EP1827716A1 - Method for treating a polymer material, device for implementing said method and use of said device for treating hollow bodies - Google Patents

Method for treating a polymer material, device for implementing said method and use of said device for treating hollow bodies

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Publication number
EP1827716A1
EP1827716A1 EP05850613A EP05850613A EP1827716A1 EP 1827716 A1 EP1827716 A1 EP 1827716A1 EP 05850613 A EP05850613 A EP 05850613A EP 05850613 A EP05850613 A EP 05850613A EP 1827716 A1 EP1827716 A1 EP 1827716A1
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EP
European Patent Office
Prior art keywords
treating
article
mbar
gas
plasma
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EP05850613A
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German (de)
French (fr)
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EP1827716B1 (en
Inventor
Nasser Beldi
Patrick Chollet
Fabrice Oge
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Innovative Systems & Technologies
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Innovative Systems & Technologies
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Classifications

    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • 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
    • B05D3/14—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 electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B05D3/144—Pretreatment of polymeric substrates
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers

Definitions

  • the present invention relates to the technical field of surface treatment processes of polymeric material objects, these objects being intended for the packaging of gaseous products, liquid or solid, or the packaging of mixtures of such products.
  • the invention more particularly relates to techniques for deposition on the surface of polymeric materials using a precursor gas vapor chemically activated by an electric discharge under a reduced atmosphere, in order to modify the physicochemical properties of the surface.
  • said object made of polymeric material.
  • the method according to the invention finds an application and an important industrial interest in that it makes it possible to reduce the diffusion of gases and liquids through the wall of the polymer object.
  • the method according to the invention makes it possible in particular to improve the barrier properties of HDPE containers vis-à-vis gasoline, White Spirit (refined petroleum distillation cup, containing less than 0.05% of benzene) , water, n-butyl acetate, oxygen.
  • White Spirit refined petroleum distillation cup, containing less than 0.05% of benzene
  • the process of the invention finds, in particular, a major industrial interest in that it makes it possible to increase the hydrocarbon diffusion barrier properties obtained by low-pressure plasma deposition on a given polymer material, by electric discharge under a reduced atmosphere.
  • a fluorinated gas or a gaseous composition comprising at least one fluorinated gas.
  • Polymeric materials are light, flexible, resistant, less expensive and easier to install compared to metals or glasses.
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • the resistance of these polymers is too low for their use to be possible in the packaging of certain solvents and low molecular weight volatile compounds, certain acids such as acetic acid, or surfactant solutions.
  • Such products packaged in a container of polymeric material may degrade both the surface of the container in contact with said product and, on the other hand, various properties of the polymeric material thus leading in time to irreversible mechanical embrittlement of said container.
  • This operation of depositing a thin-film material on such substrates made of polymeric material can be carried out for example by high vacuum vapor deposition (commonly referred to as PVD, Physical Vapor Deposition) or plasma deposition under primary vacuum
  • PCVD Plasma Chemical Vapor
  • the techniques for depositing a thin film material by plasmas consist in using a gas or a gaseous mixture from which the atomic elements forming the molecular structure of said layered material are present.
  • Such gases or gas mixtures are called precursors.
  • This (s) gas. is (are) introduced into a reaction chamber in the state of vapor at low pressure and then decomposed (s) by an electric discharge thus forming the plasma.
  • the plasma vapor thus created releases atoms and molecules that are more or less unstable but very which recombine and condense in a thin layer on the surface of the polymer to be coated.
  • HMDSO hexamethyldisiloxane
  • Fluorinated thin-film material deposits on polymer surfaces improve the hydrocarbon diffusion barrier effect of said polymer surface (see US 4869,922)
  • the use of the plasma deposition technique can be very advantageous and constitute an extremely interesting alternative to the conventional fluorination method.
  • said conventional fluorination method conventionally consists in exposing the polymer material surface to a fluorinated gas under precise pressure and temperature conditions, for a very long time, up to several hours.
  • Plasma deposition makes it possible to obtain hydrocarbon diffusion barrier performances comparable to those obtained by conventional fluorination, while using however very small amounts of precursor gas and generally very long completion times. shorter.
  • gases or gas mixtures used in this case must change the energy state and sometimes even the chemical state of the polymer surface without, if possible, causing the growth of a thin layer of an amorphous material.
  • gases it is possible to cite, in a non exhaustive, argon, oxygen, carbon dioxide, hydrogen or a combination of these gases.
  • the coating on polymeric material is obtained at low pressure from a gaseous plasma of 1,1,1-tetrafluoroethane (C 2 H 2 F 4 , or H 2 FC-CF 3 ), a mixture conventionally designated by the name HFC R134a.
  • a gaseous plasma of 1,1,1-tetrafluoroethane C 2 H 2 F 4 , or H 2 FC-CF 3
  • HFC R134a 1,1,1-tetrafluoroethane
  • the coating of polymeric material is obtained at low pressure from a gaseous plasma of pentafluoroethane (C 2 HF 5 or HF 2 C-CF 3), produced conventionally designated under the name HFC R125.
  • the invention makes it possible, inter alia, to obtain a coating having barrier properties to several compounds simultaneously under very advantageous technical-economical conditions.
  • the inventors have surprisingly discovered that the improvement of the hydrocarbon diffusion barrier properties obtained by low pressure plasma deposition on a given polymer material can vary in a very wide range of gain, which may range from one to several tens, depending on the fluorinated gas or the gaseous composition comprising at least one fluorinated gas brought to the plasma state employed, and this for otherwise identical operating conditions (flow rate). gases, pressure, temperature, electric discharge power for plasma generation, plasma generation technique, duration of plasma application).
  • gas comprising at least one fluorinated gas.
  • the inventors have also discovered that, surprisingly, it can be extremely advantageous to make a first deposition layer and then proceed with the deposition of the fluorinated layer, without being able to explain it clearly.
  • the authors propose carrying out a first hydrogenated amorphous carbon deposition with a low-pressure acetylene gas brought to the plasma state, and then producing a second fluorinated carbon deposit using a plasma of R134 (C 2 H 2 F 4 , or H 2 FC-CF 3 or Tetrafluoroethane-1, 1,1,2)
  • R134 C 2 H 2 F 4 , or H 2 FC-CF 3 or Tetrafluoroethane-1, 1,1,2
  • reaction fluids used are inert, not dangerous and inexpensive, which makes the invention very advantageous from one point of time. from an economic point of view.
  • the inventors have also been able to verify that the production of the second fluorinated layer from the gas R134 is particularly interesting because the hydrogen and / or the hydrogenated molecules released by this precursor, by their incorporation in said second fluorinated layer, very substantially improve the stability of the layer.
  • the second fluorinated layer was made from other fluorocarbon gases such as C 2 F 6 , C ⁇ F or C 4 Fs which generally require the addition of hydrogen or else from other fluorinated gases which are a priori similar to R134 gas.
  • the polymer surface for which it is desired to improve the hydrocarbon diffusion barrier properties is introduced into a vacuum-tight treatment chamber.
  • the emptying of the air initially contained in said treatment chamber is carried out by conventional pumping means up to a vacuum level of between 0.001 mbar and 1 mbar; preferentially below 0.1 mbar.
  • the gas or gas mixture is released near the polymer surface which has been introduced into the treatment chamber which will be called the treatment zone.
  • All the reactions described above which occur in the entire volume defined by the presence of the plasma also occurs in the immediate vicinity of the polymer. They depend on a certain number of process parameters such as the pressure or even the nature of the energy used to create the plasma for example but also and mainly of the gas or gaseous mixture used.
  • the energies used for the creation of said plasma may be derived from a DC voltage, a high frequency RF, a radio frequency (13.46 MHz and its harmonics for example) or even microwaves (915 MHz , 2,450 MHz).
  • the volume densities of power involved are between 0.01 W / cm 3 and 10 W / cm 3 , but preferably between 0.1 W / cm 3 and 3 W / cm 3 .
  • the frequencies preferentially used are those, industrial, of 40 kHz, 13.56 MHz and 2450 MHz.
  • the plasma state then has the effect of bringing into a partial ionization state of said gas or gas mixture.
  • the particles resulting from these excitation and decomposition mechanisms can then be recombined with one another to result in more or less unstable particles which can then condense on the surface of the polymer which is immersed in this plasma mixture, or condense on the surface of the polymer.
  • a sufficient plasma phase time which can be between a second and a few minutes but preferably at least one second and at most thirty seconds, the application of energy is stopped which stops any generation of plasma.
