WO2001083412A2 - Method for purification of tetrafluoromethane and use thereof - Google Patents
Method for purification of tetrafluoromethane and use thereof Download PDFInfo
- Publication number
- WO2001083412A2 WO2001083412A2 PCT/JP2001/003664 JP0103664W WO0183412A2 WO 2001083412 A2 WO2001083412 A2 WO 2001083412A2 JP 0103664 W JP0103664 W JP 0103664W WO 0183412 A2 WO0183412 A2 WO 0183412A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tetrafluoromethane
- impurities
- compounds
- pore size
- ethylene
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/007—Preparation of halogenated hydrocarbons from carbon or from carbides and halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
Definitions
- the present invention relates a method for the purification of tetrafluoromethane (hereinafter it may be referred to as "FC-14" or “CF 4 ”) and a use of the purified tetrafluoromethane.
- FC-14 tetrafluoromethane
- CF 4 tetrafluoromethane
- FC-14 is used as an etching gas or a cleaning gas in, for example, the manufacturing of semiconductor devices, therefore, a high-purity product thereof is demanded.
- FC-14 For the production of FC-14, various methods have heretofore been proposed. Specifically the following methods, for example, are known: (1) a method of reacting dichlorodifluoromethane with hydrogen fluoride in the presence of a catalyst;
- FC-14 a method of thermally decomposing tetrafluoro- ethylene.
- these methods for producing FC-14 have a problem in that intermediates of FC-14 or by-products produced by the reaction or impurities derived from raw materials form an azeotropic mixture or an azeotrope-like mixture with the objective FC-14 and the separation thereof is extremely difficult.
- a purification method for treating FC-14 containing trifluoromethane (CHF 3 ), as an impurity, with zeolite or a carbonaceous adsorbent has been proposed (see, Japanese Patent No. 2,924,660).
- FC-14 containing ethylene compounds, hydrocarbon compounds, carbon monoxide and/or carbon dioxide, as impurities is purified and thereby high-purity FC-14 almost free of these impurities can be obtained with good profitability.
- the present invention has been made under these circumstances and the object of the present invention is to provide a purification method where FC-14 is contacted with an adsorbent to remove by adsorption those impurities and whereby high-purity FC-14 can be obtained in an industrially advantageous manner with good profitability.
- the present inventors have found that, in a process for producing high-purity FC-14, when FC-14 containing ethylene compounds, hydrocarbon compounds, carbon monoxide and/or carbon dioxide, as impurities, is contacted with an adsorbent comprising zeolite having a specific average pore size and a specific Si/Al ratio and/or a carbonaceous adsorbent (Molecular Sieving Carbon) having a specific average pore size, the impurities can be selectively adsorbed and removed and high-purity FC-14 almost free of impurities can be obtained.
- the present invention has been accomplished based on this finding.
- the present invention provides a method for the purification of tetrafluoromethane and use of the purified tetrafluoromethane, described in (1) to (15) below.
- a method for the purification of tetrafluoromethane comprising contacting tetrafluoromethane containing one or more ethylene compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbon dioxide, as impurities, with zeolite having an average pore size of 3.4 to 11 A and an Si/Al ratio of 1.5 or less and/or a carbonaceous adsorbent having an average pore size of 3.4 to 11 A to reduce the amount of the impurities.
- a cleaning gas comprising the tetrafluoromethane product described in (12) above.
- the present invention provides "a method for the purification of tetrafluoromethane, comprising contacting FC-14 containing one or more ethylene compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbon dioxide, as impurities, with zeolite having an average pore size of 3.4 to 11 A and an Si/Al ratio of 1.5 or less and/or a carbonaceous adsorbent having an average pore size of 3.4 to 11 A to reduce the amount of the impurities", "a tetrafluoromethane product having a purity of 99.9997 mass% or more, which is obtained by performing the purification according to the above-described method” , and "an etching gas and a cleaning gas containing the above-described tetrafluoromethane product".
- FC-14 for example, a method of reacting trifluoromethane with fluorine gas, a method of reacting carbon with fluorine gas and a method of thermally decomposing tetrafluoroethylene are known.
- FC-14 obtained contains one or more ethylene compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbon dioxide, as impurities, due to impurities in the raw materials, for example, organic trace impurities, trace oxygen, trace water content or the like.
- the hydrocarbon compounds contained may be one or more compounds selected from methane (CH 4 ), ethane (C 2 H 6 ) and propane (C 3 H 8 ).
