JPH1018083A - Production of metal material coated with titanium oxide - Google Patents
Production of metal material coated with titanium oxideInfo
- Publication number
- JPH1018083A JPH1018083A JP8171245A JP17124596A JPH1018083A JP H1018083 A JPH1018083 A JP H1018083A JP 8171245 A JP8171245 A JP 8171245A JP 17124596 A JP17124596 A JP 17124596A JP H1018083 A JPH1018083 A JP H1018083A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- film
- metal material
- cathode
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000007769 metal material Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 239000007800 oxidant agent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 229910052719 titanium Inorganic materials 0.000 abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005370 electroosmosis Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 57
- 238000000034 method Methods 0.000 description 31
- 239000002245 particle Substances 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- -1 titanium alkoxide Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- 239000003973 paint Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001112 coagulating effect Effects 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910001924 platinum group oxide Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化チタン被覆金
属材料の製造方法に関するものである。更に詳しく述べ
るならば、本発明は、ステンレス、アルミニウム、鉄、
亜鉛めっき鋼、および銅、などの金属材料の表面に、陰
極電解により光触媒機能を有する酸化チタン皮膜を形成
する方法に関するものである。The present invention relates to a method for producing a titanium oxide-coated metal material. More specifically, the present invention relates to stainless steel, aluminum, iron,
The present invention relates to a method for forming a titanium oxide film having a photocatalytic function on a surface of a metal material such as galvanized steel and copper by cathodic electrolysis.
【０００２】[0002]
【従来の技術】酸化チタンは、固体材料の表面に高い光
触媒効果を付与させることが可能であり、例えば金属、
ガラス、セラミックなどの素材表面に、光触媒効果を有
する酸化チタン皮膜を形成させることにより、当該材料
表面に付着汚れの分解、大気および水質の浄化、防錆、
並びに細菌および藻類の繁殖防止、などの機能を付与
し、これを各種用途に利用できることが知られている。2. Description of the Related Art Titanium oxide can impart a high photocatalytic effect to the surface of a solid material.
By forming a titanium oxide film having a photocatalytic effect on the surface of a material such as glass and ceramic, decomposition of dirt attached to the material surface, purification of air and water quality, rust prevention,
Also, it is known that a function such as prevention of reproduction of bacteria and algae is imparted, and this can be used for various purposes.
【０００３】このため、より良好な酸化チタン皮膜を素
材表面に形成することを目的として、これまでに種々の
酸化チタン被覆方法が提案されてきた。[0003] Therefore, various titanium oxide coating methods have been proposed so far for the purpose of forming a better titanium oxide film on the surface of a material.
【０００４】各種材料表面を酸化チタンにより被覆する
方法としては、チタンのアルコキシドの加水分解生成物
を塗布する方法、すなわちゾル−ゲル法が最も一般的で
あり、これに類する他の技術としては、例えば特開平４
−８３５３７号公報に示されるチタンアルコキシドにア
ミド、および／又はグリコールを添加し、その反応生成
物を利用する方法、および特開平７−１００３７８号公
報に示されているように、チタンアルコキシドにアルコ
ールアミン類を添加し、その反応生成物を塗料成分とし
て用いる方法が開示されている。[0004] As a method of coating the surface of various materials with titanium oxide, a method of applying a hydrolysis product of an alkoxide of titanium, that is, a sol-gel method, is the most common, and other techniques similar thereto include: For example, JP
JP-A-83537 discloses a method of adding an amide and / or glycol to a titanium alkoxide and utilizing a reaction product thereof, and as disclosed in JP-A-7-100378, an alcoholamine is added to a titanium alkoxide. And a method of using the reaction product as a paint component.
【０００５】また、この他には、特開平６−２９３５１
９号公報に記載されているように水熱処理により結晶化
させた酸化チタン微粒子を分散剤を使用して水中に分散
させ、これを塗布する方法、および結晶性酸化チタン粒
子に、水ガラス、コロイダルシリカ、弗素系樹脂などの
バインダーを混和し、これを固体材料表面に塗布する方
法などが知られている。[0005] In addition, Japanese Patent Laid-Open Publication No.
No. 9, a method of dispersing titanium oxide fine particles crystallized by hydrothermal treatment in water using a dispersant and applying the same, and adding water glass and colloidal to the crystalline titanium oxide particles There is known a method in which a binder such as silica or a fluorine-based resin is mixed and applied to the surface of a solid material.
【０００６】しかし、上記のゾル−ゲル法では、塗料の
粘度や塗布条件によって形成される皮膜の厚さが変化し
易く、皮膜の性能を高めるために厚膜化すると、乾燥の
際の皮膜の収縮が大きいため皮膜と基体表面との間の密
着性が低くなり、剥離し易くなるなどの問題点がある。
また、ゾル−ゲル法では、原料に有機チタン化合物を使
用するため原料が高価な点も問題であった。However, in the above-mentioned sol-gel method, the thickness of the formed film tends to change depending on the viscosity of the paint and the application conditions. Due to the large shrinkage, there is a problem that the adhesion between the film and the substrate surface is lowered, and the film is easily peeled off.
Also, the sol-gel method has a problem that the raw material is expensive because an organic titanium compound is used as the raw material.
