JP3636231B2 - Method for purifying aqueous hydrogen peroxide - Google Patents
Method for purifying aqueous hydrogen peroxide Download PDFInfo
- Publication number
- JP3636231B2 JP3636231B2 JP23842995A JP23842995A JP3636231B2 JP 3636231 B2 JP3636231 B2 JP 3636231B2 JP 23842995 A JP23842995 A JP 23842995A JP 23842995 A JP23842995 A JP 23842995A JP 3636231 B2 JP3636231 B2 JP 3636231B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- purification
- resin
- column
- impurities
- 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.)
- Expired - Lifetime
Links
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は過酸化水素水または過酸化水素を含有する水溶液中の不純物を除去する精製方法に関する。本発明により高純度に精製された過酸化水素水または過酸化水素を含有する水溶液は、特にシリコンウエハ等の半導体基板の洗浄に好適に用いられる。
【０００２】
【従来の技術】
シリコンウエハの洗浄には塩基性もしくは酸性の過酸化水素水溶液が広く使用され、集積回路の高密度化に伴い洗浄液の高純度化が強く要求されている。そのため、この用途で用いられる過酸化水素水も極めて高純度のものが要求され、現在では過酸化水素水中の有機不純物は１０ｐｐｍ以下、金属不純物は１ｐｐｂ以下が要求されている。
通常、過酸化水素水溶液中の不純物の除去法としては、一般的にイオン交換樹脂、キレート樹脂、吸着樹脂等による処理が知られており、これらの樹脂等を用いて不純物の除去処理を工業的に実施する場合には、操作性に優れた除去効率の高い流通法（カラム法）が一般的に使用されている。
【０００３】
【発明が解決しようとする問題点】
過酸化水素または過酸化水素を含む水溶液を種々の充填物を用いたカラム法で精製する場合には、過酸化水素の特有の性質として自己分解により泡が発生し、この泡が樹脂の周りに付着するため精製効率即ち不純物の除去効率を低下させるという問題点が生じる。
【０００４】
【問題を解決するための手段】
本発明者らは上記の問題を解決すべく鋭意検討した結果、過酸化水素の分解によって生じた泡の溶解度を高めながら精製することが有効で、特に精製塔の上部に圧力を加えることが極めて有効であることを見いだし本発明を完成するに至った。即ち精製塔の上部に圧力を加えることによって、過酸化水素の分解によって生じる泡の溶解度を上げることができ、泡の量を減少させることができる。また、泡の大きさを小さく抑えることができ、精製塔からの泡の排除も効率的に行うことができるため、精製に用いた樹脂と過酸化水素水溶液との接触面積が圧力を加えない場合よりも増加し不純物の除去を効率的に行うことが可能となる。ここで精製塔上部とは下降流の場合は入口側、上昇流の場合は出口側を示す。
精製塔の上部に加える圧力は分解による泡の溶解度を高め、且つ泡の大きさを抑えることができれば特に制限はないが、好ましくは０．５Ｋｇ／ｃｍ2 以上が好ましい。
【０００５】
本発明の精製法において、操作温度に制限は特にないが、好ましくは−３０〜４０℃、より好ましくは−２５〜２５℃、更に好ましくは−５〜１５℃で行うのが良い。低温で操作することにより、泡の溶解度も更に高まりより安定した運転が可能となり、より効率的に不純物の除去が可能となる。また、充填物の劣化を抑制し、充填物の活性をより長い時間維持することもできる。
精製に用いる充填物は過酸化水素水中の不純物を除去できるものであれば特に制限はないが、一般的にはイオン交換樹脂、キレート樹脂、吸着樹脂が好的に使用される。また、これらの樹脂を組み合わせて使用することも可能であり、組み合わせる数（精製塔の数）および組み合わせる順序に関しても特に制限はない。
【０００６】
