JP2004256859A - Method for manufacturing thin film of photocatalytic anatase type titanium dioxide - Google Patents
Method for manufacturing thin film of photocatalytic anatase type titanium dioxide Download PDFInfo
- Publication number
- JP2004256859A JP2004256859A JP2003047772A JP2003047772A JP2004256859A JP 2004256859 A JP2004256859 A JP 2004256859A JP 2003047772 A JP2003047772 A JP 2003047772A JP 2003047772 A JP2003047772 A JP 2003047772A JP 2004256859 A JP2004256859 A JP 2004256859A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- titanium dioxide
- anatase
- type titanium
- 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 75
- 239000010409 thin film Substances 0.000 title claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 238000007740 vapor deposition Methods 0.000 claims abstract description 11
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 abstract description 8
- 239000011521 glass Substances 0.000 abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Images
Landscapes
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、アナターゼ型二酸化チタン（以下、ＴｉＯ２ともいう。）光触媒とその製造方法とに関するものである。更に詳しくは、本発明は、酸素雰囲気下でのレーザー蒸着成膜法により炭化チタン（ＴｉＣ） 焼結体から製造されるアナターゼ型ＴｉＯ２薄膜光触媒材料とその製造方法とに関するものである。
【０００２】
【従来の技術】
ＴｉＯ２光触媒の結晶構造にはアナターゼ型、ルチル型、そしてブルッカイト型の三つの種類があり、その光触媒活性はアナターゼ型が最も高いことが知られている。しかしながら、従来、光触媒材料としてＴｉＯ２の薄膜を製造する場合には、アナターゼ相とルチル相とが混在した膜が製造されアナターゼ相のみの膜を製造することは困難であった。また、従来用いられているゾルゲル法により製造されるＴｉＯ２膜は、基板との密着性が悪いという欠点を有している。これらのことから、光触媒活性が高く、更に基板との密着性にすぐれたアナターゼ型二酸化チタン薄膜を製造する必要性が存在する。
【０００３】
【発明が解決しようとする課題】
本発明は、上記した従来技術における欠点を解消するためになされたものであって、その目的とするところは、レーザー蒸着成膜法を用いることにより、光触媒活性の高いアナターゼ相のみを有する二酸化チタン薄膜を製造することである。
【０００４】
また、他の目的は、ゾルゲル法に代えてレーザー蒸着成膜法を用いることにより、基板との密着性にすぐれたアナターゼ型二酸化チタン薄膜を製造することである。
【０００５】
更に、他の目的は、ガラス基板を用いることにより、経済的にも望ましいアナターゼ型二酸化チタン薄膜を製造することである。
【０００６】
【課題を解決するための手段】
要するに、本発明は、レーザー蒸着成膜法により、石英ガラス基板上にアナターゼ型二酸化チタン薄膜を製造する方法であって、炭化チタン焼結体をターゲットとして用い、基板温度が４５０〜５５０℃であり、更に、光触媒活性の高いアナターゼ相のみを有する二酸化チタン薄膜が製造されることを特徴とする製造方法である。
【０００７】
更に、本発明においては、基板として石英ガラス基板を用いることができる。
【０００８】
【発明の実施の形態】
本発明に係るアナターゼ型二酸化チタン薄膜の製造方法は、レーザー蒸着成膜法によるものである。ここで「レーザー蒸着成膜法」とは、酸素を含む雰囲気下でチタンを含むターゲットにレーザーを照射することにより、ＴｉＯ２薄膜を基板上に蒸着させる方法である。本発明の製造方法においては、特に、ターゲットと基板の温度が重要な項目である。
【０００９】
本発明において用いることができるターゲットは、炭化チタン（ＴｉＣ） 焼結体である。また、基板は石英ガラス基板を用いることができるが、当業者であればこれ以外の基板を適宜選択することができる。基板温度、並びに酸素の圧力は、用いる基板の種類に依存するが、当業者であれば適宜条件を設定することができる。
【００１０】
本発明に係る製造方法において、３０ｍＴｏｒｒの酸素ガス雰囲気下でＴｉＣ焼結体にレーザーを照射することにより、石英ガラス基板上にアナターゼ型ＴｉＯ２薄膜を製造する。このとき、基板温度は４５０〜５５０℃（好ましくは、５００℃）、蒸着時間は１〜３時間（好ましくは、２時間）である。照射に使用するレーザーの種類は、ターゲットにエネルギーを付与して蒸発させることができるものであれば特に制限はないが、例えば、ＫｒＦレーザー（波長：２４８ｎｍ、エネルギー：１５０ｍＪ、繰り返し周波数：１０Ｈｚ）を用いることができる。
【００１１】
本明細書中において「二酸化チタン薄膜」とは、ミクロンオーダーの厚さの二酸化チタン膜を意味し、好ましくは、数ミクロンの厚さの二酸化チタン膜をいう。
【００１２】
以下、実施例を示し、更に本発明について詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
【００１３】
【実施例】
（実施例１）
