EP1534876A2 - Method of forming a coating on a plastic glazing - Google Patents

Method of forming a coating on a plastic glazing

Info

Publication number
EP1534876A2
EP1534876A2 EP03758205A EP03758205A EP1534876A2 EP 1534876 A2 EP1534876 A2 EP 1534876A2 EP 03758205 A EP03758205 A EP 03758205A EP 03758205 A EP03758205 A EP 03758205A EP 1534876 A2 EP1534876 A2 EP 1534876A2
Authority
EP
European Patent Office
Prior art keywords
temperature
coating
substrate
plastic
glazing
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Withdrawn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
EP03758205A
Other languages
German (de)
French (fr)
Inventor
Heinrich Kliem
Heinrich Kliem
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.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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 Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP1534876A2 publication Critical patent/EP1534876A2/en
Withdrawn legal-status Critical Current

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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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • C23C16/46—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 characterised by the method used for heating the substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

  • the present invention relates to plastic glazing. Their interest is for example linked to a search for lightening on various types of vehicles or to obtaining complex shapes.
  • Various transparent plastics can be used, such as polycarbonate, polymethyl methacrylate, polypropylene, polyurethane, polyvinyl butyral, poly (ethylene glycol terephthalate), poly (butylene glycol terephthalate), ionomer resin such as ethylene / neutralized (meth) acrylic acid copolymer with a polyamine, cycloolefinic copolymer such as ethylene / norbornene or ethylene / cyclopentadiene, polycarbonate / polyester copolymer, ethylene / vinyl acetate copolymer and the like, alone or in mixtures.
  • the relative scratchability of plastic substrates justifies the almost generalized formation of anti-scratch protective coatings in applications such as glazing.
  • the coatings consisting for example of carbon, hydrogen, silicon and oxygen, can be formed according to any known process for depositing thin layers, in particular exothermic deposition techniques, under vacuum, at more or less reduced or atmospheric pressure; in this regard, the PECVD (Plasma Enhanced Chemical Vapor Deposition) processes can be cited hereinafter referred to as plasma CVD, electron beam evaporation, sputtering magnetron, ionically assisted CVD, ion source CVD, etc.
  • These layers may contain anti-UV agents and / or be associated with one or more other functional layers.
  • the inventors have noted the creation of particularly sensitive microcracks for layers with good abrasion and scratch resistance and all the more important that the glazing is used at high temperature, the ranges of use generally accepted for motor vehicles. being from -30 ° C to 90 ° C, or more generally -40 ° C to 100 ° C, and from -70 ° C to 100 ° C for aircraft.
  • application EP 1 022 354 A2 describes the heating of the plastic substrate prior to the formation of a layer by plasma CVD without even mentioning any possible creation of cracks.
  • the inventors have now defined the criteria making it possible to delay considerably, if not to suppress the formation of cracks, even when the plastic glazing is used at relatively high temperatures, of the order of 100 ° C. for example.
  • the subject of the invention is a process for forming a coating on at least part of a plastic substrate, distinguished by the fact of being carried out at a temperature at least equal to the maximum temperature of use of the coated substrate minus 20 ° C.
  • This temperature is that at which the substrate itself is stabilized from the start of the actual formation of the coating.
  • the creation of microcracks is considerably delayed even when the coated substrate is used at high temperature, of the order of 100 ° C. and more in particular.
  • the method implements a plasma CVD.
  • a coating based on silicon, oxygen, carbon, hydrogen among others, and with adjustable properties is obtained from one or more precursors such as silane, hexamethyldisiloxane, tetramethyldisiloxane ...
