WO2002036850A2 - Procede et dispositif de revetement de corps creux - Google Patents

Procede et dispositif de revetement de corps creux Download PDF

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Publication number
WO2002036850A2
WO2002036850A2 PCT/EP2001/012689 EP0112689W WO0236850A2 WO 2002036850 A2 WO2002036850 A2 WO 2002036850A2 EP 0112689 W EP0112689 W EP 0112689W WO 0236850 A2 WO0236850 A2 WO 0236850A2
Authority
WO
WIPO (PCT)
Prior art keywords
hollow body
coating
interior
plasma
electromagnetic radiation
Prior art date
Application number
PCT/EP2001/012689
Other languages
German (de)
English (en)
Other versions
WO2002036850A3 (fr
Inventor
Rainer Dahlmann
Original Assignee
Vereinigung Zur Förderung Des Instituts Für Kunststoffverarbeitung In Industrie Und Handwerk An Der Rheinisch-Westfälischen Rwth Aachen E.V.
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
Application filed by Vereinigung Zur Förderung Des Instituts Für Kunststoffverarbeitung In Industrie Und Handwerk An Der Rheinisch-Westfälischen Rwth Aachen E.V. filed Critical Vereinigung Zur Förderung Des Instituts Für Kunststoffverarbeitung In Industrie Und Handwerk An Der Rheinisch-Westfälischen Rwth Aachen E.V.
Priority to AU2002216000A priority Critical patent/AU2002216000A1/en
Publication of WO2002036850A2 publication Critical patent/WO2002036850A2/fr
Publication of WO2002036850A3 publication Critical patent/WO2002036850A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical 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
    • C23C16/50—Chemical 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 using electric discharges
    • C23C16/511—Chemical 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 using electric discharges using microwave discharges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to a method for coating hollow bodies according to the preamble of claim 1 and a device according to the preamble of claim 25.
  • Hollow bodies made of plastics are increasingly used primarily for packaging liquid fillers.
  • the barrier properties of plastics such as polyethylene or polyethylene terephthalate are often not sufficient to ensure adequate storage stability to reach. For this reason, there is a great need for economically feasible technologies to improve the barrier properties of hollow plastic articles.
  • technologies for improving the barrier can be found, for example, in the use of so-called high barrier materials or in combination with high barrier materials in the form of multilayer composites.
  • a disadvantage of the inner coating applied in this way can be that the layer surfaces produced come into contact with food. It cannot be ruled out that layer components get into the filling material and in the simplest case lead to changes in taste. Likewise, the method does not necessarily ensure that layer particles completely detach from the wall of the hollow body and thus get into the food.
  • This aspect is harmless for the outer coating, as there is no direct contact with the product.
  • the problem is that a coating zone with a sufficiently large volume that is adapted to the geometry of the bottle has to be created.
  • the hollow bodies are rotated through a plasma zone.
  • This PVD process is additionally supported by a plasma and focused on one zone.
  • a disadvantage of this method is that the wall of the coating chamber is continuously co-coated.
  • gas supply and plasma source systems can also be coated, so that the process conditions can change in the course of some coating processes.
  • the coating chamber is comparatively large in relation to the volume of the hollow body, so that high pump capacities are required.
  • the invention is based on the object of specifying a method and a device for coating hollow bodies in which the evacuation periods and the pump capacity can be reduced for the external coating of hollow bodies.
  • the invention advantageously provides that after evacuation of an external space surrounding the hollow body, layer-forming gases, vapors or mixtures thereof are introduced into the vacuum chamber, which can be excited into a plasma, and electromagnetic radiation is coupled in through the interior of the hollow body
  • the process parameters are set such that a plasma is ignited only in the exterior and the ignition of a plasma is prevented in the interior of the hollow body.
  • the invention enables CVD coating, in particular the outer coating of hollow bodies, with a complex geometry. A plasma is only generated on the outside of the hollow body.
  • the advantage of the invention is that, compared to the PVD method, higher pressures in the range of approximately 10 Pa ⁇ p ⁇ 1000 Pa are possible. Furthermore, since they are surrounded by the hollow body to be coated, the energy sources are not subject to continuous coating, so that the process conditions remain constant from coating to coating.