  • a second deposition cycle is performed by reproducing according to the cycle described above from a new gas or gas mixture.
  • the first cycle may be a step of preparing the surface of the polymer which consists in "chemically cleaning" said surface of the polymer.
  • the polymer surface is prepared by preferably using an argon plasma or an argon + hydrogen mixture.
  • the inventors have also found that it could be advantageous to use a carbon dioxide plasma to increase the number of oxidized sites on the surface of the favorable polymer, in particular to obtain better performance of the oxygen barrier deposits by example.
  • the pressure conditions are then between 0.01 mbar and 5 mbar, but preferably between 0.05 mbar and 1 mbar.
  • the power conditions are those described above and the plasma preparation times are generally between 1 second and 30 seconds depending on the nature of the polymer surface to be prepared.
  • the barrier layer or the various sub-layers constituting the barrier layer are deposited.
  • this barrier layer may consist of a single layer or the superposition of two or more layers of different chemical nature.
  • the inventors produce two types of sub-layers: a first sublayer of hydrogenated amorphous carbon and a second sublayer of fluorinated amorphous carbon.
  • the first sublayer of hydrogenated amorphous carbon is produced from acetylene gas, the beneficial feature of which is a more or less significant collapse of the pressure when this gas is put into a plasma state, thus favoring the obtaining of a more stable deposit. homogeneous.
  • the second fluorinated amorphous carbon sublayer is made from the precursor gas R134 of chemical formulation C 2 F4H 2 or from the precursor gas R125 of chemical formulation C 2 FsH according to the application.
  • R125 is used in some cases, because it allows a better stability and chemical resistance in particular to products having a significant surfactant effect.
  • HDPE High Density Polyethylene
  • Rectangular means a container whose wall is of a thickness of at least one mm as is the case in the present example.
  • Such a container is placed in a cylindrical metal processing chamber connected to a microwave emitting device emitting at 2450 MHz with conventional standard size waveguide means.
  • the device makes it possible to produce a differential pressure between the internal volume of the container and the external volume so that the external pressure is greater than the internal pressure. In this way, if the external pressure is large enough, the generation of plasma is only inside the container and the deposit is then formed on the inner wall of the latter.
  • the treatment of the container is in several stages.
  • the pumping circuit is in communication with the treatment chamber and the internal volume of the polymer container.
  • Vacuum is achieved using a conventional vacuum prime pump.
  • the pressure inside the container is reduced to a pressure of less than 0.05 mbar while the outside pressure is maintained at about 30 mbar.
  • a mixing flow of argon gas and hydrogen is introduced into the container in proportions 90/10 although this is not a requirement so that the internal pressure is found at a value between 0.05 and
  • a microwave energy is then applied with a power of about 200 W, which allows the creation a surface preparation plasma maintained for a period of 6 seconds. After this time, the microwave energy and the gas mixture flow rate are cut off.
  • a flow of acetylene gas is introduced into the container so that the internal pressure is found at a value between 0.05 and 0.3 mbar.
  • Microwave energy is then applied with a power of about 300 W, which allows the creation of a deposition plasma maintained for a period of one second.
  • a flow of gas R134 is introduced into the container so that the internal pressure is found at a value between 0.05 and 0.3 mbar.
  • Microwave energy is then applied with a power of about 300 W, which allows the creation of a deposition plasma maintained for a period of six seconds. After this time, the microwave energy and the gas flow are cut off.
  • the pumping circuit is isolated from the treatment chamber and the internal volume of the polymer container.
  • the treatment chamber and the polymer container are returned to atmospheric pressure.
  • the containers are filled with a liquid load of about 100 grams, then their openings are closed with a heat-sealable aluminum film.
  • the containers are placed in study at 40 ° C. for a certain time.
  • the permeability is measured by weighing at regular intervals of at least 1 day over a period that may extend over several months. Loss of product by diffusion through the wall of the container is then expressed in mg / day.
  • Oxygen permeability is measured with an OXTRAN (MOCON) device for a period of at least 24 hours.
  • the permeability is expressed in this case in cmVday.
  • the product loss values are given after a conditioning time (in days) indicated in parentheses.
  • the containers thus treated have shown a very good barrier to several compounds such as gasoline, white spirit, water, n-butyl acetate, oxygen.
  • a greater or lesser part of said product is trapped in the mass of the polymer thus resulting in weight gain.
  • Flexible means a container whose wall is of a thickness less than 1 mm as is the case in this example for which the thickness is 0.5 mm.
  • Such a container is placed in a cylindrical metal processing chamber connected to a microwave emitting device emitting at 2450 MHz with conventional standard size waveguide means.
  • the power is adjusted in each phase in relation to the surface to be treated.
  • the containers thus treated have shown a very good barrier to several compounds such as gasoline, White Spirit, water, n-Butyl acetate, oxygen and conventional hydrocarbons.
  • such untreated containers have a hydrocarbon diffusion barrier of 3000 mg / day, whereas these same treated containers have a hydrocarbon diffusion barrier of 25 mg / day at 40 ° C. .
  • HDPE High Density Polyethylene
  • Such a container is placed in a cylindrical metal processing chamber connected to a microwave emitting device emitting at 2450 MHz with conventional standard size waveguide means.
  • the power is adjusted in each phase in relation to the surface to be treated.
  • the containers thus treated have shown a very good barrier to several compounds such as gasoline, White Spirite, water, n-butyl acetate, oxygen and conventional hydrocarbons.
  • such untreated containers have a 1400 mg / day white spirit diffusion barrier, whereas these same treated containers have a barrier to diffusion of 15 mg / day at 40 0 C and after 2 months of maceration.

Abstract

The invention concerns a method for treating a polymer to coat the surface thereof with a barrier-effect coating characterized in that it comprises a discharge plasma in a tetrafluoroethane-1, 1, 1,2. or pentafluoroethane gas. The invention also concerns a device for implementing said method for treating hollow bodies. The invention further concerns the use of such a device for treating a rigid or flexible hollow body made of HDPE.

Description

PROCEDE DE TRAITEMENT D'UN MATERIAU POLYMERE, DISPOSITIF PROCESS FOR PROCESSING POLYMER MATERIAL, DEVICE
POUR IA MISE EN ŒUVRE DE CE PROCEDE ET UTILISATION DE CEFOR IMPLEMENTING THIS METHOD AND USE THEREOF
DISPOSITIF AU TRAITEMENT DE CORPS CREUXDEVICE FOR TREATING HOLLOW BODIES
DOMAINE TECHNIQUE DE L'INVENTIONTECHNICAL FIELD OF THE INVENTION
La présente invention se rapporte au domaine technique des procédés de traitement de surface d'objets en matériau polymère, ces objets étant destinés au conditionnement de produits gazeux, liquides ou solides, ou au conditionnement de mélanges de tels produits.The present invention relates to the technical field of surface treatment processes of polymeric material objects, these objects being intended for the packaging of gaseous products, liquid or solid, or the packaging of mixtures of such products.
L'invention concerne plus particulièrement les techniques de dépôt sur la surface de matériaux polymères à l'aide d'une vapeur de gaz précurseur chimiquement activée par une décharge électrique sous atmosphère réduite, dans le but de modifier les propriétés physico-chimiques de la surface dudit objet en matériau polymère.The invention more particularly relates to techniques for deposition on the surface of polymeric materials using a precursor gas vapor chemically activated by an electric discharge under a reduced atmosphere, in order to modify the physicochemical properties of the surface. said object made of polymeric material.
Le procédé selon l'invention trouve une application et un intérêt industriel important en ce qu'il permet de diminuer la diffusion des gaz et des liquides à travers la paroi de l'objet en polymère.The method according to the invention finds an application and an important industrial interest in that it makes it possible to reduce the diffusion of gases and liquids through the wall of the polymer object.
Le procédé selon l'invention permet notamment d'améliorer les propriétés barrières de récipients en PEHD vis-à-vis de l'essence, du White Spirit (coupe de distillation du pétrole, raffinée, contenant moins de 0,05 % de benzène), de l'eau, du n-Butyle acétate, de l'oxygène.The method according to the invention makes it possible in particular to improve the barrier properties of HDPE containers vis-à-vis gasoline, White Spirit (refined petroleum distillation cup, containing less than 0.05% of benzene) , water, n-butyl acetate, oxygen.
