EP1537253A1 - Vorrichtung und verfahren zur behandlung von werkst cken - Google Patents

Vorrichtung und verfahren zur behandlung von werkst cken

Info

Publication number
EP1537253A1
EP1537253A1 EP03735458A EP03735458A EP1537253A1 EP 1537253 A1 EP1537253 A1 EP 1537253A1 EP 03735458 A EP03735458 A EP 03735458A EP 03735458 A EP03735458 A EP 03735458A EP 1537253 A1 EP1537253 A1 EP 1537253A1
Authority
EP
European Patent Office
Prior art keywords
treatment
fluid
fluid supply
phase
pump
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Withdrawn
Application number
EP03735458A
Other languages
German (de)
English (en)
French (fr)
Inventor
Stephan Behle
Andreas LÜTTRINGHAUS-HENKEL
Gregor Arnold
Matthias Bicker
Jürgen Klein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
Original Assignee
Schott AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE10224395A external-priority patent/DE10224395A1/de
Priority claimed from DE2002125609 external-priority patent/DE10225609A1/de
Priority claimed from DE10234374A external-priority patent/DE10234374A1/de
Priority claimed from DE2002153512 external-priority patent/DE10253512A1/de
Priority claimed from DE2002153513 external-priority patent/DE10253513B4/de
Priority claimed from DE10258681A external-priority patent/DE10258681A1/de
Application filed by Schott AG filed Critical Schott AG
Publication of EP1537253A1 publication Critical patent/EP1537253A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54Apparatus specially adapted for continuous coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/4205Handling means, e.g. transfer, loading or discharging means
    • B29C49/42069Means explicitly adapted for transporting blown article
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00Details of bottles or jars not otherwise provided for
    • B65D23/02Linings or internal coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0004Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • C23C16/0272Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/029Graded interfaces
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04Coating on selected surface areas, e.g. using masks
    • C23C16/045Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/401Oxides containing silicon
    • C23C16/402Silicon dioxide
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/32431Constructional details of the reactor
    • H01J37/32733Means for moving the material to be treated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/62Plasma-deposition of organic layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00Shaping characteristics in general
    • B29C2791/001Shaping in several steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/4205Handling means, e.g. transfer, loading or discharging means
    • B29C49/42073Grippers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/4205Handling means, e.g. transfer, loading or discharging means
    • B29C49/42073Grippers
    • B29C49/42075Grippers with pivoting clamps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/4205Handling means, e.g. transfer, loading or discharging means
    • B29C49/42093Transporting apparatus, e.g. slides, wheels or conveyors
    • B29C49/42095Rotating wheels or stars
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/4205Handling means, e.g. transfer, loading or discharging means
    • B29C49/42093Transporting apparatus, e.g. slides, wheels or conveyors
    • B29C49/42105Transporting apparatus, e.g. slides, wheels or conveyors for discontinuous or batch transport
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/4205Handling means, e.g. transfer, loading or discharging means
    • B29C49/42113Means for manipulating the objects' position or orientation
    • B29C49/42115Inversion, e.g. turning preform upside down
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/42384Safety, e.g. operator safety
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/64Heating or cooling preforms, parisons or blown articles
    • B29C49/68Ovens specially adapted for heating preforms or parisons
    • B29C49/6835Ovens specially adapted for heating preforms or parisons using reflectors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65GTRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
    • B65G2201/00Indexing codes relating to handling devices, e.g. conveyors, characterised by the type of product or load being conveyed or handled
    • B65G2201/02Articles
    • B65G2201/0235Containers
    • B65G2201/0244Bottles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/14Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

  • the invention relates to a device and a method for treating workpieces with fluids in general and for coating hollow bodies in particular.
  • Plastics in particular transparent plastics, are becoming increasingly important and are replacing glass as the preferred material in many areas.
  • Plastic bottles can also have some disadvantages compared to glass bottles, for example, the plastics used, such as PET, are not sufficiently impermeable to gas, so that the shelf life of carbonated beverages is shorter than that of glass bottles, unless special efforts are made. For this reason, the plastic bottles are coated on the inside, which leads to an increase in shelf life.
  • Typical sample throughputs are in the range of 10,000 bottles per hour.
  • Such a machine with a conveyor carousel for the treatment of hollow bodies is known from the publication WO 00/58631, in which 20 identical treatment stations are arranged on the conveyor carousel.
  • the invention defined in the above-mentioned document is based on the problem that with a large
  • the 20 stations are divided into two groups, each group being assigned to an independent and equivalent pressure source or the groups being differentiated according to which pumps they are connected to.