  • This technique also makes it easy to form stacks of layers.
  • the process is carried out at a temperature at least equal to the maximum temperature for using the coated substrate.
  • the coating is formed at a temperature generally not exceeding 125 ° C, or up to 135 ° C for particular grades.
  • the process is carried out at a temperature as close as possible to this degradation temperature of the plastic.
  • cooling means are used to avoid reaching the degradation temperature of the plastic.
  • This use is then particularly advantageous when proceeding according to the previous embodiment, as close as possible to this degradation temperature. It can provide sufficient deposition time to obtain the required thicknesses, in several or even all at once.
  • an advantageous embodiment consists in forming the coating in several stages.
  • the method comprises the operations consisting successively of a) stabilizing the substrate to be coated at a temperature at least equal to its maximum operating temperature minus 20 ° C., b) forming the coating while ensuring that the temperature of the substrate does not reach the degradation temperature of the plastic, c) repeat operations a) and b) if necessary, depending on the thickness and other characteristics desired for the coating.
  • the substrate is made of polycarbonate, the coating being formed at a temperature at least equal to 120 ° C.
  • the subject of the invention is also a product comprising a plastic substrate provided with a coating formed according to the method described above, the average thickness of the coating being at least 2 ⁇ m, preferably at least 4 ⁇ m, and particularly preferably at least 6 ⁇ m.
  • Another object of the invention is the application of this product as a piece of plastic material which is not necessarily transparent such as a bodywork (door, fender, bonnet, deflector or equivalent in applications other than automotive), as glazing, in particular for land, water or air vehicle, in particular for motor vehicle, safety glazing for helmet or of the type requiring resistance in the heat.
  • a bodywork door, fender, bonnet, deflector or equivalent in applications other than automotive
  • glazing in particular for land, water or air vehicle, in particular for motor vehicle, safety glazing for helmet or of the type requiring resistance in the heat.
  • the application of glazing of the invention for buildings or urban furniture - advertising billboards, bus shelters, etc. - is also interesting.
  • the invention is illustrated by the following embodiment.
  • EXAMPLE A polycarbonate sheet 300 X 850 mm and 4 mm thick, sold by the Bayer Company under the registered trademark Makrolon, is subjected to the deposition of a coating by plasma CVD.
  • the deposit chamber is equipped with a microwave plasma source of 350
  • the coating is formed according to the following four steps:
  • the temperature reached by the substrate at the end of steps 2 and 4 is 124-125 ° C, that is to say just below the softening temperature of the polycarbonate.
  • it omits to act on the temperature of the substrate: 5 ⁇ m of coating is deposited in a single operation.
  • the substrate temperature ranges from around 20 ° C (room temperature) to 85 ° C.
  • the substrate is initially heated to 120 ° C, but a thickness of 5 ⁇ m of coating is deposited “at once”.
  • the substrate is at a temperature of 130-132 ° C, higher than the degradation temperature of the polycarbonate; its deformation makes it incompatible with an application as a transparent product in which even minimal optical quality is required.
  • the glazings resulting from the first and second tests are subjected to 500 rounds of the Taber cycle with a CS 10 F grinding wheel under a load of 500 g; the haze measured is less than 10% in both cases, which indicates satisfactory abrasion resistance.
  • the distances between the cracks observed in the coatings are of the order of 100 ⁇ m to 1 mm. Their appearance often precedes delamination of the coating.
  • the specific deposition process of the invention therefore makes it possible to avoid or delay the appearance of microcracks; the beneficial consequences on the adhesion of the coating to the substrate, as well as on the optical quality of the product, are obvious.