イオン交換樹脂としてはカチオン交換樹脂とアニオン交換樹脂があり、カチオン交換樹脂としてはイオン交換基としてＳＯ3 Ｈ基を有するものが好ましい。このカチオン交換樹脂は一般的にはスチレンージビニルベンゼン架橋共重合体を硫酸でスルホン化することによって得られるものであり、カチオン交換樹脂として強酸性であることが好ましい。一方、アニオン交換樹脂としては第４級アンモニウム基を有する強塩基性樹脂、第３級アンモニウム基を有する弱塩基性樹脂またはビニルピリジン系樹脂であるが、好ましくは第４級アンモニウム基を有する強塩基性樹脂であり、特に好ましいのは、第４級アンモニウム基の炭酸塩または重炭酸塩を有する樹脂である。また、強塩基性であることがより好ましい。
キレート樹脂としてはイミノジ酢酸型、ポリアミン型、ホスホン酸型、Ｎ−メチルグルカミン型など、金属イオンに対してキレート力を持つ樹脂であればいずれも使用できる。特に好ましいのはホスホン酸型キレート樹脂とＮ−メチルグルカミン型のキレート樹脂で、さらに好ましい樹脂はイミノホスホン酸型キレート樹脂もしくはイミノジホスホン酸型キレート樹脂である。
【０００７】
吸着樹脂としてはマクロポアーを有する不溶性の三次元架橋構造ポリマーであって、イオン交換基のような官能基は持たず、大きな比表面積を有し、ｖａｎｄｅｒ ｗａａｌｓ力によりいろいろの有機物を吸着する無極性の多孔質吸着樹脂またはハロゲン化変性多孔質吸着樹脂が好ましい。無極性の多孔質吸着樹脂としてはスチレン−ジビニル系共重合体や、アクリル酸エステル、メタクリル酸エステルまたはビニルピリジンなどの重合体が使用される。またハロゲン化変性多孔質吸着樹脂として好ましいものとしては、特にブロム化スチレン−ジビニルベンゼン共重合体を挙げることができる。
精製原料となる過酸化水素または過酸化水素を含む水溶液中の過酸化水素の濃度に関しては特に限定されるものではないが、好ましくは９０重量％以下、より好ましくは７０重量％以下である。
以下に本発明の実施例を示す。
【０００８】
【実施例】
実施例１
不純物として総リン酸根１０ｐｐｍを含む３１重量％の過酸化水素水原液をアニオン交換樹脂アンバーライトＩＲＡ−４００（重炭酸塩型、オルガノ（株）製）２０ｍｌを充填した内径１５ｍｍ、長さ３０ｃｍのテフロン製カラムに５℃の温度で下降流で通液した。このときカラム下部に絞りを付け、カラム上部に１Ｋｇ／ｃｍ2 の圧力を加えるように通液を行った。通液中、安定した通液を行うことができ、精製後の過酸化水素水中の総リン酸根は０．１ｐｐｍ以下であった。
【０００９】
比較例１
不純物として総リン酸根１０ｐｐｍを含む３１重量％の過酸化水素水原液をアニオン交換樹脂アンバーライトＩＲＡ−４００（重炭酸塩型、オルガノ（株）製）２０ｍｌを充填した内径１５ｍｍ、長さ３０ｃｍのテフロン製カラムに５℃の温度で下降流で通液した。このときカラム下部に特に絞りは付けず、カラム上部に圧力は加えず（０．３Ｋｇ／ｃｍ2 以下）に通液を行った。通液中、発生した泡が樹脂やカラム内壁に付着して精製塔内に残留し、安定した通液処理ができなかった。精製後の過酸化水素水中の総リン酸根は２ｐｐｍであった。
【００１０】
実施例２
不純物として鉄５ｐｐｂを含む６０重量％の過酸化水素水原液をキレート樹脂ダイヤイオンＣＲＡ−１００（イミノメチレンホスホン酸型、三菱化学（株）製）２０ｍｌを充填した内径１５ｍｍ、長さ３０ｃｍのテフロン製カラムに５℃の温度で下降流で通液した。このときカラム下部に絞りを付け、カラム上部に１Ｋｇ／ｃｍ2 の圧力を加えるように通液を行った。通液中、安定した通液を行うことができ、精製後の過酸化水素水中の鉄は０．１ｐｐｂ以下であった。
【００１１】
比較例２
不純物として鉄５ｐｐｂを含む６０重量％の過酸化水素水原液をキレート樹脂ダイヤイオンＣＲＡ−１００（イミノメチレンホスホン酸型、三菱化学（株）製）２０ｍｌを充填した内径１５ｍｍ、長さ３０ｃｍのテフロン製カラムに５℃の温度で下降流で通液した。このときカラム下部に特に絞りは付けず、カラム上部に圧力は加えず（０．３Ｋｇ／ｃｍ2 以下）に通液を行った。通液中、発生した泡が樹脂やカラム内壁に付着して精製塔内に残留し、安定した通液処理ができなかった。精製後の過酸化水素水中の鉄は１．５ｐｐｂであった。
【００１２】
実施例３
不純物として全有機炭素４０ｐｐｍを含む３１重量％の過酸化水素水原液を吸着樹脂セパビーズＳＰ２０７（臭素化変性スチレン−ジビニルベンゼン架橋共重合体、比重１．２、三菱化学（株）製）２０ｍｌを充填した内径１５ｍｍ、長さ３０ｃｍのテフロン製カラムに１０℃の温度で下降流で通液した。このときカラム下部に絞りを付け、カラム上部に１．５Ｋｇ／ｃｍ2 の圧力を加えるように通液を行った。通液中、短絡路の発生は全く認められず安定した通液を行うことができ、精製後の過酸化水素水中の全有機炭素量は５ｐｐｍであった。
【００１３】
比較例３
