JP2001149790A - Coating material excellent in photocatalytic performance and manufacturing method therefor - Google Patents
Coating material excellent in photocatalytic performance and manufacturing method thereforInfo
- Publication number
- JP2001149790A JP2001149790A JP33493999A JP33493999A JP2001149790A JP 2001149790 A JP2001149790 A JP 2001149790A JP 33493999 A JP33493999 A JP 33493999A JP 33493999 A JP33493999 A JP 33493999A JP 2001149790 A JP2001149790 A JP 2001149790A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- film
- crystal
- photocatalytic
- coating material
- 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.)
- Withdrawn
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000013078 crystal Substances 0.000 claims abstract description 118
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 117
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000758 substrate Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 238000004544 sputter deposition Methods 0.000 claims description 13
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 12
- 238000004332 deodorization Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 238000007796 conventional method Methods 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 87
- 230000015572 biosynthetic process Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- 238000003917 TEM image Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、優れた光触媒活性
を有する酸化チタン被覆材料およびその製造方法に関す
る。[0001] The present invention relates to a titanium oxide coating material having excellent photocatalytic activity and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化チタンは波長４００ｎｍ以下の紫外
線を照射することにより光触媒性を発現し、その酸化作
用により有機物を分解できることが知られている。そこ
で、この様な光触媒性を利用して、空気中や水中の微量
汚染物質を浄化したり、材料表面の汚れや菌を分解する
方法が盛んに検討されており、酸化チタンに代表される
光触媒材料を被覆した様々な応用製品が、水浄化、空気
浄化、消臭、油分の分解等幅広い分野で実用化されてい
る。2. Description of the Related Art It is known that titanium oxide exhibits photocatalytic properties when irradiated with ultraviolet rays having a wavelength of 400 nm or less, and is capable of decomposing organic substances by its oxidizing action. Therefore, methods for purifying trace contaminants in the air or water using such photocatalytic properties or decomposing dirt and bacteria on the material surface are being actively studied. Various applied products coated with materials have been put to practical use in a wide range of fields such as water purification, air purification, deodorization, and oil decomposition.
【０００３】一般に酸化チタンは粉体で供給され、なか
でも高い光触媒特性を示すのは、アナターゼ型酸化チタ
ン結晶であることが知られている。実際の使用に際して
は当該酸化チタン粉末が散逸しないように、フッ素系樹
脂やシリコン系のバインダーに固定し、基材の表面に塗
布する等の方法が採用されている（工業調査会「光触媒
の世界」，ｐ４５〜４８）。ところがバインダーを用い
ると、全酸化チタン粉末のうち外気と接触する表面部分
に露出する面積が小さくなり、光触媒作用面が減少する
ことから、酸化チタンが本来有している優れた光触媒作
用を有効に発揮させることができず、現実に現れる効果
は著しく低下するという問題を抱えている。[0003] In general, titanium oxide is supplied as a powder, and it is known that an anatase type titanium oxide crystal exhibiting particularly high photocatalytic properties. In actual use, in order to prevent the titanium oxide powder from dissipating, a method of fixing the powder to a fluorine-based resin or a silicon-based binder and applying the titanium oxide powder to the surface of a substrate has been adopted (see the Industrial Research Council, ", P. 45-48). However, when a binder is used, the area exposed to the surface portion of the total titanium oxide powder that comes into contact with the outside air is reduced, and the photocatalytic surface is reduced, so that the excellent photocatalytic action inherent to titanium oxide can be effectively used. There is a problem that it cannot be exerted, and the effect that actually appears is significantly reduced.
【０００４】そこで、酸化チタンの有効表面積を増加さ
せるべく様々な検討がなされている（例えば特開平１１
−７１１３８等）が、当該有効表面積を増加させるべく
酸化チタン粒子を露出させると、粒子が剥がれ易くな
る。即ち、バインダーを用い、酸化チタンを頑丈に固定
しようとすると有効表面積が減少し、一方、有効表面積
を増やそうとすると酸化チタンを頑丈に固定できなくな
ることから、光触媒性と耐久性の両特性を発揮させるこ
とは極めて困難であった。Accordingly, various studies have been made to increase the effective surface area of titanium oxide (for example, Japanese Patent Application Laid-Open No.
However, when the titanium oxide particles are exposed to increase the effective surface area, the particles are easily peeled off. In other words, when the binder is used to fix titanium oxide firmly, the effective surface area decreases.On the other hand, when the effective surface area is increased, titanium oxide cannot be fixed firmly, exhibiting both photocatalytic properties and durability. It was extremely difficult to do so.
【０００５】一方、酸化チタンを皮膜として直接生成さ
せる方法として、基材に有機チタン化合物溶液［Ｔｉに
アルコールを結合させたアルコキシド（イソプロポキシ
ド、ブトキシド等）やアセチルアセトナート等］を塗布
し、４００℃以上の高温で焼成する方法（工業調査会
「光触媒の世界」，ｐ５１〜５２；特開平７−１００３
７８）や；陽極酸化膜及び酸化チタン粉体含有薄膜をス
プレーコーティング、スピンコーティング、ディップコ
ーティング、スパッタリング等の方法でコーティングし
た後、２００〜６００℃で加熱する方法が提案されてい
る（特開平１０−１２１２６６）。このうち後者の方法
（陽極酸化膜上に酸化チタン皮膜を形成する方法）で
は、光触媒特性に優れた被覆材料が得られるが、それで
も、最も光触媒特性に優れると言われているアナターゼ
型酸化チタン粉末に比べ、光触媒特性に著しく劣るもの
である。更に上記方法では、バインダー法やゾル−ゲル
法の場合と同様、高い光触媒特性を得る為に、金属酸化
膜形成時に数百度の高温にまで加熱する必要があり、ま
た、陽極酸化膜用基材としてチタン含有基材を用いなけ
ればならない等、使用できる基材が限定される等の問題
を抱えている。On the other hand, as a method of directly forming titanium oxide as a film, an organic titanium compound solution [alkoxide (isopropoxide, butoxide, etc.) in which alcohol is bonded to Ti, acetylacetonate, etc.) is applied to a substrate, Firing at a high temperature of 400 ° C. or more (Industrial Research Institute, “The World of Photocatalysts”, pp. 51-52;
78) A method has been proposed in which an anodized film and a thin film containing titanium oxide powder are coated by a method such as spray coating, spin coating, dip coating, or sputtering, and then heated at 200 to 600 ° C. -122266). In the latter method (the method of forming a titanium oxide film on an anodized film), a coating material having excellent photocatalytic properties can be obtained. Nevertheless, anatase-type titanium oxide powder which is said to be most excellent in photocatalytic properties is obtained. The photocatalytic properties are remarkably inferior to the above. Further, in the above method, similarly to the case of the binder method or the sol-gel method, it is necessary to heat the metal oxide film to a high temperature of several hundred degrees in order to obtain high photocatalytic properties. There is a problem that a base material that can be used is limited, for example, a titanium-containing base material must be used.
【０００６】また、上記以外の成膜方法として、ＰＶＤ
法やＣＶＤ法によりアナターゼ型酸化チタンを直接形成
する方法も提案されている（例えば特開平１１−１３０
４３４、特開平９−１９２４９８等）。しかしながら、
高い光触媒特性を得る為には酸化チタンの結晶性や配向
性が充分である必要があり、また上記方法を用いたとし
ても、依然として、アナターゼ型酸化チタン粉末に比
べ、格段に劣った光触媒特性しか得られていないのが実
状である。As a film forming method other than the above, PVD is used.