Abstract

The invention relates to a method of forming a coating on at least part of a plastic substrate. The invention is characterised in that it is performed at a temperature that is at least equal to the maximum use temperature of the coated substrate minus 20 DEG C. The invention also relates to a product thus obtained having a minimum average coating thickness of 2 mu m and to the use of said product as a vehicle body part, glazing for a transport vehicle, for buildings or street furniture and for safety and heat-resistant glazing.

Description

PROCEDE DE FORMATION D'UN REVETEMENT SUR UN VITRAGE EN PROCESS FOR FORMING A COATING ON GLAZING IN
MATIERE PLASTIQUEPLASTIC MATERIAL
La présente invention a trait aux vitrages en matière plastique. Leur intérêt est par exemple lié à une recherche d'allégement sur divers types de véhicules ou à l'obtention de formes complexes. Diverses matières plastiques transparentes peuvent être employées, telles que polycarbonate, polyméthacrylate de méthyle, polypropylène, polyuréthane, polyvinylbutyral, poly(téréphtalate d'éthylèneglycol), poly(téréphtalate de butylèneglycol), résine ionomère telle que copolymère éthylène/acide (méth)acrylique neutralisé par une polyamine, copolymère cyclooléfinique tel qu'éthylène/norbornène ou éthylène/cyclopentadiène, copolymère polycarbonate/polyester, copolymère éthylène/acétate de vinyle et similaires, seuls ou en mélanges.The present invention relates to plastic glazing. Their interest is for example linked to a search for lightening on various types of vehicles or to obtaining complex shapes. Various transparent plastics can be used, such as polycarbonate, polymethyl methacrylate, polypropylene, polyurethane, polyvinyl butyral, poly (ethylene glycol terephthalate), poly (butylene glycol terephthalate), ionomer resin such as ethylene / neutralized (meth) acrylic acid copolymer with a polyamine, cycloolefinic copolymer such as ethylene / norbornene or ethylene / cyclopentadiene, polycarbonate / polyester copolymer, ethylene / vinyl acetate copolymer and the like, alone or in mixtures.
La rayabilité relative des substrats en matière plastique justifie la formation quasi-généralisée de revêtements protecteurs anti-rayures dans les applications en tant que vitrages notamment. Les revêtements constitués par exemple de carbone, hydrogène, silicium et oxygène, peuvent être formés selon tous procédés connus de dépôt de couches minces, notamment des techniques de dépôt exothermique, sous vide , à pression plus ou moins réduite ou atmosphérique; à cet égard peuvent être cités les procédés de PECVD (Plasma Enhanced Chemical Vapour Déposition) désigné par la suite CVD plasma, évaporation par faisceau d'électrons, magnétron à pulvérisation cathodique, CVD assisté ioniquement, CVD par source ionique....The relative scratchability of plastic substrates justifies the almost generalized formation of anti-scratch protective coatings in applications such as glazing. The coatings consisting for example of carbon, hydrogen, silicon and oxygen, can be formed according to any known process for depositing thin layers, in particular exothermic deposition techniques, under vacuum, at more or less reduced or atmospheric pressure; in this regard, the PECVD (Plasma Enhanced Chemical Vapor Deposition) processes can be cited hereinafter referred to as plasma CVD, electron beam evaporation, sputtering magnetron, ionically assisted CVD, ion source CVD, etc.
Ces couches peuvent contenir des agents anti-UV et/ou être associées à une ou plusieurs autres couches fonctionnelles.These layers may contain anti-UV agents and / or be associated with one or more other functional layers.
Les inventeurs ont constaté la création de microfissurations particulièrement sensibles pour les couches à bonne résistance à l'abrasion et aux rayures et d'autant plus importante que le vitrage est utilisé à température élevée, les plages d'utilisations admises en général pour les véhicules automobiles étant de -30°C à 90°C, ou plus largement -40°C à 100°C, et de - 70°C à 100°C pour les avions. D'autre part la demande EP 1 022 354 A2 décrit le chauffage du substrat en matière plastique préalablement à la formation d'une couche par CVD plasma sans même mentionner une éventuelle création de fissures. Les inventeurs ont à présent défini les critères permettant de retarder considérablement, sinon de supprimer la formation de fissures, même lors d'utilisations du vitrage en matière plastique à températures relativement élevées, de l'ordre de 100°C par exemple. A cet effet, l'invention a pour objet un procédé de formation d'un revêtement sur au moins une partie d'un substrat en matière plastique, se distinguant par le fait d'être effectué à une température au moins égale à la température maximale d'utilisation du substrat revêtu moins 20°C. Cette température est celle à laquelle le substrat lui-même est stabilisé dès le début de la formation proprement dite du revêtement. Ainsi la création de microfissures est-elle considérablement retardée même quand le substrat revêtu est utilisé à température élevée, de l'ordre de 100°C et plus notamment.The inventors have noted the creation of particularly sensitive microcracks for layers with good abrasion and scratch resistance and all the more important that the glazing is used at high temperature, the ranges of use generally accepted for motor vehicles. being from -30 ° C to 90 ° C, or more generally -40 ° C to 100 ° C, and from -70 ° C to 100 ° C for aircraft. On the other hand, application EP 1 022 354 A2 describes the heating of the plastic substrate prior to the formation of a layer by plasma CVD without even mentioning any possible creation of cracks. The inventors have now defined the criteria making it possible to delay considerably, if not to suppress the formation of cracks, even when the plastic glazing is used at relatively high temperatures, of the order of 100 ° C. for example. To this end, the subject of the invention is a process for forming a coating on at least part of a plastic substrate, distinguished by the fact of being carried out at a temperature at least equal to the maximum temperature of use of the coated substrate minus 20 ° C. This temperature is that at which the substrate itself is stabilized from the start of the actual formation of the coating. Thus the creation of microcracks is considerably delayed even when the coated substrate is used at high temperature, of the order of 100 ° C. and more in particular.
De manière privilégiée dans le cadre de l'invention, le procédé met en œuvre une CVD plasma. Un revêtement à base de silicium, oxygène, carbone, hydrogène entre autres, et à propriétés réglables est obtenu à partir d'un ou plusieurs précurseurs tels que silane, hexaméthyldisiloxane, tétraméthyldisiloxane...In a preferred manner in the context of the invention, the method implements a plasma CVD. A coating based on silicon, oxygen, carbon, hydrogen among others, and with adjustable properties is obtained from one or more precursors such as silane, hexamethyldisiloxane, tetramethyldisiloxane ...
Cette technique permet aussi aisément de former des empilements de couches. On procède à pression plus ou moins réduite ou atmosphérique, avec des micro-ondes ou des radiofréquences.This technique also makes it easy to form stacks of layers. One proceeds to a more or less reduced or atmospheric pressure, with microwaves or radiofrequencies.
De préférence, le procédé est mis en œuvre à une température au moins égale à la température maximale d'utilisation du substrat revêtu.Preferably, the process is carried out at a temperature at least equal to the maximum temperature for using the coated substrate.
Il est en outre souhaitable, dans le cas de substrats transparents pour lesquels une qualité optique est requise, d'effectuer le procédé à une température inférieure à la température de dégradation de la matière plastique. Par ces termes, on entend par exemple la température de ramollissement, de fusion ou de transition de phase de la matière plastique, à laquelle elle commence à se déformer. Ainsi quand le substrat est en polycarbonate, la formation du revêtement est-elle effectuée à une température n'excédant pas en général 125°C, ou jusqu'à 135°C pour des grades particuliers.It is also desirable, in the case of transparent substrates for which optical quality is required, to carry out the process at a temperature below the degradation temperature of the plastic. By these terms is meant, for example, the softening, melting or phase transition temperature of the plastic, at which it begins to deform. Thus when the substrate is made of polycarbonate, the coating is formed at a temperature generally not exceeding 125 ° C, or up to 135 ° C for particular grades.
Dans une réalisation avantageuse de l'invention, le procédé est effectué à une température la plus proche possible de cette température de dégradation de la matière plastique.In an advantageous embodiment of the invention, the process is carried out at a temperature as close as possible to this degradation temperature of the plastic.
De préférence, notamment quand la technique de dépôt est exothermique, des moyens de refroidissement sont employés afin d'éviter d'atteindre la température de dégradation de la matière plastique. Cet emploi est alors particulièrement avantageux lorsque l'on procède selon la réalisation précédente, le plus près possible de cette température de dégradation. Il peut permettre de disposer de la durée de dépôt suffisante pour obtenir les épaisseurs requises, en plusieurs voire en une seule fois.Preferably, especially when the deposition technique is Exothermic, cooling means are used to avoid reaching the degradation temperature of the plastic. This use is then particularly advantageous when proceeding according to the previous embodiment, as close as possible to this degradation temperature. It can provide sufficient deposition time to obtain the required thicknesses, in several or even all at once.
Dans le but de procéder dans les plages de températures les plus favorables selon l'invention, un mode de réalisation avantageux consiste à former le revêtement en plusieurs étapes. En particulier, le procédé comprend les opérations consistant successivement à a) stabiliser le substrat à revêtir à une température au moins égale à sa température maximale d'utilisation moins 20°C, b) former le revêtement en veillant à ce que la température du substrat n'atteigne pas la température de dégradation de la matière plastique, c) effectuer à nouveau les opérations a) et b) si nécessaire, en fonction de l 'épaisseur et autres caractéristiques recherchées pour le revêtement.In order to proceed in the most favorable temperature ranges according to the invention, an advantageous embodiment consists in forming the coating in several stages. In particular, the method comprises the operations consisting successively of a) stabilizing the substrate to be coated at a temperature at least equal to its maximum operating temperature minus 20 ° C., b) forming the coating while ensuring that the temperature of the substrate does not reach the degradation temperature of the plastic, c) repeat operations a) and b) if necessary, depending on the thickness and other characteristics desired for the coating.
Bien que cela ne soit pas une limitation de l'invention, de nombreux procédés envisagés dans le cadre de celle-ci comprennent des techniques de dépôt exothermique, dans lesquelles la température du substrat croît pendant le dépôt du revêtement ; il peut donc être nécessaire, comme déjà dit, d'interrompre ce dépôt pour éviter que le substrat n'atteigne la température de dégradation de sa matière constitutive, puis de le refroidir à la température minimale requise conformément à l'invention.Although this is not a limitation of the invention, many methods contemplated therein include exothermic deposition techniques, in which the temperature of the substrate increases during deposition of the coating; it may therefore be necessary, as already said, to interrupt this deposition to prevent the substrate from reaching the degradation temperature of its constituent material, then to cool it to the minimum temperature required in accordance with the invention.
Selon une variante particulièrement intéressante, le substrat est en polycarbonate , le revêtement étant formé à une température au moins égale à 120°C.According to a particularly advantageous variant, the substrate is made of polycarbonate, the coating being formed at a temperature at least equal to 120 ° C.
L'invention a également pour objet un produit comprenant un substrat en matière plastique muni d'un revêtement formé selon le procédé décrit ci- dessus, l'épaisseur moyenne du revêtement étant d'au moins 2 μm, de préférence au moins 4 μm, et de manière particulièrement préférée au moins 6 μm.The subject of the invention is also a product comprising a plastic substrate provided with a coating formed according to the method described above, the average thickness of the coating being at least 2 μm, preferably at least 4 μm, and particularly preferably at least 6 μm.
Un autre objet de l'invention est l'application de ce produit comme pièce en matière plastique non nécessairement transparente telle qu'élément de carrosserie (portière, aile, capot moteur, déflecteur ou équivalent dans des applications autres qu'automobiles), comme vitrage, notamment pour véhicule terrestre, aquatique ou aérien, en particulier pour véhicule automobile, vitrage de sécurité pour casque ou du type exigeant une résistance à la chaleur. L'application d'un vitrage de l'invention pour le bâtiment ou le mobilier urbain - panneau publicitaire, abribus...- est également intéressante. L'invention est illustrée par l'exemple de réalisation suivant.Another object of the invention is the application of this product as a piece of plastic material which is not necessarily transparent such as a bodywork (door, fender, bonnet, deflector or equivalent in applications other than automotive), as glazing, in particular for land, water or air vehicle, in particular for motor vehicle, safety glazing for helmet or of the type requiring resistance in the heat. The application of glazing of the invention for buildings or urban furniture - advertising billboards, bus shelters, etc. - is also interesting. The invention is illustrated by the following embodiment.
EXEMPLE Une feuille de polycarbonate de 300 X 850 mm et 4 mm d'épaisseur, commercialisée par la Société Bayer sous la marque enregistrée Makrolon, est soumise au dépôt d'un revêtement par CVD plasma.EXAMPLE A polycarbonate sheet 300 X 850 mm and 4 mm thick, sold by the Bayer Company under the registered trademark Makrolon, is subjected to the deposition of a coating by plasma CVD.
La chambre de dépôt est équipée d'une source plasma micro-onde de 350The deposit chamber is equipped with a microwave plasma source of 350
X 900 mm composée de plusieurs antennes micro-ondes individuelles travaillant en mode post-décharge avec une puissance maximale totale de 16 kW à la fréquence de 2,45 GHz. Les gaz nécessaires pour le procédé de dépôtX 900 mm composed of several individual microwave antennas working in post-discharge mode with a maximum total power of 16 kW at the frequency of 2.45 GHz. The gases required for the deposition process
(oxygène, argon et hexaméthyldisiloxane sont amenés dans la chambre à travers des contrôleurs de débits massiques et des tuyaux métalliques chauffés à 45°C. Dans un premier essai conforme à l'invention, le revêtement est formé selon les quatre étapes suivantes :(oxygen, argon and hexamethyldisiloxane are brought into the chamber through mass flow controllers and metal pipes heated to 45 ° C. In a first test in accordance with the invention, the coating is formed according to the following four steps:
1) chauffage du substrat à 120°C ;1) heating the substrate to 120 ° C;
2) dépôt de 2,5 μm de revêtement ;2) deposit of 2.5 μm of coating;
3) refroidissement du substrat jusqu'à 120°C par arrêt du dépôt (exothermique) et3) cooling of the substrate to 120 ° C. by stopping the deposition (exothermic) and
4) dépôt de 2,5 μm de revêtement.4) deposit of 2.5 μm of coating.
La température atteinte par le substrat à la fin des étapes 2 et 4 est de 124-125 °C, c'est-à-dire juste inférieure à la température de ramollissement du polycarbonate. Dans un second essai on omet d'agir sur la température du substrat : on dépose en une seule opération 5 μm de revêtement. La température du substrat varie d'environ 20°C (température ambiante) à 85°C.The temperature reached by the substrate at the end of steps 2 and 4 is 124-125 ° C, that is to say just below the softening temperature of the polycarbonate. In a second test, it omits to act on the temperature of the substrate: 5 μm of coating is deposited in a single operation. The substrate temperature ranges from around 20 ° C (room temperature) to 85 ° C.
Dans un troisième essai, on chauffe initialement le substrat à 120 °C , mais on dépose « en une fois » une épaisseur de 5 μm de revêtement. A l'issue de la formation de la couche, le substrat est à une température de 130-132 °C, supérieure à la température de dégradation du polycarbonate ; sa déformation le rend incompatible avec une application comme produit transparent dans lequel une qualité optique même minimale, est requise .In a third test, the substrate is initially heated to 120 ° C, but a thickness of 5 μm of coating is deposited “at once”. At the end of the layer formation, the substrate is at a temperature of 130-132 ° C, higher than the degradation temperature of the polycarbonate; its deformation makes it incompatible with an application as a transparent product in which even minimal optical quality is required.
Les vitrages résultant des premier et deuxième essais sont soumis à 500 tours de cycle Taber avec une meule CS 10 F sous une charge de 500g ; le voile mesuré est inférieur à 10 % dans les deux cas, ce qui traduit une résistance à l'abrasion satisfaisante.The glazings resulting from the first and second tests are subjected to 500 rounds of the Taber cycle with a CS 10 F grinding wheel under a load of 500 g; the haze measured is less than 10% in both cases, which indicates satisfactory abrasion resistance.
D'autres vitrages résultant des premier et deuxième essais sont soumis à un cyclage thermique (ECER 43 10 X -30°C +90 °C en dix jours) , d'autres encore à un stockage à 90°C , et d'autres enfin à une cuisson dans l'eau bouillante. Sont évaluées la présence de fissures, respectivement le moment où elles apparaissent. Les résultats sont consignés dans le tableau ci-dessous.Other glazings resulting from the first and second tests are subjected to thermal cycling (ECER 43 10 X -30 ° C +90 ° C in ten days), still others to storage at 90 ° C, and others finally cooking in boiling water. The presence of cracks is assessed, respectively when they appear. The results are shown in the table below.
TABLEAUBOARD
Les distances entre les fissures observées dans les revêtements sont de l'ordre de 100 μm à 1 mm. Leur apparition précède souvent une délamination du revêtement.The distances between the cracks observed in the coatings are of the order of 100 μm to 1 mm. Their appearance often precedes delamination of the coating.
Le procédé de dépôt spécifique de l'invention permet donc d'éviter ou de retarder l'apparition de microfissures ; les conséquences bénéfiques sur l'adhésion du revêtement sur le substrat, ainsi que sur la qualité optique du produit, sont évidentes. The specific deposition process of the invention therefore makes it possible to avoid or delay the appearance of microcracks; the beneficial consequences on the adhesion of the coating to the substrate, as well as on the optical quality of the product, are obvious.

