EP1144715B1 - Couche barriere de diffusion avec effet barriere important - Google Patents

Couche barriere de diffusion avec effet barriere important Download PDF

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Publication number
EP1144715B1
EP1144715B1 EP99955637A EP99955637A EP1144715B1 EP 1144715 B1 EP1144715 B1 EP 1144715B1 EP 99955637 A EP99955637 A EP 99955637A EP 99955637 A EP99955637 A EP 99955637A EP 1144715 B1 EP1144715 B1 EP 1144715B1
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EP
European Patent Office
Prior art keywords
barrier layer
diffusion barrier
substrate
plasma
gases
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.)
Expired - Lifetime
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EP99955637A
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German (de)
English (en)
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EP1144715A2 (fr
EP1144715A3 (fr
Inventor
Eva Maria Moser
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Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
EMPA
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Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
EMPA
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Publication of EP1144715A3 publication Critical patent/EP1144715A3/fr
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    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/24995—Two or more layers
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3854—Woven fabric with a preformed polymeric film or sheet
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674—Nonwoven fabric with a preformed polymeric film or sheet

Definitions

  • the present invention relates to a substrate with a deposited organic Diffusion barrier layer according to the preamble of claim 1.
  • the invention further relates to a method for producing a Substrate with a diffusion barrier layer and uses thereof.
  • PE films are not such that they are sensitive to those mentioned at the beginning Can adequately protect materials. For this reason in a known manner, laminate structures with several layers of polymers, for example ethyl vinyl alcohol (EVOH), used to make the rather low Barrier properties of the individual layers against gases compensate.
  • EVOH ethyl vinyl alcohol
  • plastic films with thin diffusion barrier or barrier layers coated which are made of metal or metal oxides consist. These coatings must be thin, elastic and free of pores (pinholes) or hairline cracks (microcracks) and they may be theirs Do not lose permeation properties even during a long storage period.
  • Metal oxide barrier layers are optically transparent, microwaveable and meet the ecological requirements, but their scope is rather limited due to their stiffness.
  • Plasma polymerized coatings with fluorine- or sulfur-containing compounds enable the reduction of solvent permeation in plastic containers.
  • multilayered Systems consisting of oxide-like barrier layers are embedded in polymer-like materials.
  • Thin hydrocarbon barrier layers proved to be good alternatives to the rigid and brittle metal oxide barrier layers, such as in WO, A1 96/28587 and EP, A1 0739655. This thin hydrocarbon coatings are preferred using DC magnetron discharge processes, High frequency or microwave discharge produced.
  • DE, A1 4316349 describes the production of diffusion barrier layers in hollow bodies, this using a microwave process happens.
  • EP-A1 0176636 discloses a polymerized thin film of high Density, high hardness and high toughness This layer is on the surface of a substrate deposited by plasma polymerization. That for generation
  • the gas used in the plasma contains a halogenated alkane and / or an alkane with optionally hydrogen and / or a halogen.
  • the atomic ratio Halogen / hydrogen in the gas is in the range from 0.1: 1 to 5: 1.
  • the Plasma temperature in the area of the reaction zone is 6000 ° K or higher, however below 30,000 ° K.
  • the pressure during the polymerization is included 0.001 to 1 torr.
  • the thin polymer layer is used for numerous objects used as a protective layer, also as a harder surface, anti-rust layer, Scratch protection, gas barrier, etc.
  • the protective layer is particularly suitable as a protective film for magnetic data carriers.
  • the object of the present invention is to provide a substrate with a to create improved diffusion barrier layer, which have better barrier properties with respect to oxygen and other gases, in particular even in high ambient humidity.
  • At least one element has in the diffusion barrier layer Group according to the previous paragraph a content of 0.1 - 3 at%.
  • the diffusion barrier layer is based on carbon and hydrogen built up, preferably with a content of 20-80 at%, in particular each 30-70 at%.