不純物として全有機炭素４０ｐｐｍを含む３１重量％の過酸化水素水原液を吸着樹脂セパビーズＳＰ２０７（臭素化変性スチレンージビニルベンゼン架橋共重合体、比重１．２、三菱化学（株）製）２０ｍｌを充填した内径１５ｍｍ、長さ３０ｃｍのテフロン製カラムに１０℃の温度で下降流で通液した。このときカラム下部に特に絞りは付けず、カラム上部に圧力は加えず（０．３Ｋｇ／ｃｍ2 以下）に通液を行った。通液中、発生した泡が精製塔内に残留して短絡路が発生し安定した通液処理ができなかった。精製後の過酸化水素水中の全有機炭素量は２０ｐｐｍであった。
【００１４】
【発明の効果】
本発明によれば、精製中に発生する過酸化水素の分解による泡の溶解度を高め、且つ泡の大きさを小さく抑えることができ、精製塔からの泡の排除も効率的に行えるため、安定した通液が可能となり、効率よくより高純度に精製された過酸化水素水を得ることができる。[0001]
[Industrial application fields]
The present invention relates to a purification method for removing impurities in a hydrogen peroxide solution or an aqueous solution containing hydrogen peroxide. The hydrogen peroxide solution purified to a high purity according to the present invention or the aqueous solution containing hydrogen peroxide is particularly suitably used for cleaning a semiconductor substrate such as a silicon wafer.
[0002]
[Prior art]
A basic or acidic aqueous hydrogen peroxide solution is widely used for cleaning silicon wafers, and a high purity of the cleaning liquid is strongly demanded as the density of integrated circuits increases. Therefore, the hydrogen peroxide solution used in this application is also required to have a very high purity. At present, the organic impurities in the hydrogen peroxide solution are required to be 10 ppm or less, and the metal impurities are required to be 1 ppb or less.
Usually, as a method for removing impurities in an aqueous hydrogen peroxide solution, treatment with ion exchange resin, chelate resin, adsorption resin, etc. is generally known, and impurities removal treatment using these resins etc. is industrial. In general, a flow method (column method) having excellent operability and high removal efficiency is generally used.
[0003]
[Problems to be solved by the invention]
When purifying hydrogen peroxide or an aqueous solution containing hydrogen peroxide by a column method using various packing materials, bubbles are generated by autolysis as a characteristic property of hydrogen peroxide, and these bubbles are generated around the resin. Since it adheres, there arises a problem that the purification efficiency, that is, the impurity removal efficiency is lowered.
