WO1997047578A1 - Process for improving color of basic metal organic salts by employing c7-c17 alkyl glycidyl esters and stabilizing halogen-containing polymers therewith - Google Patents
Process for improving color of basic metal organic salts by employing c7-c17 alkyl glycidyl esters and stabilizing halogen-containing polymers therewith Download PDFInfo
- Publication number
- WO1997047578A1 WO1997047578A1 PCT/US1997/010297 US9710297W WO9747578A1 WO 1997047578 A1 WO1997047578 A1 WO 1997047578A1 US 9710297 W US9710297 W US 9710297W WO 9747578 A1 WO9747578 A1 WO 9747578A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- halogen
- glycidyl
- containing polymer
- composition
- alkaline earth
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/138—Phenolates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
Definitions
- the present invention relates to a process for producing
- the invention concerns a process for
- metal organic salts of the present invention are used as stabilizers for
- halogen-containing polymers such as polyvinyl chloride (PVC) .
- carboxylic acids alkyl phenols, and sulfonic acids are disclosed in the
- salts are low plate-out, excellent color hold, good long-term heat
- alkyl phenol is also a major cause for the development of color in the final product. This problem
- Propylene oxide is classified as a possible carcinogen
- Propylene oxide is also listed as a severe eye irritant, and
- the present invention relates to a process for improving
- the C 7 -C 17 alkyl glycidyl esters suitable for use include
- liquid glycidyl esters preferably glycidyl neodecanoate.
- the preferred glycidyl ester is glycidyl neodecanoate which
- the glycidyl neodecanoate possesses a high boiling
- propylene oxide possesses a low boiling point (94°F) and high vapor
- neodecanoate is sufficient to carry out the chemistry. This is in
- At least one phenol at least one monocarboxylic acid, and optionally at
- the process is conducted in an
- the color-producing component is not inhibited and/or destroyed in
- the color improving reaction may proceed in different
- the glycidyl ester may
- alkali or alkaline earth metal organic salts is used to refer to metal compositions wherein the ratio of total metal contained
- Metal ratio as used herein
- composition to the number of equivalents of the organic moiety.
- the process of the present invention may be used to calculate the process of the present invention.
- step (A) the mixture utilized in step (A) comprises at
- At least one alkaline earth metal base and at least one phenol, at least one
- ratio of equivalents of monocarboxylic acid to phenol being at least
- component and may be derived from any of the alkali or alkaline earth
- Metal bases derived from alkaline earth metals are preferred.
- the calcium and barium bases are particularly preferred.
- the metal bases include the metal oxides and hydroxides, and in some
- polynuclear phenolic compounds may also be a bisphenol such as is
- the alkyl phenols may contain one or more alkyl groups on the aromatic
- alkyl groups be sufficient to yield oil-soluble overbased metal phenates.
- the monocarboxylic acid may also contain at least one monocarboxylic acid.
- the monocarboxylic acid may also contain at least one monocarboxylic acid.
- acids may be aliphatic or aromatic monocarboxylic acids or mixtures
- mixture useful in step (A) optionally may contain at least one aliphatic compound
- promoter is not critical. The promoters are included in the mixture to
- salts or other type of chemically combined water with the metal salts.
- reaction mixtures used to prepare the basic metal salts ordinarily will
- a diluent Generally, any hydrocarbon diluent can be employed,
- hydrocarbon diluent will be a non-volatile
- diluent such as the various natural and synthetic oils of lubricating
- the amount of basic alkali or alkaline earth metal base is the amount of basic alkali or alkaline earth metal base
- metal base included may be any amount up to that amount which is
- the step of the process (B) involves treating the mixtures
- the titratable basicity is determined using a phenolphthalein.
- the titratable basicity is reduced to a base number below about 10.
- step (A) The ingredients in step (A) are mixed, generally heated and
- temperatures used for this step may be any temperature above ambient
- carbon dioxide carbon disulfide, hydrogen sulfide, etc.
- carbon dioxide carbon disulfide, hydrogen sulfide, etc.
- phenates include, for example, U. S. Patent Nos. 2,989,463 and
- invention involves (C) treating the reaction mixture with at least one
- composition or reaction product obtained is obtained from the composition or reaction product obtained.
- step (B) is post-treated with at least one C 7 -C 17 alkyl glycidyl ester.