【０００７】また、結晶成長させた酸化チタンをバイン
ダーと混合して塗料を調製し、この塗料を基体表面上に
塗布する方法では、得られる皮膜中の酸化チタン含有率
が低いため、光触媒能が充分に発揮されないという問題
があった。In the method of preparing a paint by mixing the crystal-grown titanium oxide with a binder and applying the paint on the surface of the substrate, the titanium oxide content in the obtained film is low, so that the photocatalytic activity is low. There was a problem that it was not sufficiently exhibited.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、金属材料の
表面に光触媒性を有する酸化チタン皮膜を形成する場合
に、従来のゾル−ゲル法などが有する問題点を解決し、
安価な無機チタン化合物を原料として使用し、形成され
る皮膜の厚さを１μｍ以上にしても、基体と皮膜との密
着性が損なわれない光触媒性に優れた酸化チタン皮膜被
覆金属材料の製造方法を提供しようとするものである。SUMMARY OF THE INVENTION The present invention solves the problems of the conventional sol-gel method and the like when forming a titanium oxide film having photocatalytic properties on the surface of a metal material.
A method for producing a metal material coated with a titanium oxide film having excellent photocatalytic properties that does not impair the adhesion between the substrate and the film even when the thickness of the formed film is 1 μm or more using an inexpensive inorganic titanium compound as a raw material. It is intended to provide.
【０００９】[0009]
【課題を解決するための手段】本発明者は、上記の技術
的課題を解決する手段について鋭意検討した結果、皮膜
成分である酸化チタンを構成するためのチタンを酸性の
電解浴中に、４価のチタンイオンとして存在せしめ、あ
わせてこの浴に硝酸イオン、亜硝酸イオン等のような酸
化窒素イオンおよびハロゲンを含む酸素酸イオンの少な
くとも１種を酸化剤として共存させ、この電解浴中で導
電性金属材料を陰極体とし、不溶性電極を陽極体として
電解処理することにより浴中のチタンを水和酸化チタン
として陰極金属材料表面に電解析出させうることを見出
した。Means for Solving the Problems As a result of intensive studies on the means for solving the above-mentioned technical problems, the present inventor has found that titanium for constituting titanium oxide as a film component is placed in an acidic electrolytic bath. At least one of nitric oxide ions such as nitrate ions and nitrite ions and oxyacid ions containing halogen as oxidizing agents. It has been found that titanium in a bath can be electrolytically deposited on the surface of a cathode metal material as a hydrated titanium oxide by performing an electrolytic treatment using a conductive metal material as a cathode body and an insoluble electrode as an anode body.
【００１０】また、本発明者は、前記電解析出により形
成された水和酸化チタン皮膜は、それを乾燥後、２００
℃以上で焼成することにより、光触媒活性を有し、密着
性に優れた二酸化チタン皮膜を形成し得ることを見出し
た。The inventor of the present invention has found that the hydrated titanium oxide film formed by the electrolytic deposition is dried after drying.
It has been found that by firing at a temperature of not less than ° C, a titanium dioxide film having photocatalytic activity and excellent adhesion can be formed.
【００１１】さらに発明者は、上記と同様の酸化剤イオ
ンを含有させた電解浴中に、４価のチタンイオンの代わ
りにコロイド状酸化チタンを含有させることにより、金
属材料表面上に酸化チタンが析出し、このようにして形
成された酸化チタン皮膜は、８０〜２００℃程度の乾燥
のみにより、良好な光触媒活性を示す酸化チタン皮膜を
形成し得ることを見出した。Further, the inventor of the present invention has proposed that titanium oxide is contained on the surface of a metal material by containing colloidal titanium oxide instead of tetravalent titanium ion in an electrolytic bath containing the same oxidizing agent ion as described above. It has been found that the titanium oxide film deposited and thus formed can form a titanium oxide film exhibiting good photocatalytic activity only by drying at about 80 to 200 ° C.
【００１２】また同時に、本発明者は、前記と同様な酸
化剤イオンを含む電解浴中に、４価のチタンイオンとコ
ロイド状酸化チタンとの両者を含有させることにより、
形成される酸化チタン皮膜の密着性がさらに向上するこ
とを見出した。At the same time, the present inventor has proposed that an electrolytic bath containing the same oxidizing agent ions as described above contains both tetravalent titanium ions and colloidal titanium oxide,
It has been found that the adhesion of the formed titanium oxide film is further improved.
【００１３】即ち本発明に係る酸化チタン被覆金属材料
の製造方法（１）は、ＮＯn - ，ＣｌＯn - ，ＢｒＯn
- 、およびＩＯn - （ｎは１，２、または３を表す）か
らなる群より選択された少なくとも１種を含む酸化剤
と、Ｔｉ4+イオンとを含み、０．１〜５の範囲内にある
ｐＨ値を有する電解液中に、被処理金属材料からなる陰
極体と、不溶性電極からなる陽極体とを配置し、これに
電解処理を施して、前記金属材料表面上に水和酸化チタ
ン含有皮膜を形成し、この皮膜を２００℃以上の温度で
焼成することを特徴とするものである。[0013] That method of manufacturing a titanium oxide-coated metal material according to the present invention (1) is, NO n -, ClO n - , BrO n
-, and IO n - (n is 1, 2 or 3 representing,) comprising an oxidizing agent containing at least one selected from the group consisting of, and Ti 4+ ions, in the range of 0.1 to 5 In an electrolytic solution having a certain pH value, a cathode body made of a metal material to be treated and an anode body made of an insoluble electrode are arranged, and subjected to an electrolytic treatment, and hydrated titanium oxide is placed on the surface of the metal material. A coating film is formed, and the coating film is fired at a temperature of 200 ° C. or higher.