Le procédé de l'invention trouve en particulier un intérêt industriel majeur en ce qu'il permet d'augmenter les propriétés de barrière à la diffusion aux hydrocarbures obtenues par dépôt plasma basse pression sur un matériau polymère donné, par décharge électrique sous atmosphère réduite d'un gaz fluoré ou d'une composition gazeuse comprenant au moins un gaz fluoré. ETAT DE LA TECHNIQUEThe process of the invention finds, in particular, a major industrial interest in that it makes it possible to increase the hydrocarbon diffusion barrier properties obtained by low-pressure plasma deposition on a given polymer material, by electric discharge under a reduced atmosphere. a fluorinated gas or a gaseous composition comprising at least one fluorinated gas. STATE OF THE ART
L'utilisation des polymères dans le domaine du conditionnement—et—de—1-a—eon-s-e-r-vation—de~pxσdα±t*s~ "divers, notamment produits alimentaires, produits chimiques, présente de nombreux avantages.The use of polymers in the field of packaging-and-1-a-eon-ser-vation-of ~ pxσdα ± t * s ~ "various, including food, chemical products, has many advantages.
Les matériaux polymères sont en effet légers, souples, résistants, moins coûteux et de mise en œuvre plus facile comparativement aux métaux ou aux verres.Polymeric materials are light, flexible, resistant, less expensive and easier to install compared to metals or glasses.
Malheureusement, leurs propriétés de barrière par rapport à la diffusion de certains produits liquides ou gazeux, comme l'oxygène ou le dioxyde de carbone, sont généralement mauvaises comparées à celles des métaux et du verre.Unfortunately, their barrier properties relative to the diffusion of certain liquid or gaseous products, such as oxygen or carbon dioxide, are generally poor compared to those of metals and glass.
Ceci est en particulier vrai pour les polymères les plus employés dans l'industrie du conditionnement comme le PE (polyéthylène) , le PP (polypropylène) ou encore le PET (polyéthylène téréphtalate) .This is particularly true for the polymers most used in the packaging industry such as PE (polyethylene), PP (polypropylene) or PET (polyethylene terephthalate).
Par ailleurs, la résistance de ces polymères est trop faible pour que leur emploi soit possible dans le conditionnement de certains solvants et composés volatiles à faible poids moléculaire, certains acides comme l'acide acétique, ou encore des solutions de tensioactifs.Moreover, the resistance of these polymers is too low for their use to be possible in the packaging of certain solvents and low molecular weight volatile compounds, certain acids such as acetic acid, or surfactant solutions.
Des tels produits conditionnés dans un récipient en matériau polymère peuvent dégrader d'une part la surface du récipient en contact avec ledit produit et d'autre part diverses propriétés du matériau polymère conduisant ainsi dans le temps à une fragilisation mécanique irréversible dudit récipient.Such products packaged in a container of polymeric material may degrade both the surface of the container in contact with said product and, on the other hand, various properties of the polymeric material thus leading in time to irreversible mechanical embrittlement of said container.
De plus, à cause des phénomènes de diffusion, ces mêmes produits peuvent migrer lentement et de façon continue de l'intérieur du récipient en matériau polymère vers l'extérieur en traversant la paroi dudit récipient en matériau polymère et se propager ainsi dansMoreover, because of the diffusion phenomena, these same products can migrate slowly and continuously from the inside of the container of polymer material outwardly through the wall of said container made of polymeric material and thus propagate in
1'environnement. Durant cette migration, une part plus ou moins importante de ces produits est piégée, augmentant ainsi le poids initial du récipient en matériau polymère.1'environnement. During this migration, more or less important of these products is trapped, thus increasing the initial weight of the container of polymeric material.
_ ..JJfL-. variation de poids .peut- —être -de. plusieurs pourcents et, avec le temps, la paroi du récipient en matériau polymère gonfle, sa composition chimique se modifie._ ..JJfL-. variation in weight. may-be. several percents and, with time, the container wall of polymer material swells, its chemical composition changes.
Ses propriétés mécaniques évoluent parfois de manière dramatique et une fragilisation mécanique irréversible dudit récipient peut être constatée. Le dépôt d'un matériau en couche mince, reconnu pour ses propriétés de barrière ou ses propriétés de protection, sur la surface interne et/ou externe d'un récipient en matériau polymère est largement connu et employé depuis de nombreuses années à titre de solution aux différents problèmes posés ci-dessus.Its mechanical properties sometimes evolve dramatically and an irreversible mechanical embrittlement of said container can be seen. The deposition of a thin-layer material, recognized for its barrier properties or its protective properties, on the inner and / or outer surface of a container of polymer material is widely known and has been used for many years as a solution. to the different problems posed above.
Cette opération de dépôt d'un matériau en couche mince sur de tels substrats en matériau polymères peut être réalisée par exemple par dépôt en phase vapeur sous vide poussé (communément désigné par PVD, Physical Vapor Déposition) ou dépôt en phase plasma sous vide primaireThis operation of depositing a thin-film material on such substrates made of polymeric material can be carried out for example by high vacuum vapor deposition (commonly referred to as PVD, Physical Vapor Deposition) or plasma deposition under primary vacuum
(communément désigné par PCVD, Plasma Chemical Vapor(commonly referred to as PCVD, Plasma Chemical Vapor
Déposition ou encore PECVD, Plasma Enhanced Chemical VaporDeposition or PECVD, Plasma Enhanced Chemical Vapor
Déposition) .Deposition).
D'une façon plus précise, les techniques de dépôt d'un matériau en couche mince par plasmas consistent à utiliser un gaz ou un mélange gazeux à partir duquel les éléments atomiques formant la structure moléculaire dudit matériau en couche sont présents.More specifically, the techniques for depositing a thin film material by plasmas consist in using a gas or a gaseous mixture from which the atomic elements forming the molecular structure of said layered material are present.
De tels gaz ou mélanges gazeux sont dits précurseurs. Ce(s) gaz. est (sont) introduits dans une chambre de réaction à l'état de vapeur à basse pression puis décomposé(s) par une décharge électrique formant ainsi le plasma.Such gases or gas mixtures are called precursors. This (s) gas. is (are) introduced into a reaction chamber in the state of vapor at low pressure and then decomposed (s) by an electric discharge thus forming the plasma.
La vapeur de plasma ainsi créée libère des atomes et des molécules plus ou moins instables mais très réactionnelles qui se recombinent et se condensent en une couche mince sur la surface du polymère à revêtir.The plasma vapor thus created releases atoms and molecules that are more or less unstable but very which recombine and condense in a thin layer on the surface of the polymer to be coated.
_ Le document -US -3—4-85-~666• --(de "~Ï9'65") divulgue un procédé de réalisation d'une couche barrière à base de nitrure de silicium. Le document US 3442686 (de 1969) divulgue un procédé de réalisation d'une couche barrière à base d'oxyde de silicium. Les documents US 4756964 (de_ The document -US -3-4-85- ~ 666 • - (from "~ i9 '65") discloses a method for producing a barrier layer based on silicon nitride. Document US 3442686 (of 1969) discloses a method for producing a barrier layer based on silicon oxide. US 4756964 (from
1986) et WO99/49991 décrivent des dépôts de carbone. Le document US 4830873 (de 1985) décrit la réalisation d'une couche de protection contre les agressions chimiques et physiques, le gaz précurseur utilisé étant un mélange de1986) and WO99 / 49991 describe carbon deposits. Document US Pat. No. 4,830,873 (of 1985) describes the production of a protective layer against chemical and physical aggression, the precursor gas used being a mixture of
HMDSO (hexamethyldisiloxane) et d'oxygène.HMDSO (hexamethyldisiloxane) and oxygen.
Les dépôts de matériaux en couches minces fluorées sur des surfaces en polymère permettent l'amélioration de l'effet de barrière à la diffusion des hydrocarbures de ladite surface en polymère (voir le document US 4869 922)Fluorinated thin-film material deposits on polymer surfaces improve the hydrocarbon diffusion barrier effect of said polymer surface (see US 4869,922)
Pour la réalisation d'une barrière à la diffusion des hydrocarbures de surface en polymère ci-dessus citée, l'utilisation de la technique de dépôt par plasma peut être très avantageuse et constituer une alternative extrêmement intéressante à la méthode classique de fluoration.In order to provide a diffusion barrier for the surface hydrocarbons in polymer mentioned above, the use of the plasma deposition technique can be very advantageous and constitute an extremely interesting alternative to the conventional fluorination method.
En effet, ladite méthode classique de fluoration consiste conventionnellement à exposer la surface en matériau polymère à un gaz fluoré dans des conditions de pression et de température précises, pendant un temps très long, pouvant atteindre plusieurs heures.Indeed, said conventional fluorination method conventionally consists in exposing the polymer material surface to a fluorinated gas under precise pressure and temperature conditions, for a very long time, up to several hours.