A method of directly forming anatase-type titanium oxide by a CVD method or a CVD method has also been proposed (for example, JP-A-11-130).
434, JP-A-9-192498). However,
In order to obtain high photocatalytic properties, it is necessary that the crystallinity and orientation of titanium oxide are sufficient, and even if the above method is used, the photocatalytic properties are still extremely inferior to those of anatase type titanium oxide powder. The fact is that it has not been obtained.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記事情に鑑
みてなされたものであり、その目的は、従来法が抱える
不具合（形成温度に伴う基材の制約等）もなく優れた光
触媒性を発揮し、しかも耐久性（密着性）にも優れてお
り、防臭、殺菌等の幅広い分野に適用可能な酸化チタン
被覆材料、及び当該被覆材料の製造方法を提供すること
にある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an excellent photocatalytic property without problems (restriction of a substrate due to a forming temperature, etc.) which the conventional method has. An object of the present invention is to provide a titanium oxide coating material which exhibits excellent durability (adhesion) and is applicable to a wide range of fields such as deodorization and sterilization, and a method for producing the coating material.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決し得た本
発明に係る光触媒性に優れた被覆材料とは、基材表面
に、アナターゼ型酸化チタンの柱状結晶を有する光触媒
皮膜が被覆された材料であって、該光触媒皮膜は、柱状
結晶粒間に隙間のあるラス状構造を有するものであると
ころに要旨を有する。上記光触媒皮膜中、柱状結晶が光
触媒皮膜表面の垂線方向から４５°以内に配向している
結晶粒の占める比率が５０体積％以上であるものは好ま
しい態様である。Means for Solving the Problems A coating material having excellent photocatalytic properties according to the present invention, which has solved the above-mentioned problems, comprises a substrate in which a photocatalytic film having columnar crystals of anatase type titanium oxide is coated. The gist is that the photocatalyst film has a lath-like structure with gaps between columnar crystal grains. In the above-mentioned photocatalytic film, a preferred embodiment is one in which the proportion of crystal grains in which the columnar crystals are oriented within 45 ° from the perpendicular direction of the photocatalytic film surface is 50% by volume or more.
【０００９】また、上記光触媒皮膜の最表面には、柱状
結晶の成長面とは異なる結晶面のファセット構造を有す
ることが好ましく、この様な態様とすることにより光触
媒特性が著しく向上する。上記態様では、柱状結晶中、
当該柱状結晶の成長面とは異なる結晶面のファセット構
造を有する結晶粒の占める比率が５０体積％以上である
ものが推奨される。Further, it is preferable that the outermost surface of the photocatalytic film has a facet structure of a crystal plane different from the growth plane of the columnar crystal. By adopting such an embodiment, the photocatalytic properties are remarkably improved. In the above embodiment, in the columnar crystal,
It is recommended that the ratio of crystal grains having a facet structure different from the growth plane of the columnar crystal be 50% by volume or more.
【００１０】また、本発明では上記光触媒皮膜の厚さが
０．２μｍ以上であることが好ましい。In the present invention, the thickness of the photocatalyst film is preferably 0.2 μm or more.
【００１１】更に上記課題を解決し得た本発明に係る被
覆材料の製造方法は、プラズマを用いたスパッタリング
法により光触媒皮膜を成膜するところに要旨を有するも
のである。好ましくは、アンバランスドマグネトロンス
パッタリング法により光触媒皮膜を成膜する方法が推奨
される。The method for producing a coating material according to the present invention, which has further solved the above problems, has a gist in forming a photocatalytic film by a sputtering method using plasma. Preferably, a method of forming a photocatalytic film by an unbalanced magnetron sputtering method is recommended.
【００１２】[0012]
【発明の実施の形態】本発明者らは上記問題を解決する
に当たり、アナターゼ型酸化チタン結晶の結晶構造に着
目し、その結晶配向を種々変化させ、光触媒特性との関
係を調べてみた。その結果、アナターゼ型酸化チタンの
柱状結晶粒間に隙間のある所謂ラス状構造を有する皮膜
を用いれば極めて優れた特性が得られることを見出し、
本発明を完成した。DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to solve the above problems, the present inventors focused on the crystal structure of anatase-type titanium oxide crystal, varied its crystal orientation, and examined its relationship with photocatalytic properties. As a result, they have found that extremely excellent characteristics can be obtained by using a film having a so-called lath-like structure with gaps between columnar crystal grains of anatase-type titanium oxide,
The present invention has been completed.
【００１３】ここで、本発明における「ラス状構造」と
は、アナターゼ型酸化チタンの柱状結晶粒間に隙間のあ
る構造を意味する。即ち、本発明は、酸化チタン被覆材
料の光触媒特性を向上する為には、アナターゼ型酸化チ
タン含有光触媒皮膜（以下、単に「皮膜」と略記する場
合がある）の構造をラス状構造にすれば良いことを見出
した点に技術的思想を有するものであり、本発明の如
く、ラス状構造と光触媒特性の関係を明らかにしたもの
は従来より知られておらず新規である。Here, the “lath-like structure” in the present invention means a structure having gaps between columnar crystal grains of anatase type titanium oxide. That is, in the present invention, in order to improve the photocatalytic properties of the titanium oxide-coated material, the structure of the anatase-type titanium oxide-containing photocatalytic film (hereinafter, may be simply abbreviated as “film”) may be a lath-like structure. They have a technical idea in that they have found a good point, and those which clarify the relationship between the lath-like structure and the photocatalytic properties as in the present invention have not been known so far and are novel.
【００１４】例えば特開平１１−１３０４３４には、
「主としてアナターゼ型柱状結晶の集合体からなる酸化
チタン膜」が開示されている。これは、「触媒活性が高
い酸化チタン膜を得る為にはアナターゼ型の結晶系がリ
ッチである必要がある」という視点にたち検討されたも
のであり、「酸化チタン膜が柱状のアナターゼ型集合体
からなるものは顕著な光触媒活性を有する」ことを見出
し、特定されたものである。しかしながら、上記公報を
精査しても、「アナターゼ型酸化チタンの結晶構造は柱
状結晶を有することが必要である」ことが記載されてい
るのみで、当該結晶がラス状構造を有することまでは開
示も示唆もされていない。For example, JP-A-11-130434 discloses that
"Titanium oxide film mainly composed of aggregate of anatase type columnar crystals" is disclosed. This was studied from the viewpoint that "an anatase-type crystal system must be rich in order to obtain a titanium oxide film having high catalytic activity". It has been found that a substance consisting of a body has a remarkable photocatalytic activity. " However, even if the above publication is examined, it is only described that "the crystal structure of anatase-type titanium oxide needs to have a columnar crystal", and it is disclosed that the crystal has a lath-like structure. Neither was suggested.
【００１５】また、特開平１１−１５２３９６には、
「基材表面に、結晶配向膜が結晶表面と垂直方向に（０
０１），（１００）、（２１１）、（１０１）及び（１
１０）からなる結晶面から選択された方向に配向された
ものである二酸化チタン結晶配向膜を有する材料」が開
示されている。上記公報は、「特定方向に配向された二
酸化チタンの結晶配向膜を形成することにより、顕著な
抗菌作用、防汚作用等の優れた特性を有する」という知
見に基づいてなされたものであり、結晶面と光触媒特性
の関係は開示されているが、ラス状構造とした場合に光
触媒特性がどの様に変化するかについては全く言及して
いない。Japanese Patent Application Laid-Open No. 11-152396 discloses that
"On the substrate surface, the crystal orientation film is perpendicular to the crystal surface (0
01), (100), (211), (101) and (1)
10) A material having a titanium dioxide crystal orientation film which is oriented in a selected direction from the crystal plane composed of 10). The above publication is based on the finding that "by forming a crystal orientation film of titanium dioxide oriented in a specific direction, it has excellent properties such as remarkable antibacterial action and antifouling action", Although the relationship between the crystal plane and the photocatalytic property is disclosed, it does not mention at all how the photocatalytic property changes in the case of a lath-like structure.