【００１４】また、本発明の酸化チタン被覆金属材料の
製造方法（２）は、ＮＯn - ，ＣｌＯn - ，ＢｒＯn -
およびＩＯn - （ｎは１，２、または３を表す）からな
る群より選択された少なくとも１種を含む酸化剤と、コ
ロイド状酸化チタンとを含み、０．１〜５の範囲内にあ
るｐＨ値を有する電解液中に、被処理金属材料からなる
陰極体と、不溶性電極からなる陽極体とを配置し、これ
に電解処理を施して、前記金属材料表面上に、酸化チタ
ンを含有する皮膜を形成し、この皮膜を乾燥または焼成
することを特徴とするものである。[0014] A method of manufacturing a titanium oxide-coated metal material of the present invention (2) is, NO n -, ClO n - , BrO n -
And IO n - (n is 1, 2 or 3 representing,) an oxidizing agent containing at least one selected from the group consisting of, and a colloidal titanium oxide, in the range of 0.1 to 5 In an electrolytic solution having a pH value, a cathode body made of a metal material to be treated and an anode body made of an insoluble electrode are arranged, subjected to electrolytic treatment, and containing titanium oxide on the surface of the metal material. A film is formed, and the film is dried or fired.
【００１５】さらに、本発明の酸化チタン被覆金属材料
の製造方法（３）は、ＮＯn - ，ＣｌＯn - ，ＢｒＯn
- およびＩＯn - （ｎは１，２、または３を表す）から
なる群より選択された少なくとも１種を含む酸化剤と、
Ｔｉ4+イオンと、コロイド状酸化チタンとを含み、０．
１〜５の範囲内にあるｐＨ値を有する電解液中に、被処
理金属材料からなる陰極体と、不溶性電極からなる陽極
体とを配置し、これに電解処理を施して、前記金属材料
表面上に、水和酸化チタンおよび酸化チタンを含有する
皮膜を形成し、この皮膜を乾燥または焼成することを特
徴とするものである。Furthermore, the manufacturing method of the titanium oxide-coated metal material of the present invention (3) is, NO n -, ClO n - , BrO n
- the oxidizing agent (n is representative of the 1, 2, or 3) containing at least one selected from the group consisting of, - and IO n
Containing Ti 4+ ions and colloidal titanium oxide;
A cathode body made of a metal material to be treated and an anode body made of an insoluble electrode are arranged in an electrolytic solution having a pH value in the range of 1 to 5, and an electrolytic treatment is performed on the cathode body to form a surface of the metal material. A film containing hydrated titanium oxide and titanium oxide is formed thereon, and the film is dried or fired.
【００１６】前記本発明方法（１）および（３）におい
て、電解浴中に含まれるＴｉ4+イオン濃度の範囲は、好
ましくは０．１〜５０ｇ／リットル、より好ましくは
０．５〜２０ｇ／リットルである。In the methods (1) and (3) of the present invention, the range of the concentration of the Ti 4+ ion contained in the electrolytic bath is preferably 0.1 to 50 g / liter, more preferably 0.5 to 20 g / liter. Liters.
【００１７】前記４価チタンイオン濃度が０．１ｇ／リ
ットル未満では、十分な皮膜の厚さが得られないことが
あり、またそれが５０ｇ／リットルを超えると電解液の
持ち出し損失が多くなり不経済になることがある。If the tetravalent titanium ion concentration is less than 0.1 g / l, a sufficient film thickness may not be obtained, and if it exceeds 50 g / l, the loss of taking out the electrolyte increases and the It can be economic.
【００１８】[0018]
【発明の実施の形態】本発明方法（１）および（３）に
おいて、電解液に含まれるＴｉ4+イオンは、硫酸チタ
ン、オキシ硫酸チタン、四塩化チタン、オキシ塩化チタ
ンなどの水溶性チタン塩を水中に溶解することにより形
成されることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION In the methods (1) and (3) of the present invention, the Ti 4+ ion contained in the electrolytic solution is a water-soluble titanium salt such as titanium sulfate, titanium oxysulfate, titanium tetrachloride and titanium oxychloride. Is preferably formed by dissolving in water.
【００１９】また、水和酸化チタンを陰極電解により金
属材料表面上に析出させるためには、電解液中にＮＯn
- ，ＣｌＯn - ，ＢｒＯn - ，ＩＯn - （ｎは１，２、
または３を表す）例えばＮＯ3 - ，ＮＯ2 - ，Ｃｌ
Ｏ- ，ＣｌＯ2 - ，ＢｒＯ- 、およびＩＯ3 - からなる
群より選択された少なくとも１種を含む酸化剤を含むこ
とが必要である。Further, the hydrated titanium oxide in order to deposit on the metal material surface by cathodic electrolysis, NO n in the electrolyte
-, ClO n -, BrO n -, IO n - (n is 1,
Or 3) For example, NO 3 − , NO 2 − , Cl
It is necessary to include an oxidizing agent containing at least one selected from the group consisting of O − , ClO 2 − , BrO − , and IO 3 − .
【００２０】これらの酸化剤イオンのうち、ＮＯ3 - イ
オンが最も好ましく、次にＮＯ2 -イオンが好ましく、
次にＣｌＯ- ，ＣｌＯ2 - ，ＢｒＯ- 、およびＩＯ3 -
が好ましい。Of these oxidant ions, NO 3 - ions are most preferred, followed by NO 2 - ions,
Next ClO -, ClO 2 -, BrO -, and IO 3 -
Is preferred.
【００２１】酸化イオンの好ましい濃度（合計濃度）の
範囲は、０．１〜２０ｇ／リットルであり、より好まし
い合計濃度範囲は０．２〜８ｇ／リットルである。The preferable range of the concentration (total concentration) of the oxide ions is 0.1 to 20 g / liter, and the more preferable range of the total concentration is 0.2 to 8 g / liter.