  • the rotating distributor it is determined at which times of the rotary movement of the conveyor carousel a specific pump is connected to a specific treatment station, for which purpose the distributor contains a rotating ring with 20 openings and a fixed ring with 3 slots each for the two groups ,
  • the machine is designed so that two stations in the same group are not connected to the corresponding pump at the same time.
  • the invention described defines as its subject matter a machine capable of containing a large number of stations and at the same time guaranteeing that a pressure source is only connected to at most one treatment station at a time.
  • the use of the rotatable distributor is particularly disadvantageous. Such distributors are extremely difficult to seal and are susceptible to interference from foreign bodies. In addition, the distributor does not allow any variation of the process flow due to the fixed opening arrangement, so that this is an inflexible concept.
  • the object of the invention is therefore to provide a device and a method for treating workpieces which avoid or at least reduce the disadvantages of known devices or methods.
  • Another object of the invention is to provide a device and a method for treating workpieces which work reliably and ensure high throughput.
  • Another object of the invention is to provide an apparatus and a method for treating workpieces who are flexibly adaptable to the needs of the user or the desired process flow.
  • a still further object of the invention is to provide an apparatus and a method for treating workpieces, which ensures an improved fluid supply, which in particular allows low-interruption operation.
  • Yet another object of the invention is one
  • a device for treating workpieces in particular for internally coating hollow bodies, is provided.
  • Workpieces to be coated are in particular plastic containers, e.g. Beverage bottles.
  • the device according to the invention comprises at least one treatment device, preferably a plurality of identical treatment devices, each of which is set up to receive at least one workpiece or a plastic bottle, and a fluid supply device which supplies the treatment device with at least one process fluid the coating supplies.
  • the device further comprises at least one fluid control device, in particular a first valve arrangement with a plurality of valves, the fluid supply to the treatment devices being controllable by means of the first valve arrangement, in particular by means of the valves.
  • Gas supply is highly flexible and variably programmable using the first valve arrangement.
  • the timing or the process sequence, which the device defines can be changed and easily adapted to different requirements.
  • the invention enables short switching times and thus a quick change in the process parameters.
  • the device according to the invention works reliably and with a high throughput.
  • the invention permits efficient and thus long-term cost-effective treatment or coating of the workpieces of excellent quality.
  • a plurality of, in particular identical, treatment devices is preferably provided and the first valve arrangement comprises a plurality of, in particular identical, valve groups, each treatment device being assigned a separate valve group.
  • the valve groups preferably each comprise a plurality of possibly identical valves.
  • the device defines a plurality of, in particular different, process phases, each of which is treated by the treatment devices. More precisely, each treatment facility runs through all of them in succession
  • Process phases so that in particular at least two or all treatment devices are in different process phases at at least one or at any time.
  • Each process phase is assigned a predetermined state of the first valve arrangement, the state for each phase being variably adjustable by means of a recipe.
  • a recipe is understood to mean a, in particular predetermined, process sequence via the control.
  • freely adjustable parameters e.g. Switching times, switching angles and / or switching times etc. achieve greater flexibility.
  • the recipe the assignment to the process phases and / or the duration of the process phases for different workpieces, e.g. different bottle volumes and geometries set differently, which makes the invention even more flexible.
  • each process phase is temporally correlated with a predetermined state of the valve group permanently assigned to the respective treatment device.
  • the process phases become everyone Treatment device controlled by the associated valve group or the respective process phase of each treatment device is defined by the state of the associated valve group.
  • the first valve arrangement in particular each valve group or the valves, can preferably be controlled by means of control signals, preferably independently of one another.
  • the valve arrangement or the valve block or the valves are controlled in particular electrically, pneumatically and / or hydraulically etc., which has a positive effect on the control times and thus on the process speed.
  • the device defines at least two or more process phases, the workpiece being coated with a first or second coating during at least a first and a second process or coating phase.
  • the first and second coating in particular comprise different materials.
  • Treatment devices are each assigned at least one orifice plate with a predetermined opening, preferably of the same size, for reducing the pressure in the fluid supply.
  • the orifice defines a predetermined flow rate at a defined pre-pressure. This is an extremely simple and inexpensive way of reducing pressure.
  • the device comprises a
  • Fluid distribution device by means of which the fluid is distributed to the treatment devices and / or a flow quantity setting means, e.g. a mass flow controller, which in the fluid flow direction before the
  • Fluid distribution device is arranged.
  • the fluid or gas flow can thus be set centrally for all treatment facilities.