- glycidyl esters may be generally characterized by
- R is a C 7 -C 17 alkyl group. Specific examples include the
- a molar ratio of phenol to the glycidyl ester should be
- a halogen-containing polymer such as a vinyl halide resin
- Vinyl halide resin as
- H 2 C CHCI to polyvinyl chloride (CH 2 CHCI— ) classroom wherein the halogen is
- vinyl halide resins examples include vinylidene chloride
- polyvinyl bromide polyvinyl fluoride
- compositions are well known. These metal compounds serve to capture
- the heavy metal can be lead,
- the stabilizers are usually
- metal salts of a carboxylic acid advantageously of a C 8 -C 24 carbon
- chain link monocarboxylic acid such as lauric, oleic, stearic, octoic, or
- the metal stabilizer is a mixed metal salt of a carboxylic
- nonylphenol and 600 parts of mineral oil is prepared and purged with
- the nitrogen to remove any oxygen present in the system.
- hydroxide monohydrate are added incrementally over a 30-minute period
- the carbon dioxide feed is then stopped while maintaining
- the ASTM color is found to be less than 1 .5.
- neodecanoate treated product was lighter in color than the commercial
- nonylphenol and 600 parts of mineral oil is prepared and purged with
- the nitrogen to remove any oxygen present in the system.
- hydroxide monohydrate are added incrementally over a 30-minute period
- the carbon dioxide feed is then stopped while maintaining
- Example 1 This illustrated that the internal epoxide, e.g., butyl epoxy
- the ASTM color was found to be less than 1 .5.
- Example 1 was formulated as a stabilizer for PVC and
- STABILIZER A As follows:
- Hydrocarbon Solvent 1 7.3 A presently available 28% overbased barium dodecyl
- STABILIZER B As follows:
- STABILIZER A and STABILIZER B were each formulated in
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9706923-0A BR9706923A (en) | 1996-06-13 | 1997-06-12 | Process for improving the placement of organic salts of basic metals using c7-c17 glycidyl alkyl esters and stabilizing polymers containing halogen with them. |
AU33919/97A AU710482B2 (en) | 1996-06-13 | 1997-06-12 | Process for improving colour of basic metal organic salts by employing c7-c17 alkyl glycidyl esters and stabilising halogen-containing polymers therewith |
KR1019980703410A KR100284870B1 (en) | 1996-06-13 | 1997-06-12 | How to improve the color of basic metal organic salts using C7-C17 alkyl glycidyl esters and to stabilize halogen-containing polymers using this method |
CA002235741A CA2235741C (en) | 1996-06-13 | 1997-06-12 | Process for improving color of basic metal organic salts by employing c7-c17 alkyl glycidyl esters and stabilizing halogen-containing polymers therewith |
DE69706420T DE69706420T2 (en) | 1996-06-13 | 1997-06-12 | METHOD FOR IMPROVING THE COLOR OF BASIC ORGANIC METAL SALTS BY THE USE OF C7-C17-ALKYL-GLYCIDYLE ESTERS, AND STABILIZING POLYMERS CONTAINING HALOGEN THEREFOR |
JP10501860A JPH11501333A (en) | 1996-06-13 | 1997-06-12 | Method for improving color of basic metal organic salt by using alkyl glycidyl ester and method for stabilizing halogen-containing polymer by using basic metal organic salt |
AT97929985T ATE204844T1 (en) | 1996-06-13 | 1997-06-12 | METHOD FOR IMPROVING THE COLOR OF BASIC ORGANIC METAL SALTS BY USING C7-C17-ALKYL-GLYCIDYLE ESTERS, AND STABILIZING HALOGEN-CONTAINING POLYMERS THEREFROM |
EP97929985A EP0906263B1 (en) | 1996-06-13 | 1997-06-12 | Process for improving color of basic metal organic salts by employing c7-c17 alkyl glycidyl esters and stabilizing halogen-containing polymers therewith |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1967796P | 1996-06-13 | 1996-06-13 | |
US60/019,677 | 1997-06-09 | ||
US08/870,698 | 1997-06-09 | ||
US08/870,698 US5830935A (en) | 1996-06-13 | 1997-06-09 | Color of basic metal organic salts by employing C7 -C17 alkyl glycidyl esters and stabilized halogen-containing polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997047578A1 true WO1997047578A1 (en) | 1997-12-18 |