【００１６】この様に酸化チタン皮膜の結晶構造に着目
した技術はこれまでにも開示されているが、当該皮膜を
ラス状構造にした場合、光触媒特性が著しく向上すると
いう本発明の技術的思想は開示も示唆もされていないこ
とが分かる。Although the technique focusing on the crystal structure of the titanium oxide film has been disclosed, the technical idea of the present invention is that the photocatalytic property is remarkably improved when the film has a lath-like structure. Is not disclosed or suggested.
【００１７】具体的には、本発明では、アナターゼ型酸
化チタン柱状結晶の結晶粒間にラス状構造を有すること
が必要であるが、一層優れた光触媒特性を得る為には、
光触媒皮膜中、アナターゼ型酸化チタンの柱状結晶が光
触媒皮膜表面の垂線方向から４５°以内に配向している
結晶粒の占める体積比率が５０％以上であることが推奨
される。これにより、基材等から光触媒特性を劣化させ
る不純物が拡散するといった問題や、基材との密着性低
下といった問題もなく、極めて優れた光触媒被覆材料が
得られるからである。上記結晶粒の体積率は大きければ
大きい程、光触媒特性も向上する。より好ましくは７０
体積％以上、更に好ましくは８０体積％以上である。Specifically, in the present invention, it is necessary to have a lath-like structure between the crystal grains of the anatase type titanium oxide columnar crystal. To obtain more excellent photocatalytic properties,
In the photocatalytic film, it is recommended that the volume ratio of crystal grains in which the columnar crystals of anatase type titanium oxide are oriented within 45 ° from the perpendicular direction of the photocatalytic film surface is 50% or more. As a result, an extremely excellent photocatalyst coating material can be obtained without the problem that impurities that deteriorate the photocatalytic properties are diffused from the substrate or the like and the problem that the adhesion to the substrate is deteriorated. The greater the volume fraction of the crystal grains, the better the photocatalytic properties. More preferably 70
% By volume or more, more preferably 80% by volume or more.
【００１８】詳細には、アナターゼ型酸化チタンの＜１
０１＞方向が光触媒皮膜表面の垂線方向から４５°以内
に配向している結晶粒（以下、＜１０１＞配向結晶粒と
呼ぶ）の占める比率が５０体積％以上であるものが好ま
しく、同様にして、＜１００＞配向結晶粒の占める比率
が５０体積％以上であるもの；＜００１＞配向結晶粒の
占める比率が５０体積％以上であるものも本発明の好ま
しい態様である。More specifically, <1 of anatase type titanium oxide
It is preferable that the ratio of crystal grains in which the <01> direction is oriented within 45 ° from the perpendicular direction of the photocatalytic film surface (hereinafter referred to as <101> oriented crystal grains) is 50% by volume or more. , <100> oriented crystal grains account for 50% by volume or more; <001> oriented crystal grains account for 50% by volume or more are also preferred embodiments of the present invention.
【００１９】これに対し、上記結晶粒の体積率が５０％
を下回る場合には以下の不具合を有する。例えば＜１０
１＞配向結晶粒の体積率が５０％未満の場合、当該皮膜
面内方向で（１０１）結晶面が優先成長した結晶が形成
され、結晶粒間の隙間形成が著しく低下する為、所望の
ラス構造は得られ難い。また、＜１０１＞配向結晶粒が
充分形成されない場合には、最表面部には（１００）面
または（００１）面のファセット構造（後記する）が形
成されず、優れた光触媒特性を発揮させることができな
い。この様な問題は、上記＜１０１＞配向結晶粒の他、
＜１００＞配向晶粒、＜００１＞配向結晶粒の場合であ
っても同様に見られる。On the other hand, the volume ratio of the crystal grains is 50%.
If the value is lower than the above, the following problems are caused. For example, <10
1> When the volume fraction of the oriented crystal grains is less than 50%, crystals in which the (101) crystal plane grows preferentially are formed in the in-plane direction of the film, and the formation of gaps between the crystal grains is significantly reduced. The structure is difficult to obtain. Further, when the <101> oriented crystal grains are not sufficiently formed, a facet structure (described later) of the (100) plane or the (001) plane is not formed at the outermost surface portion, and excellent photocatalytic properties are exhibited. Can not. Such a problem arises in addition to the <101> oriented crystal grains,
The same can be seen in the case of <100> oriented crystal grains and <001> oriented crystal grains.
【００２０】皮膜中、上記結晶粒以外の成分は特に限定
されず任意であり、上記特定方向に配向していないアナ
ターゼ型酸化チタン結晶は勿論のこと、ルチル型酸化チ
タン結晶も含まれ、更に、これらとは全く異なる成分が
存在していても良く、これらの成分が存在することによ
り所望の光触媒特性が低下することはない。むしろ、上
記結晶粒以外の領域が、Ｎｉ，Ｐｄ，Ｐｔ等の金属相、
或いは酸化チタンと異なる成分の化合物相である場合；
皮膜表面にＮｉ，Ｐｄ，Ｐｔ等の金属相、或いは酸化チ
タンと異なる成分の化合物相が粒子として分散された状
態の場合には、当該領域において、光触媒によるカソー
ド反応が酸化チタン領域に比べて起こり易くなり、その
結果、光触媒のアノード反応とカソード反応のサイトが
分離され、両反応の相殺による損失が最小限となること
から、光触媒特性が一層高められることが多い、という
利点がある。In the film, components other than the above-mentioned crystal grains are not particularly limited and are arbitrary. The above-mentioned components include not only the anatase-type titanium oxide crystal not oriented in the specific direction but also the rutile-type titanium oxide crystal. Components completely different from these may be present, and the presence of these components does not lower the desired photocatalytic properties. Rather, the region other than the crystal grains is a metal phase such as Ni, Pd, or Pt,
Or when the compound phase is a component different from titanium oxide;
When a metal phase such as Ni, Pd, or Pt or a compound phase having a component different from titanium oxide is dispersed as particles on the surface of the film, a cathode reaction by a photocatalyst occurs in the region in comparison with the titanium oxide region. This has the advantage that the sites of the anodic and cathodic reactions of the photocatalyst are separated, minimizing the losses due to the offset of the two reactions, and thus further enhancing the photocatalytic properties.
【００２１】上述した通り、本発明に用いられる皮膜
は、基本的にはラス状構造を有するが、更に上記皮膜の
最表面に、アナターゼ型酸化チタン柱状結晶の成長面と
は異なる結晶面のファセット構造を有するものは光触媒
特性が一層向上する。即ち、本発明によれば、ラス状構
造（隙間）を有する皮膜を形成することにより優れた光
触媒特性が発揮されるが、更に、光触媒作用面である皮
膜最表面に、当該隙間に結晶作用面が配向したファセッ
ト構造を有する皮膜を形成すれば、当該最表面部での光
触媒作用面増大が著しく向上し、その結果、光触媒特性
が格段に高められることが本発明者らの研究により始め
て明らかになった。As described above, the film used in the present invention basically has a lath-like structure, and a facet having a crystal face different from the growth surface of the anatase type titanium oxide columnar crystal is formed on the outermost surface of the film. Those having a structure have further improved photocatalytic properties. That is, according to the present invention, excellent photocatalytic properties are exhibited by forming a film having a lath-like structure (gap), and further, a crystal action surface is provided on the outermost surface of the film, which is a photocatalytic surface. The formation of a film having a facet structure in which the surface is oriented significantly increases the photocatalytic surface at the outermost surface, and as a result, the photocatalytic properties are remarkably improved. became.
