DE4320388A1 - Process for the pretreatment of plastic part surfaces to be painted - Google Patents

Process for the pretreatment of plastic part surfaces to be painted

Info

Publication number
DE4320388A1
DE4320388A1 DE19934320388 DE4320388A DE4320388A1 DE 4320388 A1 DE4320388 A1 DE 4320388A1 DE 19934320388 DE19934320388 DE 19934320388 DE 4320388 A DE4320388 A DE 4320388A DE 4320388 A1 DE4320388 A1 DE 4320388A1
Authority
DE
Germany
Prior art keywords
treatment gas
fluorine
plastic parts
mbar
gas
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Withdrawn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
DE19934320388
Other languages
German (de)
Inventor
Bernd Moeller
Horst Schiffer
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.)
AHLBRANDT SYSTEM GmbH
Original Assignee
AHLBRANDT SYSTEM GmbH
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 AHLBRANDT SYSTEM GmbH filed Critical AHLBRANDT SYSTEM GmbH
Priority to DE19934320388 priority Critical patent/DE4320388A1/en
Priority to DE59405938T priority patent/DE59405938D1/en
Priority to DK94106295T priority patent/DK0629654T3/en
Priority to ES94106295T priority patent/ES2115799T3/en
Priority to EP94106295A priority patent/EP0629654B1/en
Priority to AT94106295T priority patent/ATE166089T1/en
Publication of DE4320388A1 publication Critical patent/DE4320388A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08J7/126—Halogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
    • B05D3/044—Pretreatment
    • B05D3/0446—Pretreatment of a polymeric substrate
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

Plastic parts made from polyethylene, polypropylene or comparable materials are pretreated for painting (coating, varnishing, enamelling) by exposure in a reaction container to a fluorine-containing treatment gas at an absolute pressure of from about 333 to 400 mbar. The treatment gas contains 3-5 per cent by volume of fluorine and, in addition to at least one other inert gas constituent, 3-4.5 per cent by volume of oxygen. The exposure time of the treatment gas is from about 10 to 180 seconds.

Description

Die Erfindung betrifft ein Verfahren zur Vorbehandlung von zu lackierenden Oberflächen von Kunststoffteilen aus Polyäthylen-, Polypropylen oder vergleichbaren Werkstoffen durch Einwirkung eines fluorhaltigen Behandlungsgases in­ nerhalb einer geschlossenen Reaktionskammer auf die Kunststoffteile.The invention relates to a method for pretreatment of surfaces to be painted from plastic parts Polyethylene, polypropylene or comparable materials by exposure to a treatment gas containing fluorine in within a closed reaction chamber on the Plastic parts.

Ein Verfahren der vorstehenden Art ist beispielsweise in der DE-A-41 05 179 beschrieben. Bei ihm wird die Reakti­ onskammer mit den in ihr untergebrachten Kunststoffteilen zunächst evakuiert. Dann läßt man aus einem Speicherbe­ hälter ein dort zuvor bereitetes Behandlungsgas, welches Fluor enthält, in die Reaktionskammer strömen, so daß die Oberflächenbehandlung erfolgen kann. Bei dem bekannten Verfahren wird davon ausgegangen, daß die Reaktionskammer möglichst weitgehend evakuiert werden muß, bevor das Be­ handlungsgas eingelassen wird. Tatsächlich arbeitet das Verfahren mit Drücken von 0,2 bar in der Reaktionskammer. Die Erzeugung noch geringerer Drücke würde einen tech­ nisch zu hohen Aufwand bedingen und zu unerwünscht langen Abpumpzeiten führen.A method of the above type is described, for example, in DE-A-41 05 179. With him the reacti Chamber with the plastic parts housed in it first evacuated. Then you leave a storage area contain a previously prepared treatment gas, which Contains fluorine, flow into the reaction chamber so that the Surface treatment can be done. With the well-known Process is assumed to be the reaction chamber must be evacuated as far as possible before the loading gas is admitted. It actually works Process with pressures of 0.2 bar in the reaction chamber. The generation of even lower pressures would be a tech nisch too much effort and too long Pump down times.

