EP0914876B1 - Process and apparatus for treating the surface of a substrate with an electrical discharge between two electrodes in a gas mixture - Google Patents

Process and apparatus for treating the surface of a substrate with an electrical discharge between two electrodes in a gas mixture Download PDF

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Publication number
EP0914876B1
EP0914876B1 EP98402730A EP98402730A EP0914876B1 EP 0914876 B1 EP0914876 B1 EP 0914876B1 EP 98402730 A EP98402730 A EP 98402730A EP 98402730 A EP98402730 A EP 98402730A EP 0914876 B1 EP0914876 B1 EP 0914876B1
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EP
European Patent Office
Prior art keywords
substrate
electrodes
roller
pair
surface treatment
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EP98402730A
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German (de)
French (fr)
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EP0914876A1 (en
Inventor
Alain Villermet
François Coeuret
Panayotis Cocolios
Bernd c/o Softal Electronic GmbH Martens
Eckhard C/O Softal Electronic Gmbh Prinz
Jürgen c/o Softal Electronic GmbH Salge
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Softal Elektronik GmbH
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Softal Elektronik GmbH
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/10—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by contact with a member carrying the treating material
    • D06B1/14—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by contact with a member carrying the treating material with a roller
    • D06B1/148—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by contact with a member carrying the treating material with a roller the treating material being supplied to the roller by spraying or pouring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length

Definitions

  • the subject of the present invention is a method and a device for surface treatment of a moving substrate, by electrical discharge in a controlled gas atmosphere between two electrodes, the atmosphere gas comprising in particular one or more compounds capable of generate by-products that can accumulate and / or deposit on discharge electrodes.
  • these by-products could be solid as powders (as for example in the case of silanes), or else liquids or pasty as in the case of certain hydrocarbons (giving rise to example with the deposition of compounds with aliphatic chains).
  • the gas mixtures envisaged can be, depending on the treatment and the very varied target substrates, generally comprising a neutral carrier gas and a or several compounds among the reducing and oxidizing gases, one of the components of the mixture therefore being of the type capable of generating by-products can accumulate and / or deposit on the electrodes of the landfill, as is the case for example with silanes or hydrocarbons.
  • substrates targeted by the present invention can for example be present in sheet or film form, foams, continuous or not depending on the subject considered. We are particularly interested here in non-conductive substrates made of polymer materials, textiles (woven or not), paper etc ...
  • GB 1012746 (Radiation Research Coup.) Describes a method for the surface treatment of a moving substrate by electrical discharge according to the preamble of claim 1.
  • the active gas mixture allowing to obtain good levels of treatment can be of different compositions, which depend essentially the intended application with the treated polymer film. So far, the gas mixture most often included nitrogen as the carrier gas, a oxidizing gas and a few hundred ppm silane.
  • the object of the present invention is therefore in particular to propose a method and device for advantageously solving this problem technique by avoiding the accumulation on the electrodes of by-products (solid and / or liquid and / or still pasty) resulting from chemical reactions caused by electrical discharge to the processing atmosphere.
  • One of the conditions necessary for a good implementation of the invention is to provide a device capable of ensuring an injection homogeneous gas mixture over the entire length from the electrodes used to create the landfill. Indeed a strictly homogeneous distribution is essential to obtain a homogeneous treatment of the polymer film.
  • the two electrodes are rollers on which the running film is applied and which are arranged in parallel to each other at an appropriate interval, and thus a discharge is thus created between two electrode rollers.
  • the method according to the invention for the surface treatment of a substrate running, by electric discharge created between two electrodes in a gas mixture capable of generating by-products which can deposit on the electrodes, in which one of the electrodes is a roller on which can be applied the substrate, means being provided for injecting the gas mixture between the electrodes, is then characterized in that one has at least one substrate processing stage, each stage comprising at least one pair of roller electrodes, and an injector of the gas mixture between the rollers, and in that the treatment of the substrate as follows: successively pass the substrate one first time between the two electrode rollers, applying it to the first electrode roller, where it undergoes a first surface treatment, then a second time between the two electrode rollers, applying it to the second roller electrode, where it undergoes a second surface treatment.
  • the invention relates to the field of "scrolling" surface treatment methods, so the facilities that we qualify as “open”, hence the presence of certain air inlets, the surface treatment also being carried out necessarily at atmospheric pressure or at a pressure close to the atmospheric pressure.
  • the invention also relates to a device for surface treatment. of a moving substrate, by electrical discharge created between two electrodes in a gas mixture capable of generating by-products which can be deposited on the electrodes, in which one of the electrodes is a roller on which the substrate can be applied, means being provided for injecting the gas mixture between the electrodes, and characterized in that that the second electrode is a roller on which the moving substrate can also be applied and which is arranged parallel to the other roller at an appropriate interval, by the fact that the device comprises means, able to pass the substrate a first time between the two electrode rollers, by applying it to the first roller electrode, where it can undergo a first surface treatment, and subsequently pass the substrate a second time between the two electrode rollers, coming apply it on the second electrode roller, where it can undergo a second surface treatment.
  • the device can also include means for ensuring good scrolling of the film in the device, and therefore in particular to bring the substrate into the area discharge and bring it out, or even, when the device includes several processing stages, to transfer the substrate between the stages.
  • the second discharge can be either off or on, which means the substrate can be treated twice or four times. Indeed, the substrate can pass first in the first discharge stage where it is treated by the first discharge zone, then after passing over a tying roller, the film can pass into the second discharge stage where it can again be treated by the second discharge zone (if it is on). After embarrassment on others rolls, the film passes a second time into the second discharge zone then also, after a tie-in roll in the first area of dump.
  • the lengths of the two electrodes in the pair are not necessarily identical, and on the other hand, the ratio of dimensions between one or the other of the electrodes and the substrate.
  • the gas injection width relative to the dimensions of the substrate to be treated.
  • the electrodes remain protected by the substrate itself for the entire duration of the treatment, since the substrate covers all or part of the surface of the electrodes, ie their “useful” surface, in each zone of electric shock, the formation of by-product deposits on the electrodes being in fact the fruit of the combination of the presence of a electric shock and the presence of the gas mixture likely to generate by-products.
  • -X- passes a second time between the two electrode rollers, applying to the second roller electrode of the pair, where it undergoes a second surface treatment (at right now the first electrode mentioned above is covered by an upstream portion of the moving substrate, i.e. which followed -X- in the scrolling).
  • the by-products thus formed are progressively evacuated by suction systems housed in the hood and / or by the surface of the moving substrate, without accumulating on the electrodes.
  • the system can operate almost continuously 24 hours a day.
  • the device shown is intended for the surface treatment of substrates, for example of polymer films, by electrical discharge between two electrodes in a gas mixture likely to give rise to the formation of by-products during treatment, for example in a gas mixture containing monosilane.
  • the embodiment represented here comprises two stages (or zones) 1, 2 superimposed surface treatment of a polymer film 3, a block suction 4 arranged below the upper treatment stage 2, and a second block 5 for suction and evacuation of the gaseous effluents resulting from the treatment, located below the first treatment stage 1.
  • the assembly is contained inside a cover 6, the film entering and emerging from the system through the spaces provided between the suction unit 5 and the tying roller 21 and the tying roller 19 respectively.
  • Each treatment or discharge stage 1, 2 includes for the mode embodiment shown two electrode rollers 9, 11 arranged parallel to each other and with their longitudinal axis horizontal. These rollers 9, 11 therefore constitute two electrodes, produced in an appropriate metallic material. They can be, at least for one of them, covered with a suitable dielectric material. Means not shown and known per se are provided for placing the electrodes 9, 11 under high voltage (several thousand volts) to cause a discharge electric between them. At the ends of each roller 9, 11 are arranged here jacks 12, 13 allowing the associated roller 11, 9 to be moved forward or backward. This mode is only illustrative of one of the possible functioning of the system, we could indeed also work with fixed rollers.
  • each pair of roller electrodes 9, 11 and in a plane vertical passing between them is positioned an injector 14 of a mixture gas from a gas chamber 15 placed above the injector 14 (referenced 32 in FIG. 2), which as well as the associated chamber 15 preferably extend over the entire length of the respective rollers 9, 11.
  • rollers 9, 11 are supported at their ends by the walls opposite sides 16, 17 of the cover 6 and can be rotated by the film 3 itself driven by a not shown motorization system.
  • electrode rollers driven by a motor or simply by the film itself (depending on the film considered and its resistance characteristics mechanical).
  • first treatment stage 1 Below the first treatment stage 1 are arranged here two tying rollers 19, 21.
  • a second pair of tying rollers 22, 23 is arranged above the first discharge zone 1, and finally two interlocking rollers 24, 25 are mounted above the electrode rollers 9, 11 of the second discharge zone 2.
  • Each tying roller (19, 21, 22, 23.) is here driven by a motor (not shown), in order to facilitate the movement of the film 3.
  • the tying rollers could be driven by the film itself in certain cases.
  • the film 3 enters the cover 6 through the slot formed between the roller 21 and the block 44 which will be described later, then comes apply to the first tying roller 21, then passes between the two electrodes 9, 11 of the first discharge stage 1, from there the film 3 passes over the interlocking roller 23, located above the discharge stage 1, comes then apply to the roller electrode 9 of the upper stage 2, then to the upper tying roller 25.
  • the film is then returned by the roller 24 to the electrode roller 11, then is applied to the interlocking roller 22 from which it is returned to the electrode roller 11 of the first floor. After which the film is discharged through the exit slot formed between the lower feed roller 19 and the suction block 44.
  • the film 3 undergoes four consecutive phases of treatment by electrical discharge, for example by corona discharge. between the electrodes 9, 11 of the two floors.
  • the device comprises two discharge stages 1, 2, a single stage 1 being able sufficient for many applications.
  • the film 3 passes directly from the interlocking roller 23 onto the roller 22 before being returned to the inter-electrode space where there undergoes a second surface treatment before emerging from the cover by the tether roller 19.
  • Each chamber 15 is supplied with a gas mixture with at least one from its ends by a pipe crossing the wall of the cover 6. From this compartment the gas mixture enters the injection nozzle 14 extending here continuously from one end to the other of the gas 15 and roller electrodes.
  • the nozzle 14 can be fixed under the chamber 15 by any suitable means known to those skilled in the art.
  • the gas injection nozzle is here provided, so completely advantageous means making it possible to conceal part of the length of this nozzle, in order to limit the length over which the mixture is injected gaseous. Indeed, it is then possible to adapt this injection length gaseous to the width of the film 3 to be treated, when this width is less than the length of the electrode roller 9.
  • a roller 11a constituting an electrode roller supported by a longitudinal axis 34 whose ends are supported by the side walls 16, 17 of the cover 6, the length of the roller 11a then being equal to the width of the film 3 to be treated.
  • the aforementioned means may include for example as is the case here flaps 36 articulated on the nozzle 32, each provided with a curved end to close the injection slot of the nozzle 32, and of hooks 38 for maneuvering. The upper ends of these can be hung on a retainer.
  • flaps 36 can thus be staggered along the injector 32, in order to adjust its effective injection length.
  • the treatment device is finally provided, at its lower part below interlock rollers 19, 21, of a unit 42 ( Figures 1 and 3) suction of gaseous effluents from electrical discharges, as well as the air entrained on the surface of the film 3 in its movement.
  • the suction unit 42 includes, associated with each roller 19/21, a block 43 and a block intermediate 44 interposed between the block 43 and the roller (19, 21).
  • Each block intermediate 44 has a lower face 45 of support, on the end of the block 43 and which may be flat, and a concave upper face 46, forming a cylindrical conjugate portion of the cylindrical surface of the associated roller (19, 21).
  • an appropriate spacing e ( Figure 5), through which the film 3 maintained applied to the surface of the respective roller 19, 21.
  • each block 44 is provided a respective slot 47, 48 suction of the gaseous effluents resulting from the treatment and the air entrained by the film in its running, this slot 47, 48 opening into the block 43.
  • the two slots 47, 48 are respectively placed opposite the rollers 21 and 19.
  • Figure 1 describes, for reasons of ease of viewing and reading, especially a vertical arrangement of discharge zones and therefore of the displacement of the film in space, we conceive that any other type of arrangement of the discharge areas is possible (vertical, horizontal, mixed) the whole being to provide the rollers of embarrassment necessary to bring the substrate to treatment in the one or more discharge areas and therefore in particular to transport it between each discharge zone when the device comprises several.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
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Description

