JPH0517132A - Production of fine plate particle of alumina - Google Patents
Production of fine plate particle of aluminaInfo
- Publication number
- JPH0517132A JPH0517132A JP3193668A JP19366891A JPH0517132A JP H0517132 A JPH0517132 A JP H0517132A JP 3193668 A JP3193668 A JP 3193668A JP 19366891 A JP19366891 A JP 19366891A JP H0517132 A JPH0517132 A JP H0517132A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- particles
- particle size
- aluminum hydroxide
- hydrothermal treatment
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗料用顔料やセラミッ
クス原料等に適した微細板状粒子を水熱処理により効率
的に製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing fine plate-like particles suitable for paint pigments, ceramic raw materials, etc. by hydrothermal treatment.
【０００２】[0002]
【従来の技術】従来より微細アルミナ粒子の製造方法と
してはいろいろな方法が知られている。一般的にはボー
ルミル等の機械的な手段を用い粉砕することによりサブ
ミクロンオーダーの微細アルミナ粒子を製造している
が、この場合、微細な粒子は得られるが、板状の微細な
粒子を得ることはできない。又、アルミナ粒子の工業的
な製造方法としては、バイヤー法によるものが知られて
いるが、この方法を用いた場合、高純度のアルミナ粒子
が得にくいとともに粒子の形状が粒状になりやすいとい
う問題がある。2. Description of the Related Art Conventionally, various methods have been known as a method for producing fine alumina particles. Generally, fine alumina particles of submicron order are manufactured by crushing using a mechanical means such as a ball mill. In this case, fine particles can be obtained, but plate-like fine particles are obtained. It is not possible. Further, as an industrial production method of alumina particles, a method by the Bayer method is known, but when this method is used, it is difficult to obtain high-purity alumina particles and the shape of the particles tends to be granular. There is.
【０００３】板状アルミナ粒子の製造方法としては、例
えば特公昭３５−６９７７号公報に見られるように、仮
焼工程で弗化アルミニウム等の鉱化剤を添加する方法が
知られている。又、水熱合成法によるアルミナ粒子の製
造方法としては、例えば特公昭３７−７７５０号公報及
び特公昭３９−１３４６５号公報に記載のものが知られ
ている。As a method for producing plate-like alumina particles, for example, a method of adding a mineralizing agent such as aluminum fluoride in a calcination step is known as disclosed in Japanese Patent Publication No. 35-6977. Further, as a method for producing alumina particles by the hydrothermal synthesis method, for example, those described in JP-B-37-7750 and JP-B-39-13465 are known.
【０００４】[0004]
【発明が解決しようとする課題】上記板状アルミナ粒子
の製造方法のうち、鉱化剤を添加する方法は粒子の微細
化および装置の寿命等の点で問題がある。又、水熱合成
法の場合は、それらの公報中の記載から分かるように、
粒子の大きさは数ミクロンから数百ミクロン程度であ
り、粒子の微細化の点で問題を有する。そこで、本発明
は、サブミクロンオーダーの微細な板状アルミナ粒子を
効率的に製造できる製造方法を提供することを目的とす
る。Among the above-mentioned methods for producing plate-like alumina particles, the method of adding a mineralizer has problems in terms of grain refinement and device life. In the case of the hydrothermal synthesis method, as can be seen from the description in those publications,
The size of the particles is on the order of a few microns to a few hundreds of microns, and there is a problem in terms of grain refinement. Therefore, an object of the present invention is to provide a manufacturing method capable of efficiently manufacturing fine plate-like alumina particles of submicron order.
【０００５】[0005]
【課題を解決するための手段】本発明は、サブミクロン
オーダーに粒度調整した水酸化アルミニウム又はアルミ
ナ水和物を水又はアルカリ水溶液中で温度３５０℃以
上、圧力２００気圧以下に水熱処理することを特徴とす
る微細板状アルミナ粒子の製造方法である。According to the present invention, hydrothermal treatment of aluminum hydroxide or alumina hydrate whose particle size is adjusted to the submicron order is performed in water or an alkaline aqueous solution at a temperature of 350 ° C. or more and a pressure of 200 atm or less. It is a characteristic method for producing fine plate-like alumina particles.
