JPH11279299A - Resin substrate having photocatalytic function - Google Patents
Resin substrate having photocatalytic functionInfo
- Publication number
- JPH11279299A JPH11279299A JP10083534A JP8353498A JPH11279299A JP H11279299 A JPH11279299 A JP H11279299A JP 10083534 A JP10083534 A JP 10083534A JP 8353498 A JP8353498 A JP 8353498A JP H11279299 A JPH11279299 A JP H11279299A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- light
- base material
- photocatalytic function
- resin base
- 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
- 239000011347 resin Substances 0.000 title claims abstract description 67
- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000000758 substrate Substances 0.000 title claims abstract description 37
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 72
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 48
- 150000002500 ions Chemical class 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 238000005286 illumination Methods 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 16
- 238000013032 photocatalytic reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000007943 implant Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000000113 methacrylic resin Substances 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000005468 ion implantation Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 helmet shields Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000003550 marker Substances 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒機能を有す
る樹脂基材に関する。詳しくは金属イオンが注入された
酸化チタンを有し、可視光によっても光触媒機能を発現
することができる樹脂基材に関する。[0001] The present invention relates to a resin substrate having a photocatalytic function. More specifically, the present invention relates to a resin base material having titanium oxide into which metal ions have been implanted and capable of exhibiting a photocatalytic function even with visible light.
【０００２】[0002]
【従来の技術】光触媒は、そのバンドギャップ以上のエ
ネルギーを持つ波長の光を照射すると光触媒機能を発現
する物質のことであり、このような物質として、酸化チ
タン、酸化亜鉛、酸化タングステン、酸化鉄、チタン酸
ストロンチウム、硫化カドミウム、セレン化カドミウム
などの金属化合物半導体粉末が挙げられる。これらのな
かで、酸化チタンが透明性、耐久性に優れ、無害である
ことから最も広く検討が進められている。上記の光触媒
物質に、そのバンドギャップ以上のエネルギーを持つ波
長の光が照射されると、光励起により伝導帯に電子が、
価電子帯に正孔が生成する。光照射で生じたこれらの電
子−正孔対のうち、電子の有する高い還元力、正孔の有
する高い酸化力が、有機物の分解や水の分解などに利用
される。しかしながら、酸化チタンのバンドギャップ以
上のエネルギーを持つ光の波長は、通常、約３８０ｎｍ
以下であり、このため酸化チタンの光触媒作用は紫外域
の光線でしか発現できない。したがって、例えば、太陽
光には５％程度しか紫外線が含まれておらず、実際によ
り効率的にかつ高活性に反応を進行させるためには水銀
ランプのような紫外光照射ができる光源が別途必要であ
った。2. Description of the Related Art A photocatalyst is a substance that exhibits a photocatalytic function when irradiated with light having a wavelength greater than its band gap. Examples of such a substance include titanium oxide, zinc oxide, tungsten oxide, and iron oxide. And metal compound semiconductor powders such as strontium titanate, cadmium sulfide, and cadmium selenide. Among these, titanium oxide has been studied most widely because it is excellent in transparency and durability and is harmless. When the above photocatalytic substance is irradiated with light having a wavelength having energy equal to or larger than the band gap, electrons are excited in the conduction band by photoexcitation,
Holes are generated in the valence band. Among these electron-hole pairs generated by light irradiation, the high reducing power of the electrons and the high oxidizing power of the holes are used for the decomposition of organic substances and the decomposition of water. However, the wavelength of light having energy equal to or greater than the band gap of titanium oxide is usually about 380 nm.
For this reason, the photocatalytic action of titanium oxide can be expressed only by ultraviolet rays. Therefore, for example, sunlight contains only about 5% of ultraviolet light, and a light source capable of irradiating ultraviolet light, such as a mercury lamp, is required separately in order to actually promote the reaction more efficiently and highly active. Met.
【０００３】可視光領域（約４００〜８００ｎｍ）の光
を有効に利用するために、例えば、色素を酸化チタンに
吸着させる研究などが行われている。また、特開平９−
２６２４８２号には、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃ
ｕ、Ｍｎ、Ａｇ、ＰｄおよびＰｔよりなる群から選ばれ
た少なくとも１種の金属イオンが１×１０15イオン／ｇ
−酸化チタン以上の割合で酸化チタンの表面から内部に
含有されている光触媒が開示されている。In order to make effective use of light in the visible light region (about 400 to 800 nm), for example, studies have been made on adsorbing a dye to titanium oxide. Further, Japanese Unexamined Patent Publication No.
