JP2003001118A - Photocatalytic particle and its manufacturing method - Google Patents
Photocatalytic particle and its manufacturing methodInfo
- Publication number
- JP2003001118A JP2003001118A JP2001189025A JP2001189025A JP2003001118A JP 2003001118 A JP2003001118 A JP 2003001118A JP 2001189025 A JP2001189025 A JP 2001189025A JP 2001189025 A JP2001189025 A JP 2001189025A JP 2003001118 A JP2003001118 A JP 2003001118A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- photocatalytic
- fine particles
- titanium oxide
- porous silica
- 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.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 134
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000010419 fine particle Substances 0.000 claims abstract description 97
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 47
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 23
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 238000006303 photolysis reaction Methods 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 16
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 14
- 239000003973 paint Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 150000007530 organic bases Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001782 photodegradation Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101100333170 Oryza sativa subsp. japonica EHD1 gene Proteins 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 210000004877 mucosa Anatomy 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
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- WPPVEXTUHHUEIV-UHFFFAOYSA-N trifluorosilane Chemical compound F[SiH](F)F WPPVEXTUHHUEIV-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒性粒子およ
びその製造方法に関し、より詳細には、光触媒活性を利
用した、塗料、繊維製品、シックハウス解消剤、工業排
水・排ガスの無害化処理剤等に用いられ、分解・除去、
消臭、抗菌、防汚、防曇等の作用を奏する光触媒性粒子
およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photocatalytic particles and a method for producing the same, and more particularly, to paints, textile products, sick house eliminating agents, industrial wastewater / exhaust gas detoxifying agents, etc. which utilize photocatalytic activity. Used for, disassembly and removal,
The present invention relates to a photocatalytic particle that exhibits actions such as deodorant, antibacterial, antifouling, and antifogging and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化チタン等の半導体粒子に、そのバン
ドギャップ以上のエネルギーを有する光を照射すると、
光励起により生成した電子と正孔が半導体粒子表面に移
動し、周囲に存在するイオン種や分子種に作用して、光
触媒反応と呼ばれる様々な反応を引き起こす。特に、酸
化チタン微粒子は、その表面に生じた正孔が、強力な酸
化力を有していることから、塗料、繊維製品、シックハ
ウスの解消、工業排水・排ガスの無害化処理等への応用
が種々提案されており、一部は既に実施されている。2. Description of the Related Art When semiconductor particles such as titanium oxide are irradiated with light having an energy larger than the band gap,
Electrons and holes generated by photoexcitation move to the surface of semiconductor particles and act on ionic species and molecular species present in the surroundings to cause various reactions called photocatalytic reactions. In particular, since the holes generated on the surface of titanium oxide fine particles have a strong oxidizing power, they can be applied to paints, textile products, elimination of sick houses, detoxification of industrial wastewater and exhaust gas, etc. Various proposals have been made, and some have already been implemented.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、酸化チ
タン微粒子を光触媒として用いて、汚染物質を分解・除
去、消臭、抗菌等しようとする場合、一般に、除去すべ
き汚染物質等の被処理物質の濃度は、非常に低いもので
ある。例えば、室内の空気洗浄・消臭の場合には、新建
材・壁紙等の接着剤から発生し、シックハウス症候群の
主な原因とされているホルムアルデヒドガスが被処理物
質となるが、これは２〜５ｐｐｍ程度の低濃度でも、目
や気道粘膜に対する刺激性があると言われている。However, in the case of using titanium oxide fine particles as a photocatalyst for decomposing / removing pollutants, deodorizing, antibacterial, etc., in general, it is necessary to remove the pollutants to be removed. The concentration is very low. For example, in the case of indoor air cleaning and deodorization, formaldehyde gas, which is generated from adhesives such as new building materials and wallpaper, and is the main cause of sick house syndrome, becomes the substance to be treated. It is said that even a low concentration of about 5 ppm is irritating to the eyes and airway mucosa.
【０００４】したがって、このような低濃度の被処理物
質の分解・除去等の反応効率を向上させるためには、被
処理物質の拡散律速を回避するため、酸化チタン微粒子
の周囲における被処理物質の濃度を高くする必要があ
る。また、その一方では、反応律速を回避するため、光
触媒性粒子としての高い触媒活性も求められる。Therefore, in order to improve the reaction efficiency such as decomposition / removal of the low-concentration substance to be treated, in order to avoid the diffusion control of the substance to be treated, the substance to be treated around the titanium oxide fine particles is prevented. It is necessary to increase the concentration. On the other hand, in order to avoid the reaction rate limitation, high catalytic activity as photocatalytic particles is also required.
【０００５】しかしながら、酸化チタン微粒子自体は、
吸着力が弱いため、従来から、活性炭、多孔質セラミッ
クス、無機繊維等の吸着力が高い物質とともに使用する
等の工夫がなされている。However, the titanium oxide fine particles themselves are
Since it has a weak adsorptive power, it has been conventionally devised to use it together with a substance having a high adsorptive power such as activated carbon, porous ceramics, and inorganic fibers.
【０００６】具体的には、シリカゲル等の担体表面に、
酸化チタンのゾルを塗布する方法、シリカゲル等の担体
表面に、バインダーを介して、酸化チタン被膜を形成さ
せる方法、ゼオライト等の担体の細孔内に、チタン含有
溶液を吸収させ、焼結させる方法等が挙げられる。しか
しながら、これらの方法によって得られた光触媒性粒子
によっては、上記被処理物質の分解・除去等の反応効率
の向上は十分なものであるとは言えなかった。Specifically, on the surface of a carrier such as silica gel,
Method of applying titanium oxide sol, method of forming titanium oxide film on the surface of carrier such as silica gel via a binder, method of absorbing titanium-containing solution in pores of carrier such as zeolite and sintering Etc. However, it cannot be said that the photocatalytic particles obtained by these methods sufficiently improve the reaction efficiency such as decomposition and removal of the substance to be treated.
【０００７】ところで、塗料、繊維製品等に、酸化チタ
ン微粒子または上記方法によって得られた光触媒性粒子
を用いる場合には、酸化チタン微粒子が、有機繊維、有
機バインダー、プラスチック製品等の有機基材と直接接
触することになる。このとき、前記有機基材は、光エネ
ルギーを受けた酸化チタン微粒子の光触媒作用によっ
て、光分解されて劣化してしまうという不都合が生じ
る。この光分解性は、酸化チタン微粒子の光触媒活性が
高いほど大きくなるため、有機基材の光分解による劣化
を阻止することは、上記のような、高い光触媒活性が要
求されることとは相反するものであった。By the way, when titanium oxide fine particles or photocatalytic particles obtained by the above method are used for paints, textiles, etc., the titanium oxide fine particles are used as organic base materials such as organic fibers, organic binders and plastic products. You will be in direct contact. At this time, the organic base material is photodecomposed and deteriorated by the photocatalytic action of the titanium oxide fine particles having received the light energy. Since this photodegradability increases as the photocatalytic activity of the titanium oxide fine particles increases, preventing deterioration of the organic base material due to photodecomposition contradicts the requirement for high photocatalytic activity as described above. It was a thing.