【００２２】これらの酸化剤イオンは、これらの酸の形
で電解液に添加されても良いが、硝酸ナトリウム、硝酸
アンモニウム、亜塩素酸ナトリウムなどのようなアルカ
リ金属塩またはアンモニウム塩の形で電解液中に添加さ
れることがより好ましい。These oxidizing agent ions may be added to the electrolyte in the form of these acids, but may be added to the electrolyte in the form of an alkali metal salt such as sodium nitrate, ammonium nitrate, sodium chlorite or an ammonium salt. More preferably, it is added inside.
【００２３】酸化剤イオンの合計濃度が０．１ｇ／リッ
トル未満では、充分な皮膜付着量が得られず、また、一
旦付着したとしても、水素ガスの発生のために金属材料
表面から脱落しやすくなることがあり、またそれが２０
ｇ／リットルを超えると、酸化剤イオンが生成した皮膜
中に多く残るため金属材料の腐食が起きやすくなる。If the total concentration of the oxidizing agent ions is less than 0.1 g / liter, a sufficient amount of the coating film cannot be obtained, and even if the oxidizing agent ion once adheres, it tends to fall off from the surface of the metal material due to generation of hydrogen gas. And it is 20
If the amount exceeds g / liter, a large amount of oxidant ions remains in the formed film, so that corrosion of the metal material tends to occur.
【００２４】これらの酸化剤イオンの効果により、陰極
体で構成する金属材料表面には、電解処理の進行ととも
にチタン化合物が皮膜となって析出する。析出するチタ
ン化合物は、本発明方法（１）においては水和酸化チタ
ン（または水酸化チタン）であり、本発明方法（２）の
場合、二酸化チタンであり、本発明方法（３）の場合に
は水和酸化チタンと二酸化チタンとの混合物である。Due to the effect of these oxidant ions, a titanium compound is deposited as a film on the surface of the metal material constituting the cathode body as the electrolytic treatment proceeds. The precipitated titanium compound is hydrated titanium oxide (or titanium hydroxide) in the method (1) of the present invention, titanium dioxide in the method (2) of the present invention, and titanium dioxide in the method (3) of the present invention. Is a mixture of hydrated titanium oxide and titanium dioxide.
【００２５】また、本発明方法（１），（２）および
（３）に使用する電解液のｐＨ値は０．１〜５の範囲で
あることが必要で、好ましい範囲は０．５〜３．５であ
る。電解液のｐＨ値が０．１未満では、酸化剤イオン濃
度が十分であっても陰極表面のｐＨが十分に上昇せず、
チタン化合物の析出が困難になるため好ましくない。ま
た、ｐＨ値が５を超えると、電解液中のチタンイオンま
たはコロイド状チタン粒子が不安定となって沈降し易く
なるため好ましくない。The pH value of the electrolytic solution used in the methods (1), (2) and (3) of the present invention needs to be in the range of 0.1 to 5, and the preferred range is 0.5 to 3. .5. If the pH value of the electrolyte is less than 0.1, the pH of the cathode surface does not sufficiently increase even if the oxidant ion concentration is sufficient,
It is not preferable because precipitation of the titanium compound becomes difficult. On the other hand, when the pH value exceeds 5, the titanium ions or colloidal titanium particles in the electrolytic solution become unstable and tend to settle, which is not preferable.
【００２６】また、本発明方法（２）および（３）にお
いて使用される電解液に含まれるコロイド状酸化チタン
は、粒径が１〜１０-3μｍの範囲内にある酸化チタンコ
ロイド粒子を含むことが好ましく、より好ましい粒径は
１０-2〜１０-1μｍである。このコロイド状酸化チタン
は結晶性酸化チタンのコロイドであることが好ましく、
アナターゼ型酸化チタンのコロイドであることが最も好
ましい。The colloidal titanium oxide contained in the electrolytic solution used in the methods (2) and (3) of the present invention contains colloidal titanium oxide having a particle size in the range of 1 to 10 −3 μm. It is preferable that the particle size is more preferably 10 −2 to 10 −1 μm. The colloidal titanium oxide is preferably a colloid of crystalline titanium oxide,
Most preferably, it is a colloid of anatase type titanium oxide.
【００２７】コロイド状酸化チタン粒子の粒径が１μｍ
を超えるとコロイド粒子が沈降しやすく、皮膜と金属材
料表面との密着性も低下することがあるため好ましくな
く、また、それが１０-3μｍ未満では、得られる皮膜の
触媒活性が不十分になることがあるため好ましくない。The particle size of the colloidal titanium oxide particles is 1 μm
When the particle size exceeds 10 μm, the colloid particles are likely to settle, and the adhesion between the film and the metal material surface may be unfavorably reduced. When the particle size is less than 10 −3 μm, the obtained film has insufficient catalytic activity. It is not preferable because it may occur.
【００２８】本発明方法（２）および（３）において、
電解液中に含まれるコロイド状酸化チタンの好ましい濃
度は、３〜２００ｇ／リットルであり、より好ましい濃
度は１０〜１００ｇ／リットルである。In the methods (2) and (3) of the present invention,
The preferred concentration of the colloidal titanium oxide contained in the electrolyte is 3 to 200 g / liter, and the more preferred concentration is 10 to 100 g / liter.
【００２９】これらのコロイド状酸化チタン溶液は、チ
タン塩溶液、好ましくは硫酸チタン、オキシ硫酸チタ
ン、４塩化チタン、およびオキシ塩化チタン等のチタン
塩溶液を原料とし、この水溶液を、必要に応じて、水酸
化アルカリ溶液等で中和した後、５０℃以上の温度で５
分〜数時間加熱処理して調製し、これをそのまま使用し
てもよいが、これをさらにミクロフィルター等で濾過し
てコロイド粒子を再分散させたものを使用するか、又は
これに透析等による脱イオン処理を施して得られる、夾
雑イオンを含まないコロイド状酸化チタンを使用するこ
とにより電解液中の不純物を減少させることができるの
でより好ましい。These colloidal titanium oxide solutions are prepared from a titanium salt solution, preferably a titanium salt solution such as titanium sulfate, titanium oxysulfate, titanium tetrachloride, and titanium oxychloride. , Neutralized with an alkali hydroxide solution, etc.
It may be prepared by heat treatment for a few minutes to several hours, and may be used as it is.However, this is further filtered through a microfilter or the like to redisperse colloid particles, or dialysis or the like is used. It is more preferable to use colloidal titanium oxide containing no contaminating ions, which is obtained by performing a deionization treatment, since impurities in the electrolytic solution can be reduced.
【００３０】本発明方法（１），（２），（３）の各々
において、電解処理は、被処理体を陰極とすることが必
須であり、陽極としては、白金めっきを施されたチタ
ン、又は白金族系酸化物で被覆されたＤＳＥ（商標、ペ
ルメレック電極（株）製）のような不溶性電極を使用す
る。陽極として無処理のチタン材を使用すると、陽極表
面が不動態化して電流が流れにくくなるため、このよう
な陽極は好ましくない。In each of the methods (1), (2) and (3) of the present invention, it is essential for the electrolytic treatment that the object to be treated be a cathode, and the anode is platinum-plated titanium; Alternatively, an insoluble electrode such as DSE (trademark, manufactured by Permelec Electrode Co., Ltd.) coated with a platinum group oxide is used. If an untreated titanium material is used as the anode, the anode surface is passivated and current hardly flows, and thus such an anode is not preferable.
【００３１】電解処理における電流密度は、０．５〜５
０Ａ／ｄｍ2 が好ましく、皮膜の物性向上のためにパル
ス通電する場合は、５０Ａ／ｄｍ2 以上でもさしつかえ
ない。電解処理の通電時間は３〜１８０秒が好ましい。The current density in the electrolytic treatment is 0.5 to 5
0 A / dm 2 is preferable, and when a pulse current is applied to improve the physical properties of the film, 50 A / dm 2 or more may be used. The energization time of the electrolytic treatment is preferably 3 to 180 seconds.
【００３２】また、電解後、金属材料表面に形成された
皮膜を水洗または湯洗したのち乾燥することが好まし
い。生成した皮膜に対し、本発明方法（１）においては
焼成を施す必要があり、このため、電解処理により形成
された湿潤皮膜を好ましくは１００℃未満の温度で一旦
乾燥した後、これを２００℃以上、好ましくは２００〜
６００℃の温度で焼成する。After the electrolysis, it is preferable that the film formed on the surface of the metal material be washed with water or hot water and then dried. It is necessary to bake the formed film in the method (1) of the present invention. For this reason, the wet film formed by the electrolytic treatment is preferably dried once at a temperature lower than 100 ° C., and then dried at 200 ° C. Above, preferably 200 to
Baking at a temperature of 600 ° C.
【００３３】本発明方法（２）および（３）において
は、金属材料表面に形成された皮膜に対し、必ずしも焼
成は必要なく、２００℃未満の温度における乾燥のみで
実用に供することができるが、乾燥後、２００℃以上の
温度で焼成することが好ましく、より好ましい焼成温度
は２００〜４００℃である。In the methods (2) and (3) of the present invention, the film formed on the surface of the metal material does not necessarily need to be fired, and can be put to practical use only by drying at a temperature of less than 200 ° C. After drying, it is preferable to fire at a temperature of 200 ° C. or higher, and a more preferable firing temperature is 200 to 400 ° C.
【００３４】本発明方法（１），（２）および（３）に
おいて乾燥、または焼成後の皮膜は二酸化チタンからな
り、これはアナターゼ型二酸化チタンを主成分とする
が、電解、および焼成の条件に応じて、アナターゼ型酸
化チタンの他に、ルチル型酸化チタン、無定型酸化チタ
ンも含まれることがある。In the methods (1), (2) and (3) of the present invention, the film after drying or calcination is made of titanium dioxide, which is mainly composed of anatase type titanium dioxide. Depending on the type, rutile-type titanium oxide and amorphous titanium oxide may be included in addition to anatase-type titanium oxide.
【００３５】[0035]
【作用】本発明の方法（１），（２）および（３）によ
って酸化チタン皮膜が得られる原理は、電解中に、電解
浴中酸化剤イオンが陰極（金属材料）の表面において還
元を受け、陰極界面近傍のｐＨが急激に上昇することに
ある。この現象は、本発明方法（１），（２）および
（３）において特定された酸化剤イオンが陰極表面から
電子を受け取ることにより、陰極界面近傍にＯＨ- イオ
ンが発生（またはＨ + イオンを消費）するという特徴的
な反応を生起することによる。According to the methods (1), (2) and (3) of the present invention,
The principle that a titanium oxide film is obtained is that during electrolysis,
Oxidant ions in the bath return on the surface of the cathode (metal material)
That the pH near the cathode interface rises sharply
is there. This phenomenon is caused by the methods (1) and (2) of the present invention and
Oxidant ions specified in (3) are from the cathode surface
By receiving the electrons, OH near the cathode interface-Io
Occurs (or H +Characteristic of consuming ions)
By causing a serious reaction.