La présente invention a pour objet un procédé et un dispositif pour le traitement de surface d'un substrat en défilement, par décharge électrique dans une atmosphère gazeuse contrôlée entre deux électrodes, l'atmosphère gazeuse comportant notamment un ou plusieurs composés susceptibles de générer des sous-produits pouvant s'accumuler et/ou se déposer sur les électrodes de la décharge.The subject of the present invention is a method and a device for surface treatment of a moving substrate, by electrical discharge in a controlled gas atmosphere between two electrodes, the atmosphere gas comprising in particular one or more compounds capable of generate by-products that can accumulate and / or deposit on discharge electrodes.

A titre illustratif, ces sous-produits pourront être solides comme des poudres (comme par exemple dans le cas des silanes), ou bien encore liquides ou pâteux comme dans le cas de certains hydrocarbures (donnant lieu par exemple au dépôt de composés à chaínes aliphatiques).By way of illustration, these by-products could be solid as powders (as for example in the case of silanes), or else liquids or pasty as in the case of certain hydrocarbons (giving rise to example with the deposition of compounds with aliphatic chains).

On conçoit que de tels dépôts puissent alors s'accumuler sur les électrodes et constituer une altération de celles-ci et de façon plus générale une gêne au fonctionnement du système.It is understandable that such deposits can then accumulate on the electrodes and constitute an alteration of them and more generally discomfort with the functioning of the system.

Les mélanges gazeux envisagés peuvent être, selon le traitement et le substrat visés, très variés, comportant en général un gaz porteur neutre et un ou plusieurs composés parmi les gaz réducteurs et oxydants, l'un des composants du mélange étant donc du type susceptible de générer des sous-produits pouvant s'accumuler et/ou se déposer sur les électrodes de la décharge, comme c'est le cas par exemple des silanes ou encore des hydrocarbures.The gas mixtures envisaged can be, depending on the treatment and the very varied target substrates, generally comprising a neutral carrier gas and a or several compounds among the reducing and oxidizing gases, one of the components of the mixture therefore being of the type capable of generating by-products can accumulate and / or deposit on the electrodes of the landfill, as is the case for example with silanes or hydrocarbons.

Les "substrats " visés par la présente invention peuvent par exemple se présenter sous forme de feuille ou encore de film, de mousses, continu ou non selon la matière considérée. On s'intéresse ici tout particulièrement aux substrats non-conducteurs en matériaux polymère, textile (tissé ou non), papier etc...The "substrates" targeted by the present invention can for example be present in sheet or film form, foams, continuous or not depending on the subject considered. We are particularly interested here in non-conductive substrates made of polymer materials, textiles (woven or not), paper etc ...

En considérant l'exemple des films polymères, comme on le sait, il est couramment nécessaire de procéder à des traitements de surface de ces films polymères pour rendre leur surface "active", c'est-à-dire pour permettre de la coller, d'imprimer des informations sur celle-ci etc. Pour pouvoir imprimer, il faut que l'encre soit compatible avec la surface du film polymère, alors qu'initialement, ce n'est en général pas le cas et qu'alors un pré-traitement de la surface est nécessaire.Considering the example of polymer films, as we know, it is commonly necessary to carry out surface treatments of these films polymers to make their surface "active", that is to say to allow the paste, print information on it etc. To be able to print, the ink must be compatible with the surface of the polymer film, then that initially this is generally not the case and that then pre-processing of the surface is necessary.

Pour procéder à un traitement adéquat, il est connu de soumettre la surface du film polymère à un traitement de flammage, ou à des produits chimiques appropriés, ou encore à un traitement corona. Classiquement ces traitements corona sont effectués dans l'air, dont les molécules d'azote et d'oxygène sont transformées par la décharge électrique, pour créer de nouvelles molécules (radicaux, ions...) qui réagissent chimiquement avec la surface du polymère.To carry out an adequate treatment, it is known to submit the surface of the polymer film to a flame treatment, or to products chemicals, or corona treatment. Classically these corona treatments are performed in the air, including nitrogen molecules and oxygen are transformed by the electric discharge, to create new molecules (radicals, ions ...) which react chemically with the polymer surface.

On a également proposé, comme décrit par le brevet américain US-5,576,076, de remplacer l'air par un mélange gazeux contenant du silane. L'injection de ce mélange gazeux actif dans la zone de décharge permet d'obtenir des niveaux de traitement élevés, et donc de répondre à un certain nombre de problèmes rencontrés par les transformateurs de films polymères. Le système d'électrodes utilisé contribue non seulement à créer la décharge électrique (comme des électrodes standards) mais aussi à gérer l'injection des gaz de traitement au sein de la zone de décharge.It has also been proposed, as described by the American patent US-5,576,076, to replace the air with a gas mixture containing silane. The injection of this active gas mixture into the discharge zone allows to obtain high levels of treatment, and therefore to respond to a certain number of problems encountered by polymer film processors. The electrode system used not only helps to create the discharge electric (like standard electrodes) but also to manage the injection of process gas within the discharge area.

GB 1012746 (Radiation Research Coup.) décrit un procédé pour le traitement de surface d'un substrat en défilement par décharge électrique selon le préambule de la revendication 1.GB 1012746 (Radiation Research Coup.) Describes a method for the surface treatment of a moving substrate by electrical discharge according to the preamble of claim 1.

Le mélange gazeux actif permettant d'obtenir de bons niveaux de traitement peut être de différentes compositions, lesquelles dépendent essentiellement de l'application visée avec le film polymère traité. Jusqu'ici, le mélange gazeux comportait le plus souvent, de l'azote comme gaz porteur, un gaz oxydant et quelques centaines de ppm de silane.The active gas mixture allowing to obtain good levels of treatment can be of different compositions, which depend essentially the intended application with the treated polymer film. So far, the gas mixture most often included nitrogen as the carrier gas, a oxidizing gas and a few hundred ppm silane.

Les travaux menés à bien par la Demanderesse ont permis de démontrer que lorsque ce procédé est mis en oeuvre comme décrit dans le brevet américain précité, c'est-à-dire que le mélange gazeux actif contenant du silane et un oxydant est injecté dans la zone de décharge, il se forme de la poudre de silice qui s'accumule sur les électrodes pendant toute la durée du traitement. Cet encrassement croissant des électrodes lors du traitement empêche de procéder au traitement de surface dans de bonnes conditions pendant une durée supérieure à une heure environ, alors que le mode de fonctionnement habituel dans l'industrie est du type continu sur 24 heures.The work carried out by the Applicant has demonstrated that when this process is implemented as described in the patent cited above, that is to say that the active gas mixture containing silane and an oxidant is injected into the discharge area, it forms powder of silica which accumulates on the electrodes throughout the duration of the treatment. This increasing fouling of the electrodes during treatment prevents carry out the surface treatment under good conditions for a lasting more than an hour or so, while the operating mode usual in the industry is the 24 hour continuous type.