No. 262482 includes V, Cr, Fe, Co, Ni, C
at least one metal ion selected from the group consisting of u, Mn, Ag, Pd and Pt is 1 × 10 15 ions / g
-Disclosed is a photocatalyst which is contained from the surface to the inside of titanium oxide in a proportion of titanium oxide or more.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、色素を
吸着させた酸化チタンは、色素の寿命に問題があること
や、可視光の吸収が不十分であること等から、定常的な
光触媒反応は困難であったり、光触媒性能の向上が不十
分であった。また、特開平９−２６２４８２号に記載の
光触媒は、可視光の吸収が十分で好ましい光触媒である
が、特開平９−２６２４８２号に具体的に開示されてい
るのは粉末状のものであって、粉末での使用には限界が
あり、実用的形態ではない。However, it is difficult for titanium oxide to which a dye is adsorbed to have a steady photocatalytic reaction due to a problem with the life of the dye and insufficient absorption of visible light. And the improvement of the photocatalytic performance was insufficient. Further, the photocatalyst described in JP-A-9-262482 is a preferable photocatalyst with sufficient absorption of visible light, but what is specifically disclosed in JP-A-9-262482 is a powdery one. However, its use in powder is limited and not practical.
【０００５】本発明者はかかる事情に鑑み、可視光領域
の光を有効に利用でき、実用的な形態の光触媒について
鋭意検討した結果、特定の金属イオンを注入した酸化チ
タンを樹脂基材に付与することによって本発明を完成す
るに至った。In view of such circumstances, the present inventors have made intensive studies on photocatalysts that can effectively utilize light in the visible light range and are in a practical form. As a result, titanium oxide implanted with specific metal ions is applied to a resin base material. As a result, the present invention has been completed.
【０００６】[0006]
【課題を解決するための手段】すなわち本発明は、Ｖ、
Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｎ、Ａｇ、Ｐｄおよ
びＰｔよりなる群から選ばれた少なくとも１種の金属イ
オンが注入された酸化チタンを有する光触媒機能を有す
る樹脂基材、およびこの樹脂基材からなる照明カバー、
防音板、自動販売機前面板、看板、水槽、標識・表示体
である。That is, the present invention provides V,
Resin base material having photocatalytic function and having titanium oxide into which at least one metal ion selected from the group consisting of Cr, Fe, Co, Ni, Cu, Mn, Ag, Pd and Pt has been implanted, and the resin base Lighting cover made of wood,
Soundproof board, vending machine front board, signboard, aquarium, signage / display.
【０００７】[0007]
【発明の実施の形態】本発明で酸化チタンに注入される
金属イオンとしては、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃ
ｕ、Ｍｎ、Ａｇ、ＰｄおよびＰｔよりなる群から選ばれ
た少なくとも１種の金属イオンであり、好ましくはＶ、
Ｃｒ、Ｆｅ、Ｎｉ、Ｍｎ、更に好ましくはＶ、Ｃｒであ
る。これら金属イオンの電荷は特に制限されるものでは
ないが、通常、注入前の金属イオンが加速した状態では
１価で存在することが多い。なお注入後の金属イオン
は、通常、酸化チタン中で１〜５価で存在する。DETAILED DESCRIPTION OF THE INVENTION The metal ions implanted into titanium oxide in the present invention include V, Cr, Fe, Co, Ni, C
at least one metal ion selected from the group consisting of u, Mn, Ag, Pd and Pt;
Cr, Fe, Ni, Mn, and more preferably V, Cr. The charge of these metal ions is not particularly limited, but usually, the metal ions before injection often exist in a monovalent state in an accelerated state. Note that the metal ions after the implantation usually exist in the titanium oxide at a valence of 1 to 5.
【０００８】本発明における樹脂基材としては、アクリ
ル樹脂、カーボネート樹脂、ポリオレフィン、塩化ビニ
ル樹脂、ポリエステル、ポリアミド、ポリエーテルなど
特に限定されるものではないが、紫外光から可視光の波
長領域を含む光に対し透光性を有する基材が好ましい。
この基材を用いることによって、基材上に作製された酸
化チタン膜または酸化チタン含有膜で行われる光触媒反
応が、直接基材に照射される紫外光から可視光の波長領
域を含む光のみならず、樹脂基材を透過してくる紫外光
から可視光の波長領域を含む光により行われる。The resin substrate in the present invention is not particularly limited, such as an acrylic resin, a carbonate resin, a polyolefin, a vinyl chloride resin, a polyester, a polyamide and a polyether, but includes a wavelength region from ultraviolet light to visible light. A substrate having a property of transmitting light is preferable.
By using this substrate, if the photocatalytic reaction performed on the titanium oxide film or titanium oxide-containing film produced on the substrate is only light that includes the wavelength region from ultraviolet light to visible light that is directly applied to the substrate Instead, it is performed by light including a wavelength region from ultraviolet light to visible light transmitted through the resin base material.
【０００９】紫外光から可視光の波長領域を含む光に対
して透光性を有する樹脂基材としては、アクリル樹脂や
カーボネート系樹脂が挙げられる。アクリル樹脂が紫外
光から可視光の広い波長領域において高い透過性を有す
ることから、特に好ましい。[0009] Examples of the resin base material having a light transmitting property with respect to light including a wavelength range from ultraviolet light to visible light include acrylic resins and carbonate resins. Acrylic resin is particularly preferable because it has high transmittance in a wide wavelength range from ultraviolet light to visible light.
