MXPA00009420A - Container with material coating having barrier effect and method and apparatus for making same - Google Patents

Abstract

The invention concerns a method for forming a coating in amorphous carbon material with polymer trend on a substrate of polymer material having the shape of a container to be obtained, such as a bottle or flask, using a plasma with electromagnetic wave excitation, which consists in:introducing into a chamber (2), wherein a high vacuum has been generated, a container blank (18), made of polymer material forming said substrate;injecting into a reaction chamber (2, 18) at least a carbon precursor is gaseous phase under very low pressure, the precursor being selected among the alkane, alkene, alkyne, aromatic compounds or a combination of some of them;generating simultaneously in the reaction chamber a microwave electromagnetic excitation in the UHF (8-12) domain with relatively low power for generating a plasma in temperature conditions which maintain the polymer at a temperature lower than glass transition temperature and which bring about the deposit of a overhydrogenated carbon material with polymer trend.

Description

CONTAINER WITH COVERING OF A MATERIAL SUITABLE TO CONSTITUTE A BARRIER, AND PROCEDURE AND APPARATUS FOR ITS MANUFACTURE The present invention refers to containers such as bottles or bottles, of heterogeneous constitution, made of a material apt to constitute a barrier, and with a polymeric material . Containers of polymeric material such as PET have the drawback of not being impermeable to certain gases, particularly oxygen and carbon dioxide gas. Thus carbonated beverages progressively lose their carbon dioxide gas that migrates to the atmosphere through the polymeric material: the life span of a carbonated liquid contained in a bottle made of PET, commercially can not exceed a period of a few weeks or at most a small number of months (for example, 4 to 6 months). In this way, it also results that the oxygen in the atmosphere enters, through the polymeric material, in contact with the liquid contained in the container and thus can oxidize the latter, degrading its characteristics: the life of a bottle made by PET, filled with beer, commercially can not exceed a period of a few weeks (for example 2 to 5 weeks). It is known to increase the barrier effect, typical of the constituent polymeric materials of containers, by not coating the polymer wall with a layer of a material having a higher barrier effect. It has thus been proposed to use synthetic materials in the form of multiple layers such as those made from aliphatic polyamides and / or mixtures of different materials for this purpose. The containers are then manufactured from multilayer preforms, in which the barrier material layer is sandwiched between at least two layers of polymeric material (eg PET). The beer bottles thus constituted increased their commercial life considerably (reaching, for example, up to 12 weeks). However, a major drawback of these multi-layer containers lies in the take-off, ie the detachment of the layers between them. Furthermore, it can be said that both the manufacture of the preform and the manufacture of the container from the preform by means of blowing or stretching and blowing are complex operations and require certain precautionary measures; above, the operations are expensive. It has also been proposed to treat the containers of polymeric material by external coating with a layer of some suitable material, such as those called PVDC or thermosetting cores. On the other hand it can be said that the gain is still low as regards the barrier effect and the presence of a coating material causes certain difficulties as regards the recycling of the base polymer material. Above it can be said that all known solutions, cited above, keep the polymeric material (eg PET) in contact with the liquid, and thus they do not offer protection against the drawbacks engendered by this contact: the possibility of migration of certain constituents of the polymer in the liquid, the possibility of chemical reaction of the polymer with the liquid, the transfer of acetalheid to the liquid, etc., as well as certain phenomena capable of generating problems of organoleptia. It has also been proposed to deposit a layer of a material with a barrier effect, such as hard carbon, on a polymer wall, for example made of PET, by applying a plasma (US Pat. No. 5,041,303). EP 0 773 166 also mentions the possibility of forming said carbon layer on the inside face of the wall of the container. A layer of carbon thus deposited allows to remedy the set of drawbacks that have been previously stated. However, it is a layer, relatively thick of hard carbon or diamond-like carbon ("diamond-like carbon" or DLC). The wall of a container thus formed associates therefore an inner layer of hard carbon, DLC, which presents a considerable rigidity, an outer layer of polymeric material, PET, which presents a remarkable deformability. Due to their different and incompatible mechanical characteristics, it is common for the two layers of polymer and hard carbon to end up detaching or dislocating. In a general way it is pointed out that the manufacture of containers of polymeric material that present a barrier effect by the application of any of the techniques mentioned above is little expanded due to the complex nature of the application