JP2017119273A - Photocatalyst layer-coated aluminum material and manufacturing method therefor - Google Patents
Photocatalyst layer-coated aluminum material and manufacturing method therefor Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 228
- 239000000463 material Substances 0.000 title claims abstract description 222
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 220
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 63
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims description 51
- 238000000576 coating method Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 abstract description 28
- 239000000758 substrate Substances 0.000 abstract description 19
- 238000005530 etching Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 30
- 229940091250 magnesium supplement Drugs 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 26
- 239000010408 film Substances 0.000 description 19
- 239000002585 base Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 238000009616 inductively coupled plasma Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000004611 spectroscopical analysis Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 229910002012 Aerosil® Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000001784 detoxification Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 229960000869 magnesium oxide Drugs 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 235000012245 magnesium oxide Nutrition 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002233 thin-film X-ray diffraction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、アルミニウム材の片面又は両面に光触媒活性を有する光触媒層が形成された光触媒層被覆アルミニウム材及びその製造方法に関する。 The present invention relates to a photocatalyst layer-covered aluminum material in which a photocatalyst layer having photocatalytic activity is formed on one surface or both surfaces of an aluminum material, and a method for producing the same.
酸化チタン、酸化亜鉛、酸化ジルコニウム、酸化タングステン等の金属酸化物に代表される光触媒は、そのバンドギャップより大きいエネルギーを持つ光を照射すると、光触媒活性を発現し、その強い酸化還元作用によって、大気中、水中等に含まれる有害物質の分解又は無害化、生活空間における防臭、防汚、殺菌等のさまざまな環境浄化用途に利用できることが知られている。 Photocatalysts typified by metal oxides such as titanium oxide, zinc oxide, zirconium oxide and tungsten oxide exhibit photocatalytic activity when irradiated with light having energy larger than the band gap, and due to their strong redox action, It is known that it can be used for various environmental purification applications such as decomposition or detoxification of harmful substances contained in water and the like, deodorization, antifouling, and sterilization in living spaces.
なお、実際に環境浄化用途に利用される際には、光触媒活性を発現する部分の表面積が大きいことが望ましいため、光触媒活性を高める目的で光触媒活性を有する金属酸化物を基材表面に薄膜状に固定化して用いられることが多い。 In addition, since it is desirable that the surface area of the portion that exhibits photocatalytic activity is large when actually used for environmental purification applications, a metal oxide having photocatalytic activity is formed into a thin film on the substrate surface for the purpose of enhancing photocatalytic activity. In many cases, it is used by immobilizing it.
例えば、特許文献１には、透光性基材の表面に光触媒を含有する層が形成され、波長３４０ｎｍの光線透過率が１０％以上である透光性光触媒体が開示されており、具体的にはメタクリル系樹脂、ポリカーボネート系樹脂等の樹脂系基材やガラス、合わせガラス等のガラス系基材などの透明性基材の表面に光触媒を含有する層が形成されている。 For example, Patent Document 1 discloses a translucent photocatalyst having a layer containing a photocatalyst formed on the surface of a translucent substrate and having a light transmittance of 10% or more at a wavelength of 340 nm. A layer containing a photocatalyst is formed on the surface of a transparent base material such as a resin base material such as methacrylic resin or polycarbonate resin, or a glass base material such as glass or laminated glass.
また、特許文献２には、チタン含有金属材料からなる基材の表面に、陽極酸化膜及び酸化チタン粉体含有薄膜を順次積層した光触媒活性を有する金属材料が開示されている。 Patent Document 2 discloses a metal material having a photocatalytic activity in which an anodized film and a titanium oxide powder-containing thin film are sequentially laminated on the surface of a substrate made of a titanium-containing metal material.
更に、特許文献３には、金属基材（アルミニウム基材など）の表面を酸又はアルカリでエッチング処理した後、上記金属基材を硫酸チタニル水溶液又は硫酸チタン水溶液中に浸漬しながら上記硫酸チタニル又は硫酸チタンを加水分解して金属基材の表面に高固着性の酸化チタン系光触媒層を形成することにより、金属基材の表面に高固着性の酸化チタン系光触媒を担持させたことを特徴とする光触媒担持物が開示されている。 Further, in Patent Document 3, after etching the surface of a metal substrate (such as an aluminum substrate) with an acid or alkali, the above-mentioned titanyl sulfate or the above-mentioned metal substrate is immersed in a titanyl sulfate aqueous solution or a titanium sulfate aqueous solution. It is characterized in that titanium sulfate photocatalyst layer with high adhesion is formed on the surface of metal substrate by hydrolyzing titanium sulfate, thereby supporting titanium oxide photocatalyst with high adhesion on the surface of metal substrate. A photocatalyst support is disclosed.
しかしながら、特許文献１〜３などの従来技術には次のような問題がある。 However, the conventional techniques such as Patent Documents 1 to 3 have the following problems.
特許文献１には樹脂系基材やガラス系基材を用いることが提案されているが、樹脂系基材を用いる場合には耐熱性の問題で高温での熱処理ができないため、金属酸化物の基材への固定方法に制限がある。また、ガラス系基材を用いる場合には基材に柔軟性が無いため、ロール状の基材を引き出しながら連続的に金属酸化物を固定するような効率的な処理ができない点で生産性や加工性に問題がある。 Patent Document 1 proposes to use a resin-based substrate or a glass-based substrate. However, when a resin-based substrate is used, heat treatment cannot be performed at a high temperature due to a problem of heat resistance. There are limitations on the method of fixing to the substrate. In addition, when a glass-based substrate is used, since the substrate is not flexible, the productivity and the point that it is not possible to perform an efficient treatment such as fixing a metal oxide continuously while pulling out a roll-shaped substrate. There is a problem in workability.
特許文献２にはチタン含有金属材料からなる基材を用いてこれに陽極酸化膜及び酸化チタン含有薄膜を順次積層することが提案されているが、チタン含有基材が高価であることや複数回の積層工程が必要であるためコストや生産性に問題がある。 Patent Document 2 proposes using a base material made of a titanium-containing metal material and sequentially laminating an anodic oxide film and a titanium oxide-containing thin film on the base material. Therefore, there is a problem in cost and productivity.
かかる基材に基づく問題を改善する技術として、特許文献３には安価で加工性に優れたアルミニウム基材を用いることが提案されている。しかしながら、金属酸化物を固定するのに適したアルミニウム基材については従前報告されていない。特許文献３には、エッチング処理により粗面化したアルミニウム基材の表面に、硫酸チタニル又は硫酸チタンを加水分解させて高固着性の酸化チタン系光触媒層を形成させることが記載されており、エッチングによるアルミニウム基材の粗面化が固定性向上の要因となっている。ところが、エッチング処理を必要とする点でコストや生産性に問題がある。しかも、エッチング対象のアルミニウム基材（組成など）について特段検討されておらず、アルミニウム材の種類やその製造条件、金属酸化物の固定性を高めたり有機バインダーを分解するための熱処理によっては、却って光触媒活性が大幅に低下するという問題がある。 As a technique for improving the problems based on such a base material, Patent Document 3 proposes using an aluminum base material that is inexpensive and excellent in workability. However, no aluminum substrate suitable for fixing metal oxides has been reported previously. Patent Document 3 describes that a highly sticky titanium oxide photocatalyst layer is formed by hydrolyzing titanyl sulfate or titanium sulfate on the surface of an aluminum base material roughened by etching treatment. The roughening of the aluminum base material caused by this is a factor in improving the fixing property. However, there is a problem in cost and productivity in that an etching process is required. In addition, the aluminum base material (composition, etc.) to be etched has not been specifically examined. Depending on the type of aluminum material, its manufacturing conditions, heat treatment for improving the fixability of the metal oxide or decomposing the organic binder, There exists a problem that photocatalytic activity falls significantly.
よって、本発明は、アルミニウム基材に二酸化チタンが固定された光触媒層被覆アルミニウム材であって、アルミニウム基材をエッチング処理しなくても熱処理により二酸化チタンを良好に固定することができ、且つ当該熱処理における光触媒活性の低下が抑制された光触媒層被覆アルミニウム材を提供することを目的とする。また、光触媒層被覆アルミニウム材の好適な製造方法を提供することも目的とする。 Therefore, the present invention is a photocatalyst layer-covered aluminum material in which titanium dioxide is fixed to an aluminum base material, which can fix titanium dioxide satisfactorily by heat treatment without etching the aluminum base material, and An object of the present invention is to provide a photocatalyst layer-coated aluminum material in which a decrease in photocatalytic activity during heat treatment is suppressed. Another object of the present invention is to provide a suitable method for producing a photocatalyst layer-coated aluminum material.
本発明者は上記目的を達成すべく鋭意研究を重ねた結果、アルミニウム材の表面に二酸化チタン又はその前駆体を含有する塗膜を形成し、次いで熱処理することにより光触媒層を形成する場合に、アルミニウム材及び光触媒層に含まれるマグネシウム含有量と光触媒層中のチタン含有量を特定の割合に限定し、かつ光触媒層の厚みを特定の範囲にすることにより、光触媒活性を低下させることなく光触媒層（二酸化チタン）を良好に固定できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor formed a coating film containing titanium dioxide or a precursor thereof on the surface of an aluminum material, and then formed a photocatalyst layer by heat treatment. By limiting the magnesium content contained in the aluminum material and the photocatalyst layer and the titanium content in the photocatalyst layer to a specific ratio and making the thickness of the photocatalyst layer into a specific range, the photocatalyst layer is not reduced without reducing the photocatalytic activity. The inventors have found that (titanium dioxide) can be fixed well, and have completed the present invention.