Claims

REVENDICATIONS
1. Procédé de formation d'un revêtement sur au moins une partie d'un substrat en matière plastique, caractérisé en ce qull est effectué à une température au moins égale à la température maximale d'utilisation du substrat revêtu moins 20°C.1. A method of forming a coating on at least part of a plastic substrate, characterized in that it is carried out at a temperature at least equal to the maximum temperature of use of the coated substrate at least 20 ° C.
2. Procédé selon la revendication 1 , caractérisé en ce qu'il met en œuvre une CVD plasma.2. Method according to claim 1, characterized in that it implements a plasma CVD.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'il est effectué à une température au moins égale à la température maximale d'utilisation du substrat revêtu.3. Method according to claim 1 or 2, characterized in that it is carried out at a temperature at least equal to the maximum temperature of use of the coated substrate.
4. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'il est effectué à une température inférieure à la température de dégradation de la matière plastique.4. Method according to one of the preceding claims, characterized in that it is carried out at a temperature below the degradation temperature of the plastic.
5. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'il est effectué à une température la plus proche possible de la température de dégradation de la matière plastique.5. Method according to one of the preceding claims, characterized in that it is carried out at a temperature as close as possible to the degradation temperature of the plastic.
6. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'il met en œuvre des moyens de refroidissement.6. Method according to one of the preceding claims, characterized in that it implements cooling means.
7. Procédé selon l'une des revendications précédentes, caractérisé en ce que le revêtement est formé en plusieurs étapes.7. Method according to one of the preceding claims, characterized in that the coating is formed in several stages.
8. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'il comprend les opérations consistant successivement à a) stabiliser le substrat à revêtir à une température au moins égale à sa température maximale d'utilisation moins 20 °C , b) former le revêtement en veillant à ce que la température du substrat n'atteigne pas la température de dégradation de la matière plastique, c) effectuer à nouveau les opérations a) et b) si nécessaire, en fonction de l'épaisseur et autres caractéristiques recherchées pour le revêtement. 8. Method according to one of the preceding claims, characterized in that it comprises the operations consisting successively of a) stabilizing the substrate to be coated at a temperature at least equal to its maximum use temperature minus 20 ° C, b) forming the coating, taking care that the temperature of the substrate does not reach the degradation temperature of the plastic, c) repeat operations a) and b) if necessary, depending on the thickness and other characteristics sought for coating.
9. Procédé selon l'une des revendications précédentes, caractérisé en ce que le substrat est en polycarbonate et en ce que le procédé est effectué à une température au moins égale à 120 °C.9. Method according to one of the preceding claims, characterized in that the substrate is made of polycarbonate and in that the process is carried out at a temperature at least equal to 120 ° C.
10. Produit comprenant un substrat en matière plastique muni d'un revêtement formé selon le procédé de l'une des revendications 1 à 9, caractérisé en ce que l'épaisseur moyenne du revêtement est d'au moins 2 μm, de préférence au moins 4 μm et en particulier au moins 6 μm.10. Product comprising a plastic substrate provided with a coating formed according to the method of one of claims 1 to 9, characterized in that the average thickness of the coating is at least 2 μm, preferably at least 4 μm and in particular at least 6 μm.
11. Application du produit selon la revendication 10 comme pièce en matière plastique du type élément de carrosserie, déflecteur ou similaire, vitrage, notamment pour véhicule terrestre, aquatique ou aérien, en particulier pour véhicule automobile, vitrage pour le bâtiment ou le mobilier urbain, vitrage de sécurité pour casque ou du type exigeant une résistance à la chaleur. 11. Application of the product according to claim 10 as a plastic part of the bodywork, deflector or similar type, glazing, in particular for land, water or air vehicle, in particular for motor vehicle, glazing for building or urban furniture, safety glazing for helmet or of the type requiring heat resistance.
EP03758205A 2002-08-06 2003-08-04 Method of forming a coating on a plastic glazing Withdrawn EP1534876A2 (en)

Applications Claiming Priority (3)

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FR0210021A FR2843408B1 (en) 2002-08-06 2002-08-06 METHOD FOR FORMING A COATING ON A GLAZING OF PLASTIC MATERIAL
FR0210021 2002-08-06
PCT/FR2003/002458 WO2004015166A2 (en) 2002-08-06 2003-08-04 Method of forming a coating on a plastic glazing

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AU (1) AU2003274222A1 (en)
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US8206794B2 (en) * 2009-05-04 2012-06-26 The Boeing Company System and method for applying abrasion-resistant coatings
US20160168035A1 (en) * 2014-12-15 2016-06-16 Cpfilms Inc. Abrasion-resistant optical product with improved gas permeability

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JPH0832958B2 (en) * 1987-08-24 1996-03-29 ゼネラル・エレクトリック・カンパニイ Method for manufacturing abrasion resistant plastic articles
US5156882A (en) * 1991-12-30 1992-10-20 General Electric Company Method of preparing UV absorbant and abrasion-resistant transparent plastic articles
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JPH08133891A (en) * 1994-11-04 1996-05-28 Matsushita Electric Ind Co Ltd Method for forming thin film of diamond and forming device therefor
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FR2843408B1 (en) 2005-04-08
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BR0313236A (en) 2005-06-14
KR20050042473A (en) 2005-05-09
US20060013965A1 (en) 2006-01-19
MXPA05001438A (en) 2005-06-06
JP2005534813A (en) 2005-11-17
AU2003274222A1 (en) 2004-02-25
CN1675405A (en) 2005-09-28
WO2004015166A2 (en) 2004-02-19
FR2843408A1 (en) 2004-02-13

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