WO1999038913A1 - Method for coating plastics - Google Patents

Method for coating plastics Download PDF

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Publication number
WO1999038913A1
WO1999038913A1 PCT/DE1999/000306 DE9900306W WO9938913A1 WO 1999038913 A1 WO1999038913 A1 WO 1999038913A1 DE 9900306 W DE9900306 W DE 9900306W WO 9938913 A1 WO9938913 A1 WO 9938913A1
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WO
WIPO (PCT)
Prior art keywords
amorphous
fluoridated
perfluoropolymer
fluorinated
containers
Prior art date
Application number
PCT/DE1999/000306
Other languages
German (de)
French (fr)
Inventor
Günther Nath
Original Assignee
Nath Guenther
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 Nath Guenther filed Critical Nath Guenther
Priority to EP99907313A priority Critical patent/EP0990010A1/en
Priority to AU27125/99A priority patent/AU2712599A/en
Publication of WO1999038913A1 publication Critical patent/WO1999038913A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS 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
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
    • B65D85/84—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for corrosive chemicals
    • 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
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers

Definitions

  • plastic containers such as bottles, balloon bottles, wide-mouth bottles, wash bottles, canisters etc. for storing liquid chemical substances such as e.g. inorganic and organic solvents are widely used.
  • plastic containers which mostly consist of polyethylene or polypropylene, have the advantage in daily use in the chemical laboratory that they are lightweight, unbreakable, elastic and also particularly inexpensive.
  • plastic containers made of PE or PP or other similar hydrogen-containing polymers have the disadvantage that they do not have the required or desirable long-term resistance to diffusion compared to many aggressive, mainly organic solvents such as aliphatic or aromatic hydrocarbons or halogenated hydrocarbons or ketones, aldehydes and strong oxidizing agents, Have swelling or extraction of substances from the containers.
  • containers made of glass, metal or Teflon can be used to store such aggressive solvents, but this is associated with disadvantages such as fragility (with glass), higher weight and higher costs.
  • PTFE glass, metal or Teflon
  • PFA Teflon
  • containers made of glass, metal or Teflon can be used to store such aggressive solvents, but this is associated with disadvantages such as fragility (with glass), higher weight and higher costs.
  • a procedure has been developed in laboratory article practice in which the inner surfaces of the surfaces which are in contact with the solvents hydrogen-containing plastic containers made of PE or PP are treated by fluoridation, at least some of the near-surface hydrogen atoms being substituted by fluorine atoms (for example containers made of PE with a partially fluoridated surface from Nalgene).
  • fluorine atoms for example containers made of PE with a partially fluoridated surface from Nalgene
  • Liquid light guides are also known which are made of a Teflon®
  • Hose exist, the inner surface of which is coated with an amorphous perfluoropolymer to improve total reflection (DE 42 33 087 A1).
  • Post-treat PE or PP with a partially fluorinated inner surface in the sense that a perfluorinated inner skin or layer is created which has the optimal and desirable chemical resistance. It has been shown that amorphous perfluorinated fluoropolymers adhere particularly well to a partially fluorinated surface made of PE or PP if thin layers of these perfluorinated amorphous materials are produced from solution by simply wetting the surface with the solution and then evaporating off the solvent. In this way, layers of several ⁇ thickness can be produced. If the surfaces of the PE or PP containers are not fluoridated beforehand, the layers of perfluorinated amorphous fluoropolymers do not adhere, or much worse.
  • containers or tubes for use in the chemical laboratory are also made from other polyhydrocarbons, the surfaces of which can also be partially fluoridated and thus form a good basis for adhesion for coating with amorphous perfluoropolymers from the liquid phase.
  • Such materials are:
  • Hose made of polyhydrocarbons, in particular PE or PP, the inner surface of which has been fluoridated.
  • Teflon® AF from DuPont, which is a copolymer of tetrafluoroethylene with perfluoro-2,2-dimethyl-1,3-dioxol, or an amorphous perfluoropolymer from Ausimont, Hfylon® AD, a copolymer of tetrafluoroethylene with another special dioxol, namely 2.2 , 4-trifluoro-5-trifluoromethoxy-1,3-dioxole, as described in EPO 803 557 A1 or EPO 633 257, or
  • Teflon® SF a copolymer of tetrafluoroethylene with hexafluoropropylene (TFE / HFP) or perfluorovinylmethyl ether (TFE / PMVE), the amount of monomer copolymerized to TFE being unusually high, i.e. is in the range of 20-40 percent by weight. These are amorphous perfluoroelastomers. Such copolymers are described in EP 0656 912 B1.
  • a liquid, high-boiling (column 270 ° C) and highly viscous perfluoropolyether e.g. Fomblin® or Galden® from Ausimont
  • the weight fraction of the perfluoropolyether in the layer can be up to 30% (see also WO 98/38538).
  • the perfluorinated protective layers inside the plastic containers or tubes with partially fluorinated inner surface can be produced by partially filling these containers with the liquid solution of the amorphous fluoropolymer, then subjecting this container to a swiveling or tumbling movement so that its entire inner surface is uniformly wetted, and while maintaining the tumbling movement of the container, possibly with the aid of a warm air stream, ensures that the solvent, for example FC 75, evaporates as completely as possible. After completing this process, a uniformly thick layer of a few ⁇ is observed on the inner surface of the
  • Heating the open container to a temperature above the boiling point of the solvent ensures complete evaporation of the solvent while improving the
  • Adhesion of the layer to the base Further heating up to above the glass transition temperature of the amorphous fluoropolymer is recommended to achieve a closed and well-adhering, dense film made of the amorphous material. In the case of DuPont material Teflon® AF, this temperature is in the case of DuPont material Teflon® AF.
  • Ausimont material has an increased solubility in the perfluorinated liquids (FC 75) compared to Teflon® AF, so that even thicker layers can be achieved that are close to 10 ⁇ or even more than what Teflon® AF can only be achieved with great effort.