【００１０】本発明における光触媒機能を有する樹脂基
材として、上記の金属イオンが注入された酸化チタンよ
りなる酸化チタン膜あるいはこの酸化チタン含有膜が樹
脂基材上に形成されたものや、上記の金属イオンが注入
された酸化チタンが混練等により樹脂基材中に含有して
いるものが挙げられる。予め酸化チタンに金属イオンを
注入したものを、樹脂基材上に膜状に形成、または樹脂
基材中に含有させても良いし、酸化チタンを樹脂基材上
に膜状に形成、または樹脂基材中に含有させたものに金
属イオンを注入しても良い。As the resin base material having a photocatalytic function in the present invention, a titanium oxide film made of titanium oxide into which the above-mentioned metal ions have been implanted, or a titanium oxide film containing this titanium oxide formed on a resin base material; One in which titanium oxide into which metal ions are implanted is contained in a resin base material by kneading or the like. Titanium oxide in which metal ions have been implanted in advance may be formed in a film on a resin substrate, or may be contained in a resin substrate, or titanium oxide may be formed in a film on a resin substrate, or a resin. Metal ions may be implanted into those contained in the base material.
【００１１】酸化チタンまたは酸化チタンを有する樹脂
基材への金属イオンの注入は、金属イオンを３０ｅＶ以
上の高エネルギーに加速して、照射することによって行
われる。The implantation of metal ions into titanium oxide or a resin substrate having titanium oxide is performed by irradiating the metal ions with accelerated high energy of 30 eV or more.
【００１２】金属イオンを３０ｋｅＶ以上の高エネルギ
ーに加速する方法としては、例えば、イオン注入装置を
用いる方法が挙げられる。イオン注入装置としては半導
体分野で不純物のドーピングに使用されているような市
販の装置等を用いることができる。酸化チタンに注入さ
れる金属イオンのエネルギーは、３０ｋｅＶ以上である
が、好ましくは５０〜４００ｋｅＶ、さらに好ましくは
１００〜２００ｋｅＶである。As a method for accelerating the metal ions to a high energy of 30 keV or more, for example, a method using an ion implantation apparatus can be mentioned. As the ion implantation apparatus, a commercially available apparatus used for doping impurities in the semiconductor field can be used. The energy of the metal ions implanted into the titanium oxide is 30 keV or more, preferably 50 to 400 keV, and more preferably 100 to 200 keV.
【００１３】酸化チタンへの金属イオンの注入量は少な
くとも１×１０15イオン／ｇ−酸化チタンである。金属
イオンの注入量の単位は、酸化チタン１ｇ当たりの金属
イオンの数で表され、金属イオンの注入量が１×１０15
イオン／ｇ−酸化チタン未満であると可視光領域の光を
吸収し光触媒活性発現する効果が得られない。金属イオ
ンの注入量の上限は特に制限はないが、金属イオンの注
入量が１×１０2 1 イオン／ｇ−酸化チタンを超えると
可視光領域の光を吸収し光触媒活性が発現する効果が得
られないことがあるので好ましくない。金属イオンの注
入量の好ましい範囲は金属イオンの種類により異なる
が、通常、１×１０16〜５×１０18イオン／ｇ−酸化チ
タン、好ましくは１×１０16〜５×１０17イオン／ｇ−
酸化チタンの範囲である。The amount of metal ions implanted into titanium oxide is at least 1 × 10 15 ions / g-titanium oxide. The unit of the metal ion implantation amount is represented by the number of metal ions per gram of titanium oxide, and the metal ion implantation amount is 1 × 10 15
If it is less than ion / g-titanium oxide, the effect of absorbing light in the visible light region and exhibiting photocatalytic activity cannot be obtained. Although there is no particular upper limit on the injection amount of the metal ions, resulting an effect of expression absorbed photocatalytic activity with light in the visible light region when the injection amount of the metal ions is more than 1 × 10 2 1 Ion / g- titanium oxide This is not preferred because it may not be possible. The preferred range of the amount of metal ions to be implanted varies depending on the type of metal ions, but is usually 1 × 10 16 to 5 × 10 18 ions / g-titanium oxide, preferably 1 × 10 16 to 5 × 10 17 ions / g-.
It is in the range of titanium oxide.
【００１４】酸化チタンに注入された金属イオンは、酸
化チタンの表面に存在してもよいが、酸化チタンの内部
に大部分が存在することが好ましく、金属イオンの９０
％以上、好ましくは金属イオンの９５％以上、さらに好
ましくはが９９％以上が酸化チタンの内部に存在するこ
とが好ましい。また、酸化チタンの内部に分散された金
属イオンは均一に分散されていることが好ましい。The metal ions implanted into the titanium oxide may be present on the surface of the titanium oxide, but it is preferable that most of the metal ions exist inside the titanium oxide.