【００２２】この様に上記態様では、皮膜の最表面に、
アナターゼ型酸化チタン柱状結晶の成長面とは異なる結
晶面のファセット構造を有していることが必要である。
具体的には、とんがり状（これをファセット構造とい
う）の結晶面（作用面）が隙間方向に向いた構造を有す
ることが必要であるが、この様な構造をもつ為には、皮
膜最表面には、必ず、アナターゼ型酸化チタン柱状結晶
の成長面とは異なる結晶面が配向していなければならな
い。アナターゼ型酸化チタンの結晶方向と同一の結晶面
が配向された皮膜では、所望のファセット構造が得られ
ないからである。具体的には、例えば＜１０１＞方向柱
状結晶では、（１００）面および（００１）面の結晶
面；＜１００＞方向柱状結晶では、（１０１）面および
（００１）面の結晶面；更に＜００１＞方向柱状結晶で
は、（１０１）面および（１００）面の結晶面のファセ
ット構造を夫々有する皮膜は、極めて良好な光触媒特性
が発揮される。As described above, in the above embodiment, the outermost surface of the film is
It is necessary to have a facet structure of a crystal plane different from the growth plane of the anatase type titanium oxide columnar crystal.
Specifically, it is necessary that the pointed (this is referred to as a facet structure) crystal surface (working surface) has a structure in which the crystal surface (working surface) is oriented in the direction of the gap. In this case, a crystal plane different from the growth plane of the anatase type titanium oxide columnar crystal must be oriented. This is because a desired facet structure cannot be obtained with a film in which the same crystal plane as that of the anatase type titanium oxide is oriented. Specifically, for example, in the <101> direction columnar crystal, the (100) plane and the (001) plane crystal plane; in the <100> direction columnar crystal, the (101) plane and the (001) plane crystal plane; In the 001> -direction columnar crystal, a film having facet structures of the (101) plane and the (100) plane has extremely excellent photocatalytic properties.
【００２３】上記ファセット構造を有する本発明被覆材
料の概略断面図を図１に示す。図中、１は基材、２は＜
１０１＞方向に配向したアナターゼ型酸化チタンの柱状
結晶粒、３は（１００）面または（００１）面のファセ
ット構造、４は隙間、５はアナターゼ型酸化チタン皮膜
である。FIG. 1 is a schematic sectional view of the coating material of the present invention having the facet structure. In the figure, 1 is a substrate, 2 is <
The columnar crystal grains of anatase-type titanium oxide oriented in the 101> direction, 3 is a facet structure of (100) plane or (001) plane, 4 is a gap, and 5 is an anatase-type titanium oxide film.
【００２４】図１に示す様に、基材１の上にアナターゼ
型酸化チタン皮膜５が形成されている。この酸化チタン
皮膜５は、主に＜１０１＞配向した柱状結晶粒２からな
り、その最表面部は、主に（１００）面または（００
１）面のファセット構造を持つと共に、各結晶間には隙
間があり、所謂ラス状構造を有している。ここで、上記
＜１０１＞方向とは、アナターゼ型酸化チタン結晶の
［１０１］，［−１０１］，［１０−１］，［−１０−
１］の様な結晶学的に等価な方向を総称したものを意味
する。As shown in FIG. 1, an anatase type titanium oxide film 5 is formed on a substrate 1. The titanium oxide film 5 is mainly composed of <101> oriented columnar crystal grains 2, and the outermost surface thereof is mainly composed of a (100) plane or a (00) plane.
1) In addition to having a facet structure of the plane, there is a gap between the crystals, and the crystal has a so-called lath structure. Here, the <101> direction refers to [101], [−101], [10-1], and [−10-] of the anatase-type titanium oxide crystal.
1] is a general term for crystallographically equivalent directions as in [1].
【００２５】尚、図１には、＜１０１＞配向した柱状結
晶粒間にラス状構造を有すると共に、その最表面部は、
主に（１００）面または（００１）面のファセット構造
を有する皮膜を図示したが、本発明は上記皮膜に限定さ
れるものでは決してなく、上記以外の結晶構造であって
も、要するに、「皮膜の柱状結晶粒間にはラス状構造を
有し、且つ、当該皮膜の最表面には、アナターゼ型酸化
チタン柱状結晶の成長面とは異なる結晶面のファセット
構造を有する」皮膜は全て本発明の範囲内に包含され
る。例えば、＜１００＞配向した柱状結晶粒間にラス状
構造を有し、しかもその最表面部は、主に（１０１）面
または（００１）面のファセット構造を有する皮膜であ
っても良いし；＜００１＞配向した柱状結晶粒間にラス
状構造を有し、しかもその最表面部は、主に（１０１）
面または（１００）面のファセット構造を有する皮膜も
本発明の範囲内に包含される。FIG. 1 shows a lath-like structure between the <101> -oriented columnar crystal grains, and the outermost surface thereof has
Although a film mainly having a facet structure of the (100) plane or the (001) plane is illustrated, the present invention is not limited to the above-described film. Have a lath-like structure between the columnar crystal grains, and the outermost surface of the film has a facet structure of a crystal surface different from the growth surface of the anatase type titanium oxide columnar crystal. Included within the scope. For example, a film having a lath-like structure between <100> -oriented columnar crystal grains, and the outermost surface thereof may be a film having a facet structure mainly of a (101) plane or a (001) plane; It has a lath-like structure between the <001> oriented columnar crystal grains, and its outermost surface is mainly composed of (101)
Coatings having a facet or (100) facet structure are also included within the scope of the present invention.
【００２６】上記ファセット構造を有する結晶の比率が
高いほど光触媒特性も向上する。従って、本発明では皮
膜の最表面において、アナターゼ型酸化チタンの柱状結
晶中、５０体積％以上が、当該柱状結晶の成長面とは異
なる結晶面のファセット構造を有していることが推奨さ
れる。より好ましくは７０体積％以上、更により好まし
くは８０体積％以上である。５０体積％未満では、光触
媒特性が著しく低下する。The higher the proportion of crystals having the facet structure, the better the photocatalytic properties. Therefore, in the present invention, it is recommended that 50% by volume or more of the columnar crystals of anatase-type titanium oxide have a facet structure of a crystal surface different from the growth surface of the columnar crystals on the outermost surface of the film. . It is more preferably at least 70% by volume, still more preferably at least 80% by volume. If it is less than 50% by volume, the photocatalytic properties are significantly reduced.
【００２７】本発明において、皮膜中にアナターゼ型酸
化チタンの柱状結晶が皮膜表面の垂線方向から４５°以
内に配向している結晶粒が占める体積比率、ファセット
構造の結晶方位、及び上記柱状結晶中にファセット構造
を有する結晶粒が占める体積比率はいずれも、透過型電
子顕微鏡（ＴＥＭ）を用い、皮膜を断面観察することに
より測定することができる。また、結晶の配向性はＸ線
回折法においても確認することができる。以下、その方
法について説明する。In the present invention, the volume ratio occupied by crystal grains in which the columnar crystals of anatase type titanium oxide are oriented within 45 ° from the perpendicular direction of the film surface in the film, the crystal orientation of the facet structure, and the The volume ratio occupied by the crystal grains having a facet structure can be measured by observing the cross section of the film using a transmission electron microscope (TEM). The crystal orientation can also be confirmed by X-ray diffraction. Hereinafter, the method will be described.