  • the diffusion barrier layer is preferably largely a hydrocarbon plasma polymer with apolar framework, i.e. the diffusion barrier is made by plasma polymerization of at least a hydrocarbon monomer, preferably with a maximum of 8 carbon atoms, also with admixture of noble gases.
  • the diffusion barrier layer can by means of the plasma of a magnetron sputtering source or by the combination the atomization source and the plasma-induced gas phase polymerization getting produced.
  • the barrier layer can be by means of inductively coupled microwave discharge.
  • a mixture of hydrocarbon gas and noble gas with an excess of hydrocarbon gas is processed.
  • Helium, neon, Argon and other noble gases can be used as pure gases, but according to In a preferred embodiment, a mixture is advantageously used made of argon and helium.
  • a magnetron sputtering source preferably one Hydrocarbon noble gas mixture used, the latter in particular Form of helium, neon and / or argon.
  • the object is achieved according to the invention in that that the barrier layer by means of at least one pulsed or continuous DC magnetron sputtering source plasma or by means of inductively coupled, pulsed or continuous microwave discharge is produced.
  • the reactor is preferably initially evacuated to a pressure below 5 ⁇ 10 -3 mbar, preferably below 1 ⁇ 10 -4 mbar, then the reaction gases are fed in until a value not above about 1 bar, preferably not above 10 mbar, is reached and is maintained.
  • the power of the energy source is expediently 50-1000 W, in particular at most approximately 500 W, with a diameter of the samples of approximately 12 cm.
  • a wide range of reactive gas components can be used for the process according to the invention are used, in particular an alkane, alkene or alkyne and / or mixtures thereof, also with at least one noble gas as carrier gas.
  • Noble gas used in plasma polymerization is e.g. Helium, neon, Argon or mixtures thereof.
  • Helium is preferably used, in the case of an inductive one coupled microwave discharge a mixture of argon and helium.
  • coated substrates according to the invention is as mentioned extraordinarily diverse.
  • Preferred uses relate to coating polymeric materials, such as in particular flexible polymer films.
  • These diffusion barrier layers are extremely effective protective layers against gases, water vapor. Flavors, organic and inorganic volatile compounds as well as liquids, in particular against aqueous liquids.
  • the coated polymer films consist, for example made of polypropylene, polyethylene, polyamide, polyethylene terephthalate etc. composite films of the polymers mentioned and molded from the films, blown or deep-drawn objects, such as containers in particular, also fall under the term polymer films.
  • a further use of a substrate according to the invention with a diffusion barrier layer lies in packaging materials, in particular for the sterilization or pasteurization of a filling material arranged in the packaging.
  • Containers for the inside and outside coating that are in direct contact with food are extremely important here.
  • the diffusion barrier layers according to the invention are particularly suitable for use in a moist environment.
  • Packaging materials consist of polymers, for example polypropylene PP, polyethylene PE, polyamide PA, PET, as well as composite films, made of various polymer materials, such as PP / PE, PET / PP, PET / PE, PE / PA.
  • Such packaging materials, such as films can be provided with barrier layers according to the invention, ie coated or laminated.
  • packaging materials of this type are particularly suitable for food, since no organoleptic and chemical changes to the contents can occur in accordance with the food regulation.
  • the migration protection mentioned above and the permselectivity are also important for the packaging of foods, since foods are often packaged under protective gas (CO 2 , N 2 or mixtures thereof).
  • the higher permeability of CO 2 compared to oxygen therefore additionally protects the contents.
  • the barrier layer is often required to have a high oxygen and water vapor barrier.
  • the CVD reactor 10 has a solid, corrosion-resistant steel shell 12 and is connected to the earth 14. At least one quartz window 16 in the steel shell 12 allows the Coupling of microwaves into the interior of the reactor.
  • a microwave head 20 On the right end face 18, a microwave head 20 is installed, which of a microwave generator 22 is electrically powered.
  • a relay 30 can from a DC generator 32 with a pulse device 34 to an HF generator 36 with switch upstream bias 38.
  • Flange 40 Via a closable, which is arranged approximately longitudinally in the present case Flange 40 is connected to a pumping station.