% Or more, preferably 95% or more, more preferably 99% or more of the metal ions are present inside the titanium oxide. Further, it is preferable that the metal ions dispersed in the titanium oxide are uniformly dispersed.
【００１５】酸化チタンの結晶形は特に制限されず、ア
ナターゼ型、ルチル型、その他種々のタイプのものを用
いることができるが、アナターゼ型を含むものが好まし
い。また、酸化チタンとしては、一般的にはＴｉＯ2 が
好ましく用いられるが、チタン以外の金属とチタンとの
複合酸化物を用いることも可能である。The crystal form of titanium oxide is not particularly limited, and anatase type, rutile type and other various types can be used, but those containing anatase type are preferred. In general, TiO 2 is preferably used as titanium oxide, but it is also possible to use a composite oxide of a metal other than titanium and titanium.
【００１６】金属イオンが注入された酸化チタンを、樹
脂基材上に膜状に存在させる方法としては、金属イオン
が注入された酸化チタンを単独あるいは有機系や無機系
のバインダーと混合して溶剤に分散させたものを樹脂基
材表面にコーティングする方法、転写による方法、反応
性スパッタリングによる方法、蒸着による方法、粉体塗
装による方法、イオンクラスタービーム法、ゾル−ゲル
法などが挙げられるが、特に限定されない。As a method for allowing the titanium oxide into which metal ions have been implanted to be present in a film form on a resin base material, titanium oxide into which metal ions have been implanted is used alone or mixed with an organic or inorganic binder to form a solvent. A method of coating the resin substrate surface with the one dispersed therein, a method by transfer, a method by reactive sputtering, a method by vapor deposition, a method by powder coating, an ion cluster beam method, a sol-gel method, and the like. There is no particular limitation.
【００１７】酸化チタン膜の膜厚は特に制限はないが、
金属イオンを注入する際に、注入した金属イオンが通り
抜けない程度の５００Å〜１０００００Å程度の厚さが
好ましい。また、酸化チタン膜表面は、実用状平滑性が
高い方が埃などが付着しにくく好ましい。Although the thickness of the titanium oxide film is not particularly limited,
When metal ions are implanted, the thickness is preferably about 500 to 100,000 such that the implanted metal ions do not pass through. In addition, it is preferable that the surface of the titanium oxide film has high practical smoothness since dust and the like are less likely to adhere thereto.
【００１８】また、金属イオンが注入された酸化チタン
を樹脂基材中に練り込む方法としては、樹脂基材の原料
となるパウダー状やペレット状の樹脂成形材料と金属イ
オンが注入された酸化チタンをあらかじめ混合しておい
た後、押出成形や射出成形等により樹脂基材を得る方
法、樹脂成形材料を溶剤に溶解させた溶液に金属イオン
が注入された酸化チタンを分散させた後に得られた溶液
を溶剤キャスト方法により膜状の樹脂基材を得る方法、
金属イオンが注入された粉末を直接樹脂基材上に存在さ
せ熱圧着等により固定化させる方法などが挙げられる
が、特に限定されない。As a method of kneading the metal oxide-implanted titanium oxide into the resin base material, a powder-like or pellet-like resin molding material as a raw material of the resin base material and the titanium oxide-implanted metal oxide are used. After pre-mixing, a method of obtaining a resin base material by extrusion molding or injection molding, etc., obtained after dispersing titanium oxide in which metal ions are injected into a solution obtained by dissolving a resin molding material in a solvent A method of obtaining a film-like resin base material by a solvent casting method of the solution,
A method in which the metal ion-implanted powder is directly present on the resin base material and immobilized by thermocompression bonding or the like is exemplified, but is not particularly limited.
【００１９】酸化チタン膜または酸化チタン含有膜に金
属イオンを注入する場合、その注入量は、１ｃｍ2 あた
り １×１０14〜１×１０19イオン、好ましくは１×１
０16〜１×１０17イオンである。金属イオンの注入量が
少なすぎると、可視光領域の光を吸収して光触媒活性を
発現する効果が少なくなり、逆に多すぎると光触媒活性
を発現する効果が得られないことがあるので好ましくな
い。When metal ions are implanted into a titanium oxide film or a titanium oxide-containing film, the amount of implantation is 1 × 10 14 to 1 × 10 19 ions per cm 2 , preferably 1 × 1 19 ions.
0 16 to 1 × 10 17 ions. If the injection amount of the metal ions is too small, the effect of absorbing the light in the visible light region and exhibiting the photocatalytic activity decreases, and if too large, the effect of expressing the photocatalytic activity may not be obtained, which is not preferable. .