  • the invention allows a quick change of at least one of the following process parameters: - Composition of the process fluid or a precursor
  • Process parameters in the treatment facilities can be set independently of one another and / or at a freely selectable point in time.
  • the fluid supply device preferably provides a number of different fluids, in particular process gases, in particular each valve group for each Fluid has a separate valve and / or a separate orifice for each treatment device. This means in particular that the different fluids are fed to the treatment devices in separate feed lines and the fluid flows can be controlled independently of one another.
  • Two- or multi-layer systems are advantageous for the coating of plastics in order to meet the requirements placed on the layer-substrate composite.
  • a first organic compound for example, a first organic compound
  • the adhesion promoter layer increases the adhesion and prevents or at least prevents undesired peeling off of the layers. Furthermore, the combination of the two layers, in a synergetic manner, has the effect that the adhesion promoter layer further enhances the barrier effect.
  • a two- or multi-component coating as provided by the invention is therefore particularly advantageous in the case of workpieces in the form of plastic beverage bottles, since the shelf life of the beverage can be extended and at the same time an undesired entry of the layer material into the beverage is avoided.
  • a gas generation process with the fluid supply device and a coating process advantageous, which provides at least two different gases or gas mixtures.
  • each of the treatment devices comprises at least two or more treatment stations or reactors, which are each designed to hold a workpiece and which are in particular constructed in parallel and symmetrically and are thus switched and connected to the process stages at the same time Set the same process parameters in the treatment stations.
  • the treatment stations and thus the respectively picked workpieces of a specific treatment device pass through the process phases in such a way that the respective treatment stations are in the same process phase at least at one point in time, in particular at each point in time.
  • the treatment places are therefore preferably divided into two or more groups, with each group in particular being assigned to exactly one treatment device and the treatment places being connected in such a way that at least the evacuation of the treatment places of the same group or treatment device is synchronous, so that at least two treatment places, in particular the treatment places the same group are at least temporarily connected to the same pump at the same time.
  • the treatment places are assigned to a respective treatment device of the same valve group.
  • a number of two, one, has proven particularly useful Multiples of two, in particular four, six, eight or more treatment stations or reactors per treatment facility.
  • Treatment device can increase the throughput of the device considerably with little additional effort.
  • the process gases are in particular evenly distributed over several or all reactors, preferably 10 to 100 pieces.
  • the individual reactors either have separate gas feeds or the reactor groups, e.g. Double reactors supplied with the process gases.
  • the device preferably defines a treatment cycle with a plurality of process phases, the treatment cycle being carried out by at least one or each treatment device with a time delay to the other treatment devices.
  • at least one or each valve group passes through a predetermined cycle of states, with each process phase of a respective treatment device relating to a specific, but. controllable state of its associated valve group is correlated.
  • Each treatment device preferably runs through the identical treatment cycle, in particular at least with regard to the sequence, timing, duration and / or time interval of the phases.
  • the device according to the invention is in particular a continuous or rotary machine and comprises a static one and a movable section or rotor.
  • the treatment devices are preferably arranged on the movable section or the rotor and move or rotate with the latter.
  • Each treatment device assumes a plurality of positions or angular positions during the treatment cycle, each position being correlated to a predetermined process phase.
  • the process phases are synchronized with the positions or angular positions, this synchronization also being controllable.
  • the valve groups are preferably controlled synchronously with the angular position of the rotor.
  • the first valve arrangement is particularly preferably attached to the movable section or rotor so that it also moves or rotates. This allows a simple fluid feedthrough to be used.
  • An embodiment of the invention is particularly advantageous in which a pump device is provided for at least temporarily evacuating the treatment devices with at least one pump, e.g. a root pump.
  • the pump device can be connected to the treatment devices in a fixed manner or without a rotating distributor, and the phase-by-step evacuation, the treatment devices, more precisely the beginning and / or the end of the evacuation phases, is controlled, possibly regulated, by an evacuation control device. This is particularly advantageous in the case of the rotary system.
  • the evacuation control device controls the association between the treatment devices and the pump device and preferably comprises a second valve arrangement, so that the evacuation is controlled via valves.
  • the second or pump-side valve arrangement is preferably also subdivided into valve groups such that each treatment device is assigned a valve group, in particular one valve of the valve groups being assigned to a delivery device or vacuum pump in order to achieve independent control of the assignment of the individual vacuum pumps.
  • the valves are preferably of the same type as the valves of the first or fluid supply-side valve arrangement.
  • Treatment devices are preferably evacuated cyclically and the control by means of the evacuation control device takes place via e.g. changeable control signals.
