WO2001012517A1 - Tube with barrier layer and deposit method - Google Patents

Tube with barrier layer and deposit method Download PDF

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Publication number
WO2001012517A1
WO2001012517A1 PCT/FR2000/002165 FR0002165W WO0112517A1 WO 2001012517 A1 WO2001012517 A1 WO 2001012517A1 FR 0002165 W FR0002165 W FR 0002165W WO 0112517 A1 WO0112517 A1 WO 0112517A1
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WO
WIPO (PCT)
Prior art keywords
sleeve
layer
skirt
coating
tube
Prior art date
Application number
PCT/FR2000/002165
Other languages
French (fr)
Inventor
Mohamed Benmalek
Alain Jupin
Original Assignee
Cebal S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cebal S.A. filed Critical Cebal S.A.
Priority to AU70092/00A priority Critical patent/AU7009200A/en
Publication of WO2001012517A1 publication Critical patent/WO2001012517A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • 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
    • B65D35/02—Body construction

Definitions

  • the invention relates to a method for continuously depositing barrier property coatings for polymeric skirts of flexible tubes. These tubes are typically intended for storing and distributing liquid to pasty products containing perfumes, aromas or being sensitive to oxidation.
  • Skirts of flexible tubes were previously metallic or metalloplastic and had, due to the presence of a metallic layer, a perfect barrier property to vapor, aromas and various gases (in particular oxygen).
  • EP 0 612 612 describes such a structure: the EVOH layer is an intermediate layer between two polyolefin layers (themselves which can be a superposition of layers of low density polyethylene, of linear low density polyethylene and / or of high density polyethylene), each layer being connected over its entire surface to the EVOH layer by means of layers of adhesive material of EAA or EMA type.
  • the skirts are obtained either by putting a multilayer strip in the shape of a cylinder by matching (contact or superposition) of its two longitudinal edges (see for example US 1 007 779) then longitudinal welding along these edges - the tube having a such a skirt is in this case called “laminated tube” -, either by direct coextrusion of a hollow cylindrical extrudate - the tube having such a skirt is in this case called “extruded (or coextruded) tube” -.
  • a cylindrical tube is obtained which we will call hereinafter “sleeve” to distinguish it from the complete flexible tube which is used to store and distribute a pasty product.
  • This sleeve is then cut lengthwise to obtain the skirt, one end of which will be fixed to a tube head. Once the tube head has been plugged, the skirt + head assembly is presented upside down so that it can be filled by the end which remains open of the skirt and the latter is finally welded after filling.
  • the sleeve takes its final shape and is cooled at the outlet of the die by passing through a particular device called a vacuum calibrator and within which the sleeve is shaped on a film of water and then put in contact with a calibration ring by pressure difference between the inside of the tube - which is under atmospheric pressure - and the outside of the tube - which is subjected to a more or less high vacuum depending on the thickness of the sleeve and the rheology (s) (co) extruded material (s) -.
  • EVOH is sensitive to humidity, which requires a minimum thickness of internal layers, typically made of polyethylene (PE).
  • PE polyethylene
  • the EVOH layer must be thick enough to have effective barrier properties but it must not be too thick compared to the other layers: EVOH is particularly rigid and elastic, which degrades the "dead fold" property of the multilayer obtained - property characterizing a plastic behavior in bending (weak effect of the elastic return on the bending angle) sometimes translated by "crushability".
  • the compromise found requires, for barely satisfactory barrier properties, a relatively large total thickness of the multilayer.
  • the object of the invention is to define a method making it possible, for laminated tubes as for extruded tubes, to obtain a skirt structure free from a barrier material as rigid as EVOH but which, for the same total thickness - typically 250 - 500 microns -, barrier properties and crushability at least as good as those of the structure of the prior art, the barrier properties being moreover substantially constant over the entire periphery of the skirt, even for laminated tubes .
  • a first object of the invention is a flexible tube provided with a skirt and a head, intended for storing and distributing liquid to pasty products containing perfumes, aromas or sensitive to oxidation, characterized in that said skirt carries over its entire external surface a coating of thickness between 400 and 1500 ⁇ comprising at least one layer 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 combination of one or more of the following metals (Si, Mg, AI, Ti, Zr, Nb, Ta, Mo, W, V).
  • Such a skirt can thus be free of a rigid polymer layer with barrier properties, for example a layer of copolymer (ethylene, vinyl alcohol (EVOH)).
  • a layer of copolymer ethylene, vinyl alcohol (EVOH)
  • the coating according to the invention in fact, despite its small thickness, gives the structure of the skirt satisfactory barrier properties.
  • the thickness of the coating is variable depending on the material chosen.
  • the deposited layer remains flexible relative to its substrate and thus retains perfect mechanical strength during handling of the skirt. It must be thick enough to give the structure barrier properties that translate
  • the skirt of the flexible tube according to the invention comprises at least one layer of a thermoplastic material such as a polyolefin, a polyester of the polyethylene terephthalate (PET) type or a copolyester.
  • a thermoplastic material such as a polyolefin, a polyester of the polyethylene terephthalate (PET) type or a copolyester.
  • PET polyethylene terephthalate
  • said layer is located outside the skirt and serves as a target for the deposit.
  • at least one layer comprises a polymer loaded with pulverulent material such as calcium carbonate or mica.
  • This coating is a ductile outer layer which satisfactorily resists bending fatigue. It is possible to directly print on this coating a text or a decoration. It is not necessary to cover it with a polymeric protective and / or printing layer. This does not however preclude the possibility of adding a layer of varnish on this coating to protect the printed decoration, to give a particular visual appearance (mat, gloss, satin, etc.), or even to provide additional functionality to said skirt.
  • Another object of the invention is an additional step in the process of manufacturing flexible plastic tube skirts in which the external surface of the tube skirt is coated after shaping the sleeve - preferably just after shaping, in the procession and before cutting the skirt - by a layer of thickness between 400 and 1500 A 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 combination of one or more of the following metals (Si, Mg, Al, Ti, Zr, Nb, Ta, Mo, W, V).
  • the skirt is subjected to the deposition of a coating after shaping. It goes without saying if the skirt is extruded because the coating can only be done afterwards. But if it is laminated, that is to say formed from a strip, it would be possible to directly use a strip already coated on one of its faces with one of the materials described above. In this case, by looking at the longitudinal edges (contact or overlapping) and then welding them, a longitudinal zone would have been created having lost its continuous coating, which would prevent having a diffusion barrier over the entire skirt.
  • this deposition is carried out continuously, on parade, before the skirts are cut, on the external surface of the sleeve obtained from coextrusion or obtained w after welding of the longitudinal edges of the strip, at a speed compatible with the rates of industrial production. , typically greater than 10 m / min.
  • this deposition is carried out using a plasma reactor for surface treatment.
  • Plasma can be generated under different types of discharge: microwave, radio frequency, medium frequency alternating current, luminescent discharge, discharge through a dielectric barrier (the plastic sleeve itself constituting the dielectric barrier) or discharge corona type. Due to the nature of the substrate to be covered, the plasma generated is a cold plasma. The last two types of plasma generation have the advantage of being carried out at atmospheric pressure but impose a short distance between electrode and substrate.
  • the material to be deposited comes from a solid, it is necessary to carry out a cathode sputtering or an evaporation of the source in a place sufficiently distant from the target - which otherwise would not support heating -, which requires placing several sources around the sleeve to obtain the most regular deposit thickness possible, the sleeve passing through a vacuum enclosure.
  • the plasma 0 is generated by excitation of a gas flowing between electrodes where a electrical voltage difference - continuous or alternating - is applied in a high vacuum.
  • the coating does not require evaporation or sputtering but can be obtained by condensation after decomposition of a body or a gaseous compound, the plasma can be generated
  • the working pressure can vary between one hundredth and one thousandth of a torr, • either by dielectric barrier discharge or corona type discharge: in in this case, the working pressure may be close to atmospheric pressure, which is appreciable under the specific conditions of a procession at the parade where a high vacuum is difficult to obtain.
  • a particularly advantageous embodiment of the invention consists in injecting into a chamber surrounding the sleeve, near the surface of the sleeve, a gaseous body or compound which circulates between two electrodes, and in bringing one of the electrodes to the ground and the 'other at a voltage of ten kV so that a discharge occurs and generates the plasma.
  • the latter method has the advantage of being able to be carried out under a pressure close to atmospheric pressure, preferably between 200 and 760 millimeters of mercury. This simplifies and decreases the cost of treatment installations when the sleeve passes through.
  • a pressure slightly lower than atmospheric pressure makes it possible to better control the purity of the gas circulating around the sleeve since the air is mainly extracted from the enclosure and then replaced by a controlled gas, thus avoiding the formation of undesirable impurities ( risk of reaction with nitrogen in the air, water vapor, etc.).
  • a deposit of amorphous carbon on the outer surface of a polyethylene sleeve by passing a stream of hydrocarbon gas - acetylene in this case - in an enclosure surrounding the sleeve and containing a system of electrodes between which a difference of voltage of the order of 10kV.
  • a gas such as HMDSO (hexamethyldisiloxane) or TMDSO (tetramethyldisiloxane) instead of acetylene.