【０００８】本発明は、上記技術的課題を解決するため
になされたものであり、酸化チタン微粒子を含む光触媒
性粒子全体の吸着力を向上させるとともに、酸化チタン
微粒子の光触媒としての触媒活性およびその活性持続性
を向上させることができ、しかも、有機基材に対する光
分解作用を抑制することができる光触媒性粒子およびそ
の製造方法を提供することを目的とするものである。The present invention has been made to solve the above technical problems, and improves the adsorption power of the entire photocatalytic particles containing titanium oxide fine particles, and at the same time, the catalytic activity of the titanium oxide fine particles as a photocatalyst and the same. It is an object of the present invention to provide photocatalytic particles capable of improving activity sustainability and suppressing the photodegradation effect on an organic substrate, and a method for producing the same.
【０００９】[0009]
【課題を解決するための手段】本発明に係る光触媒性粒
子は、多孔質シリカ微粒子に担持された酸化チタン微粒
子の表面に、さらに、多孔質シリカ微粒子が付着形成さ
れ、かつ、粒径が１μｍ以下であることを特徴とする。
このように構成された光触媒性粒子によれば、強い吸着
力を有し、担持される酸化チタン微粒子近傍の被処理物
質の濃度を高くすることができ、さらに、酸化チタン微
粒子の高い光触媒活性との相乗効果によって、光触媒活
性およびその活性持続性を向上させることができる。し
かも、外表面の多孔質シリカ微粒子によって、該光触媒
性粒子と直接接触する有機基材に対する光分解作用を抑
制することができる。The photocatalytic particles according to the present invention have titanium oxide fine particles supported on the porous silica fine particles, on which the fine silica particles are further adhered and formed, and the particle diameter is 1 μm. It is characterized by the following.
According to the photocatalytic particles configured as described above, the photocatalytic particles have a strong adsorption force and can increase the concentration of the substance to be treated in the vicinity of the carried titanium oxide fine particles, and further, the high photocatalytic activity of the titanium oxide fine particles can be obtained. The photocatalytic activity and its activity persistence can be improved by the synergistic effect of. Moreover, the porous silica fine particles on the outer surface can suppress the photodecomposition effect on the organic base material that is in direct contact with the photocatalytic particles.
【００１０】前記酸化チタン微粒子の粒径が５ｎｍ以上
１００ｎｍ以下であり、前記酸化チタン微粒子の表面に
付着形成された多孔質シリカ微粒子の粒径が１０ｎｍ以
上２００ｎｍ以下であり、かつ、前記光触媒性粒子の粒
径が０．０２５μｍ以上１μｍ以下であることが好まし
い。十分な光触媒活性および溶媒への分散性等の観点か
ら、上記範囲内の粒径とすることが好ましく、塗料用途
にも好適に用いることができる。The titanium oxide fine particles have a particle diameter of 5 nm or more and 100 nm or less, the porous silica fine particles adhered and formed on the surface of the titanium oxide fine particles have a particle diameter of 10 nm or more and 200 nm or less, and the photocatalytic particles. It is preferable that the particle size is 0.025 μm or more and 1 μm or less. From the viewpoint of sufficient photocatalytic activity, dispersibility in a solvent, and the like, it is preferable that the particle diameter be within the above range, and it can be suitably used for coating applications.
【００１１】また、前記光触媒性粒子の表面において、
酸化チタン微粒子が露出している部分の面積は、該光触
媒性粒子の表面積に対して、３０％以上９０％以下であ
ることが好ましい。酸化チタンの光触媒活性を十分に発
揮させる観点から、光触媒性粒子の表面における酸化チ
タンの露出面積を規定したものである。On the surface of the photocatalytic particles,
The area of the exposed titanium oxide fine particles is preferably 30% or more and 90% or less of the surface area of the photocatalytic particles. From the viewpoint of fully exhibiting the photocatalytic activity of titanium oxide, the exposed area of titanium oxide on the surface of the photocatalytic particles is defined.
【００１２】さらにまた、前記光触媒性粒子の組成は、
シリカに対する酸化チタンのモル比が、０．０１以上
０．５以下であることが好ましい。多孔質シリカによる
被処理物質の吸着性を十分に発揮させる観点から、光触
媒粒子の組成比を規定したものである。Furthermore, the composition of the photocatalytic particles is
The molar ratio of titanium oxide to silica is preferably 0.01 or more and 0.5 or less. The composition ratio of the photocatalyst particles is defined from the viewpoint of sufficiently exhibiting the adsorptivity of the substance to be treated by the porous silica.
【００１３】本発明に係る光触媒性粒子の製造方法は、
多重バーナーを用いて、ケイ素化合物およびチタン化合
物を酸水素火炎中にて加水分解することにより、酸化チ
タン微粒子を担持した多孔質シリカ微粒子の表面に多孔
質シリカ微粒子が付着形成された光触媒性粒子を得るこ
とを特徴とする。このように、気相合成により光触媒性
粒子を製造することによって、多孔質シリカ微粒子表面
に酸化チタン微粒子を均質に担持させ、さらに、その表
面に多孔質シリカ微粒子を容易に付着形成させることが
でき、しかも、粒径が均等な粒子を得ることができる。
このため、吸着力、光触媒活性およびその活性持続性に
も優れ、かつ、有機基材に対する光分解作用が抑制され
た光触媒性粒子を得ることができる。The method for producing photocatalytic particles according to the present invention comprises:
By using a multi-burner to hydrolyze silicon compounds and titanium compounds in an oxyhydrogen flame, photocatalytic particles in which porous silica fine particles are adhered and formed on the surface of porous silica fine particles carrying titanium oxide fine particles are formed. It is characterized by obtaining. Thus, by producing the photocatalytic particles by gas phase synthesis, it is possible to uniformly support the titanium oxide fine particles on the surface of the porous silica fine particles and to easily adhere and form the porous silica fine particles on the surface. Moreover, it is possible to obtain particles having a uniform particle size.
Therefore, it is possible to obtain photocatalytic particles which are excellent in adsorption power, photocatalytic activity, and activity sustainability thereof, and whose photodegradation action on the organic base material is suppressed.
【００１４】前記製造方法においては、前記多重バーナ
ーの内側のノズル管にケイ素化合物、外側のノズル管に
チタン化合物を導入し、さらに外側のノズル管にケイ素
化合物を導入して、酸水素火炎中にて加水分解すること
が好ましい。バーナーノズルをこのような構成とするこ
とにより、担体となる多孔質シリカ微粒子表面に、酸化
チタン微粒子を、均質かつ容易に担持させることがで
き、さらに、前記酸化チタン微粒子の表面に、多孔質シ
リカ微粒子を容易に付着形成させることができる。In the above-mentioned manufacturing method, a silicon compound is introduced into the inner nozzle tube of the multi-burner, a titanium compound is introduced into the outer nozzle tube, and a silicon compound is introduced into the outer nozzle tube so that the oxyhydrogen flame is exposed. It is preferable to hydrolyze. With such a structure of the burner nozzle, titanium oxide fine particles can be uniformly and easily supported on the surface of the porous silica fine particles serving as a carrier, and the surface of the titanium oxide fine particles can be further covered with porous silica. The fine particles can be easily attached and formed.