  • the evacuation and / or the fluid supply are preferably variable and / or individually controllable with respect to the respective treatment devices.
  • the pump device preferably comprises at least two pumps, which are assigned to different pressure ranges and effect a cascaded or step-by-step evacuation.
  • each treatment device is first connected to a first pump and evacuated to a first pressure value, in order subsequently to be separated from the first pump and connected to a second pump and to be evacuated by the second pump to a second, lower pressure value.
  • each treatment device passes through several different process phases during the rotation of the rotor
  • the pump device comprises at least one first and second pump stage, which are assigned to different pressure ranges and the corresponding treatment device is successively evacuated by means of the first and second pump stage.
  • at least a third and / or fourth is the
  • Process phases each have a coating phase, during which the corresponding treatment device is evacuated by means of the pump device, in particular by means of a third or fourth pump stage, while at the same time a process gas for plasma coating is supplied.
  • first and second pump stages each consist of exactly one first and second vacuum pump, respectively, so that all treatment devices are connected to the first vacuum pump in their first pumping phase and to the second vacuum pump in their second pumping phase and are evacuated.
  • the pump device is preferably arranged or fastened in a rotating manner on or on the rotor.
  • first and second are preferred
  • Treatment station of the respective treatment facility is simultaneously connected to the pump stage associated with the respective process or pumping phase and evacuated. This is because the inventors have found that it is advantageous to evacuate several treatment stations or stations at the same time with the same pump, since the process flow can be improved and an increased throughput can be achieved in this way.
  • Treatment facilities at different times and / or with respect to the treatment places of a particular treatment facility take place simultaneously.
  • the parameter changes are switched cyclically with respect to the rotation of the rotor or at equal time intervals.
  • different process parameters are set simultaneously in at least two reactors. Furthermore, there is at least one treatment device in each of the first and second coating phases in essentially each rotor position, so that the treatment devices are subdivided into a first and a second process group with a first and a second parameter setting at all times.
  • the number of reactors with the first parameter setting is preferably less than or equal to the number of reactors with the second parameter setting that the second coating phase takes just as long or longer than the first.
  • This concept is particularly advantageous for rotary devices, but can also be used in batch plants in which individual reactor groups are supplied with process gas with a time delay.
  • the advantage for batch systems is that a lower total flow for the entire device and thus also a lower suction capacity for the vacuum pumps is required than when the gases are simultaneously introduced into all treatment facilities or a completely synchronized process.
  • the two successive coating phases preferably differ in at least one of the following parameters:
  • the fluid supply device is preferably arranged on the static section of the device, so that fluid storage containers or bottles can advantageously be changed without having to stop the rotor.
  • the fluid supply device preferably comprises at least two fluid supply devices with different fluid base materials for producing the at least two coatings, so that the first and second layers with the first and second fluid are applied during two different process or coating phases.
  • the workpieces are coated with chemical vapor deposition (CVD), in particular plasma-enhanced CVD (plasma enhanced CVD, PECVD) or CVD with pulsed plasma (plasma impulse CVD / PICVD).
  • CVD chemical vapor deposition
  • the fluid is preferably supplied to the treatment devices via a rotatable sealing connection in the fluid supply, by means of which the fluid supply device is connected to the treatment devices, if necessary indirectly, with the interposition of further devices, in particular the first valve arrangement, the fluid in particular when the device is operating at the outlet of the connection is continuously removable for the treatment facilities.
  • the flow amount setting means are arranged downstream of the fluid supply device, downstream of the flow amount setting means there is a separate mixing device for mixing the fluid from the fluid supply device with at least one additional fluid for each fluid supply device, the connection is arranged downstream of the mixing device, and the fluid distribution device is downstream of the connection, the orifices are arranged downstream of the fluid distribution device and / or the valve groups are each arranged downstream of the associated orifices.
  • the screens are preferably located and / or valves close to the respective reactor, for example at a distance of ⁇ 50 cm, ⁇ 30 cm or ⁇ 15 cm and / or arranged on the rotor.
  • each treatment device, or its treatment places going through a treatment cycle which comprises at least the following process phases, preferably in this order: equipping and closing the treatment device,
  • the device comprises a fluid supply device which comprises a first fluid supply device for a first fluid base material, a fluid supply for a first mixed fluid, a mixing device by means of which the first fluid base material and the first mixed fluid are mixed fluid-tight first line which connects the first fluid supply device to the mixing device, a fluid-tight second line which connects the fluid supply for the first mixed fluid to the mixing device, and a first flow quantity setting means in the first line, in particular upstream of the mixing device, by means of which the flow quantity of the first fluid base is adjustable includes.