of the different procedures, by slow rhythms of the production and in consideration of the important costs of such fabrications. The object of the invention is essentially to remedy simultaneously all of the above-mentioned problems, which present themselves in containers with improved barrier effect, currently known, and to propose a container that offers an effective protection of its contents since it can be manufactured at an industrial level. , with the help of uncomplicated means and under acceptable economic conditions. For such purposes and according to the first of its aspects, the invention relates to a container, such as a bottle or bottle, of heterogeneous constitution of a material having a barrier effect and a polymeric material which, since It is constituted in accordance with the present invention, characterized in that the material with barrier effect consists of an amorphous carbon material with polymeric tendency, which covers a substrate of polymeric material. The substrate is constituted by a preform of the container that already has the final shape of the container. For an amorphous carbon material with a polymeric tendency, it is meant to identify the carbon that not only contains the CH3 and CH2 bonds already present in the hard carbon, but also the CH3 bonds that are absent in the hard carbon (to fix the ideas, the proportions of the CH3, CH2 and CH bonds are respectively 0.40 and 60 in the hard carbon and 25, 60 and 15 in the amorphous carbon with polymeric tendency, while the proportions of the electronic states sp3, sp2 and sp are respectively 68, 30 and 2 for hard carbon and 53, 45 and 2 for carbon of polymeric type). The choice of an amorphous carbon material with a polymeric tendency makes it possible to solve the problem caused by the rigidity of hard carbon or DLC: in fact, amorphous carbon materials with a polymeric tendency have a mechanical rigidity that is clearly less high than that of hard carbon and deformability of a layer of such material is comparable to that of a polymeric material such as PET: a wall of the container constituted according to the present invention by such amorphous carbon material with polymeric tendency that adheres to a substrate of polymeric material such as for example PET, as a consequence can experience the current deformations without resulting in a detachment of these two layers. It is understood that amorphous carbon materials with a polymer tendency have, as an inherent factor of their physical-chemical structure, a coefficient of molecular permeability lower than that of the hard carbon used to date and it was thought that the barrier effect they produce, It is less perfect. For the rest it is a reason why these materials had been discarded to date and that the carbon barrier layers were made of hard carbon or DLC. Now surprisingly, the tests carried out with the amorphous carbon materials with polymeric tendency showed that the barrier effect obtained under certain operating conditions is in a high enough degree the practice for the conditioning of carbonated liquids or oxidizable liquids. Equally you can contemplate the use of so-called carbon-type nanocomposites (or DLN), that is, compounds with double network mutually overlapped, stabilized and random, of which one is a network of amorphous carbon with polymeric tendency (ac: H) with up to 50% sp3 links) while the other can be a network of silica stabilized by oxygen (a-Si: 0), and of nanocomposites with the inclusion of metal atoms. The coating of the amorphous carbon material with a polymeric tendency advantageously has a thickness of less than about 3000 A (furthermore, too large a thickness gives the carbon layer too high a mechanical rigidity with the risk of causing it to break and / or detach it) , and preferably between 800 and 1500? It will be noted that the polymer-type amorphous carbon, although it is all transparent in the indicated thicknesses, presents an amber color, which contributes to the protection against ultraviolet rays (in particular the protection of beer). It has been noted that in certain operating conditions, the effectiveness of the ultraviolet ray barrier of this protection is a function of the thickness of the coating and in a very interesting way it grows to a high degree with the ambient light intensity (factor of approximately 8 in darkness, but a factor of about 30 in daylight). The polymeric material that, in practical applications, is a polyolefin or polyester such as PET or PEN, due to the inherent rigidity of the carbon layer can even see its reduced thickness. In this connection, it will be noted that the carbon coating contributes to reducing the deformation of the container wall under the action of the pressure of a gaseous liquid, such as a carbonated liquid. The container therefore retains a stable shape and its interior volume remains constant: no change in the composition of the liquid contained therein results. Although the coating made of material with a barrier effect can be arranged outside the blank, that is the roughing of the container, it is preferable, however, that this coating constitutes the inner layer of the container in such a way that it contributes to isolating the polymeric material. and the liquid contained in the container: this way the barrier effect is extended and it is impossible to produce an eventual migration of the constituents of the polymer to the liquid, a possible chemical reaction between substances of the polymer and the liquid, an eventual migration of acetallic towards the liquid, etc. It will be stressed here that the basis of the constitution of a container according to the invention rests on the establishment of chemical bonds between the surface carbon atoms of the polymer substrate have an available chemical bond and the atoms of the carbon material that is they come into contact with the polymer through a free chemical bond, thus being ready to be combined with an available bond of the surface carbons of the polymeric substrate. Under these conditions, it is by means of an extremely potent chemical bond in which the coating of carbon material is bound to the polymeric substrate. The carbonaceous material also has the polymeric tendency explained above and thus the powerful chemical bond with a relative aptitude towards the deformability of the carbon coating is accompanied. These two characteristics together lead to a structure that no longer presents the drawbacks (detachment of the layers in particular) from the previous hard carbon or DLC containers. To deposit the carbon coating with carbon atoms having a free chemical bond, ready to be bonded with that of a polymeric surface carbon atom, a plasma deposition process can be applied. Thus, according to a second of its aspects, the invention proposes a method that applies a plasma with excitation by electromagnetic wave to form a container, such as a bottle or bottle, of heterogeneous constitution made of a material with barrier effect and a polymeric material forming a substrate that has the conformation of said container that must be obtained and is characterized in that said polymeric material is coated. It forms the substrate with a barrier effect material carrying an amorphous carbon material having a polymeric tendency and in which the following steps are resorted to: a blank or roughing of the container of polymeric material is introduced into an enclosure. In the above-mentioned substrate, at least one carbonated precursor in the gaseous state is injected into a reaction chamber under a very low pressure of less than 10 millibars, the precursor being selected from alkanes, alkenes, alkynes, aromatics or a combination of some of them, it is stable in the reaction chamber an electromagnetic microwave excitation in the AC UHF mpo with a relatively low power, which is suitable for generating a plasma under the conditions of temperature, which on the one hand keep the polymer at a temperature lower than that of the glassy transition and that on the other hand causes the deposit of a material of amorphous carbon with polymeric tendency. In a first possible mode of execution, the roughing of the container of polymeric material is closed while the gaseous carbonated precursor is injected into the enclosure which then constitutes the reaction chamber, thanks to the amorphous carbon coating with its polymeric tendency. is deposited on the external face of the roughing of the container. In a second possible mode of application, the gaseous carbonated precursor is introduced into the preform, that is the roughing of the container of polymeric material which then constitutes the reaction chamber, while a marked depression is created within the slab of the container, and thanks to This results in the formation of a plasma only inside the slab while the amorphous carbon coating with polymeric tendency is deposited on the inner face of the slab of the container. Furthermore, in order to avoid deformation of the container as a result of the vacuum that reigns therein, a depression is simultaneously caused in the enclosure to reduce the pressure differential between the inside and the outside of the slab. Furthermore, preferably in this case, the enclosure has a transverse dimension close to that of the body of the roughing of the container so as to combine perfectly well with the roughing of the container, and to require the use of low power vacuum placing elements. Thanks to the dispositions that characterize the process to which the present invention alludes, it has the capacity to generate the deposit of a coating made of amorphous carbon material with a polymeric tendency that will have a reduced thickness, that is to say less than 3000? and which will be specifically comprised between 800 and 1500?, in a short time, of the order of a few seconds, and that will not be greater than 20 seconds, with a modest microwave power of the order of a few hundred watts (for example from approximately 200 to 600 w), giving rise to a power density of the order of 0.5 to 2 watts per cubic centimeter. As a result, the corresponding temperature rise in the polymeric material constituting the roughing of the container and serving as a substrate for the deposit (internal or external depending on the case) of the carbonaceous coating is still relatively low and lower than the transition temperature. polymer glass (around 80 ° C for PET). These are the conditions of formation of the carbon coating under the action of a microwave plasma under low pressure (which is not more than a few millibars and which in practice is of the order of 0.01 to 0.5 millibars) or "cold plasma" that lead to an amorphous carbon structure with a polymeric tendency, that is, it is constituted by a network of amorphous carbon overhydrogenated, which has the advantageous characteristics mentioned above. In addition to obtaining a container with a layer having a barrier effect and a good mechanical condition on the polymeric substrate, the process according to the invention also offers the remarkable advantage of facilitating the manufacture of sterile containers usable in the chains of aseptic conditioning. The plasma generated during the process of a deposition of the carbon coating may be sufficient to obtain a desired cleaning of the internal surface of the slab of the container. To obtain a high degree of asepsis, one can contemplate the system of applying a bactericidal agent previously pulverized in the form of micro-droplets or introduced in the form of steam, for example, thanks to a bubbler, on the internal surface of the slab container (for example hydrogen peroxide, phosphoric acid, water vapor, etc.). The subsequent generation of a plasma under the above-mentioned conditions can create a strongly reducing medium (for example the generation of natural oxygen) which is capable of reducing the initial bacterial contamination in order to meet the requirements of sterilization. For the application of the above procedure, the invention proposes, according to a third of its aspects, an apparatus that applies a plasma with excitation by electromagnetic wave to form a container, such as a bottle or a bottle of heterogeneous constitution, which is made of a material with barrier effect and a polymeric material forming a substrate (roughing of container) having the conformation of said container that has been obtained, this apparatus carrying a plasma generating device, with an enclosure provided with injection elements of a gaseous precursor and electromagnetic excitation elements, this apparatus being characterized in that, for coating the polymeric material forming substrate made of barrier effect material, it forms a substrate of barrier material containing an amorphous carbon material with a polymeric tendency. The injection elements of the precursor are linked to a generator of a precursor in the gaseous state selected from alkanes, alkenes and alkynes, aromatics or a combination of some of them, and is characterized in that to coat the polymeric material that forms the substrate made of a material with a barrier effect carrying an amorphous carbon material with a polymeric tendency, the injection elements flow into the chamber and are practiced in such a way that they can deliver the gaseous precursor under a very low pressure of less than 10 millibars, and because the electromagnetic excitation elements are suitable for generating microwaves, in the UHF field. In a first embodiment, the enclosure has dimensions clearly superior to those of the roughing of the container subject to treatment and the injection elements open into the enclosure on the outside of the slab of the container, and thus, with the slab of the container in closed condition , the apparatus generated a plasma on the outside of the roughing of the container and it turns out that on the external surface of the roughing of the container the coating of amorphous carbon material with polymeric tendency is deposited. In a second embodiment, the injection elements of the gaseous precursor discharge into the slab of the container deposited in the enclosure and are provided here pumping elements that are opened in the roughing of the container and that are suitable for generating within said a marked depression is deformed, and thus the plasma is generated inside the roughing of the container while the coating of amorphous carbon material with polymeric tendency is deposited on the inner surface of the roughing of the container. To avoid deformation of the roughing due to the depression that reigns in the interior, a depression is simultaneously created inside the enclosure to reduce the pressure differential between the inside and the outside of the slab. Thus, advantageously, the enclosure is provided with an immovable sealing cap made to withstand the injector of the injection elements of the gaseous precursor and the suction hole for the pumping elements. In addition, it carries support elements suitable for supporting a roughing of the container by the neck of the same by applying the sprue of the roughing of the container in a watertight manner, that is, hermetically closed, against the inner face of the lid, to surround the mentioned holes. of aspiration and injection. In addition, it is expedient for the support elements to be axially movable so as to bring the roughing of the container against the inner face of the lid, which covers the suction and injection orifices prior to the coating tank or when separating the container obtained after the coating deposit. Preferably, in order to facilitate the use of the pump elements and avoid having to resort to oversized elements, the enclosure has a transverse dimensional of that of the body of the slab of the container. Thanks to the arrangements according to the invention, in particular to the reduced durations of treatment, it is possible to apply industrially a manufacturing process of a container with a layer having a barrier effect and allowing to produce such containers with a rhythm compatible with the current requirements in terms of liquid conditioning. The invention will be better understood upon noting the detailed description that follows, and which refers to certain embodiments presented solely by way of non-limiting examples. In this description, reference is made to the appended drawings, in which: Figures 1 to 3 illustrate schematically, in section, respectively three embodiments of an apparatus that allows constituting a container carrying a layer of material with effect of barrier according to the invention, and Figure 4 is a sectional view of a preferred embodiment of the apparatus according to Figure 1, practiced for the purpose of forming a layer of material with barrier effect that is inside the container. Referring first to Figure 1, the apparatus comprises a cavity 1, with conductive walls, for example metal, which is sized according to the object to be treated and the desired coupling mode and which contains an enclosure 2 defined by the walls 3. which are made of a transparent material for electromagnetic microwaves, and which are manufactured for example of quartz. The enclosure 2 is closed for example in the upper part by a moving layer 4 that allows the placement of the object subject to treatment in the enclosure and its removal after treatment. That in order to generate a vacuum there is attached the enclosure 2 to external pumping elements (not shown) at least by means of a joint: in figure 1 two joints 5 have been applied respectively in the bottom and in the cover 4 (The pumping is symbolized by arrows 6). For the injection, preferably under a pressure of less than 1 millibar, of at least one gaseous precursor inside the enclosure 2, at least one injector 7 attached to at least one gaseous or liquid precursor generator (not shown) is mounted, as a deposit, as a mixer or a bubbler. The injector 7 passes through the cover to which it is fixed, extending for example coaxially in the joint 5 of the pumping elements. The cavity 1 is connected to an electromagnetic microwave generator (not shown) by a waveguide 8 extending radially with respect to the side wall of the cavity 1. This waveguide is provided with regulating elements, such as be immersion screws 12, which allow the union of the cavity. On the opposite side (ie diametrically opposed if the cavity of revolution is cylindrical as in practice frequently occurs) a waveguide section 9 provided with an axially movable connecting piston 10 and which constitutes a device for short transverse circuit. Finally, in the cavity 1, two annular plates 11 that surround the enclosure 12 and which constitute longitudinal short circuits for the microwaves are disposed respectively from top to bottom. In the case where it is a matter of depositing carbon on the substrate made of polymeric material, that is to say on the wall of the roughing of the container of polymeric material, the gaseous precursor can be chosen between alkanes (for example methane), alkenes, alkynes (for example acetylene) and aromatics. The pressure within the reaction chamber (constituted either by the enclosure or the roughing of the container as will be explained later) must be reduced, preferably less than about 10 millibars, and in practice of the order of 0.01 to 0.5 millibars. Furthermore, it is essential that the heating experienced by the polymeric material of the substrate remain low enough so that the glass transition temperature of the polymer (which is, for example, of the order of 80 ° C for PET) is not reached. Therefore, it is necessary to apply for the deposit application, an unimportant microwave power, for example of a few hundred watts at most with microwaves of the UHF range (for example of the order of 2.45 GHz). Considering the deposit conditions, especially the low carbon deposition temperature, a highly hydrogenated amorphous carbon is obtained, which not only contains CH and CH2 radicals but also a notable fraction of CH3 radicals. It is therefore a carbon with a polymeric tendency or "soft" carbon, which has a lower rigidity than hard carbon or DLC. This carbon layer with a polymeric tendency therefore has a deformation capacity which makes it useful to accompany even the smallest deformations of the constituent polymer of the substrate. This results in a better mechanical coupling of the polymeric substrate and the carbon and thus they are reduced to a high extent and even the risks of a detachment are eliminated. On the other hand, it must be borne in mind that although it has a lower rigidity than hard carbon or DLC, or carbon with a polymeric tendency or "soft" carbon, it also retains a remarkable rigidity, which for any reason is significantly higher than that of the constituent polymer of the substrate. This makes it possible to attribute to the carbon layer the function of conferring a part of the intrinsic rigidity of the container achieved; thus the polymer substrate can be discharged from a part of the mechanical strength function within the manufactured container. In this way the thickness of the polymer substrate and therefore the amount of polymer entering into the manufacture of any container can be reduced. In addition, the presence of the carbon layer reinforces the mechanical strength of the container and due to this fact reduces or even suppresses the deformation capacity of a container filled with a highly carbonated liquid: the shape and therefore the volume of the container remain stable and in this way a partial degassing of the liquid is avoided.

It is obvious that the advantages just mentioned accompany that basic advantage indicated above and that it is sought in the foreground, consisting of obtaining a barrier effect that is particularly opposed to gaseous exchanges between the liquid contained in the container and the atmosphere . Finally, thanks to the means applied according to the invention, it is possible to realize a deposit speed of several hundred angstroms per second and obtain processing times of the order of a few seconds, which are thus clearly compatible with the manufacturing processes at an industrial level. Of course, other embodiments of the installation can also be envisaged to generate the typical plasma for depositing the amorphous carbon layer with a polymeric tendency that is to be obtained within the framework of the present invention. Thus, in FIG. 2, keeping the same arrangement of the cavity 1 and of the enclosure 2 (the same reference numbers are kept to designate the organs identical to those of FIG. 1), the microwave excitation is achieved here from an antenna 13 which penetrates radially in the cavity 1 through the side wall thereof and which is connected via a coaxial conductor 14 to a waveguide 15 transversely. Figure 3 illustrates another embodiment with an axial-type microwave cavity starting from an antenna 13 that is mounted in the bottom of the cavity 1, basically in the transverse direction to said bottom and approximately coaxially to the enclosure 2. The short Longitudinal circuit is provided here by means of the single upper annular plate 11 in that a single pumping orifice 5 has been practiced inside the enclosure 2. The various embodiments of the equipment that we have just indicated allow the deposition of the carbon material on the external face of the roughing of the container made of polymeric material: the enclosure 2 presents in such a case a volume considerably greater than that of the roughing of the container so that the plasma can be developed, while the roughing of the container is placed in a place of opening to avoid an interior deposit. However, as indicated above, an external layer of material only provides a partial barrier effect which does not interfere with the interactions between the polymer of the substrate and the generally liquid content. The achievement of a total barrier effect can thus only be achieved by a layer with a barrier effect disposed on the substrate inside the container. The deposit of such inner layer requires an arrangement of the treatment facility. Figure 4 shows a variant of the equipment according to figure 1, arranged for the deposit of an internal carbon layer. The enclosure 2 preferably has a shape such that its transverse or diametral dimension can be a little higher than that of the roughing of the container to be treated, in order to facilitate the emptying of the enclosure described later. To avoid deformation of the roughing as a result of the depression that prevails inside, a depression is simultaneously created inside the enclosure to reduce and even cancel the pressure differential that exists between the inside and the outside of the slab. The cover 4, which is vertically movable (double arrow 16) to allow the placement of the roughing of the container and the extraction of the treated container, is crossed by a vertical support arm 17 for grinding the container 18. This arm is vertically movable (double arrow 19) and can be rotary. The lid 4 has an inner lining 20 provided with an axial passage 21 in which or in relation to which the interior 7 of gaseous precursor opens. At its lower end, the axial passage 21 is formed in the seat 22 in such a way as to be able to receive in a remarkably tight manner, that is to say, the sprue 23 of the roughing throat of the container 18, in order to achieve a precise axial positioning of the container. roughing of the container. The lining 20 also has an annular opening, traversed by said support arm 17, which communicates the central passage 22. This opening forms the suction hole 5 in the direction of the pump elements for the establishment of the vacuum. To ensure the proper conditions for the establishment of the plasma in the roughing of the single container, there is established within it a marked depression at the same time that the compensation depression mentioned above is created within the enclosure. Thanks to this assembly one is able to create a plasma within the roughing of the container which in this way constitutes the reaction chamber itself, which allows an internal deposit of the carbon material. By way of example, the equipment of Figure 4 is applied using acetylene as a gaseous precursor which is introduced into the gargante of the roughing of the container by an injector of 4 mm in diameter, with a flow rate of 80 sccm and under a pressure of 0.25 mbar . The residual pressure inside the slab is of the order of 0.2 millibars and it has been noted that a residual pressure of 50 millibars inside the enclosure would be sufficient to prevent the deformation of the slab under these conditions. Microwave excitation of the UHF field is achieved with a frequency of 2.45 GHz (that is, a wavelength range = 12 cm under vacuum). The microwave power is of the order of 180. Under these conditions it has been possible to carry out a carbon deposit with a growth rate of the order of 250 k / s, that is, a layer having a thickness of the order of 1500? Can be obtained. in a time of about 6 seconds. According to a second example, equipment of the type according to FIG. 4 has been applied by injecting acetylene in the roughing of the vessel under a flow rate of approximately 160 sccm under a pressure of the order of 0.1 millibar. In this case, with a microwave power of the order of 350 for a 1/2 liter bottle or approximately 500 for a 1 liter bottle, an effective barrier layer is obtained in a time of about 2 to 3 seconds. . The application of a plasma in the manufacturing process of the container, allows, in accordance with the treatment conditions (particularly the duration), contemplate the realization, in a simple way, of a cleaning or asepsis treatment system (sterilization) inside the container in the facilities in which the manufacture of the container, filling and packing in an aseptic medium is carried out online. The plasma generated during the deposition of the carbon layer can be made in sufficient degrees to obtain a first degree cleaning of the internal surface of the slab. For a treatment with a higher intensity level, a simple oxygen plasma creates reactive species, for example metastable, of atomic or molecular oxygen, which are able, under the action of their own energies, to reduce the initial bacterial contamination in a proportion enough to respond to the criterion of sanitation. These treatments are carried out in times less than a few tens of seconds that are compatible with industrial facilities. To obtain a high-grade sterilization, one must resort to a bactericidal agent such as hydrogen peroxide H202 in which, after a certain time of contact with the roughing, an oxygen plasma is activated. The physical-chemical phenomena generated by the plasma within the mixture of hydrogen peroxide and oxygen give rise to reactive species mentioned as well as others that are strongly reducing and that can have a high bactericidal power. The plasma treatment can also be considered as a technique for eliminating a bactericidal agent such as phosphoric acid, which is reducing in nature. Here we can emphasize that, independently of its bactericidal function, hydrogen peroxide behaves as a creator of free radicals between the carbon atoms of the polymer that are present on the surface of the substrate. Result in an increase in the number of free radicals on the surface of the polymer, ready to collect or receive the carbon atoms deposited on the surface, and therefore a reinforcement of the chemical bonds established between the polymer and the carbon deposited on its surface is achieved. Therefore, it can be contemplated to precede the deposition in a plasma atmosphere of the carbon layer by spraying hydrogen peroxide on the surface of the substrate then subjected to an oxygen plasma in order to obtain a better adhesion of the carbon layer. to the polymer.