[0004]
[Means for solving problems]
As a result of intensive studies to solve the above problems, the inventors of the present invention are effective in refining while increasing the solubility of bubbles generated by the decomposition of hydrogen peroxide. In particular, it is extremely important to apply pressure to the upper part of the purification tower. The inventors have found that the present invention is effective and have completed the present invention. That is, by applying pressure to the upper part of the purification tower, the solubility of bubbles generated by the decomposition of hydrogen peroxide can be increased, and the amount of bubbles can be reduced. In addition, since the size of the foam can be kept small and the foam can be efficiently removed from the purification tower, the contact area between the resin used for purification and the aqueous hydrogen peroxide solution does not apply pressure. Thus, the impurities can be efficiently removed. Here, the upper part of the purification tower indicates an inlet side in the case of a downward flow and an outlet side in the case of an upward flow.
The pressure applied to the upper part of the purification tower is not particularly limited as long as the solubility of bubbles by decomposition can be increased and the size of the bubbles can be suppressed, but preferably 0.5 Kg / cm 2 or more.
[0005]
In the purification method of the present invention, the operation temperature is not particularly limited, but is preferably −30 to 40 ° C., more preferably −25 to 25 ° C., and further preferably −5 to 15 ° C. By operating at a low temperature, the solubility of bubbles is further increased, and a more stable operation is possible, and impurities can be more efficiently removed. Further, the deterioration of the filler can be suppressed, and the activity of the filler can be maintained for a longer time.
The packing used for purification is not particularly limited as long as impurities in hydrogen peroxide water can be removed, but generally ion exchange resins, chelate resins, and adsorption resins are preferably used. In addition, these resins can be used in combination, and there is no particular limitation on the number of combinations (the number of purification columns) and the order of combination.
[0006]
Examples of the ion exchange resin include a cation exchange resin and an anion exchange resin, and the cation exchange resin preferably has an SO 3 H group as an ion exchange group. This cation exchange resin is generally obtained by sulfonating a styrene-divinylbenzene crosslinked copolymer with sulfuric acid, and is preferably strongly acidic as a cation exchange resin. On the other hand, the anion exchange resin is a strong basic resin having a quaternary ammonium group, a weak basic resin having a tertiary ammonium group, or a vinylpyridine resin, preferably a strong base having a quaternary ammonium group. Resin having a quaternary ammonium group carbonate or bicarbonate is particularly preferable. Moreover, it is more preferable that it is strongly basic.
As the chelating resin, any resin such as iminodiacetic acid type, polyamine type, phosphonic acid type, and N-methylglucamine type can be used as long as it has a chelating power for metal ions. Particularly preferred are phosphonic acid type chelating resins and N-methylglucamine type chelating resins, and more preferred are iminophosphonic acid type chelating resins or iminodiphosphonic acid type chelating resins.
[0007]
The adsorbing resin is an insoluble three-dimensional crosslinked structure polymer having macropores, has no functional group such as an ion exchange group, has a large specific surface area, and is a nonpolar that adsorbs various organic substances by the vaner waals force A porous adsorption resin or a halogenated modified porous adsorption resin is preferred. As the nonpolar porous adsorption resin, a styrene-divinyl copolymer, a polymer such as an acrylic ester, a methacrylic ester or vinyl pyridine is used. Moreover, as a preferable thing as halogenated modified porous adsorption resin, a brominated styrene-divinylbenzene copolymer can be mentioned especially.
The concentration of hydrogen peroxide in the raw material to be purified or an aqueous solution containing hydrogen peroxide is not particularly limited, but is preferably 90% by weight or less, more preferably 70% by weight or less.
Examples of the present invention are shown below.