本実施例においては、ターゲットとしてＴｉＣ焼結体、基板として石英ガラス基板を用いた。３０ｍＴｏｒｒの酸素雰囲気下基板温度５００℃で、レーザー蒸着成膜法（ＫｒＦレーザー、波長：２４８ｎｍ、エネルギー：１５０ｍＪ、繰り返し周波数：１０Ｈｚ）により、ターゲットから約７ｃｍ離れている基板上に二酸化チタン薄膜を２時間蒸着した。図１は、得られた二酸化チタン薄膜のＸ線回折（ＸＲＤ）パターンを示す図である。図中、●符号のピークはアナターゼ型結晶構造に特徴的な回折ピークであり、▽符号のピークはＸＲＤ測定に使用した鉄製の試料ホルダーの回折ピークである。ＸＲＤの結果より、ルチル相が混在していない多結晶のアナターゼ相のみの薄膜が製造されたことが明らかとなった。また、得られた膜は平滑でありその厚さは約２００ナノメートルであった。
【００１４】
次いで、ＴｉＯ２光触媒の特性の一つである親水性の有無を評価するため水の接触角の測定を行った。その結果を図２に示す。接触角の測定は、純水の液滴２．６μｌを試料に滴下することにより行った。約１時間の紫外線照射後、測定された接触角は約１０度であった。この結果により、本発明の製造方法によるアナターゼ型二酸化チタン薄膜は親水性にすぐれていることが明らかになった。
【００１５】
（比較例）
基板温度を２００℃とした以外は実施例１と同様の操作を行った。本実施例により得られた薄膜試料は、ＸＲＤパターンよりアモルファスであることが明らかとなった。更に、水の接触角測定から親水性を有さないことが分かった。
【００１６】
【発明の効果】
本発明は、上記のように、ターゲットとして炭化チタン焼結体を用い基板温度を４５０〜５５０℃としたレーザー蒸着成膜法を用いることにより、光触媒活性の高いアナターゼ相のみを有する二酸化チタン薄膜を製造できるという効果がある。
【００１７】
また、ゾルゲル法に代えてレーザー蒸着成膜法を用いることにより、基板との密着性にすぐれたアナターゼ型二酸化チタン薄膜を製造できるという効果がある。
【００１８】
更に、ガラス基板を用いることにより、経済的にも望ましいアナターゼ型二酸化チタン薄膜を製造できるという効果がある。
【図面の簡単な説明】
【図１】図１は、本発明の製造方法により得られた二酸化チタン薄膜のＸ線回折（ＸＲＤ）パターンを示す図である。
【図２】図２は、紫外線照射時間による水の接触角の変化を表す図であり、本発明の製造方法により得られた二酸化チタン薄膜の親水性の評価を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an anatase type titanium dioxide (hereinafter, also referred to as TiO 2 ) photocatalyst and a method for producing the same. More specifically, the present invention relates to an anatase-type TiO 2 thin-film photocatalytic material produced from a titanium carbide (TiC) sintered body by a laser vapor deposition method in an oxygen atmosphere, and a method for producing the same.
[0002]
[Prior art]
There are three types of crystal structures of TiO 2 photocatalysts: anatase type, rutile type, and brookite type, and it is known that the anatase type has the highest photocatalytic activity. However, conventionally, when producing a TiO 2 thin film as a photocatalytic material, a film in which an anatase phase and a rutile phase are mixed has been produced, and it has been difficult to produce a film having only an anatase phase. Further, the TiO 2 film produced by the conventionally used sol-gel method has a drawback that adhesion to a substrate is poor. Accordingly, there is a need to produce an anatase-type titanium dioxide thin film having high photocatalytic activity and excellent adhesion to a substrate.
[0003]
[Problems to be solved by the invention]
The present invention has been made in order to solve the above-mentioned drawbacks in the prior art, and it is an object of the present invention to provide a titanium dioxide having only an anatase phase having a high photocatalytic activity by using a laser vapor deposition method. It is to produce a thin film.
[0004]
Another object is to produce an anatase type titanium dioxide thin film having excellent adhesion to a substrate by using a laser vapor deposition method instead of the sol-gel method.
[0005]
Still another object is to produce an economically desirable anatase-type titanium dioxide thin film by using a glass substrate.