L'accumulation de poudre sur les électrodes est une conséquence de différents phénomènes :

  • la physico-chimie de la décharge électrique : en effet la poudre de silice formée est le produit de réactions intervenant dans la phase gazeuse sous l'excitation de la décharge. En modifiant les conditions opératoires (composition du mélange gazeux, caractéristiques électriques de la décharge...), il est possible de modifier la proportion de poudre formée.
  • la mise en contact de la poudre formée avec les électrodes : en effet lorsque la poudre est formée en phase gazeuse (et cela même en faibles proportions optimisées selon le paragraphe précédent), l'accumulation n'intervient que s'il y a mise en contact de la poudre avec les électrodes.
The accumulation of powder on the electrodes is a consequence of different phenomena:
  • the physico-chemistry of the electrical discharge: in fact the silica powder formed is the product of reactions occurring in the gas phase under the excitation of the discharge. By modifying the operating conditions (composition of the gas mixture, electrical characteristics of the discharge, etc.), it is possible to modify the proportion of powder formed.
  • bringing the powder formed into contact with the electrodes: in fact when the powder is formed in the gaseous phase (and this even in small proportions optimized according to the preceding paragraph), the accumulation occurs only if there is contact of the powder with the electrodes.

La présente invention a donc notamment pour but de proposer un procédé et un dispositif permettant de résoudre avantageusement ce problème technique en évitant l'accumulation sur les électrodes des sous-produits (solides et/ou liquides et/ou encore pâteux) résultants des réactions chimiques provoquées par la décharge électrique dans l'atmosphère de traitement.The object of the present invention is therefore in particular to propose a method and device for advantageously solving this problem technique by avoiding the accumulation on the electrodes of by-products (solid and / or liquid and / or still pasty) resulting from chemical reactions caused by electrical discharge to the processing atmosphere.

Une des conditions nécessaires pour une bonne mise en oeuvre de l'invention est de réaliser un dispositif capable d'assurer une injection homogène du mélange gazeux sur toute la longueur dès électrodes utilisées pour créer la décharge. En effet une répartition rigoureusement homogène est essentielle pour obtenir un traitement homogène du film polymère.One of the conditions necessary for a good implementation of the invention is to provide a device capable of ensuring an injection homogeneous gas mixture over the entire length from the electrodes used to create the landfill. Indeed a strictly homogeneous distribution is essential to obtain a homogeneous treatment of the polymer film.

Conformément à l'invention, les deux électrodes sont des rouleaux sur lesquels le film en défilement est appliqué et qui sont disposés parallèlement l'un à l'autre à un intervalle approprié, et l'on crée donc ainsi une décharge électrique entre deux rouleaux-électrodes.According to the invention, the two electrodes are rollers on which the running film is applied and which are arranged in parallel to each other at an appropriate interval, and thus a discharge is thus created between two electrode rollers.

Le procédé selon l'invention, pour le traitement de surface d'un substrat en défilement, par décharge électrique créée entre deux électrodes dans un mélange gazeux susceptible de générer des sous-produits pouvant se déposer sur les électrodes, dans lequel l'une des électrodes est'un rouleau sur lequel peut être appliqué le substrat, des moyens étant prévus pour injecter le mélange gazeux entre les électrodes, se caractérise alors en ce que l'on dispose d'au moins un étage de traitement du substrat, chaque étage comprenant au moins une paire de rouleaux-électrodes, et un injecteur du mélange gazeux entre les rouleaux, et en ce que l'on procède au traitement du substrat de la façon suivante : on fait successivement passer le substrat une première fois entre les deux rouleaux-électrodes, en venant l'appliquer sur le premier rouleau-électrode, où il subit un premier traitement de surface, puis une seconde fois entre les deux rouleaux-électrodes, en venant l'appliquer sur le second rouleau-électrode, où il subit un second traitement de surface.The method according to the invention, for the surface treatment of a substrate running, by electric discharge created between two electrodes in a gas mixture capable of generating by-products which can deposit on the electrodes, in which one of the electrodes is a roller on which can be applied the substrate, means being provided for injecting the gas mixture between the electrodes, is then characterized in that one has at least one substrate processing stage, each stage comprising at least one pair of roller electrodes, and an injector of the gas mixture between the rollers, and in that the treatment of the substrate as follows: successively pass the substrate one first time between the two electrode rollers, applying it to the first electrode roller, where it undergoes a first surface treatment, then a second time between the two electrode rollers, applying it to the second roller electrode, where it undergoes a second surface treatment.

Le procédé selon l'invention peut par ailleurs adopter l'une ou plusieurs des caractéristiques suivantes :

  • la largeur du substrat est au moins égale à la longueur de l'espace inter-électrodes où l'on observe la combinaison de la présence d'une décharge électrique et de la présence dudit mélange gazeux susceptible de générer des sous-produits ;
  • on dispose de rouleaux d'embarrement, le nombre de rouleaux d'embarrement dont on dispose étant au moins suffisant pour permettre de procéder audits premier et second traitements de surface de la façon suivante :
  • i) le substrat vient s'appliquer sur un premier rouleau d'embarrement d'une première paire de rouleaux d'embarrement, puis passe entre les deux rouleaux-électrodes en venant s'appliquer sur le premier rouleau-électrode, où il subit le dit premier traitement de surface;
  • j) le substrat vient ensuite s'appliquer sur un premier rouleau d'embarrement d'une seconde paire de rouleaux d'embarrement, avant de venir s'appliquer sur le second rouleau d'embarrement de la seconde paire de rouleaux d'embarrement;
  • k) le substrat passe alors à nouveau entre les deux rouleaux-électrodes en venant s'appliquer sur le second rouleau-électrode, où il subit ledit second traitement de surface, avant de venir s'appliquer sur le second rouleau d'embarrement de la première paire de rouleaux d'embarrement.
  • on dispose de deux étages de traitement du substrat, et l'on procède, entre ledit premier traitement de surface du substrat et ledit second traitement de surface du substrat, à deux traitements de surface supplémentaires du substrat dans le second étage de traitement, de la façon suivante :
  • i) après avoir subit ledit premier traitement de surface et avant de subir le dit second traitement de surface, on fait passer le substrat une première fois entre les deux rouleaux-électrodes du second étage, en venant l'appliquer sur le premier rouleau-electrode du second étage, où il subit un premier traitement de surface supplémentaire;
  • j) on fait ultérieurement passer le substrat une seconde fois entre les deux rouleaux-électrodes (9, 11) du second étage, en venant l'appliquer sur le second rouleau-electrode (11) du second étage, où il subit un second traitement de surface supplémentaire.
  • on adapte la longueur, d'au moins l'une des électrodes de ladite au moins une paire, à la largeur du substrat à traiter ;
  • on injecte le mélange gazeux entre les deux rouleaux-électrodes de ladite au moins une paire, sur une longueur d'injection substantiellement égale à la largeur du substrat à traiter.
The method according to the invention can also adopt one or more of the following characteristics:
  • the width of the substrate is at least equal to the length of the inter-electrode space where the combination of the presence of an electrical discharge and the presence of said gaseous mixture capable of generating by-products is observed;
  • we have tie-in rollers, the number of tie-in rollers available which is at least sufficient to allow us to carry out the first and second surface treatments as follows:
  • i) the substrate is applied to a first interlocking roller of a first pair of interlocking rollers, then passes between the two electrode rollers and is applied to the first electrode roller, where it undergoes the said first surface treatment;
  • j) the substrate is then applied to a first tie-in roller of a second pair of tie-in rollers, before coming to be applied to the second tie-in roll of the second pair of tie-in rollers;
  • k) the substrate then again passes between the two electrode rollers, being applied to the second electrode roller, where it undergoes said second surface treatment, before coming to be applied to the second feed roll of the first pair of locking rollers.
  • two substrate treatment stages are available, and between said first substrate surface treatment and said second substrate surface treatment, two additional surface treatments of the substrate are carried out in the second treatment stage, as follows:
  • i) after having undergone said first surface treatment and before undergoing said second surface treatment, the substrate is passed a first time between the two electrode rollers of the second stage, by applying it to the first electrode roller the second floor, where it undergoes a first additional surface treatment;
  • j) the substrate is subsequently passed a second time between the two electrode rollers (9, 11) of the second stage, by applying it to the second electrode roller (11) of the second stage, where it undergoes a second treatment additional surface.
  • the length of at least one of the electrodes of said at least one pair is adapted to the width of the substrate to be treated;
  • the gas mixture is injected between the two electrode rollers of said at least one pair, over an injection length substantially equal to the width of the substrate to be treated.

Comme on l'aura compris à la lecture de ce qui précède, l'invention concerne le domaine des procédés de traitement de surface " en défilement ", donc les installations que l'on qualifie de "ouvertes", d'où la présence de certaines entrées d'air, le traitement de surface s'effectuant également nécessairement à la pression atmosphérique ou à une pression proche de la pression atmosphérique. On conçoit en effet que l'on peut, sans sortir du cadre de la présente invention, travailler à des pressions se situant à quelques dizaines de millibars, voire quelques centaines de millibars autour de la pression atmosphérique. As will be understood from reading the above, the invention relates to the field of "scrolling" surface treatment methods, so the facilities that we qualify as "open", hence the presence of certain air inlets, the surface treatment also being carried out necessarily at atmospheric pressure or at a pressure close to the atmospheric pressure. We can see that we can, without going outside the framework of the present invention, working at pressures within a few tens of millibars or even a few hundred millibars around the atmospheric pressure.