  • Another advantage is that the size and shape of the vacuum chamber can be adapted to the contour of the hollow body, so that evacuation periods and the pump capacity to be made available can be minimized.
  • the internal pressure of the gas located in the interior of the hollow body is preferably set such that ignition of a plasma in the interior is prevented.
  • Microwaves are introduced into the interior of the hollow body as electromagnetic radiation.
  • Rod antennas are preferably used to couple the microwaves.
  • the rod antennas are partially provided with an electromagnetic shield which serves to homogenize the plasma fire in the axial direction of the antenna and / or to adapt the radiation intensity to complex hollow body geometries.
  • the antenna can be made of a cylinder made of a non-microwave active material, e.g. Quartz glass.
  • the layer deposition can be homogenized by adjusting the ratio of layer-forming gases and carrier gases.
  • hydrocarbons or silicon-containing starting materials are introduced as layer-forming gases or vapors.
  • Argon and / or oxygen can also be used as carrier gases.
  • the hollow body e.g. a bottle consists at least partially of a polymer material.
  • a higher pressure is set in the interior of the hollow body than in the exterior of the hollow body and the hollow body is coated with stretching.
  • the pressure in the interior of the hollow body can be several times the atmospheric pressure. During the coating process, the excess pressure in the interior stretches the hollow body.
  • the coating under stretch has the advantage that the stretch that is applied when the hollow body is subsequently filled does not lead to the layers being torn open.
  • the invention is designed in such a way that negative pressures can also be generated in the interior of the hollow body if pre-stretching does not appear expedient.
  • the hollow body is fixed in the receptacle, the cup-shaped vacuum chamber is lowered above it and the Outside space evacuated via the pump.
  • Suitable gases such as silicon-containing or hydrocarbon-containing or fluorohydrocarbon-containing gases, vapors or mixtures, are then passed into the space between the bottle and the chamber housing and a plasma is generated on the outside of the hollow body by switching on the microwave generator, so that the coating process is initiated , Possibly.
  • plasma or plasma post-treatments can be carried out, for example to clean the surface or to saturate radicals in the surface of the layer.
  • the vacuum chamber is then vented and opened.
  • the microwave intensity can be homogenized on the outside of the hollow body contour by means of partial metallic covers of the antenna. Further access to the homogenization of the layer deposition is possible by adapting the process parameters and using carrier gases.
  • the electromagnetic shielding can consist, for example, of metal sheets or foils which taper to a point towards the free end of the rod antenna and thus only partially cover the circumference of the rod antenna.
  • the interior of the hollow body can be filled or flowed with a gas or a liquid before, during and / or after the coating process, with the aim of cooling, cleaning or sterilizing the inside of the bottle.
  • the electromagnetic radiation can pulsate in time, i.e. be coupled in with time-varying power.
  • gradient layers can be applied during the coating process, the properties of which change continuously or step by step as the layer thickness increases.
  • This process variant allows gradients in the internal tension of the layers to be built up or compensated for, for example with the aim of improving the behavior of the layers under mechanical stress (elongation / bending).
  • the outside of the hollow body can be provided with a scratch-resistant layer, which can be used, for example, for decorative purposes and / or to protect a barrier layer from partial destruction by mechanical loads.
  • the rod antenna can be inserted into the hollow body, and the housing forming the vacuum chamber can consist of two movable half-shells (or of several shells) which enclose the hollow body with the aid of a locking mechanism and thus produce a closed volume which defines the hollow body and the exterior surrounds in which a negative pressure is generated.
  • the inner contour of the vacuum chamber can be adapted to the outer contour of the hollow body, for example in order to minimize pumping volumes and / or to optimize gas flows.
  • the manufacturing process of the hollow body e.g. injection molding, stretch blow molding and / or blow molding process