  • a substrate holder 42 is inside of the CVD reactor 10 positioned.
  • On this substrate holder 42 is closed coating substrate 44 mounted.
  • an entire battery of substrates 44 is installed in the CVD reactor 10.
  • the substrate holder 42 is connected to the bias 38 via a further relay 46. When the relay 46 is switched over, the substrate holder 42 is grounded
  • a gas system 48 also includes four gas supply lines 50 one adjustable valve 52 each for the feed of reaction and carrier gases. Furthermore, the gas system 48 is designed in a manner known per se, the feed takes place via the cylindrical jacket-shaped steel casing 12. A branch line 54 leads to the quartz window 16 of the microwave head 20th
  • the CVD reactor 10 is evacuated by a forevacuum pump 60 with an upstream turbopump 62, via a butterfly regulating valve 64, which can be actuated electro-magnetically
  • pressure measuring equipment 56 is introduced into the CVD reactor 10, which is highly sensitive and can measure pressures up to the range of 1.10 -9 mbar.
  • a CVD reactor 10 is used to carry out all machining processes according to the invention suitable, using a wide variety of gases and mixtures thereof, flow rates, working pressures and other known and proven plasma process parameters. Machining processes are in the frequency domain from 10 kHz to 100 GHz and possible in DC operation, while a negative potential is applied to the substrate 44 via the bias 38 or is connected to earth 14.
  • the reaction start pressure in the reactor is, for example, about 10 -2 mbar.
  • the power for a sample with a diameter of up to about 12 cm is 50 to 1000 W, microwaves or direct current input power.
  • a carbon target 27 of a purity of at least 99.9% (quality designation: pure) and a continuous electrical energy supply or a pulse frequency of 25 kHz, for example, are selected, the microwave discharges are also selected by means of continuous or pulsed mode carried out.
  • FIG. 1a shows a partial section through a in a CVD reactor 10 according to FIG. 1 coated substrate 44, in the form of a flexible polymer film, with a Diffusion barrier layer 58 with a thickness d of approximately 100 nm.
  • FIG. 2 shows the transmission spectra of an approximately 20 ⁇ m thick, uncoated BOPP (biaxially oriented polypropylene) film and three about 50 nm thick coated BOPP films 44 shown.
  • the wavelength is on the abscissa the UV radiation in nm, the ordinate the transmission in %.
  • the dashed, uncoated BOPP film has in the area a UV wavelength of about 200 nm as the three coated BOPP films, a striking drop in transmission.
  • Characteristic properties of the three selected layers A, B and C of Fig. 2 are characterized in Table 1, e.g. as another optical Properties of the refractive index and total light transmission specified. For light-sensitive food, the shelf life can still increase. A corresponding increase in the layer thickness would do this Enhance the effect.
  • Tables 1 to 3 below list the properties of various diffusion barrier layers 58 (FIG. 1a) and their production conditions.
  • Table 2 lists the permeation properties of the hydrocarbon barrier layers at different atmospheric humidity.
  • Table 3 shows the permselectivity, ie the different permeability for gases, of pure hydrocarbon layers.
  • Table 1 shows a summary of the properties of diffusion barrier layers 58 of different thickness (FIG. 1a) made of amorphous hydrocarbon on a 12 ⁇ m thick PET film.
  • F 5 for example, the oxygen, water vapor, nitrogen, and carbon dioxide gas -Permeable core, the density, the refractive index as well as the chemical composition are listed.
  • the corresponding values for an uncoated PET film and a film coated with inorganic SiO x are listed.
  • the permselectivity of plasma-polymerized barrier layers shown in Table 3 is based on isostatic permeability measurements with a dry gas mixture of CO 2 , O 2 and N 2 at a slightly elevated room temperature.
  • Table 3 shows the oxygen permeation of a pure as reference examples PET film and a PET film coated with silicon oxide.
  • the pure PET film shows a high oxygen permeation when dry, which, however, decreases with increasing moisture. This behavior is Material-specific, it is known that other polymer films do not behave in this way.
  • the oxygen permeation only reduced by approx. 8% with the increase in air humidity. consequently the polar metal oxide layer causes a weakening of the property of PET, during which the apolar hydrocarbon layers turn into PET have comparable permeation behavior.
  • a major disadvantage of Silicon oxide barrier layers for packaging also lies in the fact that the Oxygen permeation after sterilization compared to those according to the invention Hydrocarbon layers is much higher, which is especially in the Case of food packaging and in medical technology extremely unfavorable is.