【００１５】また、前記チタン化合物は、ケイ素化合物
に対するモル比が、０．０１以上０．５以下となるよう
に導入されることが好ましい。上記のように、多孔質シ
リカによる被処理物質の吸着性を十分に発揮させること
ができる光触媒性粒子を得る等の観点から、原料供給量
比を規定したものである。The titanium compound is preferably introduced so that the molar ratio to the silicon compound is 0.01 or more and 0.5 or less. As described above, the raw material supply ratio is defined from the viewpoint of obtaining photocatalytic particles capable of sufficiently exhibiting the adsorptivity of the substance to be treated by the porous silica.
【００１６】また、前記製造方法により製造された光触
媒性粒子は、さらに、還元性ガス雰囲気中で熱処理する
ことが好ましい。この熱処理により、酸化チタン微粒子
を担持した多孔質シリカ微粒子の表面に多孔質シリカ微
粒子が付着形成された光触媒性粒子は、紫外線が照射さ
れた場合だけでなく、可視光線が照射された場合にも光
触媒活性を発揮することが可能となる。Further, it is preferable that the photocatalytic particles produced by the above production method are further heat-treated in a reducing gas atmosphere. By this heat treatment, the photocatalytic particles in which the porous silica fine particles are adhered and formed on the surface of the porous silica fine particles carrying the titanium oxide fine particles are not only exposed to ultraviolet rays, but also to visible light rays. It becomes possible to exhibit photocatalytic activity.
【００１７】前記熱処理温度は、前記製造方法により製
造された光触媒性粒子の５０％が焼結する温度以下であ
ることが好ましい。全粒子数の５０％を超える粒子に焼
結が起こると、十分な光触媒活性を得ることができな
い。The heat treatment temperature is preferably lower than the temperature at which 50% of the photocatalytic particles produced by the production method are sintered. If sintering occurs in particles exceeding 50% of the total number of particles, sufficient photocatalytic activity cannot be obtained.
【００１８】また、前記熱処理は、水素ガス雰囲気中、
３００℃以上６００℃以下で行われることが、より好ま
しい。上記と同様に、焼結する粒子の割合を考慮した上
での、より好ましい温度範囲である。The heat treatment is performed in a hydrogen gas atmosphere,
More preferably, it is performed at 300 ° C. or higher and 600 ° C. or lower. Similar to the above, it is a more preferable temperature range in consideration of the ratio of particles to be sintered.
【００１９】[0019]
【発明の実施の形態】以下、本発明を、図面を参照して
詳細に説明する。図１は、本発明に係る光触媒性粒子の
構造の典型例を示したものである。図１に示すように、
本発明に係る光触媒性粒子は、通常、非晶性の多孔質シ
リカ微粒子１の表面に、該多孔質シリカ微粒子１よりも
微細の酸化チタン微粒子２が担持され、前記酸化チタン
微粒子２の表面に、さらに、多孔質シリカ微粒子３が付
着形成された構造からなる。図１においては、担体
（核）となる多孔質シリカ微粒子１の表面の全面が、酸
化チタン微粒子２によって覆われており、前記酸化チタ
ン微粒子２の表面は、部分的に多孔質シリカ微粒子３に
よって覆われたものであり、斑状に酸化チタン微粒子２
の表面が露出している。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to the drawings. FIG. 1 shows a typical example of the structure of the photocatalytic particles according to the present invention. As shown in Figure 1,
In the photocatalytic particles according to the present invention, the amorphous silica fine particles 1 usually carry fine titanium oxide fine particles 2 finer than the porous silica fine particles 1 on the surface thereof. Further, it has a structure in which porous silica fine particles 3 are adhered and formed. In FIG. 1, the entire surface of the porous silica fine particles 1 serving as a carrier (nucleus) is covered with titanium oxide fine particles 2, and the surface of the titanium oxide fine particles 2 is partially covered with the porous silica fine particles 3. Titanium oxide fine particles 2 which are covered and are patchy
The surface of is exposed.
【００２０】このように構成された光触媒性粒子は、強
い吸着力を有し、担持される酸化チタン微粒子近傍の被
処理物質の濃度を高くすることができ、さらに、酸化チ
タン微粒子の高い光触媒活性との相乗効果によって、光
触媒活性およびその活性持続性を向上させることができ
る。しかも、外表面の多孔質シリカ微粒子によって、有
機基材が、酸化チタン微粒子と直接接触することにより
受ける光分解作用を抑制することができる。The photocatalytic particles having such a structure have a strong adsorbing power and can increase the concentration of the substance to be treated in the vicinity of the supported titanium oxide fine particles, and further, the high photocatalytic activity of the titanium oxide fine particles. The photocatalytic activity and its activity persistence can be improved by a synergistic effect with. In addition, the porous silica fine particles on the outer surface can suppress the photodecomposition effect that the organic base material receives by directly contacting the titanium oxide fine particles.
【００２１】前記光触媒性粒子の粒径は、１μｍ以下、
より好ましくは、０．０３μｍ以上１μｍ以下の範囲で
ある。なお、ここでいう粒径とは、粒子の最大粒径であ
る。前記光触媒性粒子の粒径が１μｍを超える場合は、
比表面積が小さくなるため、酸化チタン微粒子が付着す
る多孔質シリカ微粒子の表面積が小さくなり、十分な光
触媒活性を得ることができなくい。また、例えば、塗料
のように溶媒に分散させて用いる場合、粒子が大きい
と、平滑な塗膜を得ることができないという不都合を生
じる。一方、粒径が０．０３μｍ未満の場合には、粒子
が飛散しやすく、取扱いが困難となる。また、塗料のよ
うに溶媒に分散させて用いる場合、粒子が小さいと、カ
サ比重が小さいことにも起因して、凝集しやすくなり、
分散性が低下することとなる。The diameter of the photocatalytic particles is 1 μm or less,
More preferably, it is in the range of 0.03 μm or more and 1 μm or less. The particle size here is the maximum particle size of the particles. When the diameter of the photocatalytic particles exceeds 1 μm,
Since the specific surface area becomes small, the surface area of the porous silica fine particles to which the titanium oxide fine particles adhere becomes small, and it becomes difficult to obtain sufficient photocatalytic activity. Further, for example, in the case of being used by being dispersed in a solvent such as paint, if the particles are large, there arises a disadvantage that a smooth coating film cannot be obtained. On the other hand, when the particle size is less than 0.03 μm, the particles are likely to scatter and the handling becomes difficult. Further, when used by dispersing in a solvent like a paint, if the particles are small, it is easy to aggregate due to the fact that the bulk specific gravity is also small,
Dispersibility will be reduced.
【００２２】前記担体（核）となる多孔質シリカ粒子
は、通常、表面に１〜５ｎｍ程度の微細開気孔を密に有
する非晶質シリカである。このため、粒子の表面積が大
きく、かつ、表面形状が複雑であり、その表面に担持さ
れた酸化チタン微粒子に、多数の触媒活性点を付与する
作用を奏するとともに、該酸化チタン微粒子を強力に保
持することができる。The porous silica particles serving as the carrier (nucleus) are usually amorphous silica having dense open pores of about 1 to 5 nm on the surface. Therefore, the surface area of the particles is large, and the surface shape is complicated, and the titanium oxide fine particles carried on the surface have the effect of imparting a large number of catalytically active sites, and also strongly retain the titanium oxide fine particles. can do.