  • an internal electrode is used.
  • extruded tubes examples 1
  • the latter is held in place using a support mechanically connected to the extrusion die (in the extension of the needle for example).
  • laminated tubes examples 2
  • the electrode is held in place by means of a support inserted into the notch formed by the edges of the strip a few centimeters upstream from the longitudinal welding station.
  • the support is long enough for the active part of the electrode to act downstream of the welding station. In this way, the coating is deposited on the entire circumference of the skirt.
  • the internal electrode is a solid metal cylinder or, preferably, a hollow cylindrical grid, lighter and easier to position and hold in place.
  • the electrodes preferably have a common length corresponding to the length of the enclosure, but it is possible to make them shorter by placing them upstream of the gas stream: the gas is injected into the enclosure and circulates from upstream to downstream of such that it first crosses the electrical discharge zone, that a plasma is generated under the effect of the discharges and then propagates from upstream to downstream over the entire length of the enclosure, the deposition taking place thus over the entire length of the enclosure.
  • Figure 1 shows schematically in section the sleeve and a cylinder-cylinder electrode system (dielectric barrier discharge) used when it is possible to place an electrode inside the sleeve, which is the case for laminated skirts and for most of the geometry of the extruded skirts.
  • FIG. 2 shows a knife-type electrode system used when it is not possible to introduce and maintain an electrode inside the sleeve.
  • Figure 3 shows schematically another embodiment of the method also usable when it is not possible to introduce an electrode inside the sleeve.
  • the latter device is also suitable for sputtering deposition of a solid target.
  • Example 1 Deposition of a layer of amorphous carbon on the outer surface of an extruded polyethylene sleeve.
  • the industrial installation making it possible to manufacture flexible skirts for extruded tubes is a chain grouping, from upstream to downstream, one or more screw extruders supplying an extrusion or coextrusion die, a calibrator accompanied by a cooling device, the whole measuring approximately 3 meters, finally a cutter who drives the sleeve at a controlled speed then cuts the latter to the desired lengths of skirts.
  • the sleeve is shaped on a film of water and then brought into contact with a calibration ring by pressure difference between the inside of the tube - which is under atmospheric pressure - and the outside of the tube - which is subjected to a more or less extensive vacuum depending on the thickness of the sleeve and the rheology of the (co) extruded material (s).
  • the sleeve 1 is too thin to withstand a pressure difference of the order of one atmosphere between its inner wall (which is at atmospheric pressure) and its outer wall.
  • techniques which do not require a high vacuum to generate the plasma are doubly advantageous, on the one hand because it is not necessary to ensure a good seal in an enclosure surrounding the moving sleeve, on the other hand because it is not necessary to provide one or more shapers intended to maintain the sleeve in its desired shape, said shapers themselves presenting an obstacle to deposition.
  • the particular device of this example generates the plasma at atmospheric pressure. It is introduced between the calibrator and the cooling device. At this stage of travel, the sleeve is still hot and its outer surface, made of low density polyethylene, is not yet stabilized, which constitutes favorable conditions for deposition.
  • the device for cooling the extruded tube which measures several meters, being here downstream of the deposition device, the internal electrode 2 is fixed to the end of the needle of the die, which has been extended over a reasonable distance. , of the order of half a meter (in general, a calibrator 30-40 centimeters long is sufficient).
  • the die is electrically grounded.
  • the internal electrode 2 is in the form of a hollow cylindrical grid having a diameter close to that of the sleeve 1, to one or two millimeters.
  • a cylindrical enclosure 3 surrounds the sleeve over two meters. It defines between its wall and that of the sleeve a space 4 where the acetylene circulates. This space includes an external cylindrical electrode 5 having a diameter a few millimeters larger than that of the sleeve.
  • the order of magnitude of the average deposition speed is 50 A / s, which makes it possible, with a length of 2 m and a running speed of the sleeve of l 'order of 10 m / min to deposit a layer of 600 ⁇ of amorphous carbon.
  • the sleeve follows a stress cycle inspired by the Gelbo Flex test according to ASTM E-392 and gives satisfactory results up to 100/200 cycles.
  • the coating obtained has a more homogeneous surface appearance but it has proved necessary to limit the deformations imposed on the sleeve by the pressure difference on either side of its wall.
  • the plasma assisted deposition chamber was placed downstream of the cooling device. It would also have been possible to place a perforated shaping tube around the sleeve.
  • Example 2 Deposition of an amorphous carbon layer on the outer surface of a laminated polyethylene sleeve.
  • a multilayer strip is formed into a cylinder by superposition of its two longitudinal edges over 2.5 mm. A few centimeters upstream of the longitudinal welding station, the edges are still sufficiently distant from one another so that the support of an internal electrode, of the same type as that described in Example 1, can be introduced, the latter being sufficiently slender so that its active part is facing the enclosure, identical to that described in Example 1 and placed a few centimeters downstream of the longitudinal welding station.
  • the electrode is carried by a rod which crosses the welding zone and can thus constitute, directly or by means of a ring fitted on said rod, electrically and thermally insulated therefrom, a metallic mass participating in the contribution. of energy for the welding of the edges of the plastic strip - (high frequency welding).
  • Example 3 Deposition of an amorphous carbon layer on the outer surface of a thin polyethylene sleeve. ( Figure 2)
  • the skirt is coextruded with an internal layer of 150 ⁇ m of PE loaded with calcium carbonate and an external layer of LDPE of 50 ⁇ m.
  • the conventional calibration device with its cooling device so that the coating device according to the invention can no longer be put downstream of said cooling device, that is to say that is to say more than four meters from the die.
  • the enclosure 23 surrounding the sleeve 1 it is preferable to equip the enclosure 23 surrounding the sleeve 1 with a knife-knife type electrode system (21, 22) illustrated in FIG. 2.
  • a plasma is formed between the knives whose tip is inclined with respect to the radial direction so that the external surface of the sleeve 1 is in the vicinity of the discharge zone between the tips of the electrodes 21 and 22.
  • a series of electrodes 21 and 22 spaced about 3 mm apart and constituting nested turns on a cylinder with a diameter of 040 mm.
  • the electrodes 21 are brought to a potential V of approximately 10 kV and the electrodes 22 are brought to ground.
  • Example 4 - CVD plasma deposition of a carbon layer on the outer surface of a thick polyethylene sleeve Figure 3).
  • the device comprises a cylindrical enclosure 33 two meters long. Between its wall and that of the sleeve 1, it delimits a space in which an argon-acetylene mixture circulates. This space has two electrodes 35 and 32 outside the sleeve.
  • the electrode 35 has the largest diameter and is spaced a few centimeters from an electrode 32 in the form of a cylindrical grid, itself spaced from the sleeve 1 by only a few millimeters.
  • the pressure during deposition is fixed at 0.25 Torr.
  • An acetylene-argon mixture is injected with a C 2 H / Ar ratio of the order of 10%.
  • the plasma generated by a source excited at 250 kHz with an electrical power of 70 W, extends beyond the air gap between the electrodes and passes through electrode 32 which is a grid with large meshes (of the order of cm 2 ) whose envelope surface rests on a cylinder. The plasma passes through this grid and comes to be flush with the surface of the sleeve 1 while providing the carbon for the coating.
  • the tube used To resist the pressure difference between the interior - at atmospheric pressure - and the exterior (0.25 torr), the tube used must be fairly thick - at least 0.7 mm.
  • Example 5 Deposition of a layer of a material related to a compound rich in silica and alumina on the outer surface of a PET sleeve.
  • the enclosure includes an electrode device of the same type as that shown diagrammatically in FIG. 3 (35 and 32).
  • the larger diameter electrode differs from the previous one (35) in that it constitutes the source of the material to be deposited, in this case it is made of an aluminum and silicon alloy, of the AS17U4G type.
  • Oxygen is introduced into the enclosure under a flow of 0.5 cm3 per minute and argon is introduced under a flow of 55 cm3 per minute .
  • the pressure during deposition is fixed at 0.3 Pa.
  • the electric power delivered to the target is 150 W.
  • a plasma is formed in the argon-oxygen mixture.
  • the ions bombard the aluminum-silicon alloy target and cause sputtering.
  • the electrode of smaller diameter is a cylindrical grid with large meshes (of the order of cm 2 ) which allows the plasma and the material to be deposited to pass.
  • the external surface of the sleeve is treated for a time of the order of 15 s, which limits the running speed to 8 meters / minute.
  • the downstream station of the chain including the cutting device and the part of the spiked chain collecting the cut skirts, is placed in an enclosure subjected to a pressure below the atmospheric pressure, typically between 0.1 and 0.5 atmospheres.
  • Example 6 Gradual deposition of layers of amorphous carbon and silica on the outer surface of an extruded polyethylene sleeve
  • the device of Example 1 is slightly modified to obtain a coating comprising several layers.
  • the internal electrode 2 here has the length of the cylindrical enclosure 3.
  • the cylindrical enclosure 3 is supplied with each of - l è ⁇
  • the upstream end of the sleeve is supplied with acetylene
  • the downstream end of the sleeve is supplied with hexamethyldisiloxane (HMDSO).
  • HMDSO hexamethyldisiloxane
  • a discharge duct located in the middle of the cylindrical enclosure 3 promotes the circulation of the plasma between each of the ends and the central part of the enclosure. This results in a gradual deposition of layers first rich in amorphous carbon then rich in silica.
  • the hydrogenated amorphous carbon located in a sublayer, ensures better bonding on the polyethylene substrate and ensures greater 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 the conditions imposed for the subsequent printing of the tube skirt.

Abstract

The invention concerns a flexible tube for storing or dispensing liquid to pasty products containing perfumes, flavours or oxidation-sensitive, provided with a skirt bearing over its whole outer surface a layer having a thickness between 400 and 1500 ANGSTROM of a material or 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 several of the following metals (Si, Mg, Al, Ti, Zr, Nb, Ta, Mo, W, V). The coating is carried out using cold plasma, preferably under atmospheric pressure by decomposition of a gas compound and condensation on the substrate assisted by a plasma generated by dielectric barrier discharge or by corona discharge.

Description

TUBE A COUCHE BARRIERE ET PROCEDE DE DEPOT BARRIER LAYER TUBE AND DEPOSITION METHOD
DOMAINE TECHNIQUETECHNICAL AREA
L'invention concerne un procédé permettant de déposer en continu des revêtements à propriété barrière pour les jupes polymériques de tubes souples. Ces tubes sont typiquement destinés à stocker et distribuer des produits liquides à pâteux contenant des parfums, des arômes ou étant sensibles à l'oxydation.The invention relates to a method for continuously depositing barrier property coatings for polymeric skirts of flexible tubes. These tubes are typically intended for storing and distributing liquid to pasty products containing perfumes, aromas or being sensitive to oxidation.
ETAT DE LA TECHNIQUESTATE OF THE ART
Les jupes de tubes souples étaient auparavant métalliques ou métalloplastiques et possédaient, de par la présence d'une couche métallique, une parfaite propriété barrière à la vapeur, aux arômes et aux différents gaz (notamment l'oxygène).Skirts of flexible tubes were previously metallic or metalloplastic and had, due to the presence of a metallic layer, a perfect barrier property to vapor, aromas and various gases (in particular oxygen).
Pour des raisons de recyclage des films multicouches métalloplastiques, on a cherché à remplacer la couche métallique par une couche polymérique conférant à l'ensemble des propriétés barrières satisfaisantes. Mais cette matière n'a pas pu être trouvée parmi les polyoléfines couramment utilisées sur les tubes produits à bon marché et en très grandes quantités. On a fait appel alors à des structures constituées de plusieurs couches coextrudées comportant au moins une couche à effet barrière de diffusion, en une matière plastique telle que l'EVOH (copolymère éthylène - alcool vinylique), certains polyamides (PA) ou polyamides modifiés. EP 0 612 612 décrit une telle structure: la couche en EVOH est une couche intermédiaire entre deux couches en polyoléfines (elles-mêmes pouvant être une superposition de couches en polyéthylène basse densité, en polyéthylène basse densité linéaire et/ou en polyéthylène haute densité), chaque couche étant reliée sur toute sa surface à la couche en EVOH par l'intermédiaire de couches en matière adhésive de type EAA ou EMA.For reasons of recycling metalloplastic multilayer films, attempts have been made to replace the metallic layer with a polymeric layer which gives satisfactory barrier properties as a whole. But this material could not be found among the polyolefins commonly used on tubes produced inexpensively and in very large quantities. We then used structures consisting of several coextruded layers comprising at least one diffusion barrier effect layer, made of a plastic material such as EVOH (ethylene-vinyl alcohol copolymer), certain polyamides (PA) or modified polyamides. EP 0 612 612 describes such a structure: the EVOH layer is an intermediate layer between two polyolefin layers (themselves which can be a superposition of layers of low density polyethylene, of linear low density polyethylene and / or of high density polyethylene), each layer being connected over its entire surface to the EVOH layer by means of layers of adhesive material of EAA or EMA type.
Les jupes sont obtenues soit en mettant une bande multicouche en forme de cylindre par mise en correspondance (contact ou superposition) de ses deux bords longitudinaux (voir par exemple US 1 007 779) puis soudure longitudinale le long de ces bords - le tube possédant une telle jupe est dans ce cas dit "tube laminé" - , soit par coextrusion directe d'un extrudat creux cylindrique - le tube possédant une telle jupe est dans ce cas dit "tube extrudé (ou coextrudé) " - . Dans les deux cas, on obtient un tube cylindrique que nous appellerons par la suite "manchon" pour le distinguer du tube souple complet qui sert à stocker et distribuer un produit pâteux. Ce manchon est ensuite découpé en longueur pour obtenir la jupe dont une extrémité sera fixée à une tête de tube. Une fois la tête de tube bouchée, l'ensemble jupe + tête est présenté tête en bas de façon à ce que l'on puisse le remplir par l'extrémité restée ouverte de la jupe et celle-ci est enfin soudée après remplissage.The skirts are obtained either by putting a multilayer strip in the shape of a cylinder by matching (contact or superposition) of its two longitudinal edges (see for example US 1 007 779) then longitudinal welding along these edges - the tube having a such a skirt is in this case called "laminated tube" -, either by direct coextrusion of a hollow cylindrical extrudate - the tube having such a skirt is in this case called "extruded (or coextruded) tube" -. In both cases, a cylindrical tube is obtained which we will call hereinafter "sleeve" to distinguish it from the complete flexible tube which is used to store and distribute a pasty product. This sleeve is then cut lengthwise to obtain the skirt, one end of which will be fixed to a tube head. Once the tube head has been plugged, the skirt + head assembly is presented upside down so that it can be filled by the end which remains open of the skirt and the latter is finally welded after filling.
En ce qui concerne la fabrication du tube extrudé, le manchon prend sa forme définitive et est refroidi en sortie de filière en passant par un dispositif particulier appelé calibreur sous vide et au sein duquel le manchon est mis en forme sur film d'eau puis mis en contact avec une bague de calibrage par différence de pression entre l'intérieur du tube - qui est sous pression atmosphérique - et l'extérieur du tube - qui est soumis à une dépression plus ou moins poussée suivant l'épaisseur du manchon et la rhéologie de(s) la matière(s) (co)extrudée(s) - . PROBLEME POSEAs regards the manufacture of the extruded tube, the sleeve takes its final shape and is cooled at the outlet of the die by passing through a particular device called a vacuum calibrator and within which the sleeve is shaped on a film of water and then put in contact with a calibration ring by pressure difference between the inside of the tube - which is under atmospheric pressure - and the outside of the tube - which is subjected to a more or less high vacuum depending on the thickness of the sleeve and the rheology (s) (co) extruded material (s) -. PROBLEM
La présence d'un matériau à propriétés barrières tel que l'EVOH présente un certain nombre d'inconvénients en raison du coût de ce matériau et des difficultés de mise en oeuvre et d'utilisation du multicouche. L'EVOH est sensible à l'humidité, ce qui nécessite une épaisseur minimale de couches internes, typiquement en polyéthylène (PE). La couche en EVOH doit être suffisamment épaisse pour avoir des propriétés barrières efficaces mais elle ne doit pas être trop épaisse par rapport aux autres couches: l'EVOH est particulièrement rigide et élastique, ce qui dégrade la propriété "dead fold" du multicouche obtenu - propriété caractérisant un comportement plastique en flexion (faible effet du retour élastique sur l'angle de pliage) parfois traduite par "écrasabilité". Le compromis trouvé impose, pour des propriétés barrières tout juste satisfaisantes, une épaisseur totale du multicouche relativement importante.The presence of a material with barrier properties such as EVOH presents a certain number of drawbacks due to the cost of this material and the difficulties of implementation and use of the multilayer. EVOH is sensitive to humidity, which requires a minimum thickness of internal layers, typically made of polyethylene (PE). The EVOH layer must be thick enough to have effective barrier properties but it must not be too thick compared to the other layers: EVOH is particularly rigid and elastic, which degrades the "dead fold" property of the multilayer obtained - property characterizing a plastic behavior in bending (weak effect of the elastic return on the bending angle) sometimes translated by "crushability". The compromise found requires, for barely satisfactory barrier properties, a relatively large total thickness of the multilayer.
D'autre part, en ce qui concerne les tubes laminés, on constate une moins bonne barrière de diffusion des gaz et des parfums au niveau de la soudure longitudinale certainement due à la mise en fusion locale des différents composants du multicouche et aux déformations dues aux contraintes engendrées par l'accotement ou la superposition des bords longitudinaux de la bande.On the other hand, with regard to laminated tubes, there is a less good diffusion barrier for gases and perfumes at the level of the longitudinal weld, certainly due to the local melting of the various components of the multilayer and to the deformations due to stresses caused by the shoulder or the superposition of the longitudinal edges of the strip.
L'invention a pour but de définir un procédé permettant, pour les tubes laminés comme pour les tubes extrudés, d'obtenir une structure de jupe exempte d'un matériau barrière aussi rigide que l'EVOH mais qui ait, pour la même épaisseur totale - typiquement 250 - 500 microns -, des propriétés barrières et une écrasabilité au moins aussi bonnes que celles de la structure de l'art antérieur, les propriétés barrières étant de plus sensiblement constantes sur toute la périphérie de la jupe, même pour les tubes laminés. OBJET DE L'INVENTIONThe object of the invention is to define a method making it possible, for laminated tubes as for extruded tubes, to obtain a skirt structure free from a barrier material as rigid as EVOH but which, for the same total thickness - typically 250 - 500 microns -, barrier properties and crushability at least as good as those of the structure of the prior art, the barrier properties being moreover substantially constant over the entire periphery of the skirt, even for laminated tubes . OBJECT OF THE INVENTION
Un premier objet de l'invention est un tube souple muni d'une jupe et d'une tête, destiné à stocker et distribuer des produits liquides à pâteux contenant des parfums, des arômes ou sensibles à l'oxydation, caractérisé en ce que ladite jupe porte sur toute sa surface externe un revêtement d'épaisseur comprise entre 400 et 1500 Â comportant au moins une couche 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).A first object of the invention is a flexible tube provided with a skirt and a head, intended for storing and distributing liquid to pasty products containing perfumes, aromas or sensitive to oxidation, characterized in that said skirt carries over its entire external surface a coating of thickness between 400 and 1500 Å comprising at least one layer 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 combination of one or more of the following metals (Si, Mg, AI, Ti, Zr, Nb, Ta, Mo, W, V).
Une telle jupe peut ainsi être exempte d'une couche polymérique rigide à propriétés barrières, par exemple une couche de copolymère (éthylène, alcool vinylique (EVOH)). Le revêtement selon l'invention confère en effet, malgré sa faible épaisseur, à la structure de la jupe des propriétés barrières satisfaisantes. L'épaisseur du revêtement est variable selon le matériau choisi.Such a skirt can thus be free of a rigid polymer layer with barrier properties, for example a layer of copolymer (ethylene, vinyl alcohol (EVOH)). The coating according to the invention in fact, despite its small thickness, gives the structure of the skirt satisfactory barrier properties. The thickness of the coating is variable depending on the material chosen.
Elle est limitée pour que la couche déposée reste souple par rapport à son substrat et conserve ainsi une parfaite tenue mécanique au cours des manipulations de la jupe. Elle doit être suffisamment épaisse pour conférer à la structure des propriétés barrières se traduisantIt is limited so that the deposited layer remains flexible relative to its substrate and thus retains perfect mechanical strength during handling of the skirt. It must be thick enough to give the structure barrier properties that translate
• 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)• for oxygen, with a permeability of less than 1 ml / m 2 / day / atmosphere (standard ASTMD3985) • for water vapor, with a permeability of less than 2 g / m 2 / day / atmosphere (standard ASTM F327 )
• et pour les arômes, par une perméabilité inférieure à 0,5 10-° g/m2/jour/mmHg Lα jupe du tube souple selon l'invention comprend au moins une couche en une matière thermoplastique telle qu'une polyoléfine, en un polyester du type polyéthylène téréphtalate (PET) ou un copolyester. En cas de structure multicouche, ladite couche est située à l'extérieur de la jupe et sert de cible accueillant le dépôt. De préférence, afin d'améliorer encore les propriétés d'écrasabilité, au moins une couche comporte un polymère chargé en matériau pulvérulent tel que le carbonate de calcium ou le mica.• and for aromas, by a permeability of less than 0.5 10- ° g / m 2 / day / mmHg The skirt of the flexible tube according to the invention comprises at least one layer of a thermoplastic material such as a polyolefin, a polyester of the polyethylene terephthalate (PET) type or a copolyester. In the case of a multilayer structure, said layer is located outside the skirt and serves as a target for the deposit. Preferably, in order to further improve the crushability properties, at least one layer comprises a polymer loaded with pulverulent material such as calcium carbonate or mica.
Ce revêtement est une couche externe ductile qui résiste de manière satisfaisante à la fatigue en flexion. Il est possible d'imprimer directement sur ce revêtement un texte ou un décor. Il n'est pas nécessaire de le recouvrir d'une couche polymérique de protection et/ou d'impression. Ceci n'interdit pas toutefois la possibilité d'ajouter une couche de vernis sur ce revêtement pour protéger le décor imprimé, donner un aspect visuel particulier (mat, brillant, satiné, etc.), ou encore apporter une fonctionnalité supplémentaire à ladite jupe.This coating is a ductile outer layer which satisfactorily resists bending fatigue. It is possible to directly print on this coating a text or a decoration. It is not necessary to cover it with a polymeric protective and / or printing layer. This does not however preclude the possibility of adding a layer of varnish on this coating to protect the printed decoration, to give a particular visual appearance (mat, gloss, satin, etc.), or even to provide additional functionality to said skirt.
Un autre objet de l'invention est une étape supplémentaire du procédé de fabrication des jupes de tubes souples en matière plastique dans laquelle la surface externe de la jupe de tube est revêtue après mise en forme du manchon - de préférence juste après mise en forme, au défilé et avant découpe de la jupe - par une couche d'épaisseur comprise entre 400 et 1500 A 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).Another object of the invention is an additional step in the process of manufacturing flexible plastic tube skirts in which the external surface of the tube skirt is coated after shaping the sleeve - preferably just after shaping, in the procession and before cutting the skirt - by a layer of thickness between 400 and 1500 A 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 combination of one or more of the following metals (Si, Mg, Al, Ti, Zr, Nb, Ta, Mo, W, V).
La jupe est soumise au dépôt d'un revêtement après mise en forme. Cela va de soi si la jupe est extrudée car le revêtement ne peut se faire qu'après. Mais si elle est laminée, c'est-à-dire formée à partir d'une bande, il serait possible d'utiliser directement une bande déjà revêtue sur l'une de ses faces par l'un des matériaux décrits plus haut. Dans ce cas, en mettant en regard les bords longitudinaux (contact ou superposition) puis en les soudant, on créerait une 5 zone longitudinale ayant perdu son revêtement continu, ce qui empêcherait d'avoir une barrière de diffusion sur la totalité de la jupe.The skirt is subjected to the deposition of a coating after shaping. It goes without saying if the skirt is extruded because the coating can only be done afterwards. But if it is laminated, that is to say formed from a strip, it would be possible to directly use a strip already coated on one of its faces with one of the materials described above. In this case, by looking at the longitudinal edges (contact or overlapping) and then welding them, a longitudinal zone would have been created having lost its continuous coating, which would prevent having a diffusion barrier over the entire skirt.
De préférence, on effectue ce dépôt en continu, au défilé, avant découpe des jupes, sur la surface externe du manchon issu de la coextrusion ou obtenu w après soudure des bords longitudinaux de la bande, à une vitesse compatible avec les cadences de production industrielles, typiquement supérieures à 10 m/mn.Preferably, this deposition is carried out continuously, on parade, before the skirts are cut, on the external surface of the sleeve obtained from coextrusion or obtained w after welding of the longitudinal edges of the strip, at a speed compatible with the rates of industrial production. , typically greater than 10 m / min.
De préférence, on effectue ce dépôt en utilisant un réacteur plasma de i traitement de surface. Le plasma peut être généré sous différents types de décharges: micro-ondes, radiofréquences, courant alternatif de moyenne fréquence, décharge luminescente, décharge au travers d'une barrière diélectrique (le manchon en matière plastique constituant lui-même la barrière diélectrique) ou décharge de type corona. En raison de la nature du substrat à 0 recouvrir, le plasma engendré est un plasma froid. Les deux derniers types de génération de plasma présentent l'avantage de se faire sous pression atmosphérique mais imposent une faible distance entre électrode et substrat.Preferably, this deposition is carried out using a plasma reactor for surface treatment. Plasma can be generated under different types of discharge: microwave, radio frequency, medium frequency alternating current, luminescent discharge, discharge through a dielectric barrier (the plastic sleeve itself constituting the dielectric barrier) or discharge corona type. Due to the nature of the substrate to be covered, the plasma generated is a cold plasma. The last two types of plasma generation have the advantage of being carried out at atmospheric pressure but impose a short distance between electrode and substrate.
Lorsque le matériau à déposer provient d'un solide, il faut effectuer une 5 pulvérisation cathodique ou une évaporation de la source en un endroit suffisamment éloigné de la cible -qui sinon ne supporterait pas réchauffement - , ce qui impose de placer plusieurs sources autour du manchon pour obtenir une épaisseur de dépôt la plus régulière possible, le manchon défilant dans une enceinte sous vide. Dans le cas de la pulvérisation cathodique, le plasma 0 est généré par excitation d'un gaz circulant entre des électrodes où une différence de tension électrique - continue ou alternative - est appliquée dans un vide poussé.When the material to be deposited comes from a solid, it is necessary to carry out a cathode sputtering or an evaporation of the source in a place sufficiently distant from the target - which otherwise would not support heating -, which requires placing several sources around the sleeve to obtain the most regular deposit thickness possible, the sleeve passing through a vacuum enclosure. In the case of sputtering, the plasma 0 is generated by excitation of a gas flowing between electrodes where a electrical voltage difference - continuous or alternating - is applied in a high vacuum.
Si le revêtement ne nécessite ni évaporation ni pulvérisation cathodique mais peut être obtenu par condensation après décomposition d'un corps ou d'un composé gazeux, le plasma peut être généréIf the coating does not require evaporation or sputtering but can be obtained by condensation after decomposition of a body or a gaseous compound, the plasma can be generated
• 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 dans les conditions particulières d'un traitement au défilé où un vide poussé est difficile à obtenir.• either by low, medium or high frequency excitation or even by microwave: in this case, the working pressure can vary between one hundredth and one thousandth of a torr, • either by dielectric barrier discharge or corona type discharge: in in this case, the working pressure may be close to atmospheric pressure, which is appreciable under the specific conditions of a procession at the parade where a high vacuum is difficult to obtain.
Un mode de réalisation particulièrement avantageux de l'invention consiste à injecter dans une enceinte entourant le manchon, à proximité de la surface du manchon, un corps ou composé gazeux qui circule entre deux électrodes, et à porter une des électrodes à la terre et l'autre à une tension d'une dizaine de kV de telle sorte qu'une décharge se produise et génère le plasma.A particularly advantageous embodiment of the invention consists in injecting into a chamber surrounding the sleeve, near the surface of the sleeve, a gaseous body or compound which circulates between two electrodes, and in bringing one of the electrodes to the ground and the 'other at a voltage of ten kV so that a discharge occurs and generates the plasma.
Ce dernier procédé présente l'avantage de pouvoir être effectué sous une pression proche de la pression atmosphérique, de préférence entre 200 et 760 millimètres de mercure. Ceci simplifie et diminue le coût des installations de traitement au défilé du manchon. Une pression légèrement plus faible que la pression atmosphérique permet de mieux contrôler la pureté du gaz circulant autour du manchon puisque l'air est en majeure partie extrait de l'enceinte puis remplacé par un gaz contrôlé, évitant ainsi la formation d'impuretés indésirables (risque de réaction avec l'azote de l'air, la vapeur d'eau, etc....). Dans les premiers exemples présentés ci-après, on effectue un dépôt de cαrbone amorphe sur la surface extérieure d'un manchon en polyéthylène en faisant passer un courant de gaz hydrocarbure - de l'acétylène en l'occurrence - dans une enceinte entourant le manchon et contenant un système d'électrodes entre lesquelles on applique une différence de tension de l'ordre de lOkV. Si l'on veut effectuer un dépôt de silice, on fait circuler un gaz tel que l'HMDSO (hexaméthyldisiloxane) ou le TMDSO (tétraméthyldisiloxane) à la place de l'acétylène.The latter method has the advantage of being able to be carried out under a pressure close to atmospheric pressure, preferably between 200 and 760 millimeters of mercury. This simplifies and decreases the cost of treatment installations when the sleeve passes through. A pressure slightly lower than atmospheric pressure makes it possible to better control the purity of the gas circulating around the sleeve since the air is mainly extracted from the enclosure and then replaced by a controlled gas, thus avoiding the formation of undesirable impurities ( risk of reaction with nitrogen in the air, water vapor, etc.). In the first examples presented below, a deposit of amorphous carbon on the outer surface of a polyethylene sleeve by passing a stream of hydrocarbon gas - acetylene in this case - in an enclosure surrounding the sleeve and containing a system of electrodes between which a difference of voltage of the order of 10kV. If we want to deposit silica, we circulate a gas such as HMDSO (hexamethyldisiloxane) or TMDSO (tetramethyldisiloxane) instead of acetylene.
Dans un mode préféré de l'invention, on utilise une électrode interne. Dans le cas des tubes extrudes (exemple 1 ), celle-ci est maintenue en place à l'aide d'un support relié mécaniquement à la filière d'extrusion (dans le prolongement de l'aiguille par exemple). Dans le cas des tubes laminés (exemple 2), l'électrode est maintenue en place à l'aide d'un support introduit dans l'échancrure formée par les bords de la bande quelques centimètres en amont du poste de soudure longitudinale. Le support est suffisamment long pour que la partie active de l'électrode agisse en aval du poste de soudure. De la sorte, le dépôt du revêtement est effectué sur la totalité de la circonférence de la jupe. L'électrode interne est un cylindre métallique massif ou, de préférence, une grille cylindrique creuse, plus légère et plus facile à positionner et à maintenir en place.In a preferred embodiment of the invention, an internal electrode is used. In the case of extruded tubes (example 1), the latter is held in place using a support mechanically connected to the extrusion die (in the extension of the needle for example). In the case of laminated tubes (example 2), the electrode is held in place by means of a support inserted into the notch formed by the edges of the strip a few centimeters upstream from the longitudinal welding station. The support is long enough for the active part of the electrode to act downstream of the welding station. In this way, the coating is deposited on the entire circumference of the skirt. The internal electrode is a solid metal cylinder or, preferably, a hollow cylindrical grid, lighter and easier to position and hold in place.
Les électrodes ont de préférence une longueur commune correspondant à la longueur de l'enceinte mais il est possible de les réaliser plus courtes en les plaçant en amont du courant gazeux: le gaz est injecté dans l'enceinte et circule d'amont en aval de telle sorte qu'il traverse d'abord la zone de décharge électrique, qu'un plasma est généré sous l'effet des décharges puis se propage d'amont en aval sur toute la longueur de l'enceinte, le dépôt s'effectuant ainsi sur toute la longueur de l'enceinte. La figure 1 schématise en coupe le manchon et un système d'électrodes cylindre-cylindre (décharge barrière diélectrique) utilisé lorsqu'il est possible de placer une électrode à l'intérieur du manchon, ce qui est le cas pour les jupes laminées et pour la plupart des géométries des jupes extrudées.The electrodes preferably have a common length corresponding to the length of the enclosure, but it is possible to make them shorter by placing them upstream of the gas stream: the gas is injected into the enclosure and circulates from upstream to downstream of such that it first crosses the electrical discharge zone, that a plasma is generated under the effect of the discharges and then propagates from upstream to downstream over the entire length of the enclosure, the deposition taking place thus over the entire length of the enclosure. Figure 1 shows schematically in section the sleeve and a cylinder-cylinder electrode system (dielectric barrier discharge) used when it is possible to place an electrode inside the sleeve, which is the case for laminated skirts and for most of the geometry of the extruded skirts.
La figure 2 représente un système d'électrodes de type couteaux utilisé lorsqu'il n'est pas possible d'introduire et de maintenir une électrode à l'intérieur du manchon.FIG. 2 shows a knife-type electrode system used when it is not possible to introduce and maintain an electrode inside the sleeve.
La figure 3 schématise un autre mode de réalisation du procédé également utilisable lorsqu'il n'est pas possible d'introduire une électrode à l'intérieur du manchon. Ce dernier dispositif est par ailleurs adapté au dépôt par pulvérisation cathodique d'une cible solide.Figure 3 shows schematically another embodiment of the method also usable when it is not possible to introduce an electrode inside the sleeve. The latter device is also suitable for sputtering deposition of a solid target.
EXEMPLES (Figure 1)EXAMPLES (Figure 1)
Exemple 1 - Dépôt d'une couche de carbone amorphe sur la surface extérieure d'un manchon en polyéthylène extrudé.Example 1 - Deposition of a layer of amorphous carbon on the outer surface of an extruded polyethylene sleeve.
L'installation industrielle permettant de fabriquer des jupes souples pour tubes extrudes est une chaîne regroupant, d'amont en aval, une ou plusieurs extrudeuses à vis alimentant une filière d'extrusion ou de coextrusion, un calibreur accompagné d'un dispositif de refroidissement, l'ensemble mesurant 3 mètres environ, enfin un tireur-coupeur qui entraîne le manchon à une vitesse contrôlée puis coupe ce dernier aux longueurs de jupes voulues. Au sein du calibreur le manchon est mis en forme sur film d'eau puis mis en contact avec une bague de calibrage par différence de pression entre l'intérieur du tube - qui est sous pression atmosphérique - et l'extérieur du tube - qui est soumis à une dépression plus ou moins poussée suivant l'épaisseur du manchon et la rhéologie de(s) la matière(s) (co)extrudée(s).The industrial installation making it possible to manufacture flexible skirts for extruded tubes is a chain grouping, from upstream to downstream, one or more screw extruders supplying an extrusion or coextrusion die, a calibrator accompanied by a cooling device, the whole measuring approximately 3 meters, finally a cutter who drives the sleeve at a controlled speed then cuts the latter to the desired lengths of skirts. Within the calibrator, the sleeve is shaped on a film of water and then brought into contact with a calibration ring by pressure difference between the inside of the tube - which is under atmospheric pressure - and the outside of the tube - which is subjected to a more or less extensive vacuum depending on the thickness of the sleeve and the rheology of the (co) extruded material (s).
En général, le manchon 1 est trop mince pour résister à une différence de pression de l'ordre d'une atmosphère entre sa paroi intérieure (qui est à la pression atmosphérique) et sa paroi extérieure. Ainsi, les techniques ne nécessitant pas un vide poussé pour générer le plasma sont doublement avantageuses, d'une part parce qu'il n'est pas nécessaire d'assurer une bonne étanchéité dans une enceinte entourant le manchon en mouvement, d'autre part parce qu'il n'est pas nécessaire de prévoir un ou plusieurs conformateurs destinés à maintenir le manchon dans sa forme voulue, lesdits conformateurs présentant eux-mêmes un obstacle au dépôt.In general, the sleeve 1 is too thin to withstand a pressure difference of the order of one atmosphere between its inner wall (which is at atmospheric pressure) and its outer wall. Thus, techniques which do not require a high vacuum to generate the plasma are doubly advantageous, on the one hand because it is not necessary to ensure a good seal in an enclosure surrounding the moving sleeve, on the other hand because it is not necessary to provide one or more shapers intended to maintain the sleeve in its desired shape, said shapers themselves presenting an obstacle to deposition.
Le dispositif particulier de cet exemple génère le plasma à la pression atmosphérique. Il est introduit entre le calibreur et le dispositif de refroidissement. A ce stade du défilement, le manchon est encore chaud et sa surface extérieure, en polyéthylène basse densité, n'est pas encore stabilisée, ce qui constitue des conditions favorables au dépôt.The particular device of this example generates the plasma at atmospheric pressure. It is introduced between the calibrator and the cooling device. At this stage of travel, the sleeve is still hot and its outer surface, made of low density polyethylene, is not yet stabilized, which constitutes favorable conditions for deposition.
Le dispositif de refroidissement du tube extrudé, qui mesure plusieurs mètres, se trouvant ici en aval du dispositif de dépôt, l'électrode interne 2 est fixée à l'extrémité de l'aiguille de la filière, qui a été prolongée sur une distance raisonnable, de l'ordre du demi mètre (en général, un calibreur long de 30-40 centimètres suffit). La filière est portée électriquement à la masse. L'électrode interne 2 se présente sous la forme d'une grille cylindrique creuse ayant un diamètre voisin de celui du manchon 1, a un ou deux millimètres près. Une enceinte cylindrique 3 entoure le manchon sur deux mètres. Elle délimite entre sa paroi et celle du manchon un espace 4 où circule l'acétylène. Cet espace comporte une électrode cylindrique externe 5 ayant un diamètre supérieur de quelques millimètres à celui du manchon.The device for cooling the extruded tube, which measures several meters, being here downstream of the deposition device, the internal electrode 2 is fixed to the end of the needle of the die, which has been extended over a reasonable distance. , of the order of half a meter (in general, a calibrator 30-40 centimeters long is sufficient). The die is electrically grounded. The internal electrode 2 is in the form of a hollow cylindrical grid having a diameter close to that of the sleeve 1, to one or two millimeters. A cylindrical enclosure 3 surrounds the sleeve over two meters. It defines between its wall and that of the sleeve a space 4 where the acetylene circulates. This space includes an external cylindrical electrode 5 having a diameter a few millimeters larger than that of the sleeve.
En appliquant une tension voisine de 20 kV, puisée à 250 kHz, l'ordre de grandeur de la vitesse moyenne de dépôt est de 50 A/s, ce qui permet avec une longueur de 2 m et une vitesse de défilé du manchon de l'ordre de 10 m/mn de déposer une couche de 600 Â de carbone amorphe.By applying a voltage close to 20 kV, drawn at 250 kHz, the order of magnitude of the average deposition speed is 50 A / s, which makes it possible, with a length of 2 m and a running speed of the sleeve of l 'order of 10 m / min to deposit a layer of 600 Å of amorphous carbon.
Une fois revêtu extérieurement d'une couche de carbone amorphe, le manchon a été soumis aux tests suivants:Once coated on the outside with an amorphous carbon layer, the sleeve was subjected to the following tests:
- traction Des éprouvettes sont découpées à l'emporte-pièce dans le manchon et sont soumises à une traction longitudinale tandis que la surface revêtue est observée au microscope électronique à balayage. L'allongement réparti à partir duquel les premières microfissurations sont apparues est supérieur à 8%. - fatigue en flexion- traction Specimens are cut out with a punch in the sleeve and are subjected to longitudinal traction while the coated surface is observed under a scanning electron microscope. The distributed elongation from which the first microcracks appeared is greater than 8%. - bending fatigue
Le manchon suit un cycle de sollicitations inspiré du test Gelbo Flex selon ASTM E-392 et donne des résultats satisfaisants jusqu'à 100/200 cycles.The sleeve follows a stress cycle inspired by the Gelbo Flex test according to ASTM E-392 and gives satisfactory results up to 100/200 cycles.
Un manchon revêtu extérieurement de silice et réalisé selon l'exemple 1 , le gaz acétylène ayant été remplacé par un mélange HMDSO - acétylène. Il a été soumis aux mêmes tests:A sleeve coated externally with silica and produced according to Example 1, the acetylene gas having been replaced by an HMDSO-acetylene mixture. It was subjected to the same tests:
- traction: premières microfissurations observées à partir de 5 %- traction: first microcracks observed from 5%
- fatigue en flexion: résultats satisfaisants jusqu'à 50/100 cycles. Le dispositif particulier de cet exemple a ensuite été aménagé pour générer le plasma à une pression légèrement inférieure à la pression atmosphérique.- fatigue in bending: satisfactory results up to 50/100 cycles. The particular device of this example was then arranged to generate the plasma at a pressure slightly lower than atmospheric pressure.
En faisant varier la pression entre 300 de 600 millimètres de mercure, (cette dernière valeur correspond au vide peu poussé régnant habituellement dans les enceintes des calibreurs), le revêtement obtenu a un aspect de surface plus homogène mais il s'est avéré nécessaire de limiter les déformations imposées au manchon par la différence de pression de part et d'autre de sa paroi. Pour ce faire, on a placé l'enceinte de dépôt assisté plasma en aval du dispositif de refroidissement. Il aurait également été possible de placer autour du manchon un tube conformateur perforé.By varying the pressure between 300 and 600 millimeters of mercury, (this latter value corresponds to the low vacuum usually prevailing in the chambers of the calibrators), the coating obtained has a more homogeneous surface appearance but it has proved necessary to limit the deformations imposed on the sleeve by the pressure difference on either side of its wall. To do this, the plasma assisted deposition chamber was placed downstream of the cooling device. It would also have been possible to place a perforated shaping tube around the sleeve.
Exemple 2 - Dépôt d'une couche de carbone amorphe sur la surface extérieure d'un manchon en polyéthylène laminé.Example 2 - Deposition of an amorphous carbon layer on the outer surface of a laminated polyethylene sleeve.
Une bande multicouche est mise en forme de cylindre par superposition de ses deux bords longitudinaux sur 2,5 mm. Quelques centimètres en amont du poste de soudure longitudinale, les bords sont encore suffisamment éloignés l'un de l'autre pour que l'on puisse introduire le support d'une électrode interne, du même type que celle décrite dans l'exemple 1, celle-ci étant suffisamment élancée pour que sa partie active se trouve au regard de l'enceinte, identique à celle décrite dans l'exemple 1 et placée quelques centimètres en aval du poste de soudure longitudinale. L'électrode est portée par une tige qui traverse la zone de soudure et peut ainsi constituer, directement ou par le moyen d'une bague emmanchée sur ladite tige, isolée électriquement et thermiquement de celle-ci, une masse métallique participant à l'apport d'énergie en vue de la soudure des bords de la bande plastique - (soudure haute fréquence). Exemple 3 - Dépôt d'une couche de carbone amorphe sur la surface extérieure d'un manchon en polyéthylène de faible épaisseur. (Figure 2)A multilayer strip is formed into a cylinder by superposition of its two longitudinal edges over 2.5 mm. A few centimeters upstream of the longitudinal welding station, the edges are still sufficiently distant from one another so that the support of an internal electrode, of the same type as that described in Example 1, can be introduced, the latter being sufficiently slender so that its active part is facing the enclosure, identical to that described in Example 1 and placed a few centimeters downstream of the longitudinal welding station. The electrode is carried by a rod which crosses the welding zone and can thus constitute, directly or by means of a ring fitted on said rod, electrically and thermally insulated therefrom, a metallic mass participating in the contribution. of energy for the welding of the edges of the plastic strip - (high frequency welding). Example 3 - Deposition of an amorphous carbon layer on the outer surface of a thin polyethylene sleeve. (Figure 2)
Dans cet exemple, on cherche à traiter une jupe de tube plus mince que les jupes de tube souple actuelles. La jupe est coextrudée avec une couche interne de 150 μm en PE chargé en carbonate de calcium et une couche externe en PEBD de 50 μm.In this example, we seek to treat a thinner tube skirt than the current flexible tube skirts. The skirt is coextruded with an internal layer of 150 μm of PE loaded with calcium carbonate and an external layer of LDPE of 50 μm.
En raison des contraintes dimensionnelles imposées, on préfère conserver le dispositif de calibrage conventionnel avec son dispositif de refroidissement de telle sorte que le dispositif de revêtement selon l'invention ne peut plus être mis qu'en aval dudit dispositif de refroidissement, c'est-à-dire à plus de quatre mètres de la filière.Due to the dimensional constraints imposed, it is preferable to keep the conventional calibration device with its cooling device so that the coating device according to the invention can no longer be put downstream of said cooling device, that is to say that is to say more than four meters from the die.
Dans ce cas, il est préférable d'équiper l'enceinte 23 entourant le manchon 1 avec un système d'électrodes du type couteau - couteau (21 , 22) illustré en figure 2. Un plasma se forme entre les couteaux dont la pointe est inclinée par rapport à la direction radiale de telle sorte que la surface externe du manchon 1 se trouve dans le voisinage de la zone de décharge entre les pointes des électrodes 21 et 22. Ainsi, pour revêtir un manchon de 035 mm, on dispose en alternance une série d'électrodes 21 et 22 distantes de 3 mm environ et constituant des spires imbriquées sur un cylindre de diamètre 040 mm. Les électrodes 21 sont portées à un potentiel V de 10 kV environ et les électrodes 22 sont portées à la masse. Exemple 4 - Dépôt plasma CVD d'une couche de carbone sur la surface extérieure d'un manchon épais en polyéthylène (Figure 3).In this case, it is preferable to equip the enclosure 23 surrounding the sleeve 1 with a knife-knife type electrode system (21, 22) illustrated in FIG. 2. A plasma is formed between the knives whose tip is inclined with respect to the radial direction so that the external surface of the sleeve 1 is in the vicinity of the discharge zone between the tips of the electrodes 21 and 22. Thus, to coat a sleeve of 035 mm, it is alternately available a series of electrodes 21 and 22 spaced about 3 mm apart and constituting nested turns on a cylinder with a diameter of 040 mm. The electrodes 21 are brought to a potential V of approximately 10 kV and the electrodes 22 are brought to ground. Example 4 - CVD plasma deposition of a carbon layer on the outer surface of a thick polyethylene sleeve (Figure 3).
Le dispositif comporte une enceinte cylindrique 33 longue de deux mètres. Elle délimite entre sa paroi et celle du manchon 1 un espace dans lequel circule un mélange argon - acétylène. Cet espace comporte deux électrodes 35 et 32 extérieures au manchon. L'électrode 35 a le diamètre le plus grand et est distante de quelques centimètres d'une électrode 32 sous forme de grille cylindrique, elle-même distante du manchon 1 de quelques millimètres seulement.The device comprises a cylindrical enclosure 33 two meters long. Between its wall and that of the sleeve 1, it delimits a space in which an argon-acetylene mixture circulates. This space has two electrodes 35 and 32 outside the sleeve. The electrode 35 has the largest diameter and is spaced a few centimeters from an electrode 32 in the form of a cylindrical grid, itself spaced from the sleeve 1 by only a few millimeters.
La pression lors du dépôt est fixée à 0,25 Torr. On injecte un mélange acétylène - argon avec un rapport C2H /Ar de l'ordre de 10%. Le plasma, généré par une source excitée à 250 kHz avec une puissance électrique de 70 W, s'étend au- delà de l'entrefer compris entre les électrodes et traverse l'électrode 32 qui est une grille à larges mailles (de l'ordre du cm2) dont la surface enveloppe s'appuie sur un cylindre. Le plasma traverse cette grille et vient affleurer la surface du manchon 1 en apportant le carbone du revêtement.The pressure during deposition is fixed at 0.25 Torr. An acetylene-argon mixture is injected with a C 2 H / Ar ratio of the order of 10%. The plasma, generated by a source excited at 250 kHz with an electrical power of 70 W, extends beyond the air gap between the electrodes and passes through electrode 32 which is a grid with large meshes (of the order of cm 2 ) whose envelope surface rests on a cylinder. The plasma passes through this grid and comes to be flush with the surface of the sleeve 1 while providing the carbon for the coating.
Pour résister à la différence de pression entre l'intérieur - à la pression atmosphérique - et l'extérieur (0,25 torr), le tube utilisé doit être assez épais -au moins 0,7 mm.To resist the pressure difference between the interior - at atmospheric pressure - and the exterior (0.25 torr), the tube used must be fairly thick - at least 0.7 mm.
Exemple 5 - Dépôt d'une couche d'un matériau apparenté à un composé riche en silice et en alumine sur la surface extérieure d'un manchon en PET.Example 5 - Deposition of a layer of a material related to a compound rich in silica and alumina on the outer surface of a PET sleeve.
L'enceinte comporte un dispositif d'électrodes du même type que celui schématisé en figure 3 (35 et 32). Toutefois l'électrode de plus grand diamètre diffère de la précédente (35) en ce sens qu'elle constitue la source du matériau à déposer, en l'occurrence elle est en un alliage d'aluminium et silicium, du type AS17U4G.The enclosure includes an electrode device of the same type as that shown diagrammatically in FIG. 3 (35 and 32). However the larger diameter electrode differs from the previous one (35) in that it constitutes the source of the material to be deposited, in this case it is made of an aluminum and silicon alloy, of the AS17U4G type.
Le procédé utilisé reprend les conditions décrites dans le brevet FR 2 712 310. De l'oxygène est introduit dans l'enceinte sous un flux de 0,5 cm3 par minute et de l'argon est introduit sous un flux de 55 cm3 par minute. La pression lors du dépôt est fixée à 0,3 Pa. La puissance électrique délivrée à la cible est de 150 W. Sous l'effet de l'excitation un plasma se forme dans le mélange argon- oxygène. Les ions viennent bombarder la cible en alliage aluminium -silicium et entraînent la pulvérisation cathodique. L'électrode de plus petit diamètre est une grille cylindrique à larges mailles (de l'ordre du cm2) qui laisse passer le plasma et le matériau à déposer. La surface externe du manchon est traitée pendant un temps de l'ordre de 15 s, ce qui limite la vitesse de défilement à 8 mètres/minute.The process used incorporates the conditions described in patent FR 2 712 310. Oxygen is introduced into the enclosure under a flow of 0.5 cm3 per minute and argon is introduced under a flow of 55 cm3 per minute . The pressure during deposition is fixed at 0.3 Pa. The electric power delivered to the target is 150 W. Under the effect of the excitation, a plasma is formed in the argon-oxygen mixture. The ions bombard the aluminum-silicon alloy target and cause sputtering. The electrode of smaller diameter is a cylindrical grid with large meshes (of the order of cm 2 ) which allows the plasma and the material to be deposited to pass. The external surface of the sleeve is treated for a time of the order of 15 s, which limits the running speed to 8 meters / minute.
Pour éviter une déformation excessive du manchon, épais de 200 μm, le poste aval de la chaîne, incluant le dispositif de coupe et la partie de la chaîne à picots recueillant les jupes coupées, est placé dans une enceinte soumise à une pression inférieure à la pression atmosphérique, typiquement comprise entre 0,1 et 0,5 atmosphères.To avoid excessive deformation of the 200 μm thick sleeve, the downstream station of the chain, including the cutting device and the part of the spiked chain collecting the cut skirts, is placed in an enclosure subjected to a pressure below the atmospheric pressure, typically between 0.1 and 0.5 atmospheres.
Exemple 6 - Dépôt graduel de couches en carbone amorphe et en silice sur la surface extérieure d'un manchon en polyéthylène extrudéExample 6 Gradual deposition of layers of amorphous carbon and silica on the outer surface of an extruded polyethylene sleeve
Le dispositif de l'exemple 1 est légèrement modifié pour obtenir un revêtement comportant plusieurs couches. L'électrode interne 2 a ici la longueur de l'enceinte cylindrique 3. L'enceinte cylindrique 3 est alimentée en chacune de - l è ¬The device of Example 1 is slightly modified to obtain a coating comprising several layers. The internal electrode 2 here has the length of the cylindrical enclosure 3. The cylindrical enclosure 3 is supplied with each of - l è ¬
ses extrémités par un gaz différent: l'extrémité en amont du manchon est alimentée en acétylène, l'extrémité en aval du manchon est alimentée en hexaméthyldisiloxane (HMDSO). Un conduit d'évacuation situé dans le milieu de l'enceinte cylindrique 3 favorise la circulation du plasma entre chacune des extrémités et la partie centrale de l'enceinte. On obtient ainsi un dépôt graduel de couches d'abord riches en carbone amorphe puis riches en silice. Le carbone amorphe hydrogéné, situé en sous-couche, assure une meilleure liaison sur le substrat en polyéthylène et assure une plus grande souplesse au revêtement obtenu. La couche de silice complète l'effet barrière de la couche de carbone tout en limitant la coloration due au carbone. Le revêtement externe ainsi obtenu, comportant en surface une grande proportion de silice, est mieux adapté aux conditions imposées pour l'impression ultérieure de la jupe de tube.its ends by a different gas: the upstream end of the sleeve is supplied with acetylene, the downstream end of the sleeve is supplied with hexamethyldisiloxane (HMDSO). A discharge duct located in the middle of the cylindrical enclosure 3 promotes the circulation of the plasma between each of the ends and the central part of the enclosure. This results in a gradual deposition of layers first rich in amorphous carbon then rich in silica. The hydrogenated amorphous carbon, located in a sublayer, ensures better bonding on the polyethylene substrate and ensures greater 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 the conditions imposed for the subsequent printing of the tube skirt.
La position exacte du conduit d'évacuation dans la partie centrale de l'enceinte cylindrique et les débits d'alimentation en gaz respectifs sont choisis de façon à obtenir les proportions desdites couches offrant le meilleur compromis correspondant aux propriétés recherchées du revêtement.The exact position of the exhaust duct in the central part of the cylindrical enclosure and the respective gas supply rates are chosen so as to obtain the proportions of said layers offering the best compromise corresponding to the desired properties of the coating.
AVANTAGES DU PROCEDE SELON L'INVENTIONADVANTAGES OF THE PROCESS ACCORDING TO THE INVENTION
• possibilité de diminuer l'épaisseur de la jupe de tube: gain en coût de matière première; • absence de matériau rigide: propriétés "dead fold" améliorées;• possibility of reducing the thickness of the tube skirt: saving in cost of raw material; • absence of rigid material: improved dead fold properties;
• possibilité de choisir le mélange de matériaux optimal vis-à-vis du compromis souplesse - propriétés barrières;• possibility of choosing the optimal mix of materials with regard to the flexibility - barrier properties compromise;
• le dépôt est mince et déformable: les propriétés barrières sont maintenues même après utilisation poussée du tube souple. • the deposit is thin and deformable: the barrier properties are maintained even after extensive use of the flexible tube.

Claims

REVENDICATIONS
1 ) Tube souple muni d'une jupe et d'une tête, destiné à stocker et distribuer des produits liquides à pâteux contenant des parfums, des arômes ou sensibles à l'oxydation, caractérisé en ce que ladite jupe porte sur toute sa surface externe un revêtement d'épaisseur comprise entre 400 et 1500 À comportant au moins une couche 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).1) 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 skirt carries over its entire external surface a coating with a thickness between 400 and 1500 Å comprising at least one layer 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 combination of one or more of the following metals (Si, Mg, Al, Ti, Zr, Nb, Ta, Mo, W, V).
2) Tube souple selon la revendication 1 , caractérisé en ce que ladite couche d'épaisseur comprise entre 400 et 1500 Â confère à ladite jupe des propriétés barrières se traduisant • pour l'oxygène, par une perméabilité inférieure à 1 ml/m2/jour (norme ASTMD3985)2) flexible tube according to claim 1, characterized in that said layer of thickness between 400 and 1500 Å gives said skirt barrier properties resulting • for oxygen, by a permeability of less than 1 ml / m 2 / day (ASTMD3985 standard)
• pour la vapeur d'eau, par une perméabilité inférieure à 2 g/m2/jour (norme ASTM F327)• for water vapor, with a permeability of less than 2 g / m 2 / day (standard ASTM F327)
• et pour les arômes, par une perméabilité inférieure à 0,5 Î O-6 g/m2/jour/mmHg• and for aromas, by a permeability of less than 0.5 Î O -6 g / m 2 / day / mmHg
3) Tube selon la revendication 1 ou 2 caractérisé en ce que ladite jupe comprend au moins une couche en une matière thermoplastique telle qu'une polyoléfine, en un polyester du type polyéthylène téréphtalate (PET) ou un copolyester.3) Tube according to claim 1 or 2 characterized in that said skirt comprises at least one layer of a thermoplastic material such as a polyolefin, a polyester of the polyethylene terephthalate (PET) type or a copolyester.
4) Tube selon l'une quelconque des revendications 1 à 3, 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. 5) Procédé de fabrication de jupes de tubes souples en matière plastique comprenant une étape de mise en forme d'un manchon cylindrique puis la découpe à longueur desdites jupes caractérisé en ce que la surface externe du manchon est revêtue après mise en forme dudit manchon par une couche d'épaisseur comprise entre 400 et 1500 À 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).4) Tube according to any one of claims 1 to 3, characterized in that said skirt comprises at least one layer of a polymer loaded with pulverulent material such as calcium carbonate or mica. 5) A method of manufacturing flexible plastic tube skirts comprising a step of shaping a cylindrical sleeve then cutting to length of said skirts characterized in that the external surface of the sleeve is coated after shaping of said sleeve by a layer of thickness between 400 and 1500 Å 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 combination d one or more of the following metals (Si, Mg, Al, Ti, Zr, Nb, Ta, Mo, W, V).
6) Procédé selon la revendication 5 où le dépôt du revêtement est effectué à l'aide d'un plasma froid.6) Method according to claim 5 wherein the deposition of the coating is carried out using a cold plasma.
7) Procédé selon la revendication 5 ou 6 où le dépôt du revêtement est effectué au défilé sur la surface externe du manchon, avant découpe en longueur desdites jupes.7) A method according to claim 5 or 6 wherein the coating is deposited on the external surface of the sleeve, before cutting the length of said skirts.
8) Procédé selon l'une quelconque des revendications 5 à 7, où la surface externe du manchon est en une matière thermoplastique, telle qu'une polyoléfine, en un polyester tel que le polyéthylène téréphtalate ou en un copolyester.8) A method according to any one of claims 5 to 7, wherein the outer surface of the sleeve is a thermoplastic material, such as a polyolefin, a polyester such as polyethylene terephthalate or a copolyester.
9) Procédé selon l'une quelconque des revendications 5 à 8 où la jupe comporte une couche en polyoléfine chargée en poudre de carbonate de calcium ou de mica.9) Method according to any one of claims 5 to 8 wherein the skirt comprises a polyolefin layer loaded with powder of calcium carbonate or mica.
10) Procédé selon l'une quelconque des revendications 6 à 9 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. 1 1 ) Procédé selon la revendication 10 où le matériau du revêtement est du carbone amorphe hydrogéné obtenu par décomposition d'un courant de gaz acétylène circulant dans une enceinte autour du manchon.10) Method according to any one of claims 6 to 9 wherein the coating material is obtained by condensation after decomposition of a gaseous body or chemical compound, and where the plasma is generated under the effect of a dielectric barrier discharge or corona discharge. 1 1) A method according to claim 10 wherein the coating material is hydrogenated amorphous carbon obtained by decomposition of a stream of acetylene gas flowing in an enclosure around the sleeve.
12) Tube selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le revêtement comprend une sous-couche riche en carbone et une couche superficielle riche en silice 12) Tube according to any one of claims 1 to 4, characterized in that the coating comprises a sublayer rich in carbon and a surface layer rich in silica
PCT/FR2000/002165 1999-08-13 2000-07-28 Tube with barrier layer and deposit method WO2001012517A1 (en)

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FR9910568A FR2797433B1 (en) 1999-08-13 1999-08-13 TUBE HAVING A FLEXIBLE SKIRT COATED EXTERNALLY WITH A BARRIER LAYER AND METHOD FOR CONTINUOUSLY DEPOSITING THE SAME
FR99/10568 1999-08-13

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CN108752006A (en) * 2018-08-14 2018-11-06 华南理工大学 A kind of plasma nitrided method for preparing nano crystal titanium nitride micro mist of room temperature

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WO2002018221A1 (en) * 2000-08-29 2002-03-07 Aisapack Holding Sa Soft package with protective layer

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US4756964A (en) * 1986-09-29 1988-07-12 The Dow Chemical Company Barrier films having an amorphous carbon coating and methods of making
FR2700727A1 (en) * 1993-01-27 1994-07-29 Cebal A method of manufacturing a wall tube containing more than 60% plastic and having a skirt and a retreinte head, and corresponding tube.
FR2712310A1 (en) * 1993-11-09 1995-05-19 Pechiney Recherche Transparent barrier coating for flexible polymeric packaging film
WO1996005055A1 (en) * 1994-08-16 1996-02-22 Minnesota Mining And Manufacturing Company Barrier films

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US4756964A (en) * 1986-09-29 1988-07-12 The Dow Chemical Company Barrier films having an amorphous carbon coating and methods of making
FR2700727A1 (en) * 1993-01-27 1994-07-29 Cebal A method of manufacturing a wall tube containing more than 60% plastic and having a skirt and a retreinte head, and corresponding tube.
FR2712310A1 (en) * 1993-11-09 1995-05-19 Pechiney Recherche Transparent barrier coating for flexible polymeric packaging film
WO1996005055A1 (en) * 1994-08-16 1996-02-22 Minnesota Mining And Manufacturing Company Barrier films

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CN108752006A (en) * 2018-08-14 2018-11-06 华南理工大学 A kind of plasma nitrided method for preparing nano crystal titanium nitride micro mist of room temperature
CN108752006B (en) * 2018-08-14 2021-03-26 华南理工大学 Method for preparing nanocrystalline titanium nitride micro powder by room temperature plasma nitridation

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