  • the diffusion barrier layers according to the invention shown in tabular form are characterized by the fact that the elongation to the point of micro-cracking Product can be tailored.
  • the area for a good diffusion barrier is 1 to 10%, but can sometimes be more.
  • the crack elongation depends of course on the layer thickness, which is usually 10 to 1000 nm, preferably ⁇ 300 nm, in particular 20 to 200 nm.
  • the flexibility of the layers is due to their polymer-like nature, which also excellent adhesion of the diffusion barrier layers according to the invention effected on polymeric substrates.
  • the coated ones Substrates mechanically resistant and can, for example, on all possible machines for the production of composite films processed (wrapped and shaped).
  • the plasma reactor is evacuated to a base pressure of ⁇ 2 x 10 -5 mbar. Carbon is sputtered from the carbon target; in addition, a polymerizable C x H y gas mixture is continuously fed into the plasma reactor via the gas inlets. In addition, an inert gas or an inert gas mixture can be admitted into the plasma chamber. The plasma is ignited by supplying the energy (direct current, continuous or pulsed).
  • the diffusion barrier layer consisting of pure hydrocarbon, is deposited on the substrate, the process duration and the belt speed determining the layer thickness, gas concentration, gas.
  • the plasma reactor is evacuated to a base pressure of ⁇ 2 x 10 -5 mbar.
  • a polymerizable C x H y gas mixture which can additionally be mixed with noble gases, is fed continuously into the plasma reactor via the gas inlets.
  • the microwave energy (2.45 GHz) (pulsed or continuous) is injected inductively. After the plasma is ignited, the desired energy is set so that the pure hydrocarbon plasma layer is deposited.
  • Parameters for examples 1 and 2 relate to the CVD reactor shown in FIG. 1.
  • the oxygen permeability was determined at 0% relative humidity, 23 ° C ASTM D 3985-95, using a Mocon OX-TRAN 2/20 Device measured.
  • the water vapor permeability measurements were made with a Lyssy permeation tester L 80-4000.
  • Total light transmission the coated and untreated PET films were according to ASTM D 10003-92 (CIE: Y-Value, 10 °, D65).
  • the layer thickness was measured using a profilometer (Tencor P10) Determined silicone wafer.
  • the hydrogen content, possible impurities and the density of the coatings were on coated Si (100) substrates examined, using so-called Rutherford backscattering (RBS), Elastic Recoil Detection Analysis (ERDA) and X-ray photoelectronic Spectroscopy (XPS).
  • RBS Rutherford backscattering
  • ERDA Elastic Recoil Detection Analysis
  • XPS X-ray photoelectronic Spectroscopy
  • the elastic behavior became by stretching the coated foils (Elongation, flexibility) using a method based on interferometry examined.
  • the method for measuring the elastic behavior was on developed by EMPA.
  • the formation of microcracks on the stretched test films and their influence on the diffusion barrier properties was determined by combining scanning electron microscopy and measurements of the Permeability.
  • the AFM images of the substrates and the coated PET films were performed under room temperature conditions using a Bioscope AFM (Digital instruments) and an Explorer AFM (TopoMetrix, Model TMX 2000) determined in the scanning mode and non-contact mode.
  • a periodic investigation of the diffusion properties was carried out during a Year of carefully stored test samples (23 ° C, 0% relative humidity) carried out to determine the long-term behavior.
  • An untreated PET film has a 10 to 20 nm wide "clusters" and an RMS roughness of approximately 0.8 nm. All examined Coatings show a very homogeneous morphology with one RMS roughness of 1.5 - 2.5 nm and a grain size of 20 - 40 nm Structure of the coated films is very similar and is neither dependent on the type of discharge and the deposition parameters.
  • the substrate holder with the samples was both grounded and in the frequency domain "biased" from 10 kHz to 200 MHz.
  • the ions in the plasma edge layer are against the Accelerates substrate towards which they hit with a higher energy.
  • the density of the coatings is expected to be higher and the permeability values lower.
  • the flexibility of the coatings takes away Increase in density.
  • the deposition rate increases due to the creation of a negative potential.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Laminated Bodies (AREA)
  • Chemical Vapour Deposition (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Physical Vapour Deposition (AREA)
  • Glass Compositions (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Claims (11)

