EP1572777A1 - Herstellung eines polyester-hohlkörpers oder dessen preforms mit reduziertem acetaldehydgehalt - Google Patents
Herstellung eines polyester-hohlkörpers oder dessen preforms mit reduziertem acetaldehydgehaltInfo
- Publication number
- EP1572777A1 EP1572777A1 EP03750233A EP03750233A EP1572777A1 EP 1572777 A1 EP1572777 A1 EP 1572777A1 EP 03750233 A EP03750233 A EP 03750233A EP 03750233 A EP03750233 A EP 03750233A EP 1572777 A1 EP1572777 A1 EP 1572777A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyester
- preform
- hollow body
- acetaldehyde content
- polyester material
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Definitions
- the invention relates to a process for producing a hollow polyester body or its preform with reduced acetaldehyde content from a drop-shaped, spherical or spherical polyester granulate with a granule diameter of less than 2 mm.
- the invention also relates to a polyester material for the production of a hollow polyester body or its preforms with a reduced acetaldehyde content.
- the polymerization takes place in the melt phase up to an IV value of more than 0.4dl / g, typically about 0.6dl / g.
- the polyester melt is then solidified and formed into mostly uniform particles (granules), the shaping and solidification also being able to take place simultaneously or in the reverse order.
- a solid-phase polycondensation then takes place in order to achieve an IV value of more than 0.7dl / g, typically of about 0.8dl / g.
- PET polyethylene terephthalate
- the disadvantages of this manufacturing process are that a relatively large part of the polymerization takes place in the melt phase, which has significantly higher investment costs compared to solid-phase polycondensation.
- degradation reactions also take place in the melt phase, which increase with increasing viscosity (ie with increasing IV value).
- the resulting damage to the polymer chain can only be partially in the undo the subsequent solid phase polycondensation process.
- the formation of vinyl ester groups, which disintegrate during further processing, for example in an injection molding process, to form acetaldehyde is particularly disadvantageous.
- Degradation reactions that lead to discoloration (yellowing) of the PET are also disadvantageous.
- DuPont has described in a series of patents ways of shaping (US 5633018; US 5744074, US 5730913) and at the same time to form a special crystal structure (US 8840868; US 5532233; US 5510454; US 5714262; US 5830982), which lead to improved behavior lead in the solid phase polycondensation process.
- the molding process is very complex and expensive in terms of apparatus, and the post-condensed polyester has a very high melting point, which leads to high processing temperatures in the injection molding process (see US 553233, Example 5).
- the high melting point results on the one hand from the necessarily very high post-condensation temperature and on the other hand from the crystal structure described.
- the equation shows that the melting temperature of a polymer is always lower than the equilibrium melting temperature, by a value that is inversely proportional to the polymer crystal size.
- WO 01/42334 describes a process which optimizes the PET production in such a way that a preform (preform) with improved properties can be produced.
- the particle manufacturing process has not been optimized. Dripping is even explicitly excluded.
- the process is also limited to polyethylene terephthalate with a high copolymer content, which on the one hand has a negative influence on the treatment in the SSP and on the other hand limits the area of application of the PET produced in this way.
- PET polyethylene terephthalate
- the molecular weight of the polyester is set to an IV value of 0.15 to 0.4dl / g in the melt-phase polymerization production step; the melt is dripped into a drop-shaped, spherical or spherical shape and then solidified; the molecular weight of the polyester is increased to an IV value greater than 0.65 dl / g in the manufacturing step of solid-phase polycondensation; and
- polyester material treated in this way is introduced into a shaping agent in order to shape it in order to obtain the hollow body or its preform.
- the polyester material treated in this way can be at least partially plasticized before and / or during its shaping.
- the actual shaping takes place by melting and injection molding the polyester material treated in this way.
- the shaping is carried out by extrusion blow molding of the polyester material treated in this way.
- the melting can be done by various methods. For example by mechanical energy input, heat conduction or heat radiation, in particular by means of an extrusion device and / or a microwave device.