- zeolite having an average pore size of 3.4 to 11 A and an Si/Al ratio of 1.5 or less and/or a carbonaceous adsorbent (Molecular Sieving Carbon) having an average pore size of 3.4 to 11 A is used as the adsorbent.
- a gas adsorption process using Ar gas may be used for measuring the average pore size.
- the adsorbent is ( 1 ) zeolite having an average pore size of 3.4 to 11 A and an Si/Al ratio of 1.5 or less, (2) a carbonaceous adsorbent having an average pore size of 3.4 to 11 A (Molecular Sieving Carbon) or (3) an adsorbent obtained by adding a carbonaceous adsorbent having an average pore size of 3.4 to 11 A to zeolite having an average pore size of 3.4 A to 11 A and an Si/Al ratio of 1.5 or less.
- the Si/Al ratio as used herein is an atomic ratio.
- the impurities in FC-14 may be unsaturated compounds such as ethylene, monofluoroethylene, difluoroethylene and tetrafluoroethylene, hydrocarbon compounds such as methane, ethane and propane, and oxygen-containing compounds such as carbon monoxide and carbon dioxide.
- unsaturated compounds such as ethylene, monofluoroethylene, difluoroethylene and tetrafluoroethylene, hydrocarbon compounds such as methane, ethane and propane, and oxygen-containing compounds such as carbon monoxide and carbon dioxide.
- the impurities preferred are ethylene, tetrafluoroethylene, methane, ethane, carbon monoxide and carbon dioxide, and more preferred are ethylene and ethane.
- FC-14 The difference in the molecular size between the objective FC-14 and these impurities is small, therefore, selective adsorption and removal of the impurities in FC- 14 can hardly be attained only by the difference in the molecular size.
- the following three kinds of adsorbents are used as an adsorbent which can selectively adsorb and remove the impurities .
- the first adsorbent is zeolite having an average pore size of 3.4 to 11 A and an Si/Al ratio of 1.5 or less. Specific examples thereof include MS-4A. MS-4A has an average pore size of about 3.5 A and an Si/Al ratio of 1.0.
- zeolite having an average pore size of less than 3.4 A, for example, a pore size of about 3.2 A is used, a reduction in the impurity content cannot be verified, even where the Si/Al ratio is 1.5 or less.
- the second adsorbent is a carbonaceous adsorbent (Molecular Sieving Carbon) having an average pore size of 3.4 to 11 A.
- a carbonaceous adsorbent having an average pore size of about 4 A like the above- described zeolite, can reduce the impurity content to 5 ppm or less and thereby, high-purity FC-14 can be obtained.
- FC-14 high-purity FC-14
- a carbonaceous adsorbent having an average pore size in excess of 11 A reduction in the impurity content cannot be verified and, for example, in the case of activated carbon having an average pore size of about 35 A, which is commonly used and exhibits strong adsorption activity, almost no reduction of impurities can be verified.
- the third adsorbent is an adsorbent obtained by adding (mixing) a carbonaceous adsorbent (the second adsorbent) having an average pore size of 3.4 to 11 A to zeolite (the first adsorbent) having an average pore size of 3.4 to 11 A and preferably having an Si/Al ratio of 1.5 or less.
- the impurity content can be reduced to even 3 ppm or less and thereby FC-14 having higher purity can be obtained.
- the above-described zeolite and carbonaceous adsorbent can be used alone but two or more kinds of the adsorbents may also be used in combination at a desired proportion.
- the mixing ratio between zeolite and the carbonaceous adsorbent may be varied according to the concentration of impurities .
- the ethylene compounds, hydrocarbon compounds, carbon monoxide and/or carbon dioxide as impurities contained in FC-14 are not particularly limited on the concentration, however, the concentration is preferably 0.1 mass% or less, more preferably 0.05 mass% or less.
- the perfluoroco pounds can be separated and removed by performing a distillation operation either before or after the step of treatment with the above- described adsorbent.
- the method of contacting FC-14 containing impurities with an adsorbent is not limited and, for example, FC-14 containing impurities may be contacted with the adsorbent in a gaseous phase, by gas-liquid contacting or in a liquid phase. Among these, the method of contacting FC-14 containing impurities with the absorbent in a liquid phase is efficient and preferred.
- a known method such as batch system or continuous system may be used, however, industrially, a method of providing, for example, two units of fixed bed-type absorption towers may generally be employed and when one unit reaches its saturated adsorption limit, the other unit is then used and the first unit is subjected to regeneration.