[0008]
【Example】
Example 1
Teflon with an inner diameter of 15 mm and a length of 30 cm filled with 20 ml of an anion exchange resin Amberlite IRA-400 (bicarbonate type, manufactured by Organo Corp.) with 31 wt% hydrogen peroxide stock solution containing 10 ppm of total phosphate radicals as impurities The column was passed down the column at a temperature of 5 ° C. At this time, the bottom of the column was squeezed, and the solution was passed so as to apply a pressure of 1 kg / cm 2 to the top of the column. Stable liquid flow could be performed during liquid flow, and the total phosphate group in the hydrogen peroxide water after purification was 0.1 ppm or less.
[0009]
Comparative Example 1
Teflon with an inner diameter of 15 mm and a length of 30 cm filled with 20 ml of an anion exchange resin Amberlite IRA-400 (bicarbonate type, manufactured by Organo Corp.) with 31 wt% hydrogen peroxide stock solution containing 10 ppm of total phosphate radicals as impurities The column was passed down the column at a temperature of 5 ° C. At this time, liquid passage was performed without applying any restriction to the lower part of the column and applying no pressure to the upper part of the column (0.3 Kg / cm 2 or less). During the liquid flow, the generated bubbles adhered to the resin and the inner wall of the column and remained in the purification tower, and stable liquid flow treatment could not be performed. The total phosphate radical in the hydrogen peroxide water after purification was 2 ppm.
[0010]
Example 2
60% by weight hydrogen peroxide stock solution containing 5 ppb of iron as impurities filled with 20 ml of chelate resin Diaion CRA-100 (iminomethylenephosphonic acid type, manufactured by Mitsubishi Chemical Corporation), made of Teflon with an inner diameter of 15 mm and a length of 30 cm The column was passed in a downward flow at a temperature of 5 ° C. At this time, the bottom of the column was squeezed, and the solution was passed so as to apply a pressure of 1 kg / cm 2 to the top of the column. Stable liquid flow was possible during liquid flow, and iron in the hydrogen peroxide water after purification was 0.1 ppb or less.
[0011]
Comparative Example 2
60% by weight hydrogen peroxide stock solution containing 5 ppb of iron as impurities filled with 20 ml of chelate resin Diaion CRA-100 (iminomethylenephosphonic acid type, manufactured by Mitsubishi Chemical Corporation), made of Teflon with an inner diameter of 15 mm and a length of 30 cm The column was passed in a downward flow at a temperature of 5 ° C. At this time, liquid passage was performed without applying any restriction to the lower part of the column and applying no pressure to the upper part of the column (0.3 Kg / cm 2 or less). During the liquid flow, the generated bubbles adhered to the resin and the inner wall of the column and remained in the purification tower, and stable liquid flow treatment could not be performed. The iron in the hydrogen peroxide solution after purification was 1.5 ppb.
[0012]
Example 3
Filled with 20 ml of adsorption resin Sepa beads SP207 (brominated modified styrene-divinylbenzene cross-linked copolymer, specific gravity 1.2, manufactured by Mitsubishi Chemical Corporation) with 31 wt% hydrogen peroxide stock solution containing 40 ppm total organic carbon as impurities Then, a Teflon column having an inner diameter of 15 mm and a length of 30 cm was passed in a downward flow at a temperature of 10 ° C. At this time, the bottom of the column was squeezed, and the solution was passed so as to apply a pressure of 1.5 kg / cm 2 to the top of the column. During the liquid flow, no short circuit was observed and stable liquid flow was possible. The total amount of organic carbon in the hydrogen peroxide water after purification was 5 ppm.
[0013]
Comparative Example 3
Filled with 20 ml of adsorption resin Sepa beads SP207 (brominated modified styrene-divinylbenzene cross-linked copolymer, specific gravity 1.2, manufactured by Mitsubishi Chemical Corporation) with 31 wt% hydrogen peroxide stock solution containing 40 ppm total organic carbon as impurities Then, a Teflon column having an inner diameter of 15 mm and a length of 30 cm was passed in a downward flow at a temperature of 10 ° C. At this time, liquid passage was performed without applying any restriction to the lower part of the column and applying no pressure to the upper part of the column (0.3 Kg / cm 2 or less). During the flow of liquid, the generated bubbles remained in the purification tower, causing a short circuit, and a stable liquid flow treatment could not be performed. The total amount of organic carbon in the hydrogen peroxide water after purification was 20 ppm.