Cette technique de fluoration, qui est d'un investissement très coûteux, nécessite l'utilisation de gaz fluorés en grande quantité qu'il est nécessaire de retraiter en fin de phase de fluoration.This fluorination technique, which is a very expensive investment, requires the use of fluorinated gases in large quantities that must be reprocessed at the end of the fluorination phase.
Le dépôt par plasma permet d'obtenir des performances de barrière à la diffusion des hydrocarbures comparables à celles obtenues par fluoration classique en utilisant cependant des quantités de gaz précurseur très faibles et des temps de réalisation en général beaucoup plus courts.Plasma deposition makes it possible to obtain hydrocarbon diffusion barrier performances comparable to those obtained by conventional fluorination, while using however very small amounts of precursor gas and generally very long completion times. shorter.
Cependant, les deux inconvénients majeurs de la technique—de -dépôt - par plasma sont- l'utilisation de gaz précurseurs généralement très coûteux et les procédés de mise en oeuvre souvent complexes qui en font une technique très difficilement industrialisable.However, the two major drawbacks of the plasma deposition technique are the use of precursor gases which are generally very expensive and the often complex methods of implementation which make them a technique that is very difficult to industrialize.
La réalisation d'une barrière à la diffusion des hydrocarbures de surface en polymère trouve une importante application dans le domaine des réservoirs automobiles. Le document DE 3027531 (de 1980) décrit une méthode de traitement de tels réservoirs à carburant en polymère PE haute densité (PEHD ou HDPE) par une technique plasma PECVD dans laquelle le précurseur est une vapeur de gaz fluoré ou un mélange de gaz fluorés introduit à basse pression. Le document DE3908418 décrit l'utilisation du mélange d'un précurseur fluoré CHF3 et du C4H6. Le document EP 0739655 décrit la réalisation de multicouches à partir des précurseurs C2H4, CF3H.Achieving a barrier to the diffusion of surface hydrocarbons made of polymer finds an important application in the field of automobile tanks. Document DE 3027531 (of 1980) describes a method of treating such high density PE polymer fuel tanks (HDPE or HDPE) by a PECVD plasma technique in which the precursor is a fluorinated gas vapor or a mixture of fluorinated gases introduced. at low pressure. DE3908418 discloses the use of the mixture of a CHF 3 and C 4 H 6 fluorinated precursor. EP 0739655 describes the production of multilayers from precursors C 2 H 4 , CF 3 H.
La mise en œuvre industrielle des techniques ci- dessus évoquées reste délicate et peu adaptée aux contraintes technico-économiques, du fait notamment du coût élevé des gaz précurseurs et des temps de cycle élevés.The industrial implementation of the aforementioned techniques remains delicate and poorly adapted to techno-economic constraints, particularly because of the high cost of precursor gases and high cycle times.
Préalablement à la réalisation du dépôt d'une couche mince à effet de barrière à la diffusion sur une surface en polymère, il est souvent procédé à une préparation de ladite surface en polymère avec par exemple la même technique de génération de plasma sous basse pression que celle utilisée pour réaliser ledit dépôt de couche mince. Les gaz ou les mélanges gazeux utilisés dans ce cas doivent modifier l'état énergétique et parfois même chimique de la surface en polymère sans entraîner si possible la croissance d'une couche mince d'un matériau amorphe. Parmi ces gaz on peut citer, de manière non exhaustive, l'argon, l'oxygène, le dioxyde de carbone, l'hydrogène ou une combinaison de ces gaz.Prior to performing the deposition of a diffusion barrier thin layer on a polymer surface, it is often carried out a preparation of said polymer surface with for example the same technique of low pressure plasma generation as that used to make said thin film deposition. The gases or gas mixtures used in this case must change the energy state and sometimes even the chemical state of the polymer surface without, if possible, causing the growth of a thin layer of an amorphous material. Among these gases, it is possible to cite, in a non exhaustive, argon, oxygen, carbon dioxide, hydrogen or a combination of these gases.
Le document .US 453-627.1 (de 1983).. décrd-t-par exemple l'emploi d'un plasma d'oxygène. Le brevet EP 0460966 (de 1991) décrit la génération de plasma à pression atmosphérique, comme un traitement corona, pour préparer la surface.The document . US Pat. No. 4,523,627 (1983) describes, for example, the use of an oxygen plasma. EP 0460966 (1991) describes the generation of plasma at atmospheric pressure, such as a corona treatment, to prepare the surface.
PRESENTATION SOMMAIRE DE L'INVENTION Dans un premier mode de réalisation actuellement préféré de la présente invention, le revêtement sur matériau polymère est obtenu à basse pression à partir d'un plasma gazeux de tétrafluoroéthane-1, 1, 1, 2 (C2H2F4, ou H2FC-CF3) , mélange désigné conventionnellement par l'appellation HFC Rl34a.SUMMARY PRESENTATION OF THE INVENTION In a presently preferred embodiment of the present invention, the coating on polymeric material is obtained at low pressure from a gaseous plasma of 1,1,1-tetrafluoroethane (C 2 H 2 F 4 , or H 2 FC-CF 3 ), a mixture conventionally designated by the name HFC R134a.
Dans un deuxième' mode de réalisation actuellement préféré de la présente invention, le revêtement sur matériau polymère est obtenu à basse pression à partir d'un plasma gazeux de pentafluoroéthane (C2HF5 ou HF2C-CF3) , produit conventionnellement désigné sous l'appellation HFC R125.In a second guidance currently preferred embodiment of the present invention, the coating of polymeric material is obtained at low pressure from a gaseous plasma of pentafluoroethane (C 2 HF 5 or HF 2 C-CF 3), produced conventionally designated under the name HFC R125.
D'autres objets et avantages de la présente invention apparaîtront clairement dans la description détaillée ci-dessous. L'invention permet, entre autres, l'obtention d'un revêtement ayant des propriétés barrières à plusieurs composés simultanément dans des conditions technico- économiques très avantageuses.Other objects and advantages of the present invention will become apparent from the detailed description below. The invention makes it possible, inter alia, to obtain a coating having barrier properties to several compounds simultaneously under very advantageous technical-economical conditions.
DESCRIPTION DETAILLEE DE L'INVENTIONDETAILED DESCRIPTION OF THE INVENTION
Les inventeurs ont découvert de manière très surprenante que l'amélioration des propriétés de barrière à la diffusion aux hydrocarbures obtenue par dépôt plasma basse pression sur un matériau polymère donné pouvait varier dans une plage de gain très large, pouvant aller de un à plusieurs dizaines, selon le gaz fluoré ou la composition gazeuse comprenant au moins un gaz_Jluoré porté à l'état de plasma employé, et ceci pour des conditions opératoires par ailleurs identiques (débit des gaz, pression, température, puissance de la décharge électrique pour la génération du plasma, technique de génération du plasma, durée de l'application du plasma).The inventors have surprisingly discovered that the improvement of the hydrocarbon diffusion barrier properties obtained by low pressure plasma deposition on a given polymer material can vary in a very wide range of gain, which may range from one to several tens, depending on the fluorinated gas or the gaseous composition comprising at least one fluorinated gas brought to the plasma state employed, and this for otherwise identical operating conditions (flow rate). gases, pressure, temperature, electric discharge power for plasma generation, plasma generation technique, duration of plasma application).
Les inventeurs ne sont pas en mesure de donner une explication de cette surprenante découverte.The inventors are not able to give an explanation of this surprising discovery.
Les inventeurs ont constaté que, dans le domaine exploré, il n'y a pas de corrélations évidentes entre les performances de barrière à la diffusion aux hydrocarbures et les rapports entre les différentes quantités d'atomes par unité de volume de gaz fluoré ou de composition gazeuse comprenant au moins un gaz fluoré.The inventors have found that, in the field under study, there are no obvious correlations between the hydrocarbon diffusion barrier performance and the ratios between the different quantities of atoms per unit volume of fluorinated gas or composition. gas comprising at least one fluorinated gas.
Les inventeurs ont également découvert que, de manière surprenante, il peut être extrêmement avantageux de réaliser une première couche de dépôt particulière puis de procéder ensuite au dépôt de la couche fluorée, sans pouvoir l'expliquer de manière claire.The inventors have also discovered that, surprisingly, it can be extremely advantageous to make a first deposition layer and then proceed with the deposition of the fluorinated layer, without being able to explain it clearly.
De manière préférentielle, les auteurs proposent la réalisation d'un premier dépôt de carbone amorphe hydrogéné avec un gaz d'acétylène à basse pression porté à l'état de plasma, puis la réalisation d'un second dépôt de carbone fluoré à l'aide d'un plasma de R134 (C2H2F4, ou H2FC-CF3 ou Tétrafluoroéthane-1, 1,1,2)Preferably, the authors propose carrying out a first hydrogenated amorphous carbon deposition with a low-pressure acetylene gas brought to the plasma state, and then producing a second fluorinated carbon deposit using a plasma of R134 (C 2 H 2 F 4 , or H 2 FC-CF 3 or Tetrafluoroethane-1, 1,1,2)
Outre les excellentes performances de propriétés de barrière à la diffusion aux hydrocarbures obtenues, un des avantages d'un tel procédé est que les fluides réactionnels utilisés sont inertes, pas dangereux et peu onéreux, ce qui rend l'invention très avantageuse d'un point de vue économique.In addition to the excellent performance of hydrocarbon diffusion barrier properties obtained, one of the advantages of such a process is that the reaction fluids used are inert, not dangerous and inexpensive, which makes the invention very advantageous from one point of time. from an economic point of view.
Les inventeurs ont par ailleurs pu vérifier que la réalisation de la seconde couche fluorée à partir du gaz R134 est particulièrement intéressante, parce que l'hydrogène et/ou les molécules hydrogénées libérées par ce précurseur permettaient, par leur incorpjoration dans ladite seconde couche fluorée, d'améliorer très sensiblement la stabilité de la couche.The inventors have also been able to verify that the production of the second fluorinated layer from the gas R134 is particularly interesting because the hydrogen and / or the hydrogenated molecules released by this precursor, by their incorporation in said second fluorinated layer, very substantially improve the stability of the layer.
Ils attribuent ce comportement à des phénomènes de saturation des liaisons pendantes qui permet de diminuer les contraintes mécaniques aux interfaces.They attribute this behavior to phenomena of saturation of the hanging links which makes it possible to reduce the mechanical stresses at the interfaces.
Cette particularité n'a pas été constatée lorsque la seconde couche fluorée était réalisée à partir d'autres gaz fluorocarbonés comme le C2F6, CβFç ou le C4Fs qui nécessitent généralement l'addition d'hydrogène ou bien encore à partir d'autres gaz fluorés pourtant a priori similaires au gaz R134. Du point de vue opératoire, la surface polymère pour laquelle on souhaite améliorer les propriétés de barrière à la diffusion aux hydrocarbures est introduite dans une chambre de traitement étanche au vide.This particularity was not observed when the second fluorinated layer was made from other fluorocarbon gases such as C 2 F 6 , Cβ F or C 4 Fs which generally require the addition of hydrogen or else from other fluorinated gases which are a priori similar to R134 gas. From the operating point of view, the polymer surface for which it is desired to improve the hydrocarbon diffusion barrier properties is introduced into a vacuum-tight treatment chamber.
On réalise le vidage de l'air contenu initialement de ladite chambre de traitement grâce à des moyens conventionnels de pompage, jusque un niveau de vide compris entre 0.001 mbar et 1 mbar; préférentiellement en dessous de 0.1 mbar.The emptying of the air initially contained in said treatment chamber is carried out by conventional pumping means up to a vacuum level of between 0.001 mbar and 1 mbar; preferentially below 0.1 mbar.
Ensuite, un débit de gaz ou de mélange gazeux est introduit dans ladite chambre de traitement.Then, a flow of gas or gas mixture is introduced into said processing chamber.
Cela a généralement pour effet d'augmenter la pression à l'intérieur de la chambre de traitement à des valeurs comprises entre 0.002 mbar et 10 mbar; le débit étant choisi de préférence pour atteindre une pression en dessous de 1 mbar mais au-dessus de 0.01 mbar.This generally has the effect of increasing the pressure inside the treatment chamber to values between 0.002 mbar and 10 mbar; the flow rate being preferably chosen to reach a pressure below 1 mbar but above 0.01 mbar.
Le gaz ou le mélange gazeux est libéré à proximité de la surface polymère qui a été introduite dans la chambre de traitement que l'on appellera zone de traitement.The gas or gas mixture is released near the polymer surface which has been introduced into the treatment chamber which will be called the treatment zone.
Dans cette zone de traitement, une énergie électrique ou électromagnétique est appliquée à l'aide de moyens spécifiques de génération et de transport de la dite énergie, ce qui a généralement pour effet de porter le gaz ou le mélange gazeux à l'état de plasma .si certaines conditions de pression et de densité de puissance d'énergie sont réunies.In this treatment zone, electrical or electromagnetic energy is applied using specific means for generating and transporting said energy, which generally has the effect of bringing the gas or gas mixture to the plasma state .si certain pressure conditions and energy power density are combined.
L'ensemble des réactions décrites plus haut et qui se produisent dans tout le volume délimité par la présence du plasma se produit également à proximité immédiate du polymère. Elles dépendent d'un certain nombre de paramètres de procédé comme la pression ou bien encore la nature de l'énergie utilisée pour créer le plasma par exemple mais aussi et principalement du gaz ou du mélange gazeux utilisé. Les énergies utilisées pour la création dudit plasma peuvent être issues d'une tension continue (DC), d'une haute fréquence HF, d'une radiofréquence (13,46 MHz et ses harmoniques par exemple) ou bien encore de microondes (915 MHz, 2 450 MHz) . Les densités volumiques de puissance mises en jeu sont comprises entre 0.01 W/cm3 et 10 W/cm3, mais préférentiellement comprises entre 0.1 W/cm3 et 3 W/cm3.All the reactions described above which occur in the entire volume defined by the presence of the plasma also occurs in the immediate vicinity of the polymer. They depend on a certain number of process parameters such as the pressure or even the nature of the energy used to create the plasma for example but also and mainly of the gas or gaseous mixture used. The energies used for the creation of said plasma may be derived from a DC voltage, a high frequency RF, a radio frequency (13.46 MHz and its harmonics for example) or even microwaves (915 MHz , 2,450 MHz). The volume densities of power involved are between 0.01 W / cm 3 and 10 W / cm 3 , but preferably between 0.1 W / cm 3 and 3 W / cm 3 .
Les fréquences préférentiellement utilisées sont celles, industrielles, de 40 kHz, 13.56 MHz et 2450 MHz. L'état plasma a alors pour effet de porter dans un état d'ionisation partielle dudit gaz ou mélange gazeux.The frequencies preferentially used are those, industrial, of 40 kHz, 13.56 MHz and 2450 MHz. The plasma state then has the effect of bringing into a partial ionization state of said gas or gas mixture.
Les particules issues de ces mécanismes d'excitation et de décomposition peuvent alors soit se recombiner entre-elles pour aboutir à des particules plus ou moins instables qui peuvent alors se condenser sur la surface du polymère qui se trouve plongée dans ce mélange plasma, soit également se condenser sur la surface du polymère.The particles resulting from these excitation and decomposition mechanisms can then be recombined with one another to result in more or less unstable particles which can then condense on the surface of the polymer which is immersed in this plasma mixture, or condense on the surface of the polymer.
On observe alors, pour le procédé de dépôt, la réalisation d'une couche de dépôt dont l'épaisseur dépend du temps d'application de la phase plasma.We then observe, for the deposition process, the realization of a deposition layer whose thickness depends the time of application of the plasma phase.
Donc, après un temps de phase plasma suffisant qui peut être compris entre une seconde et__que_l_ques minutes mais préférentiellement au moins de une seconde et au plus de trente secondes, l'application d'énergie est arrêtée ce qui stoppe toute génération de plasma.Thus, after a sufficient plasma phase time which can be between a second and a few minutes but preferably at least one second and at most thirty seconds, the application of energy is stopped which stops any generation of plasma.
Le débit de gaz ou de mélange gazeux est également arrêté, puis l'enceinte est remise à la pression atmosphérique. Dans une variante, avant de remettre l'enceinte à la pression atmosphérique, un second cycle de dépôt est réalisé en reproduisant selon le cycle décrit précédemment à partir d'un nouveau gaz ou mélange gazeux.The flow of gas or gas mixture is also stopped, then the chamber is returned to atmospheric pressure. In a variant, before returning the chamber to atmospheric pressure, a second deposition cycle is performed by reproducing according to the cycle described above from a new gas or gas mixture.
Dans une autre variante, plusieurs cycles sont réalisés avec différents gaz ou mélanges gazeux permettant ainsi de revêtir la surface du polymère d'autant ' de couches.In another variant, several cycles are performed with different gases or gas mixtures and especially for coating the surface of the polymer 'layers.
Dans une autre variante, le premier cycle peut être une étape de préparation de la surface du polymère qui consiste à « nettoyer chimiquement » ladite surface du polymère.In another variant, the first cycle may be a step of preparing the surface of the polymer which consists in "chemically cleaning" said surface of the polymer.
Dans cette dernière variante, il est procédé à une préparation de la surface du polymère en utilisant de manière préférentielle un plasma d'argon ou de mélange argon + hydrogène.In this latter variant, the polymer surface is prepared by preferably using an argon plasma or an argon + hydrogen mixture.
Les inventeurs ont également constaté qu'il pouvait être avantageux d'utiliser un plasma de dioxyde de carbone pour augmenter le nombre de sites oxydés sur la surface du polymère favorable en particulier à l'obtention de meilleures performances des dépôts barrières à l'oxygène par exemple.The inventors have also found that it could be advantageous to use a carbon dioxide plasma to increase the number of oxidized sites on the surface of the favorable polymer, in particular to obtain better performance of the oxygen barrier deposits by example.
Les conditions de pression sont comprises alors entre 0.01 mbar et 5 mbar mais de façon préférentielle comprises entre 0.05 mbar et 1 mbar. Les conditions de puissance sont celles décrites plus haut et les temps de préparation plasma sont généralement compris entre 1 seconde et 30 secondes selon la nature de la surface polymère à préparer. Après cette phase de préparation, il est procédé au dépôt de la couche barrière ou des différentes sous-couches constituant la couche barrière.The pressure conditions are then between 0.01 mbar and 5 mbar, but preferably between 0.05 mbar and 1 mbar. The power conditions are those described above and the plasma preparation times are generally between 1 second and 30 seconds depending on the nature of the polymer surface to be prepared. After this preparation phase, the barrier layer or the various sub-layers constituting the barrier layer are deposited.
Ainsi, cette couche barrière peut être constituée d'une couche unique ou de la superposition de deux ou plusieurs couches de nature chimique différente.Thus, this barrier layer may consist of a single layer or the superposition of two or more layers of different chemical nature.
De manière préférentielle, et selon une variante préférée, les inventeurs réalisent deux types de sous- couches : une première sous-couche de carbone amorphe hydrogéné et une seconde sous-couche du carbone amorphe fluoré.Preferably, and according to a preferred variant, the inventors produce two types of sub-layers: a first sublayer of hydrogenated amorphous carbon and a second sublayer of fluorinated amorphous carbon.
La première sous-couche de carbone amorphe hydrogéné est réalisée à partir du gaz acétylène dont la particularité bénéfique est un effondrement plus ou moins important de la pression quand ce gaz est mis dans un état de plasma favorisant ainsi l'obtention d'un dépôt plus homogène.The first sublayer of hydrogenated amorphous carbon is produced from acetylene gas, the beneficial feature of which is a more or less significant collapse of the pressure when this gas is put into a plasma state, thus favoring the obtaining of a more stable deposit. homogeneous.
La seconde sous-couche de carbone amorphe fluoré est réalisée à partir du gaz précurseur R134 de formulation chimique C2F4H2 ou bien à partir du gaz précurseur R125 de formulation chimique C2FsH selon l'application.The second fluorinated amorphous carbon sublayer is made from the precursor gas R134 of chemical formulation C 2 F4H 2 or from the precursor gas R125 of chemical formulation C 2 FsH according to the application.
Le R125 est utilisé dans certains cas, car il permet une meilleure stabilité et résistance chimique notamment aux produits ayant un effet tensio-actif important.R125 is used in some cases, because it allows a better stability and chemical resistance in particular to products having a significant surfactant effect.
RESULTATSRESULTS
Résultats 1Results 1
Des récipients en polymère Polyéthylène Haute Densité (PEHD) rigides, creux et à ouverture totale, d'une contenance de 0,2 litre ont été traités selon le procédé de l'invention.Polyethylene High Density Polyethylene (HDPE) polymer containers, rigid, hollow and with total opening, of a 0.2 liter capacity were treated according to the process of the invention.
On entend par_rigide un récipient dont—la paroi est d'une épaisseur d'au moins un mm comme c'est le cas dans le présent exemple.Rectangular means a container whose wall is of a thickness of at least one mm as is the case in the present example.
Un tel récipient est placé dans une chambre de traitement métallique de forme cylindrique reliée à un dispositif d'émission de micro-ondes émettant à 2450 MHz avec des moyens classiques de guide d'ondes aux dimensions standards.Such a container is placed in a cylindrical metal processing chamber connected to a microwave emitting device emitting at 2450 MHz with conventional standard size waveguide means.
Dans la pratique, le dispositif permet de réaliser une pression différentielle entre le volume interne du récipient et le volume externe de sorte que la pression extérieure soit supérieure à la pression interne. De cette façon, si la pression externe est suffisamment grande, la génération du plasma se fait uniquement à l'intérieur du récipient et le dépôt est alors réalisé sur la paroi interne de ce dernier.In practice, the device makes it possible to produce a differential pressure between the internal volume of the container and the external volume so that the external pressure is greater than the internal pressure. In this way, if the external pressure is large enough, the generation of plasma is only inside the container and the deposit is then formed on the inner wall of the latter.
Conformément à la présente invention, le traitement du récipient se fait en plusieurs étapes.According to the present invention, the treatment of the container is in several stages.
Le circuit de pompage est mis en communication avec la chambre de traitement et du volume interne du récipient en polymère.The pumping circuit is in communication with the treatment chamber and the internal volume of the polymer container.
Le vide est réalisé à l'aide d'une pompe primaire à vide classique.Vacuum is achieved using a conventional vacuum prime pump.
La pression à l'intérieur du récipient est ramenée jusqu'à une pression inférieure à 0.05 mbar alors que la pression à l'extérieur est maintenue à environ 30 mbar.The pressure inside the container is reduced to a pressure of less than 0.05 mbar while the outside pressure is maintained at about 30 mbar.
Un débit de mélange de gaz argon et hydrogène est introduit dans le récipient dans des proportions 90/10 bien que cela ne soit pas une exigence de sorte que la pression interne se retrouve à une valeur comprise entre 0.05 etA mixing flow of argon gas and hydrogen is introduced into the container in proportions 90/10 although this is not a requirement so that the internal pressure is found at a value between 0.05 and
1 mbar.1 mbar.
Une énergie micro-ondes est alors appliquée avec une puissance d'environ 200 W, ce qui permet la création d'un plasma de préparation de surface maintenu pendant une durée de 6 secondes. Après ce temps, l'énergie micro-ondes et le débit de mélange de gaz sont coupés.A microwave energy is then applied with a power of about 200 W, which allows the creation a surface preparation plasma maintained for a period of 6 seconds. After this time, the microwave energy and the gas mixture flow rate are cut off.
Un débit de gaz acétylène est introduit dans le récipient de sorte que la pression interne se retrouve à une valeur comprise entre 0.05 et 0.3 mbar.A flow of acetylene gas is introduced into the container so that the internal pressure is found at a value between 0.05 and 0.3 mbar.
Une énergie micro-ondes est alors appliquée avec une puissance d'environ 300 W, ce qui permet la création d'un plasma de dépôt maintenu pendant une durée de une seconde.Microwave energy is then applied with a power of about 300 W, which allows the creation of a deposition plasma maintained for a period of one second.
Après ce temps, l'énergie micro-onde et le débit de gaz sont coupés.After this time, the microwave energy and the gas flow are cut off.
Un débit de gaz R134 est introduit dans le récipient de sorte que la pression interne se retrouve à une valeur comprise entre 0.05 et 0.3 mbar.A flow of gas R134 is introduced into the container so that the internal pressure is found at a value between 0.05 and 0.3 mbar.
Une énergie micro-ondes est alors appliquée avec une puissance d'environ 300 W, ce qui permet la création d'un plasma de dépôt maintenu pendant une durée de six secondes. Après ce temps, l'énergie micro-onde et le débit de gaz sont coupés.Microwave energy is then applied with a power of about 300 W, which allows the creation of a deposition plasma maintained for a period of six seconds. After this time, the microwave energy and the gas flow are cut off.
Le circuit de pompage est isolé de la chambre de traitement et du volume interne du récipient en polymère.The pumping circuit is isolated from the treatment chamber and the internal volume of the polymer container.
La chambre de traitement et le récipient en polymère sont remis à la pression atmosphérique.The treatment chamber and the polymer container are returned to atmospheric pressure.
Il a été suivi un protocole de conditionnement et de mesure qui est décrit dans les normes relatives au transport de matières dangereuses.It was followed a conditioning and measurement protocol that is described in the standards for the transport of hazardous materials.
Les récipients sont remplis d'une charge de liquide d'environ 100 grammes, puis leurs ouvertures sont fermées à l'aide d'un film aluminium thermo-scellable.The containers are filled with a liquid load of about 100 grams, then their openings are closed with a heat-sealable aluminum film.
Ainsi conditionnés, les récipients sont placés en étude à 40 0C pendant un certain temps. On mesure la perméabilité par pesées à intervalles réguliers d'au moins 1 jour sur une période pouvant s'étaler sur plusieurs mois. Les pertes de produit par diffusion au travers de la paroi du récipient sont alors exprimés en mg/jour.Thus packaged, the containers are placed in study at 40 ° C. for a certain time. The permeability is measured by weighing at regular intervals of at least 1 day over a period that may extend over several months. Loss of product by diffusion through the wall of the container is then expressed in mg / day.
La mesure de perméabilité à l'oxygène est faite avec un appareil OXTRAN (MOCON) sur une durée d'au moins 24 heures. La perméabilité est exprimée dans ce cas en cmVjour.Oxygen permeability is measured with an OXTRAN (MOCON) device for a period of at least 24 hours. The permeability is expressed in this case in cmVday.
Les performances de barrières à la diffusion de produits standards ont été mesurées et sont rappelées dans le tableau 1.The performance of barriers to the diffusion of standard products have been measured and are recalled in Table 1.
Les valeurs de pertes de produit sont données après un temps de conditionnement (en jours) indiqué entre parenthèses.The product loss values are given after a conditioning time (in days) indicated in parentheses.
Tableau 1 : Performances barrières à la diffusion,Table 1: Performance barriers to diffusion,
Les récipients ainsi traités ont montré une très bonne barrière à plusieurs composés tels que l'essence, le White Spirit, l'eau, le n-Butyle acétate, l'oxygène. Lors du processus de diffusion du produit contenu au travers d'une paroi en polymère, une part plus ou moins grande dudit produit est piégée dans la masse du polymère se traduisant ainsi à une prise de poids.The containers thus treated have shown a very good barrier to several compounds such as gasoline, white spirit, water, n-butyl acetate, oxygen. During the diffusion process of the product contained through a polymer wall, a greater or lesser part of said product is trapped in the mass of the polymer thus resulting in weight gain.
L'application du procédé inventif tel que décrite ci dessus, sur ces récipients en polymères, donnent également une amélioration de leur tenue à la prise de poids après 40 jours de conditionnement.The application of the inventive method as described above, on these polymer containers, also give an improvement in their resistance to the setting of weight after 40 days of conditioning.
De même, une amélioration à la tenue à l'-abrasion est constatée.Similarly, an improvement in abrasion resistance is noted.
Ces résultats ont pu être confirmés par une expertise réalisée par le TNO (Netherlands Organisation for Applied Scientific Reseacrch) .These results have been confirmed by an expert report made by the Netherlands Organization for Applied Scientific Reseacr (TNO).
Résultats 2 Des récipients en polymère Polyéthylène Haute Densité (PEHD) souples, creux, d'une contenance de 0,5 litre ont été traités selon le procédé de l'invention.Results 2 Hollow flexible flexible polyethylene polymer (HDPE) containers with a capacity of 0.5 liter were treated according to the method of the invention.
On entend par souple un récipient dont la paroi est d'une épaisseur inférieure à 1 mm comme c'est le cas dans le présent exemple pour lequel l'épaisseur est de 0.5 mm.Flexible means a container whose wall is of a thickness less than 1 mm as is the case in this example for which the thickness is 0.5 mm.
Un tel récipient est placé dans une chambre de traitement métallique de forme cylindrique reliée à un dispositif d'émission de micro-ondes émettant à 2450 MHz avec des moyens classiques de guide d'ondes aux dimensions standards.Such a container is placed in a cylindrical metal processing chamber connected to a microwave emitting device emitting at 2450 MHz with conventional standard size waveguide means.
Ces récipients sont traités de manière similaire à la procédure décrite dans les résultats 1 ci-dessus.These containers are treated similarly to the procedure described in results 1 above.
La puissance est ajustée dans chaque phase en relation avec la surface à traiter. Les récipients ainsi traités ont montré une très bonne barrière à plusieurs composés tels que l'essence, le White Spirit, l'eau, le n-Butyle acétate, l'oxygène et hydrocarbures classiques.The power is adjusted in each phase in relation to the surface to be treated. The containers thus treated have shown a very good barrier to several compounds such as gasoline, White Spirit, water, n-Butyl acetate, oxygen and conventional hydrocarbons.
Par exemple, de tels récipients —non traités présentent un pouvoir de barrière à la diffusion aux hydrocarbures de 3000 mg/jour, alors que ces mêmes récipients traités ont un pouvoir de barrière à la diffusion aux hydrocarbures de 25 mg/jour à 40 0C.For example, such untreated containers have a hydrocarbon diffusion barrier of 3000 mg / day, whereas these same treated containers have a hydrocarbon diffusion barrier of 25 mg / day at 40 ° C. .
Résultats 3 : Des récipients en polymère Polyéthylène Haute Densité (PEHD) rigides, creux et à ouverture totale, d'une contenance de 5 litres. ont été traités selon le procédé de l'invention.Results 3: Polyethylene High Density Polyethylene (HDPE) polymer containers, rigid, hollow and full opening, with a capacity of 5 liters. have been treated according to the process of the invention.
Un tel récipient est placé dans une chambre de traitement métallique de forme cylindrique reliée à un dispositif d'émission de micro-ondes émettant à 2450 MHz avec des moyens classiques de guide d'ondes aux dimensions standards.Such a container is placed in a cylindrical metal processing chamber connected to a microwave emitting device emitting at 2450 MHz with conventional standard size waveguide means.
Ces récipients sont traités de manière similaire à la procédure décrite dans les résultats 1 ci-dessus.These containers are treated similarly to the procedure described in results 1 above.
La puissance est ajustée dans chaque phase en relation avec la surface à traiter.The power is adjusted in each phase in relation to the surface to be treated.
Les récipients ainsi traités ont montré une très bonne barrière à plusieurs composés tels que l'essence, le White Spirite, l'eau, le n-Butyle acétate, l'oxygène et hydrocarbures classiques.The containers thus treated have shown a very good barrier to several compounds such as gasoline, White Spirite, water, n-butyl acetate, oxygen and conventional hydrocarbons.
Par exemple, de tels récipients non traités présentent un pouvoir de barrière à la diffusion au white spirit de 1400 mg/jour, alors que ces mêmes récipients traités ont un pouvoir de barrière à la diffusion au white spirit de 15 mg mg/jour à 40 0C et après 2 mois de macération. For example, such untreated containers have a 1400 mg / day white spirit diffusion barrier, whereas these same treated containers have a barrier to diffusion of 15 mg / day at 40 0 C and after 2 months of maceration.

Claims

REVENDICATIONS
1. Procédé de traitement d'un article en matériau polymère pour y déposer un revêtement à effet barrière sur au moins une de ses faces, caractérisé en ce qu'il comprend la création d'un plasma de décharge dans un gaz précurseur de tétrafluoroéthane-1,1,1,2. ou de pentafluoroéthane et en ce qu'il comprend, avant la création d'un plasma de décharge dans un gaz de tétrafluoroéthane-1,1,1,2 ou de pentafluoroéthane, la création d'un plasma de décharge dans un gaz d'acétylène à basse pression.1. A method of treating an article of polymer material to deposit a barrier coating on at least one of its faces, characterized in that it comprises the creation of a discharge plasma in a tetrafluoroethane precursor gas. 1,1,1,2. or pentafluoroethane and in that it comprises, before the creation of a discharge plasma in a 1,1,1,2-tetrafluoroethane gas or pentafluoroethane, the creation of a plasma discharge plasma in a gas of acetylene at low pressure.
2. Procédé de traitement d'un article en matériau polymère selon la revendication 1, caractérisé en ce que les densités volumiques de puissance sont comprises entre 0.01 W/cm3 et 10 W/cm3, préférentiellement entre 0.1 W/cm3 et 3 W/cm3.2. Process for treating an article of polymer material according to claim 1, characterized in that the power density densities are between 0.01 W / cm 3 and 10 W / cm 3 , preferably between 0.1 W / cm 3 and 3. W / cm 3 .