即ち、本発明は、以下の光触媒層被覆アルミニウム材及びその製造方法に関する。
１．アルミニウム材と、前記アルミニウム材の片面又は両面に形成された二酸化チタンを含む光触媒層とを有する光触媒層被覆アルミニウム材であって、
（１）前記アルミニウム材及び／又は前記光触媒層がマグネシウム原子を含有し、
（２）前記光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭ１とし、同じ単位面積当たりの前記光触媒層中のチタン原子のモル数をＭ２とし、Ｍ１／Ｍ２で表されるモル比が、前記アルミニウム材の片面に前記光触媒層が形成されている場合は１．６０以下であり、前記アルミニウム材の両面に前記光触媒層が形成されている場合は１．４５以下であり、
（３）前記光触媒層の厚みは、０．０５μｍ以上、５μｍ以下である、
ことを特徴とする光触媒層被覆アルミニウム材。
２．前記アルミニウム材の厚みは、５μｍ以上、１ｍｍ以下である、上記項１に記載の光触媒層被覆アルミニウム材。
３．前記二酸化チタンは粒子であり、当該粒子同士がネッキングしている、上記項１又は２に記載の光触媒層被覆アルミニウム材。
４．上記項１〜３のいずれかに記載の光触媒層被覆アルミニウム材を備えることを特徴とする光触媒機能を有する物品。
５．アルミニウム材の片面又は両面に二酸化チタン及び／又はその前駆体を含む塗膜を形成する工程１と、前記塗膜を、酸化性雰囲気中４００℃以上、６６０℃未満の温度で熱処理することにより光触媒層を得る工程２とを有する光触媒層被覆アルミニウム材の製造方法であって、
（１）前記アルミニウム材及び／又は前記光触媒層がマグネシウム原子を含有し、
（２）前記光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭｘとし、同じ単位面積当たりの前記光触媒層中のチタン原子のモル数をＭｙとし、Ｍｘ／Ｍｙで表されるモル比が、前記アルミニウム材の片面に前記光触媒層が形成されている場合は１．６０以下であり、前記アルミニウム材の両面に前記光触媒層が形成されている場合は１．４５以下であり、
（３）前記光触媒層の厚みは、０．０５μｍ以上、５μｍ以下である、
ことを特徴とする光触媒層被覆アルミニウム材の製造方法。
That is, the present invention relates to the following photocatalyst layer-coated aluminum material and a method for producing the same.
1. A photocatalyst layer-covered aluminum material having an aluminum material and a photocatalyst layer containing titanium dioxide formed on one or both surfaces of the aluminum material,
(1) The aluminum material and / or the photocatalyst layer contains a magnesium atom,
(2) M 1 is the number of moles of magnesium atoms per unit area in the photocatalyst layer-covered aluminum material, M 2 is the number of moles of titanium atoms in the photocatalyst layer per unit area, and M 1 / M 2 Is less than 1.60 when the photocatalyst layer is formed on one side of the aluminum material, and 1.45 when the photocatalyst layer is formed on both sides of the aluminum material. And
(3) The thickness of the photocatalyst layer is 0.05 μm or more and 5 μm or less.
A photocatalyst layer-coated aluminum material.
2. The photocatalyst layer-covered aluminum material according to Item 1, wherein the aluminum material has a thickness of 5 μm or more and 1 mm or less.
3. Item 3. The photocatalyst layer-coated aluminum material according to Item 1 or 2, wherein the titanium dioxide is a particle, and the particle is necked.
4). An article having a photocatalytic function, comprising the photocatalyst layer-coated aluminum material according to any one of Items 1 to 3.
5. Step 1 of forming a coating film containing titanium dioxide and / or a precursor thereof on one or both surfaces of an aluminum material, and heat-treating the coating film at a temperature of 400 ° C. or more and less than 660 ° C. in an oxidizing atmosphere. A method for producing a photocatalyst layer-covered aluminum material comprising the step 2 of obtaining a layer,
(1) The aluminum material and / or the photocatalyst layer contains a magnesium atom,
(2) the number of moles of the magnesium atoms per unit area in the photocatalytic layer coated aluminum material as M x, the number of moles of titanium atoms of the photocatalyst layer per the same unit area and M y, M x / M y Is less than 1.60 when the photocatalyst layer is formed on one side of the aluminum material, and 1.45 when the photocatalyst layer is formed on both sides of the aluminum material. And
(3) The thickness of the photocatalyst layer is 0.05 μm or more and 5 μm or less.
A method for producing a photocatalyst layer-coated aluminum material.
本発明の光触媒層被覆アルミニウム材は、アルミニウム材と、前記アルミニウム材の片面又は両面に形成された二酸化チタンを含む光触媒層とを有する光触媒層被覆アルミニウム材であって、特に前記光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭ１とし、同じ単位面積当たりの前記光触媒層中のチタン原子のモル数をＭ２とし、Ｍ１／Ｍ２で表されるモル比が、前記アルミニウム材の片面に前記光触媒層が形成されている場合は１．６０以下であり、前記アルミニウム材の両面に前記光触媒層が形成されている場合は１．４５以下であり、前記光触媒層の厚みが０．０５μｍ以上、５μｍ以下であることにより、その製造過程で光触媒層の固定性を高める４００℃以上の熱処理に供しても光触媒活性の低下が抑制されている。かかる本発明の光触媒層被覆アルミニウム材は、大気中、水中等に含まれる有害物質の分解又は無害化、生活空間における防臭、防汚、殺菌等のさまざまな環境浄化用途に利用することができる。 The photocatalyst layer-covered aluminum material of the present invention is a photocatalyst layer-covered aluminum material having an aluminum material and a photocatalyst layer containing titanium dioxide formed on one or both sides of the aluminum material, and in particular, the photocatalyst layer-covered aluminum material the number of moles of the magnesium atoms per unit area and M 1 in the number of moles of titanium atoms of the photocatalyst layer per the same unit area and M 2, the molar ratio represented by M 1 / M 2 is the When the photocatalyst layer is formed on one surface of the aluminum material, the thickness is 1.60 or less, and when the photocatalyst layer is formed on both surfaces of the aluminum material, the thickness is 1.45 or less. Is 0.05 μm or more and 5 μm or less, so that the photocatalyst can be subjected to heat treatment at 400 ° C. or higher to improve the fixing property of the photocatalyst layer in the production process. Decrease in activity is suppressed. The photocatalyst layer-coated aluminum material of the present invention can be used for various environmental purification applications such as decomposition or detoxification of harmful substances contained in the air, water, etc., deodorization, antifouling, and sterilization in living spaces.
以下、本発明の光触媒層被覆アルミニウム材及びその製造方法について説明する。 Hereinafter, the photocatalyst layer-coated aluminum material of the present invention and a method for producing the same will be described.
１．本発明の光触媒層被覆アルミニウム材
本発明の光触媒層被覆アルミニウム材は、アルミニウム材と、前記アルミニウム材の片面又は両面に形成された二酸化チタンを含む光触媒層とを有する光触媒層被覆アルミニウム材であって、
（１）前記アルミニウム材及び／又は前記光触媒層がマグネシウム原子を含有し、
（２）前記光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭ１とし、同じ単位面積当たりの前記光触媒層中のチタン原子のモル数をＭ２とし、Ｍ１／Ｍ２で表されるモル比が、前記アルミニウム材の片面に前記光触媒層が形成されている場合は１．６０以下であり、前記アルミニウム材の両面に前記光触媒層が形成されている場合は１．４５以下であり、
（３）前記光触媒層の厚みは、０．０５μｍ以上、５μｍ以下である、
ことを特徴とする。
1. The photocatalyst layer-coated aluminum material of the present invention The photocatalyst layer-coated aluminum material of the present invention is a photocatalyst layer-coated aluminum material having an aluminum material and a photocatalyst layer containing titanium dioxide formed on one or both surfaces of the aluminum material. ,
(1) The aluminum material and / or the photocatalyst layer contains a magnesium atom,
(2) M 1 is the number of moles of magnesium atoms per unit area in the photocatalyst layer-covered aluminum material, M 2 is the number of moles of titanium atoms in the photocatalyst layer per unit area, and M 1 / M 2 Is less than 1.60 when the photocatalyst layer is formed on one side of the aluminum material, and 1.45 when the photocatalyst layer is formed on both sides of the aluminum material. And
(3) The thickness of the photocatalyst layer is 0.05 μm or more and 5 μm or less.
It is characterized by that.
上記特徴を有する本発明の光触媒層被覆アルミニウム材は、特に前記光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭ１とし、同じ単位面積当たりの前記光触媒層中のチタン原子のモル数をＭ２とし、Ｍ１／Ｍ２で表されるモル比が、前記アルミニウム材の片面に前記光触媒層が形成されている場合は１．６０以下であり、前記アルミニウム材の両面に前記光触媒層が形成されている場合は１．４５以下であり、前記光触媒層の厚みが０．０５μｍ以上、５μｍ以下であることにより、その製造過程で光触媒層の固定性を高める４００℃以上の熱処理に供しても光触媒活性の低下が抑制されている。 Photocatalytic layer coated aluminum material of the present invention having the above characteristics, especially the number of moles of the magnesium atoms per unit area in the photocatalytic layer coated aluminum material as M 1, per the same unit area of the titanium atoms of the photocatalyst layer the number of moles and M 2, the molar ratio represented by M 1 / M 2 is, if the photocatalyst layer on one surface of the aluminum material is formed is 1.60 or less, the both surfaces of the aluminum material When the photocatalyst layer is formed, the heat treatment is 1.45 or less, and the thickness of the photocatalyst layer is 0.05 μm or more and 5 μm or less, thereby improving the fixability of the photocatalyst layer in the production process thereof at 400 ° C. or more. Even if it uses for, the fall of photocatalytic activity is suppressed.
上記Ｍ１／Ｍ２で表されるモル比は、Ｍ１は光触媒層被覆アルミニウム材の単位面積当たりのマグネシウム原子の含有量、Ｍ２は光触媒層中の単位面積あたりのチタン原子の含有量からそれぞれのモル数を算出し、これらのモル数からＭ１／Ｍ２で表されるモル比を計算することにより得られる。なお、単位面積の面とは、アルミニウム材に形成される光触媒層形成面を意味する。 The molar ratio represented by M 1 / M 2 is as follows: M 1 is the content of magnesium atoms per unit area of the photocatalyst layer-covered aluminum material, and M 2 is the content of titanium atoms per unit area in the photocatalyst layer. It is obtained by calculating the number of moles and calculating the mole ratio represented by M 1 / M 2 from the number of moles. In addition, the surface of a unit area means the photocatalyst layer formation surface formed in an aluminum material.