L'invention concerne également un dispositif pour le traitement de surface d'un substrat en défilement, par décharge électrique créée entre deux électrodes dans un mélange gazeux susceptible de générer des sous-produits pouvant se déposer sur les électrodes, dans lequel l'une des électrodes est un rouleau sur lequel peut être appliqué le substrat, des moyens étant prévus pour injecter le mélange gazeux entre les électrodes, et se caractérisant en ce que la seconde électrode est un rouleau sur lequel le substrat en défilement peut également être appliqué et qui est disposé parallèlement à l'autre rouleau à un intervalle approprié, par le fait que le dispositif comprend des moyens, aptes à faire passer le substrat une première fois entre les deux rouleaux-électrodes, en venant l'appliquer sur le premier rouleau-électrode, où il peut subir un premier traitement de surface, et à faire ultérieurement passer le substrat une seconde fois entre les deux rouleaux-électrodes, en venant l'appliquer sur le second rouleau-électrode, où il peut subir un second traitement de surface.The invention also relates to a device for surface treatment. of a moving substrate, by electrical discharge created between two electrodes in a gas mixture capable of generating by-products which can be deposited on the electrodes, in which one of the electrodes is a roller on which the substrate can be applied, means being provided for injecting the gas mixture between the electrodes, and characterized in that that the second electrode is a roller on which the moving substrate can also be applied and which is arranged parallel to the other roller at an appropriate interval, by the fact that the device comprises means, able to pass the substrate a first time between the two electrode rollers, by applying it to the first roller electrode, where it can undergo a first surface treatment, and subsequently pass the substrate a second time between the two electrode rollers, coming apply it on the second electrode roller, where it can undergo a second surface treatment.

Le dispositif selon l'invention peut également adopter l'une ou plusieurs des caractéristiques suivantes :

  • il comprend un capot comprenant au moins un étage de traitement du substrat, chaque étage comprenant une paire de rouleaux-électrodes, et des moyens d'injection d'un mélange gazeux entre les rouleaux-électrodes ;
  • il comprend au moins deux paires de rouleaux d'embarrement, le nombre de paires de rouleaux d'embarrement du dispositif étant au moins suffisant pour permettre d'assurer la présence d'une paire de rouleaux d'embarrement de part et d'autre de chaque paire de rouleaux-électrodes ;
  • les moyens d'injection du mélange gazeux comprennent, pour chaque paire de rouleaux-électrodes, une buse d'injection gazeuse s'étendant de manière continue d'une extrémité à l'autre d'au moins l'un des rouleaux-électrodes associés ;
  • la buse d'injection gazeuse est pourvue de moyens pour occulter une partie de la longueur de ladite buse afin de pouvoir régler et limiter la longueur sur laquelle est injecté le mélange gazeux, et d'adapter par exemple cette longueur à celle de l'une ou l'autre des électrodes
  • la longueur de l'une au moins des électrodes de la ou chaque paire est égale à la largeur du substrat à traiter ;
  • lesdits moyens pour occulter comprennent des volets articulés latéralement sur la buse, munis chacun d'une extrémité recourbée adaptée pour obturer la fente d'injection de la buse, et d'organes de manoeuvre tels que des crochets ;
  • le dispositif comporte une unité d'aspiration des effluents gazeux issus de la décharge électrique et de l'air entraíné par le substrat dans son défilement ;
  • l'unité d'aspiration est disposée sous une paire de rouleaux d'embarrement disposée au-dessous des rouleaux-électrodes ;
  • l'unité d'aspiration comprend, associés à chaque rouleau d'embarrement de la dite paire, un ensemble comportant un bloc d'aspiration et un bloc intermédiaire interposé entre ce bloc d'aspiration et le rouleau d'embarrement considéré, et ayant une surface concave conjuguée de la surface cylindrique du rouleau d'embarrement, avec entre ces surfaces un écartement approprié, et en ce que dans chaque bloc est ménagée une fente d'aspiration de l'atmosphère gazeuse circulant entre le rouleau et la surface du bloc intermédiaire, cette fente débouchant dans le bloc d'aspiration.
The device according to the invention can also adopt one or more of the following characteristics:
  • it comprises a cover comprising at least one stage for processing the substrate, each stage comprising a pair of roller-electrodes, and means for injecting a gaseous mixture between the roller-electrodes;
  • it comprises at least two pairs of interlocking rollers, the number of pairs of interlocking rollers of the device being at least sufficient to ensure the presence of a pair of interlocking rollers on either side of each pair of electrode rollers;
  • the means for injecting the gas mixture comprises, for each pair of electrode rollers, a gas injection nozzle extending continuously from one end to the other of at least one of the associated electrode rollers ;
  • the gas injection nozzle is provided with means for obscuring part of the length of said nozzle in order to be able to adjust and limit the length over which the gas mixture is injected, and to adapt for example this length to that of one either of the electrodes
  • the length of at least one of the electrodes of the or each pair is equal to the width of the substrate to be treated;
  • said means for obscuring comprise flaps articulated laterally on the nozzle, each provided with a curved end adapted to close the injection slot of the nozzle, and operating members such as hooks;
  • the device comprises a suction unit for gaseous effluents from the electric discharge and from the air entrained by the substrate in its travel;
  • the suction unit is arranged under a pair of interlocking rollers arranged below the electrode rollers;
  • the suction unit comprises, associated with each embedding roller of said pair, an assembly comprising a suction block and an intermediate block interposed between this suction block and the embedding roller considered, and having a concave conjugate surface of the cylindrical surface of the interlocking roller, with an appropriate spacing between these surfaces, and in that in each block is formed a suction slot for the gaseous atmosphere circulating between the roller and the surface of the intermediate block , this slot opening into the suction block.

Comme on l'aura compris à la lecture de ce qui précède, le dispositif peut comprendre également des moyens permettant d'assurer un bon défilement du film dans le dispositif, et donc en particulier d'amener le substrat dans la zone de décharge et de l'en faire ressortir, voire, quand le dispositif comporte plusieurs étages de traitement, de transférer le substrat entre les étages.As will be understood from reading the above, the device can also include means for ensuring good scrolling of the film in the device, and therefore in particular to bring the substrate into the area discharge and bring it out, or even, when the device includes several processing stages, to transfer the substrate between the stages.

Ces moyens de "convoyage" du substrat peuvent être, comme c'est le cas par exemple très couramment sur les installations de traitement de surface de films polymères, des rouleaux d'embarrement.These means of "conveying" the substrate can be, as is the case for example very commonly on surface treatment installations polymer films, tying rollers.

Si le dispositif comporte deux étages de traitement, la deuxième décharge peut être soit éteinte, soit allumée, ce qui signifie que le substrat peut être traité deux fois ou quatre fois. En effet, le substrat peut passer d'abord dans le premier étage de décharge où il est traité par la première zone de décharge, puis après passage sur un rouleau d'embarrement, le film peut passer dans le deuxième étage de décharge où il peut à nouveau être traité par la seconde zone de décharge (si celle-ci est allumée). Après embarrement sur d'autres rouleaux, le film passe une seconde fois dans la deuxième zone de décharge puis également, après un rouleau d'embarrement dans la première zone de décharge.If the device has two processing stages, the second discharge can be either off or on, which means the substrate can be treated twice or four times. Indeed, the substrate can pass first in the first discharge stage where it is treated by the first discharge zone, then after passing over a tying roller, the film can pass into the second discharge stage where it can again be treated by the second discharge zone (if it is on). After embarrassment on others rolls, the film passes a second time into the second discharge zone then also, after a tie-in roll in the first area of dump.

Comme on l'aura compris à la lecture de ce qui précède, d'une part les longueurs des deux électrodes de la paire ne sont pas nécessairement identiques, et d'autre part, on peut choisir selon l'invention le rapport de dimensions entre l'une ou l'autre des électrodes et le substrat. On peut également choisir selon l'invention la largeur d'injection des gaz par rapport aux dimensions du substrat à traiter. As will be understood from reading the above, on the one hand the lengths of the two electrodes in the pair are not necessarily identical, and on the other hand, the ratio of dimensions between one or the other of the electrodes and the substrate. We can also choose according to the invention the gas injection width relative to the dimensions of the substrate to be treated.

Ainsi, compte tenu du choix de la configuration adoptée, si le mélange gazeux de traitement contient un gaz susceptible de conduire à la formation de sous-produits sous l'excitation de la décharge électrique (comme c'est le cas des silanes), les électrodes restent protégées par le substrat lui-même pendant toute la durée du traitement, puisque le substrat couvre tout ou partie de la surface des électrodes i.e de leur surface « utile », dans chaque zone de décharge électrique, la formation de dépôts de sous-produits sur les électrodes étant en fait le fruit de la combinaison de la présence d'une décharge électrique et de la présence du mélange gazeux susceptible de générer des sous-produits.Thus, taking into account the choice of configuration adopted, if the mixture gaseous treatment contains a gas which can lead to the formation of by-products under the excitation of electric shock (as it is the case silanes), the electrodes remain protected by the substrate itself for the entire duration of the treatment, since the substrate covers all or part of the surface of the electrodes, ie their “useful” surface, in each zone of electric shock, the formation of by-product deposits on the electrodes being in fact the fruit of the combination of the presence of a electric shock and the presence of the gas mixture likely to generate by-products.

