幅
をＡ1とし、７回目と８回目の分析の積算スペクトルに
あるピークの半価幅をＢ1としたとき、式（I） Ｘ1＝Ｂ1／Ａ1 （I） により算出される指数Ｘ1が０．９以下であり、かつ、
紫外可視拡散反射スペクトルを測定して、波長２５０ｎ
ｍ〜５５０ｎｍの吸光度の積分値をＣ1とし、波長４０
０ｎｍ〜５５０ｎｍの吸光度の積分値をＤ1としたと
き、式（II） Ｙ1＝Ｄ1／Ｃ1 （II） により算出される指数Ｙ1が０．０７５以上であること
を特徴とする酸化チタン。1. An X-ray photoelectron spectroscopy is performed eight times to obtain an integrated spectrum of the first and second analyzes and an integrated spectrum of the seventh and eighth analyzes of the electronic state of titanium. the peak in the binding energy 458eV~460eV among the first and the half width of a peak in the accumulated spectrum of the second analysis and a 1, 7 th and peak half in the integrated spectrum of the eighth analysis when the valence width B 1, index X 1 calculated by the equation (I) X 1 = B 1 / a 1 (I) is 0.9 or less, and,
The UV-visible diffuse reflection spectrum is measured, and the wavelength is 250 n.
The integrated value of absorbance m~550nm and C 1, wavelength 40
When the integrated value of absorbance of 0nm~550nm was D 1, oxidation index Y 1 calculated by the equation (II) Y 1 = D 1 / C 1 (II) is characterized in that 0.075 or more Titanium.
II） Ｚ1＝Ｙ1×Ｅ1 （III） 〔式（III）中、Ｙ1は式（II）により算出される指数を
表す。〕により算出される指数Ｚ1が０．７５以上であ
る請求項１記載の酸化チタン。Wherein when the size of the crystallite was E 1, formula (I
II) Z 1 = Y 1 × E 1 (III) [In the formula (III), Y 1 represents an index calculated by the formula (II). The titanium oxide according to claim 1, wherein the index Z1 calculated by the formula [ 1] is 0.75 or more.
化率をＦ1としたとき、式（IV） Ｗ1＝Ｙ1×Ｅ1×Ｆ1 （IV） 〔式（IV）中、Ｙ1は式（II）により算出される指数を
表す。〕により算出される指数Ｗ1が０．４以上である
請求項１又は２記載の酸化チタン。3. Formula (IV) W 1 = Y 1 × E 1 × F 1 (IV) [Equation (IV)] where E 1 is the crystallite size and F 1 is the anatase conversion rate. Y 1 represents an index calculated by the formula (II). 3. The titanium oxide according to claim 1, wherein the index W1 calculated by the formula [ 1] is 0.4 or more.
１項に記載の酸化チタンを含む光触媒体。4. A photocatalyst comprising the titanium oxide according to claim 1 as a catalyst component.
化チタンと溶媒とを含む光触媒体コーティング剤。5. A photocatalyst coating agent comprising the titanium oxide according to claim 1 and a solvent.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002040609A1 (en) * | 2000-11-17 | 2002-05-23 | Ecodevice Laboratory Co., Ltd. | Coating responding to visible light, coating film and article |
| US7521391B2 (en) | 2004-03-17 | 2009-04-21 | Sumitomo Chemical Company, Limited | Coating composition of photocatalyst |
| EP2130587A2 (en) | 2008-06-05 | 2009-12-09 | Sumitomo Chemical Company, Limited | Photocatalyst dispersion liquid and process for producing the same |
| EP2223896A1 (en) | 2009-02-04 | 2010-09-01 | Sumitomo Chemical Company, Limited | Hydrophilizing agent, method of producing hydrophilizing agent and hydrophilic product |
| EP2281628A2 (en) | 2009-08-07 | 2011-02-09 | Sumitomo Chemical Company, Limited | Method for producing noble metal-supported photocatalyst particles |
| DE102010045549A1 (en) | 2009-09-16 | 2011-08-25 | Sumitomo Chemical Company, Limited | Photocatalyst composite and using this photocatalytically active product |
| CN104380311A (en) * | 2012-04-10 | 2015-02-25 | 拜斯帕尔有限公司 | Method for classification of a sample on the basis of spectral data, method for creating a database and method for using this database, and corresponding computer program, data storage medium and system |
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2000
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002040609A1 (en) * | 2000-11-17 | 2002-05-23 | Ecodevice Laboratory Co., Ltd. | Coating responding to visible light, coating film and article |
| JPWO2002040609A1 (en) * | 2000-11-17 | 2004-03-25 | 有限会社環境デバイス研究所 | Visible light responsive paints, coatings and articles |
| US7521391B2 (en) | 2004-03-17 | 2009-04-21 | Sumitomo Chemical Company, Limited | Coating composition of photocatalyst |
| EP2130587A2 (en) | 2008-06-05 | 2009-12-09 | Sumitomo Chemical Company, Limited | Photocatalyst dispersion liquid and process for producing the same |
| EP2223896A1 (en) | 2009-02-04 | 2010-09-01 | Sumitomo Chemical Company, Limited | Hydrophilizing agent, method of producing hydrophilizing agent and hydrophilic product |
| EP2281628A2 (en) | 2009-08-07 | 2011-02-09 | Sumitomo Chemical Company, Limited | Method for producing noble metal-supported photocatalyst particles |
| DE102010045549A1 (en) | 2009-09-16 | 2011-08-25 | Sumitomo Chemical Company, Limited | Photocatalyst composite and using this photocatalytically active product |
| CN104380311A (en) * | 2012-04-10 | 2015-02-25 | 拜斯帕尔有限公司 | Method for classification of a sample on the basis of spectral data, method for creating a database and method for using this database, and corresponding computer program, data storage medium and system |
| CN104380311B (en) * | 2012-04-10 | 2018-06-26 | 拜斯帕尔有限公司 | The method and the method using the database of sample classification method, establishment database according to modal data and corresponding system |
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