  • the outer coating in terms of plant technology, for example by using the blow mold by slightly opening it as a vacuum chamber and the expanding mandrel by modification as an antenna for coupling in the electromagnetic radiation.
  • the coating of the hollow body can be combined with a fluid injection process for producing the hollow body.
  • a hollow body can be formed by connecting additional elements to the component which form a hollow body in combination with the component and are therefore suitable for coating with this method.
  • shell-shaped or cup-shaped components are particularly suitable which, in combination with at least one additional element temporarily provided for coating, for example a lid, form a hollow body.
  • tubular or tubular components are also suitable, which also form a hollow body by closing all openings.
  • almost any component shape can be supplemented with additional elements to form a hollow body. After coating, the supplementary elements can be removed.
  • the single figure shows a device for coating hollow bodies 1 made of plastic with a vacuum chamber 2 surrounded by a housing 3, in which the hollow body 1 is arranged.
  • the hollow body 1 consists, for example, of a PET bottle, which is kept upside down and sealed in a base 5 of the device.
  • the vacuum chamber 2 can be evacuated in the area of an outer space 4 relative to the hollow body 1 with the aid of a vacuum pump 10.
  • gases, vapors or mixtures thereof which can be excited into a plasma as a result of electromagnetic radiation, can be introduced into the outer space 4 via a gas feed device 14.
  • the gas supply device 14 has a riser pipe 7 in the vacuum chamber 2, which ends at the upper end of the housing 3, so that the introduced gases and vapors reach the outside space 4 from above.
  • the bell-shaped housing 3 can be removed upwards to populate the hollow body receptacle, while the base 5 is fixed.
  • a device 12 for generating electromagnetic radiation preferably a microwave generator, couples microwaves via at least one rod antenna 8, which extends coaxially to the hollow body 1 into an interior space 6 of the hollow body 1.
  • the rod antenna 8 is partially provided with an electromagnetic shield 20, which is either cylindrical, as shown in the single figure, or consists of elements tapering towards the free end of the rod antenna 8.
  • the electromagnetic shielding from a metallic cover 20 serves to emit the radiation only at the level of the hollow body and to homogenize the plasma fire in the axial direction of the antenna. It enables the radiation intensity to be adapted to complex hollow body geometries.
  • the rod antenna 8 and the partial metallic cover 20 are surrounded by a sleeve-shaped cylinder 22 made of a non-microwave-active material, for example quartz glass.
  • a sleeve-shaped cylinder 22 made of a non-microwave-active material, for example quartz glass.
  • the interior 6 can only contain air under atmospheric pressure or can be pressurized to achieve a higher elongation of the hollow body. If an expansion of the hollow body 1 is not desired, the interior 6 can also be evacuated.
  • the inner pressure in the interior 6 is set in the outer coating in such a way that ignition of a plasma is prevented.
  • a second gas supply device 16 it is also possible to carry out an inner coating sequentially in addition to the outer coating, by introducing gases, vapors or their mixtures, which can be excited into a plasma, into the interior 6 of the hollow body 1 and by a second , conventional device for generating electromagnetic radiation is used, which for example couples microwaves from the outside.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Vapour Deposition (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un procédé de revêtement de corps creux (1), au moyen d'un dépôt de couche constitué d'un plasma. Selon ce procédé, un corps creux est revêtu de l'extérieur dans une chambre à vide (2). Cette invention est caractérisée en ce qu'un rayonnement électromagnétique est injecté à travers l'intérieur du corps creux et des gaz, des vapeurs ou des mélanges de ceux-ci sont introduits dans la chambre à vide (2), dans l'espace extérieur (4) entourant le corps creux (1), et peuvent être activés afin de former un plasma, les paramètres de processus étant réglés de façon à éviter l'activation d'un plasma dans l'espace intérieur (6) du corps creux (1).
PCT/EP2001/012689 2000-11-03 2001-11-02 Procede et dispositif de revetement de corps creux WO2002036850A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002216000A AU2002216000A1 (en) 2000-11-03 2001-11-02 Method and device for coating hollow bodies