[0006]
[Means for Solving the Problems]
In short, the present invention is a method for producing an anatase type titanium dioxide thin film on a quartz glass substrate by a laser vapor deposition method, wherein a titanium carbide sintered body is used as a target, and the substrate temperature is 450 to 550 ° C. And a method for producing a titanium dioxide thin film having only an anatase phase having high photocatalytic activity.
[0007]
Further, in the present invention, a quartz glass substrate can be used as the substrate.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The method for producing an anatase type titanium dioxide thin film according to the present invention is based on a laser vapor deposition method. Here, the “laser deposition film forming method” is a method in which a TiO 2 thin film is deposited on a substrate by irradiating a target containing titanium with a laser in an atmosphere containing oxygen. In the manufacturing method of the present invention, the temperature of the target and the substrate are particularly important items.
[0009]
The target that can be used in the present invention is a titanium carbide (TiC) sintered body. Although a quartz glass substrate can be used as the substrate, those skilled in the art can appropriately select other substrates. The substrate temperature and the oxygen pressure depend on the type of the substrate to be used, but those skilled in the art can appropriately set conditions.
[0010]
In the manufacturing method according to the present invention, an anatase-type TiO 2 thin film is manufactured on a quartz glass substrate by irradiating a laser to the TiC sintered body in an oxygen gas atmosphere of 30 mTorr. At this time, the substrate temperature is 450 to 550 ° C. (preferably 500 ° C.), and the vapor deposition time is 1 to 3 hours (preferably 2 hours). The type of laser used for irradiation is not particularly limited as long as it can impart energy to the target and evaporate it. For example, a KrF laser (wavelength: 248 nm, energy: 150 mJ, repetition frequency: 10 Hz) is used. Can be used.
[0011]
As used herein, the term “titanium dioxide thin film” refers to a titanium dioxide film having a thickness on the order of microns, preferably a titanium dioxide film having a thickness of several microns.
[0012]
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0013]
【Example】
(Example 1)
In this example, a TiC sintered body was used as a target, and a quartz glass substrate was used as a substrate. At a substrate temperature of 500 ° C. in an oxygen atmosphere of 30 mTorr, a titanium dioxide thin film is deposited on a substrate approximately 7 cm away from the target by a laser vapor deposition method (KrF laser, wavelength: 248 nm, energy: 150 mJ, repetition frequency: 10 Hz). Time deposited. FIG. 1 is a diagram showing an X-ray diffraction (XRD) pattern of the obtained titanium dioxide thin film. In the figure, the peak with the symbol ● is a diffraction peak characteristic of the anatase crystal structure, and the peak with the symbol Δ is the diffraction peak of the iron sample holder used for the XRD measurement. The results of XRD revealed that a thin film of only a polycrystalline anatase phase without rutile phase was produced. The obtained film was smooth and had a thickness of about 200 nanometers.
[0014]
Next, the contact angle of water was measured to evaluate the presence or absence of hydrophilicity, which is one of the characteristics of the TiO 2 photocatalyst. The result is shown in FIG. The measurement of the contact angle was performed by dropping 2.6 μl of pure water droplet onto the sample. After about one hour of UV irradiation, the measured contact angle was about 10 degrees. These results revealed that the anatase-type titanium dioxide thin film produced by the production method of the present invention was excellent in hydrophilicity.
[0015]
(Comparative example)
The same operation as in Example 1 was performed except that the substrate temperature was set to 200 ° C. It became clear that the thin film sample obtained in this example was amorphous from the XRD pattern. Furthermore, it was found from the contact angle measurement of water that it did not have hydrophilicity.
[0016]
【The invention's effect】
As described above, the present invention provides a titanium dioxide thin film having only an anatase phase having high photocatalytic activity by using a titanium carbide sintered body as a target and using a laser vapor deposition method with a substrate temperature of 450 to 550 ° C. There is an effect that it can be manufactured.
[0017]
Further, by using a laser deposition method instead of the sol-gel method, there is an effect that an anatase type titanium dioxide thin film having excellent adhesion to a substrate can be produced.
[0018]
Further, the use of a glass substrate has the effect that an anatase-type titanium dioxide thin film that is economically desirable can be produced.
[Brief description of the drawings]
FIG. 1 is a view showing an X-ray diffraction (XRD) pattern of a titanium dioxide thin film obtained by a production method of the present invention.