Abstract

The invention relates to a method for producing surfaces on substrates made of polymeric hydrocarbons, especially made of polyethylene or polypropylene, which are at least partially fluorinated by pretreating them with fluorine gas. The polymeric hydrocarbons are subsequently coated with an amorphous perfluoropolymer dissolved in fluorinated liquids by means of dipcoating. After tempering, a chemically inert layer results which adheres well and which protects the substrate against aggressive chemical solvents. According to the same method, superficial partially fluorinated tubing made of polyethylene can be coated inside with a thin layer of an amorphous perfluoropolymer and said tubing can then be used as sheathing tubing for fluid light guides.

Description

VERFAHREN ZUM BESCHICHTEN VON KUNSTSTOFFEN METHOD FOR COATING PLASTICS
Es ist bekannt, daß im chemischen Labor Behälter aus Kunststoff, wie Flaschen, Ballonflaschen, Weithalsflaschen, Spritzflaschen, Kanister etc. zur Aufbewahrung von flüssigen chemischen Substanzen wie z.B. anorganischen und organischen Lösungsmitteln vielfach Verwendung finden. Diese Kunststoffbehälter, die meistens aus Polyethylen oder Polypropylen bestehen, haben im täglichen Umgang im Chemielabor den Vorteil, daß sie leichtgewichtig, unzerbrechlich, elastisch und auch besonders kostengünstig sind.It is known that in the chemical laboratory plastic containers such as bottles, balloon bottles, wide-mouth bottles, wash bottles, canisters etc. for storing liquid chemical substances such as e.g. inorganic and organic solvents are widely used. These plastic containers, which mostly consist of polyethylene or polypropylene, have the advantage in daily use in the chemical laboratory that they are lightweight, unbreakable, elastic and also particularly inexpensive.
Diese Kunststoffbehälter aus PE oder PP oder anderen, ähnlichen wasserstoffhaltigen Polymeren haben jedoch den Nachteil, daß sie gegenüber vielen aggressiven, hauptsächlich organischen Lösungsmitteln wie aliphatischen oder aromatischen Kohlenwasserstoffen oder halogenisierten Kohlenwasserstoffen oder Ketonen, Aldehyden sowie starken Oxidationsmitteln nicht die erforderliche oder wünschenswerte Langzeitbeständigkeit hinsichtlich Diffusion, Quellung oder Extraktion von Substanzen aus den Behältern aufweisen.However, these plastic containers made of PE or PP or other similar hydrogen-containing polymers have the disadvantage that they do not have the required or desirable long-term resistance to diffusion compared to many aggressive, mainly organic solvents such as aliphatic or aromatic hydrocarbons or halogenated hydrocarbons or ketones, aldehydes and strong oxidizing agents, Have swelling or extraction of substances from the containers.
Man kann zur Aufbewahrung derartig aggressiver Lösungsmittel allerdings Behälter aus Glas, Metall oder Teflon (PTFE, FEP, PFA) verwenden, was aber mit Nachteilen wie Zerbrechlichkeit (bei Glas), höherem Gewicht und höheren Kosten verbunden ist. Es hat sich aus diesem Grund im Laufe der letzten Jahre in der Laborartikel-Praxis ein Verfahren entwickelt, bei dem die inneren, in Kontakt mit den Lösungsmitteln stehenden Oberflächen der wasserstoffhaltigen Kunststoffbehälter aus PE oder PP durch Fluoridierung behandelt werden, wobei wenigstens ein Teil der