ここで、光触媒層被覆アルミニウム材の製造工程においては、二酸化チタン及び／又はその前駆体を含む塗膜を酸化性雰囲気中４００℃以上の温度で熱処理する工程が含まれるが、当該熱処理の前後において単位面積当たりのチタン原子のモル数は変わらないとみなせる。つまり、酸化性雰囲気中で熱処理する工程前の単位面積当たりのチタン原子のモル数を用いて、Ｍ１／Ｍ２で表されるモル比を算出することができる。 Here, the manufacturing process of the photocatalyst layer-covered aluminum material includes a step of heat-treating a coating film containing titanium dioxide and / or its precursor in an oxidizing atmosphere at a temperature of 400 ° C. or higher. The number of moles of titanium atoms per unit area can be regarded as unchanged. That is, the molar ratio represented by M 1 / M 2 can be calculated using the number of moles of titanium atoms per unit area before the heat treatment in an oxidizing atmosphere.
また、光触媒層被覆アルミニウム材を用いてチタン原子のモル数を算出する場合、光触媒層を溶解せず、アルミニウム材のみを溶解することができる溶剤を用いてアルミニウム材のみを除去し、残った光触媒層を洗浄後、光触媒層を溶解することができる溶剤を用いて光触媒層を溶解し、当該溶液を高周波誘導結合プラズマ（ＩＣＰ）発光分光分析を行うことによってチタン原子の含有量を測定し、チタン原子のモル数を算出する。 In addition, when calculating the number of moles of titanium atoms using the photocatalyst layer-coated aluminum material, the photocatalyst layer is not dissolved, only the aluminum material is removed using a solvent that can dissolve only the aluminum material, and the remaining photocatalyst After washing the layer, the photocatalyst layer is dissolved using a solvent capable of dissolving the photocatalyst layer, and the solution is subjected to high frequency inductively coupled plasma (ICP) emission spectroscopic analysis to measure the content of titanium atoms. Calculate the number of moles of atoms.
アルミニウム材に含まれるマグネシウムは、アルミニウム材の製造過程において不可避的に含まれるマグネシウム、及びアルミニウム材の用途によって要求される強度、伸び、耐食性、溶接性等の特性を満たすために意図的に添加されるマグネシウムの一方又は両方が挙げられる。 Magnesium contained in the aluminum material is intentionally added to satisfy the magnesium, which is inevitably contained in the manufacturing process of the aluminum material, and the properties such as strength, elongation, corrosion resistance, and weldability required by the use of the aluminum material. Or one or both of magnesium.
アルミニウム材に含まれるマグネシウムは、熱処理されたときにアルミニウム材表面に集積し、二酸化チタン及び／又はその前駆体を含む塗膜と反応して光触媒層に含まれる二酸化チタンを光触媒活性の低い化合物（主にチタン酸マグネシウム）に変化させるため、光触媒能力を著しく低下させる。光触媒層被覆アルミニウム材において、上記Ｍ１／Ｍ２で表されるモル比を、前記アルミニウム材の片面に光触媒層が形成される場合は１．６０以下に設定し、前記アルミニウム材の両面に光触媒層が形成される場合は１．４５以下に設定し、光触媒層の厚みを０．０５μｍ以上、５μｍ以下とすることにより、熱処理時にアルミニウム材の表面に集積するマグネシウムと二酸化チタン及び／又はその前駆体との反応が抑制され、優れた光触媒性能が維持される。 Magnesium contained in the aluminum material accumulates on the surface of the aluminum material when heat-treated, and reacts with the coating film containing titanium dioxide and / or its precursor to convert the titanium dioxide contained in the photocatalyst layer into a compound having a low photocatalytic activity ( Mainly magnesium titanate), so the photocatalytic ability is significantly reduced. In the photocatalyst layer-coated aluminum material, the molar ratio represented by M 1 / M 2 is set to 1.60 or less when the photocatalyst layer is formed on one surface of the aluminum material, and the photocatalyst is formed on both surfaces of the aluminum material. When the layer is formed, it is set to 1.45 or less, and the thickness of the photocatalyst layer is set to 0.05 μm or more and 5 μm or less, so that magnesium and titanium dioxide and / or its precursor accumulated on the surface of the aluminum material during the heat treatment. Reaction with the body is suppressed, and excellent photocatalytic performance is maintained.
ここで、上記Ｍ１／Ｍ２で表されるモル比は、限りなく０に近い方がよく、０に近いほどマグネシウムと二酸化チタン及び／又はその前駆体との反応が抑制されるため、優れた光触媒性能を維持する。当該モル比（Ｍ１／Ｍ２）は、０＜（Ｍ１／Ｍ２）≦１．６０（片面形成の場合）又は１．４５（両面形成の場合）で表すことができるが、明確な下限値を設定する場合には、好ましくは０．００００１以上、より好ましくは０．０００１以上とする。 Here, the molar ratio represented by M 1 / M 2 is preferably as close to 0 as possible, and the closer to 0, the more the reaction between magnesium and titanium dioxide and / or its precursor is suppressed. Maintain the photocatalytic performance. The molar ratio (M 1 / M 2 ) can be expressed as 0 <(M 1 / M 2 ) ≦ 1.60 (in the case of single-sided formation) or 1.45 (in the case of double-sided formation). When setting a lower limit, it is preferably 0.00001 or more, more preferably 0.0001 or more.
また、光触媒層の厚みを０．０５μｍ未満とすると、用途によっては光触媒能力が不足する問題や、５μｍを超えると光触媒層の柔軟性が低下して光触媒層とアルミニウム材との密着性が低下するおそれもある。光触媒層の厚みは、特に０．１μｍ以上、２μｍ以下の範囲とすることがアルミニウム材との密着性を確保しつつ、優れた光触媒性能を示す点から好ましい。紫外線が照射される環境下で使用する場合、２μｍを超えても光触媒能力に差が出にくいため、かかる環境下では２μｍ以下が好ましい。 Moreover, if the thickness of the photocatalyst layer is less than 0.05 μm, the photocatalytic ability may be insufficient depending on the application, and if it exceeds 5 μm, the flexibility of the photocatalyst layer is lowered and the adhesion between the photocatalyst layer and the aluminum material is lowered. There is also a fear. The thickness of the photocatalyst layer is particularly preferably in the range of 0.1 μm or more and 2 μm or less from the viewpoint of excellent photocatalytic performance while ensuring adhesion with an aluminum material. When used in an environment irradiated with ultraviolet rays, even if it exceeds 2 μm, it is difficult to make a difference in the photocatalytic ability. Therefore, in such an environment, 2 μm or less is preferable.
本発明の光触媒層被覆アルミニウム材は、光触媒層とアルミニウム材との間にアルミニウムの酸化物層を有することが好ましい。また、アルミニウムの酸化物層は光触媒層とアルミニウム材との間の全領域で存在することが好ましい。アルミニウムの酸化物層を有することにより、光触媒層で生じた電子がアルミニウム材に流れることを防止でき、光触媒層の光触媒能力を更に高めることができると考えられる。また、アルミニウムの酸化物層は光触媒層と強固に結合し、結果として光触媒層とアルミニウム材との密着性を高めることができると考えられる。 The photocatalyst layer-covered aluminum material of the present invention preferably has an aluminum oxide layer between the photocatalyst layer and the aluminum material. The aluminum oxide layer is preferably present in the entire region between the photocatalyst layer and the aluminum material. By having an aluminum oxide layer, it is considered that electrons generated in the photocatalyst layer can be prevented from flowing into the aluminum material, and the photocatalytic ability of the photocatalyst layer can be further enhanced. In addition, it is considered that the oxide layer of aluminum is firmly bonded to the photocatalyst layer, and as a result, the adhesion between the photocatalyst layer and the aluminum material can be improved.
なお、アルミニウムの酸化物層は光触媒層と一部の領域が交わっていてもよい。アルミニウムの酸化物層が光触媒層の一部の領域と交わる（侵入する）ことで、アルミニウムの酸化物層と光触媒層がより強固に固定され、結果として光触媒層とアルミニウム材との密着性をさらに高めることができると考えられる。 The aluminum oxide layer may intersect with a part of the photocatalyst layer. The aluminum oxide layer intersects (invades) a part of the photocatalyst layer, so that the aluminum oxide layer and the photocatalyst layer are more firmly fixed. As a result, the adhesion between the photocatalyst layer and the aluminum material is further increased. It can be increased.
アルミニウムの酸化物層の厚みは１０ｎｍ以上、１μｍ以下が好ましく、特に２０ｎｍ以上、５００ｎｍ以下が好ましい。１０ｎｍ以下であると光触媒層で生じた電子がアルミニウム材に流れ易くなると考えられ光触媒性能が低下することや、光触媒層とアルミニウム材との密着性が低下するため好ましくなく、１μｍを超えると柔軟性が低下してハンドリングや後加工の際にクラックが生じ易くなり、光触媒層にもクラックが生じて脱落する可能性がある。 The thickness of the aluminum oxide layer is preferably 10 nm or more and 1 μm or less, and particularly preferably 20 nm or more and 500 nm or less. If it is 10 nm or less, it is considered that electrons generated in the photocatalyst layer are likely to flow into the aluminum material, so that the photocatalytic performance is lowered, and the adhesion between the photocatalyst layer and the aluminum material is lowered. , The cracks are likely to occur during handling and post-processing, and the photocatalyst layer may crack and fall off.
光触媒層に含まれる光触媒活性を有する物質としては、二酸化チタンであれば特に限定されないが、良好な光触媒性能を発揮する点で、特にアナターゼ型の結晶からなる二酸化チタンが好ましい。また、二酸化チタンに異種元素をドーピングしたものや二酸化チタンの表面に異種元素を担持したものでもよい。 The substance having photocatalytic activity contained in the photocatalyst layer is not particularly limited as long as it is titanium dioxide, but titanium dioxide composed of anatase type crystals is particularly preferable in terms of exhibiting good photocatalytic performance. Moreover, what doped the different element in titanium dioxide, and what carried the different element on the surface of titanium dioxide may be used.