【００２３】また、本発明に係る酸化チタン微粒子は、
担体である多孔質シリカ微粒子に担持される光触媒成分
である。この酸化チタン微粒子の粒径は、５ｎｍ以上１
００ｎｍ以下の範囲であることが好ましく、特に、担体
となる多孔質シリカ微粒子に対する粒径比が０．０１〜
０．５であることが、被処理物質に対する吸着性と光触
媒活性等の観点から好ましい。The titanium oxide fine particles according to the present invention are
It is a photocatalyst component supported on porous silica fine particles as a carrier. The particle size of the titanium oxide fine particles is 5 nm or more 1
It is preferably in the range of 00 nm or less, and particularly, the particle diameter ratio to the porous silica fine particles serving as a carrier is 0.01 to
A value of 0.5 is preferable from the viewpoint of adsorbability for the substance to be treated and photocatalytic activity.
【００２４】さらにまた、前記酸化チタン微粒子の表面
に付着形成される多孔質シリカ微粒子の粒径は、２０ｎ
ｍ以上１００ｎｍ以下の範囲であることが好ましく、特
に、前記酸化チタン微粒子に対する粒径比が４〜２０で
あることが、酸化チタン微粒子に直接接触する有機基材
の光分解による劣化を抑制する観点、および、被処理物
質に対しては十分な光触媒活性を発揮させる観点等から
好ましい。Furthermore, the particle diameter of the porous silica fine particles adhered and formed on the surface of the titanium oxide fine particles is 20 n.
It is preferably in the range of m or more and 100 nm or less, and in particular, having a particle size ratio to the titanium oxide fine particles of 4 to 20 suppresses deterioration due to photolysis of the organic base material that is in direct contact with the titanium oxide fine particles. , And is preferable from the viewpoint of exhibiting sufficient photocatalytic activity for the substance to be treated.
【００２５】本発明に係る光触媒性粒子の表面の状態
は、酸化チタン微粒子が露出している部分の面積が、該
光触媒性粒子の表面積に対して、３０％以上９０％以下
であることが好ましい。より好ましくは、５０％以上８
０％以下である。前記酸化チタン微粒子が露出している
部分の面積比が９０％を超える場合、有機基材と直接接
触する面積が大きくなり、該有機基材の光分解による劣
化を促進させることとなる。一方、前記面積比が３０％
未満である場合は、十分な光触媒活性を得ることができ
ない。Regarding the surface condition of the photocatalytic particles according to the present invention, the area of the exposed titanium oxide fine particles is preferably 30% or more and 90% or less of the surface area of the photocatalytic particles. . More preferably, 50% or more 8
It is 0% or less. When the area ratio of the exposed portion of the titanium oxide fine particles exceeds 90%, the area of direct contact with the organic base material becomes large, and the deterioration of the organic base material due to photolysis is promoted. On the other hand, the area ratio is 30%
If it is less than the above range, sufficient photocatalytic activity cannot be obtained.
【００２６】また、前記光触媒性粒子全体の組成は、シ
リカに対する酸化チタンのモル比が、０．０１以上０．
５以下であることが、多孔質シリカによる被処理物質の
吸着性を十分に発揮させる観点から好ましい。The composition of the entire photocatalytic particles is such that the molar ratio of titanium oxide to silica is 0.01 or more and 0.1.
It is preferably 5 or less from the viewpoint of sufficiently exhibiting the adsorptivity of the substance to be treated by the porous silica.
【００２７】次に、上記のような光触媒性粒子を得るた
めの本発明に係る製造方法を、以下に説明する。本発明
に係る製造方法は、多重式酸水素火炎バーナーを用い
て、ケイ素化合物およびチタン化合物を酸水素火炎中に
て加水分解させるものである。すなわち、高純度合成石
英を製造する際に用いられる、いわゆるＶＡＤ（Vapor-
phase axial deposition）法に類似した方法である。こ
のように、本発明に係る製造方法は、気相合成により光
触媒性粒子を製造するものであるため、多孔質シリカ微
粒子表面に酸化チタン微粒子を均質に担持させ、さら
に、その表面に多孔質シリカ微粒子を付着形成させるこ
とができ、しかも、粒径が均等な粒子を得ることができ
る。このため、吸着性、光触媒活性およびその活性持続
性にも優れ、かつ、有機基材に対する光分解作用が抑制
された光触媒性粒子を得ることができる。Next, a manufacturing method according to the present invention for obtaining the above-mentioned photocatalytic particles will be described below. The production method according to the present invention uses a multi-type oxyhydrogen flame burner to hydrolyze a silicon compound and a titanium compound in an oxyhydrogen flame. That is, the so-called VAD (Vapor-) used when manufacturing high-purity synthetic quartz is used.
This is a method similar to the phase axial deposition) method. As described above, since the production method according to the present invention is to produce photocatalytic particles by gas phase synthesis, titanium oxide fine particles are uniformly supported on the surface of porous silica fine particles, and further, porous silica is provided on the surface. Fine particles can be adhered and formed, and particles having a uniform particle size can be obtained. Therefore, it is possible to obtain photocatalytic particles that are excellent in adsorptivity, photocatalytic activity, and their activity sustainability and that suppress the photodegradation action on the organic base material.
【００２８】具体的な製造方法としては、例えば、図２
に示すように構成された装置により、チャンバ１１内に
多重式酸水素火炎バーナーのバーナーノズル１２の先端
部１２ａから水素ガス、酸素ガスとともに、ケイ素化合
物、チタン化合物をそれぞれ霧状またはガス状に噴射さ
せる。そして、前記ケイ素化合物およびチタン化合物
を、水素と酸素の火炎燃焼反応により生じる熱および水
により、通常６００〜１３００℃程度となる高温下に
て、加水分解反応させることによって、多孔質シリカ微
粒子の表面に酸化チタン微粒子が付着し、さらに、その
表面に多孔質シリカ微粒子が付着した粒子、すなわち、
本発明に係る光触媒性粒子１３が生成し、チャンバ１１
内の底部に堆積する。なお、チャンバ１１内に生成した
ガスは、該チャンバ１１に設けられた排気口１４から排
気される。As a concrete manufacturing method, for example, FIG.
With the device configured as shown in FIG. 1, a silicon compound and a titanium compound are injected into the chamber 11 from the tip portion 12a of the burner nozzle 12 of the multiple oxyhydrogen flame burner together with hydrogen gas and oxygen gas in the form of mist or gas, respectively. Let Then, the silicon compound and the titanium compound are hydrolyzed by the heat and water generated by the flame combustion reaction of hydrogen and oxygen at a high temperature of usually about 600 to 1300 ° C., whereby the surface of the porous silica fine particles. Titanium oxide fine particles are attached to the particles, and further, porous silica fine particles are attached to the surface of the particles, that is,
The photocatalytic particles 13 according to the present invention are generated, and the chamber 11
Deposit on the bottom of the inside. The gas generated in the chamber 11 is exhausted from the exhaust port 14 provided in the chamber 11.