[0014]
【The invention's effect】
According to the present invention, the solubility of bubbles due to the decomposition of hydrogen peroxide generated during purification can be increased, the size of the bubbles can be kept small, and the bubbles can be efficiently eliminated from the purification tower. Thus, it is possible to obtain a hydrogen peroxide solution that is efficiently purified to a higher purity.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23842995A JP3636231B2 (en) | 1995-09-18 | 1995-09-18 | Method for purifying aqueous hydrogen peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23842995A JP3636231B2 (en) | 1995-09-18 | 1995-09-18 | Method for purifying aqueous hydrogen peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0977504A JPH0977504A (en) | 1997-03-25 |
| JP3636231B2 true JP3636231B2 (en) | 2005-04-06 |
Family
ID=17030082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23842995A Expired - Lifetime JP3636231B2 (en) | 1995-09-18 | 1995-09-18 | Method for purifying aqueous hydrogen peroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3636231B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4030262B2 (en) | 2000-06-21 | 2008-01-09 | 三徳化学工業株式会社 | Method for producing purified hydrogen peroxide water |
-
1995
- 1995-09-18 JP JP23842995A patent/JP3636231B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0977504A (en) | 1997-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5232680A (en) | Method for purifying hydrogen peroxide for microelectronics uses | |
| KR950014206B1 (en) | Method for purifying impure aqueous hydrogen peroxide solution | |
| JP3797390B2 (en) | Method for producing purified hydrogen peroxide | |
| JPH01153509A (en) | Production of high-purity hydrogen peroxide | |
| US6054109A (en) | Method of purifying aqueous solution of hydrogen peroxide | |
| US6187189B1 (en) | Process for the preparation of an ultrapure solution of hydrogen peroxide by ion exchange with recycling | |
| JP7242833B2 (en) | Method for purifying hydrogen peroxide | |
| JP3874036B2 (en) | Method for producing purified aqueous hydrogen peroxide solution | |
| US6939527B2 (en) | Method for the purification of hydrogen peroxide solutions | |
| KR20160054493A (en) | Anion exchanger, mixture of anion exchanger and cation exchanger, mixed bed comprising anion exchanger and cation exchanger, production processes therefor, and method for purifying aqueous hydrogen peroxide solution | |
| JP3636231B2 (en) | Method for purifying aqueous hydrogen peroxide | |
| KR20010013064A (en) | Method for preparing an ultrapure hydrogen peroxide solution by ion exchange in the presence of ion acetate | |
| JP4087052B2 (en) | Regeneration method of ion exchange resin | |
| JP3171058B2 (en) | Hydrogen peroxide water purification method | |
| KR20020028796A (en) | Use of Monodisperse Ion Exchangers for Arsenic/Antimony Removal | |
| US4336140A (en) | Water purification process | |
| US5614165A (en) | Process for purification of hydrogen peroxide | |
| JP4691276B2 (en) | Method and apparatus for recovering high purity boron-containing water | |
| CN113304724A (en) | Preparation method of functional inorganic silica-based adsorption material | |
| JP4013646B2 (en) | Anion exchange resin, method for producing the same, and method for producing purified hydrogen peroxide water using the same | |
| JP4507271B2 (en) | Method for recovering hydrofluoric acid | |
| JPH09278416A (en) | Production of high purity hydrogen peroxide solution | |
| JP3907937B2 (en) | Method for treating boron-containing eluent containing alkali | |
| EP0626342B1 (en) | Process for purification of hydrogen peroxide | |
| JP2800043B2 (en) | Purification of impure aqueous hydrogen peroxide solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040629 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041006 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041117 |
|
| 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: 20041215 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20041228 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080114 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090114 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100114 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100114 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110114 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120114 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120114 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130114 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140114 Year of fee payment: 9 |
|
| EXPY | Cancellation because of completion of term |