Die US-A-4,296,151 beschreibt auch schon ein Verfahren zur Oberflächenbehandlung von Kunststoffteilen, welches mit Normaldrücken arbeitet. Als Behandlungsgas wird dort ein Gemisch aus 10 Vol-% Fluor und 90 Vol-% Stickstoff verwendet. Für beide beschriebene Ausführungsbeispiele wird ausdrücklich gesagt, daß durch das Behandlungsgas die Luft in der Reaktionskammer ausgetauscht werden soll. US-A-4,296,151 already describes a method for the surface treatment of plastic parts, which works with normal pressures. As a treatment gas there is a mixture of 10% by volume fluorine and 90% by volume nitrogen used. For both exemplary embodiments described it is expressly said that through the treatment gas the air in the reaction chamber is to be exchanged.  

Die Vorstellung, daß bei der Fluorbehandlung Sauerstoff in der Reaktionskammer schädlich ist und das Behandlungs­ gas möglichst ausschließlich aus Fluor und einem Inertgas bestehen soll, kommt besonders stark in der FR-A-2,154, 694 zum Ausdruck. Diese Schrift befaßt sich mit der Fluo­ rierung von Polyestergewebe zum Zwecke eines anschlie­ ßenden Färbens des Gewebes. Mehrfach ist in dieser Schrift gesagt, daß das Behandlungsgas praktisch keinen Sauerstoff enthalten soll. Als Grund hierfür wird ange­ führt, daß durch das Fehlen von Sauerstoff sich die er­ forderliche Behandlungszeit verkürzt.The idea that in fluorine treatment oxygen in the reaction chamber is harmful and the treatment gas, if possible, exclusively from fluorine and an inert gas is said to exist particularly strongly in FR-A-2,154, 694 expressed. This document deals with the fluo ration of polyester fabric for the purpose of a subsequent eating dyeing of the fabric. There is multiple in this Scripture said that the treatment gas practically none Should contain oxygen. The reason for this is given leads to the lack of oxygen which he shortened required treatment time.

Der Erfindung liegt das Problem zugrunde, ein Verfahren der eingangs genannten Art zur Vorbehandlung von zu lac­ kierenden Oberflächen von Kunststoffteilen derart auszu­ bilden, daß sich die Oberflächen in möglichst kurzer Zeit für den nachfolgenden Lackiervorgang optimal eignen.The problem underlying the invention is a method of the type mentioned at the outset for the pretreatment of lac tracing surfaces of plastic parts in this way form the surfaces in the shortest possible time ideal for the subsequent painting process.

Diese Problem wird erfindungsgemäß dadurch gelöst, daß das Behandlungsgas einen absoluten Druck von etwa 333 bis 400 mbar hat, 3-5 Vol-% Fluor und zusätzlich zu zumin­ dest einem anderen inerten Gasbestandteil 3-4,5 Vol-% Sauerstoff enthält und daß die Einwirkzeit des Behand­ lungsgases etwa 10 bis 180 Sekunden beträgt.This problem is solved according to the invention in that the treatment gas has an absolute pressure of about 333 to 400 mbar, 3-5 vol% fluorine and in addition to at least one other inert gas component 3-4.5 vol% Contains oxygen and that the exposure time of the treatment tion gas is about 10 to 180 seconds.

Die Erfindung baut auf der im Gegensatz zum bisherigen Kenntnisstand stehenden Erkenntnis auf, daß zu lackie­ rende Oberflächen optimal mit einem Behandlungsgas fluo­ riert werden können, welches einen Restsauerstoffgehalt aufweist. Bei einer Behandlung unter den erfindungsgemä­ ßen Bedingungen ergibt sich eine optimale Haftung von in der Automobilbranche verwendetem Lack auf den Kunststoff­ teilen, so daß das Verfahren insbesondere zur Vorbehand­ lung von für Kraftfahrzeuge bestimmten Kunststoffteilen geeignet ist. Ein weiterer Vorteil des erfindungsgemäßen Verfahrens liegt darin, daß die mit ihm vorbehandelten Kunststoffteile im Gegensatz zu durch Flämmen oder Koro­ naentladungen vorbehandelten Kunststoffteilen vor dem Lackieren abgewaschen werden können, ohne daß ihre für das Lackieren vorteilhafte Oberfläche dadurch Schaden nimmt. Die Kunststoffteile können sogar durch eine soge­ nannte Power-wash hindurchgefahren werden. Diese Abwasch­ barkeit ist vorteilhaft, wenn es aus Gründen des Produk­ tionsablaufes erforderlich ist, die Kunststoffteile nach der Fluorierung vor dem Lackieren zunächst zwischenzula­ gern und sich dadurch vor dem Lackieren abzuwaschende Staubteilchen auf den Kunststoffteilen sammeln können.The invention builds on the contrary to the previous one State of knowledge on that to lackie surfaces with a treatment gas fluo can be riert, which has a residual oxygen content having. In a treatment under the invention conditions, optimal adhesion of in automotive paint used on the plastic share, so that the process especially for pretreatment development of plastic parts intended for motor vehicles suitable is. Another advantage of the invention The procedure is that the pretreated with it  Plastic parts in contrast to by flame or Koro pretreated plastic parts before the Paint can be washed off without their for painting advantageous surface thereby damage takes. The plastic parts can even by a so-called called Power Wash. This washing up Availability is advantageous if it is for product reasons tion sequence is required, the plastic parts after fluorination before painting like to wash off before painting Can collect dust particles on the plastic parts.