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10054653.6 2000-11-03
DE2000154653 DE10054653A1 (de) 2000-11-03 2000-11-03 Verfahren und Vorrichtung zum Beschichten von Hohlkörper

Publications (2)

Publication Number Publication Date
WO2002036850A2 true WO2002036850A2 (fr) 2002-05-10
WO2002036850A3 WO2002036850A3 (fr) 2002-07-18

Family

ID=7662108

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/012689 WO2002036850A2 (fr) 2000-11-03 2001-11-02 Procede et dispositif de revetement de corps creux

Country Status (3)

Country Link
AU (1) AU2002216000A1 (fr)
DE (1) DE10054653A1 (fr)
WO (1) WO2002036850A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007022976A2 (fr) 2005-08-24 2007-03-01 Schott Ag Procede et dispositif de traitement au plasma a l'interieur de corps creux

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10253513B4 (de) * 2002-11-16 2005-12-15 Schott Ag Mehrplatz-Beschichtungsvorrichtung und Verfahren zur Plasmabeschichtung
EP1537253A1 (fr) * 2002-05-24 2005-06-08 Schott Ag Dispositif et procede de traitement de pieces
DE10224547B4 (de) * 2002-05-24 2020-06-25 Khs Corpoplast Gmbh Verfahren und Vorrichtung zur Plasmabehandlung von Werkstücken
DE102004045046B4 (de) * 2004-09-15 2007-01-04 Schott Ag Verfahren und Vorrichtung zum Aufbringen einer elektrisch leitfähigen transparenten Beschichtung auf ein Substrat
DE102011104730A1 (de) 2011-06-16 2012-12-20 Khs Corpoplast Gmbh Verfahren zur Plasmabehandlung von Werkstücken sowie Werkstück mit Gasbarriereschicht
DE102012201955A1 (de) * 2012-02-09 2013-08-14 Krones Ag Powerlanze und plasmaunterstützte Beschichtung mit Hochfrequenzeinkopplung

Citations (7)

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Publication number Priority date Publication date Assignee Title
US5223308A (en) * 1991-10-18 1993-06-29 Energy Conversion Devices, Inc. Low temperature plasma enhanced CVD process within tubular members
US5308649A (en) * 1992-06-26 1994-05-03 Polar Materials, Inc. Methods for externally treating a container with application of internal bias gas
US5368888A (en) * 1991-11-04 1994-11-29 General Electric Company Apparatus and method for gas phase coating of hollow articles
EP0773167A1 (fr) * 1994-08-11 1997-05-14 Kirin Beer Kabushiki Kaisha Recipients de plastique a revetement mince de carbone, leur appareil de fabrication et procede associe
WO1997044503A1 (fr) * 1996-05-22 1997-11-27 Tetra Laval Holdings & Finance S.A. Procede et appareil de traitement des surfaces interieures de recipients
FR2783667A1 (fr) * 1998-03-27 2000-03-24 Sidel Sa Appareil pour la fabrication d'un recipient en matiere a effet barriere
WO2001031680A1 (fr) * 1999-10-25 2001-05-03 Sidel Actis Services Circuit de vide pour un dispositif de traitement d'un recipient a l'aide d'un plasma a basse pression

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JPS63241177A (ja) * 1987-03-27 1988-10-06 Canon Inc マイクロ波プラズマｃｖｄ装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5223308A (en) * 1991-10-18 1993-06-29 Energy Conversion Devices, Inc. Low temperature plasma enhanced CVD process within tubular members
US5368888A (en) * 1991-11-04 1994-11-29 General Electric Company Apparatus and method for gas phase coating of hollow articles
US5308649A (en) * 1992-06-26 1994-05-03 Polar Materials, Inc. Methods for externally treating a container with application of internal bias gas
EP0773167A1 (fr) * 1994-08-11 1997-05-14 Kirin Beer Kabushiki Kaisha Recipients de plastique a revetement mince de carbone, leur appareil de fabrication et procede associe
WO1997044503A1 (fr) * 1996-05-22 1997-11-27 Tetra Laval Holdings & Finance S.A. Procede et appareil de traitement des surfaces interieures de recipients
FR2783667A1 (fr) * 1998-03-27 2000-03-24 Sidel Sa Appareil pour la fabrication d'un recipient en matiere a effet barriere
WO2001031680A1 (fr) * 1999-10-25 2001-05-03 Sidel Actis Services Circuit de vide pour un dispositif de traitement d'un recipient a l'aide d'un plasma a basse pression

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 013, no. 042 (C-564), 30. Januar 1989 (1989-01-30) & JP 63 241177 A (CANON INC), 6. Oktober 1988 (1988-10-06) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007022976A2 (fr) 2005-08-24 2007-03-01 Schott Ag Procede et dispositif de traitement au plasma a l'interieur de corps creux
WO2007022976A3 (fr) * 2005-08-24 2007-04-26 Schott Ag Procede et dispositif de traitement au plasma a l'interieur de corps creux
US8747962B2 (en) 2005-08-24 2014-06-10 Schott Ag Method and device for the internal plasma treatment of hollow bodies

Also Published As

Publication number Publication date
DE10054653A1 (de) 2002-05-08
WO2002036850A3 (fr) 2002-07-18
AU2002216000A1 (en) 2002-05-15

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