【００２８】まず、皮膜の断面を１０万倍程度の拡大率
で観察した後、膜全体から得られる電子線回折より、ア
ナターゼ型酸化チタンに対応する回折スポット又は回折
リングを選択し、この回折波を結像して得られる暗視野
像を観察する。そうすると、回折波に対応するアナター
ゼ型酸化チタン結晶粒のみ明るくなるので、所望のアナ
ターゼ型酸化チタンを特定することができる。First, after observing the cross section of the film at a magnification of about 100,000 times, a diffraction spot or a diffraction ring corresponding to anatase type titanium oxide is selected from electron beam diffraction obtained from the entire film, and this diffraction wave is obtained. Is observed. Then, only the anatase-type titanium oxide crystal grains corresponding to the diffracted wave become bright, so that a desired anatase-type titanium oxide can be specified.
【００２９】次に、上記方法により特定したアナターゼ
型酸化チタン結晶粒の一つ一つに、ＦＥ−ＴＥＭ（Fiel
d Emission ＴＥＭ：電界放射型透過電子顕微鏡）を用
いて電子線を細く絞って照射し、１個の結晶粒から得ら
れる回折スポットの方位を解析すると、当該結晶粒の柱
状結晶がどの方向を向いているかを判定することができ
る。この解析法によれば、電子線をｎｍオーダーまで細
く絞っても十分な電子線輝度が得られるという優れた特
徴を有している。Next, FE-TEM (Fiel TEM)
When the direction of the diffraction spot obtained from one crystal grain is analyzed by narrowing and irradiating an electron beam using d Emission TEM (field emission transmission electron microscope), the direction of the columnar crystal of the crystal grain is determined. Can be determined. According to this analysis method, there is an excellent feature that sufficient electron beam luminance can be obtained even if the electron beam is narrowed down to the order of nm.
【００３０】これらの操作を繰返すことにより、アナタ
ーゼ型酸化チタンの柱状結晶が光触媒膜表面の垂線（法
線）から４５°以内に配向している結晶粒が皮膜中に占
める体積率％を算出することができる。By repeating these operations, the volume percentage of the crystal grains in which the columnar crystals of anatase type titanium oxide are oriented within 45 ° from the perpendicular (normal) of the photocatalytic film surface is calculated. be able to.
【００３１】本発明では、上記アナターゼ型酸化チタン
皮膜の厚さは０．２μｍ以上であることが好ましい。
０．２μｍ未満では、アナターゼ型酸化チタン柱状結晶
の特定方向への配向、及びラス状構造の形成が充分でな
く、所望の優れた光触媒特性が得られない。より好まし
くは０．４μｍ以上、更により好ましくは０．５μｍ以
上、最も好ましくは１μｍ以上である。尚、厚さが１．
５μｍを超えると、膜厚の増加に伴う光触媒特性上昇効
果は飽和してしまう。In the present invention, the thickness of the anatase type titanium oxide film is preferably 0.2 μm or more.
If it is less than 0.2 μm, the orientation of the anatase type titanium oxide columnar crystal in a specific direction and the formation of a lath-like structure are not sufficient, and desired excellent photocatalytic properties cannot be obtained. It is more preferably at least 0.4 μm, still more preferably at least 0.5 μm, most preferably at least 1 μm. The thickness is 1.
If it exceeds 5 μm, the effect of increasing the photocatalytic properties with an increase in the film thickness is saturated.
【００３２】上記酸化チタン皮膜の構成成分は、実質的
にチタンと酸素であるが、本発明の作用を損なわない範
囲で他の許容成分を含んでいても良く、この様な態様も
本発明の範囲内に包含される。上記許容成分としては、
チタンに含まれる不純物元素、成膜時に混入する恐れの
ある雰囲気ガス成分（例えばアルゴン等）等が挙げられ
る他、一般的に知られている光触媒特性向上元素（例え
ば白金、金、パラジウム、ルテニウム、ニッケル、コバ
ルト、クロム、モリブデン、鉄、タングステン、亜鉛
等）も例示される。The constituent components of the titanium oxide film are substantially titanium and oxygen, but may contain other allowable components as long as the function of the present invention is not impaired. Included within the scope. As the above acceptable components,
In addition to an impurity element contained in titanium, an atmosphere gas component (for example, argon, etc.) which may be mixed during film formation, and the like, a generally known photocatalytic property improving element (for example, platinum, gold, palladium, ruthenium, Nickel, cobalt, chromium, molybdenum, iron, tungsten, zinc, etc.) are also exemplified.
【００３３】上記酸化チタン皮膜の膜厚は、前述の透過
型電子顕微鏡（ＴＥＭ）の断面観察法により、容易に測
定することができる。The thickness of the titanium oxide film can be easily measured by the above-mentioned cross-sectional observation method using a transmission electron microscope (TEM).
【００３４】本発明の被覆材料は、基材表面に上記酸化
チタン皮膜が直接被覆された単層タイプで構成されてい
ても良いが、上記皮膜と基材の密着性向上を目的とし
て、その界面に、酸化物や窒化物等の中間層を設けた複
層タイプにする態様も本発明の範囲内に包含される。The coating material of the present invention may be composed of a single-layer type in which the above-mentioned titanium oxide film is directly coated on the surface of the substrate. In addition, an embodiment in which a multilayer type in which an intermediate layer such as an oxide or a nitride is provided is also included in the scope of the present invention.
【００３５】尚、本発明の被覆材料は、光触媒膜を特定
したところに最重要ポイントが存在するものであり、当
該光触媒膜が形成される基材の種類については特に限定
されず、例えば鉄、チタン、アルミ、銅等の金属および
その合金；シリコンウエハー；更には樹脂やガラス、セ
ラミックス等を使用することができる。The coating material of the present invention has the most important point where the photocatalytic film is specified, and the type of the substrate on which the photocatalytic film is formed is not particularly limited. Metals such as titanium, aluminum and copper and alloys thereof; silicon wafers; and resins, glass, ceramics and the like can be used.
【００３６】次に、本発明の被覆材料を製造する方法に
ついて説明する。本発明において、所望の酸化チタン皮
膜を形成する為には、活性度の高いプラズマを用いたス
パッタリング法を採用することが推奨される。これによ
り、結晶性および配向性が高く、しかも光触媒特性に極
めて優れた酸化チタン皮膜を低温にて再現性良く形成す
ることができる。Next, a method for producing the coating material of the present invention will be described. In the present invention, in order to form a desired titanium oxide film, it is recommended to employ a sputtering method using highly active plasma. This makes it possible to form a titanium oxide film having high crystallinity and orientation and extremely excellent photocatalytic properties at a low temperature with good reproducibility.
【００３７】本発明に用いられる皮膜は、上記ファセッ
ト構造を有することが推奨されるが、その為には、特に
アンバランスドマグネトロンスパッタリングを用いて成
膜することが推奨される。通常の成膜法では、プラズマ
中若しくは膜成長表面でのチタンと酸素の反応性が不充
分で、（１０１）面とは異なる結晶面を成長面とする柱
状晶が現れ、所望のラス状構造やファセット構造が得ら
れ難いが、アンバランスドマグネトロンスパッタリング
法を採用すれば、所望の上記構造が容易に得られるから
である。It is recommended that the film used in the present invention has the above-mentioned facet structure. For this purpose, it is particularly recommended to form the film using unbalanced magnetron sputtering. In the ordinary film forming method, the reactivity between titanium and oxygen in the plasma or the film growth surface is insufficient, and columnar crystals having a crystal plane different from the (101) plane as a growth plane appear, and a desired lath-like structure is formed. This is because it is difficult to obtain a facet structure or a facet structure, but if the unbalanced magnetron sputtering method is employed, the desired structure can be easily obtained.