Vorteilhaft ist bei dem erfindungsgemäßen Verfahren auch, daß Quetschnähte nach dem Flämmen oder Feinschleifen ebenfalls sehr gut behandelt werden, daß die behandelten Oberflächen langzeitstabil und daß die Ergebnisse der Oberflächenbehandlung stets reproduzierbar sind.It is also advantageous in the method according to the invention that pinch seams after flaming or fine grinding are also treated very well that the treated Surfaces long-term stable and that the results of the Surface treatment are always reproducible.

Wie der Sauerstoff bei der Oberflächenbehandlung wirkt, ist nicht eindeutig zu klären. Es wird angenommen, daß sich der Sauerstoff sich auf der Oberfläche anlagert und dadurch ihre Eigenschaften vorteilhaft verändert. Überra­ schenderweise spielt allerdings die Größe der Oberfläche aller in den Reaktionsbehälter eingebrachten Teile keine Rolle, das heißt, bei großen Oberflächen muß weder die Behandlungsdauer noch die Konzentration an Sauerstoff im Behandlungsgas erhöht werden.How oxygen works in surface treatment cannot be clearly clarified. It is believed that the oxygen accumulates on the surface and thereby advantageously changing their properties. Overra however, the size of the surface plays a role none of the parts placed in the reaction container Roll, that is, with large surfaces, neither Duration of treatment still the concentration of oxygen in the Treatment gas can be increased.

Das erfindungsgemäße Verfahren kann sehr einfach ausge­ führt werden, wenn gemäß einer vorteilhaften Ausgestal­ tung die Reaktionskammer zunächst auf einen absoluten Druck von 200 mbar evakuiert und dann ein Gasgemisch aus 10 Vol-% F₂ und 90 Vol-% N₂ so lange zugegeben wird, bis der absolute Druck auf 400 mbar angestiegen ist. Dieses Verfahren ist besonders wirtschaftlich, weil Behandlungs­ gas mit 10 Vol-% F₂ und 90 Vol-% N₂ im Handel in Flaschen abgefüllt erhältlich ist.The method according to the invention can be implemented very simply leads if according to an advantageous Ausgestal tion the reaction chamber first to an absolute Evacuated pressure of 200 mbar and then a gas mixture 10 vol% F₂ and 90 vol% N₂ is added until the absolute pressure has risen to 400 mbar. This Procedure is particularly economical because of treatment  gas with 10 vol% F₂ and 90 vol% N₂ in bottles bottled is available.

Claims (2)