3. Procédé de traitement d'un article en matériau polymère selon la revendication 1 ou 2, caractérisé en ce que les fréquences sont de 40 kHz, 13.56 MHz ou 2450 MHz.3. Process for treating an article of polymer material according to claim 1 or 2, characterized in that the frequencies are 40 kHz, 13.56 MHz or 2450 MHz.
4. Procédé de traitement d'un article en matériau polymère selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le temps de phase plasma est compris entre une seconde et quelques minutes, préférentiellement entre une seconde et trente secondes.4. A method of treating an article of polymeric material according to any one of claims 1 to 3, characterized in that the plasma phase time is between one second and a few minutes, preferably between one second and thirty seconds.
5. Procédé de traitement d'un article en matériau polymère selon l'une quelconque des revendications 1 a 4, caractérisé en. ce que le gaz précurseur est introduit dans la chambre réactionnelle à un débit tel que la pression à l'intérieur de cette chambre de traitement est portée à des valeurs comprises entre 0.002 mbar et 10 mbar,- de préférence entre 0.01 mbar et 1 mbar.5. A method of treating an article of polymeric material according to any one of claims 1 to 4, characterized in. that the precursor gas is introduced into the reaction chamber at a rate such that the pressure inside this treatment chamber is brought to values between 0.002 mbar and 10 mbar, preferably between 0.01 mbar and 1 mbar.
6. Procédé de traitement d'un article en matériau polymère selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il ' comprend en outre une préparation préalable de la surface de l'article en matériau polymère à revêtir, cette préparation mettant en œuvre un plasma de décharge à basse pression dans un gaz comprenant au moins un des gaz suivants oxygène, hydrogène, argon, dioxyde de carbone, hélium, azote.6. A method of treating an article of polymeric material according to any one of claims 1 to 5, characterized in that it 'further comprises a preparation prior to the surface of the article of polymer material to be coated, this preparation using a low-pressure discharge plasma in a gas comprising at least one of the following gases oxygen, hydrogen, argon, carbon dioxide, helium, nitrogen.
7. Procédé de traitement d'un article en matériau polymère selon la revendication 6, caractérisé en ce que, pour l'étape de préparation de surface, le plasma de décharge à basse pression est un plasma de mélange d'argon/hydrogène, la pression étant comprise entre 0.01 mbar et 5 mbar, de préférence comprise entre 0.05 rαbar et 1 mbar.7. Process for treating an article of polymer material according to claim 6, characterized in that, for the surface preparation step, the low-pressure discharge plasma is an argon / hydrogen mixing plasma, the pressure being between 0.01 mbar and 5 mbar, preferably between 0.05 rαbar and 1 mbar.
8. Procédé de traitement d'un article en matériau polymère selon la revendication 7, caractérisé en ce que, pour la préparation de surface, les densités volumiques de puissance sont comprises entre 0.01 W/cm3 et 10 W/cm3, préférentiellement entre 0.1 W/cm3 et 3 W/cm3* 8. Process for treating an article of polymer material according to claim 7, characterized in that, for the surface preparation, the power density densities are between 0.01 W / cm 3 and 10 W / cm 3 , preferably between 0.1 W / cm 3 and 3 W / cm 3 *
9. Procédé de traitement d'un article en matériau polymère selon la revendication 7 ou 8, caractérisé en ce que le temps de préparation de surface par plasma est compris entre une seconde et trente secondes.9. A method of treating an article of polymer material according to claim 7 or 8, characterized in that the plasma surface preparation time is between one second and thirty seconds.
10. Procédé de traitement d'un article en matériau polymère selon l'une quelconque des revendications 1 à 9, dans lequel un revêtement supplémentaire est réalisé avec un plasma de décharge à basse pression dans un gaz de C2H2 ou de pentafluoroéthane à basse pression.A method of treating an article of polymeric material according to any one of claims 1 to 9, wherein further coating is performed with a low pressure discharge plasma in a C 2 H 2 gas or pentafluoroethane at low pressure.
11. Procédé de traitement d'un article en matériau polymère selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le polymère est un polyéthylène, un polypropylène, un polyamide, un PET, un polychlorure de vinyle,11. A method of treating an article of polymeric material according to any one of claims 1 to 10, characterized in that the polymer is a polyethylene, a polypropylene, a polyamide, a PET, a polyvinyl chloride,
12. Procédé de traitement d'un article en matériau polymère selon l'une quelconque des revendications 1 à 11, caractérisé en ce que l'article est un récipient creux et à ouverture totale. 12. A method of treating an article of polymeric material according to any one of claims 1 to 11, characterized in that the article is a hollow container and full opening.
13. Application du procédé selon la revendication13. Application of the process according to the claim
12 au traitement d'un récipient rigide ou souple en polyéthylène haute densité (PEHD) , caractérisée en ce que la pr'ession à l'intérieur du récipient est ramenée jusqu'à une pression inférieure à 0.05 mbar alors que la pression à l'extérieur est maintenue à environ 30 mbar, et en ce qu'un débit de mélange de gaz argon et hydrogène est introduit dans le récipient de sorte que la pression interne se retrouve à une valeur comprise entre 0.05 et 1 mbar, une énergie micro-ondes étant alors appliquée avec une puissance d'environ 200 W, provoquant la création d'un plasma de préparation de surface maintenu pendant une durée de β secondes, l'énergie micro-ondes et le débit de mélange de gaz étant coupés après ce temps de préparation de surface.12 the treatment of a rigid or flexible high-density polyethylene (HDPE), characterized in that the pr 'ession inside the container is reduced to a pressure below 0.05 mbar, while the pressure in the outside is maintained at about 30 mbar, and in that a mixing flow of argon gas and hydrogen is introduced into the container so that the internal pressure is found at a value between 0.05 and 1 mbar, a microwave energy being then applied with a power of approximately 200 W, causing the creation of a surface preparation plasma maintained for a duration of β seconds, the microwave energy and the gas mixture flow rate being cut after this time of surface preparation.
14. Application selon la revendication 13, caractérisée en ce qu'un débit de gaz acétylène est ensuite introduit dans le récipient de sorte que la pression interne se retrouve à une valeur comprise entre 0.05 et 0.3 mbar, une énergie micro-ondes étant alors appliquée avec une puissance d'environ 300 W, provoquant la création d'un plasma de dépôt maintenu pendant une durée de une seconde, l'énergie micro-ondes et le débit de gaz étant par la suite coupés. 14. Application according to claim 13, characterized in that a flow of acetylene gas is then introduced into the container so that the internal pressure is found at a value between 0.05 and 0.3 mbar, a microwave energy then being applied with a power of about 300 W, causing the creation of a deposition plasma maintained for a period of one second, the microwave energy and the gas flow being thereafter cut.
15. Application selon la revendication 13 ou 14, caractérisée en ce qu'un débit de gaz précurseur tétrafluoroéthane-1,1, 1,2 est introduit dans le récipient de sorte que la pression interne se retrouve à une valeur comprise entre 0.05 et 0.3 mbar, une énergie micro-ondes étant alors appliquée avec une puissance d'environ 300 W, provoquant la création d'un plasma de dépôt maintenu pendant une durée de six secondes, après quoi l'énergie micro-ondes et le débit de gaz sont coupés. 15. Application according to claim 13 or 14, characterized in that a tetrafluoroethane-1,1,1,2 precursor gas flow rate is introduced into the container so that the internal pressure is found to be between 0.05 and 0.3. mbar, a microwave energy is then applied with a power of about 300 W, causing the creation of a deposition plasma maintained for a period of six seconds, after which the microwave energy and the gas flow are cut.
EP05850613.0A 2004-12-23 2005-12-23 Method for treating a polymer material, device for implementing said method and use of said device for treating hollow bodies Active EP1827716B1 (en)

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FR0413862A FR2880027B1 (en) 2004-12-23 2004-12-23 PROCESS FOR PROCESSING A POLYMERIC MATERIAL, DEVICE FOR CARRYING OUT SAID METHOD AND USE OF SAID DEVICE FOR TREATING HOLLOW BODIES
PCT/FR2005/003277 WO2006070136A1 (en) 2004-12-23 2005-12-23 Method for treating a polymer material, device for implementing said method and use of said device for treating hollow bodies

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FR2880027A1 (en) 2006-06-30
US20080081129A1 (en) 2008-04-03
EP1827716B1 (en) 2014-05-21

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