【００３８】具体的には、アンバランスドマグネトロン
スパッタリングを用い、金属チタンターゲット又は酸化
チタンターゲットをアルゴン酸素混合ガス雰囲気中、成
膜中の基材温度４００℃以下で成膜することが推奨され
る。成膜中の基材温度が４００℃を超えると、結晶粒の
成長や結晶配向の低下により、所望のラス状構造が得ら
れなくなり、光触媒特性が低下する。上記成膜温度は低
ければ低い方が、ラス状構造の形成には好ましく、特に
２５０℃以下であれば、一層優れた光触媒特性が得られ
る。Specifically, it is recommended to use an unbalanced magnetron sputtering to form a metal titanium target or a titanium oxide target in an argon-oxygen mixed gas atmosphere at a substrate temperature of 400 ° C. or less during film formation. . If the substrate temperature during the film formation exceeds 400 ° C., a desired lath-like structure cannot be obtained due to the growth of crystal grains and a decrease in crystal orientation, and the photocatalytic properties deteriorate. The lower the film forming temperature is, the better the lath-like structure is formed. Particularly, if the film forming temperature is 250 ° C. or lower, more excellent photocatalytic properties can be obtained.
【００３９】尚、上記アンバランスドスパッタリングと
は、例えばＢ．Ｗｉｎｄｏｗらにより開示された通り
［Ｊ．Ｖａｃ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，Ａ４（１９
８６），ｐ１９６〜２０２］、通常のスパッタリングと
はカソード構造が異なるものである。即ち、通常のスパ
ッタリングでは、例えばフェライト、Ｓｍ系希土類磁石
またはＮｄ希土類磁石につき、丸形ターゲット中心部と
周辺部で同じ磁気特性を持つ磁石を配し、ターゲット近
傍に磁力線の閉ループを形成するのに対し、アンバラン
スドスパッタリングでは、中心部と周辺部で異なる磁気
特性を持つ磁石を配することにより、一層強力な磁石に
より発する磁力線の一部が基板近傍まで達する様に調整
されたところに特徴がある。その結果、アンバランスド
スパッタリングでは、この磁力線に沿ってスパッタリン
グ時に発生したプラズマが基板付近まで拡散するという
効果が得られる。特にＵＢＭ（Unbalanced Magnetron）
スパッタリングを採用すれば、基板付近まで達する磁力
線に沿ってＡｒイオン及び電子が、通常のスパッタリン
グに比べて大量に基板及び薄膜に到達するイオンアシス
ト効果が得られる結果、結晶性が向上することが知られ
ている。The above-mentioned unbalanced sputtering is described in, for example, B.S. As disclosed by Windows et al. [J. Vac. Sci. Technol. , A4 (19
86), pp. 196-202], which has a different cathode structure from ordinary sputtering. That is, in normal sputtering, for example, for a ferrite, Sm-based rare earth magnet, or Nd rare earth magnet, magnets having the same magnetic characteristics are arranged at the center and the periphery of the round target to form a closed loop of lines of magnetic force near the target. On the other hand, unbalanced sputtering is characterized by the fact that magnets with different magnetic properties are arranged in the central part and the peripheral part, so that some of the lines of magnetic force generated by the stronger magnet reach the vicinity of the substrate. is there. As a result, in unbalanced sputtering, there is obtained an effect that plasma generated at the time of sputtering is diffused to the vicinity of the substrate along the lines of magnetic force. Especially UBM (Unbalanced Magnetron)
It is known that if sputtering is used, Ar ions and electrons along the lines of magnetic force reaching the vicinity of the substrate can reach the substrate and the thin film in a larger amount as compared with ordinary sputtering, and as a result, the crystallinity is improved. Have been.
【００４０】尚、プラズマ自体を活性化し、イオン化を
促進する方法によっても同様の効果が得られる。上記イ
オン化促進方法としては、結合誘導プラズマ（ＩＣ
Ｐ）、高周波（ＲＦ）、電子サイクロトロン共鳴（ＥＣ
Ｒ）等が知られているが、これらに限定される趣旨では
決してなく、最近開発されている種々のイオン化促進手
法を適用することができる。The same effect can be obtained by activating the plasma itself to promote ionization. As the above-mentioned ionization promoting method, a coupling induction plasma (IC
P), radio frequency (RF), electron cyclotron resonance (EC)
R) and the like are known, but are not limited to these, and various ionization promoting techniques recently developed can be applied.
【００４１】以下実施例に基づいて本発明を詳述する。
ただし、下記実施例は本発明を制限するものではなく、
前・後記の趣旨を逸脱しない範囲で変更実施することは
全て本発明の技術範囲に包含される。Hereinafter, the present invention will be described in detail with reference to examples.
However, the following examples do not limit the present invention,
All modifications and alterations without departing from the spirit of the preceding and following descriptions are included in the technical scope of the present invention.
【００４２】[0042]
【実施例】実施例１および比較例１〜４ 直流電源によるアンバランスドマグネトロンスパッタリ
ングにより、熱酸化膜（１３０ｎｍ厚）付きの４インチ
系シリコンウエハー基材に約０．７μｍの酸化チタン薄
膜を厚形成した。尚、スパッタリングターゲットには純
度９９．９５％の金属チタンターゲットを用い、スパッ
タリングにおける雰囲気ガスとしては、高純度アルゴン
−２０％酸素混合ガスを用い、全ガス圧を５ｍｔｏｒｒ
（６６５ｍＰａ）とした。ターゲットに対する投入パワ
ー密度は約１．１３Ｗ／ｃｍ2とした。EXAMPLES Example 1 and Comparative Examples 1 to 4 A thickness of about 0.7 μm of a titanium oxide thin film was formed on a 4-inch silicon wafer substrate having a thermal oxide film (130 nm thick) by unbalanced magnetron sputtering using a DC power supply. Formed. The sputtering target used was a metal titanium target having a purity of 99.95%, the atmosphere gas used for sputtering was a high-purity argon-20% oxygen mixed gas, and the total gas pressure was 5 mtorr.
(665 mPa). The power density applied to the target was about 1.13 W / cm 2 .
【００４３】次に、成膜時に基板裏面を水冷板に接触さ
せ、基板温度を約２０℃に保持することにより、実施例
１の被覆材料を得た。この様にして得られた酸化チタン
薄膜の断面ＴＥＭ像写真を図２に示す。図中、柱状結晶
粒間の白く見える部分が隙間として現れる空間である。
本実施例では、アナターゼ型酸化チタン結晶の＜１０１
＞配向度は８２体積％であった。また、最表面部におい
て（１００）面または（００１）面のファセット構造を
有する結晶の比率［以下、（１００）（００１）ファセ
ット面比率と呼ぶ］は６０体積％以上であった。Next, at the time of film formation, the back surface of the substrate was brought into contact with a water-cooled plate, and the temperature of the substrate was maintained at about 20 ° C., thereby obtaining the coating material of Example 1. FIG. 2 shows a cross-sectional TEM image photograph of the titanium oxide thin film thus obtained. In the figure, white portions between columnar crystal grains are spaces that appear as gaps.