Family
ID=26692490
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/010297 WO1997047578A1 (en) | 1996-06-13 | 1997-06-12 | Process for improving color of basic metal organic salts by employing c7-c17 alkyl glycidyl esters and stabilizing halogen-containing polymers therewith |
Country Status (11)
Country | Link |
---|---|
US (1) | US5830935A (en) |
EP (1) | EP0906263B1 (en) |
JP (1) | JPH11501333A (en) |
KR (1) | KR100284870B1 (en) |
AT (1) | ATE204844T1 (en) |
AU (1) | AU710482B2 (en) |
BR (1) | BR9706923A (en) |
CA (1) | CA2235741C (en) |
DE (1) | DE69706420T2 (en) |
TW (1) | TW464669B (en) |
WO (1) | WO1997047578A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7323508B2 (en) | 2001-11-28 | 2008-01-29 | Akzo Nobel N.V. | Neutral carbonated alkaline earth metal carboxylates |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7163912B2 (en) | 2001-05-18 | 2007-01-16 | Omg Americas, Inc. | Lubricant compositions containing an overbased amorphous alkaline earth metal salt as a metal protectant |
US6689893B2 (en) * | 2001-05-18 | 2004-02-10 | Omg Americas, Inc. | Shelf stable haze free liquids of overbased alkaline earth metal salts |
US6773631B2 (en) | 2001-05-18 | 2004-08-10 | Hammond Group, Inc. | Liquid overbased mixed metal stabilizer composition of calcium, barium and zinc for stabilizing halogen-containing polymers |
US6639090B2 (en) | 2001-05-18 | 2003-10-28 | Omg Americas, Inc. | Powdered overbased amorphous alkaline earth metal salts and processes for making |
US6613723B2 (en) | 2001-12-06 | 2003-09-02 | Exxonmobil Chemical Patents Inc. | Overbased barium complexes of C8 to C10 carboxylic acids |
WO2004094351A2 (en) * | 2003-04-23 | 2004-11-04 | Akzo Nobel N.V. | Novel high metal content intermediates |
US20060194704A1 (en) * | 2003-07-11 | 2006-08-31 | Akzo Nobel N.V. | Highly over-based light colored liquid alkaline earth metal carboxylate |
US20090264327A1 (en) * | 2008-04-21 | 2009-10-22 | Omg Americas, Inc. | Overbased metal carboxylate precursor and process for making |
US9102610B2 (en) | 2011-11-29 | 2015-08-11 | Am Stabilizers Corporation | Process for preparing liquid overbased metal carboxylates, mixed metal stabilizers containing same, and stabilized halogen-containing polymers therewith |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57182399A (en) * | 1981-05-02 | 1982-11-10 | Asahi Denka Kogyo Kk | Manufacture of metal soap bar |
US4665117A (en) * | 1985-12-20 | 1987-05-12 | The Lubrizol Corporation | Basic metal salts having improved color and stability and vinyl halide polymers containing same |
EP0469482A1 (en) * | 1990-08-01 | 1992-02-05 | Hoechst Aktiengesellschaft | Method of purifying salts of long chain aliphatic carboxylic acids and their application as plastic additives |
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US2582452A (en) * | 1948-12-16 | 1952-01-15 | Diamond Alkali Co | Transparent, flame-resistant polystyrene |
US2671064A (en) * | 1950-05-10 | 1954-03-02 | Monsanto Chemicals | Method of stabilizing halogen containing resins with cadmium salts and epoxy esters |
US2616904A (en) * | 1951-03-16 | 1952-11-04 | Lubrizol Corp | Organic alkaline earth metal complex and method of making same |
US2767164A (en) * | 1952-11-03 | 1956-10-16 | Lubrizol Corp | Complexes containing phosporus and sulphur and methods of making same |
US2760970A (en) * | 1953-04-06 | 1956-08-28 | Lubrizol Corp | Process for the preparation of substantially pure metal salts of organic sulfonic acids |
US2802816A (en) * | 1953-11-02 | 1957-08-13 | Lubrizol Corp | Method of making organic lithium compounds |
US2798852A (en) * | 1954-02-15 | 1957-07-09 | Lubrizol Corp | Oil-soluble metal-containing materials and methods for preparing same |
US3027325A (en) * | 1955-11-07 | 1962-03-27 | Lubrizol Corp | Oil-soluble calcium carbonate dispersions and method of preparation |
US2889295A (en) * | 1956-07-16 | 1959-06-02 | Monsanto Chemicals | Vinyl halide polymers stabilized with phosphites and benzoic acid esters |