Claims (24)

1. CLAIMS 1. A container, such as a bottle or bottle, of heterogeneous constitution of material with barrier effect and a polymeric material, characterized in that the material with barrier effect contains an amorphous carbon material with polymeric tendency, which covers a substrate of material polymeric 2. The container according to claim 1, characterized in that the material with barrier effect is a nanocomposite based on amorphous carbon with polymeric tendency. 3. The container according to claim 2, characterized in that the material with barrier effect is a nanocomposite based on amorphous carbon with polymeric tendency and including metal atoms. The container according to any of the preceding claims, characterized in that the coating made of material with barrier effect has a thickness of less than approximately 3000 A. The container according to claim 4, characterized in that the coating made of material with effect of barrier has a thickness between 50 and 1500 Á. The container according to any of the preceding claims, characterized in that the polymeric material is a polyolefin or a polyester, particularly PET or PEN. The container according to any of the preceding claims, characterized in that the coating of material with barrier effect is arranged on the substrate inside the container. The container according to any of claims 1 to 6, characterized in that the coating of material with barrier effect is arranged on the substrate outside the container. 9. A method that applies a plasma with excitation by an electromagnetic wave to form a container, such as a bottle or bottle, of heterogeneous constitution of a material having a barrier effect and a polymeric material to form a substrate having the conformation of said container to be obtained, characterized in that the aforementioned polymeric material that forms the substrate is coated with a barrier effect material containing an amorphous carbon material with a polymeric tendency, by applying the following steps: it is introduced into an enclosure (2). ), in which a vacuum has been created, pushed, a roughing of the container (18), constituted by a polymeric material forming the aforementioned substrate; - at least one carbonated precursor in the gaseous state is injected into a reaction chamber (2, 18) under a very low pressure, the precursor being selected from among the alkanes, alkenes or alkynes, aromatics or a combination of some of them and - simultaneously establishes the reaction chamber an electromagnetic excitation of microwave in the UHF field with a relatively low power, able to give rise to a plasma under conditions of temperature that on the one hand keep the polymer at a temperature lower than that of the transition to glass and that on the other hand cause the deposit of an amorphous carbon material with a polymer tendency. The process according to claim 9, characterized in that the roughing of the container (18) of polymeric material is closed while the gaseous carbonated precursor is injected into the enclosure (2) on the outside of the slab, constituting the volume comprised between the enclosure and the outside of the roughing the reaction chamber, thanks to which the coating of the amorphous carbon material with polymeric tendency is formed on the external surface of the slab of the container. 11. The process according to claim 9, characterized in that the gaseous carbonate precursor is introduced into the roughing of the container (18) of polymeric material that later constitutes the reaction chamber, while a marked depression is created within the slab of the container. , thanks to which the plasma is formed only inside the slab and the coating of amorphous carbon material with polymeric tendency is deposited on the internal surface of the slab of the container and a depression is simultaneously created in the enclosure to reduce the pressure differential between the inside and the outside of the roughing. 12. The method according to claim 11, characterized in that the enclosure (2) has a transverse dimension close to that of the body of the roughing of the container (18) so that a perfect combination with the roughing of the container is achieved in order to facilitate the formation of the vacuum inside the container. The process according to any of claims 9 to 12, characterized in that the gaseous precursor is injected under a pressure of less than 1 millibar. 1 . The process according to any of claims 13, characterized in that before the formation of the inner lining of amorphous carbon material with a polymeric tendency, an oxygen plasma capable of generating natural oxygen is formed in the roughing of the container (18). clean the roughing of the container. 15. The process according to any of claims 9 to 13, characterized in that before the formation of the inner lining of amorphous carbon material with polymeric tendency, a bactericidal agent is sprayed into the container of the container (18) and a plasma of oxygen, thanks to which the plasma gives rise to the formation of a strongly reducing medium able to reduce bacterial contamination. 16. The apparatus that applies a plasma with excitation by means of an electromagnetic wave to form a container such as a bottle, a bottle, of heterogeneous constitution and of material with barrier effect and a polymeric material that forms a substrate (roughing of container (18) ) which has the conformation of the said container to be obtained, this equipment containing a plasma generating device, with an enclosure (2) provided with injection elements (7) of a gaseous precursor as well as elements of electromagnetic excitation (8-12) ), characterized in that in order to coat the polymeric material forming the substrate with a barrier effect material containing an amorphous carbon material with a polymeric tendency, the injection elements (7) of the precursor are joined to a generator of a precursor in the state gaseous selected among alkanes, alkenes, alkynes, aromatics or a combination of some of them, and injection elements are practiced in such a way that it is delivered to the gaseous precursor under a very low pressure, while the electromagnetic excitation elements (8-12) are suitable for generating microwaves within the UHF field. The equipment according to claim 16, characterized in that the enclosure (2) has dimensions clearly superior to those of the roughing of the container (18), subject to treatment and because the injection elements open into the enclosure (2) to the outside of the slab of the container (18), thanks to which with the roughing of the container closed, the equipment generates a plasma outside the roughing of the container and is on the external surface of the slab of the container that is depositing the coating of amorphous carbon material with polymer trend The equipment according to claim 16, characterized in that the injection elements (7) of the gaseous precursor discharge into the slab of the container (18), arranged in the enclosure (2), because pumping elements (6) are provided. which open inside the roughing of the container (18) and which are suitable for generating a marked depression therein, thanks to which the plasma is generated inside the roughing of the container that constitutes a reaction chamber and is on the inner surface of the roughing of the container where the coating of amorphous carbon material with polymeric tendency is deposited, and because the pumping elements (6) are further arranged to simultaneously give inside the enclosure (2) a depression in order to reduce the pressure differential between the inside and the outside of the roughing. The equipment according to claim 18, characterized in that the enclosure (2) is provided with a mobile closing cap (4) for sealing the injector (7) of the injection means of the gaseous precursor and the orifice (5) for the suction of the pumping means and because it also contains support elements (17) suitable for supporting a container slab (18) by the neck thereof by applying the sprue (23) of the container slab in a hermetically closed manner in against the inside face (22) of the lid, so as to surround the mentioned suction and injection holes. The equipment according to claim 19, characterized in that the support elements (17) are axially displaceable (19) for carrying the roughing of the container against the inner face of the cover (4) thus covering the said suction and injector holes. prior to the deposit of the coating or with the separation of the container manufactured after depositing the coating. The equipment according to claims 16 to 20, characterized in that the excitation elements with microwaves comprise a waveguide (8) radially connected to a cavity (1) surrounding the enclosure (2), the cavity (1) being provided. with elements (11) of longitudinal short circuit that surround the enclosure while the waveguide is provided with elements (10) of transverse short circuit. 22. The apparatus according to any of claims 18 to 21, characterized in that the enclosure (2) has a transverse dimension close to that of the neck of the slab of the container (18). 23. The equipment according to any of claims 16 to 20, characterized in that the excitation elements with microwaves comprise an antenna (13) attached to a waveguide (15) and arranged radially in a cavity (1) surrounding the enclosure ( 2), the cavity (1) of longitudinal short circuit elements (11) being provided. The equipment according to any of claims 16 to 20, characterized in that the excitation elements with microwaves comprise an antenna (13) attached to a waveguide (15) and arranged coaxially in a cavity (1) surrounding the enclosure ( 2), the cavity (1) of longitudinal short circuit elements (11) being provided.