【００２０】本発明の光触媒機能を有する樹脂基材を用
いた光触媒反応においては、紫外光から可視光領域の波
長領域を含む光を照射して行うことができる。すなわち
本発明の樹脂基材では、これまで不可能とされてきた可
視光領域（約４００〜８００ｎｍ）の光の吸収が起こる
ことから、紫外光のみならず可視光領域の光によっても
光触媒反応が可能となる。照射される光としては、紫外
光のみでもよく、また可視光のみでもよく、特定の波長
の光でもよい。また、この範囲外の光、例えば、赤外光
や遠紫外光が含まれていてもよいが、２５０〜５００ｎ
ｍの範囲の光を多く含んでいる光を照射することが好ま
しい。The photocatalytic reaction using the resin base material having a photocatalytic function of the present invention can be performed by irradiating light having a wavelength range from ultraviolet light to visible light. That is, in the resin substrate of the present invention, light absorption in the visible light region (about 400 to 800 nm), which has been impossible so far, occurs, so that the photocatalytic reaction is caused not only by ultraviolet light but also by light in the visible light region. It becomes possible. Irradiation light may be only ultraviolet light, only visible light, or light of a specific wavelength. Further, light outside this range, for example, infrared light or far ultraviolet light may be included, but 250 to 500 n
It is preferable to irradiate light containing much light in the range of m.
【００２１】本発明の光触媒機能を有する樹脂基材は、
種々の形状で、種々の用途に用いられる。例えば、樹脂
製ガラス、ヘルメットのシールド、建材、ゴーグル、陳
列ケース、浴槽、洗面台、照明カバー、防音板、自動販
売機前面板、看板、水槽、標識・標示体などが挙げられ
る。The resin substrate having a photocatalytic function of the present invention comprises:
Used in various applications in various shapes. For example, resin glass, helmet shields, building materials, goggles, display cases, bathtubs, washstands, lighting covers, soundproofing boards, vending machine front panels, signboards, aquariums, signs / signs, and the like.
【００２２】特に、樹脂基材が紫外光から可視光の波長
領域を含む光に対して透光性の場合に、基材の両面から
の光を利用できることから、照明カバー、防音板、自動
販売機前面板、看板、水槽、標識・標示体に用いると光
触媒反応が効率的に進み、好ましい。In particular, when the resin base material is transparent to light including the wavelength range from ultraviolet light to visible light, light from both sides of the base material can be used. It is preferable to use it for a front panel, a signboard, a water tank, and a sign / marker because the photocatalytic reaction proceeds efficiently.
【００２３】本発明の光触媒機能を有する樹脂基材は種
々の光触媒反応に用いることができる。例えば、窒素酸
化物の存在下に紫外光から可視光の波長領域を含む光を
本発明の樹脂基材に照射することによる窒素酸化物の分
解反応が挙げられる。この反応を利用すれば、各種の燃
焼期間より排出された人体に悪影響を及ぼす窒素酸化物
の効率的な除去にも本発明の樹脂基材は適用できる可能
性がある。建造物、道路用の防音板、道路周辺の標識・
標示体などに本発明の樹脂基材を適用すれば、太陽光あ
るいは電灯などの人工光源による光を照射することで、
大気中の窒素酸化物を分解除去して無害化する試みにも
適用可能である。The resin substrate having a photocatalytic function of the present invention can be used for various photocatalytic reactions. For example, there is a decomposition reaction of nitrogen oxide by irradiating the resin base material of the present invention with light including a wavelength region from ultraviolet light to visible light in the presence of nitrogen oxide. If this reaction is utilized, the resin substrate of the present invention may be applicable to the efficient removal of nitrogen oxides that have a bad effect on the human body discharged from various combustion periods. Buildings, soundproofing boards for roads, signs around roads
If the resin substrate of the present invention is applied to a sign or the like, by irradiating light from an artificial light source such as sunlight or an electric light,
The present invention is also applicable to an attempt to detoxify and remove nitrogen oxides in the atmosphere.
【００２４】また、水中有機物の存在下に紫外光から可
視光の波長領域を含む光を本発明の樹脂基材に照射する
ことによる、有機物の分解が挙げられる。この反応を用
いれば、水中に混入する有害有機物の効率的な除去に本
発明の樹脂基材を適用可能である。本発明の樹脂基材を
用いた水槽などに、太陽光あるいは電灯などの人工光源
による光を照射することで、水中の有害有機物を分解除
去して無害化するという利用形態が考えられる。この場
合、本発明の樹脂基材は光触媒性能を有する酸化チタン
が樹脂に固定化されていることから、光触媒酸化チタン
粉体を用いた懸濁反応に比べ反応後に触媒を水から分離
する必要がなく好ましい。さらに本発明の樹脂基材は可
視光での光触媒反応が可能なため、可視光領域で透過性
を有する基材であれば紫外光を吸収しやすいものでも使
用することが可能になる。Further, the decomposition of an organic substance can be mentioned by irradiating the resin substrate of the present invention with light containing a wavelength range from ultraviolet light to visible light in the presence of an organic substance in water. If this reaction is used, the resin substrate of the present invention can be applied to efficient removal of harmful organic substances mixed in water. A water tank or the like using the resin substrate of the present invention may be illuminated with sunlight or an artificial light source such as an electric light to decompose and remove harmful organic substances in water to make the water harmless. In this case, since the titanium oxide having photocatalytic performance is immobilized on the resin in the resin substrate of the present invention, it is necessary to separate the catalyst from water after the reaction as compared with the suspension reaction using the titanium oxide photocatalyst powder. Preferred. Further, since the resin substrate of the present invention is capable of performing a photocatalytic reaction with visible light, it is possible to use a substrate that is transparent in the visible light region and that can easily absorb ultraviolet light.