【００２９】前記光触媒性粒子１３の生成過程をさらに
詳細に説明すると、まず、多重式酸水素炎バーナーのバ
ーナーノズル１２に導入されたケイ素化合物を、酸水素
火炎中で加水分解して、多孔質シリカ微粒子を生成させ
る。そして、この生成した多孔質シリカ微粒子の表面
に、バーナーノズル１２に導入されたチタン化合物を酸
水素火炎中で加水分解反応させることにより生成した酸
化チタン微粒子を付着させて、酸化チタン微粒子を担持
した多孔質シリカ微粒子が得られる。さらに、前記酸化
チタン微粒子を担持した多孔質シリカ微粒子の表面に
は、バーナーノズル１２に導入されたケイ素化合物を酸
水素火炎中で加水分解反応させることにより生成した多
孔質シリカ微粒子を付着させることにより、本発明に係
る光触媒性粒子１３が得られる。前記光触媒性粒子１３
の粒径は、ケイ素化合物、チタン化合物および酸素ガ
ス、水素ガスの流量、バーナーノズル１２の調整によっ
て制御することができる。The production process of the photocatalytic particles 13 will be described in more detail. First, the silicon compound introduced into the burner nozzle 12 of the multiple oxyhydrogen flame burner is hydrolyzed in an oxyhydrogen flame to give a porous structure. Generates silica fine particles. Then, titanium oxide fine particles produced by hydrolyzing the titanium compound introduced into the burner nozzle 12 in an oxyhydrogen flame are adhered to the surface of the produced porous silica fine particles to carry the titanium oxide fine particles. Porous silica fine particles are obtained. Furthermore, by attaching the porous silica fine particles produced by hydrolyzing the silicon compound introduced into the burner nozzle 12 in an oxyhydrogen flame to the surface of the porous silica fine particles carrying the titanium oxide fine particles, The photocatalytic particles 13 according to the present invention can be obtained. The photocatalytic particles 13
The particle size can be controlled by adjusting the flow rates of the silicon compound, titanium compound, oxygen gas, and hydrogen gas, and the burner nozzle 12.
【００３０】前記多重式酸水素火炎バーナーとしては、
酸素ガス、水素ガス、ケイ素化合物（２ライン）、チタ
ン化合物等の４種類５ライン以上のガスをそれぞれ供給
することができる多重ノズル口を備えた酸水素火炎用バ
ーナーであれば、特に限定されることなく、使用するこ
とができる。例えば、図３に示すような構造からなるバ
ーナーノズル１２を備えた多重式酸水素火炎バーナー
が、好適に用いられる。なお、図３（ａ）は、バーナー
ノズルの縦断面図であり、（ｂ）は、横断面図である。
図３に示したバーナーノズル１２は、同心円の環状多重
管からなり、最内管２１および最外環状管２５にケイ素
化合物、前記最外環状管の内側の中間環状管２４にチタ
ン化合物、さらに、前記中間環状管２４の内側の中間環
状管２２、２３に酸素または水素のそれぞれが導入さ
れ、先端部１２ａから噴射される。バーナーノズル１２
をこのような構成とすることにより、担体となる多孔質
シリカ微粒子の表面に、酸化チタン微粒子を均質かつ容
易に担持させることができ、さらに、その表面に多孔質
シリカ微粒子を付着形成させることができる。As the multiple oxyhydrogen flame burner,
The burner for an oxyhydrogen flame is particularly limited as long as it is a burner for an oxyhydrogen flame having multiple nozzle ports capable of supplying four types of gas of 5 lines or more such as oxygen gas, hydrogen gas, silicon compound (2 lines), and titanium compound. Can be used without. For example, a multiple oxyhydrogen flame burner equipped with a burner nozzle 12 having a structure as shown in FIG. 3 is preferably used. 3A is a vertical cross-sectional view of the burner nozzle, and FIG. 3B is a horizontal cross-sectional view.
The burner nozzle 12 shown in FIG. 3 is composed of concentric annular multiple tubes, a silicon compound in the innermost tube 21 and the outermost annular tube 25, a titanium compound in the intermediate annular tube 24 inside the outermost annular tube, and further, Oxygen or hydrogen is introduced into the intermediate annular pipes 22 and 23 inside the intermediate annular pipe 24, and is injected from the tip portion 12a. Burner nozzle 12
With such a constitution, the titanium oxide fine particles can be uniformly and easily supported on the surface of the porous silica fine particles serving as a carrier, and further, the porous silica fine particles can be adhered and formed on the surface. it can.
【００３１】また、反応を均等に進行させる等の観点か
ら、環状多重管のラインを増加させ、酸素、水素、ケイ
素化合物、チタン化合物が導入されるそれぞれの環状管
の間に、チッ素、アルゴン、ヘリウム等の不活性ガス等
を導入させることが好ましい。特に、前記ケイ素化合物
とチタン化合物が液体または溶液である場合には、前記
不活性ガス等を中間の環状管に導入し、この不活性ガス
等を用いて、霧状またはガス状に噴射させることが、こ
れらの化合物の加水分解反応を均等に進行させ、高い光
触媒活性を発揮する構造および粒径である光触媒性粒子
を得る観点から好ましい。From the viewpoint of allowing the reaction to proceed uniformly, the lines of the annular multi-tube are increased so that nitrogen, argon and argon are introduced between the respective annular tubes into which oxygen, hydrogen, silicon compound and titanium compound are introduced. It is preferable to introduce an inert gas such as helium. In particular, when the silicon compound and the titanium compound are liquids or solutions, the inert gas or the like is introduced into an intermediate annular pipe, and the inert gas or the like is used to spray it in a mist or gas state. However, it is preferable from the viewpoint of uniformly advancing the hydrolysis reaction of these compounds to obtain photocatalytic particles having a structure and a particle size that exhibit high photocatalytic activity.
【００３２】上記製造方法においては、得られる光触媒
性粒子１３の粒径が、上記のように、１μｍ以下、好ま
しくは、０．０２５〜１μｍ程度になるように調節され
る。粒径の調節は、ケイ素化合物含有ガス、チタン化合
物含有ガス、酸素ガス、水素ガスの各流量、バーナーノ
ズル先端部１２ａにおけるガス流線速度等を適宜調整す
ることによって行われる。前記線速度が速いほど、得ら
れる光触媒性粒子の粒径は小さくなり、光触媒活性は向
上するが、その反面、使用時の分散性は低下する。In the above manufacturing method, the particle size of the photocatalytic particles 13 obtained is adjusted to 1 μm or less, preferably about 0.025 to 1 μm, as described above. The particle size is adjusted by appropriately adjusting the respective flow rates of the silicon compound-containing gas, the titanium compound-containing gas, the oxygen gas, and the hydrogen gas, the gas stream linear velocity at the tip 12a of the burner nozzle, and the like. The higher the linear velocity, the smaller the particle size of the photocatalytic particles obtained and the photocatalytic activity is improved, but on the other hand, the dispersibility during use is decreased.
【００３３】また、前記チタン化合物とケイ素化合物と
の供給量比は、上記した光触媒性粒子の組成を基準とし
て、チタン化合物のケイ素化合物に対するモル比が、
０．０１〜０．５となるように導入される。前記多孔質
シリカ微粒子の構成原料としては、四塩化ケイ素、トリ
クロロシラン等の塩化物、四フッ化ケイ素、トリフルオ
ロシラン等のフッ化物等のほか、アルコキシド等のケイ
素化合物を挙げることができる。また、前記チタン微粒
子の構成原料としては、四塩化チタン、三塩化チタン等
の塩化物、フッ化物、硫酸塩、アルコキシド等のチタン
化合物を挙げることができる。The ratio of the titanium compound and the silicon compound supplied is such that the molar ratio of the titanium compound to the silicon compound is based on the composition of the photocatalytic particles described above.