【０００６】本発明は、出発原料として水酸化アルミニ
ウム又はベーマイト等のアルミナ水和物をあらかじめボ
ールミル等で粉砕してサブミクロンオーダーに粒度調整
したものを用い、これを水又は苛性ソーダ、炭酸ソーダ
等のアルカリ水溶液とともに密閉オートクレーブ中に充
填し、高温、高圧にて水熱処理することにより行われ
る。出発原料である水酸化アルミニウム又はアルミナ水
和物をサブミクロンオーダーに粒度調整することは、最
終アルミナ粒子の寸法をサブミクロンオーダーに揃える
ために必要である。温度、圧力の条件に関しては、Ａｌ
2Ｏ3−Ｈ2Ｏ系状態図で、α−アルミナの安定な領域で
なければならない。温度を３５０℃以上と限定する理由
は、３５０℃未満ではα−アルミナを得ることができな
いためである。特に上限については限定していないが、
装置に係るもので、経済性を考慮した範囲内が好まし
く、高温ほどα−アルミナの生成速度は大きく、短時間
で微細な粒子が得られ、低温ほどα−アルミナの生成速
度は小さく、長時間の処理を必要とするため粗大な粒子
となる。なおいずれにおいても粒子形状は板状である。
又、圧力を２００気圧以下と限定する理由は２００気圧
を越える圧力では、得られる粒子の形状が肉厚の大きな
粗大なものとなるためである。又、下限については、当
然開放系では水熱系が成り立たないので、好ましくは５
０気圧以上がよい。The present invention uses, as a starting material, alumina hydrate such as aluminum hydroxide or boehmite, which has been crushed in advance with a ball mill or the like to have a particle size adjusted to the submicron order. It is carried out by filling a closed autoclave with an alkaline aqueous solution and subjecting it to hydrothermal treatment at high temperature and high pressure. It is necessary to adjust the particle size of the starting material, aluminum hydroxide or hydrated alumina, to the submicron order in order to make the dimensions of the final alumina particles to the submicron order. Regarding temperature and pressure conditions, Al
In the 2 O 3 -H 2 O phase diagram, it must be in the stable region of α-alumina. The reason for limiting the temperature to 350 ° C. or higher is that α-alumina cannot be obtained below 350 ° C. The upper limit is not particularly limited,
It is related to the apparatus, preferably within a range considering economic efficiency, the higher the temperature, the higher the production rate of α-alumina, and the finer particles can be obtained in a shorter time. As a result, it becomes coarse particles. In each case, the particle shape is plate-like.
The reason why the pressure is limited to 200 atm or less is that when the pressure exceeds 200 atm, the shape of the obtained particles becomes large and coarse. As for the lower limit, a hydrothermal system does not hold in an open system, so it is preferably 5
0 atm or higher is recommended.
【０００７】本発明の製造方法により、結晶形が六方晶
形で特定の結晶面が平板状に成長した微細なα−アルミ
ナ粒子を得ることができる。さらに、この粒子は対角長
１μｍ未満、厚さ０．１μｍ未満のものとすることがで
きる。かかるα−アルミナ粒子は塗料用顔料、セラミッ
クスの成形分野において、可塑性を有するアルミナ原料
等として使用できる。By the production method of the present invention, fine α-alumina particles having a hexagonal crystal form and a specific crystal plane grown in a flat plate form can be obtained. Further, the particles can have a diagonal length of less than 1 μm and a thickness of less than 0.1 μm. Such α-alumina particles can be used as a raw material for alumina having plasticity in the field of molding pigments for coatings and ceramics.
【０００８】[0008]
【実施例】以下、実施例に基づいて本発明を具体的に説
明する。バイヤー法によって得た水酸化アルミニウムを
ボールミルにて中心径０．７μｍに粒度調整したもの１
０ｇに、所定量の純水を加えてスラリーを作成し、これ
を小型オートクレーブに充填し、各加熱温度、圧力２０
０ｋｇ／ｃｍ2にて水熱処理を行った。処理後の生成物
を水洗、濾過、乾燥してアルミナ粉末を得、これを試料
として平均粒子径と水熱処理温度との関係を調べた。な
お、上記において純水の量を所定量としたのは、温度お
よび圧力の条件によってその量が異なるためである。EXAMPLES The present invention will be specifically described below based on examples. Aluminum hydroxide obtained by the Bayer method, the particle size of which was adjusted to a central diameter of 0.7 μm by a ball mill 1
A predetermined amount of pure water was added to 0 g to prepare a slurry, which was filled in a small autoclave and heated at each heating temperature and pressure of 20.
Hydrothermal treatment was performed at 0 kg / cm 2 . The product after the treatment was washed with water, filtered and dried to obtain an alumina powder, and the alumina powder was used as a sample to examine the relationship between the average particle size and the hydrothermal treatment temperature. In addition, the amount of pure water is set to a predetermined amount in the above description because the amount is different depending on the conditions of temperature and pressure.