【００３６】これらの酸化剤イオンとともに電解浴中に
Ｔｉ4+イオンが存在する場合（本発明方法（１）および
（３））、陰極界面で発生したＯＨ- イオンと浴中のＴ
ｉ4+イオンとが反応してチタンの水酸化物（水和酸化
物）が沈澱析出する。When Ti 4+ ions are present in the electrolytic bath together with these oxidizing agent ions (methods (1) and (3) of the present invention), OH − ions generated at the cathode interface and T 4 in the bath are reduced.
Reaction with i 4+ ions precipitates and precipitates titanium hydroxide (hydrated oxide).
【００３７】また、浴中にコロイド状酸化チタンが存在
する場合（本発明方法（２），（３））、酸化チタンコ
ロイドはｐＨ５未満ではほぼ安定であるが、ｐＨが５よ
り高く上昇すると電荷を失い、ゲル化、凝集析出すると
いう特性を有し、前記のような陰極界面近傍におけるｐ
Ｈの上昇により陰極表面に析出する。When colloidal titanium oxide is present in the bath (methods (2) and (3) of the present invention), the titanium oxide colloid is almost stable at a pH lower than 5, but when the pH rises above 5, the charge becomes higher. And has the property of gelling and coagulating and precipitating.
The H precipitates on the cathode surface due to the rise of H.
【００３８】陰極金属材料表面で生ずる反応の例を下式
（１）および（２）に示し、焼成による脱水反応を下記
式（３）に示す。 反応（１）ＮＯ3 - ＋６Ｈ2 Ｏ＋８ｅ→ＮＨ3 ＋９ＯＨ- ＮＯ2 - ＋５Ｈ2 Ｏ＋６ｅ→ＮＨ3 ＋７ＯＨ- 反応（２）Ｔｉ4+＋４ＯＨ- →Ｔｉ（ＯＨ）4 ＴｉＯ2 （コロイドゾル）→ＴｉＯ2 （ゲル） 反応（３）Ｔｉ（ＯＨ）4 →ＴｉＯ2 （酸化チタン）＋２Ｈ2 ＯExamples of the reaction occurring on the surface of the cathode metal material are shown in the following formulas (1) and (2), and the dehydration reaction by firing is shown in the following formula (3). Reaction (1) NO 3 - + 6H 2 O + 8e → NH 3 + 9OH - NO 2 - + 5H 2 O + 6e → NH 3 + 7OH - Reaction (2) Ti 4+ + 4OH - → Ti (OH) 4 TiO 2 ( colloidal sol) → TiO 2 ( Gel) Reaction (3) Ti (OH) 4 → TiO 2 (titanium oxide) + 2H 2 O
【００３９】生成した酸化チタン皮膜の性質がゾル−ゲ
ル法など他の製造方法により得られるものに比較して優
れている理由としては、本発明方法において、水酸化物
が析出する際の陰極表面での過飽和度が非常に高いため
極めて微細な粒子からなる皮膜が析出すること、および
電解中に析出した皮膜から電気浸透作用により徐々に吸
着水や不純物アニオン（ＳＯ4 2- ，Ｃｌ- 等）が除去さ
れるため、密度、および純度が高く、厚さの厚い皮膜が
形成されることなどが考えられる。The reason that the properties of the formed titanium oxide film are superior to those obtained by other manufacturing methods such as the sol-gel method is that the method of the present invention is characterized in that the surface of the cathode when hydroxide is deposited is reduced. The supersaturation at the surface is so high that a film consisting of very fine particles is deposited, and the water deposited during electrolysis gradually absorbs water and impurity anions (SO 4 2- , Cl - etc.) by electroosmosis. It is conceivable that a high-density and high-purity film having a large thickness is formed because of the removal of the metal.
【００４０】また、通電したクーロン量、電解時間に比
例して上記反応がおこるため、薄膜から厚膜まで皮膜の
厚さを正確に制御することができる。Since the above reaction occurs in proportion to the amount of supplied coulomb and the electrolysis time, the thickness of the film from a thin film to a thick film can be accurately controlled.
【００４１】[0041]
【実施例】下記に本発明の製造方法の実施例を示し、本
発明の内容を具体的に説明する。EXAMPLES Examples of the production method of the present invention will be shown below to specifically explain the contents of the present invention.
【００４２】実施例１〜８および比較例１〜４ 酸化チタン被覆金属板の作製 前処理：被処理金属材料として、寸法１００mm×５０mm
の、ステンレススチール（ＳＵＳ３０４）板、鋼板（Ｓ
ＰＣＣ）、アルミニウム板（５０５２）、または銅板を
使用し、これらを、電解処理前に、アルカリ性水系脱脂
剤（ＦＣ−Ｗ１１２０：日本パーカライジング（株）
製）の２０ｇ／リットル濃度溶液により、６０℃×３分
間の脱脂処理を施し、水洗した。 Examples 1 to 8 and Comparative Examples 1 to 4 Preparation of Titanium Oxide Coated Metal Sheet Pretreatment: 100 mm × 50 mm as a metal material to be treated
Stainless steel (SUS304) plate, steel plate (S
PCC), an aluminum plate (5052), or a copper plate, and these are subjected to an alkaline aqueous degreasing agent (FC-W1120: Nippon Parkerizing Co., Ltd.) before electrolytic treatment.