- the treating temperature, the treated amount and the treating pressure are not particularly limited, however, the treating temperature is preferably low and suitably from -50°C to +50°C.
- the treating pressure may suffice if, in the case of a liquid phase, the liquid phase can be maintained and in the case of a gaseous phase, the treating pressure is not particularly limited.
- FC-14 ethylene compounds, hydrocarbon compounds, carbon monoxide and/or carbon dioxide contained in FC-14 can be effectively adsorbed and removed and thereby high-purity FC-14 can be obtained.
- the purity of FC-14 obtained is 99.9997 mass% or more and for the analysis of FC-14 products having a purity of 99.9997 mass% or more, (1) gas chromatography (GC) using TCD method, FID method (each including the precut method) or ECD method, or (2) an analysis instrument such as gas chromatography mass spectrometer (GC-MS) may be used.
- the obtained high-purity FC-14 can be used as an etching gas at the etching step in a process of producing a semiconductor device.
- the high-purity FC- 14 can be used as a cleaning gas at a cleaning step in a process of producing a semiconductor device.
- a thin or thick film is formed using a CVD method, a sputtering method or a vapor deposition method and the film is etched to form a circuit pattern.
- cleaning is performed to remove unnecessary deposits accumulated on the inner wall of the apparatus, jig and the like, because unnecessary deposits cause generation of particles and must be removed occasionally to produce a good-quality film.
- the etching may be performed under various dry etching conditions such as plasma etching and microwave etching, and FC-14 may be used by mixing it with an inert gas such as He, N 2 and Ar, or with a gas such as HCl, 0 2 and H 2 , at an appropriate proportion.
- FC-14 may be used by mixing it with an inert gas such as He, N 2 and Ar, or with a gas such as HCl, 0 2 and H 2 , at an appropriate proportion.
- FC-14 had the composition shown in Table 2 below.
- Difluoromethane (CH 2 F 2 ) was reacted with fluorine gas in the presence of a diluting gas, then the reacted gas was introduced into an alkali cleaning tower to remove hydrogen fluoride generated and the slight amount of unreacted fluorine gas.
- the product gas rich in FC-14 was purified by fractional distillation according to a
- FC-14 had the composition shown in Table 3 below.
- Example 2 Into a 200 ml stainless steel cylinder, 20 g of 5 zeolite (Molecular Sieves 13X, produced by Union Showa K.K., average pore size: 10 A, Si/Al ratio: 1.23) was filled and vacuum dried, then about 70 g of FC-14 of Raw Material Example 1 was filled while cooling the cylinder, and the contents were occasionally stirred at room 0 temperature (about 18°C). After about 8 hours, the liquid phase part was analyzed by gas chromatography. The analysis results are shown in Table 5 below. Table 5
- the purity of the FC-14 obtained is 99.9997 mass% or more.
- the amount of impurities contained in tetrafluoromethane which had been 0 heretofore very difficult to remove, particularly ethylene compounds, hydrocarbon compounds, carbon monoxide and/or carbon dioxide can be reduced.