- the melting preferably takes place at a temperature which is 5 ° C. or more below a temperature TO, where TO corresponds to the optimal processing temperature at which an equivalent polyester can be processed from a conventional manufacturing process.
- the shaping is carried out by sintering the polyester material treated in this way, the polyester material being introduced into a mold and shaped into a preform by sintering.
- the polyester material is introduced into the mold preferably by gravitational forces, by movement by means of a delivery medium and / or by inertial forces, in particular by centrifugal forces.
- the polyester is a polyethylene terephthalate or a copolymer of polyethylene terephthalate, and the maximum temperature in the solid phase polycondensation manufacturing step is at or below 230 ° C, preferably at or below 225 ° C.
- the granulate diameter is expediently in the range from 0.4 to 1.9 mm, preferably in the range from 0.7 to 1.6 mm.
- polyester is a copolymer of polyethylene terephthalate, preferably
- the diol component consists of more than 94% ethylene glycol and the dicarboxylic acid component consists of approximately 100% terephthalic acid, or b) the diol component consists of more than 98% ethylene glycol, or c) the dicarboxylic acid Component consists of more than 96% terephthalic acid.
- the step of preheating to the post-condensation temperature in solid-phase polycondensation preferably takes place in a period of from 1 to 10 minutes, preferably from 2 to 8 minutes.
- the polyester is expediently removed from the dropletizing device with the aid of a discharge device, the discharge device preferably being a fluidized-bed or fluidized-bed apparatus with a perforated floor through which gas flows and one or more product outlet openings.
- a hollow body in particular a bottle, with a reduced acetaldehyde content can ultimately be produced from the preform with a reduced acetaldehyde content.
- the object of the invention is also achieved by a polyester material for producing a hollow polyester body or its preform with a reduced acetaldehyde content, the polyester material being present in the form of drop-shaped, spherical or spherical polyester granules with a granule diameter of less than 2 mm, characterized in that that
- the molecular weight of the polyester material was set to an IV value of 0.15 to 0.4dl / g in a melt phase polymerization production step;
- the polyester material can be melted into its shape and introduced into a shaping agent in order to obtain the polyester hollow body or its preform.
- polyester material With this polyester material, a hollow body or its preform can be obtained with a significantly lower acetaldehyde content than with the previously known polyester materials.
- the melting of the polyester material can be carried out at a temperature which is 5 ° C. or more below a temperature T0, where T0 corresponds to the optimal processing temperature at which an equivalent polyester from a conventional manufacturing process is processed can.
- the polyester material is in particular a polyethylene terephthalate or a copolymer of polyethylene terephthalate, the maximum temperature in the manufacturing step of the solid-phase polycondensation being at or below 230 ° C., preferably at or below 225 ° C.
- the polyester material it proves to be particularly advantageous if the granule diameter is in the range from 0.4 to 1.9 mm, preferably in the range from 0.7 to 1.6 mm.
- the step of preheating the polyester material to the post-condensation temperature in the solid-phase polycondensation is advantageously carried out in a period of 1 to 10 minutes and preferably in a period of 2 to 8 minutes.
- the polyester is a polymer which is obtained by polycondensation from its monomers, a diol component and a dicarboxylic acid component. While various, mostly linear or cyclic diol components can be used, the use of predominantly ethylene glycol is preferred. Likewise, various mostly aromatic dicarboxylic acid components can be used, although the use of mostly terephthalic acid is preferred.
- the polyester consists of a copolymer of polyethylene terephthalate, either:
- the diol component consists of more than 94% ethylene glycol and the dicarboxylic acid component consists approximately 100% of terephthalic acid or
- the diol component consists of ethylene glycol or
- the dicarboxylic acid component consists of more than 96% terephthalic acid.
- the polyester monomers are polymerized or polycondensed in the liquid phase in order to achieve an IV value of 0.15 to 0.4 dl / g.
- An IV value between 0.20 and 0.35dl / g is preferred.
- the process usually takes place at elevated temperature in a vacuum to remove the low molecular weight polycondensation cracked products, but can also take place at atmospheric pressure or increased pressure if the low molecular weight polycondensation cracked products are removed, for example with the aid of an inert entraining gas.
- additives can be added in the liquid phase polymerization, such as, for example, catalysts, stabilizers, coloring additives, reactive chain extension additives, etc.
- the polyester melt is converted into a drop-shaped, spherical or spherical shape by dropletization and then solidified.
- Solid particles (granules) with a granulate diameter of less than 2 mm, typically between 0.4 and 1.9 mm, preferably between 0.7 and 1.6 mm are produced, the ideal size being able to be derived in accordance with the requirements of solid-phase polycondensation.
- the dropletization is usually achieved via a dropletization nozzle, the dropletization taking place in a gas-filled space.
- the gas can be air or an inert gas such as nitrogen.
- other gaseous, liquid or solid components can also be contained in the gas. can be, for example, polycondensation fission products, additives, mists of liquid cooling media or dusts for nucleation or prevention of sticking.
- the vibration excitation can either be exerted on the polyester melt or at least on part of the dropletizing apparatus, in particular on the nozzle. A large number of still liquid polyester particles are formed.
- the polyester particles In order to solidify the polyester particles, they have to be cooled, which usually begins in a first part of a falling section and is continued or completed in a second part of a falling section. At the end of the fall, the polyester particles can be cooled further in a cooling medium or on a cooling surface, in particular in a cooling liquid. In order to ensure the uniformity of the particles, they may only hit a cooling surface when they are essentially dimensionally stable and the crystal structure on the contact surface does not change differently from the rest of the particle.
- a gas stream is preferably maintained in the falling section, which may be one or more gas streams which differ in their flow direction, flow speed, temperature and composition.
- the cooling and solidification should take place in such a way that no crystal structure with excessively large crystallites is formed, which then has a high melting point during late melting.
- Working temperatures required, the average crystallite size, measured by the method described in US 5510454, is less than 9nm, preferably less than 8nm.
- a discharge device with which the polyester particles are removed from the dropping device.
- the movement can be achieved by mechanical movement or by swirling in a gas or liquid stream.
- the discharge device is a fluidized bed or fluidized bed apparatus with a perforated base through which gas flows and one or more product outlet openings.
- the molecular weight of the polyester granules, which were produced by dropletization, is increased by a solid-phase polycondensation to an IV value greater than 0.65 dl / g.
- the solid-phase polycondensation comprises the steps of crystallization (insofar as this is still necessary after the dropletization), preheating, the post-condensation reaction, cooling and the preparation and processing of the necessary process gases.
- Both continuous and batch processes can be used, for example in equipment such as fluidized bed, bubble bed or fixed bed reactors as well as in reactors with stirring tools or self-moving reactors such as rotary kilns or tumble dryers.
- the solid phase polycondensation can take place either at normal pressure, at elevated pressure or under vacuum. It is known to use the highest possible post-condensation temperatures in order to achieve the shortest possible post-condensation time.
- the crystallinity is also raised to a very high level, which in turn leads to high processing temperatures.
- the maximum temperature during the solid-phase polycondensation is at or below 230 ° C., preferably at or below 225 ° C.
- the reaction leads to an asymptotic approach to a maximum IV-value that is still below the desired target IV -Value lies. Accordingly, the maximum temperature during solid phase polycondensation should be at or above 205 ° C, preferably at or above 210 ° C.
- reaction rate in solid-phase polycondensation is at least partially diffusion-controlled and thus increases with decreasing granule size.
- the polyester To produce a preform from the post-condensed polyester granules, the polyester must first be melted and then injected into a mold and cooled again.
- the polyester granulate is usually first dried and processed using an injection molding process.
- the configuration of the injection molding system e.g. extruder size and length, screw configuration, bowl size and configuration as well as the number of preforms per bowl
- the nature of the preform produced eg preform weight and size
- the processing conditions are optimized so that the PET is completely melted (e.g. to prevent the preforms from becoming cloudy) and that the PET is thermally damaged as little as possible, which requires the lowest possible melt temperature (e.g. by keep the amount of acetaldehyde that forms in the injection molding process low).
- the highest possible productivity should be achieved, which can be achieved by keeping the times for the process steps, which result in the entire cycle time, as short as possible, so that the time to inject the PET into the trough must be kept as short as possible .
- This temperature can be set on the one hand by setting the various heating zones of the injection molding machine and is, on the other hand, influenced by the mechanical energy consumption via the extruder.
- the step of cooling the polyester in the trough should also take place as quickly as possible after the injection and at a high cooling rate.
- the invention makes it possible to provide a PET which allows the optimum processing temperature to be reduced in comparison with the optimal processing temperature (TO) of a conventionally produced PET for a given combination of a system configuration and preform specification, the PET according to the invention having a comparable composition (comparable comonomers and their content) to the conventionally produced PET.
- the invention also makes it possible to process a PET produced according to the invention in such a way that the processing temperature is 5 ° C. or more below the optimal processing temperature (TO) of a conventionally produced PET, the PET according to the invention being of a comparable composition (comparable comonomers and their content) the conventionally produced PET.
- TO optimal processing temperature
- the processing temperature thus reduced also reduces the acetaldehyde content in the preform.
- the absolute content of acetaldehyde in the preform results from the polyester material specification, the configuration of the injection molding system, the processing conditions in the system and the specification of the preform.
- An alternative method for preform production can be carried out by sintering granules, which are pressed into a mold with heating if necessary.
- the invention makes it possible to provide a PET which makes it possible to lower the optimum processing temperature, in comparison to the optimal processing temperature (TO) of a conventionally produced PET, for a given combination of a system configuration, and preform specification, the PET according to the invention has a comparable composition (comparable comonomers and their content) to the conventionally produced PET.
- the invention also makes it possible to process a PET produced according to the invention in such a way that the processing temperature is 5 ° C. or more below the optimal processing temperature (TO) of a conventionally produced PET, the PET according to the invention being of a comparable composition (comparable comonomers and their content) the conventionally produced PET.
- the processing temperature thus reduced also reduces the acetaldehyde content in the preform.
- the absolute content of acetaldehyde in the preform is based on the polyester material specification, the configuration of the sintering plant, the processing conditions in the plant and the specification of the preform.
- the preform produced in this way can also be an intermediate form from which the final preform is produced by subsequent shaping
- the invention makes it possible to produce a preform whose acetaldehyde content, compared to the acetaldehyde content (AAO) of a conventionally produced preform, is reduced for a given combination of a system configuration and preform specification, the preform according to the invention being made from a polyester with a comparable material specification to a conventionally produced one Preform.
- the invention also makes it possible to produce a preform whose acetaldehyde content is 10% or more below the acetaldehyde content (AAO) of a conventionally produced preform, the preform according to the invention being produced from a polyester with a comparable material specification to a conventionally produced preform.
- AAO acetaldehyde content
- the reduced acetaldehyde content in the preform according to the invention is achieved without carrying out additional process steps for reducing the acetaldehyde content in the polyester granulate and without adding additives which can bind acetaldehyde.
- a hollow body (for example a bottle) can then be produced from the preform by blowing into a larger mold, it being possible to assume that, with a given preform specification and the associated hollow body specification, the acetaldehyde content in the hollow body is proportional to the acetaldehyde content in the preform.
- the hollow body can also be produced directly from the polyester granulate, for example by extrusion blow molding.
- the invention makes it possible to provide a PET which allows the optimum processing temperature to be reduced in comparison with the optimal processing temperature (TO) of a conventionally produced PET for a given combination of a system configuration and hollow body specification, the PET according to the invention having a comparable one Composition (comparable comonomers and their content) to the conventionally produced PET.
- the invention also makes it possible to process a PET produced according to the invention in such a way that the processing temperature is 5 ° C. or more below the optimal processing temperature (TO) of a conventionally produced PET, the PET according to the invention being of a comparable composition (comparable comonomers and their content) the conventionally produced PET.
- TO optimal processing temperature
- the processing temperature thus reduced also reduces the acetaldehyde content in the hollow body.