光触媒層に含まれる光触媒活性を有する物質として二酸化チタンを単独で使用する場合、紫外線が照射される環境下で用いられることが好ましい。紫外線が照射される環境下で使用することにより、光触媒層被覆アルミニウム材の光触媒活性が発揮され易い。 When titanium dioxide is used alone as a substance having photocatalytic activity contained in the photocatalyst layer, it is preferably used in an environment irradiated with ultraviolet rays. When used in an environment irradiated with ultraviolet rays, the photocatalytic activity of the photocatalyst layer-covered aluminum material is easily exhibited.
光触媒層は多孔質であればよく、光触媒層に含まれる光触媒活性を有する物質の形状としては、比表面積や充填率の点で粒子状であることが好ましい。粒子の大きさ（粒子径）としては、１ｎｍ以上、１μｍ以下が好ましく、特に５ｎｍ以上、２００ｎｍ以下がより好ましい。１ｎｍ未満であると光触媒層が緻密になりすぎて比表面積が低下し、分解対象となるガスが光触媒層内に入り難い点で好ましくなく、１μｍを超えると比表面積が大きくならないので、光触媒能力が低下する点で好ましくない。 The photocatalyst layer may be porous, and the shape of the substance having photocatalytic activity contained in the photocatalyst layer is preferably particulate in terms of specific surface area and filling rate. The particle size (particle diameter) is preferably 1 nm or more and 1 μm or less, and more preferably 5 nm or more and 200 nm or less. If it is less than 1 nm, the photocatalyst layer becomes too dense and the specific surface area decreases, and it is not preferable in that the gas to be decomposed hardly enters the photocatalyst layer, and if it exceeds 1 μm, the specific surface area does not increase. It is not preferable in terms of reduction.
また、光触媒層の強度を高める点では、光触媒活性粒子同士が適度にネッキングした構造であることが好ましい。適度にネッキングした構造では、粒子同士の一部が溶融又は粉末同士が繋がった状態となっているが、略円形状を有する部分は近似的に粒子状とみなせる。なお、粒子径は走査透過型電子顕微鏡（ＳＴＥＭ：Scanning Transmission Electron Microscopy）により断面観察した写真から任意の粒子５０個を選び出し、ネッキング部分を除いて粒子径を算出し、その平均値により求められる。 Further, in terms of increasing the strength of the photocatalyst layer, it is preferable that the photocatalytic active particles have a structure in which the photocatalytic active particles are appropriately necked. In a structure that is appropriately necked, a part of the particles is in a melted state or a state in which the powders are connected to each other, but a portion having a substantially circular shape can be regarded as approximately a particle shape. The particle diameter is obtained from an average value obtained by selecting 50 arbitrary particles from a photograph obtained by observing a cross section with a scanning transmission electron microscope (STEM), excluding the necking portion, and calculating the particle diameter.
光触媒層において、無機系のバインダーは二酸化チタンの表面を被覆して光触媒性能を低下させるおそれがあるため、シリカゾル等の二酸化チタン前駆体以外の無機系のバインダーは添加量を極力抑えるか、使用しないことが好ましい。 In the photocatalyst layer, inorganic binders may cover the surface of titanium dioxide and reduce the photocatalytic performance. Therefore, inorganic binders other than titanium dioxide precursors such as silica sol should be used as little as possible or not used. It is preferable.
光触媒層被覆アルミニウム材に使用できるアルミニウム材としては、その組成の点で、マグネシウム（Ｍｇ）以外は特に限定されない。光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭ１とし、同じ単位面積当たりの光触媒層中のチタン原子のモル数をＭ２とし、Ｍ１／Ｍ２で表されるモル比が、アルミニウム材の片面に光触媒層が形成されている場合は１．６０以下、アルミニウム材の両面に光触媒層が形成されている場合は１．４５以下となっていればよい。なお、モル比の詳細は前述の通りである。 The aluminum material that can be used for the photocatalyst layer-covered aluminum material is not particularly limited except magnesium (Mg) in terms of its composition. The number of moles of the magnesium atoms per unit area of the photocatalytic layer coated aluminum material as M 1, the number of moles of titanium atoms in the photocatalyst layer per the same unit area and M 2, mol represented by M 1 / M 2 The ratio may be 1.60 or less when the photocatalyst layer is formed on one surface of the aluminum material, and 1.45 or less when the photocatalyst layer is formed on both surfaces of the aluminum material. The details of the molar ratio are as described above.
例えば、純アルミニウム又はアルミニウム合金の箔又は板を用いることができる。このようなアルミニウム材は、アルミニウム純度がＪＩＳ Ｈ ２１０２に記載された方法に準じて測定された値で９５質量％以上のものが好ましい。 For example, a pure aluminum or aluminum alloy foil or plate can be used. Such an aluminum material preferably has an aluminum purity of 95% by mass or more as a value measured according to the method described in JIS H2102.
アルミニウム材の組成として、鉛（Ｐｂ）、珪素（Ｓｉ）、鉄（Ｆｅ）、銅（Ｃｕ）、マンガン（Ｍｎ）、クロム（Ｃｒ）、亜鉛（Ｚｎ）、チタン（Ｔｉ）、バナジウム（Ｖ）、ガリウム（Ｇａ）、ニッケル（Ｎｉ）及びホウ素（Ｂ）の少なくとも１種の合金元素を必要範囲内において添加したアルミニウム合金であってもよい。また、アルミニウム材には、上記に挙げた元素以外の不可避的不純物元素が含まれていてもよい。 As the composition of the aluminum material, lead (Pb), silicon (Si), iron (Fe), copper (Cu), manganese (Mn), chromium (Cr), zinc (Zn), titanium (Ti), vanadium (V) Further, an aluminum alloy to which at least one alloy element of gallium (Ga), nickel (Ni), and boron (B) is added within a necessary range may be used. In addition, the aluminum material may contain inevitable impurity elements other than the elements listed above.
アルミニウム材の厚みは５μｍ以上、１ｍｍ以下が好ましく、５．５μｍ以上、３００μｍ以下がより好ましい。５μｍ未満では強度不足によりハンドリングが困難になる問題があり、１ｍｍを超えるとロール状での生産が困難になり、生産性に劣る問題がある。 The thickness of the aluminum material is preferably 5 μm or more and 1 mm or less, and more preferably 5.5 μm or more and 300 μm or less. If it is less than 5 μm, there is a problem that handling becomes difficult due to insufficient strength, and if it exceeds 1 mm, production in a roll shape becomes difficult and there is a problem that productivity is inferior.
アルミニウム材は、必要に応じて表裏を貫通する穴が形成されていてもよい。貫通する穴が形成されていることにより、ガスを透過させることができるため、光触媒層被覆アルミニウム材を空気清浄機などのフィルターとして使用することができる。 The aluminum material may have a hole penetrating the front and back as necessary. The formation of the through-hole allows gas to pass therethrough, so that the photocatalyst layer-covered aluminum material can be used as a filter for an air cleaner or the like.
また、光触媒層被覆アルミニウム材は、片面又は両面に凹凸部が形成されていてもよい。凹凸部が形成されていることで単位面積当たりの表面積を高めることができ、光触媒性能を更に高めることができる。 In addition, the photocatalyst layer-coated aluminum material may have uneven portions on one side or both sides. The surface area per unit area can be increased by forming the concavo-convex portions, and the photocatalytic performance can be further improved.
本発明の光触媒層被覆アルミニウム材の具体的な態様について、図面を参照しながら例示的に説明する。図３に示される実施例１の光触媒層被覆アルミニウム材のエネルギー分散型Ｘ線分光法（ＥＤＸ）による線分析の断面写真は、本発明の光触媒層被覆アルミニウム材の好ましい一態様を示す図である。 A specific embodiment of the photocatalyst layer-coated aluminum material of the present invention will be exemplarily described with reference to the drawings. The cross-sectional photograph of the line analysis by the energy dispersive X-ray spectroscopy (EDX) of the photocatalyst layer-coated aluminum material of Example 1 shown in FIG. 3 is a diagram showing a preferred embodiment of the photocatalyst layer-coated aluminum material of the present invention. .
図３の上段は、光触媒層被覆アルミニウム材の断面構造を示す。アルミニウム材の一例であるアルミニウム箔の表面上に光触媒層が形成されている。 The upper part of FIG. 3 shows a cross-sectional structure of the photocatalyst layer-coated aluminum material. A photocatalytic layer is formed on the surface of an aluminum foil which is an example of an aluminum material.
本発明の光触媒層被覆アルミニウム材は、種々の物品に適用することにより、光触媒活性を有する物品を構成することができる。光触媒活性を有する物品は特に限定されないが、例えば、大気中、水中等に含まれる有害物質の分解又は無害化、生活空間の脱臭、生活空間における固体表面の汚染防止、生活空間の抗菌・殺菌等のさまざまな環境浄化用途に利用する物品が挙げられる。具体的には、上記の物品として、壁紙、ブラインド、カーテン、ガードレール等の建築材料、空気清浄機、エアコン、冷蔵庫等の工業用・家庭用の電化製品、熱交換器等のフィン材が挙げられる。 By applying the photocatalyst layer-coated aluminum material of the present invention to various articles, articles having photocatalytic activity can be constituted. Although the article having photocatalytic activity is not particularly limited, for example, decomposition or detoxification of harmful substances contained in the air, water, etc., deodorization of living space, prevention of solid surface contamination in living space, antibacterial / sterilization of living space, etc. Articles used for various environmental purification applications. Specifically, examples of the article include building materials such as wallpaper, blinds, curtains and guardrails, industrial and household appliances such as air purifiers, air conditioners and refrigerators, and fin materials such as heat exchangers. .