oberflächennahen Wasserstoffatome durch Fluoratome substituiert werden (z.B. Behälter aus PE mit teilfluoridierter Oberfläche der Fa. Nalgene). Leider lassen sich mit diesem Verfahren nicht sämtliche oberflächennahenHowever, containers made of glass, metal or Teflon (PTFE, FEP, PFA) can be used to store such aggressive solvents, but this is associated with disadvantages such as fragility (with glass), higher weight and higher costs. For this reason, in the course of the past few years a procedure has been developed in laboratory article practice in which the inner surfaces of the surfaces which are in contact with the solvents hydrogen-containing plastic containers made of PE or PP are treated by fluoridation, at least some of the near-surface hydrogen atoms being substituted by fluorine atoms (for example containers made of PE with a partially fluoridated surface from Nalgene). Unfortunately, not all surfaces can be obtained with this process
Wasserstoffatome durch Fluoratome ersetzen, so daß die erzeugte Oberfläche in ihrer chemischen Schutzwirkung nicht den optimalen Effekt aufweist , wie es z.B. der Fall wäre, wenn die Schutzschicht in ihrer Struktur mit Teflon® PTFE, Teflon® FEP oder Teflon® PFA übereinstimmen würde. Dennoch zeigen diese Behältnisse aus PE oder PP mit teilfluoriertenReplace hydrogen atoms with fluorine atoms, so that the surface created does not have the optimal chemical protection effect, as it e.g. the case would be if the protective layer had the same structure as Teflon® PTFE, Teflon® FEP or Teflon® PFA. Nevertheless, these containers made of PE or PP with partially fluorinated
Innenoberflächen gegenüber den nicht behandelten Behältern eine erhöhte chemikalische Beständigkeit, vor allem gegenüber Kohlenwasserstoffen, auch halogenierten Kohlenwasserstoffen und Ketonen. Es sind ferner Flüssigkeitslichtleiter bekannt, welche aus einem Teflon®-Internal surfaces have an increased chemical resistance compared to the untreated containers, especially against hydrocarbons, also halogenated hydrocarbons and ketones. Liquid light guides are also known which are made of a Teflon®
Schlauch bestehen, dessen innere Oberfläche mit einem amorphen Perfluorpolmer zur Verbesserung der Totalreflektion beschichtet ist (DE 42 33 087 A1). Es hat sich nun in erfinderischer Weise eine einfache Möglichkeit ergeben, diese vielfach im Laborbetrieb verwendeten und verbreiteten Behälter ausHose exist, the inner surface of which is coated with an amorphous perfluoropolymer to improve total reflection (DE 42 33 087 A1). In an inventive manner, there has now been a simple possibility of using these containers, which are widely used and widely used in laboratory operation
PE oder PP mit teilfluorierter Innenoberfläche in dem Sinne nachzubehandeln, daß eine perfluorierte Innenhaut oder Schicht entsteht, welche die optimale und wünschenswerte Chemikalienbeständigkeit aufweist. Es hat sich nämlich gezeigt, daß amorphe perfluorierte Fluorpolymere auf einer teilfluorierten Oberfläche aus PE oder PP besonders gut haften, wenn dünne Schichten aus diesen perfluorierten amorphen Materialien aus Lösung durch einfaches Benetzen der Oberfläche mit der Lösung und anschließender Abdunstung des Lösungsmittels hergestellt werden. Auf diese Weise lassen sich Schichten von mehreren μ Dicke