  • the first fluid base material is particularly preferably liquid in the first fluid storage device.
  • the first line is heated in order to vaporize the first fluid base material, so that the first fluid base material and the first mixed fluid are both miscible in the gaseous state on the mixing device.
  • a process fluid which is gaseous at room temperature is thus provided at the outlet of the mixing device.
  • the fluid supply device preferably also has a second flow quantity setting means, which is arranged in the second line, in particular upstream of the mixing device and by means of which the flow quantity of the first mixed fluid is set.
  • the fluid supply device preferably also comprises a second fluid supply device, which is constructed like the first fluid supply device, and the first and second fluid supply devices contain different fluid base materials. This will e.g. for coating with two different ones
  • the process gases are preferably mixtures of firstly a metal- or silicon-containing and / or hydrocarbon-containing fluid and secondly at least one further fluid which contains oxygen, nitrogen, argon and / or helium.
  • An HMDS ⁇ / ⁇ 2 mixture from the first and an HMDSN / ⁇ 2 mixture from the second fluid supply device are particularly preferred.
  • the first and / or second further preferably comprise
  • Fluid supply device each have two redundant containers with the same fluid base material.
  • the redundant containers are connected to one another in particular upstream of the first flow quantity setting means and can be separated therefrom with a valve in each case.
  • the device preferably also comprises one
  • Flushing device for purging the treatment devices or reactors with a purge gas, preferably oxygen, nitrogen and / or dried air. It is preferred to rinse after the second layer has been applied, before or after and / or continuously after the aeration. Unused gas is thus advantageously removed, so that undesirable reactions with the atmospheric humidity can be avoided or reduced. Furthermore, the absorption of the process gases on a surface of the workpiece is reduced. In a preferred embodiment, all are rinsed
  • Treatment facilities at different times, preferably cyclically or at the same time intervals.
  • the invention is explained in more detail below on the basis of exemplary embodiments and with reference to the drawings, the same and similar elements being provided with the same reference symbols and the features of different embodiments being able to be combined with one another.
  • Fig. La-lh is a schematic representation of a first
  • Fig. 3 is a schematic representation of the device from Fig. La-lh. Fig. 4 'is an enlarged section X from Fig. 3 and
  • FIG. 5 shows a further enlarged detail from FIG. 3 with the fluid supply device 80.
  • FIG. 1 a shows a schematic illustration of a rotor 32 of a device 30 according to the invention.
  • Each treatment facility comprises two treatment stations or reactors, which are numbered from 1 to 24.
  • the treatment facilities are evenly distributed, i.e. with an angular distance of 30 °.
  • a start phase S a first pump phase PI, a second pump phase PII, a first coating phase BI, a second coating phase BII, a ventilation phase V, a final phase E, and an auxiliary phase A
  • FIG. 1 a shows a temporal state in which the treatment places 1 and 2 are in the star phase S.
  • Treatment places specified. Treatment places 3 and 4 are in the first pumping phase PI, treatment places 5 and 6 in the second pumping phase PII, treatment places 7 and 8 in the first coating phase BI, treatment places 9 to 16 in the second
  • Coating phase BII the treatment places 17 to 20 in the ventilation phase V, the treatment places 21 and 22 in the final phase E and the treatment places 23 and 24 in the auxiliary phase A.
  • FIGS. 1c to 1h a further rotated state of the rotor is shown, the reactors 1 and 2 each being in a further process phase.
  • FIGS. 1 a to 1 h thus show a complete treatment cycle, the illustration of the states in which the process phase of reactors 1 and 2 does not change not being shown.
  • the treatment device with the reactors 1 and 2 is in the start phase S, in which the treatment device is opened. Furthermore, the two are in one insertion process
  • Reactors 1 and 2 are simultaneously and identically equipped with a PET bottle and closed again.
  • the two reactors 3 and 4 are simultaneously connected to a first pump stage in order to be evacuated to a first pressure value.
  • the treatment devices are evacuated gradually and therefore very effectively by means of the first and second pumping stages.
  • the two PET bottles located in the reactors 7 and 8 are coated from the inside with a first coating, more precisely an SiO x C y adhesive layer.
  • a first coating more precisely an SiO x C y adhesive layer.
  • HMDSO hexa-methyl-disiloxane
  • oxygen is used as the process gas. This mixture is introduced into the two reactors 7 and 8 simultaneously.
  • Reactors 7 and 8 are in the first
  • Coating phase BI supplied with a first process gas and evacuated in flow through a third vacuum pump.