２．本発明の光触媒層被覆アルミニウム材の製造方法
本発明の光触媒層被覆アルミニウム材の製造方法は、アルミニウム材の片面又は両面に二酸化チタン及び／又はその前駆体を含む塗膜を形成する工程１と、前記塗膜を、酸化性雰囲気中４００℃以上、６６０℃未満の温度で熱処理することにより光触媒層を得る工程２とを有する製造方法であって、
（１）前記アルミニウム材及び／又は前記光触媒層がマグネシウム原子を含有し、
（２）前記光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭｘとし、同じ単位面積当たりの前記光触媒層中のチタン原子のモル数をＭｙとし、Ｍｘ／Ｍｙで表されるモル比が、前記アルミニウム材の片面に前記光触媒層が形成されている場合は１．６０以下であり、前記アルミニウム材の両面に前記光触媒層が形成されている場合は１．４５以下であり、
（３）前記光触媒層の厚みは、０．０５μｍ以上、５μｍ以下である、
ことを特徴とする。
2. Method for Producing Photocatalyst Layer-Coated Aluminum Material of the Present Invention The method for producing the photocatalyst layer-coated aluminum material of the present invention comprises the step 1 of forming a coating film containing titanium dioxide and / or a precursor thereof on one or both sides of an aluminum material; A step 2 of obtaining a photocatalyst layer by heat-treating the coating film at a temperature of 400 ° C. or higher and lower than 660 ° C. in an oxidizing atmosphere,
(1) The aluminum material and / or the photocatalyst layer contains a magnesium atom,
(2) the number of moles of the magnesium atoms per unit area in the photocatalytic layer coated aluminum material as M x, the number of moles of titanium atoms of the photocatalyst layer per the same unit area and M y, M x / M y Is less than 1.60 when the photocatalyst layer is formed on one side of the aluminum material, and 1.45 when the photocatalyst layer is formed on both sides of the aluminum material. And
(3) The thickness of the photocatalyst layer is 0.05 μm or more and 5 μm or less.
It is characterized by that.
以下、工程ごとに説明する。 Hereinafter, it demonstrates for every process.
工程１は、アルミニウム材の片面又は両面に二酸化チタン及び／又はその前駆体を含む塗膜を形成する。 Step 1 forms a coating film containing titanium dioxide and / or a precursor thereof on one side or both sides of an aluminum material.
基材としてのアルミニウム材は、光触媒層被覆アルミニウム材中のマグネシウム原子の含有量が、光触媒層中のチタン原子の含有量に対するモル比（Ｍｘ／Ｍｙ）で、前記アルミニウム材の片面に光触媒層が形成される場合は１．６０以下、前記アルミニウム材の両面に光触媒層が形成される場合は１．４５以下に調整できる限り特に限定されない。 The aluminum material as the base material has a photocatalyst on one side of the aluminum material in which the content of magnesium atoms in the photocatalyst layer-coated aluminum material is a molar ratio (M x / M y ) to the content of titanium atoms in the photocatalyst layer. When the layer is formed, it is not particularly limited as long as it can be adjusted to 1.60 or less, and when the photocatalyst layer is formed on both surfaces of the aluminum material, it can be adjusted to 1.45 or less.
本発明の一つの実施の形態では、アルミニウム材として、純アルミニウム又はアルミニウム合金の箔若しくは板を用いることができる。アルミニウム材の厚みは５μｍ以上、１ｍｍ以下が好ましく、５．５μｍ以上、３００μｍ以下がより好ましい。５μｍ未満では強度不足によりハンドリングが困難になる問題があり、１ｍｍを超えるとロール状での生産が困難になり、生産性に劣る問題がある。 In one embodiment of the present invention, a pure aluminum or aluminum alloy foil or plate can be used as the aluminum material. The thickness of the aluminum material is preferably 5 μm or more and 1 mm or less, and more preferably 5.5 μm or more and 300 μm or less. If it is less than 5 μm, there is a problem that handling becomes difficult due to insufficient strength, and if it exceeds 1 mm, production in a roll shape becomes difficult and there is a problem that productivity is inferior.
アルミニウム材は、公知の方法によって製造されるものを使用できる。例えば、上記の所定の組成を有するアルミニウム又はアルミニウム合金の溶湯を調製し、この溶湯を鋳造して得られた鋳塊を適切に均質化処理する。その後、この鋳塊に熱間圧延と冷間圧延を施すことにより、基材としてのアルミニウム材を得ることができる。なお、上記の冷間圧延工程の途中で１５０℃以上４００℃以下の温度で中間焼鈍処理を施してもよい。また、アルミニウム材の表面には、二酸化チタン及び／又はその前駆体を含む塗膜の形成前に適宜前処理を行ってもよい。更に光触媒層被覆アルミニウム材の製造工程のいずれかの時点で最終製品の用途に応じてパンチングやラス加工等の穴空け加工を施してもよい。後述の工程２の熱処理を複数のシート状の基材（塗膜形成後のアルミニウム材）を積層した状態、又は帯状の当該基材をロール状に巻いた状態で行う場合、熱処理前に穴空け加工を行えば、穴によって雰囲気の通りがよくなり、全面で均一な熱処理を行いやすくなる。 As the aluminum material, one produced by a known method can be used. For example, a molten aluminum or aluminum alloy having the above predetermined composition is prepared, and an ingot obtained by casting the molten metal is appropriately homogenized. Then, the aluminum material as a base material can be obtained by subjecting this ingot to hot rolling and cold rolling. In addition, you may perform an intermediate annealing process at the temperature of 150 to 400 degreeC in the middle of said cold rolling process. In addition, the surface of the aluminum material may be appropriately pretreated before formation of a coating film containing titanium dioxide and / or a precursor thereof. Further, at any point in the manufacturing process of the photocatalyst layer-covered aluminum material, punching such as punching or lath processing may be performed depending on the use of the final product. When the heat treatment in Step 2 described below is performed in a state where a plurality of sheet-like base materials (aluminum materials after coating film formation) are laminated or in a state where the belt-like base material is wound in a roll shape, a hole is formed before the heat treatment. If processing is performed, the atmosphere is improved by the holes, and uniform heat treatment is facilitated over the entire surface.
アルミニウム材の表面（片面又は両面）に二酸化チタン及び／又はその前駆体を含む塗膜を形成する方法は特に限定されない。例えば、チタン金属を含むアルコキシドの有機化合物又は金属塩の加水分解及び重縮合を利用して酸化物前駆体粒子を含む溶液（ゾル）からゲル化させた塗布液、又は、二酸化チタン粒子を溶液中で攪拌機等を用いて分散させた塗布液、又は上記の二つの塗布液の混合物を調製し、アルミニウム材の表面上に塗布すればよい。塗布の方法は特に限定されず、スピンコーティング法、バーコーティング法、フローコーティング法、ディップコーティング法、ダイコーティング法等が採用される。 The method for forming a coating film containing titanium dioxide and / or its precursor on the surface (one side or both sides) of the aluminum material is not particularly limited. For example, a coating solution obtained by gelation from a solution (sol) containing oxide precursor particles using hydrolysis and polycondensation of an organic compound or metal salt of an alkoxide containing titanium metal, or titanium dioxide particles in the solution The coating liquid dispersed using a stirrer or the like or a mixture of the above two coating liquids may be prepared and applied onto the surface of the aluminum material. The coating method is not particularly limited, and spin coating, bar coating, flow coating, dip coating, die coating, and the like are employed.
塗膜に含まれる光触媒活性を有する物質の形状としては、比表面積や充填率の点で粒子状であることが好ましい。塗膜中の粒子の大きさ（粒子径）としては、１ｎｍ以上、１μｍ以下が好ましく、特に５ｎｍ以上、２００ｎｍ以下がより好ましい。１ｎｍ未満であると工程２を経た後の光触媒層が緻密になりすぎて比表面積が低下し、分解対象となるガスが光触媒層内に入り難い点で好ましくなく、１μｍを超えると比表面積が大きくならないので、光触媒能力が低下する点で好ましくない。 The shape of the substance having photocatalytic activity contained in the coating film is preferably particulate in terms of specific surface area and filling rate. The size (particle diameter) of the particles in the coating film is preferably 1 nm or more and 1 μm or less, and more preferably 5 nm or more and 200 nm or less. If it is less than 1 nm, the photocatalyst layer after Step 2 becomes too dense and the specific surface area decreases, and it is not preferable in that the gas to be decomposed hardly enters the photocatalyst layer, and if it exceeds 1 μm, the specific surface area becomes large. This is not preferable in that the photocatalytic ability is lowered.
塗布液中に、樹脂等の有機系のバインダーを含んでもよい。有機系のバインダーであれば、酸化性雰囲気中で加熱することで、バインダーを除去することができる。なお、シリカゾル等の二酸化チタン前駆体以外の無機系のバインダーを用いた場合、二酸化チタンの表面をバインダーが被覆して光触媒性能を低下させてしまうため、前述の通り、添加量を極力抑えるか、使用しないことが好ましい。 An organic binder such as a resin may be included in the coating solution. If it is an organic binder, the binder can be removed by heating in an oxidizing atmosphere. In addition, when an inorganic binder other than a titanium dioxide precursor such as silica sol is used, the binder is coated on the surface of titanium dioxide to reduce the photocatalytic performance. It is preferable not to use it.
塗膜の厚みは、基材と光触媒層との間の密着性、及び光触媒性能を確保する観点から、５μｍ以下とし、特に２μｍ以下である事が好ましい。また、光触媒層の均一性、及び光触媒性能を確保する観点から０．０５μｍ以上とする。 The thickness of the coating film is 5 μm or less, particularly 2 μm or less, from the viewpoint of ensuring the adhesion between the substrate and the photocatalyst layer and the photocatalytic performance. In addition, the thickness is set to 0.05 μm or more from the viewpoint of ensuring the uniformity of the photocatalyst layer and the photocatalytic performance.
塗布後の塗膜の乾燥条件は特に限定されず、使用した溶媒や塗布量等によって適宜設定すればよい。 The drying conditions of the coated film after coating are not particularly limited, and may be set as appropriate depending on the solvent used, the coating amount, and the like.
塗布後の基材の片面又は両面に凹凸加工を行ってもよい。後述の工程２の熱処理を複数のシート状の基材（塗膜形成後のアルミニウム材）を積層した状態、又は帯状の当該基材をロール状に巻いた状態で行う場合、凹凸加工によって基材間の隙間が確保されて雰囲気の通りがよくなり、全面で均一な熱処理を行いやすくなる。 You may perform uneven | corrugated processing to the single side | surface or both surfaces of the base material after application | coating. When the heat treatment in Step 2 described below is performed in a state where a plurality of sheet-like base materials (aluminum materials after coating film formation) are laminated or in a state where the belt-like base material is wound in a roll shape, A gap between them is secured to improve the atmosphere and facilitate uniform heat treatment over the entire surface.