In this example, the anatase type titanium oxide crystal <101
> The degree of orientation was 82% by volume. The ratio of the crystal having a (100) facet or (001) facet structure at the outermost surface (hereinafter referred to as a (100) (001) facet face ratio) was 60% by volume or more.
【００４４】尚、比較の為に、下記比較例１〜４の被覆
材料を調製した。このうち比較例１は市販のＡ社製酸化
チタン粉末を、比較例２はＢ社製酸化チタン粉末を、夫
々シリカ系バインダーに固定した塗布型酸化チタン光触
媒被覆材料である。また、比較例３は市販のＣ社製過酸
化チタンをバインダーにした塗布型酸化チタン光触媒被
覆材料であり、比較例４はチタン基材にアセチルアセト
ンチタンを塗布し、５００℃で焼成したＤ社製酸化チタ
ン光触媒被覆材料である。For comparison, coating materials of the following Comparative Examples 1 to 4 were prepared. Among them, Comparative Example 1 is a coating type titanium oxide photocatalyst coating material obtained by fixing a commercially available titanium oxide powder manufactured by Company A to a titanium oxide powder manufactured by Company B to a silica-based binder. Comparative Example 3 is a coating type titanium oxide photocatalyst coating material using commercially available titanium peroxide as a binder manufactured by Company C, and Comparative Example 4 is a product manufactured by Company D obtained by applying acetylacetone titanium to a titanium base material and firing at 500 ° C. It is a titanium oxide photocatalyst coating material.
【００４５】これらの被覆材料について、以下の要領で
光触媒特性を調べた。即ち、ヨウ化カリウム水溶液中に
各材料を浸漬し、３６０ｎｍ波長域の強度が８００μＷ
／ｃｍ2である紫外線を３０分照射したとき、酸化反応
により生成するヨウ素量を分析することにより評価し
た。ヨウ素生成量が多いほど光触媒特性が高いことを示
している。The photocatalytic properties of these coating materials were examined in the following manner. That is, each material is immersed in an aqueous potassium iodide solution, and the intensity in the wavelength region of 360 nm is 800 μW.
/ Cm 2 for 30 minutes, the amount of iodine generated by the oxidation reaction was analyzed to evaluate. The higher the iodine generation amount, the higher the photocatalytic properties.
【００４６】図３に、実施例１及び比較例１〜４の光触
媒特性を比較したグラフを示す。FIG. 3 is a graph comparing the photocatalytic properties of Example 1 and Comparative Examples 1-4.
【００４７】このうち比較例４は、市販の酸化チタン光
触媒被覆材料のなかでも最も高い光触媒特性を有するも
のとして知られている材料であるが、実施例１の材料を
用いれば、比較例１〜３に比べて非常に優れた光触媒特
性を示すことは勿論のこと、光触媒特性に最も優れると
考えられている比較例４に比べ、約１．５倍も高い特性
を示すことが分かる。Among them, Comparative Example 4 is a material known to have the highest photocatalytic property among commercially available titanium oxide photocatalyst coating materials. It can be seen that, of course, the photocatalytic properties are much higher than that of Comparative Example 3, and that they are about 1.5 times higher than that of Comparative Example 4, which is considered to be the most excellent in photocatalytic properties.
【００４８】実施例２ 実施例１と同様の成膜条件で形成した酸化チタン薄膜に
おいて、当該薄膜の膜厚、アナターゼ型結晶の＜１０１
＞配向度、及び最表面部における（１００）（００１）
ファセット面比率を種々変化させた場合に、光触媒特性
がどの様な影響を受けるかについて調べた。これらの結
果を図４にまとめて示す。 Example 2 In a titanium oxide thin film formed under the same film forming conditions as in Example 1, the thickness of the thin film and the anatase type crystal <101
> Degree of orientation and (100) (001) at the outermost surface
We examined how the photocatalytic properties were affected when the facet surface ratio was varied. These results are summarized in FIG.
【００４９】図４より、酸化チタンの膜厚が２００ｎｍ
以上になると、＜１０１＞配向度が５０体積％以上、
（１００）（００１）ファセット面比率が５０体積％以
上になり、光触媒特性が格段に上昇することが分かる。FIG. 4 shows that the thickness of titanium oxide is 200 nm.
If the above, the <101> orientation degree is 50% by volume or more,
It can be seen that the (100) (001) facet surface ratio is 50% by volume or more, and the photocatalytic properties are significantly improved.
【００５０】実施例３ 成膜時の基材温度を変化させたこと以外は実施例１と同
様の成膜条件で形成した酸化チタン薄膜（２μｍ）にお
いて、成膜時の基材温度、アナターゼ型結晶の＜１０１
＞配向度、及び最表面部における（１００）（００１）
ファセット面比率を種々変化させた場合に、光触媒特性
がどの様な影響を受けるかについて調べた。これらの結
果を図５にまとめて示す。 Example 3 A titanium oxide thin film (2 μm) formed under the same film forming conditions as in Example 1 except that the substrate temperature during film formation was changed, the substrate temperature during film formation, anatase type <101 of the crystal
> Degree of orientation and (100) (001) at the outermost surface
We examined how the photocatalytic properties were affected when the facet surface ratio was varied. These results are summarized in FIG.
【００５１】図５より、成膜時の基材温度が４００℃以
下になると、＜１０１＞配向度が５０体積％以上、（１
００）（００１）ファセット面比率が５０体積％以上に
なり、光触媒特性が格段に上昇することが分かる。FIG. 5 shows that when the substrate temperature during film formation is 400 ° C. or less, the degree of orientation <101> is 50% by volume or more and (1
It can be seen that the (00) (001) facet surface ratio is 50% by volume or more, and the photocatalytic properties are significantly improved.
【００５２】以上の実施例１〜３では、アナターゼ型酸
化チタンの結晶が＜１０１＞配向を有し、（１００）
（００１）ファセット面を有する皮膜を代表例として掲
げ、光触媒特性との関係を調べたが、上記結晶構造の皮
膜に限定されず、他の結晶構造を有する皮膜（＜１００
＞配向を有し、（１１１）（１−１１）（１１−１）
（１−１−１）ファセット面を有する皮膜；＜００１＞
配向を有し、（１１１）（−１１１）（−１−１１）
（１−１１）ファセット面を有する皮膜）についても、
同様に優れた光触媒特性が得られることを実験により確
認している。In the above Examples 1 to 3, the crystals of anatase type titanium oxide have a <101> orientation and (100)
A film having a (001) facet face was taken as a representative example, and the relationship with the photocatalytic property was examined. However, the film is not limited to the film having the above crystal structure, and a film having another crystal structure (<100
> (111) (1-11) (11-1)
(1-1-1) Coating having facet face; <001>
Having orientation, (111) (-111) (-1-11)
(1-11) Coating having facet surface)
Experiments have confirmed that similarly excellent photocatalytic properties can be obtained.
【００５３】[0053]
【発明の効果】本発明は上記の様に構成されているの
で、従来法が抱える不具合（形成温度に伴う基材の制約
等）もなく、極めて優れた光触媒性を有し、しかも耐久
性（密着性）にも優れており、防臭、殺菌等の分野に適
用可能な酸化チタン被覆材料を、簡便且つ再現性良く提
供することができた。Since the present invention is constructed as described above, it does not have the drawbacks of the conventional method (substrate restriction due to forming temperature, etc.), has extremely excellent photocatalytic properties, and has high durability ( Thus, a titanium oxide-coated material which is excellent in adhesiveness and can be applied to fields such as deodorization and sterilization can be provided simply and with good reproducibility.