  • the second coating phase BII takes up four 30 ° sectors of the treatment cycle, since the coating should take place four times as long as the first coating phase BI. Accordingly, four treatment devices or plasma stations, more precisely the reactors 9 to 16, are simultaneously in the second coating phase BII, in which they are supplied with a second process gas and are evacuated together by a fourth vacuum pump in flow mode. There is therefore a different number of treatment devices in the first and second coating phases, in particular at all times.
  • a glass-like silicon oxide or SiO x barrier layer is deposited. It is colorless transparent.
  • a mixed gas of hexa-methyl-disilazane (HMDSN) and oxygen is introduced into the reactors to produce the barrier layer.
  • the coating in the first and second coating phases BI, BII is carried out using PICVD.
  • the PICVD method is only used for the inner coating of the bottles, but can also be used for an outer coating.
  • a great advantage of the PICVD process is an additional one
  • the double coating achieves excellent adhesion of the coating system and a high barrier improvement value (BIF) at the same time.
  • BIF barrier improvement value
  • the 0 2 entry into the bottle and the acetaldehyde exit from the PET into the drink can also be reduced.
  • the reactors 17 to 20 are aerated. After that. the reactors 21 and 22 are opened in the final phase E and the coated bottles are removed.
  • FIGS. 2a to 2b show in a tabular overview divided into 5 ° angle steps the sequence of the process phases S, PI, PII, BI, BII, V and A of all 24 reactors.
  • the coating device 30 comprises the rotor 32 and a stationary fluid supply device 80.
  • the dashed line L schematically represents the rotor or the plasma wheel 32, so that those components which are shown within the line L are arranged on or on the rotor 32 and with it co-rotate.
  • Twelve treatment devices 101 to 112 are arranged on the rotor 32, of which only the four treatment devices 101, 102, 111, 112 are shown in FIG. 3 for the sake of clarity.
  • Each treatment device 101 to 112 comprises two treatment stations or reactors for receiving a PET bottle to be coated.
  • the treatment device 101 comprises the treatment places 1 and 2, the treatment device 102 the treatment places 3 and 4 etc. up to the treatment device 112, which comprises the treatment places 23 and 24.
  • the inside of the PET bottles is coated using the PICVD technology, which is known to the person skilled in the art.
  • the same high-frequency source and the coating are assigned to the two reactors of a treatment facility in the two reactors takes place simultaneously and in an identical manner, the two reactors each comprising separate chambers or vacuum chambers.
  • the respective first reactors therefore preferably form
  • Treatment facilities 101 to 112 a second group of treatment stations, each having a reactor of the first and the second group are assigned to each other in pairs (1 and 2; 3 and 4; 5 and 6; ...; 23 and 24) and the two reactors each Couple are assigned to the same vacuum pumps and / or run through the treatment process synchronously.
  • the treatment devices 101 to 112 are assigned a fluid-tight fluid or gas control device 40, which in this example comprises a plurality of valves and orifices.
  • the gas supply to the treatment devices is timed by means of the gas control device 40.
  • the gas control device 40 comprises a first valve arrangement 50, each with a valve group 501 to 512 for each treatment device 101 to 112.
  • the parallel valve groups 501 to 512 each comprise three electrically controlled valves 501a to 512a, 501b to 512b and 512a to 512c, each of which a fixed aperture is connected upstream.
  • the division or allocation of the process gases to the treatment facilities takes place via the valves 501a / b to 512a / b.
  • a rotating rotary leadthrough or rotary coupling can also be used, in which in particular channels are provided, by means of which the cyclical gas changes are realized.
  • control via valves is more flexible and
  • Treatment facilities can thus even be controlled separately and / or differently.
  • FIG. 4 shows parts of the fluid control in greater detail than FIG. 3, in FIG.
  • valve group 501 The gas control-side valve control is explained below using the example of the first valve group 501.
  • the remaining valve groups 502 to 512 and the corresponding further components upstream and downstream of each valve group are of identical design.
  • the first valve group 501 comprises three electro-pneumatic valves 501a, 501b, 501c connected in parallel.
  • the first valve 501a supplies the treatment device 101 with the first process gas, the second valve 501b with the second process gas and the third valve 501c with a purge gas SG.
  • the supply of the operating resources or gases can be selected independently of one another and at any time or can be variably controlled.
  • the valves each have a short switching time of
  • valves are preferably at a distance of the treatment devices
  • coating parameters such as the precursor concentration, the total flow, the pressure and / or the process gas or Precursor can be controlled or changed. At least a 95 percent mixture change can be achieved in less than 200 ms.