  1. Substrat (44) comprenant une couche de barrage à la diffusion (58) organique qui y est déposée et qui comporte une structure fondamentale apolaire présentant un effet de barrage élevé par rapport aux gaz volatils, aux vapeurs et aux liquides, la couche de barrage à la diffusion (58) étant constituée d'un polymère de carbure d'hydrogène qui est produit par polymérisation du plasma et qui contient, à chaque fois, de 0,01 à 6 en pourcentage atomique d'au moins un élément du groupe constitué par l'oxygène, l'azote, le fluor, le chlore, le brome, le bore et le silicium, mais en tout au plus 12 en pourcentage atomique,
       caractérisé en ce que
       la couche de barrage à la diffusion (58) a, sur la base du carbone et de l'hydrogène, une teneur de ces deux éléments qui est comprise entre 20 et 80 % atomique, grâce à quoi l'effet de barrière de la couche de barrage à la diffusion (58) est au moins maintenu aussi dans de l'air humide.
  2. Substrat (44) comprenant une couche de barrage à la diffusion (58) (44) selon la revendication 1, caractérisé en ce que cette couche de barrage contient au moins un élément du groupe avec une teneur comprise entre 0,1 et 3 en pourcentage atomique.
  3. Substrat (44) comprenant une couche de barrage à la diffusion (58) selon la revendication 1 ou 2, caractérisé en ce que la couche de barrage à la diffusion (58) présente une teneur en en carbone et une teneur en hydrogène comprise, à chaque fois, entre 30 et 70 en pourcentage atomique.
  4. Substrat (44) comprenant une couche de barrage à la diffusion (58) selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la couche de barrage à la diffusion (58) a une épaisseur comprise entre 10 et 1000 nm, de préférence au maximum de 300 nm.
  5. Substrat (44) comprenant une couche de barrage à la diffusion (58) selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le substrat (44) est un matériau polymère ou du papier, en particulier un polycarbonate, un polytéréphtalate d'éthylène, un polypropylène, un polyéthylène, un polyamide ou aussi un matériau composite de ces corps, du papier couché, des textiles, des fibres de carbone ou aussi un matériau composite de ces derniers, un matériau céramique, du verre ou des fibres de verre.
  6. Procédé pour la fabrication d'un substrat (44) comprenant une couche de barrage à la diffusion (58) selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la couche de barrage à la diffusion (58) est fabriquée au moyen d'au moins une source de plasma à pulvérisation par un magnétron à courant continu (26) travaillant par impulsion ou en continu ou au moyen d'une décharge de micro-ondes (20) par impulsions ou en continu, à couplage inductif.
  7. Procédé selon la revendication 6, caractérisé en ce que l'on fait le vide dans un réacteur (10) pour obtenir une pression inférieure à 5·10-3 mbar, de préférence inférieure à 1 10-4 mbar, et en ce qu'ensuite, on y envoie les gaz de réaction jusqu'à ce que l'on atteigne et que l'on maintienne une valeur qui n'est pas supérieure à 1 bar, de préférence pas supérieure à 10 mbars.
  8. Procédé selon la revendication 6 ou 7, caractérisé en ce que la puissance de la source d'énergie est, dans le cas d'échantillons plats ayant un diamètre d'environ 12 cm, comprise entre 50 et 1000 W, de préférence au plus d'environ 500 W.
  9. Procédé selon l'une quelconque des revendications 6 à 8, caractérisé en ce que l'on utilise, en tant que composants de gaz de réaction, des gaz de carbure d'hydrogène, en particulier des alcanes, tels que le méthane, l'éthane ou le propane, des alcènes, tels que l'éthène, le propène ou le butène, ou des alkines, tels que le propine, tous séparément ou mélangés avec d'autres gaz de carbure d'hyydrogène.
  10. Utilisation d'un substrat (44) comprenant une couche de barrage à la diffusion (58) selon l'une quelconque des revendications 1 à 5 pour le revêtement de matériaux polymères, en particulier de films de polymères élastiques, y compris les produits recyclés.
  11. Utilisation d'un substrat (44) comprenant une couche de barrage à la diffusion (58) selon l'une quelconque des revendications 1 à 5 pour le revêtement de papier, de textiles, de fibres de carbone, de matériau céramique, de verre, de fibres de verre et/ou de matériaux composites de ces produits.
EP99955637A 1998-12-01 1999-12-01 Couche barriere de diffusion avec effet barriere important Expired - Lifetime EP1144715B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH238698 1998-12-01
CH238698 1998-12-01
PCT/CH1999/000575 WO2000032838A2 (fr) 1998-12-01 1999-12-01 Couche barriere de diffusion avec effet barriere important