【００２５】本発明のその他の光触媒反応としては、例
えば、アルケンの光異性化反応、プロピレンと水からの
エタンやメタン生成のようなアルケン・アルキンの水に
よる光水素化分解反応、一酸化炭素と水から水素と二酸
化炭素を生成する光水性ガスシフト反応などが挙げられ
る。また、屋外・屋内を問わず、樹脂基材に付着した有
機物汚れの分解除去、悪臭物質の分解除去、基材に発生
する菌に対する抗菌・殺菌作用など、種々の光触媒反応
も挙げられる。Other photocatalytic reactions of the present invention include, for example, photoisomerization of alkenes, photohydrogenolysis of alkenes and alkynes with water, such as ethane and methane from propylene and water, and carbon monoxide. A photo-water gas shift reaction that generates hydrogen and carbon dioxide from water is exemplified. In addition, various photocatalytic reactions, such as decomposition and removal of organic contaminants adhering to the resin substrate, decomposition and removal of odorous substances, and antibacterial and bactericidal actions against bacteria generated on the substrate, both outdoors and indoors, may be mentioned.
【００２６】本発明の光触媒反応は常温で行うことがで
きるが、それに限定されず各々の光触媒反応に応じて温
度を設定することができる。通常、０〜２００℃の間で
反応は実施される。The photocatalytic reaction of the present invention can be carried out at room temperature, but is not limited thereto, and the temperature can be set according to each photocatalytic reaction. Usually, the reaction is carried out between 0 and 200 ° C.
【００２７】[0027]
【発明の効果】本発明の光触媒機能を有する樹脂基材
は、光触媒反応に可視光領域の光を利用可能であり、実
用的な形態であり、種々の用途に容易に利用できる。The resin substrate having a photocatalytic function of the present invention can utilize light in the visible light range for photocatalytic reactions, is in a practical form, and can be easily used for various purposes.
【００２８】[0028]
【実施例】以下、実施例によって本発明を更に詳しく説
明するが、本発明はこれら実施例によってなんら制限さ
れるものではない。 実施例１ ７×１０16イオン／ｇ−酸化チタンのＶイオンが注入さ
れた酸化チタン粉末とメタクリル樹脂粉末を混合して得
られるイオン注入酸化チタンが混入されたメタクリル樹
脂基材を、ＮＯｘ雰囲気中に置き、可視光照射下、ＮＯ
ｘの減量を測定すれば、非照射時でほとんど認められな
いＮＯｘの減量が、照射時には認められる。この樹脂基
材は容易に成形でき、照明カバー、防音板などに利用で
きる。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Example 1 A methacrylic resin base material mixed with ion-implanted titanium oxide obtained by mixing titanium oxide powder into which V ions of 7 × 10 16 ions / g-titanium oxide were injected and methacrylic resin powder was mixed in a NOx atmosphere. Under visible light irradiation, NO
When the weight loss of x is measured, the weight loss of NOx which is hardly observed in non-irradiation is observed in irradiation. This resin substrate can be easily formed and can be used for a lighting cover, a soundproof plate, and the like.
【００２９】実施例２ メタクリル樹脂板上に形成された酸化チタン膜に６×１
０16イオン／ｃｍ2 のＣｒイオンが注入された樹脂基材
を、ＮＯｘ雰囲気中に置き、可視光照射下、ＮＯｘの減
量を測定すれば、非照射時でほとんど認められないＮＯ
ｘの減量が、照射時には認められる。この樹脂基板は照
明カバーや防音板などに使用できる。Example 2 A 6 × 1 titanium oxide film formed on a methacrylic resin plate
When the resin substrate into which the Cr ions of 0 16 ions / cm 2 were implanted was placed in an NOx atmosphere and the NOx loss was measured under visible light irradiation, NO
A decrease in x is observed at the time of irradiation. This resin substrate can be used for a lighting cover, a soundproof plate, and the like.
【００３０】比較例１ 金属イオンが注入されていない酸化チタン粉末とメタク
リル樹脂粉末を混合して得られる酸化チタンが混入され
たメタクリル樹脂基材を、ＮＯｘ雰囲気中に置き、可視
光照射下、ＮＯｘの減量を測定しても、ＮＯｘ減量はほ
とんど認められない。Comparative Example 1 A methacrylic resin base material mixed with titanium oxide obtained by mixing a titanium oxide powder into which metal ions had not been implanted and a methacrylic resin powder was placed in a NOx atmosphere, and irradiated with NOx under visible light irradiation. Even when NOx loss was measured, NOx loss was hardly recognized.