Afin de mieux illustrer simplement l'invention, i.e cette caractéristique selon laquelle le substrat en défilement est appliqué sur les deux électrodes de la paire de rouleaux-électrodes se faisant face, considérons ici une portion donnée -X- du substrat en défilement, que l'on traite dans un dispositif à un étage : la portion -X- va passer une première fois entre les deux rouleaux-électrodes, et venir s'appliquer sur un premier rouleau-électrode, où elle subit un premier traitement de surface (à ce moment-ci la seconde électrode qui lui fait face est recouverte par une portion aval du substrat en défilement, i.e une portion qui précédait -X- dans le défilement), puis -X- passe une seconde fois entre les deux rouleaux-électrodes, en venant s'appliquer sur le second rouleau-électrode de la paire, où elle subit un second traitement de surface (à ce moment-ci la première électrode précédemment évoquée est recouverte par une portion amont du substrat en défilement, i.e qui suivait -X- dans le défilement).In order to better illustrate the invention simply, i.e. this characteristic that the moving substrate is applied to the two electrodes the pair of electrode rollers facing each other, here consider a portion data -X- of the moving substrate, which is processed in a device at a stage: the portion -X- will pass for the first time between the two electrode rollers, and come to apply on a first roller electrode, where it undergoes a first surface treatment (at this time the second electrode which facing is covered by a downstream portion of the moving substrate, i.e. a portion preceding -X- in scrolling), then -X- passes a second time between the two electrode rollers, applying to the second roller electrode of the pair, where it undergoes a second surface treatment (at right now the first electrode mentioned above is covered by an upstream portion of the moving substrate, i.e. which followed -X- in the scrolling).

Toujours afin de mieux comprendre l'invention :

  • i) si l'on adapte la longueur d'au moins l'une des électrodes de la paire à la largeur du substrat, cette électrode sera de fait protégée contre les dépôts de sous-produits puisque recouverte du substrat. Quant à la seconde électrode qui lui fait face :
    • elle est également protégée de fait si elle a la même longueur que la première,
    • et si sa longueur est supérieure, elle est bien sûr protégée sur toute la largeur du substrat par recouvrement, et quant à son supplément de longueur par rapport à la première électrode, il n'est pas affecté par des dépôt de sous-produits du fait de l'absence de décharge sur ce surplus de longueur.
  • j) on l'a vu précédemment, on peut également adapter la longueur d'injection des gaz à la largeur du substrat à traiter, les électrodes seront alors également protégées contre les dépôts de sous-produits quelque soit le rapport de dimensions entre les électrodes et le substrat par le fait que :
    • la partie des électrodes recouverte par le substrat est protégée de fait ;
    • la portion des électrodes qui ne serait par recouverte par le substrat (du fait du choix d'une longueur supérieure) est également protégée du fait de l'absence de mélange gazeux susceptible de conduire à la formation de sous-produits, en regard des portions en question.
    • Always in order to better understand the invention:
  • i) if the length of at least one of the electrodes of the pair is adapted to the width of the substrate, this electrode will in fact be protected against deposits of by-products since it is covered with the substrate. As for the second electrode facing it:
    • it is also protected in fact if it has the same length as the first,
    • and if its length is greater, it is of course protected over the entire width of the substrate by covering, and as for its additional length relative to the first electrode, it is not affected by deposition of by-products because the absence of discharge on this excess length.
  • j) as we have seen previously, the injection length of the gases can also be adapted to the width of the substrate to be treated, the electrodes will then also be protected against the deposition of by-products whatever the dimension ratio between the electrodes and the substrate by the fact that:
    • the part of the electrodes covered by the substrate is effectively protected;
    • the portion of the electrodes which would not be covered by the substrate (due to the choice of a longer length) is also protected due to the absence of a gaseous mixture liable to lead to the formation of by-products, opposite the portions in question.

    • Dans tous les cas, les sous-produits ainsi formés sont au fur et à mesure évacués par des systèmes d'aspiration logés dans le capot et/ou par la surface du substrat en défilement, sans s'accumuler sur les'électrodes. Dans ces conditions, le système peut fonctionner de manière pratiquement continue 24 heures/24.In all cases, the by-products thus formed are progressively evacuated by suction systems housed in the hood and / or by the surface of the moving substrate, without accumulating on the electrodes. In these conditions, the system can operate almost continuously 24 hours a day.

    D'autres particularités et avantages de l'invention apparaítront au cours de la description qui va suivre, faite en référence aux dessins annexés qui en illustrent deux modes de réalisation à titre d'exemples non limitatifs.

    • La figure 1 est une vue en élévation en bout simplifiée d'une forme de réalisation du dispositif pour le traitement de surface d'un film polymère selon l'invention.
    • La figure 2 est une vue en élévation longitudinale partielle du dispositif dans un plan perpendiculaire à celui de la figure 1, certains éléments du dispositif n'étant pas représentés à des fins de simplification du dessin.
    • La figure 3 est une vue en élévation partielle à échelle agrandie de la partie inférieure du dispositif des figures 1 et 2.
    • La figure 4 est une vue en coupe partielle à échelle agrandie d'un détail de la figure 3.
    • La figure 5 est une vue de dessus simplifiée d'un second mode de réalisation des rouleaux-électrodes.
    Other features and advantages of the invention will become apparent during the description which follows, given with reference to the accompanying drawings which illustrate two embodiments thereof by way of non-limiting examples.
    • Figure 1 is a simplified end elevational view of an embodiment of the device for the surface treatment of a polymer film according to the invention.
    • Figure 2 is a partial longitudinal elevation view of the device in a plane perpendicular to that of Figure 1, some elements of the device are not shown for the sake of simplification of the drawing.
    • FIG. 3 is a partial elevation view on an enlarged scale of the lower part of the device of FIGS. 1 and 2.
    • FIG. 4 is a partial section view on an enlarged scale of a detail of FIG. 3.
    • Figure 5 is a simplified top view of a second embodiment of the electrode rollers.

    Le dispositif représenté est destiné au traitement de surface de substrats, par exemple de films polymères, par décharge électrique entre deux électrodes dans un mélange gazeux susceptible de donner lieu à la formation de sous-produits au cours du traitement, par exemple dans un mélange gazeux comportant du monosilane.The device shown is intended for the surface treatment of substrates, for example of polymer films, by electrical discharge between two electrodes in a gas mixture likely to give rise to the formation of by-products during treatment, for example in a gas mixture containing monosilane.

    Le mode de réalisation représenté ici comprend deux étages (ou zones) superposés 1, 2 de traitement de surface d'un film polymère 3, un bloc d'aspiration 4 disposé au-dessous de l'étage supérieur de traitement 2, et un second bloc 5 d'aspiration et d'évacuation des effluents gazeux résultant du traitement, disposé au-dessous du premier étage de traitement 1. The embodiment represented here comprises two stages (or zones) 1, 2 superimposed surface treatment of a polymer film 3, a block suction 4 arranged below the upper treatment stage 2, and a second block 5 for suction and evacuation of the gaseous effluents resulting from the treatment, located below the first treatment stage 1.

    L'ensemble est contenu à l'intérieur d'un capot 6, le film entrant et ressortant du système par les espaces ménagés entre le bloc d'aspiration 5 et respectivement le rouleau d'embarrement 21 et le rouleau d'embarrement 19.The assembly is contained inside a cover 6, the film entering and emerging from the system through the spaces provided between the suction unit 5 and the tying roller 21 and the tying roller 19 respectively.

    Chaque étage de traitement ou de décharge 1, 2 comprend pour le mode de réalisation représenté deux rouleaux-électrodes 9, 11 disposés parallèlement au voisinage l'un de l'autre et avec leur axe longitudinal horizontal. Ces rouleaux 9, 11 constituent donc deux électrodes, réalisées en un matériau métallique approprié. Elles peuvent être, au moins pour l'une d'entre elles, recouvertes d'un matériau diélectrique approprié. Des moyens non représentés et connus en soi sont prévus pour mettre les électrodes 9, 11 sous haute tension (plusieurs milliers de volts) afin de provoquer une décharge électrique entre elles. Aux extrémités de chaque rouleau 9, 11 sont disposés ici des vérins 12, 13 permettant d'avancer ou de reculer le rouleau associé 11, 9. Ce mode n'est qu'illustratif d'un des fonctionnements possibles du système, on pourrait en effet également fonctionner avec des rouleaux fixes.Each treatment or discharge stage 1, 2 includes for the mode embodiment shown two electrode rollers 9, 11 arranged parallel to each other and with their longitudinal axis horizontal. These rollers 9, 11 therefore constitute two electrodes, produced in an appropriate metallic material. They can be, at least for one of them, covered with a suitable dielectric material. Means not shown and known per se are provided for placing the electrodes 9, 11 under high voltage (several thousand volts) to cause a discharge electric between them. At the ends of each roller 9, 11 are arranged here jacks 12, 13 allowing the associated roller 11, 9 to be moved forward or backward. This mode is only illustrative of one of the possible functioning of the system, we could indeed also work with fixed rollers.