FIG. 2 is a diagram illustrating a change in a contact angle of water depending on an ultraviolet irradiation time, and is a diagram illustrating an evaluation of hydrophilicity of a titanium dioxide thin film obtained by the production method of the present invention.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003047772A JP4224850B2 (en) | 2003-02-25 | 2003-02-25 | Method for producing photocatalytic anatase-type titanium dioxide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003047772A JP4224850B2 (en) | 2003-02-25 | 2003-02-25 | Method for producing photocatalytic anatase-type titanium dioxide thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004256859A true JP2004256859A (en) | 2004-09-16 |
| JP4224850B2 JP4224850B2 (en) | 2009-02-18 |
Family
ID=33113933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003047772A Expired - Fee Related JP4224850B2 (en) | 2003-02-25 | 2003-02-25 | Method for producing photocatalytic anatase-type titanium dioxide thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4224850B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1632378A2 (en) | 2004-09-03 | 2006-03-08 | Honda Motor Co., Ltd. | Control apparatus for hybrid vehicle |
| WO2008118533A2 (en) | 2007-02-07 | 2008-10-02 | Imra America, Inc. | A method for depositing crystalline titania nanoparticles and films |
| CN116809103A (en) * | 2023-05-09 | 2023-09-29 | 西南交通大学 | Ti (titanium) 3 C 2 /TiO 2 Photocatalyst and preparation method thereof |
-
2003
- 2003-02-25 JP JP2003047772A patent/JP4224850B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1632378A2 (en) | 2004-09-03 | 2006-03-08 | Honda Motor Co., Ltd. | Control apparatus for hybrid vehicle |
| WO2008118533A2 (en) | 2007-02-07 | 2008-10-02 | Imra America, Inc. | A method for depositing crystalline titania nanoparticles and films |
| EP2671970A1 (en) | 2007-02-07 | 2013-12-11 | Imra America, Inc. | A method for depositing crystalline titania nanoparticles and films |
| US8609205B2 (en) | 2007-02-07 | 2013-12-17 | Imra America, Inc. | Method for depositing crystalline titania nanoparticles and films |
| CN116809103A (en) * | 2023-05-09 | 2023-09-29 | 西南交通大学 | Ti (titanium) 3 C 2 /TiO 2 Photocatalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4224850B2 (en) | 2009-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Byun et al. | Photocatalytic TiO2 deposition by chemical vapor deposition | |
| Ye et al. | Hydrophilic properties of nano-TiO2 thin films deposited by RF magnetron sputtering | |
| György et al. | Anatase phase TiO2 thin films obtained by pulsed laser deposition for gas sensing applications | |
| US20030054177A1 (en) | Multifunctional energy efficient window coating | |
| Conde-Gallardo et al. | TiO2 anatase thin films deposited by spray pyrolysis of an aerosol of titanium diisopropoxide | |
| Guo et al. | Investigation of structure and properties of N-doped TiO2 thin films grown by APCVD | |
| Baba et al. | Synthesis and properties of TiO2 thin films by plasma source ion implantation | |
| Yang et al. | The structure and photocatalytic activity of TiO2 thin films deposited by dc magnetron sputtering | |
| JP2000096212A (en) | Photocatalyst film coated member and its production | |
| Chen et al. | Photocatalytic TiO2 thin films deposited on flexible substrates by radio frequency (RF) reactive magnetron sputtering | |
| JP2008106342A (en) | Photocatalytic tungsten oxide thin film | |
| JP4224850B2 (en) | Method for producing photocatalytic anatase-type titanium dioxide thin film | |
| EP0967008B1 (en) | Process for preparing a film of titanium dioxide and silicon dioxide | |
| Chen et al. | Investigation into the effects of deposition parameters on TiO2 photocatalyst thin films by rf magnetron sputtering | |
| Kim et al. | Structural analysis on photocatalytic efficiency of TiO2 by chemical vapor deposition | |
| Lin et al. | Fabricating TiO 2 photocatalysts by rf reactive magnetron sputtering at varied oxygen partial pressures | |
| WO2011118700A1 (en) | Process for production of optical vanadium dioxide thin film | |
| JP2003093896A (en) | Method for forming photocatalyst titanium oxide film | |
| JP4883512B2 (en) | Fabrication method of visible light responsive titanium oxide thin film | |
| JP3550658B2 (en) | Method for producing titanium dioxide-based thin film with controlled crystal structure | |
| JP4590580B2 (en) | Titanium oxide mixed type highly active photocatalytic thin film and method for producing the same | |
| JP4963223B2 (en) | Method for producing metal oxide thin film with controlled surface microstructure and metal oxide thin film | |
| JP4565170B2 (en) | Method for producing anatase TiO2 single crystal thin film | |
| Ding et al. | A simple route to synthesize nanocrystalline TiO2 films at room temperature | |
| JP2007075696A (en) | Porous photocatalyst film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050811 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20060223 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080227 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080731 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080827 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081016 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20081114 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111205 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121205 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131205 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |