EP1250268B1 - Tube souple revetu d'une couche a effet barriere de diffusion aux gaz et aux aromes - Google Patents
Tube souple revetu d'une couche a effet barriere de diffusion aux gaz et aux aromes Download PDFInfo
- Publication number
- EP1250268B1 EP1250268B1 EP00990093A EP00990093A EP1250268B1 EP 1250268 B1 EP1250268 B1 EP 1250268B1 EP 00990093 A EP00990093 A EP 00990093A EP 00990093 A EP00990093 A EP 00990093A EP 1250268 B1 EP1250268 B1 EP 1250268B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- skirt
- coating
- flexible tube
- plasma
- layer
- 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
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
- B65D35/14—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor with linings or inserts
- B65D35/16—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor with linings or inserts for minimising or preventing corrosion of body
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
- Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
Definitions
- the invention relates to a method of manufacturing flexible tubes typically intended for store and distribute liquid to pasty products containing perfumes, aromas or being sensitive to oxidation.
- Flexible tubes were previously metallic or metalloplastic and had, of by the presence of a metal layer, a perfect vapor barrier property, aromas and different gases (especially oxygen).
- plastic tubes obtained by shock shock spinning aluminum, were gradually replaced by metalloplastic tubes and then by fully plastic tubes.
- the mass production of plastic tubes or metalloplastics is preferably done by injection of a plastic head then welding - possibly simultaneous - of said plastic head on a cylindrical skirt, obtained by cutting to a given length of a sleeve, said sleeve itself being obtained by extrusion - or coextrusion if it is multilayer - (extruded skirt) or by welding side edges of a rolled strip such that said side edges are placed look at each other (laminated skirt).
- the layer in EVOH is an intermediate layer between two polyolefin layers, themselves which can be a superposition of underlays in low density polyethylene, in linear low density polyethylene and / or high density polyethylene, each layer being connected over its entire surface to the EVOH layer by means of layers adhesive material of type EAA (ethylene-acrylic acid copolymer) or EMA (ethylene - methacrylic acid copolymer).
- adhesive material of type EAA (ethylene-acrylic acid copolymer) or EMA (ethylene - methacrylic acid copolymer).
- the tube head welded to the flexible skirt, has a distribution neck and a shoulder which connects the neck to the skirt.
- This set is then presented upside down so that the conditioner can fill it with the open end of the skirt.
- said end which remains open is finally welded and the tube, delivered in the trade, must be able to preserve the quality of the product it contains for several months of storage. If the level of losses is low since the appearance of skirts entirely plastic whose structure is comparable to that described above, it arises always the problem of the loss of aroma at the level of the head, this being generally produced by molding a polyolefin. Three groups of solutions have been proposed in answer to this problem.
- a first group of solutions consists in adding a metalloplastic insert or plastic forming diffusion barrier at the neck and shoulder.
- this insert is placed inside the tube, at the shoulder and the neck. He can be molded from a single material, preferably PBT (polybutylene terephthalate), or have multiple layers.
- PBT polybutylene terephthalate
- such a insert is made by thermoforming from a laminate having a structure comparable to that of the multi-layer skirt described above, i.e. polyolefin (s) - layer adhesive -EVOH - adhesive layer - polyolefin (s).
- a second solution is to completely change the way of making the head.
- the applicant proposes to shape the head by necking to hot one end of the skirt consisting of a laminate having an effect layer fence.
- the shrinking is carried out by formation between dies of crumpling plies, crushing of these folds then overmolding of the shoulder and the blank of neck as well made with a polyolefin so as to obtain the final shape of the head.
- a third solution consists in making the head in a polyolefin multilayer - EVOH - polyolefin by co-injection, as described in the international application W099 / 02525 presented by the plaintiff.
- this product, toothpaste or cosmetic, food, etc. product is generally consisting of a large amount of water and EVOH, which is particularly sensitive to moisture loses, in the event of contamination, a large part of its barrier properties.
- the EVOH layer must be sufficiently thick to have effective barrier properties but it must not be too thick compared to other layers: EVOH is particularly rigid and elastic, which degrades the "dead fold" property of the multilayer obtained. This property, sometimes translated by the term “crushability”, characterizes a plastic behavior in bending, with low effect of elastic return on the bending angle. The compromise found requires, for barely satisfactory barrier properties, total thickness of the multilayer relatively large.
- laminated tubes we see a poorer diffusion barrier for gases and perfumes in the weld longitudinal certainly due to the local melting of the different components of the multilayer and to the deformations due to the stresses generated by the joining or the overlapping of the longitudinal edges of the strip.
- the object of the invention is to define a process allowing, for laminated tubes as for extruded tubes, to obtain a head structure and a skirt structure free a barrier material such as EVOH, rigid and difficult to co-inject with polyolefins and which has, in the absence of an insert and for the same total thickness of the skirt - typically 250 - 500 microns -, barrier properties and at least as good crushability than those of the structure of the prior art, the barrier properties must moreover be substantially uniform over the entire periphery of the skirt, even for laminated tubes (which have a longitudinal weld).
- a barrier material such as EVOH
- a first object of the invention is a flexible tube provided with a skirt and a head, intended to store and distribute liquid to pasty products containing perfumes, aromas or sensitive to oxidation, characterized in that said tube carries over the entire surface of its wall, i.e. on the surface of the neck, shoulder and skirt, a coating comprising at least one layer of thickness between 150 and 1500 ⁇ of a material or mixture of materials belonging to the following group: carbon amorphous, hydrogenated or not, nitrogenous or not, oxides, nitrides or carbides or their mixture or a combination of one or more of the following metals (Si, Mg, Al, Ti, Zr, Nb, Ta, Mo, W, V).
- amorphous carbon, hydrogenated or not, nitrogenous or not means a material to polymer trend, characterized by a network of amorphous carbon chains likely to contain hydrogen or nitrogen bonds.
- the wall of the flexible tube according to the invention comprises, at the level of the head as at that of the skirt, at least one thermoplastic such as a polyolefin, a polyester of the polyethylene terephthalate (PET) type or a copolyester.
- thermoplastic such as a polyolefin, a polyester of the polyethylene terephthalate (PET) type or a copolyester.
- PET polyethylene terephthalate
- a copolyester a copolyester
- at least one layer of the structure of the skirt comprises a polymer loaded with a pulverulent material such as calcium carbonate or mica.
- the coating covers the inner surface of the wall of the tube, which puts it protected from the risk of scratches or chipping due to impacts on the external surface and preserves on the other hand all the possibilities of depositing varnish or printing decoration on said outer surface.
- Another object of the invention is an additional step in the process for manufacturing flexible plastic tubes in which the tube surface is coated - after assembly, typically by welding, of the head on the skirt - by depositing plasma assisted with a layer thickness between 150 and 1500 ⁇ of a material or a mixture of materials belonging to the following group: amorphous carbon, hydrogenated or not, nitrogenous or not, oxides, nitrides or carbides or their mixture or their combination of one or more of the following metals (Si, Mg, Al, Ti, Zr, Nb, Ta, Mo, W, V).
- the deposition can be carried out as much on the external surface as on the internal surface of the tube flexible plastic.
- the following examples will illustrate, unless stated specific, deposits of internal coatings and can be easily transposed to deposits of external coatings.
- this deposition is carried out on the surface of the tube, at a speed compatible with industrial production rates, typically one or several hundred tubes per minute.
- this deposition is carried out using a plasma reactor for treating area.
- Plasma can be generated under different types of discharges: arc, discharge luminescent, discharge through a dielectric barrier or corona discharge with different types of excitation: microwave, radio frequency, alternating current medium frequency.
- the last two types of plasma generation have the advantage of being able to be carried out under a pressure close to atmospheric pressure.
- the working pressure In the case where the working pressure must be very low, it is preferable to carry out the coating treatment in batch on a quantity of tubes compatible with the flow continuous tubes from the production line and the time required to obtain a high vacuum. On the other hand, if the working pressure is close to the pressure atmospheric, we can consider carrying out the treatment in the manufacturing cycle.
- the treatment is preferably carried out batch in a vacuum enclosure inside which the quantity is introduced desired tubes to be treated, the latter being at this stage in the form of a head comprising a neck and a shoulder, said head being assembled with a flexible skirt.
- a set of cylindrical electrodes comprising a external electrode surrounding the skirt of the tube and an internal electrode entering inside of the tube over the height of the skirt and the precursor gas is injected through said end open so that the plasma can move to the shoulder and the neck. So the deposition can be done downstream of the plasma formation zone and its thickness is all the more more important than the part concerned is near the skirt, which is the goal referred.
- the deposition carried out under a pressure close to atmospheric pressure and assisted by a plasma generated by barrier or corona discharge can be integrated into the chain of manufacturing, just after the welding of the head on the skirt but preferably before putting in place of the closure cap on the neck: the flexible tube has at this stage its two open ends and thus presents a configuration favorable to the free movement of precursor gas, which can easily pass through the interior volume of the tube from one end to the other.
- the device for generating the plasma by barrier discharge may comprise a set of internal and external electrodes similar to that described in the example previous (relating to the generation of plasma under low working pressure).
- a device with two is also used. electrodes with axial symmetry, the axes of symmetry of the flexible tube and electrodes being put into coincidence.
- the internal electrode has axial convexities, revealing longitudinal edges in the form of knives oriented radially and its surface envelops with a deviation of a few millimeters (typically 3) the shape of the internal surface (skirt + shoulder + neck) of the flexible tube.
- the relative rotational movement of the internal electrode and the flexible tube avoids peak effects that can lead to the appearance of appearance areas degraded.
- the device using a mode of generation of a plasma confined in the form of a bead of determined length can be adapted from that disclosed in Figure 10 and in Example 3 of application WO 99/46964.
- electrodes axisymmetric placed on either side of the flexible tube but a set of electrodes external, one placed facing an open end of the flexible tube and the other, embedded in a dielectric, substantially conforming, with a substantially offset constant, the shape of the generator of the flexible tube.
- the tube is rotated in such a way so that its wall runs past the side electrode and the deposit can thus be produced around the entire circumference.
- the tube can indeed be treated provided with its capsule clogging because the plasma is confined in a controlled size bead and it is not necessary to provide an opening at each end of the tube to facilitate the plasma circulation.
- a deposit thickness is targeted. between 150 ⁇ and 1500 ⁇ , preferably less than 300 ⁇ .
- the material to be deposited can be any material having good barrier properties to the diffusion of aromas and gases.
- the carbon with polymer tendency is chosen, that is to say comprising a network of amorphous carbon chains with hydrogen bonds, silica or alumina.
- HMDSO hexamethyl-disiloxane
- TMDSO trimethyl-disiloxane
- precursor gas a gas of organometallic compound, such as tributyl aluminum Al (C 4 H 9 ) 3 or triethyl aluminum, is preferably used as precursor gas, which is circulated diluted in a mixture.
- argon and oxygen By varying the proportion of oxygen, deposits are made containing a certain proportion of carbon of up to 20%. The Applicant has observed on such deposits that a behavior which is all the more ductile as the deposit is rich in carbon is obtained, no doubt because the silica or alumina network, in which the carbon must be incorporated, is more loose.
- the precursor chosen acetylene for example
- one of the aforementioned gases HMDSO, TMDSO, tributyl-aluminum or tri-ethyl aluminum
- an acetylene - HMDSO - argon mixture in which the proportion of argon is maintained at 40% and the proportion is varied by acetylene and HMDSO respectively from 50% - 10% to 10% - 50% allows to realize a gradual deposition of layers first rich in amorphous carbon then rich in silica - the proportion is expressed in terms of flow rate as a standard volume unit by time unit (typical flow unit: sccm (standard cubic centimeter per minute)).
- the hydrogenated amorphous carbon located in an underlay, ensures better bonding on the polymeric substrate, typically polyethylene, flexible tube and provides more great flexibility in the coating obtained.
- the silica layer completes the barrier effect of the carbon layer while limiting the coloring due to carbon.
- the external coating thus obtained comprising a large proportion of silica on the surface, is better suited to conditions imposed for the subsequent printing of the tube skirt.
- a deposit thickness is targeted. between 150 ⁇ and 1500 ⁇ , preferably 200 to 500 ⁇ .
- the duration of the deposit can be limited to a few seconds or even a few tenths of a second.
- the duration of pumping to obtain the desired vacuum In the case of a treatment requiring a high vacuum, the duration of pumping to obtain the desired vacuum.
- the working pressure of the depot is between 50 and 1000 Pa.
- the enclosure intended to contain the tubes, of volume interior as small as possible, is provided with pumping means associated with "roots" type pumps capable of achieving the primary vacuum in a few seconds.
- the void secondary target is obtained using a turbomolecular or diffusion pump.
- the procedure is carried out preferably between 200 and 760 millimeters of mercury. Slightly more pressure low than atmospheric pressure allows better control of the purity of the circulating gas in the container.
- a preliminary sweep is carried out with an inert gas, argon type to avoid the formation of impurities (risk of reaction with nitrogen in the air, water vapor, etc ...) likely to deteriorate the quality of the adhesion of the layer thus filed.
- impurities risk of reaction with nitrogen in the air, water vapor, etc
- Being able to work under pressure close to the pressure atmospheric makes it possible to envisage the economically satisfactory use of devices non-static, such as means for rotating the tube, which allows simplify the electrodes and regularize the stability of the plasma by confining it under the shape of a cord.
- Figure 1 shows schematically in axial section (1a) and in orthogonal section (1b) a first device for implementing the method according to the invention by generating a plasma under low pressure.
- Figure 2 shows in axial section (2a) and in orthogonal section (2b) a second device for implementing the method according to the invention using a means of generation of confined plasma in the form of a cord.
- Figure 3 shows in axial section (3a) and in orthogonal section (3b) a third device for implementing the method according to the invention by generating a plasma by corona type discharge.
- Example 1 Plasma assisted deposition under low pressure on the interior surface of the wall of a flexible tube ( Figures 1a and 1b).
- the flexible tube comprising a skirt 1 and a head 2, with a substantially cylindrical neck 3 and a shoulder 4, is placed in a vacuum enclosure, and rests on a plate, the skirt being framed by two coaxial cylindrical electrodes 11 and 12 , the axis of the tube and the axis of the electrodes coinciding.
- the external electrode 11 surrounds the skirt 1 up to the level of the shoulder.
- the internal electrode 12 entering the interior of the tube has a height slightly less than that of the skirt.
- An argon - acetylene mixture is introduced with a C 2 H 2 / Ar ratio of the order of 10% is injected through the orifices 13.
- the pressure during deposition is of the order of 0.25 torr.
- the external electrode 11 is brought to ground while the internal electrode 12 is brought to a voltage of the order of 20 kV, pulsed at a frequency of the order of 250 kHz.
- the plasma is entrained towards the shoulder and the neck.
- the deposition can be done downstream of the plasma formation zone.
- Example 2 Deposition assisted by plasma under low pressure on the interior surface of the wall of a blocked flexible tube.
- the tube is in the state in which it leaves usually the production line, that is to say already equipped with its capsule clogging.
- An orifice 14 (in dashed lines in FIG. 1a) is made in the support.
- the internal cylindrical electrode is surmounted by a shoulder "parallel" to the shoulder of the tube, which remains at a constant distance from said wall.
- the external electrode 11 while remaining cylindrical, has a slightly greater height than in the previous example.
- Example 3 Deposition assisted by plasma under pressure close to atmospheric pressure a layer of silica on the inner surface of a flexible tube ( Figures 2a and 2b).
- the device used in this example uses a mode of generation of a confined plasma in the form of a cord of determined length adapted from that disclosed in FIG. 10 and in example 3 of application WO 99/46964 so that the plasma cord follows the shape of the generator of the flexible tube.
- axisymmetric electrodes placed on either side of the flexible tube are not used, but a set of external electrodes, one 11a placed facing the open end of the flexible tube and the other 21b , matching substantially, with a more or less constant difference, the shape of the generator of the flexible tube.
- the tube is rotated ( R ) so that its wall runs opposite the side electrode and the deposition can thus be carried out over the entire circumference.
- the treatment could be carried out on the tube alone, before or after the tip of the head is cored (see following example). In the present case, it is carried out at the very end of the manufacturing cycle, after the head has been welded to the skirt and after the closure cap 10 has been placed on the neck 3 .
- the tube can thus be treated provided with its closure cap because the plasma is confined in a bead of controlled size and it is not necessary to provide an opening at each end of the tube to facilitate the circulation of the plasma.
- the lateral electrode 21b and its insulating envelope 22 has a configuration close to that presented in FIGS. 10a and 10e of WO99 / 46964.
- a pulsed current is preferably used, each pulsed discharge having the effect of treating a part of the internal surface of the tube in the form of a strip of determined width, depending in particular on the speed of rotation of the tube.
- Such a procedure which makes it possible to treat the entire surface by making an appropriate offset of these strips, has the advantage of limiting overheating since the plastic material of the tube has time to cool between two pulses: this time is all the more more important than dealing with nonadjacent bands.
- Example 4 Deposition assisted by plasma under pressure close to atmospheric pressure a mixed layer of silica and carbon with a polymer tendency on the surface inside of a flexible tube ( Figures 3a and 3b).
- the tube is introduced into the cavity of the external electrode 31 , the internal surface of which matches the external shape of the tube.
- An internal electrode 32 is inserted through the open end of the flexible tube inside it and the latter is rotated by means of the end 7 of the core around the internal electrode 32 .
- the internal electrode 32 has axial convexities, revealing longitudinal edges 33 in the form of radially oriented knives.
- the envelope surface of said electrode follows with a deviation of 3 millimeters the shape of the internal surface (skirt 1 + shoulder 4 + neck 3 ) of the flexible tube.
- the external electrode 31 is brought to ground and a score of kV is applied to the internal electrode 32 .
- the gas an acetylene-HMDSO-argon mixture, the flow rate of which corresponds respectively to 20 sccm, 10 sccm and 15 sccm (sccm being a unit meaning standard cm3 per minute) is injected (P) through the open end of the flexible tube. It circulates between the internal electrode 32 and the internal wall of the flexible tube and is evacuated by the vents 6 made in the core 5 .
- the plasma is generated between the edges of the electrode and the internal wall of the tube using from an excited source at a frequency of 250 kHz.
- the tube is rotated during the duration of treatment. A few seconds are enough to obtain a regular deposit of around 250 ⁇ .
- the coating is a mixed deposit of silica and carbon with tendency polymer.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Tubes (AREA)
- Laminated Bodies (AREA)
- Chemical Vapour Deposition (AREA)
Description
- pour l'oxygène, par une perméabilité inférieure à 1 ml/m2/jour/atmosphère (norme ASTMD3985)
- pour la vapeur d'eau, par une perméabilité inférieure à 2 g/m2/jour/atmosphère (norme ASTM F327)
- et pour les arômes, par une perméabilité inférieure à 0,5 10-6 g/m2/jour/mmHg
- soit par excitation basse, moyenne ou haute fréquence ou encore par micro-ondes. Dans ce cas, la pression de travail peut varier entre le centième et le millième de torr,
- soit encore par décharge barrière diélectrique ou décharge de type corona. Dans ce cas, la pression de travail peut être voisine de la pression atmosphérique, ce qui est appréciable car le temps du traitement peut être notablement diminué.
- soit par décharge barrière diélectrique ou décharge de type corona entre deux électrodes, l'une introduite à l'intérieur du tube souple et l'autre placée à l'extérieur.
- soit en utilisant un mode de génération de plasma confiné sous forme d'un cordon de longueur déterminée.
- possibilité de diminuer l'épaisseur de la jupe de tube: gain en coût de matière première;
- absence de matériau rigide: propriétés "dead fold" améliorées;
- possibilité de choisir le mélange de matériaux optimal vis-à-vis du compromis souplesse - propriétés barrières;
- le dépôt est mince et déformable: les propriétés barrières sont maintenues même après utilisation poussée du tube souple.
- ce procédé est également applicable aux tubes obtenus par injection moulage en une pièce.
Claims (14)
- Tube souple muni d'une jupe (1) et d'une tête (2) comportant un goulot (3) et une épaule (4) reliant ledit goulot à ladite jupe, destiné à stocker et distribuer des produits liquides à pâteux contenant des parfums, des arômes ou sensibles à l'oxydation, caractérisé en ce que ledit tube porte sur toute la surface de sa paroi, c'est-à-dire sur la surface du goulot (3), de l'épaule (4) et de la jupe(1), un revêtement comprenant au moins une couche d'épaisseur comprise entre 150 et 1500 Å d'un matériau ou d'un mélange de matériaux appartenant au groupe suivant: carbone amorphe, hydrogéné ou non, azoté ou non, oxydes, nitrures ou carbures ou leur mélange ou leur combinaison d'un ou plusieurs des métaux suivants (Si, Mg, AI, Ti, Zr, Nb, Ta, Mo, W, V).
- Tube souple selon la revendication 1 où la surface de la paroi du tube portant ledit revêtement est la surface interne.
- Tube souple selon la revendication 1 où la surface de la paroi du tube portant ledit revêtement est la surface externe.
- Tube souple selon la revendication 1, caractérisé en ce que ladite couche d'épaisseur comprise entre 150 et 1500 Å confère à ladite jupe des propriétés barrières se traduisantpour l'oxygène, par une perméabilité inférieure à 1 ml/m2/jour/atmosphère (norme ASTMD3985)pour la vapeur d'eau, par une perméabilité inférieure à 2 g/m2/jour/atmosphèrer (norme ASTM F327)et pour les arômes, par une perméabilité inférieure à 0,5 10-6 g/m2/jour/mmHg.
- Tube selon l'une quelconque des revendications 1 à 4 où ladite tête et ladite jupe souple comprennent au moins une couche en une matière thermoplastique telle qu'une polyoléfine, un polyester du type polyéthylène téréphtalate (PET) ou un copolyester.
- Tube selon l'une quelconque des revendications 1 à 5, caractérisé en ce que ladite jupe comprend au moins une couche en un polymère chargé en matériau pulvérulent tel que le carbonate de calcium ou le mica.
- Procédé de fabrication de tubes souples en matière plastique comprenant une étape de mise en forme d'une jupe cylindrique, la réalisation d'une tête munie d'une épaule et d'un goulot, puis l'assemblage de ladite jupe cylindrique et de la tête par soudage, caractérisé en ce qu'il comporte une étape ultérieure de dépôt sur toute la surface dudit tube d'un revêtement comprenant au moins une couche d'épaisseur comprise entre 150 et 1500 Å d'un matériau ou d'un mélange de matériaux appartenant au groupe suivant: carbone amorphe, hydrogéné ou non, azoté ou non, oxydes, nitrures ou carbures ou leur mélange ou leur combinaison d'un ou plusieurs des métaux suivants (Si, Mg, Al, Ti, Zr, Nb, Ta, Mo, W, V).
- Procédé selon la revendication 7 où le dépôt du revêtement est effectué à l'aide d'un plasma sous une pression proche de la pression atmosphérique.
- Procédé selon la revendication 8 où le matériau du revêtement est obtenu par condensation après décomposition d'un corps ou d'un composé chimique gazeux, et où le plasma est généré sous l'effet une décharge barrière diélectrique ou d'une décharge corona.
- Procédé selon la revendication 8 où le plasma est généré en utilisant un mode de plasma confiné sous la forme d'un cordon de longueur déterminée.
- Procédé selon l'une quelconque des revendications 7 à 10 dans lequel on effectue un mélange des gaz précurseurs de façon à obtenir le dépôt d'un revêtement mixte.
- Procédé selon l'une quelconque des revendications 7 à 10 dans lequel on effectue un mélange de deux gaz précurseurs, en faisant varier dans le temps les compositions complémentaires des gaz du mélange, de façon à obtenir un dépôt graduel de couches d'abord riches en un premier élément puis s'enrichissant progressivement en un deuxième élément.
- Tube souple suivant l'une quelconque des revendications 1 à 6 dans lequel ledit revêtement est un dépôt graduel de couches d'abord riches en un premier élément du groupe décrit en revendication 1 puis s'enrichissant progressivement en un deuxième élément dudit groupe décrit en revendication 1.
- Tube souple selon la revendication 13 dans lequel ledit revêtement comprend une sous-couche riche en carbone à tendance polymérique et en surface une sous-couche en silice ou en alumine.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9916618 | 1999-12-23 | ||
FR9916618A FR2802900B1 (fr) | 1999-12-23 | 1999-12-23 | Tube souple revetu interieurement d'une couche a effet barriere de diffusion aux gaz et aux aromes |
PCT/FR2000/003635 WO2001047783A2 (fr) | 1999-12-23 | 2000-12-21 | Tube souple revetu d'une couche a effet barriere de diffusion aux gaz et aux aromes |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1250268A2 EP1250268A2 (fr) | 2002-10-23 |
EP1250268B1 true EP1250268B1 (fr) | 2003-09-17 |
Family
ID=9553946
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00990093A Expired - Lifetime EP1250268B1 (fr) | 1999-12-23 | 2000-12-21 | Tube souple revetu d'une couche a effet barriere de diffusion aux gaz et aux aromes |
Country Status (11)
Country | Link |
---|---|
US (1) | US20030118760A1 (fr) |
EP (1) | EP1250268B1 (fr) |
AT (1) | ATE249977T1 (fr) |
AU (1) | AU2689201A (fr) |
BR (1) | BR0016729A (fr) |
DE (1) | DE60005405T2 (fr) |
ES (1) | ES2204742T3 (fr) |
FR (1) | FR2802900B1 (fr) |
PL (1) | PL356636A1 (fr) |
RU (1) | RU2002119583A (fr) |
WO (1) | WO2001047783A2 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2776540B1 (fr) * | 1998-03-27 | 2000-06-02 | Sidel Sa | Recipient en matiere a effet barriere et procede et appareil pour sa fabrication |
EP1520796A1 (fr) * | 2003-09-30 | 2005-04-06 | Alcan Technology & Management Ltd. | Tube en matière plastique avec une couche intérieure et méthodes pour sa fabrication |
FR2964983B1 (fr) * | 2010-09-20 | 2013-05-17 | Valeo Vision | Installation de traitement d'un objet, plus particulierement de la surface d'un objet en polymere. |
DE102011101260B4 (de) * | 2011-04-01 | 2015-08-06 | Linhardt Gmbh & Co. Kg | Tubenverpackung |
DE202011105441U1 (de) * | 2011-05-03 | 2012-08-07 | Fischbach Kg Kunststoff-Technik | Auspressbehälter |
DE102011106735A1 (de) * | 2011-05-03 | 2012-11-08 | Fischbach Kg Kunststoff-Technik | Auspressbehälter |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5424131A (en) * | 1987-11-30 | 1995-06-13 | Polyplasma, Inc. | Barrier coatings on spacecraft materials |
JP3186193B2 (ja) * | 1992-04-14 | 2001-07-11 | 三菱化学株式会社 | ガスバリアー性の付与されたオレフィン系樹脂成形品 |
JPH10157750A (ja) * | 1996-10-02 | 1998-06-16 | Taisei Kako Kk | 金属製押出チューブ及びエアゾール缶、及び金属製押出チューブの製造方法 |
-
1999
- 1999-12-23 FR FR9916618A patent/FR2802900B1/fr not_active Expired - Fee Related
-
2000
- 2000-12-21 PL PL00356636A patent/PL356636A1/xx unknown
- 2000-12-21 AT AT00990093T patent/ATE249977T1/de not_active IP Right Cessation
- 2000-12-21 DE DE60005405T patent/DE60005405T2/de not_active Expired - Fee Related
- 2000-12-21 EP EP00990093A patent/EP1250268B1/fr not_active Expired - Lifetime
- 2000-12-21 US US10/168,903 patent/US20030118760A1/en not_active Abandoned
- 2000-12-21 ES ES00990093T patent/ES2204742T3/es not_active Expired - Lifetime
- 2000-12-21 RU RU2002119583/12A patent/RU2002119583A/ru not_active Application Discontinuation
- 2000-12-21 BR BR0016729-0A patent/BR0016729A/pt not_active IP Right Cessation
- 2000-12-21 AU AU26892/01A patent/AU2689201A/en not_active Abandoned
- 2000-12-21 WO PCT/FR2000/003635 patent/WO2001047783A2/fr active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
FR2802900B1 (fr) | 2002-05-24 |
WO2001047783A2 (fr) | 2001-07-05 |
PL356636A1 (en) | 2004-06-28 |
FR2802900A1 (fr) | 2001-06-29 |
BR0016729A (pt) | 2003-02-25 |
DE60005405T2 (de) | 2004-07-01 |
DE60005405D1 (de) | 2003-10-23 |
ATE249977T1 (de) | 2003-10-15 |
US20030118760A1 (en) | 2003-06-26 |
EP1250268A2 (fr) | 2002-10-23 |
AU2689201A (en) | 2001-07-09 |
ES2204742T3 (es) | 2004-05-01 |
WO2001047783A3 (fr) | 2002-05-16 |
RU2002119583A (ru) | 2004-02-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2165005B1 (fr) | Revetement barriere depose par plasma comprenant au moins trois couches, procede d'obtention d'un tel revetement et recipient revetu d'un tel revetement | |
EP1068032B1 (fr) | Recipient avec un revetement en matiere a effet barriere et procede et appareil pour sa fabrication | |
JP4885720B2 (ja) | 医薬用ブリスター | |
JP5362941B2 (ja) | 改善された耐薬品性を有する複合材料 | |
WO2002009891A1 (fr) | Revetement barriere depose par plasma comprenant une couche d'interface, procede d'obtention d'un tel revetement et recipient ainsi revetu | |
EP1250268B1 (fr) | Tube souple revetu d'une couche a effet barriere de diffusion aux gaz et aux aromes | |
FR2649359A1 (fr) | Bande ou portion de bande pour emboutissage ou emboutissage-etirage, et son utilisation | |
EP2597175A1 (fr) | Procédé de production d'un article polymère ayant un revêtement | |
WO2001041942A2 (fr) | Procede de depôt d'un revêtement sur la paroi de boitiers metalliques | |
MXPA06013380A (es) | Deposito mejorado de plasma de vapor quimico de oxido de metal. | |
CA2570372C (fr) | Joints d'etancheite en materiau multicouche pour moyen de bouchage, typiquement pour une capsule de bouchage | |
WO2002026401A1 (fr) | Procede de depot d'un revetement interne dans un recipient en matiere plastique | |
JP2016536235A (ja) | 被覆容器 | |
EP0678398B1 (fr) | Articles à base de polyoléfines imprimés au moyen d'encres pour PVC et procédés pour leur fabrication | |
EP1827716A1 (fr) | Procede de traitemend d'un materiau polymere, dispositif pour la mise en oevre de ce procede et utilisation de ce dispositif au traitement de corps creux | |
EP3697548B1 (fr) | Couvercle pour boîte de conserve métallique, comprenant un anneau métallique et membrane pelable thermoscellée | |
WO2001012517A1 (fr) | Tube a couche barriere et procede de depot | |
JP2005145491A (ja) | ラミネ−トチュ−ブ容器 | |
NZ556466A (en) | Sealing of polyethylene or polypropylene containers using blow-fill-seal method and a metal coating | |
EP1313648A1 (fr) | Emballage souple ayant une couche protectrice | |
JP2001225424A (ja) | 透明バリア性フィルムおよびそれを使用した積層体 | |
JP4815739B2 (ja) | チュ−ブ容器用包材およびそれを使用したチュ−ブ容器 | |
BE543394A (fr) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20020607 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CEBAL S.A.S. |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030917 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030917 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030917 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030917 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 60005405 Country of ref document: DE Date of ref document: 20031023 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: FRENCH |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20031120 Year of fee payment: 4 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: WILLIAM BLANC & CIE CONSEILS EN PROPRIETE INDUSTRI |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031217 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031217 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20031221 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031221 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031229 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20031209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20031231 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20031231 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20030917 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CA Ref country code: FR Ref legal event code: CD Ref country code: FR Ref legal event code: CJ |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2204742 Country of ref document: ES Kind code of ref document: T3 |
|
BERE | Be: lapsed |
Owner name: *CEBAL S.A.S. Effective date: 20031231 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20040618 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20041123 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20041130 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20041207 Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041221 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041231 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041231 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051221 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051221 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051222 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060701 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20051221 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20051222 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20071217 Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20090831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081231 |