1. Verfahren zur Vorbehandlung von zu lackierenden Ober­ flächen von Kunststoffteilen aus Polyäthylen, Polypropy­ len oder vergleichbaren Werkstoffen durch Einwirkung eines fluorhaltigen Behandlungsgases innerhalb einer geschlossenen Reaktionskammer auf die Kunststoffteile, dadurch gekennzeichnet, daß das Behandlungsgas einen ab­ soluten Druck von etwa 333 bis 400 mbar hat, 3-5 Volu­ menprozent Fluor und zusätzlich zu zumindest einem ande­ ren inerten Gasbestandteil 3-4,5 Volumenprozent Sauer­ stoff enthält und daß die Einwirkzeit des Behandlungs­ gases etwa 10 bis 180 Sekunden beträgt.1. Process for the pretreatment of surfaces to be painted of plastic parts made of polyethylene, polypropylene or comparable materials by the action of a fluorine-containing treatment gas within a closed reaction chamber on the plastic parts, characterized in that the treatment gas has an absolute pressure of about 333 to 400 mbar , 3-5 volume percent fluorine and in addition to at least one other inert gas component contains 3-4.5 volume percent oxygen and that the exposure time of the treatment gas is about 10 to 180 seconds. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Reaktionskammer zunächst auf einen absoluten Druck von 200 mbar evakuiert und dann ein Gasgemisch aus 10 Vol-% F₂ und 90 Vol-% N₂ so lange zugegeben wird, bis der absolute Druck auf 400 mbar angestiegen ist.2. The method according to claim 1, characterized in that the reaction chamber initially to an absolute pressure evacuated from 200 mbar and then a gas mixture from 10 Vol% F₂ and 90 vol% N₂ is added until the absolute pressure has risen to 400 mbar.
DE19934320388 1993-06-19 1993-06-19 Process for the pretreatment of plastic part surfaces to be painted Withdrawn DE4320388A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE19934320388 DE4320388A1 (en) 1993-06-19 1993-06-19 Process for the pretreatment of plastic part surfaces to be painted
DE59405938T DE59405938D1 (en) 1993-06-19 1994-04-22 Process for the pretreatment of surfaces of plastic parts to be painted
DK94106295T DK0629654T3 (en) 1993-06-19 1994-04-22 Process for pre-treating varnish-coated surfaces of plastic parts
ES94106295T ES2115799T3 (en) 1993-06-19 1994-04-22 PROCEDURE FOR THE PRE-TREATMENT OF SURFACES TO BE VARNISHED OF PIECES OF SYNTHETIC MATERIAL.
EP94106295A EP0629654B1 (en) 1993-06-19 1994-04-22 Process for pretreating plastic surfaces to be painted
AT94106295T ATE166089T1 (en) 1993-06-19 1994-04-22 METHOD FOR PRETREATING PLASTIC PARTS SURFACES TO BE PAINTED

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19934320388 DE4320388A1 (en) 1993-06-19 1993-06-19 Process for the pretreatment of plastic part surfaces to be painted

Publications (1)

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DE4320388A1 true DE4320388A1 (en) 1994-12-22

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DE19934320388 Withdrawn DE4320388A1 (en) 1993-06-19 1993-06-19 Process for the pretreatment of plastic part surfaces to be painted

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19514924A1 (en) * 1995-04-22 1996-10-24 Messer Griesheim Gmbh Process for conditioning organic substrate surfaces
DE19527883A1 (en) * 1995-07-29 1997-01-30 Fluor Tech Sys Gmbh Coating for electrically non-conducting plastic, e.g.polypropylene - comprises fluorination during pretreatment stage, followed by electrostatic spray lacquering
WO2003086269A1 (en) * 2002-04-12 2003-10-23 delta T Gesellschaft für Medizintechnik mbH Containers for transporting goods at a constant temperature
US6896838B2 (en) 2001-11-21 2005-05-24 Closure Medical Corporation Halogenated polymeric containers for 1, 1-disubstituted monomer compositions
DE102007060515A1 (en) 2007-12-13 2009-06-18 Christof-Herbert Diener Surface treatment processes
DE102011009468A1 (en) 2011-01-21 2012-07-26 Innovent E.V. Use of polymer surfaces functionalized by fluorination or oxyfluorination in the presence of water for generating an antimicrobial effect

Citations (13)

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DE2500598A1 (en) * 1974-01-17 1975-07-24 Air Prod & Chem METHOD OF SURFACE TREATMENT OF A FIBER-SHAPED SYNTHETIC RESIN
US3988491A (en) * 1974-01-17 1976-10-26 Air Products And Chemicals, Inc. Fluorination of polyesters and polyamide fibers
US4296151A (en) * 1978-12-12 1981-10-20 Phillips Petroleum Company Fluorinated polymeric surfaces
DE3415381A1 (en) * 1984-04-25 1985-11-07 Kali-Chemie Ag, 3000 Hannover Process for reducing the friction of polymer surfaces
US4576837A (en) * 1985-03-19 1986-03-18 Tarancon Corporation Method of treating surfaces
EP0214635A2 (en) * 1985-09-09 1987-03-18 Lohmann GmbH & Co. KG Surface treatment of a flat plastic material
DE8703823U1 (en) * 1987-03-13 1987-04-23 Lohmann Gmbh & Co Kg, 5450 Neuwied, De
US4764405A (en) * 1987-07-22 1988-08-16 Air Products And Chemicals, Inc. Method for increasing barrier properties of thermoplastic substrates
US4833205A (en) * 1986-02-04 1989-05-23 Air Products And Chemicals, Inc. Polymeric materials having controlled physical properties
AT389315B (en) * 1987-06-09 1989-11-27 Air Prod & Chem Processes for the surface modification of polymers and their use
DD280772A1 (en) * 1989-03-23 1990-07-18 Univ Berlin Humboldt PROCESS FOR SURFACE FLUORATION OF POLYMERS
US4972030A (en) * 1988-08-22 1990-11-20 Air Products And Chemicals, Inc. Abrasion resistant composite coating material and process for making the same
EP0502303A1 (en) * 1991-02-20 1992-09-09 Ahlbrandt System GmbH Process for treating objects with a gas comprising fluor, and apparatus for carrying out the process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2500598A1 (en) * 1974-01-17 1975-07-24 Air Prod & Chem METHOD OF SURFACE TREATMENT OF A FIBER-SHAPED SYNTHETIC RESIN
US3988491A (en) * 1974-01-17 1976-10-26 Air Products And Chemicals, Inc. Fluorination of polyesters and polyamide fibers
US4296151A (en) * 1978-12-12 1981-10-20 Phillips Petroleum Company Fluorinated polymeric surfaces
DE3415381A1 (en) * 1984-04-25 1985-11-07 Kali-Chemie Ag, 3000 Hannover Process for reducing the friction of polymer surfaces
US4576837A (en) * 1985-03-19 1986-03-18 Tarancon Corporation Method of treating surfaces
EP0214635A2 (en) * 1985-09-09 1987-03-18 Lohmann GmbH & Co. KG Surface treatment of a flat plastic material
US4833205A (en) * 1986-02-04 1989-05-23 Air Products And Chemicals, Inc. Polymeric materials having controlled physical properties
DE8703823U1 (en) * 1987-03-13 1987-04-23 Lohmann Gmbh & Co Kg, 5450 Neuwied, De
AT389315B (en) * 1987-06-09 1989-11-27 Air Prod & Chem Processes for the surface modification of polymers and their use
US4764405A (en) * 1987-07-22 1988-08-16 Air Products And Chemicals, Inc. Method for increasing barrier properties of thermoplastic substrates
EP0300385A2 (en) * 1987-07-22 1989-01-25 Air Products And Chemicals, Inc. Method for increasing barrier properties of thermoplastic substrates
US4972030A (en) * 1988-08-22 1990-11-20 Air Products And Chemicals, Inc. Abrasion resistant composite coating material and process for making the same
DD280772A1 (en) * 1989-03-23 1990-07-18 Univ Berlin Humboldt PROCESS FOR SURFACE FLUORATION OF POLYMERS
EP0502303A1 (en) * 1991-02-20 1992-09-09 Ahlbrandt System GmbH Process for treating objects with a gas comprising fluor, and apparatus for carrying out the process

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19514924A1 (en) * 1995-04-22 1996-10-24 Messer Griesheim Gmbh Process for conditioning organic substrate surfaces
DE19527883A1 (en) * 1995-07-29 1997-01-30 Fluor Tech Sys Gmbh Coating for electrically non-conducting plastic, e.g.polypropylene - comprises fluorination during pretreatment stage, followed by electrostatic spray lacquering
US6896838B2 (en) 2001-11-21 2005-05-24 Closure Medical Corporation Halogenated polymeric containers for 1, 1-disubstituted monomer compositions
WO2003086269A1 (en) * 2002-04-12 2003-10-23 delta T Gesellschaft für Medizintechnik mbH Containers for transporting goods at a constant temperature
DE10216263B4 (en) * 2002-04-12 2005-03-31 delta T Gesellschaft für Medizintechnik mbH Containers of plastic for transporting and storing goods at a constant temperature and process for producing the containers
DE102007060515A1 (en) 2007-12-13 2009-06-18 Christof-Herbert Diener Surface treatment processes
DE102011009468A1 (en) 2011-01-21 2012-07-26 Innovent E.V. Use of polymer surfaces functionalized by fluorination or oxyfluorination in the presence of water for generating an antimicrobial effect

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