Was subjected to a degreasing treatment at 60 ° C. for 3 minutes with a 20 g / liter concentration solution of the above, and washed with water.
【００４３】電解液：実施例１〜８および比較例１〜４
の各々において使用された電解液の組成を表１に示す。
電解液中の酸化剤イオンは、これらのナトリウム塩また
はアンモニウム塩の溶解により生成させた。Ｔｉ4+イオ
ンは、４塩化チタン水溶液（１７％）により所定の濃度
となるよう調製された。コロイド状酸化チタンは、硫酸
チタン水溶液（３０％）を水で希釈した液に、水酸化ナ
トリウム溶液を加えてｐＨを約１とし、この混合液を８
５℃で２０分間加熱処理し、得られたコロイド溶液を拡
散透析に供して夾雑イオンの多くを除去する方法により
作製した。生成したコロイド状酸化チタンの濃度は約２
０％であり、そのｐＨは２．８であった。また、コロイ
ド粒子の平均粒子径は７０〜１００nmであり、その結晶
型はアナターゼ型であった。Electrolyte: Examples 1 to 8 and Comparative Examples 1 to 4
Table 1 shows the composition of the electrolyte solution used in each of the above.
Oxidant ions in the electrolyte were generated by dissolution of these sodium or ammonium salts. Ti 4+ ions were prepared to have a predetermined concentration with an aqueous solution of titanium tetrachloride (17%). The pH of the colloidal titanium oxide is adjusted to about 1 by adding a sodium hydroxide solution to a solution obtained by diluting an aqueous solution of titanium sulfate (30%) with water.
A heat treatment was carried out at 5 ° C. for 20 minutes, and the obtained colloid solution was subjected to diffusion dialysis to remove a large amount of contaminating ions. The concentration of the formed colloidal titanium oxide is about 2
0% and its pH was 2.8. The average particle size of the colloid particles was 70 to 100 nm, and the crystal type was anatase type.
【００４４】電解処理：前処理された金属材料板は、６
０℃に保持された電解液を、金属材料板を陰極とし、白
金めっきチタン板を陽極として下記の条件において電解
処理し、形成された皮膜を１０秒間ディップ水洗したの
ち１２０℃で５分間乾燥した。実施例１〜５および比較
例２〜４においては、乾燥された皮膜に４００℃で１０
分間焼成を施した。 （電解条件） 実施例１、実施例３、および比較例１：電流密度 ２Ａ
／ｄｍ2 、電解時間 ３０秒 実施例２、実施例５、および比較例２：電流密度 １０
Ａ／ｄｍ2 、電解時間７秒 実施例４、実施例７、および比較例３：電流密度 ０．
５Ａ／ｄｍ2 、電解時間９０秒 実施例６、実施例８、および比較例４：電流密度 ４Ａ
／ｄｍ2 、電解時間 ２５秒Electrolytic treatment: The pretreated metal material plate
The electrolytic solution held at 0 ° C. was subjected to electrolytic treatment under the following conditions using a metal material plate as a cathode and a platinum-plated titanium plate as an anode, and the formed film was dipped in water for 10 seconds and then dried at 120 ° C. for 5 minutes. . In Examples 1 to 5 and Comparative Examples 2 to 4, the dried film was coated at 400 ° C. for 10 hours.
Baking was performed for minutes. (Electrolysis conditions) Example 1, Example 3, and Comparative Example 1: Current density 2A
/ Dm 2 , electrolysis time 30 seconds Example 2, Example 5, and Comparative Example 2: Current density 10
A / dm 2 , electrolysis time 7 seconds Example 4, Example 7, and Comparative Example 3: Current density
5 A / dm 2 , electrolysis time 90 seconds Example 6, Example 8, and Comparative Example 4: Current density 4 A
/ Dm 2 , electrolysis time 25 seconds
【００４５】皮膜の評価 作製された酸化チタン被覆金属材料板の、皮膜厚さを測
定し、かつ、下記方法により皮膜の密着性および光触媒
性について試験評価した。試験結果を表２に示す。 皮膜密着性：ＪＩＳ Ｋ ５４００ 碁盤目試験法に従
って、皮膜にカッターナイフで１mm角の碁盤目状のカッ
トを施し、その上に、セロハン粘着テープ（（株）ニチ
バン製）を貼付け、引き剥がして剥離された皮膜部分の
面積を測定し、そのデータを下記基準により判定した。 Evaluation of Film The film thickness of the produced titanium oxide-coated metal material plate was measured, and the adhesion and photocatalytic property of the film were evaluated by the following methods. Table 2 shows the test results. Film adhesion: According to JIS K 5400 grid test method, the film is cut in a 1 mm square grid pattern with a cutter knife, and a cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) is affixed, peeled and peeled. The area of the coated film portion was measured, and the data was determined according to the following criteria.
【００４６】光触媒性：供試金属差材料板上の皮膜表面
に試験油としてトリステアリン酸を塗布し、ＵＶライト
（１５Ｗ）による紫外線を７２時間照射し、塗布油の分
解量（ｇ／ｍ2）を紫外線照射前後の重量差から算出し
た。Photocatalytic property: Tristearic acid was applied as a test oil to the surface of the film on the test metal difference material plate, and irradiated with UV light (15 W) for 72 hours to decompose the applied oil (g / m 2). ) Was calculated from the weight difference before and after irradiation with ultraviolet light.