- the invention makes it possible to produce a hollow body whose acetaldehyde content, compared to the acetaldehyde content (AAO) of a conventionally produced hollow body, is reduced for a given combination of a system configuration and hollow body specification, the hollow body according to the invention made of a polyester with a comparable material specification to a conventionally produced one Hollow body is made.
- the invention also makes it possible to produce a hollow body whose acetaldehyde content is 10% or more below the acetaldehyde content (AAO) of a conventionally produced hollow body, the hollow body according to the invention being produced from a polyester with a comparable material specification to a conventionally produced hollow body.
- the reduced acetaldehyde content in the hollow body according to the invention is achieved without additional process steps for reducing the acetaldehyde content in the polyester granulate, and without additives which bind acetaldehyde can be added.
- the acetaldehyde content of polyester is measured by means of gas phase ("head space 'j gas chromatography.
- the analysis sequence comprises grinding the sample under liquid nitrogen; weighing 1 g of the ground material into a 29.5 ml volume glass container sealed with a septum, a thermal treatment for 10 minutes at 150 ° C. to convert the acetaldehyde into the gas phase and subsequent gas phase f'head space ") - analysis of the acetaldehyde content.
- the quantification of the resulting peak area is based on a comparison with acetaldehyde measurements from standard calibration solutions.
- Intrinsic viscosity measured as solution viscosity in a solvent mixture
- Phenol / dichlorobenzene 50:50% by weight
- the polyester sample is dissolved at 130 ° C. for 10 minutes in order to obtain a 0.5% solution (0.5 g / dl).
- the measurement of the relative viscosity (RV) is carried out at 25 ° C with an Ubbelohde viscometer (according to DIN No. 53728 part 3, January 1985).
- the relative viscosity is the quotient of the viscosities of the solution and the pure solvent, which corresponds approximately to the ratio of the corresponding throughput times through the viscometer.
- the intrinsic viscosity is calculated from the relative viscosity according to the Huggins equation:
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10259694A DE10259694A1 (de) | 2002-12-18 | 2002-12-18 | Herstellung eines Polyester-Performs mit reduziertem Acetaldehydgehalt |
DE10259694 | 2002-12-18 | ||
PCT/CH2003/000686 WO2004055093A1 (de) | 2002-12-18 | 2003-10-22 | Herstellung eines polyester-hohlkörpers oder dessen preforms mit reduziertem acetaldehydgehalt |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1572777A1 true EP1572777A1 (de) | 2005-09-14 |
Family
ID=32403996
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03750233A Withdrawn EP1572777A1 (de) | 2002-12-18 | 2003-10-22 | Herstellung eines polyester-hohlkörpers oder dessen preforms mit reduziertem acetaldehydgehalt |
Country Status (9)
Country | Link |
---|---|
US (1) | US20060147666A1 (de) |
EP (1) | EP1572777A1 (de) |
CN (1) | CN1726245A (de) |
AU (1) | AU2003269668A1 (de) |
BR (1) | BR0316730A (de) |
DE (1) | DE10259694A1 (de) |
EA (1) | EA200500976A1 (de) |
MX (1) | MXPA05005822A (de) |
WO (1) | WO2004055093A1 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10158793A1 (de) | 2001-11-30 | 2003-06-26 | Zimmer Ag | Verfahren und Vorrichtung zur Herstellung von hochkondensierten Polyestern in der festen Phase |
DE102004010680A1 (de) * | 2004-03-04 | 2005-10-06 | Zimmer Ag | Verfahren zur Herstellung von hochkondensierten Polyestern in der festen Phase |