    Au-dessus de chaque paire de rouleaux-électrodes 9, 11 et dans un plan vertical passant entre ceux-ci, est positionné un injecteur 14 d'un mélange gazeux provenant d'une chambre de gaz 15 placée au-dessus de l'injecteur 14 (référencé 32 sur la figure 2), lequel ainsi que la chambre associée 15 s'étendent préférentiellement sur toute la longueur des rouleaux respectifs 9, 11.Above each pair of roller electrodes 9, 11 and in a plane vertical passing between them, is positioned an injector 14 of a mixture gas from a gas chamber 15 placed above the injector 14 (referenced 32 in FIG. 2), which as well as the associated chamber 15 preferably extend over the entire length of the respective rollers 9, 11.

    Les rouleaux 9, 11 sont supportés à leurs extrémités par les parois latérales opposées 16, 17 du capot 6 et peuvent être entraínés en rotation par le film 3 lui-même entraíné par un système de motorisation non représenté.The rollers 9, 11 are supported at their ends by the walls opposite sides 16, 17 of the cover 6 and can be rotated by the film 3 itself driven by a not shown motorization system.

    A titre illustratif il convient de signaler que l'on peut aussi bien fonctionner avec des rouleaux-électrodes entraínés par un moteur ou tout simplement par le film lui-même (selon le film considéré et ses caractéristiques de résistance mécanique).By way of illustration, it should be noted that one can also work well with electrode rollers driven by a motor or simply by the film itself (depending on the film considered and its resistance characteristics mechanical).

    Au-dessous du premier étage de traitement 1 sont ici disposés deux rouleaux d'embarrement 19, 21. Une seconde paire de rouleaux d'embarrement 22, 23 est disposée au-dessus de la première zone de décharge 1, et enfin deux rouleaux d'embarrement 24, 25 sont montés au-dessus des rouleaux-électrodes 9, 11 de la seconde zone de décharge 2.Below the first treatment stage 1 are arranged here two tying rollers 19, 21. A second pair of tying rollers 22, 23 is arranged above the first discharge zone 1, and finally two interlocking rollers 24, 25 are mounted above the electrode rollers 9, 11 of the second discharge zone 2.

    Chaque rouleau d'embarrement (19, 21, 22, 23.) est ici entraíné par un moteur (non représenté), afin de faciliter le défilement du film 3. Ici encore, les rouleaux d'embarrement pourraient être entraínés par le film lui-même dans certains cas. Each tying roller (19, 21, 22, 23.) is here driven by a motor (not shown), in order to facilitate the movement of the film 3. Here again, the tying rollers could be driven by the film itself in certain cases.

    Comme visible à la figure 1, le film 3 pénètre dans le capot 6 par la fente formée entre le rouleau 21 et le bloc 44 qui sera décrit plus loin, puis vient s'appliquer sur le premier rouleau d'embarrement 21, passe ensuite entre les deux électrodes 9, 11 du premier étage de décharge 1, de là le film 3 défile sur le rouleau d'embarrement 23, situé au-dessus de l'étage de décharge 1, vient ensuite s'appliquer sur le rouleau-électrode 9 de l'étage supérieur 2, puis sur le rouleau d'embarrement supérieur 25. Le film est ensuite renvoyé par le rouleau d'embarrement 24 vers le rouleau électrode 11, puis vient s'appliquer sur le rouleau d'embarrement 22 d'où il est renvoyé sur le rouleau-électrode 11 du premier étage. Après quoi le film est évacué par la fente de sortie formée entre le rouleau d'embarrement inférieur 19 et le bloc d'aspiration 44.As shown in Figure 1, the film 3 enters the cover 6 through the slot formed between the roller 21 and the block 44 which will be described later, then comes apply to the first tying roller 21, then passes between the two electrodes 9, 11 of the first discharge stage 1, from there the film 3 passes over the interlocking roller 23, located above the discharge stage 1, comes then apply to the roller electrode 9 of the upper stage 2, then to the upper tying roller 25. The film is then returned by the roller 24 to the electrode roller 11, then is applied to the interlocking roller 22 from which it is returned to the electrode roller 11 of the first floor. After which the film is discharged through the exit slot formed between the lower feed roller 19 and the suction block 44.

    Ainsi, dans ce mode de réalisation comportant deux zones ou étages de décharge 1, 2, le film 3 subit quatre phases consécutives de traitement par décharge électrique, par exemple par décharge corona. entre les électrodes 9, 11 des deux étages.Thus, in this embodiment comprising two zones or stages of discharge 1, 2, the film 3 undergoes four consecutive phases of treatment by electrical discharge, for example by corona discharge. between the electrodes 9, 11 of the two floors.

    Toutefois on comprendra qu'il n'est bien sûr pas indispensable que le dispositif comporte deux étages de décharge 1, 2, un seul étage 1 pouvant suffire pour bon nombre d'applications. Dans une telle version simplifiée à un étage, le film 3 passe directement du rouleau d'embarrement 23 sur le rouleau d'embarrement 22 avant d'être renvoyé dans l'espace inter-électrodes où il y subit un second traitement de surface avant de ressortir du capot par le rouleau d'embarrement 19.However it will be understood that it is of course not essential that the device comprises two discharge stages 1, 2, a single stage 1 being able sufficient for many applications. In such a simplified version at a stage, the film 3 passes directly from the interlocking roller 23 onto the roller 22 before being returned to the inter-electrode space where there undergoes a second surface treatment before emerging from the cover by the tether roller 19.

    Chaque chambre 15 est alimentée en mélange gazeux à au moins l'une de ses extrémités par une canalisation traversant la paroi du capot 6. De ce compartiment le mélange gazeux pénètre dans la buse d'injection 14 s'étendant ici de manière continue d'une extrémité à l'autre de la chambre de gaz 15 et des rouleaux-électrodes. La buse 14 peut être fixée sous la chambre 15 par tout moyen approprié connu de l'homme du métier.Each chamber 15 is supplied with a gas mixture with at least one from its ends by a pipe crossing the wall of the cover 6. From this compartment the gas mixture enters the injection nozzle 14 extending here continuously from one end to the other of the gas 15 and roller electrodes. The nozzle 14 can be fixed under the chamber 15 by any suitable means known to those skilled in the art.

    En outre, la buse d'injection gazeuse est ici pourvue, de façon tout à fait avantageuse de moyens permettant d'occulter une partie de la longueur de cette buse, afin de limiter la longueur sur laquelle est injecté le mélange gazeux. En effet, il est alors possible d'adapter cette longueur d'injection gazeuse à la largeur du film 3 à traiter, lorsque cette largeur est inférieure à la longueur du rouleau-électrode 9. Ainsi on voit aux figures 2 et 5 un rouleau 11a constituant un rouleau électrode soutenu par un axe longitudinal 34 dont les extrémités sont supportées par les parois latérales 16, 17 du capot 6, la longueur du rouleau 11a étant alors égale à la largeur du film 3 à traiter. In addition, the gas injection nozzle is here provided, so completely advantageous means making it possible to conceal part of the length of this nozzle, in order to limit the length over which the mixture is injected gaseous. Indeed, it is then possible to adapt this injection length gaseous to the width of the film 3 to be treated, when this width is less than the length of the electrode roller 9. Thus we see in Figures 2 and 5 a roller 11a constituting an electrode roller supported by a longitudinal axis 34 whose ends are supported by the side walls 16, 17 of the cover 6, the length of the roller 11a then being equal to the width of the film 3 to be treated.

    Afin d'adapter la longueur d'injection effective du gaz à la largeur du film 3, les moyens précités peuvent comprendre par exemple comme c'est le cas ici des volets 36 articulés sur la buse 32, munis chacun d'une extrémité recourbée pour obturer la fente d'injection de la buse 32, et de crochets 38 de manoeuvre. Les extrémités supérieures de ces derniers peuvent être accrochées sur une pièce de retenue.In order to adapt the effective gas injection length to the width of the film 3, the aforementioned means may include for example as is the case here flaps 36 articulated on the nozzle 32, each provided with a curved end to close the injection slot of the nozzle 32, and of hooks 38 for maneuvering. The upper ends of these can be hung on a retainer.

    Plusieurs volets 36 peuvent ainsi être échelonnés le long de l'injecteur 32, afin de régler sa longueur d'injection effective.Several flaps 36 can thus be staggered along the injector 32, in order to adjust its effective injection length.

    Le dispositif de traitement est enfin muni, à sa partie inférieure au-dessous des rouleaux d'embarrement 19, 21, d'une unité 42 (figures 1 et 3) d'aspiration des effluents gazeux issus des décharges électriques, ainsi que de l'air entraíné à la surface du film 3 dans son déplacement. L'unité d'aspiration 42 comprend, associés à chaque rouleau 19/21, un bloc 43 et un bloc intermédiaire 44 interposé entre le bloc 43 et le rouleau (19, 21). Chaque bloc intermédiaire 44 présente une face inférieure 45 d'appui,sur l'extrémité du bloc 43 et qui peut être plane, et une face supérieure 46 concave, formant une portion cylindrique conjuguée de la surface cylindrique du rouleau associé (19, 21). Entre la surface du rouleau 19, 21 et la surface cylindrique 46, il est prévu un écartement approprié e (figure 5), dans lequel passe le film 3 maintenu appliqué sur la surface du rouleau respectif 19, 21.The treatment device is finally provided, at its lower part below interlock rollers 19, 21, of a unit 42 (Figures 1 and 3) suction of gaseous effluents from electrical discharges, as well as the air entrained on the surface of the film 3 in its movement. The suction unit 42 includes, associated with each roller 19/21, a block 43 and a block intermediate 44 interposed between the block 43 and the roller (19, 21). Each block intermediate 44 has a lower face 45 of support, on the end of the block 43 and which may be flat, and a concave upper face 46, forming a cylindrical conjugate portion of the cylindrical surface of the associated roller (19, 21). Between the surface of the roller 19, 21 and the cylindrical surface 46, there is provided an appropriate spacing e (Figure 5), through which the film 3 maintained applied to the surface of the respective roller 19, 21.