【００４７】[0047]
【表１】 [Table 1]
【００４８】[0048]
【表２】 [Table 2]
【００４９】表１および表２が示すように、本発明の方
法による実施例１〜８においては、十分な膜厚を有する
酸化チタン皮膜が形成され、その密着性、および光触媒
性はともに優れていた。これに対し、本発明方法の範囲
外の処理条件による比較例１〜４においては、比較例１
〜３では、十分な厚さを有する皮膜が得られないためこ
の皮膜の光触媒性が不十分であり、また比較例４では、
皮膜の密着性が不良であるという問題があった。As shown in Tables 1 and 2, in Examples 1 to 8 according to the method of the present invention, a titanium oxide film having a sufficient film thickness was formed, and its adhesion and photocatalytic properties were both excellent. Was. On the other hand, in Comparative Examples 1 to 4 under processing conditions outside the range of the method of the present invention, Comparative Example 1
In Comparative Examples 4 to 3, the photocatalytic property of this film was insufficient because a film having a sufficient thickness was not obtained.
There was a problem that the adhesion of the film was poor.
【００５０】[0050]
【発明の効果】本発明の方法により、密着性および光触
媒性が良好で、十分な厚さを有する酸化チタン皮膜によ
り金属材料を被覆することができる。光触媒性に優れて
いる酸化チタン皮膜は、汚れの付着防止、抗菌、防錆、
並びに大気および水質浄化等の用途にも利用し得るもの
であるから、本発明方法の産業上の利用価値は高いもの
である。According to the method of the present invention, a metal material can be coated with a titanium oxide film having good adhesion and photocatalytic property and having a sufficient thickness. Titanium oxide film with excellent photocatalytic properties prevents dirt adhesion, antibacterial, rustproof,
In addition, the method of the present invention has high industrial utility because it can be used for applications such as air and water purification.
Claims (3)
びＩＯn - （ｎは１，２、または３を表す）からなる群
より選択された少なくとも１種を含む酸化剤と、Ｔｉ4+
イオンとを含み、０．１〜５の範囲内にあるｐＨ値を有
する電解液中に、被処理金属材料からなる陰極体と、不
溶性電極からなる陽極体とを配置し、これに電解処理を
施して前記金属材料表面上に水和酸化チタン含有皮膜を
形成し、この皮膜を２００℃以上の温度で焼成すること
を特徴とする酸化チタン被覆金属材料の製造方法。1. A NO n -, ClO n -, BrO n - and IO n - (n represents 1, 2, or 3) an oxidizing agent containing at least one selected from the group consisting of, Ti 4 +
A cathode body made of a metal material to be treated and an anode body made of an insoluble electrode are placed in an electrolytic solution containing ions and having a pH value in the range of 0.1 to 5, and an electrolytic treatment is performed on this. Forming a hydrated titanium oxide-containing film on the surface of the metal material, and firing the film at a temperature of 200 ° C. or higher.
びＩＯn - （ｎは１，２、または３を表す）からなる群
より選択された少なくとも１種を含む酸化剤と、コロイ
ド状酸化チタンとを含み、０．１〜５の範囲内にあるｐ
Ｈ値を有する電解液中に、被処理金属材料からなる陰極
体と、不溶性電極からなる陽極体とを配置し、これに電
解処理を施して、前記金属材料表面に酸化チタン含有皮
膜を形成し、この皮膜を、乾燥または焼成することを特
徴とする酸化チタン被覆金属材料の製造方法。Wherein NO n -, ClO n -, BrO n - and IO n - (n is 1, 2 or 3 representing,) an oxidizing agent containing at least one selected from the group consisting of colloidal P in the range of 0.1 to 5 containing titanium oxide
In an electrolytic solution having an H value, a cathode body made of a metal material to be treated and an anode body made of an insoluble electrode are arranged and subjected to electrolytic treatment to form a titanium oxide-containing film on the surface of the metal material. And a method for producing a titanium oxide-coated metal material, comprising drying or firing the film.
びＩＯn - （ｎは１，２、または３を表す）からなる群
より選択された少なくとも１種を含む酸化剤と、Ｔｉ4+
イオンと、コロイド状酸化チタンとを含み、０．１〜５
の範囲内にあるｐＨ値を有する電解液中に、被処理金属
材料からなる陰極体とし、不溶性電極からなる陽極体と
を配置し、これに電解処理を施して、前記金属材料表面
上に水和酸化チタンおよび酸化チタンを含有する皮膜を
形成し、この皮膜を、乾燥または焼成することを特徴と
する酸化チタン被覆金属材料の製造方法。3. NO n -, ClO n -, BrO n - and IO n - (n represents 1, 2, or 3) an oxidizing agent containing at least one selected from the group consisting of, Ti 4 +
0.1 to 5 containing ions and colloidal titanium oxide.
A cathode body made of a metal material to be treated and an anode body made of an insoluble electrode are arranged in an electrolytic solution having a pH value in the range of, and an electrolytic treatment is performed on the cathode body, and water is placed on the surface of the metal material. A method for producing a titanium oxide-coated metal material, comprising forming a film containing titanium oxide and titanium oxide, and drying or firing the film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17124596A JP3573574B2 (en) | 1996-07-01 | 1996-07-01 | Method for producing metal material coated with titanium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17124596A JP3573574B2 (en) | 1996-07-01 | 1996-07-01 | Method for producing metal material coated with titanium oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1018083A true JPH1018083A (en) | 1998-01-20 |
| JP3573574B2 JP3573574B2 (en) | 2004-10-06 |
Family
ID=15919746
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17124596A Expired - Lifetime JP3573574B2 (en) | 1996-07-01 | 1996-07-01 | Method for producing metal material coated with titanium oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3573574B2 (en) |
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