It is introduced so as to be 0.01 to 0.5. Examples of the constituent raw material of the porous silica fine particles include chlorides such as silicon tetrachloride and trichlorosilane, fluorides such as silicon tetrafluoride and trifluorosilane, and silicon compounds such as alkoxides. In addition, examples of the constituent raw material of the titanium fine particles include chlorides such as titanium tetrachloride and titanium trichloride, titanium compounds such as fluorides, sulfates and alkoxides.
【００３４】上記製造方法により得られた光触媒性粒子
は、そのまま使用しても、十分な光触媒活性を発揮する
ことができるが、その得られた粒子は、さらに、水素ガ
ス、水素ガスとチッ素ガスとの混合ガス、アンモニアガ
ス等の還元性ガス雰囲気中で熱処理することが、より好
ましい。この還元性雰囲気中での熱処理を行うことによ
り、紫外線波長領域の光照射に対してのみならず、可視
光線波長領域の光照射に対しても、高い光触媒活性を発
揮する光触媒性粒子を得ることができる。The photocatalytic particles obtained by the above-mentioned production method can exhibit a sufficient photocatalytic activity even if they are used as they are, but the obtained particles are further hydrogen gas, hydrogen gas and nitrogen. It is more preferable to perform the heat treatment in an atmosphere of a reducing gas such as a mixed gas with a gas or ammonia gas. By performing heat treatment in this reducing atmosphere, it is possible to obtain photocatalytic particles that exhibit high photocatalytic activity not only for light irradiation in the ultraviolet wavelength region but also for light irradiation in the visible light wavelength region. You can
【００３５】前記熱処理は、前記酸化チタン微粒子を担
持した多孔質シリカ微粒子の表面に多孔質シリカ微粒子
が付着形成された光触媒性粒子の５０％が焼結する温度
以下で行うことが好ましい。全粒子数の５０％を超える
粒子に焼結が起こると、十分な光触媒活性を得ることが
できなくなる。したがって、熱処理温度は、３００〜６
００℃の範囲で行うことが、特に好ましい。The heat treatment is preferably carried out at a temperature not higher than the temperature at which 50% of the photocatalytic particles in which the porous silica fine particles are adhered and formed on the surface of the porous silica fine particles carrying the titanium oxide fine particles are sintered. If sintering occurs in particles exceeding 50% of the total number of particles, sufficient photocatalytic activity cannot be obtained. Therefore, the heat treatment temperature is 300 to 6
It is particularly preferable to carry out in the range of 00 ° C.
【００３６】[0036]
【実施例】以下、本発明を実施例に基づきさらに具体的
に説明するが、本発明は下記の実施例により制限される
ものではない。
［実施例］図２に示したようなチャンバ内で、多重管バ
ーナーノズルを装着した酸水素火炎装置を用いて、この
バーナーノズルの環状管の内側から順に、四塩化ケイ素
（濃度：８０ｍｏｌ％、流量：５ｌ／ｍｉｎ）、チッ素
ガス（流量：５ｌ／ｍｉｎ）、水素ガス（流量：１２ｌ
／ｍｉｎ）、チッ素ガス（流量：５ｌ／ｍｉｎ）、酸素
ガス（流量：５ｌ／ｍｉｎ）、チッ素ガス（流量：５ｌ
／ｍｉｎ）、四塩化チタン（濃度：２０ｍｏｌ％、流
量：１ｌ／ｍｉｎ）、チッ素ガス（流量：３ｌ／ｍｉ
ｎ）、四塩化ケイ素（濃度：８０ｍｏｌ％、流量：０．
２ｌ／ｍｉｎ）を、該バーナーノズル先端部から噴射さ
せ（ガス流線速度：約０．５ｍ／ｓｅｃ）、最高温度９
００℃の酸水素火炎中にて加水分解反応させ、酸化チタ
ン微粒子を担持した多孔質シリカ微粒子の表面に多孔質
シリカ微粒子が付着形成された粒子をチャンバ内に堆積
させた。EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples. Example Using an oxyhydrogen flame device equipped with a multi-tube burner nozzle in a chamber as shown in FIG. 2, silicon tetrachloride (concentration: 80 mol%, Flow rate: 5 l / min), nitrogen gas (flow rate: 5 l / min), hydrogen gas (flow rate: 12 l)
/ Min), nitrogen gas (flow rate: 5 l / min), oxygen gas (flow rate: 5 l / min), nitrogen gas (flow rate: 5 l)
/ Min), titanium tetrachloride (concentration: 20 mol%, flow rate: 1 l / min), nitrogen gas (flow rate: 3 l / mi)
n), silicon tetrachloride (concentration: 80 mol%, flow rate: 0.
2 l / min) from the tip of the burner nozzle (gas stream linear velocity: about 0.5 m / sec), and the maximum temperature was 9
Hydrolysis reaction was carried out in an oxyhydrogen flame at 00 ° C., and particles having porous silica particles adhered and formed on the surface of the porous silica particles supporting the titanium oxide particles were deposited in the chamber.
【００３７】得られた粒子の粒径は、０．１５〜０．５
μｍの範囲のものが、９９重量％であった。また、顕微
鏡写真による目視計測の結果、得られた粒子の表面積に
対して、酸化チタン微粒子が露出している部分の面積
は、平均５０％であり、担持された酸化チタン微粒子の
平均粒径は３０ｎｍ、外表面に付着形成された多孔質シ
リカ微粒子の粒径は５０ｎｍであった。そして、この粒
子を、水素ガス気流中、４００℃で２時間熱処理し、光
触媒性粒子を得た。The particle size of the obtained particles is 0.15 to 0.5.
The value in the range of μm was 99% by weight. In addition, as a result of visual measurement using a micrograph, the area of the portion where the titanium oxide fine particles are exposed is 50% on average with respect to the surface area of the obtained particles, and the average particle diameter of the carried titanium oxide fine particles is The particle size was 30 nm, and the particle size of the porous silica fine particles adhered and formed on the outer surface was 50 nm. Then, the particles were heat-treated in a hydrogen gas stream at 400 ° C. for 2 hours to obtain photocatalytic particles.
【００３８】そして、得られた光触媒性粒子４００重量
部に、メチルトリメトキシシラン８０重量部を添加し、
これをイソプロパノールにより２倍（重量）に希釈し、
前記光触媒性粒子４２重量％を配合した光触媒性塗料を
調製した。この塗料をアクリルの平板（縦４００ｍｍ×
横１００ｍｍ×厚さ２ｍｍ）表面に、スプレー塗装によ
り、厚さ１０μｍで塗布した。Then, 80 parts by weight of methyltrimethoxysilane was added to 400 parts by weight of the obtained photocatalytic particles,
Dilute this with isopropanol to 2 times (weight),
A photocatalytic paint containing 42% by weight of the photocatalytic particles was prepared. Apply this paint to an acrylic plate (length 400 mm x
(100 mm in width × 2 mm in thickness) The surface was applied by spray coating to a thickness of 10 μm.