【００３１】比較例２ メタクリル樹脂板上に酸化チタン膜（金属イオンは注入
されていない）が存在する樹脂基材を、ＮＯｘ雰囲気中
に置き、可視光照射下、ＮＯｘの減量を測定しても、Ｎ
Ｏｘ減量はほとんど認められない。Comparative Example 2 A resin substrate having a titanium oxide film (without metal ions implanted) on a methacrylic resin plate was placed in a NOx atmosphere, and the NOx loss was measured under visible light irradiation. , N
Ox weight loss is hardly observed.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 101/00 Ｆ２１Ｖ 1/14 Ｚ Ｆ２１Ｖ 1/14 Ｂ０１Ｄ 53/36 ＺＡＢＪ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 101/00 F21V 1/14 Z F21V 1/14 B01D 53/36 ZABJ
Claims (14)
ｎ、Ａｇ、ＰｄおよびＰｔよりなる群から選ばれた少な
くとも１種の金属イオンが注入された酸化チタンを有す
る光触媒機能を有する樹脂基材。1. V, Cr, Fe, Co, Ni, Cu, M
A resin base material having a photocatalytic function comprising titanium oxide into which at least one metal ion selected from the group consisting of n, Ag, Pd and Pt has been implanted.
ｎ、Ａｇ、ＰｄおよびＰｔよりなる群から選ばれた少な
くとも１種の金属イオンが注入された酸化チタン被膜ま
たは含有被膜を表面に有する光触媒機能を有する樹脂基
材。2. V, Cr, Fe, Co, Ni, Cu, M
A resin substrate having a photocatalytic function having a surface on which a titanium oxide coating or a coating containing at least one metal ion selected from the group consisting of n, Ag, Pd and Pt is implanted.
ｎ、Ａｇ、ＰｄおよびＰｔよりなる群から選ばれた少な
くとも１種の金属イオンが注入された酸化チタンを基材
内部に有する光触媒機能を有する樹脂基材。3. V, Cr, Fe, Co, Ni, Cu, M
A resin base material having a photocatalytic function and having therein titanium oxide into which at least one metal ion selected from the group consisting of n, Ag, Pd and Pt has been implanted.
くとも１×１０15イオン／ｇ−酸化チタンである請求項
１、２、または３記載の光触媒機能を有する樹脂基材。4. The resin base material having a photocatalytic function according to claim 1, wherein the amount of metal ions implanted into the titanium oxide is at least 1 × 10 15 ions / g-titanium oxide.
ｒ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｎ、Ａｇ、Ｐｄおよび
Ｐｔよりなる群から選ばれた少なくとも１種の金属イオ
ンを注入してなる請求項１、２、または３記載の光触媒
機能を有する樹脂基材。5. A method according to claim 1, wherein the resin substrate having titanium oxide in advance has V, C
4. The resin having a photocatalytic function according to claim 1, wherein at least one metal ion selected from the group consisting of r, Fe, Co, Ni, Cu, Mn, Ag, Pd and Pt is implanted. Base material.
の金属イオンの注入量が、１ｃｍ2あたり１×１０14〜
１×１０19イオンである請求項２記載の光触媒機能を有
する樹脂基材。6. The amount of metal ions implanted into a titanium oxide film or a titanium oxide-containing film is 1 × 10 14 / cm 2 or less.
3. The resin base material having a photocatalytic function according to claim 2, which has 1 × 10 19 ions.
ーに加速した後に、酸化チタンあるいは酸化チタン膜ま
たは酸化チタン含有膜に照射し、金属イオンを注入する
ことを特徴とする請求項１記載の光触媒機能を有する樹
脂基材の製造方法。7. The photocatalytic function according to claim 1, wherein after the metal ions are accelerated to a high energy of 30 keV or more, the titanium oxide, the titanium oxide film or the titanium oxide-containing film is irradiated to implant the metal ions. A method for producing a resin substrate having:
の樹脂基材の存在下、紫外光から可視光の波長領域を含
む光を照射して行うことを特徴とする光触媒反応方法。8. A photocatalytic reaction carried out by irradiating light containing a wavelength region from ultraviolet light to visible light in the presence of the resin substrate according to any one of claims 1 to 7. Method.
の光触媒機能を有する樹脂基材からなり、紫外光から可
視光の波長領域を含む光に対して透光性を有する照明カ
バー。9. An illumination comprising the resin base material having a photocatalytic function according to any one of claims 1 to 7, and having a property of transmitting light including a wavelength region from ultraviolet light to visible light. cover.
載の光触媒機能を有する樹脂基材からなり、紫外光から
可視光の波長領域を含む光に対して透光性を有する防音
板。10. A soundproof comprising the resin base material having a photocatalytic function according to any one of claims 1 to 7 and having a light transmitting property with respect to light including a wavelength region from ultraviolet light to visible light. Board.