【０００９】平均粒子径は、粒度分布測定および走査型
電子顕微鏡観察することにより測定した。その測定結果
を図１に示す。The average particle size was measured by measuring the particle size distribution and observing with a scanning electron microscope. The measurement result is shown in FIG.
【００１０】図１から、水熱処理（水熱合成法）で生成
されるα−Ａｌ2Ｏ3粒子の生成温度に対する平均粒子径
の傾向は高温度側ほど小さく、低温度側ほど大きくなる
傾向を示すことが分かる。粒子の厚みについても平均粒
子径と同様であった。From FIG. 1, the tendency of the average particle diameter with respect to the production temperature of α-Al 2 O 3 particles produced by hydrothermal treatment (hydrothermal synthesis method) tends to be smaller on the higher temperature side and larger on the lower temperature side. You can see that. The particle thickness was the same as the average particle diameter.
【００１１】又、バイヤー法によって得た水酸化アルミ
ニウムをボールミルにて中心径０．７μｍに粒度調整し
たもの１０ｇに、所定量の純水を加えてスラリーを作成
し、これを小型オートクレーブに充填し、加熱温度５０
０℃、容器内の圧力が常圧から約６００ｋｇ／ｃｍ2ま
で変化させ、水熱処理を行った。処理後の生成物を水
洗、濾過、乾燥してアルミナ粉末を得、これを試料とし
て平均粒子径と水熱処理圧力との関係を調べた。結果を
図２に示す。Further, a predetermined amount of pure water was added to 10 g of aluminum hydroxide obtained by the Bayer method, the particle size of which was adjusted to a center diameter of 0.7 μm by a ball mill to prepare a slurry, which was filled in a small autoclave. , Heating temperature 50
Hydrothermal treatment was carried out at 0 ° C. and the pressure inside the container was changed from normal pressure to about 600 kg / cm 2 . The treated product was washed with water, filtered and dried to obtain an alumina powder, and the alumina powder was used as a sample to investigate the relationship between the average particle size and the hydrothermal treatment pressure. The results are shown in Figure 2.
【００１２】図２から、水熱処理（水熱合成法）で生成
されるα−Ａｌ2Ｏ3粒子の生成圧力に対する平均粒子径
の傾向は、圧力が低いほど微細な粒子になり、逆に圧力
が高いほど粗大な粒子になる傾向を示すことが分かる。
粒子の厚みについても平均粒子径と同様であった。From FIG. 2, the tendency of the average particle size with respect to the production pressure of α-Al 2 O 3 particles produced by hydrothermal treatment (hydrothermal synthesis method) is such that the lower the pressure, the finer the particles become, and conversely It can be seen that the higher the value is, the larger the particles tend to be.
The particle thickness was the same as the average particle diameter.
【００１３】以上のことから、温度３５０℃以上、圧力
２００気圧以下の条件で水熱処理することにより、微細
な板状アルミナ（α−Ａｌ2Ｏ3）粒子を得ることができ
ることが分かる。From the above, it is understood that fine plate-like alumina (α-Al 2 O 3 ) particles can be obtained by hydrothermal treatment under the conditions of a temperature of 350 ° C. or higher and a pressure of 200 atm or lower.
【００１４】さらに、バイヤー法による水酸化アルミニ
ウムをボールミルにて中心径０．７μｍに粒度調整を行
ったものを１０ｇ所定量のアルカリ水溶液でスラリーを
作成し、これを小型オートクレーブに充填し、温度６０
０℃、圧力２００気圧にて２時間水熱処理を行った。処
理後の生成物を水洗、濾過、乾燥してアルミナ粉末を得
た。このアルミナ粉末の電子顕微鏡写真を図３に示す。
図３から、本発明に係るアルミナ粉末は、粒径の揃った
大きさが約１．０μｍ弱、厚さが約０．１μｍであるこ
とが分かるとともに、結晶形が六方晶形で特定の結晶面
が平板状に成長した微細な板状アルミナ（α−Ａｌ
2Ｏ3）粒子であることが分かる。Further, aluminum hydroxide prepared by the Bayer method was subjected to particle size adjustment with a ball mill to a central diameter of 0.7 μm to prepare a slurry with 10 g of a predetermined amount of an alkaline aqueous solution, which was filled in a small autoclave and the temperature was adjusted to 60.