DE102004012579A1 (de) * | 2004-03-12 | 2005-09-29 | Bühler AG | Verfahren zur Herstellung eines teilkristallinen Polykondensates |
US20060047102A1 (en) | 2004-09-02 | 2006-03-02 | Stephen Weinhold | Spheroidal polyester polymer particles |
US20090234329A1 (en) | 2005-10-17 | 2009-09-17 | Kaneka Corporation | Medical Catheter Tubes and Process for Production Thereof |
DE102006012587B4 (de) | 2006-03-16 | 2015-10-29 | Lurgi Zimmer Gmbh | Verfahren und Vorrichtung zur Kristallisation von Polyestermaterial |
FR2944021B1 (fr) * | 2009-04-02 | 2011-06-17 | Solvay | Poly(hydroxyacide) ramifie et procede pour sa fabrication |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4217161A (en) * | 1976-08-10 | 1980-08-12 | Toyo Seikan Kaisha Limited | Process for making a container |
DE2807949A1 (de) * | 1978-02-24 | 1979-08-30 | Ver Verpackungs Gmbh | Verfahren zum herstellen von flaschen aus kunststoff |
US4205157A (en) * | 1979-04-02 | 1980-05-27 | The Goodyear Tire & Rubber Company | Method for production of high molecular weight polyester with low catalyst level and low carboxyl content |
US4482586A (en) * | 1982-09-07 | 1984-11-13 | The Goodyear Tire & Rubber Company | Multi-layer polyisophthalate and polyterephthalate articles and process therefor |
US5510454A (en) * | 1995-01-20 | 1996-04-23 | E. I. Du Pont De Nemours And Company | Production of poly(ethylene terephthalate) |
US5830982A (en) * | 1995-01-20 | 1998-11-03 | E. I. Du Pont De Nemours And Company | Production of poly (ethylene terephthalate) |
US6284866B1 (en) * | 1999-12-07 | 2001-09-04 | Wellman, Inc. | Method of preparing modified polyester bottle resins |
DE10019508A1 (de) * | 2000-04-19 | 2001-10-31 | Rieter Automatik Gmbh | Verfahren und Vorrichtung zur Vertropfung von Vorprodukten thermoplastischer Polyester oder Copolyester |
KR100364496B1 (ko) * | 2000-07-14 | 2002-12-12 | 에쓰대시오일 주식회사 | 마이크로파를 이용한 폴리카보네이트 수지의 제조방법 |
US6403762B1 (en) * | 2000-08-21 | 2002-06-11 | Shell Oil Company | Solid state polymerization process for poly(trimethylene terephthalate) utilizing a combined crystallization/preheating step |
DE10042476A1 (de) * | 2000-08-29 | 2002-03-28 | Tessag Ind Anlagen Gmbh | Verfahren und Vorrichtung zum Herstellen kugelförmiger Partikel aus einer Polymerschmelze |
DE50114433D1 (de) * | 2001-02-26 | 2008-11-27 | Buehler Ag | Verfahren und vorrichtung zur kontinuierlichen polykondensation von polyestermaterial in fester phase |
-
2002
- 2002-12-18 DE DE10259694A patent/DE10259694A1/de not_active Withdrawn
-
2003
- 2003-10-22 MX MXPA05005822A patent/MXPA05005822A/es unknown
- 2003-10-22 WO PCT/CH2003/000686 patent/WO2004055093A1/de not_active Application Discontinuation
- 2003-10-22 AU AU2003269668A patent/AU2003269668A1/en not_active Abandoned
- 2003-10-22 US US10/537,459 patent/US20060147666A1/en not_active Abandoned
- 2003-10-22 CN CN200380106137.5A patent/CN1726245A/zh active Pending
- 2003-10-22 EA EA200500976A patent/EA200500976A1/ru unknown
- 2003-10-22 EP EP03750233A patent/EP1572777A1/de not_active Withdrawn
- 2003-10-22 BR BR0316730-5A patent/BR0316730A/pt not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO2004055093A1 * |
Also Published As
Publication number | Publication date |
---|---|
BR0316730A (pt) | 2005-10-18 |
US20060147666A1 (en) | 2006-07-06 |
DE10259694A1 (de) | 2004-07-01 |
AU2003269668A1 (en) | 2004-07-09 |
EA200500976A1 (ru) | 2005-12-29 |
WO2004055093A1 (de) | 2004-07-01 |
MXPA05005822A (es) | 2005-08-29 |
CN1726245A (zh) | 2006-01-25 |
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