  • a fixed orifice 601a, 601b, 601c is connected upstream of the valves 501a, 501b, 501c, so that each treatment device is assigned a pair of valves and orifices.
  • the hole diameter of the panels is small against the
  • the hole diameter is approximately 0.1 mm to 5 mm, preferably 0.2 mm to 2 mm, particularly preferably in the range of 1 mm. This results in a pre-defined pressure in an equilibrium state on both sides of the orifice. This solution with orifices is considerably less expensive than the use of a large number of mass or molecular flow controllers at this point.
  • the orifices distribute the fluids evenly or symmetrically across all reactors. For example, a total flow of 9600 sccm for 24 reactors is evenly divided to 400 sccm per reactor.
  • the orifices have a relative deviation of ⁇ 20%, preferably ⁇ 10%, so that the process gases are distributed evenly over the treatment devices.
  • the gas supply is from the fluid or
  • Gas supply device 80 which provides the two different process gases via two separate supply lines or operating medium supply lines 42a, 42b posed.
  • the two process gases and the purge gas SG are continuously fed to the rotor 32 via a rotary union 82.
  • the gas supply device 80 which is shown in detail in FIG. 5, comprises a first and second fluid or gas supply device 80a, 80b, which are constructed identically. The only difference between the two gas supply devices 80a, 80b is that two different fluids
  • the two gas supply devices 80a, 80b thus provide at least two process gases or gas mixtures with different compositions, flows and / or pressures for the at least two successive or merging coating phases BI and BII, the first and the second process gas using the first process gas the second coating is made.
  • the gas exchange between the two process gases or gas mixtures can be switched over quickly, which among other things allows precise control of the concentration of the gas mixtures.
  • the first gas supply device 80a comprises a fluid supply device 81a with two fluid containers or
  • Barrels 84a, 85a both having an identical first precursor, in this example HMDSO.
  • the redundant design of the two containers 84a, 85a allows the replacement of one of the two containers while the treatment continues.
  • the HMDSO from one of the two containers 84a, 85a is sent via a first line section 86a or 87a, a first Flow amount setting means or mass flow controller 88a (so-called mass flow controller) supplied.
  • the flow quantity of the first fluid base material is controlled by means of the preferably thermal or pressure-based mass flow controller 88a.
  • the first gas supply device comprises a feed line 90a, via which gaseous oxygen (0 2 ) is made available.
  • the flow amount of oxygen is determined by means of a second flow adjustment device or mass flow
  • Controllers 92a controlled. This means that only one mass flow controller is required for each process gas component.
  • the mixing ratios, flows and / or concentrations of the process gases can be set independently of one another via the mass flow controllers 88a, 88b, 92a, 92b.
  • the first fluid base material and the oxygen are supplied via two line sections 94a and 96a to a first mixing device 98a and mixed to form the first process gas, which is then provided via line 42a on the rotary union 82 and is supplied to the treatment devices.
  • the line sections between the two fluid containers 84a, 85a and the first mixing device 98a are heated to approximately 40 ° C. in order to evaporate the first fluid base material, which is liquid in the two containers 84a, 85a.
  • the gas mixture or first process gas is gaseous even at room temperature.
  • only a relatively short section of the fluid lines is thus heated.
  • Line sections 86a, 87a, 94a, 86b, 87b and 94b are shaded.
  • an independently controllable heating device 186a and 187a is provided for the line sections 86a and 87a of the redundant fluid containers 84a and 85a, so that even one
  • an independent heating device 194a is provided for the common line section 94a.
  • the second gas supply device 80b is structurally identical to the first fluid supply device 80a. Corresponding components are provided with the same reference numbers and the addition “b” instead of "a”.
  • the two containers 84b, 85b contain HMDSN as the second precursor.
  • Different mixing ratios are preferably set via the mass flow controllers 88a, 92a, 88b, 92b by the two or optionally further fluid supply devices 81a, 81b.
  • the treatment devices 101 to 112 are assigned an evacuation control device with a second valve arrangement 70, by means of which the phase-wise evacuation of the treatment devices 101 to 112 or the reactors 1 to 24 is controlled.
  • the second valve arrangement 70 comprises for each treatment device 101 to 112 a valve group 701 to 712, each with a first and a second electrically controlled valve for successive two-stage evacuation by means of a first and a second vacuum pump 72, 74.
  • the vacuum pumps 72, 74 are designed as root pumps and are attached to the rotor 32. This advantageously eliminates a rotary feedthrough on the pump side.
  • a control valve 76, 78 for example a flapper valve, is connected upstream of the two root pumps 72, 74, which form the pump device 71.