凹凸部の形成方法は特に限定されないが、例えば、エンボス加工、プレス加工、ブラスト加工、コルゲート加工等が挙げられる。これらの中でも凹凸部形成のし易さから、エンボス加工で凹凸部を形成するのが好ましい。 Although the formation method of an uneven | corrugated | grooved part is not specifically limited, For example, embossing, press work, blasting, corrugating etc. are mentioned. Among these, it is preferable to form the concavo-convex portion by embossing because it is easy to form the concavo-convex portion.
凹凸部の形状は特に限定されないが、例えば、平面視でドット、梨地、布目、絹格子、ストライプ、絹目、チリメン、クレープ等の形状が挙げられる。 The shape of the concavo-convex portion is not particularly limited, and examples thereof include shapes such as dots, satin, cloth, silk lattice, stripe, silk, chilemen, and crepe in a plan view.
工程２は、工程１で形成した前記塗膜を、酸化性雰囲気中、４００℃以上、６６０℃未満の温度で熱処理することにより光触媒層を得る。 Step 2 obtains a photocatalyst layer by heat-treating the coating film formed in Step 1 at a temperature of 400 ° C. or higher and lower than 660 ° C. in an oxidizing atmosphere.
酸化性雰囲気中で熱処理する方法としては特に限定されない。酸化性雰囲気とは、酸素を含む雰囲気であればよく、酸素を単独で充填してもよく、又は酸素を非還元性ガスとともに充填してもよい。また、酸素としてはより酸化性の高いオゾンガスを用いてもよい。なお、酸化性雰囲気としては、酸素を２体積％以上、５０体積％以下含む空間であることが好ましい。 It does not specifically limit as a method to heat-process in an oxidizing atmosphere. The oxidizing atmosphere may be an atmosphere containing oxygen, and may be filled with oxygen alone, or may be filled with oxygen together with a non-reducing gas. Oxygen gas having higher oxidizability may be used as oxygen. The oxidizing atmosphere is preferably a space containing 2 volume% or more and 50 volume% or less of oxygen.
加熱温度は４００℃以上、６６０℃未満とし、５００℃以上、６４０℃以下が好ましい。加熱温度を４００℃以上とすることで、後述の非晶質の二酸化チタン前駆物質の結晶化や、有機系バインダーの分解、二酸化チタン粒子同士の焼結、アルミニウムの酸化物の層の形成がより効率的に進む。熱処理工程において、加熱雰囲気の圧力は特に限定されず、常圧、減圧又は加圧下であってもよい。 The heating temperature is 400 ° C. or higher and lower than 660 ° C., preferably 500 ° C. or higher and 640 ° C. or lower. By setting the heating temperature to 400 ° C. or higher, crystallization of an amorphous titanium dioxide precursor described later, decomposition of an organic binder, sintering of titanium dioxide particles, and formation of an aluminum oxide layer are more possible. Proceed efficiently. In the heat treatment step, the pressure of the heating atmosphere is not particularly limited, and may be normal pressure, reduced pressure, or increased pressure.
酸化性雰囲気中で加熱する工程を備えることで、塗布液にゾルゲル法等の非晶質の二酸化チタン前駆物質を用いた場合には、二酸化チタンの結晶化を促進し、光触媒性能を高めることができる。更に、塗布液中に有機系のバインダーを用いた場合には、二酸化チタンの表面を被覆した有機系のバインダーを分解させることで光触媒性能を高めることができる。また、二酸化チタン粒子同士の焼結により適度にネッキングが進むことで、光触媒層の強度を上げると共に、アルミニウム材とも焼結が起こり、アルミニウム材と光触媒層との密着性が向上する。さらにまた、光触媒層とアルミニウム材の間にアルミニウムの酸化物の層が厚く形成され、光触媒層で生じた電子がアルミニウム材に流れることを防止できるため、光触媒性能を高めることができる。 By providing a heating step in an oxidizing atmosphere, when an amorphous titanium dioxide precursor such as a sol-gel method is used in the coating solution, crystallization of titanium dioxide is promoted and photocatalytic performance is improved. it can. Furthermore, when an organic binder is used in the coating solution, the photocatalytic performance can be enhanced by decomposing the organic binder covering the surface of titanium dioxide. In addition, the necking proceeds moderately by sintering the titanium dioxide particles, so that the strength of the photocatalyst layer is increased and the aluminum material is also sintered, thereby improving the adhesion between the aluminum material and the photocatalyst layer. Furthermore, a thick oxide layer of aluminum is formed between the photocatalyst layer and the aluminum material, and electrons generated in the photocatalyst layer can be prevented from flowing into the aluminum material, so that the photocatalytic performance can be improved.
以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。なお、以下の実施例１〜１０及び比較例１〜４では、アルミニウム材の両面に光触媒層を形成した。 The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples. In Examples 1 to 10 and Comparative Examples 1 to 4 below, photocatalyst layers were formed on both surfaces of the aluminum material.
実施例１
厚みが３０μｍ、マグネシウムの含有量が１．７ｐｐｍである純度９９．８９質量％のアルミニウム材に、平均粒子径が約１４ｎｍの二酸化チタン（日本アエロジル製Ｐ９０）をビーズミリングにて分散させた水溶液を両面にコートし、１００℃で乾燥させて、二酸化チタンの付着量が片面約０．８５ｇ／ｍ２となるように二酸化チタンを付着させた。
Example 1
An aqueous solution in which titanium dioxide (P90 manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of about 14 nm is dispersed by bead milling in an aluminum material having a thickness of 30 μm and a magnesium content of 1.7 ppm and a purity of 99.89% by mass. Both sides were coated and dried at 100 ° C. to attach titanium dioxide so that the amount of titanium dioxide attached was about 0.85 g / m 2 on one side.
その後、空気中にて５５０℃で１０時間加熱することにより、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面を走査型電子顕微鏡（ＳＥＭ）で観察したところ、光触媒層の厚みは片面０．５μｍであった。 Then, the photocatalyst layer coat | covered aluminum material was obtained by heating at 550 degreeC for 10 hours in the air. When the obtained sample was cut with a microtome and the cross section was observed with a scanning electron microscope (SEM), the thickness of the photocatalyst layer was 0.5 μm on one side.
実施例２
厚みが３０μｍ、マグネシウムの含有量が３４ｐｐｍである純度９７．８４質量％のアルミニウム材を用いた以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面０．５μｍであった。
Example 2
A photocatalyst layer-covered aluminum material was obtained in the same manner as in Example 1 except that an aluminum material having a thickness of 30 μm and a magnesium content of 34 ppm and having a purity of 97.84% by mass was used. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 0.5 μm on one side.
実施例３
厚みが３０μｍ、マグネシウムの含有量が１０９０ｐｐｍである純度９７．８５質量％のアルミニウム材を用いた以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面０．５μｍであった。
Example 3
A photocatalyst layer-covered aluminum material was obtained in the same manner as in Example 1 except that an aluminum material having a thickness of 30 μm and a magnesium content of 1090 ppm and having a purity of 97.85% by mass was used. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 0.5 μm on one side.
実施例４
厚みが３０μｍ、マグネシウムの含有量が１１１００ｐｐｍである純度９６．９６質量％のアルミニウム材を用い、二酸化チタンの付着量を片面約１．２３ｇ／ｍ２とした以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面０．７μｍであった。
Example 4
Example 1 except that an aluminum material having a thickness of 30 μm and a magnesium content of 11100 ppm and a purity of 96.96% by mass was used, and the amount of titanium dioxide deposited was about 1.23 g / m 2 on one side. A photocatalyst layer-coated aluminum material was obtained. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 0.7 μm on one side.
実施例５
厚みが５０μｍ、マグネシウムの含有量が１１１００ｐｐｍである純度９６．９６質量％のアルミニウム材を用い、二酸化チタンの付着量を片面約２．０４ｇ／ｍ２とした以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面１．２μｍであった。
Example 5
Example 1 except that an aluminum material having a thickness of 50 μm and a magnesium content of 11100 ppm and having a purity of 96.96% by mass was used, and the amount of titanium dioxide deposited was about 2.04 g / m 2 on one side. A photocatalyst layer-coated aluminum material was obtained. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 1.2 μm on one side.
実施例６
厚みが３５μｍ、マグネシウムの含有量が２４８００ｐｐｍである純度９６．８３質量％のアルミニウム材を用い、二酸化チタンの付着量を片面約２．８１ｇ／ｍ２とした以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面１．７μｍであった。
Example 6
Example 1 except that an aluminum material having a thickness of 35 μm and a magnesium content of 24800 ppm and a purity of 96.83% by mass was used, and the amount of titanium dioxide deposited was about 2.81 g / m 2 on one side. A photocatalyst layer-coated aluminum material was obtained. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 1.7 μm on one side.
実施例７
厚みが１２μｍ、マグネシウムの含有量が１０９０ｐｐｍである純度９７．８５質量％のアルミニウム材を用いた以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面０．５μｍであった。
Example 7
A photocatalyst layer-covered aluminum material was obtained in the same manner as in Example 1 except that an aluminum material having a thickness of 12 μm and a magnesium content of 1090 ppm and having a purity of 97.85% by mass was used. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 0.5 μm on one side.
実施例８
厚みが１６０μｍ、マグネシウムの含有量が１０９０ｐｐｍである純度９７．８５質量％のアルミニウム材を用いた以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面０．５μｍであった。
Example 8
A photocatalyst layer-covered aluminum material was obtained in the same manner as in Example 1 except that an aluminum material having a thickness of 160 μm and a magnesium content of 1090 ppm and having a purity of 97.85% by mass was used. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 0.5 μm on one side.
実施例９
平均粒子径が約２１ｎｍの二酸化チタン（日本アエロジル製Ｐ２５）を用い、アルミニウム材への二酸化チタン付着後の空気中での加熱を５９０℃で１０時間とした以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面０．５μｍであった。
Example 9
In the same manner as in Example 1 except that titanium dioxide having an average particle diameter of about 21 nm (P25 manufactured by Nippon Aerosil Co., Ltd.) and heating in air after titanium dioxide adhesion to the aluminum material was performed at 590 ° C. for 10 hours, A photocatalyst layer-coated aluminum material was obtained. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 0.5 μm on one side.