載の光触媒機能を有する樹脂基材からなり、紫外光から
可視光の波長領域を含む光に対して透光性を有する自動
販売機前面板。11. An automatic material comprising the resin base material having a photocatalytic function according to any one of claims 1 to 7 and having a light transmitting property with respect to light including a wavelength region from ultraviolet light to visible light. Vending machine front panel.
載の光触媒機能を有する樹脂基材からなり、紫外光から
可視光の波長領域を含む光に対して透光性を有する看
板。12. A signboard comprising the resin base material having a photocatalytic function according to any one of claims 1 to 7, and having a light-transmitting property with respect to light including a wavelength region from ultraviolet light to visible light. .
載の光触媒機能を有する樹脂基材からなり、紫外光から
可視光の波長領域を含む光に対して透光性を有する水
槽。13. A water tank comprising the resin base material having a photocatalytic function according to any one of claims 1 to 7, and having a light transmitting property with respect to light including a wavelength region from ultraviolet light to visible light. .
載の光触媒機能を有する樹脂基材からなり、紫外光から
可視光の波長領域を含む光に対して透光性を有する標識
・標示体。14. A label comprising the resin base material having a photocatalytic function according to any one of claims 1 to 7, and having a light-transmitting property with respect to light including a wavelength region from ultraviolet light to visible light. -Sign object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10083534A JPH11279299A (en) | 1998-03-30 | 1998-03-30 | Resin substrate having photocatalytic function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10083534A JPH11279299A (en) | 1998-03-30 | 1998-03-30 | Resin substrate having photocatalytic function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11279299A true JPH11279299A (en) | 1999-10-12 |
Family
ID=13805176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10083534A Pending JPH11279299A (en) | 1998-03-30 | 1998-03-30 | Resin substrate having photocatalytic function |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11279299A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1036593A1 (en) * | 1999-03-16 | 2000-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Titanium dioxide photocatalyst with Fe3+ ions added thereon |
| EP1147812A1 (en) * | 2000-04-21 | 2001-10-24 | Showa Denko Kabushiki Kaisha | Photocatalytic powder, photocatalytic slurry, and polymer composition, coating agent, photocatalytic functional molded article and photocatalytic functional structure using the powder |
| JP2002136878A (en) * | 2000-10-31 | 2002-05-14 | Japan Atom Energy Res Inst | Nonmetallic impurity-added photocatalytic material and its manufacturing method |
| US6683023B2 (en) | 2000-04-21 | 2004-01-27 | Showa Denko K.K. | Photocatalytic powder and polymer composition |
| JP2013150989A (en) * | 2009-01-20 | 2013-08-08 | Shin-Etsu Chemical Co Ltd | Photocatalyst coating solution excellent in response to visible light |
| CN104492432A (en) * | 2014-12-13 | 2015-04-08 | 济南大学 | Hollow bimetal nanoparticle/titanium dioxide core-shell structure, and preparation method and application thereof |
| CN107917351A (en) * | 2017-10-27 | 2018-04-17 | 中山市汉庭照明科技有限公司 | A kind of LED light bulbs and preparation method having except effect of formaldehyde |
-
1998
- 1998-03-30 JP JP10083534A patent/JPH11279299A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1036593A1 (en) * | 1999-03-16 | 2000-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Titanium dioxide photocatalyst with Fe3+ ions added thereon |
| EP1147812A1 (en) * | 2000-04-21 | 2001-10-24 | Showa Denko Kabushiki Kaisha | Photocatalytic powder, photocatalytic slurry, and polymer composition, coating agent, photocatalytic functional molded article and photocatalytic functional structure using the powder |
| US6683023B2 (en) | 2000-04-21 | 2004-01-27 | Showa Denko K.K. | Photocatalytic powder and polymer composition |
| US7335620B2 (en) | 2000-04-21 | 2008-02-26 | Showa Denko K.K. | Photocatalytic powder, photocatalytic slurry, and polymer composition, coating agent, photocatalytic functional molded article and photocatalytic functional structure using the powder |
| JP2002136878A (en) * | 2000-10-31 | 2002-05-14 | Japan Atom Energy Res Inst | Nonmetallic impurity-added photocatalytic material and its manufacturing method |
| JP2013150989A (en) * | 2009-01-20 | 2013-08-08 | Shin-Etsu Chemical Co Ltd | Photocatalyst coating solution excellent in response to visible light |
| CN104492432A (en) * | 2014-12-13 | 2015-04-08 | 济南大学 | Hollow bimetal nanoparticle/titanium dioxide core-shell structure, and preparation method and application thereof |
| CN107917351A (en) * | 2017-10-27 | 2018-04-17 | 中山市汉庭照明科技有限公司 | A kind of LED light bulbs and preparation method having except effect of formaldehyde |
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