erzeugen. Wenn die Oberflächen der PE- oder PP-Behältnisse nicht vorher fluoridiert werden, haften die Schichten aus perfluorierten amorphen Fluorpolymeren nicht, bzw. wesentlich schlechter. Neben den Materialien PE und PP werden Behälter oder Schläuche für den Gebrauch im chemischen Labor aber auch aus anderen Polykohlenwasserstoffen hergestellt, deren Oberflächen ebenfalls teilfluoridiert werden können und somit ene gute Haftungsgrundlage für die Beschichtung mit amorphen Perfluorpolymeren aus flüssiger Phase bilden. Solche Materialien sind:Post-treat PE or PP with a partially fluorinated inner surface in the sense that a perfluorinated inner skin or layer is created which has the optimal and desirable chemical resistance. It has been shown that amorphous perfluorinated fluoropolymers adhere particularly well to a partially fluorinated surface made of PE or PP if thin layers of these perfluorinated amorphous materials are produced from solution by simply wetting the surface with the solution and then evaporating off the solvent. In this way, layers of several μ thickness can be produced. If the surfaces of the PE or PP containers are not fluoridated beforehand, the layers of perfluorinated amorphous fluoropolymers do not adhere, or much worse. In addition to the materials PE and PP, containers or tubes for use in the chemical laboratory are also made from other polyhydrocarbons, the surfaces of which can also be partially fluoridated and thus form a good basis for adhesion for coating with amorphous perfluoropolymers from the liquid phase. Such materials are:
Polybutylen, PVC, Polyvinylidenchlorid, Polyurethan, Polycarbonat, Polyester, Polystyrol, Polyamid, Polyacetat, Acryl-Butadien-Styrol- Copolymer, Melamin, Polymethylmethacrylat, Polymethylpenten, Polyoxymethylen, Styrol-Acrylnitril oder Silikon. Die gleichen Überlegungen gelten für Flüssigkeitslichtleiter, derenPolybutylene, PVC, polyvinylidene chloride, polyurethane, polycarbonate, polyester, polystyrene, polyamide, polyacetate, acrylic-butadiene-styrene copolymer, melamine, polymethyl methacrylate, polymethylpentene, polyoxymethylene, styrene-acrylonitrile or silicone. The same considerations apply to liquid light guides, their
Schlauch aus Polykohlenwasserstoffen, insbesondere aus PE oder PP besteht, deren innere Oberfläche fluoridiert wurde.Hose made of polyhydrocarbons, in particular PE or PP, the inner surface of which has been fluoridated.
Als perfluorierte amorphe Fluorpolymere für die Aufbringung der zusätzlichen Schutzschicht auf teilfluorierte Substratoberflächen aus PE oder PP aus Lösung eignen sich die folgenden Substanzen: Teflon® AF von DuPont, welches ein Copolymer von Tetrafluorethylen mit Perfluoro- 2,2-Dimethyl-1 ,3-Dioxol ist, oder ein amorphes Perfluorpolymer der Firma Ausimont, Hfylon® AD, ein Copolymer von Tetrafluorethylen mit einem anderen speziellen Dioxol, nämlich 2,2,4-Trifluor-5-trifluormethoxy-1 ,3- dioxol, wie beschrieben in EPO 803 557 A1 bzw. EPO 633 257, oderThe following substances are suitable as perfluorinated amorphous fluoropolymers for the application of the additional protective layer on partially fluorinated substrate surfaces made of PE or PP from solution: Teflon® AF from DuPont, which is a copolymer of tetrafluoroethylene with perfluoro-2,2-dimethyl-1,3-dioxol, or an amorphous perfluoropolymer from Ausimont, Hfylon® AD, a copolymer of tetrafluoroethylene with another special dioxol, namely 2.2 , 4-trifluoro-5-trifluoromethoxy-1,3-dioxole, as described in EPO 803 557 A1 or EPO 633 257, or
Teflon® SF, ein Copolymer von Tetrafluorethylen mit Hexafluorpropylen (TFE/HFP) oder Perfluorvinylmethyläther (TFE/PMVE), wobei der zum TFE copolymerisierte Monomer-Anteil ungewöhnlich hoch ist, d.h. im Bereich von 20 - 40 Gewichtsprozenten liegt. Es handelt sich hierbei um amorphe Perfluorelastomere. Derartige Copoiymere sind in EP 0656 912 B1 beschrieben.Teflon® SF, a copolymer of tetrafluoroethylene with hexafluoropropylene (TFE / HFP) or perfluorovinylmethyl ether (TFE / PMVE), the amount of monomer copolymerized to TFE being unusually high, i.e. is in the range of 20-40 percent by weight. These are amorphous perfluoroelastomers. Such copolymers are described in EP 0656 912 B1.
Alle diese hier erwähnten perfluorierten amorphen Polymere lassen sich leicht bei Raumtemperatur in gewissen perfluorierten aliphatischen oder aromatischen Flüssigkeiten wie z.B. in den Fluorinert-Flüssigkeiten FC 72, FC 75 oder FC 77 von 3M lösen, und zwar im Bereich von einigenAll of these perfluorinated amorphous polymers mentioned here can easily be dissolved at room temperature in certain perfluorinated aliphatic or aromatic liquids such as e.g. in the Fluorinert fluids FC 72, FC 75 or FC 77 from 3M, in the range of a few
Gewichtsprozenten.Weight percent.
Zusätzlich kann man zu den Lösungen der oben erwähnten festen amorphen Fluorpolymeren in den FC Flüssigkeiten noch einen flüssigen, hochsiedenden (Sp. 270°C) und hochviskosen Perfluorpolyether beimischen (z.B. Fomblin® oder Galden® von Firma Ausimont), welcher nach dem Abdunsten der FC Flüssigkeiten sowie nach Temperung in der aufgebrachten Schicht verbleibt und die Elastizität als auch die Haftung der Schicht auf der Substratunterlage günstig beeinflussen kann. Der Gewichtsanteil des Perfluorpolyethers in der Schicht kann bis zu 30% betragen (s.a. WO 98/38538). Die perfluorierten Schutzschichten im Inneren der Plastikbehälter oder Schläuche mit teilfluorierter Innenoberfläche lassen sich dadurch erzeugen, indem man diese Behälter teilweise mit der flüssigen Lösung des amorphen Fluorpolymers füllt, diesen Behälter dann einer Schwenk- oder Taumelbewegung unterzieht, so daß seine gesamte Innenoberfläche gleichmäßig benetzt wird, und unter Beibehaltung der Taumelbewegung des Behälters dafür sorgt, evtl. unter Zuhilfenahme eines warmen Luftstroms, daß das Lösungsmittel, z.B. FC 75, möglichst vollständig abdunstet. Nach Beendigung dieses Vorgangs beobachtet man eine gleichmäßig dicke Schicht von einigen μ auf der Innenoberfläche desIn addition to the solutions of the above-mentioned solid amorphous fluoropolymers in the FC liquids, a liquid, high-boiling (column 270 ° C) and highly viscous perfluoropolyether (e.g. Fomblin® or Galden® from Ausimont) can be added, which after evaporation of the FC Liquids and after annealing remain in the applied layer and can favorably influence the elasticity and the adhesion of the layer to the substrate base. The weight fraction of the perfluoropolyether in the layer can be up to 30% (see also WO 98/38538). The perfluorinated protective layers inside the plastic containers or tubes with partially fluorinated inner surface can be produced by partially filling these containers with the liquid solution of the amorphous fluoropolymer, then subjecting this container to a swiveling or tumbling movement so that its entire inner surface is uniformly wetted, and while maintaining the tumbling movement of the container, possibly with the aid of a warm air stream, ensures that the solvent, for example FC 75, evaporates as completely as possible. After completing this process, a uniformly thick layer of a few μ is observed on the inner surface of the
Plastikbehälters bzw. Schlauchs mit guter Haftung auf der teilfluorierten Substratfläche.Plastic container or hose with good adhesion to the partially fluorinated substrate surface.
Eine Erwärmung des offenen Behälters auf eine Temperatur oberhalb des Siedepunktes des Lösungsmittels (~ 100°C bei FC 75) sorgt für restlose Abdampfung des Lösungsmittels bei gleichzeitiger Verbesserung derHeating the open container to a temperature above the boiling point of the solvent (~ 100 ° C for FC 75) ensures complete evaporation of the solvent while improving the
Haftung der Schicht auf der Unterlage. Eine weitere Erwärmung bis oberhalb der Glasübergangstemperatur des amorphen Fluorpolymers ist empfehlenswert zur Erzielung eines geschlossenen und gut haftenden, dichten Films aus dem amorphen Material. Im Falle des DuPont-Materials Teflon® AF liegt diese Temperatur imAdhesion of the layer to the base. Further heating up to above the glass transition temperature of the amorphous fluoropolymer is recommended to achieve a closed and well-adhering, dense film made of the amorphous material. In the case of DuPont material Teflon® AF, this temperature is in the
Bereich von ca. 140°C - 240°C, je nach Modifikation des Copolymers, und im Falle des Ausimont-Materials Hyflon® AD im Bereich von 100°C - 140°C. Eine Temperung bis zu diesen hohen Temperaturen hängt natürlich von der thermischen Belastbarkeit des Plastikmaterials ab, aus dem der Behälter bzw. der Schlauch besteht, aber auch eine Temperung unterhalb der Glasübergangstemperatur verbessert die Haftung. Eine Beschichtung mit dem Ausimont-Material Hyflon® AD weist im Hinblick auf diese Temperung Vorteile auf. Ein weiterer Vorteil des Ausimont-Materials besteht darin, daß es im Vergleich zu Teflon® AF eine erhöhte Löslichkeit in den perfluorierten Flüssigkeiten (FC 75) besitzt, so daß auch größere Schichtdicken zu erzielen sind, die nahe 10μ oder sogar darüber liegen, was mit Teflon® AF nur mit größerem Aufwand zu erreichen ist. Range of approx. 140 ° C - 240 ° C, depending on the modification of the copolymer, and in the case of Ausimont material Hyflon® AD in the range of 100 ° C - 140 ° C. Annealing up to these high temperatures naturally depends on the thermal load capacity of the plastic material from which the Containers or the hose exist, but tempering below the glass transition temperature also improves the adhesion. A coating with the Ausimont material Hyflon® AD has advantages with regard to this tempering. Another advantage of the Ausimont material is that it has an increased solubility in the perfluorinated liquids (FC 75) compared to Teflon® AF, so that even thicker layers can be achieved that are close to 10μ or even more than what Teflon® AF can only be achieved with great effort.

Claims

Anspruchsfassung Claiming
1. Verfahren zur Herstellung von Oberflächen auf Substraten aus polymeren Kohlenwasserstoffen, welche durch Behandlung mit fluorhaltigen Mitteln, insbesondere Fluor-Gas, fluoridiert oder teilfluoridiert sind, dadurch gekennzeichnet, daß a) die Oberflächen mit einem in fluorierten Flüssigkeiten löslichen1. A process for the production of surfaces on substrates made of polymeric hydrocarbons which are fluoridated or partially fluoridated by treatment with fluorine-containing agents, in particular fluorine gas, characterized in that a) the surfaces are soluble in fluorinated liquids
Perfluorpolymer durch Benetzung mit der Lösung beschichtet werden; b) nach dem Benetzen das fluorierte Lösungsmittel verdampft wird, und c) die auf diese Weise erhaltene beschichtete Oberfläche getempert wird.Perfluoropolymer can be coated with the solution by wetting; b) after the wetting, the fluorinated solvent is evaporated, and c) the coated surface obtained in this way is annealed.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß die oberflächlich fluoridierten Substrate aus Polyethylen (PE) oder Polypropylen (PP) bestehen.2. The method according to claim 1, characterized in that the surface fluoridated substrates consist of polyethylene (PE) or polypropylene (PP).
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß die oberflächlich fluoridierten Substrate aus anderen polymeren3. The method according to claim 1, characterized in that the surface fluoridated substrates from other polymers
Kohlenwasserstoffen wie Polybutylen, PVC, Polyvinylidenchlorid, Polyurethan, Polycarbonat, Polyester, Polystyrol, Polyamid, Polyacetat, Acryl-B utadien-Styrol-C opoiymer, Me lamin , Polymethylmethacryiat, Polymethylpenten, Polyoxymethylen, Styrol- Acrylnitril oder Silikon bestehen.Hydrocarbons such as polybutylene, PVC, polyvinylidene chloride, polyurethane, polycarbonate, polyester, polystyrene, polyamide, polyacetate, acrylic-butadiene-styrene-copolymer, Me lamin, polymethyl methacrylate, polymethylpentene, polyoxymethylene, styrene-acrylonitrile or silicone.
7 7
4. Verfahren nach einem der Ansprüche 1 - 3, dadurch gekennzeichnet, daß das in der fluorierten Flüssigkeit gelöste Perfluorpolymer amorph ist.4. The method according to any one of claims 1-3, characterized in that the perfluoropolymer dissolved in the fluorinated liquid is amorphous.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das amorphe Perfluorpolymer eines der Materialien Teflon® AF, Hyflon® AD, Teflon® SF oder ein perfluoriertes Fluorelastomer umfaßt.5. The method according to claim 4, characterized in that the amorphous perfluoropolymer comprises one of the materials Teflon® AF, Hyflon® AD, Teflon® SF or a perfluorinated fluoroelastomer.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß den perfluorierten amorphen Polymeren ein flüssiges amorphes Perfluorpolymer wie z.B. ein hochsiedender, hochviskoser Perfluorpolyether (Fomblin®, Galden®) beigemischt ist, welcher nach dem Verdampfen des Lösungsmittels und nach Temperung in der aufgebrachten Schicht verbleibt.6. The method according to claim 5, characterized in that the perfluorinated amorphous polymer is a liquid amorphous perfluoropolymer such as e.g. a high-boiling, highly viscous perfluoropolyether (Fomblin®, Galden®) is added, which remains in the applied layer after the evaporation of the solvent and after tempering.
7. Verfahren nach Anspruch 1 - 6, dadurch gekennzeichnet, daß die Benetzung in einem Zeitraum von bis zu 2 Stunden erfolgt.7. The method according to claim 1-6, characterized in that the wetting takes place in a period of up to 2 hours.
8. Behälter aus polymeren Kohlenwasserstoffen, insbesondere aus PE und/oder PP oder den in Anspruch 5 erwähnten Materialien, deren innere Oberfläche fluoridiert ist, auf der sich eine Schicht aus einem amorphen Perfluorpolymer befindet.8. Containers made of polymeric hydrocarbons, in particular PE and / or PP or the materials mentioned in claim 5, the inner surface of which is fluoridated, on which there is a layer of an amorphous perfluoropolymer.
8 8th
9. Schlauch aus polymeren Kohlenwasserstoffen, insbesondere aus PE und/oder PP oder aus den in Anspruch 5 erwähnten Materialien, dessen innere Oberfläche fluoridiert ist, auf der sich eine Schicht aus einem amorphen Perfluorpolymer befindet.9. hose made of polymeric hydrocarbons, in particular PE and / or PP or of the materials mentioned in claim 5, the inner surface of which is fluoridated, on which there is a layer of an amorphous perfluoropolymer.
10. Verwendung eines Behälters gemäß Anspruch 8 zur Aufbewahrung von Chemikalien.10. Use of a container according to claim 8 for storing chemicals.
11. Verwendung eines Schlauches gemäß Anspruch 9 als Mantelschlauch mit totalreflektierenden Eigenschaften für Flüssigkeitslichtleiter.11. Use of a tube according to claim 9 as a jacket tube with totally reflecting properties for liquid light guides.
12. Verwendung des Verfahrens gemäß einem der Ansprüche 1 - 7 zur Herstellung von Behältern oder Flüssigkeitslichtleitern. 12. Use of the method according to any one of claims 1-7 for the production of containers or liquid light guides.
PCT/DE1999/000306 1998-01-29 1999-01-29 Method for coating plastics WO1999038913A1 (en)

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EP99907313A EP0990010A1 (en) 1998-01-29 1999-01-29 Method for coating plastics
AU27125/99A AU2712599A (en) 1998-01-29 1999-01-29 Method for coating plastics

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DE19803488.1 1998-01-29
DE19803488A DE19803488A1 (en) 1998-01-29 1998-01-29 Process for coating plastics based on polyhydrocarbons

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DE10044804B4 (en) 2000-05-31 2019-06-19 Günther Nath Highly flexible liquid light guide and method for its production

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DE10209158A1 (en) * 2002-02-26 2003-09-11 Thomas R Appel Thin layer chromatography volume-stable standard lipid solution comprises lipid dissolved in solvent pair selected from chlorinated hydrocarbon and alcohol
CA2616317C (en) 2005-07-26 2013-10-29 Basf Aktiengesellschaft Container made from plastics materials with a polymeric organofluorine interior coating for active-compound formulations for crop protection or protection of materials

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US4764405A (en) * 1987-07-22 1988-08-16 Air Products And Chemicals, Inc. Method for increasing barrier properties of thermoplastic substrates
WO1992010532A1 (en) * 1990-12-07 1992-06-25 Vascutek Limited Fluorinating polymer surfaces
DE4233087A1 (en) * 1992-10-01 1994-04-07 Nath Guenther Liq. waveguide with fluorocarbon polymer sheath - has thin Teflon AF lining layer for reduced cost and transmission losses
BE1006883A3 (en) * 1993-03-05 1995-01-17 Solvay Surface protection method for items made of thermoplastic material with asurface treatment

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10044804B4 (en) 2000-05-31 2019-06-19 Günther Nath Highly flexible liquid light guide and method for its production

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EP0990010A1 (en) 2000-04-05
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