    Dans chaque bloc 44 est ménagée une fente respective 47, 48 d'aspiration des effluents gazeux résultant du traitement et de l'air entraíné par le film dans son défilement, cette fente 47, 48 débouchant dans le bloc 43. Les deux fentes 47, 48 sont respectivement placées en vis-à-vis des rouleaux 21 et 19.In each block 44 is provided a respective slot 47, 48 suction of the gaseous effluents resulting from the treatment and the air entrained by the film in its running, this slot 47, 48 opening into the block 43. The two slots 47, 48 are respectively placed opposite the rollers 21 and 19.

    Il est ainsi possible d'aspirer l'air et les effluents gazeux, dans le bloc 43, relié à des turbines d'aspiration d'évacuation non représentées.It is thus possible to suck in air and gaseous effluents, in block 43, connected to exhaust suction turbines not shown.

    Pour ce qui est des moyens d'injection du mélange gazeux, on s'attachera préférentiellement à rechercher l'obtention d'une diffusion homogène du mélange gazeux sur toute la longueur de l'injecteur, par exemple par la réalisation d'une perte de charge entre la chambre et la buse, par exemple par l'utilisation d'un poreux ou d'une toile adaptée.Regarding the means of injection of the gas mixture, we will focus preferentially to seek the obtaining of a homogeneous diffusion of the gas mixture over the entire length of the injector, for example by the pressure drop between the chamber and the nozzle, for example by the use of a porous or suitable canvas.

    Quoique la présente invention ait été décrite en relation avec des modes de réalisations particuliers, elle ne s'en trouve pas limitée pour autant mais est au contraire susceptible de modifications et de variantes qui apparaítront à l'homme de l'art.Although the present invention has been described in relation to modes particular achievements, it is not limited thereby but is on the contrary susceptible to modifications and variants which will appear in one skilled in the art.

    Ainsi par exemple, si la figure 1 décrit, pour des raisons de facilité de visualisation et de lecture, tout particulièrement une disposition verticale des zones de décharge et donc du déplacement du film dans l'espace, on conçoit que tout autre type de disposition des zones de décharge soit envisageable (verticale, horizontale, mixte) le tout étant de prévoir les rouleaux d'embarrement nécessaires pour amener le substrat à traitement dans la ou les zones de décharges et donc en particulier pour le transporter entre chaque zone de décharge quand le dispositif en comprend plusieurs.So for example, if Figure 1 describes, for reasons of ease of viewing and reading, especially a vertical arrangement of discharge zones and therefore of the displacement of the film in space, we conceive that any other type of arrangement of the discharge areas is possible (vertical, horizontal, mixed) the whole being to provide the rollers of embarrassment necessary to bring the substrate to treatment in the one or more discharge areas and therefore in particular to transport it between each discharge zone when the device comprises several.

    De même, si l'on n'a pas décrit en détail dans ce qui précède les opérations à effectuer entre deux traitements, on conçoit par exemple qu'il est avantageux, avant d'ouvrir la structure de capots précédemment décrite, et selon la nature de l'atmosphère qui a été utilisée pour le traitement, d'en effectuer une purge à l'aide d'un gaz inerte, la combinaison purge/aspiration assurant comme c'est le cas traditionnellement les conditions de sécurité habituellement recommandées.Similarly, if we have not described in detail in the above the operations to be performed between two treatments, it can for example be understood that it is advantageous, before opening the hood structure described above, and depending on the nature of the atmosphere that was used for the treatment, purge using an inert gas, the purge / suction combination ensuring, as is traditionally the case, the security conditions usually recommended.

    Claims (16)

    1. Process for the surface treatment of a running substrate (3) by an electrical discharge created between two electrodes in a gas mixture, liable to generate by-products which can be deposited on the electrodes, in which one (9) of the electrodes is a roller against which the substrate may be applied, characterized in that at least one stage (1) for treating the substrate (3) at a pressure equal to atmospheric pressure or close to atmospheric pressure is used, means being provided for injecting the gas mixture between the electrodes, each stage (1, 2) comprising at least one pair of roller electrodes (9, 11), and an injector (32) for injecting the gas mixture between the rollers and in that the treatment of the substrate is carried out in the following manner: the substrate is made to pass in succession a first time between the two roller electrodes, by applying it against a first roller electrode of the pair, where it undergoes a first surface treatment, and then a second time between the two roller electrodes, by applying it against the second roller electrode of the pair, where it undergoes a second surface treatment.
    2. Process according to Claim 1, characterized in that the width of the substrate to be treated is at least equal to the length of the interelectrode space where the combination of the presence of an electrical discharge and the presence of the said gas mixture liable to generate by-products is observed.
    3. Process according to Claim 1 or 2, characterized in that deflector rolls (19, 21, 22, 23) are used, the number of deflector rolls used being at least sufficient to allow the said first and second surface treatments to be carried out in the following manner:
      the substrate is applied against a first deflector roll (21) of a first pair of deflector rolls (19, 21) and then passes between the two roller electrodes (9, 11) by being applied against a first roller electrode (9) of the said pair, where it undergoes the said first surface treatment;
      next, the substrate is applied against a first deflector roll (23) of a second pair of deflector rolls (22, 23) before being applied against the second deflector roll (22) of the second pair of deflector rolls (22, 23);
      the substrate then passes again between the two roller electrodes (9, 11) by being applied against the second roller electrode (11) of the said pair, where it undergoes the said second surface treatment, before being applied against the second deflector roll (19) of the first pair of deflector rolls (19, 21).
    4. Process according to one of the preceding claims, characterized in that two stages (1, 2) for treating the substrate (3) are used and in that two additional surface treatments of the substrate are carried out, between the said first surface treatment of the substrate and the said second surface treatment of the substrate, in the second treatment stage (2) in the following manner:
      after having undergone the said first surface treatment and before undergoing the said second surface treatment, the substrate is made to pass a first time between the two roller electrodes (9, 11) of the second stage, by applying it against a first roller electrode (9) of the second stage, where it undergoes a first additional surface treatment;
      subsequently, the substrate is made to pass a second time between the two roller electrodes (9, 11) of the second stage, by applying it against the second roller electrode (11) of the second stage, where it undergoes a second additional surface treatment.
    5. Process according to one of the preceding claims, characterized in that the length of at least one of the electrodes of the said at least one pair is tailored to the width of the substrate to be treated.
    6. Process according to one of the preceding claims, characterized in that the gas mixture is injected between the two roller electrodes of the said at least one pair, over an injection length substantially equal to the width of the substrate to be treated.
    7. Device for the surface treatment of a running substrate (3) by an electrical discharge created between two electrodes in a gas mixture liable to generate by-products which can be deposited on the electrodes, in which device one (9) of the electrodes is a roller against which the substrate may be applied, means being provided for injecting the gas mixture between the electrodes, characterized in that the second electrode is a roller (11) against which the running substrate may also be applied, which roller (11) is arranged so as to be parallel to the other roller (9), with a suitable gap, by the fact that the device comprises means (19, 21, 22, 23) capable of making the substrate pass a first time between the two roller electrodes (9, 11), by applying it against a first roller electrode (9), where it may undergo a first surface treatment, and in subsequently making the substrate pass a second time between the two roller electrodes (9, 11), by applying it against the second roller electrode (11), where it may undergo a second surface treatment.
    8. Device according to Claim 7, characterized in that it comprises a cover (6) comprising at least one stage (1) for treating the substrate (3), each stage (1, 2) comprising a pair of roller electrodes (9, 11), and means (32) for injecting a gas mixture between the roller electrodes.
    9. Device according to Claim 7 or 8, characterized in that it comprises at least two pairs of deflector rolls (19, 21, 22, 23), the number of pairs of deflector rolls of the device being at least sufficient to allow there to be one pair of deflector rolls on either side of each pair of roller electrodes.
    10. Device according to one of Claims 7 to 9, characterized in that the means for injecting the gas mixture comprise, for each pair of roller electrodes (9, 11), a gas injection nozzle (32) extending continuously from one end of at least one (9) of the associated roller electrodes (9, 11) to the other.
    11. Device according to Claim 10, characterized in that the gas injection nozzle (32) is provided with means for occluding part of the length of the said nozzle so as to be able to limit the length over which the gas mixture is injected and thus allow, if required, this length to be able to be tailored to that of one or other of the electrodes.
    12. Device according to Claim 11, characterized in that the said occluding means comprise slats (36) hinged laterally to the nozzle (32), each being provided with a curved end suitable for closing off the injection slot of the nozzle and with operating means, such as hooks.
    13. Device according to one of Claims 7 to 12, characterized in that the length of at least one of the electrodes of the or each pair is equal to the width of the substrate to be treated.
    14. Device according to any one of claims 7 to 13, characterized in that it includes a suction unit (42) for sucking out the gaseous effluents arising from the electrical discharge and for sucking out the air entrained by the substrate due to its running movement.
    15. Device according to Claim 14, characterized in that the suction unit is placed under a pair of deflector rolls (19, 21) placed beneath the roller electrodes (9, 11).
    16. Device according to Claim 15, characterized in that the suction unit (42) comprises, associated with each deflector roll (19, 21) of the said pair, a system which includes a suction assembly (43) and an intermediate assembly (44) interposed between this suction assembly and the deflector roll in question and which has a concave surface (46) conjugate with the cylindrical surface of the deflector roll (19, 21), there being a suitable gap (e) between these surfaces, and in that, provided in each assembly (44), there is a slot (47, 48) for sucking out the gaseous atmosphere flowing between the roll and the surface of the intermediate assembly, this slot emerging in the suction assembly (43).
    EP98402730A 1997-11-05 1998-11-02 Process and apparatus for treating the surface of a substrate with an electrical discharge between two electrodes in a gas mixture Expired - Lifetime EP0914876B1 (en)