- the high- purity tetrafluoromethane, after purification, can be used as an etching gas or a cleaning gas.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU52617/01A AU5261701A (en) | 2000-04-28 | 2001-04-26 | Method for purification of tetrafluoromethane and use thereof |
KR1020017016733A KR20020023966A (en) | 2000-04-28 | 2001-04-26 | Method for purification of tetrafluoromethane and use thereof |
US10/019,137 US6967260B2 (en) | 2000-04-28 | 2001-04-26 | Method for purification of tetrafluoromethane and use thereof |
HK05105173A HK1072594A1 (en) | 2000-04-28 | 2005-06-22 | Method for purification of tetrafluoromethane and use thereof |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000128681A JP4471448B2 (en) | 2000-04-28 | 2000-04-28 | Tetrafluoromethane purification method and use thereof |
JP2000-128681 | 2000-04-28 | ||
US23070400P | 2000-09-07 | 2000-09-07 | |
US60/230,704 | 2000-09-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001083412A2 true WO2001083412A2 (en) | 2001-11-08 |
WO2001083412A3 WO2001083412A3 (en) | 2002-04-25 |
Family
ID=26591045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/003664 WO2001083412A2 (en) | 2000-04-28 | 2001-04-26 | Method for purification of tetrafluoromethane and use thereof |
Country Status (5)
Country | Link |
---|---|
CN (1) | CN1268592C (en) |
AU (1) | AU5261701A (en) |
HK (1) | HK1072594A1 (en) |
RU (1) | RU2215730C2 (en) |
WO (1) | WO2001083412A2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004005226A1 (en) * | 2002-07-02 | 2004-01-15 | Showa Denko K. K. | Process for purifying pentafluoroethane, process for producing the same, and use thereof |
WO2004074225A1 (en) * | 2003-02-20 | 2004-09-02 | Ineos Fluor Holdings Limited | Process for the purification of (hydro)halocarbons |
WO2005044765A2 (en) * | 2003-11-10 | 2005-05-19 | Showa Denko K.K. | Purification method of, 1, 1-difluoroethane |
WO2008008695A1 (en) * | 2006-07-12 | 2008-01-17 | Honeywell International Inc. | Use of molecular sieves for the removal of hfc-23 from fluorocarbon products |
CN100455555C (en) * | 2003-11-10 | 2009-01-28 | 昭和电工株式会社 | Purification method of, 1, 1-difluoroethane |
EP3693353A1 (en) * | 2019-02-11 | 2020-08-12 | Solvay Sa | A process for the purification of fluorinated olefins |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102399126A (en) * | 2011-12-19 | 2012-04-04 | 天津市泰源工业气体有限公司 | Method for preparing high purity tetrafluoromethane through combination of rectification and adsorption |
CN103664501B (en) * | 2012-09-07 | 2015-09-23 | 佛山市华特气体有限公司 | A kind of purification process of hexafluoroethane |
CN103664502B (en) * | 2012-09-07 | 2015-09-23 | 佛山市华特气体有限公司 | A kind of octafluoropropane purification process |
CN106345264B (en) * | 2016-07-19 | 2018-10-30 | 浙江博瑞电子科技有限公司 | A kind of method of purification of organic fluorine gas using impurity decomposing agent |
KR102644490B1 (en) * | 2019-08-06 | 2024-03-08 | 가부시끼가이샤 레조낙 | Gas processing method and gas processing device |
CN114249628B (en) * | 2021-12-31 | 2023-06-20 | 华南理工大学 | CH3F and C3H8 separation method |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3026359A (en) * | 1960-03-16 | 1962-03-20 | Du Pont | Process for preparing polyfluoroalkanes of high purity |
US5417742A (en) * | 1993-12-03 | 1995-05-23 | The Boc Group, Inc. | Removal of perfluorocarbons from gas streams |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2924660B2 (en) * | 1994-09-08 | 1999-07-26 | 昭和電工株式会社 | Purification method of tetrafluoromethane |
-
2001
- 2001-04-26 WO PCT/JP2001/003664 patent/WO2001083412A2/en active Application Filing
- 2001-04-26 CN CN 01801119 patent/CN1268592C/en not_active Expired - Lifetime
- 2001-04-26 RU RU2002101934A patent/RU2215730C2/en not_active IP Right Cessation
- 2001-04-26 AU AU52617/01A patent/AU5261701A/en not_active Abandoned
-
2005
- 2005-06-22 HK HK05105173A patent/HK1072594A1/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3026359A (en) * | 1960-03-16 | 1962-03-20 | Du Pont | Process for preparing polyfluoroalkanes of high purity |
US5417742A (en) * | 1993-12-03 | 1995-05-23 | The Boc Group, Inc. | Removal of perfluorocarbons from gas streams |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 07, 31 July 1996 (1996-07-31) & JP 08 081399 A (SHOWA DENKO KK), 26 March 1996 (1996-03-26) cited in the application * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004005226A1 (en) * | 2002-07-02 | 2004-01-15 | Showa Denko K. K. | Process for purifying pentafluoroethane, process for producing the same, and use thereof |