【００３９】［比較例］Ａ型シリカゲル（平均細孔径：
２．４ｎｍ、細孔容積：０．４６ｍｌ／ｇ、比表面積：
７００ｍ2 ／ｇ）を粉砕した後、篩別し、粒径４０〜１
５０ｎｍの粒状シリカゲルを得た。この粒状シリカゲル
に、ジイソプロポキシ−ビス（アセチルアセトナート）
チタンを含浸させた後、酸素気流中、６００℃で１時間
保持して酸化し、５重量％の酸化チタンを担持したシリ
カゲル粒子からなる光触媒性粒子を得た。そして、得ら
れた光触媒性粒子を用いて、実施例と同様にして、光触
媒性塗料を調製し、この塗料を塗布した試料を作製し
た。Comparative Example A type silica gel (average pore size:
2.4 nm, pore volume: 0.46 ml / g, specific surface area:
700 m 2 / g) and then sieved to give a particle size of 40-1
50 nm granular silica gel was obtained. Diisopropoxy-bis (acetylacetonate) was added to the granular silica gel.
After impregnating with titanium, it was kept in an oxygen stream at 600 ° C. for 1 hour for oxidation to obtain photocatalytic particles consisting of silica gel particles carrying 5% by weight of titanium oxide. Then, using the obtained photocatalytic particles, a photocatalytic paint was prepared in the same manner as in Example, and a sample coated with this paint was prepared.
【００４０】上記の実施例および比較例の光触媒性塗料
を塗布した試料を、それぞれ、同型のボックス型密閉容
器（容積：２０ｌ、底面積：１０００ｃｍ2 、２０Ｗの
ブラックライトを内蔵）内に、該ボックスの底面に置い
た。次いで、これらの各容器内に、トリメチルアミン８
０ｐｐｍを注入し、ブラックライトを点灯し、２０分後
に容器内の空気中に含まれるトリメチルアミン濃度をガ
スクロマトグラフィーにより測定した。この第１回測定
においては、両者ともにトリメチルアミン濃度は０ｐｐ
ｍであった。再度、両容器に減少した分のトリメチルア
ミンを注入し、２０分後に、同様にトリメチルアミン濃
度を測定した。このような操作を繰り返し実施したとこ
ろ、実施例品を置いた容器の場合は、上記操作サイクル
を８回繰り返しても、トリメチルアミン濃度は０ｐｐｍ
であったが、比較例品の容器の場合には、２回目以降残
存トリメチルアミンが検出され、回を重ねるごとにその
濃度は増加し、８回目には除去効果が全く見られなくな
った。The samples coated with the photocatalytic paints of the above Examples and Comparative Examples were placed in the same type of box-type closed container (volume: 20 l, bottom area: 1000 cm 2 , 20 W of built-in black light). Placed on the bottom of the box. Then, in each of these vessels, trimethylamine 8
After injecting 0 ppm, the black light was turned on, and 20 minutes later, the concentration of trimethylamine contained in the air in the container was measured by gas chromatography. In this first measurement, both had a trimethylamine concentration of 0 pp.
It was m. Again, the reduced amount of trimethylamine was injected into both containers, and 20 minutes later, the trimethylamine concentration was similarly measured. When such an operation was repeatedly carried out, in the case of the container containing the example product, the trimethylamine concentration was 0 ppm even if the above operation cycle was repeated 8 times.
However, in the case of the container of the comparative example, residual trimethylamine was detected after the second time, the concentration increased each time the time was repeated, and the removal effect was not seen at all at the eighth time.
【００４１】また、上記実施例および比較例の各試料
に、４０Ｗのブラックライトを５ｃｍの距離から１００
時間連続照射したところ、比較例の試料は、塗布表面に
微細なひび割れが多数生じていた。一方、実施例の試料
については、全く変化は見られなかった。A 40 W black light was applied to each of the samples of the above-mentioned Examples and Comparative Examples at a distance of 5 cm from 100 cm.
After continuous irradiation for a long time, the sample of the comparative example had many fine cracks on the coated surface. On the other hand, no change was observed in the samples of the examples.
【００４２】[0042]
【発明の効果】以上のとおり、本発明によれば、ホルム
アルデヒドガス、工場排水中の有害物質等の被処理物質
に対する吸着力が強く、該被処理物質が低濃度である場
合においても、光触媒活性が高く、かつ、その活性持続
性に優れ、しかも、有機繊維、有機バインダー、プラス
チック製品等の有機基材に対する光分解作用が抑制され
た光触媒性粒子が得られる。したがって、本発明に係る
光触媒性粒子は、建築の外装・内装塗料、路面舗装材
料、車ボディー用塗料等の塗料分野、病院用、車内シー
ト、インテリア、衣類等の繊維製品分野、食品用プラス
チック容器、日用雑貨等のプラスチック製品分野、さら
に、環境ホルモン・環境汚染物質の除去剤、工業排水・
排ガス処理剤、衛生陶器製品等、広範な分野において応
用することができる。As described above, according to the present invention, the photocatalytic activity is high even when the substance to be treated such as formaldehyde gas and harmful substances in factory wastewater has a strong adsorption force and the substance to be treated has a low concentration. Thus, it is possible to obtain photocatalytic particles having high activity and excellent activity sustainability, and having suppressed photodegradation action on organic substrates such as organic fibers, organic binders and plastic products. Therefore, the photocatalytic particles according to the present invention are used in exterior and interior paints for construction, road surface paving materials, paints such as car body paints, hospitals, car seats, interiors, textile products such as clothes, and plastic containers for food. , Plastic products such as sundries, removal agents for environmental hormones and pollutants, industrial wastewater,
It can be applied in a wide range of fields such as exhaust gas treatment agents and sanitary ware products.
【図１】本発明に係る光触媒性粒子の構造の典型例の模
式図である。FIG. 1 is a schematic view of a typical example of the structure of photocatalytic particles according to the present invention.
【図２】本発明に係る光触媒性粒子の製造方法において
用いられる装置の概略断面図である。FIG. 2 is a schematic sectional view of an apparatus used in the method for producing photocatalytic particles according to the present invention.
【図３】多重式酸水素火炎バーナーのバーナーノズルの
一例を示す概略図である。（ａ）は、バーナーノズルの
縦断面図であり、（ｂ）は、横断面図である。FIG. 3 is a schematic view showing an example of a burner nozzle of a multi-type oxyhydrogen flame burner. (A) is a vertical cross-sectional view of the burner nozzle, and (b) is a horizontal cross-sectional view.