Hydrothermal treatment was performed at 0 ° C. and a pressure of 200 atm for 2 hours. The treated product was washed with water, filtered and dried to obtain an alumina powder. An electron micrograph of this alumina powder is shown in FIG.
It can be seen from FIG. 3 that the alumina powder according to the present invention has a uniform particle size of about 1.0 μm and a thickness of about 0.1 μm, and the hexagonal crystal form has a specific crystal plane. Of fine plate-like alumina (α-Al
It can be seen that the particles are 2 O 3 ) particles.
【００１５】[0015]
【発明の効果】以上説明したように、本発明によれば、
粒径のそろったサブミクロンオーダーの微細な板状アル
ミナ粒子を得ることができるとともに、この粒子は塗料
用の顔料、セラミックスの成形分野において、可塑性を
有するアルミナ原料などとして利用でき、産業上の種々
の用途に優れた効果を発揮する。As described above, according to the present invention,
It is possible to obtain fine plate-like alumina particles with a uniform particle size on the order of submicrons, and these particles can be used as a raw material for alumina having plasticity in the field of molding pigments for coating materials and ceramics, and are used in various industrial fields. Exhibits an excellent effect for.
【図１】水熱処理温度と得られるアルミナの平均粒子径
との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the hydrothermal treatment temperature and the average particle diameter of alumina obtained.
【図２】水熱処理圧力と得られるアルミナの平均粒子径
との関係を示すグラフである。FIG. 2 is a graph showing the relationship between the hydrothermal treatment pressure and the average particle size of the obtained alumina.
【図３】本発明の実施例で得られたアルミナの粒子構造
を示す電子顕微鏡写真である。FIG. 3 is an electron micrograph showing a particle structure of alumina obtained in an example of the present invention.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年７月１日[Submission date] July 1, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図１[Name of item to be corrected] Figure 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図１】 [Figure 1]
フロントページの続き (72)発明者 小田 喜一 愛知県名古屋市名東区平和が丘１−70 (72)発明者 福田 雄史 富山県黒部市中新403−３Front Page Continuation (72) Inventor Kiichi Oda 1-70, Heiwagaoka, Meito-ku, Nagoya, Aichi Prefecture (72) Inventor Yushi Fukuda 403-3 Chushin, Kurobe, Toyama Prefecture
Claims (1)
酸化アルミニウム又はアルミナ水和物を水又はアルカリ
水溶液中で温度３５０℃以上、圧力２００気圧以下に水
熱処理することを特徴とする微細板状アルミナ粒子の製
造方法。Claims: 1. A method of hydrothermally treating aluminum hydroxide or alumina hydrate having a particle size adjusted to a submicron order in water or an alkaline aqueous solution at a temperature of 350 ° C or higher and a pressure of 200 atm or lower. Method for producing fine plate-like alumina particles.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3193668A JP2654276B2 (en) | 1991-07-09 | 1991-07-09 | Method for producing fine plate-like alumina particles |
| EP92111532A EP0522519B1 (en) | 1991-07-09 | 1992-07-08 | Process for producing fine flaky alumina particles and alumina-based plastic material |
| DE199292111532T DE522519T1 (en) | 1991-07-09 | 1992-07-08 | METHOD FOR THE PRODUCTION OF FINE PLATE-SHAPED PARTICLES AND PLASTICS BASED ON ALUMINUM OXIDE. |
| DE69208753T DE69208753T2 (en) | 1991-07-09 | 1992-07-08 | Process for the production of fine platelet-shaped particles as well as plastic materials based on aluminum oxide |
| CA002073471A CA2073471C (en) | 1991-07-09 | 1992-07-08 | Process for producing fine flaky alumina particles and alumina-based plastic material |
| US08/301,734 US6080380A (en) | 1991-07-09 | 1994-09-07 | Process for producing fine flaky alumina particles and alumina-based plastic material |
| US08/491,114 US5587010A (en) | 1991-07-09 | 1995-06-16 | Process for producing fine flaky alumina particles and alumina-based plastic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3193668A JP2654276B2 (en) | 1991-07-09 | 1991-07-09 | Method for producing fine plate-like alumina particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0517132A true JPH0517132A (en) | 1993-01-26 |
| JP2654276B2 JP2654276B2 (en) | 1997-09-17 |
Family
ID=16311795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3193668A Expired - Fee Related JP2654276B2 (en) | 1991-07-09 | 1991-07-09 | Method for producing fine plate-like alumina particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2654276B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0761600A1 (en) * | 1995-08-24 | 1997-03-12 | Ykk Corporation | Alumina particles having high dispersibility and plasticity and process for producing the same |
| JP2004155630A (en) * | 2002-11-08 | 2004-06-03 | Showa Denko Kk | Alumina particle and method of manufacturing the same |
| KR100679611B1 (en) * | 2005-07-20 | 2007-02-08 | 주식회사 코델 | Preparing Method for Platey ?- Alumina |
| JP2007532461A (en) * | 2004-04-15 | 2007-11-15 | アルベマール・コーポレーシヨン | Flame retardant filler for plastics |