実施例１０
平均粒子径が約２１ｎｍの二酸化チタン（日本アエロジル製Ｐ２５）を用い、アルミニウム材への二酸化チタン付着後の空気中での加熱を５９０℃で１０時間とした以外は実施例６と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面１．８μｍであった。
Example 10
In the same manner as in Example 6 except that titanium dioxide having an average particle size of about 21 nm (P25 manufactured by Nippon Aerosil Co., Ltd.) and heating in air after titanium dioxide adhesion to the aluminum material was performed at 590 ° C. for 10 hours, A photocatalyst layer-coated aluminum material was obtained. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 1.8 μm on one side.
比較例１
厚みが３０μｍ、マグネシウムの含有量が１１１００ｐｐｍである純度９６．９６質量％のアルミニウム材を用いた以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面０．５μｍであった。
Comparative Example 1
A photocatalyst layer-covered aluminum material was obtained in the same manner as in Example 1 except that an aluminum material having a thickness of 30 μm and a magnesium content of 11100 ppm and having a purity of 96.96% by mass was used. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 0.5 μm on one side.
比較例２
厚みが５０μｍ、マグネシウムの含有量が１１１００ｐｐｍである純度９６．９６質量％のアルミニウム材を用い、二酸化チタンの付着量を片面約１．６５ｇ／ｍ２とした以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面１．０μｍであった。
Comparative Example 2
Using an aluminum material having a thickness of 50 μm and a magnesium content of 11100 ppm and a purity of 96.96% by mass, the same as in Example 1 except that the amount of titanium dioxide attached was about 1.65 g / m 2 on one side, A photocatalyst layer-coated aluminum material was obtained. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 1.0 μm on one side.
比較例３
厚みが３５μｍ、マグネシウムの含有量が２４８００ｐｐｍである純度９６．８３質量％のアルミニウム材を用い、二酸化チタンの付着量を片面約２．４５ｇ／ｍ２とした以外は実施例１と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面１．４μｍであった。
Comparative Example 3
Example 1 except that an aluminum material having a thickness of 35 μm and a magnesium content of 24800 ppm and a purity of 96.83 mass% was used, and the amount of titanium dioxide deposited was about 2.45 g / m 2 on one side. A photocatalyst layer-coated aluminum material was obtained. When the obtained sample was cut with a microtome and the cross section was observed with SEM, the thickness of the photocatalyst layer was 1.4 μm on one side.
以下の実施例１０、比較例５ではアルミニウム材の片面に光触媒層を形成した。 In Example 10 and Comparative Example 5 below, a photocatalytic layer was formed on one surface of an aluminum material.
比較例４
平均粒子径が約２１ｎｍの二酸化チタン（日本アエロジル製Ｐ２５）を用い、アルミニウム材への二酸化チタン付着後の空気中での加熱を５９０℃で１０時間とした以外は比較例３と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面１．５μｍであった。
Comparative Example 4
In the same manner as in Comparative Example 3 except that titanium dioxide having an average particle diameter of about 21 nm (P25 manufactured by Nippon Aerosil Co., Ltd.) and heating in air after titanium dioxide adhesion to the aluminum material was changed to 590 ° C. for 10 hours, A photocatalyst layer-coated aluminum material was obtained. When the obtained sample was cut with a microtome and the cross section was observed with an SEM, the thickness of the photocatalyst layer was 1.5 μm on one side.
実施例１１
厚みが３０μｍ、マグネシウムの含有量が１１１００ｐｐｍである純度９９．８９質量％のアルミニウム材に、平均粒子径が約１４ｎｍの二酸化チタン（日本アエロジル製Ｐ９０）をビーズミリングにて分散させた水溶液を片面にコートし、１００℃で乾燥させて、二酸化チタンの付着量が約１．９１ｇ／ｍ２となるように二酸化チタンを付着させた。
Example 11
An aqueous solution in which titanium dioxide (P90 manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of about 14 nm is dispersed on an aluminum material having a thickness of 30 μm and a magnesium content of 11100 ppm with a purity of 99.89% by mass on one side. It was coated and dried at 100 ° C. to attach titanium dioxide so that the amount of titanium dioxide attached was about 1.91 g / m 2 .
その後、空気中にて５５０℃で１０時間加熱することにより、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面を走査型電子顕微鏡（ＳＥＭ）で観察したところ、光触媒層の厚みは１．１μｍであった。 Then, the photocatalyst layer coat | covered aluminum material was obtained by heating at 550 degreeC for 10 hours in the air. When the obtained sample was cut with a microtome and the cross section was observed with a scanning electron microscope (SEM), the thickness of the photocatalyst layer was 1.1 μm.
比較例５
二酸化チタンの付着量を約１．７７ｇ／ｍ２とした以外は実施例７と同様にして、光触媒層被覆アルミニウム材を得た。得られた試料をミクロトームで切断し、断面をＳＥＭで観察したところ、光触媒層の厚みは片面１．４μｍであった。
Comparative Example 5
A photocatalyst layer-coated aluminum material was obtained in the same manner as in Example 7 except that the amount of titanium dioxide deposited was about 1.77 g / m 2 . When the obtained sample was cut with a microtome and the cross section was observed with SEM, the thickness of the photocatalyst layer was 1.4 μm on one side.
試験例１（断面観察）
実施例１及び比較例１で作製した光触媒層被覆アルミニウム材について、光触媒層の表面に白金蒸着を行い、更にカーボンペーストを積層し、次にイオンミリングにて切断することにより断面観察用の試料を作製し、電解放射型走査電子顕微鏡（ＦＥ−ＳＥＭ）を用いて断面観察を行った。
Test example 1 (cross-sectional observation)
For the photocatalyst layer-covered aluminum material produced in Example 1 and Comparative Example 1, platinum was vapor-deposited on the surface of the photocatalyst layer, a carbon paste was further laminated, and then cut by ion milling to obtain a sample for cross-sectional observation. It produced and cross-sectional observation was performed using the electrolytic emission scanning electron microscope (FE-SEM).
実施例１の断面観察像を図１に示し、比較例１の断面観察像を図２に示す。実施例１では、二酸化チタンの粒子が加熱によって焼結し、粒子同士が適度にネッキングしていることが分かる。一方、比較例１では、焼結が過剰に進み、粒子の形状が殆ど残っていない。 A cross-sectional observation image of Example 1 is shown in FIG. 1, and a cross-sectional observation image of Comparative Example 1 is shown in FIG. In Example 1, it turns out that the particle | grains of titanium dioxide are sintered by heating, and particle | grains are necked moderately. On the other hand, in Comparative Example 1, sintering proceeds excessively and almost no particle shape remains.
試験例２（エネルギー分散型Ｘ線分光法（ＥＤＸ）分析）
断面観察に用いた実施例１及び比較例１の試料について、厚み方向でＥＤＸによる線分析を行った。実施例１を図３に示し、比較例１を図４に示す。
Test example 2 (energy dispersive X-ray spectroscopy (EDX) analysis)
About the sample of Example 1 used for cross-sectional observation, and the comparative example 1, the line analysis by EDX was performed in the thickness direction. Example 1 is shown in FIG. 3, and Comparative Example 1 is shown in FIG.
実施例１では、アルミニウム材と光触媒層にマグネシウムの集積は確認されない。一方、比較例１では、アルミニウム材の表面と光触媒層にマグネシウムの集積が確認され、特に光触媒層でのマグネシウムの集積が顕著である。 In Example 1, accumulation of magnesium is not confirmed in the aluminum material and the photocatalyst layer. On the other hand, in Comparative Example 1, accumulation of magnesium was confirmed on the surface of the aluminum material and the photocatalyst layer, and in particular, accumulation of magnesium in the photocatalyst layer was remarkable.
試験例３（Ｘ線回折（ＸＲＤ）測定）
実施例１〜６及び比較例１〜３で作製した光触媒層被覆アルミニウム材について、ＸＲＤ測定を行った結果を図に示す。ＸＲＤ測定は、Ｃｕ−Ｋα線を用い、加速電圧が４０ｋＶで、走査軸２θを５°から９０°までの範囲とし、薄膜Ｘ線回折法によって行った。
Test Example 3 (X-ray diffraction (XRD) measurement)
The result of having performed XRD measurement about the photocatalyst layer covering aluminum material produced in Examples 1-6 and comparative examples 1-3 is shown in a figure. XRD measurement was performed by a thin film X-ray diffraction method using Cu-Kα rays, an acceleration voltage of 40 kV, a scanning axis 2θ ranging from 5 ° to 90 °.
実施例１及び２では、主にアルミニウムとアナターゼ型及びルチル型の二酸化チタンのピークが確認される。実施例３から６では、マグネシウムと二酸化チタンが反応して生成されたと思われる、チタン酸マグネシウム（ＭｇＴｉＯ３）のピークが確認されるが、二酸化チタンのピークも同時に確認される。比較例１から３では、ＭｇＴｉＯ３のピークは確認されるが、二酸化チタンのピークは殆ど確認されない。 In Examples 1 and 2, the peaks of aluminum and anatase-type and rutile-type titanium dioxide are mainly confirmed. In Examples 3 to 6, the peak of magnesium titanate (MgTiO 3 ), which is considered to be produced by the reaction of magnesium and titanium dioxide, is confirmed, but the peak of titanium dioxide is also confirmed at the same time. In Comparative Examples 1 to 3, the peak of MgTiO 3 is confirmed, but the peak of titanium dioxide is hardly confirmed.
試験例４（ＩＣＰ発光分光分析）
実施例１〜１１及び比較例１〜５で作製した光触媒層被覆アルミニウム材について、ＩＣＰ発光分光分析を行い、光触媒層被覆アルミニウム材における単位面積当たりのマグネシウム含有量及び光触媒層のチタン含有量を測定した。
Test Example 4 (ICP emission spectroscopic analysis)
The photocatalyst layer-coated aluminum materials prepared in Examples 1 to 11 and Comparative Examples 1 to 5 were subjected to ICP emission spectroscopic analysis, and the magnesium content per unit area in the photocatalyst layer-coated aluminum material and the titanium content of the photocatalyst layer were measured. did.