１ 多孔質シリカ微粒子 ２ 酸化チタン微粒子 ３ 多孔質シリカ微粒子 １１ チャンバ １２ バーナーノズル １２ａ バーナーノズル先端部 １３ 光触媒性粒子 １４ 排気口 ２１ 最内管 ２２、２３、２４ 中間環状管 ２５ 最外環状管 1 Porous silica particles 2 Fine particles of titanium oxide 3 Porous silica particles 11 chambers 12 burner nozzle 12a Burner nozzle tip 13 Photocatalytic particles 14 exhaust port 21 innermost tube 22, 23, 24 Intermediate annular pipe 25 outermost annular pipe
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 37/02 ３０１ Ｂ０１Ｊ 37/08 37/08 37/18 37/18 Ｃ０１Ｂ 33/18 Ｚ Ｃ０１Ｂ 33/18 Ｃ０１Ｇ 23/04 Ｂ Ｃ０１Ｇ 23/04 Ｂ０１Ｄ 53/36 Ｊ Ｃ Ｇ Ｆターム(参考） 4D048 AA17 AA22 AB03 BA06X BA07X BA41X BB01 BB17 EA01 EA04 4G047 CA02 CB04 CC03 CD04 4G069 AA03 AA08 BA02A BA02B BA04A BA04B BA48A CA01 CA10 CA17 CD10 DA05 EA02X EA02Y EB19 ED02 ED04 ED10 FA01 FA02 FB29 FB44 FC08 4G072 AA25 BB05 DD06 GG03 HH08 LL02 MM01 RR05 RR30 TT01 UU15 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B01J 37/02 301 B01J 37/08 37/08 37/18 37/18 C01B 33/18 Z C01B 33/18 C01G 23/04 B C01G 23/04 B01D 53/36 J C G F Term (Reference) 4D048 AA17 AA22 AB03 BA06X BA07X BA41X BB01 BB17 EA01 EA04 4G047 CA02 CB04 CC03 CD04 4G069 AA03 AA08 BA02ABA02 CA17A01B02BA48A17A04A48A17A02 EA02X EA02Y EB19 ED02 ED04 ED10 FA01 FA02 FB29 FB44 FC08 4G072 AA25 BB05 DD06 GG03 HH08 LL02 MM01 RR05 RR30 TT01 UU15
Claims (10)
タン微粒子の表面に、さらに、多孔質シリカ微粒子が付
着形成され、かつ、粒径が１μｍ以下であることを特徴
とする光触媒性粒子。1. A photocatalytic particle characterized in that porous silica fine particles are further adhered and formed on the surface of titanium oxide fine particles supported on the porous silica fine particles, and the particle size is 1 μm or less.
上１００ｎｍ以下であり、前記酸化チタン微粒子の表面
に付着形成された多孔質シリカ微粒子の粒径が１０ｎｍ
以上２００ｎｍ以下であり、かつ、前記光触媒性粒子の
粒径が０．０２５μｍ以上１μｍ以下であることを特徴
とする請求項１記載の光触媒性粒子。2. The particle size of the titanium oxide particles is 5 nm or more and 100 nm or less, and the particle size of the porous silica particles deposited on the surface of the titanium oxide particles is 10 nm.
2. The photocatalytic particles according to claim 1, wherein the photocatalytic particles have a particle diameter of 0.025 μm or more and 200 nm or less and a particle diameter of the photocatalytic particles of 0.025 μm or more and 1 μm or less.
チタン微粒子が露出している部分の面積が、該光触媒性
粒子の表面積に対して、３０％以上９０％以下であるこ
とを特徴とする請求項１または請求項２記載の光触媒性
粒子。3. The surface area of the photocatalytic particles where the titanium oxide fine particles are exposed is 30% or more and 90% or less of the surface area of the photocatalytic particles. The photocatalytic particle according to claim 1 or 2.
する酸化チタンのモル比が、０．０１以上０．５以下で
あることを特徴とする請求項１から請求項３までのいず
れかに記載の光触媒性粒子。4. The composition of the photocatalytic particles has a molar ratio of titanium oxide to silica of 0.01 or more and 0.5 or less, according to any one of claims 1 to 3. Photocatalytic particles.
よびチタン化合物を酸水素火炎中にて加水分解すること
により、酸化チタン微粒子を担持した多孔質シリカ微粒
子の表面に多孔質シリカ微粒子が付着形成された光触媒
性粒子を得ることを特徴とする光触媒性粒子の製造方
法。5. A multi-burner is used to hydrolyze a silicon compound and a titanium compound in an oxyhydrogen flame to form porous silica fine particles on the surface of the porous silica fine particles carrying the titanium oxide fine particles. A method for producing photocatalytic particles, characterized in that the obtained photocatalytic particles are obtained.
イ素化合物、外側のノズル管にチタン化合物を導入し、
さらに外側のノズル管にケイ素化合物を導入して、酸水
素火炎中にて加水分解することを特徴とする請求項５記
載の光触媒性粒子の製造方法。6. A silicon compound is introduced into an inner nozzle tube of the multi-burner, and a titanium compound is introduced into an outer nozzle tube,
The method for producing photocatalytic particles according to claim 5, further comprising introducing a silicon compound into the outer nozzle tube and performing hydrolysis in an oxyhydrogen flame.
するモル比が、０．０１以上０．５以下となるように導
入されることを特徴とする請求項５または請求項６記載
の光触媒性粒子の製造方法。7. The photocatalytic particles according to claim 5, wherein the titanium compound is introduced so that the molar ratio to the silicon compound is 0.01 or more and 0.5 or less. Production method.
記載の製造方法により製造された光触媒性粒子を、さら
に、還元性ガス雰囲気中で熱処理することを特徴とする
光触媒性粒子の製造方法。8. Production of photocatalytic particles, characterized in that the photocatalytic particles produced by the production method according to any one of claims 5 to 7 are further heat-treated in a reducing gas atmosphere. Method.
７までのいずれかに記載の製造方法により製造された光
触媒性粒子の５０％が焼結する温度以下であることを特
徴とする請求項８記載の光触媒性粒子の製造方法。9. The heat treatment temperature is equal to or lower than a temperature at which 50% of the photocatalytic particles produced by the production method according to any one of claims 5 to 7 are sintered. Item 9. A method for producing photocatalytic particles according to item 8.
００℃以上６００℃以下で行われることを特徴とする請
求項８または請求項９記載の光触媒性粒子の製造方法。10. The heat treatment is performed in a hydrogen gas atmosphere for 3 hours.
The method for producing photocatalytic particles according to claim 8 or 9, wherein the method is performed at a temperature of 00 ° C or higher and 600 ° C or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001189025A JP2003001118A (en) | 2001-06-22 | 2001-06-22 | Photocatalytic particle and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005193118A (en) * | 2004-01-06 | 2005-07-21 | Daiken Kagaku Kogyo Kk | Photocatalytic particle, photocatalytic solution, atomizer, air cleaner and photocatalytic base material |
| JP2008246392A (en) * | 2007-03-30 | 2008-10-16 | Hiroshima Univ | Fine particle-containing complex and its manufacturing method |
| KR102591972B1 (en) * | 2022-08-26 | 2023-10-20 | 주식회사 제이치글로벌 | Composition for antibacterial with silicate material, product applied therto, and manufacturing method for the same |
-
2001
- 2001-06-22 JP JP2001189025A patent/JP2003001118A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005193118A (en) * | 2004-01-06 | 2005-07-21 | Daiken Kagaku Kogyo Kk | Photocatalytic particle, photocatalytic solution, atomizer, air cleaner and photocatalytic base material |
| JP2008246392A (en) * | 2007-03-30 | 2008-10-16 | Hiroshima Univ | Fine particle-containing complex and its manufacturing method |
| KR102591972B1 (en) * | 2022-08-26 | 2023-10-20 | 주식회사 제이치글로벌 | Composition for antibacterial with silicate material, product applied therto, and manufacturing method for the same |
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