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EP1144715A2 EP1144715A2 (fr) 2001-10-17
EP1144715A3 EP1144715A3 (fr) 2002-11-27
EP1144715B1 true EP1144715B1 (fr) 2002-12-04

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US (1) US6686302B1 (fr)
EP (1) EP1144715B1 (fr)
AT (1) ATE229095T1 (fr)
AU (1) AU1256900A (fr)
BR (1) BR9916152A (fr)
CA (1) CA2347829A1 (fr)
DE (1) DE59903693D1 (fr)
WO (1) WO2000032838A2 (fr)

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EP1144715B1 (fr) 1998-12-01 2002-12-04 Eidgenössische Materialprüfungs- und Forschungsanstalt EMPA Couche barriere de diffusion avec effet barriere important
US6827966B2 (en) 2001-05-30 2004-12-07 Novartis Ag Diffusion-controllable coatings on medical device
US7296534B2 (en) * 2003-04-30 2007-11-20 Tokyo Electron Limited Hybrid ball-lock attachment apparatus
CH700481A1 (de) * 2009-02-26 2010-08-31 Micropast Gmbh Verfahren zum Haltbarmachen von Lebensmitteln.
GB201003275D0 (en) * 2010-02-26 2010-04-14 Portal Medical Ltd Method of manufacturing a medicament dispenser device
GB201717996D0 (en) * 2017-10-31 2017-12-13 Portal Medical Ltd Medicament dispenser device

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EP0176636B1 (fr) 1984-09-28 1990-05-09 Japan Synthetic Rubber Co., Ltd. Film polymère mince et objet contenant un tel film
SE503260C2 (sv) 1992-06-15 1996-04-29 Akerlund & Rausing Ab Förfarande för framställning av en barriärfilm medelst plasmabehandling
WO1994027745A1 (fr) * 1993-06-01 1994-12-08 Kautex Werke Reinold Hagen Aktiengesellschaft Procede et systeme d'application d'un revetement polymere sur la surface interieure de corps creux en matiere plastique
DE4318086A1 (de) 1993-06-01 1994-12-08 Kautex Werke Gmbh Verfahren und Einrichtung zum Herstellen einer polymeren Deckschicht in Kunststoff-Hohlkörpern
EP1144715B1 (fr) 1998-12-01 2002-12-04 Eidgenössische Materialprüfungs- und Forschungsanstalt EMPA Couche barriere de diffusion avec effet barriere important

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Publication number Publication date
DE59903693D1 (de) 2003-01-16
US6686302B1 (en) 2004-02-03
EP1144715A2 (fr) 2001-10-17
CA2347829A1 (fr) 2000-06-08
WO2000032838A3 (fr) 2002-10-10
BR9916152A (pt) 2001-09-04
WO2000032838A2 (fr) 2000-06-08
EP1144715A3 (fr) 2002-11-27
ATE229095T1 (de) 2002-12-15
AU1256900A (en) 2000-06-19

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