《マグネシウム含有量の測定方法》
光触媒層被覆アルミニウム材０．１００ｇを平板状で採取し、１８％塩酸４ｍｌと３０％硝酸１ｍｌの混合溶液を用いてアルミニウム材のみを溶解させた。溶液を濾過し、液層と固形分（光触媒層に相当）に分離した後、液層を採取してＩＣＰ発光分光分析を行い、アルミニウム材のマグネシウム量を測定した。さらに固形分を洗浄後に５０％弗酸６ｍｌと６０％硝酸２ｍｌの混合溶液に加え、マイクロウェーブ加熱分解によって溶解させ、ＩＣＰ発光分光分析を行い、固形分のマグネシウム量を測定した。それぞれのマグネシウム量を合算し、光触媒層被覆アルミニウム材におけるマグネシウム含有量とした。
<Method for measuring magnesium content>
A photocatalyst layer-coated aluminum material (0.100 g) was collected in a flat plate shape, and only the aluminum material was dissolved using a mixed solution of 18% hydrochloric acid (4 ml) and 30% nitric acid (1 ml). The solution was filtered and separated into a liquid layer and a solid content (corresponding to a photocatalyst layer), and then the liquid layer was collected and subjected to ICP emission spectroscopic analysis to measure the magnesium content of the aluminum material. Further, after washing the solid content, it was added to a mixed solution of 6 ml of 50% hydrofluoric acid and 2 ml of 60% nitric acid, dissolved by microwave thermal decomposition, ICP emission spectroscopic analysis was performed, and the magnesium content of the solid content was measured. The respective magnesium amounts were added together to obtain the magnesium content in the photocatalyst layer-covered aluminum material.
《チタン含有量の測定方法》
光触媒層被覆アルミニウム材０．１００ｇを平板状で採取し、１８％塩酸４ｍｌと３０％硝酸１ｍｌの混合溶液を用いてアルミニウム材のみを溶解させた。溶液を濾過し、液層と固形分（光触媒層に相当）に分離した後、さらに固形分を洗浄後に５０％弗酸６ｍｌと６０％硝酸２ｍｌの混合溶液に加え、マイクロウェーブ加熱分解によって溶解させ、ＩＣＰ発光分光分析を行い、固形分のチタン含有量を測定した。
<< Method for measuring titanium content >>
A photocatalyst layer-coated aluminum material (0.100 g) was collected in a flat plate shape, and only the aluminum material was dissolved using a mixed solution of 18% hydrochloric acid (4 ml) and 30% nitric acid (1 ml). The solution is filtered and separated into a liquid layer and a solid content (corresponding to a photocatalyst layer). After further washing, the solid content is added to a mixed solution of 6 ml of 50% hydrofluoric acid and 2 ml of 60% nitric acid, and dissolved by microwave pyrolysis. ICP emission spectroscopic analysis was performed to measure the titanium content of the solid content.
試験例５（光触媒能力測定）
実施例１〜１１及び比較例１〜５で作製した光触媒層被覆アルミニウム材を３０ｍｍ×３０ｍｍにカットして１Ｌのガスバッグの中に入れ、真空に引いた後に、アセトアルデヒド濃度を１００ｐｐｍに調整した空気を０．５Ｌ注入した。１０分間放置した後、高輝度平行光束光源装置（ワコム電創製 ＨＸ−５０４、光源：キセノンランプ ＫＸＬ−５００Ｆ）を用いて、試料表面の３６５ｎｍにおける紫外線強度が３．０ｍＷ／ｃｍ２となるように片面に光を照射した。１時間照射後、ガスバッグ内のガスをサンプリングし、アセトアルデヒド濃度をガスクロマトグラフ（島津製作所製 ＧＣ−２０１４）にて測定した。
Test Example 5 (photocatalytic ability measurement)
The photocatalyst layer-covered aluminum materials produced in Examples 1 to 11 and Comparative Examples 1 to 5 were cut into 30 mm × 30 mm, placed in a 1 L gas bag, and after vacuuming, the acetaldehyde concentration was adjusted to 100 ppm. Of 0.5 L was injected. After standing for 10 minutes, using a high-intensity parallel beam light source device (Wacom Denso HX-504, light source: xenon lamp KXL-500F), the UV intensity at 365 nm on the sample surface is 3.0 mW / cm 2. One side was irradiated with light. After irradiation for 1 hour, the gas in the gas bag was sampled, and the acetaldehyde concentration was measured with a gas chromatograph (GC-2014, manufactured by Shimadzu Corporation).
試験例４、試験例５の測定結果並びに実施例及び比較例のまとめを、光触媒層を両面に形成したものについては下記表１、片面に形成したものについては下記表２に示す。また、実施例及び比較例に用いたアルミニウム材の主要な含有元素量の一覧を下記表３に示す。 The measurement results of Test Example 4 and Test Example 5 and the summary of Examples and Comparative Examples are shown in Table 1 below for the photocatalyst layer formed on both sides and in Table 2 below for those formed on one side. In addition, Table 3 below shows a list of main contained element amounts of the aluminum materials used in Examples and Comparative Examples.
ここで、光触媒層中のチタン原子に対する光触媒層被覆アルミニウム材中のマグネシウム原子のモル比については、ＩＣＰ発光分光分析で得られた各原子の含有量から単位面積あたりの各原子のモル数を計算し、これらのモル数からモル比を計算した。 Here, regarding the molar ratio of the magnesium atom in the photocatalyst layer-covered aluminum material to the titanium atom in the photocatalyst layer, the number of moles of each atom per unit area is calculated from the content of each atom obtained by ICP emission spectroscopic analysis. The molar ratio was calculated from the number of moles.
実施例１〜１１では、１時間の照射によってアセトアルデヒドが０ｐｐｍ（検出限界以下）か、少なくとも半分以下まで減少している。一方、比較例１〜５では、減少量が５ｐｐｍ未満で、殆ど光触媒能力を示していない。 In Examples 1 to 11, acetaldehyde was reduced to 0 ppm (below the detection limit) or at least half or less by irradiation for 1 hour. On the other hand, in Comparative Examples 1-5, the amount of reduction is less than 5 ppm, and hardly shows photocatalytic ability.
（考 察）
以上の結果から、光触媒層中のチタン原子に対する光触媒層被覆アルミニウム材中のマグネシウム原子のモル比を算出したところ、光触媒層が片面に形成される場合はモル比が１．６０以下、両面に形成される場合はモル比が１．４５以下であり、光触媒層の厚みが０．０５μｍ以上、５μｍ以下である実施例１〜１１は、比較例１〜５と比較して光触媒能力に優れていることが分かる。
(Discussion)
From the above results, the molar ratio of magnesium atoms in the photocatalyst layer-covered aluminum material to the titanium atoms in the photocatalyst layer was calculated. When the photocatalyst layer was formed on one side, the molar ratio was 1.60 or less and formed on both sides. Examples 1 to 11 in which the molar ratio is 1.45 or less and the thickness of the photocatalyst layer is 0.05 μm or more and 5 μm or less are superior in photocatalytic ability as compared with Comparative Examples 1 to 5. I understand that.
Claims (5)
（１）前記アルミニウム材及び／又は前記光触媒層がマグネシウム原子を含有し、
（２）前記光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭ１とし、同じ単位面積当たりの前記光触媒層中のチタン原子のモル数をＭ２とし、Ｍ１／Ｍ２で表されるモル比が、前記アルミニウム材の片面に前記光触媒層が形成されている場合は１．６０以下であり、前記アルミニウム材の両面に前記光触媒層が形成されている場合は１．４５以下であり、
（３）前記光触媒層の厚みは、０．０５μｍ以上、５μｍ以下である、
ことを特徴とする光触媒層被覆アルミニウム材。 A photocatalyst layer-covered aluminum material having an aluminum material and a photocatalyst layer containing titanium dioxide formed on one or both surfaces of the aluminum material,
(1) The aluminum material and / or the photocatalyst layer contains a magnesium atom,
(2) M 1 is the number of moles of magnesium atoms per unit area in the photocatalyst layer-covered aluminum material, M 2 is the number of moles of titanium atoms in the photocatalyst layer per unit area, and M 1 / M 2 Is less than 1.60 when the photocatalyst layer is formed on one side of the aluminum material, and 1.45 when the photocatalyst layer is formed on both sides of the aluminum material. And
(3) The thickness of the photocatalyst layer is 0.05 μm or more and 5 μm or less.
A photocatalyst layer-coated aluminum material.
（１）前記アルミニウム材及び／又は前記光触媒層がマグネシウム原子を含有し、
（２）前記光触媒層被覆アルミニウム材における単位面積当たりの前記マグネシウム原子のモル数をＭｘとし、同じ単位面積当たりの前記光触媒層中のチタン原子のモル数をＭｙとし、Ｍｘ／Ｍｙで表されるモル比が、前記アルミニウム材の片面に前記光触媒層が形成されている場合は１．６０以下であり、前記アルミニウム材の両面に前記光触媒層が形成されている場合は１．４５以下であり、
（３）前記光触媒層の厚みは、０．０５μｍ以上、５μｍ以下である、
ことを特徴とする光触媒層被覆アルミニウム材の製造方法。 Step 1 of forming a coating film containing titanium dioxide and / or a precursor thereof on one or both surfaces of an aluminum material, and heat-treating the coating film at a temperature of 400 ° C. or more and less than 660 ° C. in an oxidizing atmosphere. A method for producing a photocatalyst layer-covered aluminum material comprising the step 2 of obtaining a layer,
(1) The aluminum material and / or the photocatalyst layer contains a magnesium atom,
(2) the number of moles of the magnesium atoms per unit area in the photocatalytic layer coated aluminum material as M x, the number of moles of titanium atoms of the photocatalyst layer per the same unit area and M y, M x / M y Is less than 1.60 when the photocatalyst layer is formed on one side of the aluminum material, and 1.45 when the photocatalyst layer is formed on both sides of the aluminum material. And
(3) The thickness of the photocatalyst layer is 0.05 μm or more and 5 μm or less.
A method for producing a photocatalyst layer-coated aluminum material.
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