  • the gas pressure for the respective process gas is controlled or regulated by means of the flapper valves.
  • the first valve 701a to 712a of the valve groups 701 to 712 is opened, so that each treatment device is connected to the first root pump 72 and is evacuated.
  • the first valve 701a to 712a of the valve groups 701 to 712 closes and essentially simultaneously opens the second valve 701b to 712b of the valve groups 701 to 712 in order to connect the treatment devices 101 to 112 to the second root pump 74, so that the treatment devices are evacuated in the second pumping phase PII.
  • a gas ballast valve 73 or 75 is connected upstream of the root pumps 72, 74 (only shown in FIG. 4), by means of which the process gas concentration in the exhaust gas can be reduced. This is particularly advantageous in the case of explosive gas mixtures, since in particular unused process gas is diluted and the explosion limit can thus be safely undershot.
  • the PET bottles are coated PICVD accordance with an organic adhesive layer.
  • valves 501a to 512a close and substantially simultaneously the valves 501b to 512b open to the treatment devices with the second
  • At least two of the valve groups 501 to 512 are particularly preferably switched synchronously, the associated treatment devices changing from one to another process phase and such that one Treatment device changes to the previous process phase of another treatment device.
  • the treatment device 101 with the stations 1 and 2 changes from the second coating phase BII to the ventilation phase V and synchronously, that is to say the changes simultaneously
  • Treatment device 109 with the stations 17 and 18 in the second ventilation phase BII.
  • the treatment devices preferably remain connected to the second root pump 74 in order to enable the PICVD coating in flow mode.
  • Treatment devices 101 to 112 optionally aerated with nitrogen or dried air.

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EP03735458A 2002-05-24 2003-05-26 Vorrichtung und verfahren zur behandlung von werkst cken Withdrawn EP1537253A1 (de)

Applications Claiming Priority (23)

Application Number Priority Date Filing Date Title
DE10223288 2002-05-24
DE10223288 2002-05-24
DE10224395A DE10224395A1 (de) 2002-05-24 2002-06-01 Verfahren und Vorrichtung zur Plasmabehandlung von Werkstücken
DE10224395 2002-06-03
DE10225607 2002-06-07
DE10225607A DE10225607A1 (de) 2002-05-24 2002-06-07 Verfahren und Vorrichtung zur Plasmabehandlung von Werkstücken
DE2002125609 DE10225609A1 (de) 2002-06-07 2002-06-07 Verfahren und Vorrichtung zur Plasmabehandlung von Werkstücken
DE10225609 2002-06-07
DE10225985 2002-06-11
DE10225985A DE10225985A1 (de) 2002-05-24 2002-06-11 Verfahren und Vorrichtung zur Plasmabehandlung von Werkstücken
DE10227637A DE10227637A1 (de) 2002-05-24 2002-06-20 Verfahren und Vorrichtung zur Plasmabehandlung von Werkstücken
DE10227637 2002-06-20
DE10229529 2002-07-01
DE10229529A DE10229529A1 (de) 2002-05-24 2002-07-01 Verfahren und Vorrichtung zur Behandlung von Werkstücken
DE10234374 2002-07-27
DE10234374A DE10234374A1 (de) 2002-07-27 2002-07-27 Verfahren und Vorrichtung zur Handhabung von Werkstücken
DE10253513 2002-11-16
DE2002153512 DE10253512A1 (de) 2002-11-16 2002-11-16 Rundläufermaschine für CVD-Beschichtungen
DE10253512 2002-11-16
DE2002153513 DE10253513B4 (de) 2002-11-16 2002-11-16 Mehrplatz-Beschichtungsvorrichtung und Verfahren zur Plasmabeschichtung
DE10258681A DE10258681A1 (de) 2002-08-07 2002-12-13 Verfahren zum Herstellen von glatten Barriereschichten und Verbundmaterial mit glatter Barriereschicht
DE10258681 2002-12-13
PCT/EP2003/005473 WO2003100120A2 (de) 2002-05-24 2003-05-26 Vorrichtung und verfahren zur behandlung von werkstücken

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US7810448B2 (en) 2010-10-12
MXPA04011431A (es) 2005-08-15
WO2003100120A2 (de) 2003-12-04
AU2003237678A1 (en) 2003-12-12
US20060099340A1 (en) 2006-05-11
CN100469943C (zh) 2009-03-18
CA2484023A1 (en) 2003-12-04
JP2005531688A (ja) 2005-10-20
CN1656245A (zh) 2005-08-17

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