US3046224A (en) * | 1957-06-10 | 1962-07-24 | Socony Mobil Oil Co Inc | High barium content complex salts of sulfonic acids and petroleum fractions containing the same |
US2989463A (en) * | 1958-09-26 | 1961-06-20 | Lubrizol Corp | Lubricants containing basic metal additives |
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US2971041A (en) * | 1959-08-24 | 1961-02-07 | Universal Cyclops Steel Corp | Telescoping immersion thermocouple |
US3147232A (en) * | 1961-03-20 | 1964-09-01 | Lubrizol Corp | Stabilizers for vinyl chloride polymer compositions comprising alkaline earth metal compounds |
US3194823A (en) * | 1963-03-18 | 1965-07-13 | Lubrizol Corp | Organic complexes |
US3342733A (en) * | 1964-10-05 | 1967-09-19 | Exxon Research Engineering Co | Preparation of colloidal carbonates in hydrocarbon media |
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GB1121578A (en) * | 1967-11-06 | 1968-07-31 | Lubrizol Corp | Reaction products of high molecular weight hydrocarbon succinic acid compounds, amines and heavy metal compounds |
US3773664A (en) * | 1971-09-09 | 1973-11-20 | Lubrizol Corp | Basic barium-containing compositions |
US4159973A (en) * | 1978-03-06 | 1979-07-03 | Tenneco Chemicals, Inc. | Stabilizer systems and vinyl halide resin compositions containing same |
JPS54137044A (en) * | 1978-04-17 | 1979-10-24 | Adeka Argus Chem Co Ltd | Halogen-containing resin composition |
US4661544A (en) * | 1985-12-20 | 1987-04-28 | The Lubrizol Corporation | Homogeneous stabilizer compositions for vinyl halide polymers |
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TW321670B (en) * | 1994-04-15 | 1997-12-01 | Ciba Sc Holding Ag |
-
1997
- 1997-06-09 US US08/870,698 patent/US5830935A/en not_active Expired - Lifetime
- 1997-06-12 CA CA002235741A patent/CA2235741C/en not_active Expired - Fee Related
- 1997-06-12 KR KR1019980703410A patent/KR100284870B1/en not_active IP Right Cessation
- 1997-06-12 BR BR9706923-0A patent/BR9706923A/en not_active IP Right Cessation
- 1997-06-12 JP JP10501860A patent/JPH11501333A/en active Pending
- 1997-06-12 AU AU33919/97A patent/AU710482B2/en not_active Ceased
- 1997-06-12 DE DE69706420T patent/DE69706420T2/en not_active Expired - Lifetime
- 1997-06-12 AT AT97929985T patent/ATE204844T1/en not_active IP Right Cessation
- 1997-06-12 WO PCT/US1997/010297 patent/WO1997047578A1/en active IP Right Grant
- 1997-06-12 EP EP97929985A patent/EP0906263B1/en not_active Expired - Lifetime
- 1997-06-13 TW TW086108207A patent/TW464669B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57182399A (en) * | 1981-05-02 | 1982-11-10 | Asahi Denka Kogyo Kk | Manufacture of metal soap bar |
US4665117A (en) * | 1985-12-20 | 1987-05-12 | The Lubrizol Corporation | Basic metal salts having improved color and stability and vinyl halide polymers containing same |
EP0469482A1 (en) * | 1990-08-01 | 1992-02-05 | Hoechst Aktiengesellschaft | Method of purifying salts of long chain aliphatic carboxylic acids and their application as plastic additives |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 8251, Derwent World Patents Index; AN 82-09937j, XP002041445, "Metallic soap mfr. - ..." * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7323508B2 (en) | 2001-11-28 | 2008-01-29 | Akzo Nobel N.V. | Neutral carbonated alkaline earth metal carboxylates |
Also Published As
Publication number | Publication date |
---|---|
CA2235741A1 (en) | 1997-12-18 |
BR9706923A (en) | 2000-01-04 |
KR100284870B1 (en) | 2001-04-02 |
JPH11501333A (en) | 1999-02-02 |
CA2235741C (en) | 2001-09-18 |
KR19990067400A (en) | 1999-08-16 |
EP0906263A1 (en) | 1999-04-07 |
TW464669B (en) | 2001-11-21 |
AU3391997A (en) | 1998-01-07 |
DE69706420D1 (en) | 2001-10-04 |
AU710482B2 (en) | 1999-09-23 |
US5830935A (en) | 1998-11-03 |
EP0906263B1 (en) | 2001-08-29 |
DE69706420T2 (en) | 2002-04-11 |
ATE204844T1 (en) | 2001-09-15 |
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