【図１】本発明における酸化チタン皮膜の構造を示す概
略断面図である。FIG. 1 is a schematic sectional view showing the structure of a titanium oxide film in the present invention.
【図２】実施例１の酸化チタン皮膜の断面ＴＥＭ像を示
す写真である。FIG. 2 is a photograph showing a cross-sectional TEM image of the titanium oxide film of Example 1.
【図３】実施例１及び比較例１〜４の酸化チタン被覆材
料における光触媒特性を比較したグラフである。FIG. 3 is a graph comparing the photocatalytic properties of the titanium oxide-coated materials of Example 1 and Comparative Examples 1 to 4.
【図４】酸化チタン皮膜の膜厚、アナターゼ型結晶の＜
１０１＞配向度、最表面部における（１００）（００
１）ファセット面比率と、光触媒特性との関係を示すグ
ラフ。FIG. 4 shows the thickness of the titanium oxide film and the anatase type crystal.
101> degree of orientation, (100) (00)
1) A graph showing the relationship between the facet surface ratio and the photocatalytic properties.
【図５】成膜時の基材温度、アナターゼ型結晶の＜１０
１＞配向度、及び最表面部における（１００）（００
１）ファセット面比率と、光触媒特性との関係を示すグ
ラフ。FIG. 5: Substrate temperature during film formation, <10 of anatase crystal
1> Degree of orientation and (100) (00
1) A graph showing the relationship between the facet surface ratio and the photocatalytic properties.
１ 基材 ２ ＜１０１＞方向に配向したアナターゼ型酸化チタン
の柱状結晶粒 ３ （１００）面または（００１）面のファセット構造 ４ 隙間 ５ アナターゼ型酸化チタン皮膜Reference Signs List 1 base material 2 columnar crystal grains of anatase-type titanium oxide oriented in <101> direction 3 facet structure of (100) plane or (001) plane 4 gap 5 anatase-type titanium oxide film
Claims (7)
柱状結晶を有する光触媒皮膜が被覆された材料であっ
て、 該光触媒皮膜は、柱状結晶粒間に隙間のあるラス状構造
を有するものであることを特徴とする光触媒性に優れた
被覆材料。1. A material in which a photocatalytic film having columnar crystals of anatase-type titanium oxide is coated on the surface of a substrate, wherein the photocatalytic film has a lath-like structure having gaps between the columnar crystal grains. A coating material having excellent photocatalytic properties.
膜表面の垂線方向から４５°以内に配向している結晶粒
の占める比率が５０体積％以上である請求項１に記載の
被覆材料。2. The coating material according to claim 1, wherein in the photocatalytic film, a ratio of crystal grains in which the columnar crystals are oriented within 45 ° from a perpendicular direction of the surface of the photocatalytic film is 50% by volume or more.
の成長面とは異なる結晶面のファセット構造を有するも
のである請求項１または２に記載の被覆材料。3. The coating material according to claim 1, wherein the outermost surface of the photocatalytic film has a facet structure of a crystal surface different from a growth surface of the columnar crystal.
中、当該柱状結晶の成長面とは異なる結晶面のファセッ
ト構造を有する結晶粒の占める比率が５０体積％以上で
ある請求項３に記載の被覆材料。4. The columnar crystal according to claim 3, wherein, at the outermost surface of the photocatalytic film, a ratio of crystal grains having a facet structure of a crystal face different from a growth face of the columnar crystal occupies 50% by volume or more. Coating material.
である請求項１〜４のいずれかに記載の被覆材料。5. The coating material according to claim 1, wherein said photocatalytic film has a thickness of 0.2 μm or more.
り光触媒皮膜を成膜することを特徴とする請求項１〜５
のいずれかに記載の製造方法。6. A photocatalytic film is formed by a sputtering method using plasma.
The method according to any one of the above.
ング法により光触媒皮膜を成膜するものである請求項６
に記載の製造方法。7. A photocatalytic film is formed by an unbalanced magnetron sputtering method.
The production method described in 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33493999A JP2001149790A (en) | 1999-11-25 | 1999-11-25 | Coating material excellent in photocatalytic performance and manufacturing method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33493999A JP2001149790A (en) | 1999-11-25 | 1999-11-25 | Coating material excellent in photocatalytic performance and manufacturing method therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001149790A true JP2001149790A (en) | 2001-06-05 |
Family
ID=18282930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33493999A Withdrawn JP2001149790A (en) | 1999-11-25 | 1999-11-25 | Coating material excellent in photocatalytic performance and manufacturing method therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001149790A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002253975A (en) * | 2001-03-02 | 2002-09-10 | Hachinohe National College Of Technology | Oxide photocatalytic material using organometallic compound and its application article |
| WO2003028885A1 (en) * | 2001-09-28 | 2003-04-10 | Shibaura Mechatronics Corporation | Photocatalyst element, method and device for preparing the same |
| WO2006006637A1 (en) * | 2004-07-09 | 2006-01-19 | National Institute For Materials Science | Magnetron sputtering device making magnetic flux arrangement (balanced type/unbalanced type) switchable and film forming method for inorganic thin film material using this device, and dual-type magnetron sputtering device and film forming method for inorganic thin film material making possible low-temperature film forming b |
| JP2006022388A (en) * | 2004-07-09 | 2006-01-26 | National Institute For Materials Science | Magnetron sputtering cathode designed so that magnetic flux arrangement is easily switched into balance type/unbalance type |
| JP2009101357A (en) * | 2001-11-29 | 2009-05-14 | Shibaura Mechatronics Corp | Apparatus for producing photocatalytic body |
| JP2016132594A (en) * | 2015-01-20 | 2016-07-25 | 本田技研工業株式会社 | Production method of carbon nanotube and production apparatus of the same |
-
1999
- 1999-11-25 JP JP33493999A patent/JP2001149790A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002253975A (en) * | 2001-03-02 | 2002-09-10 | Hachinohe National College Of Technology | Oxide photocatalytic material using organometallic compound and its application article |
| WO2003028885A1 (en) * | 2001-09-28 | 2003-04-10 | Shibaura Mechatronics Corporation | Photocatalyst element, method and device for preparing the same |
| CN1332763C (en) * | 2001-09-28 | 2007-08-22 | 芝浦机械电子装置股份有限公司 | Photocatalyst element, method and device for preparing the same |
| US7799731B2 (en) | 2001-09-28 | 2010-09-21 | Shibaura Mechatronics Corporation | Photocatalyst element, method and device for preparing the same |
| US8022011B2 (en) | 2001-09-28 | 2011-09-20 | Shibaura Mechatronics Corporation | Photocatalyst element, method and device for preparing the same |
| JP2009101357A (en) * | 2001-11-29 | 2009-05-14 | Shibaura Mechatronics Corp | Apparatus for producing photocatalytic body |
| WO2006006637A1 (en) * | 2004-07-09 | 2006-01-19 | National Institute For Materials Science | Magnetron sputtering device making magnetic flux arrangement (balanced type/unbalanced type) switchable and film forming method for inorganic thin film material using this device, and dual-type magnetron sputtering device and film forming method for inorganic thin film material making possible low-temperature film forming b |
| JP2006022388A (en) * | 2004-07-09 | 2006-01-26 | National Institute For Materials Science | Magnetron sputtering cathode designed so that magnetic flux arrangement is easily switched into balance type/unbalance type |
| JP2016132594A (en) * | 2015-01-20 | 2016-07-25 | 本田技研工業株式会社 | Production method of carbon nanotube and production apparatus of the same |
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