US7084316B2 (en) | 2002-07-02 | 2006-08-01 | Showa Denko K.K. | Process for purifying pentafluoroethane, process for producing the same, and use thereof |
WO2004074225A1 (en) * | 2003-02-20 | 2004-09-02 | Ineos Fluor Holdings Limited | Process for the purification of (hydro)halocarbons |
US7829058B2 (en) | 2003-02-20 | 2010-11-09 | Ineos Fluor Holdings Limited | Process for the purification of (hydro) halocarbons |
AU2004213223B2 (en) * | 2003-02-20 | 2009-10-08 | Mexichem Amanco Holding, S.A. De C.V. | Process for the purification of (hydro)halocarbons |
CN100455555C (en) * | 2003-11-10 | 2009-01-28 | 昭和电工株式会社 | Purification method of, 1, 1-difluoroethane |
WO2005044765A3 (en) * | 2003-11-10 | 2006-03-02 | Showa Denko Kk | Purification method of, 1, 1-difluoroethane |
US7696392B2 (en) | 2003-11-10 | 2010-04-13 | Showa Denko K.K. | Purification method of 1,1-difluoroethane |
WO2005044765A2 (en) * | 2003-11-10 | 2005-05-19 | Showa Denko K.K. | Purification method of, 1, 1-difluoroethane |
WO2008008695A1 (en) * | 2006-07-12 | 2008-01-17 | Honeywell International Inc. | Use of molecular sieves for the removal of hfc-23 from fluorocarbon products |
US7597744B2 (en) | 2006-07-12 | 2009-10-06 | Honeywell International Inc. | Use of molecular sieves for the removal of HFC-23 from fluorocarbon products |
EP3415220A1 (en) * | 2006-07-12 | 2018-12-19 | Honeywell International Inc. | Use of molecular sieves for the removal of hfc-23 from fluorocarbon products |
EP3693353A1 (en) * | 2019-02-11 | 2020-08-12 | Solvay Sa | A process for the purification of fluorinated olefins |
WO2020164912A1 (en) * | 2019-02-11 | 2020-08-20 | Solvay Sa | A process for the purification of fluorinated olefins |
CN113227023A (en) * | 2019-02-11 | 2021-08-06 | 索尔维公司 | Process for purifying fluorinated olefins |
Also Published As
Publication number | Publication date |
---|---|
HK1072594A1 (en) | 2005-09-02 |
WO2001083412A3 (en) | 2002-04-25 |
RU2215730C2 (en) | 2003-11-10 |
AU5261701A (en) | 2001-11-12 |
CN1561318A (en) | 2005-01-05 |
CN1268592C (en) | 2006-08-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5132555B2 (en) | Method for producing high purity hexafluoropropylene and cleaning gas | |
KR100519140B1 (en) | Process for producing perfluorocarbons and use thereof | |
US7094935B2 (en) | Adsorbent for purifying perfluorocarbon, process for producing same, high purity octafluoropropane and octafluorocyclobutane, and use thereof | |
US7208644B2 (en) | Production and use of hexafluoroethane | |
WO2001083412A2 (en) | Method for purification of tetrafluoromethane and use thereof | |
US7084316B2 (en) | Process for purifying pentafluoroethane, process for producing the same, and use thereof | |
EP1307416B1 (en) | Process for preparing octafluorocyclobutane | |
US7041264B2 (en) | Process for purifying octafluoropropane | |
US6274782B1 (en) | Method for purifying hexafluoroethane | |
KR20010072868A (en) | Purification of 1,1,1,3,3-pentafluorobutane | |
JP4471448B2 (en) | Tetrafluoromethane purification method and use thereof | |
KR960004870B1 (en) | Process for the purification of 1,1,1,2-tetrafluoroethane | |
US6967260B2 (en) | Method for purification of tetrafluoromethane and use thereof | |
US20070197843A1 (en) | Method for purification of 1,1-dichloroethane and process for production of 1,1-difluroethane using this method | |
JP3856408B2 (en) | Method for purifying hexafluoroethane | |
JP4666874B2 (en) | Purification and production method of pentafluoroethane and use thereof | |
KR100543253B1 (en) | Production and use of hexafluoroethane | |
US6489523B1 (en) | Process for producing hexafluoroethane and use thereof | |
WO2001098240A2 (en) | Process for producing hexafluoroethane and use thereof | |
KR0159176B1 (en) | Method for purification of 1,1-difluoroethane | |
JP2005162738A (en) | Method for purifying 1,1-difluoroethane and application thereof | |
JP5105672B2 (en) | Method for purifying tetrachloroethylene and method for producing pentafluoroethane using the method | |
JP2005336164A (en) | Method for purification of 1, 1-dichloroethane and process for production of 1, 1-difluoroethane using the method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 01801119.5 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10019137 Country of ref document: US Ref document number: 1020017016733 Country of ref document: KR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase in: |
Ref document number: 2002 2002101934 Country of ref document: RU Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
122 | Ep: pct application non-entry in european phase |