    Applications Claiming Priority (2)

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    FR9713910 1997-11-05
    FR9713910A FR2770425B1 (en) 1997-11-05 1997-11-05 METHOD AND DEVICE FOR THE SURFACE TREATMENT OF A SUBSTRATE BY ELECTRIC SHOCK BETWEEN TWO ELECTRODES IN A GAS MIXTURE

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    EP0914876A1 EP0914876A1 (en) 1999-05-12
    EP0914876B1 true EP0914876B1 (en) 2001-10-10

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    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE102009006484A1 (en) 2009-01-28 2010-07-29 Ahlbrandt System Gmbh Device for modifying the surfaces of sheet, plate and sheet goods with a device for generating a plasma
    DE102009048824A1 (en) 2009-10-09 2011-04-28 Linde Ag Radiation curing device for workpieces in automobile industry, has flow mechanism arranged in line such that gas in cycle is led in section of pipe, where cycle is connected with supply mechanism, so that inert gas is formed in cycle

    Families Citing this family (14)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    KR20010088089A (en) * 2000-03-10 2001-09-26 구자홍 Method of improving hydrophile in plasma polymerization system
    US8948059B2 (en) 2000-12-26 2015-02-03 Polycom, Inc. Conference endpoint controlling audio volume of a remote device
    US7864938B2 (en) * 2000-12-26 2011-01-04 Polycom, Inc. Speakerphone transmitting URL information to a remote device
    US9001702B2 (en) * 2000-12-26 2015-04-07 Polycom, Inc. Speakerphone using a secure audio connection to initiate a second secure connection
    US8976712B2 (en) * 2001-05-10 2015-03-10 Polycom, Inc. Speakerphone and conference bridge which request and perform polling operations
    US8705719B2 (en) 2001-12-31 2014-04-22 Polycom, Inc. Speakerphone and conference bridge which receive and provide participant monitoring information
    US7787605B2 (en) 2001-12-31 2010-08-31 Polycom, Inc. Conference bridge which decodes and responds to control information embedded in audio information
    US8126029B2 (en) * 2005-06-08 2012-02-28 Polycom, Inc. Voice interference correction for mixed voice and spread spectrum data signaling
    DE102005029360B4 (en) * 2005-06-24 2011-11-10 Softal Corona & Plasma Gmbh Two methods for continuous atmospheric pressure Plasma treatment of workpieces, in particular material plates or sheets
    US7666766B2 (en) * 2005-09-27 2010-02-23 Semiconductor Energy Laboratory Co., Ltd. Film formation apparatus, method for forming film, and method for manufacturing photoelectric conversion device
    JP5649510B2 (en) * 2010-08-19 2015-01-07 キヤノンアネルバ株式会社 Plasma processing apparatus, film forming method, method for manufacturing metal plate having DLC film, method for manufacturing separator
    CN104870103A (en) * 2012-12-20 2015-08-26 帝人芳纶有限公司 Vibrational spreader bar for spreading unidirectional yarns
    CN104210227B (en) * 2013-06-05 2017-12-08 广东隆兴包装实业有限公司 The corona unit of plane stamp cover machine
    JP6183870B1 (en) * 2016-05-31 2017-08-23 春日電機株式会社 Surface reformer

    Family Cites Families (25)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE1100939B (en) * 1956-11-02 1961-03-02 Siemens Ag Device for the surface treatment of thermoplastic material webs
    US3068510A (en) * 1959-12-14 1962-12-18 Radiation Res Corp Polymerizing method and apparatus
    DE1571132A1 (en) * 1962-11-07 1970-04-02 Radiation Res Corp Method and device for the production of a polymerized coating
    GB1100414A (en) * 1964-05-19 1968-01-24 Ici Ltd Treatment of plastics surfaces with an electrical discharge to improve their bonding properties
    US3443980A (en) * 1966-04-15 1969-05-13 Du Pont Process of producing laminar film structures
    US3482092A (en) * 1967-04-27 1969-12-02 Du Pont Rotating turret electrode holder
    DE1753895A1 (en) * 1968-06-07 1976-09-23 Klaus Kalwar METHOD AND EQUIPMENT FOR ELECTRIC TREATMENT OF THE EXTERNAL SURFACE OF A TUBE FILM
    DE1779400C3 (en) * 1968-08-07 1978-04-13 Klaus 4803 Steinhagen Kalwar Electrode arrangement for multi-sided electrical pretreatment of foil webs
    US3674667A (en) * 1969-07-23 1972-07-04 Allis Chalmers Mfg Co Process for increasing water repellency of cotton cloth
    US3730753A (en) * 1971-07-30 1973-05-01 Eastman Kodak Co Method for treating a web
    US3959104A (en) * 1974-09-30 1976-05-25 Surface Activation Corporation Electrode structure for generating electrical discharge plasma
    DE3115958C2 (en) * 1981-04-22 1983-12-29 Hahne, Ernst August, 4123 Allschwill "Process for moistening a flexible, web-shaped carrier material provided with a coating that has solidified by drying
    JPS57187328A (en) * 1981-05-13 1982-11-18 Toray Ind Inc Surface treatment of plastic film
    US4466258A (en) * 1982-01-06 1984-08-21 Sando Iron Works Co., Ltd. Apparatus for low-temperature plasma treatment of a textile product
    US4457145A (en) * 1983-03-29 1984-07-03 Sando Iron Works Co., Ltd. Apparatus for treating a textile product continuously with the use of low-temperature plasma
    US4529664A (en) * 1983-09-20 1985-07-16 Bethlehem Steel Corporation Method of producing improved metal-filled organic coatings and product thereof
    DE8327709U1 (en) * 1983-09-27 1984-01-05 Kroos, Liselotte, 8135 Söcking Device for processing film-like layers by means of a spark discharge
    US4678681A (en) * 1984-10-05 1987-07-07 Hiraoka & Co. Ltd. Process for preparation of water-proof sheets
    AT402486B (en) * 1988-11-17 1997-05-26 Gunze Kk METHOD AND DEVICE FOR TREATING THE CORONA DISCHARGE OF A MULTI-LAYER TUBE FILM
    US5053246A (en) * 1990-03-30 1991-10-01 The Goodyear Tire & Rubber Company Process for the surface treatment of polymers for reinforcement-to-rubber adhesion
    US5629054A (en) * 1990-11-20 1997-05-13 Canon Kabushiki Kaisha Method for continuously forming a functional deposit film of large area by micro-wave plasma CVD method
    DE4117332C2 (en) * 1991-05-31 1995-11-23 Ivanovskij Ni Skij Eksperiment Process for treating moving substrate using an electrical discharge plasma and device for carrying it out
    FR2703073B1 (en) * 1993-03-26 1995-05-05 Lorraine Laminage Process and device for the continuous coating of a metallic material in movement by a deposit of polymer with a composition gradient, and product obtained by this process.
    FR2704558B1 (en) 1993-04-29 1995-06-23 Air Liquide METHOD AND DEVICE FOR CREATING A DEPOSIT OF SILICON OXIDE ON A SOLID TRAVELING SUBSTRATE.
    US5792517A (en) * 1996-04-25 1998-08-11 Japan Vilene Company Process for treating the outer-inner surfaces of a porous non-conductor

    Cited By (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE102009006484A1 (en) 2009-01-28 2010-07-29 Ahlbrandt System Gmbh Device for modifying the surfaces of sheet, plate and sheet goods with a device for generating a plasma
    WO2010085941A2 (en) 2009-01-28 2010-08-05 Ahlbrandt System Gmbh Apparatus for modifying the surfaces of web, plate and sheet products using a device for generating plasma
    DE102009048824A1 (en) 2009-10-09 2011-04-28 Linde Ag Radiation curing device for workpieces in automobile industry, has flow mechanism arranged in line such that gas in cycle is led in section of pipe, where cycle is connected with supply mechanism, so that inert gas is formed in cycle

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    ZA9810064B (en) 1999-05-04
    US6312767B2 (en) 2001-11-06
    US20010002288A1 (en) 2001-05-31
    CN1216729A (en) 1999-05-19
    TW425312B (en) 2001-03-11
    DE69801972D1 (en) 2001-11-15
    AU730583B2 (en) 2001-03-08
    AU8956398A (en) 2000-06-08
    FR2770425B1 (en) 1999-12-17
    KR19990044989A (en) 1999-06-25
    EP0914876A1 (en) 1999-05-12
    ATE206642T1 (en) 2001-10-15
    BR9804566A (en) 1999-12-14
    JPH11221519A (en) 1999-08-17
    AR017567A1 (en) 2001-09-12
    CA2253082A1 (en) 1999-05-05
    NZ332508A (en) 2000-04-28
    DE69801972T2 (en) 2002-04-11
    FR2770425A1 (en) 1999-05-07

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