| JP2010502539A (en) * | 2006-08-28 | 2010-01-28 | コリア リサーチ インスティテュート オブ ケミカル テクノロジー | Flaky alpha-alumina crystal having a large aspect ratio and method for producing the same |
| US8343415B2 (en) | 2007-01-15 | 2013-01-01 | Saint-Gobain Ceramics & Plastics, Inc. | Ceramic particulate material and processes for forming same |
-
1991
- 1991-07-09 JP JP3193668A patent/JP2654276B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0761600A1 (en) * | 1995-08-24 | 1997-03-12 | Ykk Corporation | Alumina particles having high dispersibility and plasticity and process for producing the same |
| JP2004155630A (en) * | 2002-11-08 | 2004-06-03 | Showa Denko Kk | Alumina particle and method of manufacturing the same |
| JP2007532461A (en) * | 2004-04-15 | 2007-11-15 | アルベマール・コーポレーシヨン | Flame retardant filler for plastics |
| KR100679611B1 (en) * | 2005-07-20 | 2007-02-08 | 주식회사 코델 | Preparing Method for Platey ?- Alumina |
| JP2010502539A (en) * | 2006-08-28 | 2010-01-28 | コリア リサーチ インスティテュート オブ ケミカル テクノロジー | Flaky alpha-alumina crystal having a large aspect ratio and method for producing the same |
| US8343415B2 (en) | 2007-01-15 | 2013-01-01 | Saint-Gobain Ceramics & Plastics, Inc. | Ceramic particulate material and processes for forming same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2654276B2 (en) | 1997-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5306680A (en) | Fine flaky boehmite particles and process for the preparation of the same | |
| RU2136596C1 (en) | Method of preparing alpha-aluminum powder and alpha-aluminum powder | |
| EP0505896B1 (en) | Process for the production of a colloidal boehmite | |
| US4657754A (en) | Aluminum oxide powders and process | |
| KR100292424B1 (en) | Method of Making Alpha-Alumina | |
| Her et al. | Preparation of well-defined colloidal barium titanate crystals by the controlled double-jet precipitation | |
| US5800922A (en) | Method of making a gelation-resistant alumina | |
| JP2001180930A (en) | Laminar boehmite particle and its manufacturing method | |
| US5445807A (en) | Production of aluminum compound | |
| JP4281943B2 (en) | Method for producing plate-like alumina particles | |
| CN108530057B (en) | Preparation of morphology-controllable CaTiO applied to energy storage by sol-gel method3Method for producing ceramic | |
| JPH07206432A (en) | Alpha-alumina powder and its production | |
| CZ345192A3 (en) | Process for producing aluminium alpha-oxide powder | |
| EP3599221A1 (en) | Alpha alumina with high purity and high relative density, a method for its production and its use | |
| JPH0517132A (en) | Production of fine plate particle of alumina | |
| JP2869287B2 (en) | Method for producing plate-like boehmite particles | |
| US5587010A (en) | Process for producing fine flaky alumina particles and alumina-based plastic material | |
| CA2073471C (en) | Process for producing fine flaky alumina particles and alumina-based plastic material | |
| JP2005170700A (en) | Zirconium oxide particle and method for producing the same | |
| JPH06316413A (en) | Production of lamellar alumina particle | |
| JP3087403B2 (en) | Method for producing spherical alumina | |
| EP0536381A4 (en) | ||
| VASYLKIV et al. | Synthesis and sintering of zirconia nano-powder by non-isothermal decomposition from hydroxide | |
| JP3030356B2 (en) | Twinned alumina particles and method for producing the same | |
| JPH06144830A (en) | Production of extremely easily sinterable alumina |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080523 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080523 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080523 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090523 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090523 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090523 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090523 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090523 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090523 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100523 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100523 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100523 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110523 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110523 Year of fee payment: 14 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R314531 |
|
| S804 | Written request for registration of cancellation of exclusive licence |
Free format text: JAPANESE INTERMEDIATE CODE: R314805 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110523 Year of fee payment: 14 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |