EP1755804B1 - Method for making decorated bottle caps with improved mechanical strength and device for implementing said method - Google Patents
Method for making decorated bottle caps with improved mechanical strength and device for implementing said method Download PDFInfo
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- EP1755804B1 EP1755804B1 EP05763703A EP05763703A EP1755804B1 EP 1755804 B1 EP1755804 B1 EP 1755804B1 EP 05763703 A EP05763703 A EP 05763703A EP 05763703 A EP05763703 A EP 05763703A EP 1755804 B1 EP1755804 B1 EP 1755804B1
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- European Patent Office
- Prior art keywords
- typically
- blank
- treatment
- blanks
- skirt
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D51/00—Making hollow objects
- B21D51/16—Making hollow objects characterised by the use of the objects
- B21D51/38—Making inlet or outlet arrangements of cans, tins, baths, bottles, or other vessels; Making can ends; Making closures
- B21D51/44—Making closures, e.g. caps
- B21D51/50—Making screw caps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D51/00—Making hollow objects
- B21D51/16—Making hollow objects characterised by the use of the objects
- B21D51/38—Making inlet or outlet arrangements of cans, tins, baths, bottles, or other vessels; Making can ends; Making closures
- B21D51/44—Making closures, e.g. caps
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49826—Assembling or joining
- Y10T29/49885—Assembling or joining with coating before or during assembling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49826—Assembling or joining
- Y10T29/49906—Metal deforming with nonmetallic bonding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4998—Combined manufacture including applying or shaping of fluent material
Definitions
- the invention relates to the field of closure capsules or overcap capsules, and typically metal capsules based on aluminum or tin.
- the invention relates more particularly to a method of manufacturing these capsules, according to the preamble of claim 1.
- the invention aims to solve both problems simultaneously.
- said treatment is carried out at ambient temperature, which is extremely advantageous both with regard to energy savings and with regard to the disadvantages of softening the metal, and other on the other hand, it is produced in masked time insofar as it can be implemented while being associated with all or part of a decoration step, and this without slowing down the rate of said decorating step, so that said step of degreasing is not in itself a step, so it is a very economical implementation operation.
- said energy radiation treatment may be a treatment comprising the formation of a plasma or an ionic or electronic efflux.
- Said treatment may be a treatment typically using a high electric field, typically at least 5 kV, and a high frequency current, typically at least 10 kHz.
- said treatment can be carried out using two bars or electrodes (40) for transmitting said corona, a lateral electrode (40 "), typically parallel to said skirt (12), for reaching and treating said skirt (12) ), and a front electrode (40 '), substantially perpendicular to said lateral electrode (40 ") and parallel to said head (11), for reaching and treating said head (11).
- said electrodes (40, 40 ', 40 ") may comprise an electrically conductive metallic core (41) covered with a dielectric ceramic layer (42).
- this type of electrode (40) is particularly adapted to treat the outer metal surface of the stamped blanks (1), to remove its residues of shaping lubricant, and then to allow the attachment of a lacquer.
- the Applicant has been able to observe that the treatment according to the invention, both under high voltage and at a high frequency, carried out at ambient temperature and at ambient air, was both economical with the low energy consumed, the installed power being about 500 W, reliable, not very dangerous in its implementation, and not very aggressive for the metal because, with the electrodes used, the emitted discharge is regularly distributed over the whole length of the electrode in view of the capsule (1), so that there is no risk of "breakdown" with a point of passage of a localized current that could punctually damage said blank (1).
- said treatment can be performed by virtue of a potential difference between said electrodes (40, 40 ', 40 ") and said stamped blank (1), typically ranging from 10 at 30 kV, so as to form said high electric field, said electrodes (40, 40 ', 40 ") being brought to a potential of 10-30 kV and said blank (1) being grounded or at a zero potential, said potential difference serving to regulate said intensity of said treatment, said electrodes (40, 40 ', 40 ") being at a distance d from the surfaces of said blank (1) to be treated less than 4 mm.
- said lateral electrode (40 ") may be arranged parallel to a generatrix of said skirt (12), so that, by rotation of said blank (1), all of said skirt (12) is subjected to energy radiation emitted by said lateral electrode (40 "), in a constant manner over the entire height of said skirt (12).
- Said rotation of said blank (1) can extend over 1 to 2 turns, for a time at most equal to 1 second, said blank rotating on itself, having been placed on an arm or stud (52 ', 53' ) rotating on itself along an axis of rotation (520, 530).
- said treatment can also be a so-called "cold” plasma treatment, typically carried out at atmospheric pressure.
- the treatment can be carried out at ambient temperature, typically on the run, and without requiring a particular gaseous atmosphere, so as to limit investment costs and operating costs.
- Said lubricant may comprise a volatile organic solvent and a lubricating compound capable of rapidly degrading under the action of said treatment.
- Said compound may be a paraffin oil.
- said lacquering step may comprise a so-called spraying step in which the entire outside surface of said defatted blank is typically covered with a lacquer by spraying or spray application, so as to form a lacquered blank (3) .
- Said spraying step may be followed by a first so-called “dust-off” drying, at a temperature below 100 ° C., and typically at a temperature of 80 ° C, for a time typically less than 2 minutes, so that said lacquered blank (3) can then be directly decorated or printed.
- said lacquered blank (3) can be printed, typically by screen printing but possibly by offset or flexography, on its skirt (12) and possibly on the head (11), then subjected to a second drying, typically at a temperature of 140 ° C, for a time typically less than four minutes, so as to obtain a printed capsule.
- a raised pattern can be formed on said head (11) of said blank (1, 2, 3) or said printed capsule, said relief pattern being typically formed in using a punch and die set bearing said pattern.
- Said strip or format metal may be aluminum, typically of the 8000 series, in a state typically ranging from the 1/4 hard state to a 3/4 hard state, and at a thickness of 0 , 18 mm to 0.30 mm, and preferably from 0.21 mm to 0.25 mm.
- said electrode (40, 40 ', 40 ") may be a cylindrical electrode with an outside diameter typically ranging from 15 mm to 20 mm, and length ranging from 100 to 150 mm, with a metal core (41) of length from 50 to 90 mm, said electrode (40, 40 ', 40 ") comprising an outer sheath or layer of dielectric ceramic (42) having a thickness of 0.5 to 3 mm.
- said electrode (40, 40 ', 40 ") can be placed at said distance d from said blank (1), that is to say, either of said head (11), or of a generatrix of said skirt (12), said distance d ranging from 0.2 to 4 mm, and typically from 1 mm to 2 mm
- d 1.5 mm.
- Another object of the invention is formed by capping capsules formed by the process according to the invention.
- Another object of the invention is formed by overcap capsules formed by the process according to the invention.
- Another object of the invention is constituted by a use of the method according to the invention for forming capping capsules or overcaping capsules, according to claim 21.
- Another object of the invention is formed by a device (5) for implementing, continuously, the degreasing process of blanks (1) which is implemented in the method of the invention.
- Said degreasing station may comprise two treatment stations, a first station (51) for treating said head (11) of said preform (1) to be degreased (1) and a second station (52) for treating said skirt (12). ) with typically a separate treatment of said head (11) and said skirt (12) of said blank (1) to degrease (1).
- Said plurality of stations or stations further comprises, after said degreasing station or said degreasing stations, a lacquering station (54) and a drying station (55).
- the continuous treatment device (5) has been developed in accordance with Figures 1a and 1b .
- this device was fed, at the station (51), blanks (1) such as outputs of the stamping press.
- blanks (1) were formed from aluminum strip varnished on both sides, the stamping having been made with a lubricant forming a solution of a mineral oil in an alcoholic medium.
- the degreasing treatment was carried out either with STT (type SG2) fixed frequency (40 kHz) and variable power from 0 to 715 W, or with a Softal (type 3003) device with a variable frequency between 16 kHz and 40 kHz, and 4 power positions (366 W, 426 W, 493 W and 500W).
- the STT device was used at 50% of its power, ie 350W, while the Softal device was used with a power of 500 W.
- An electrode (40, 40 ', 40 ") with a useful length of 70 mm was used as shown in FIG. figure 1b .
- the degreasing device (4) comprises, as illustrated in the figure 1a a high-voltage, high-frequency current generator (44), a fixed support (45) for the electrodes (40), and the electrodes (40 ', 40 ") arranged in such a way that at every fraction of a turn or not the turntable (50), a blank (1) is positioned at the distance d of the electrodes.
- the degreasing treatment time was 0.55 seconds, the blank (1) making from 1 to 2 turns on itself.
- the distance d was set at 1.5 mm.
- a plasma (58) is formed on the surface of the blank (1) to be treated, at room temperature and ambient air. Such a plasma can be observed visually laterally by the presence of a light emission forming a homogeneous blue layer covering the treated metal surface.
- the blanks (1) are placed on studs (51 ', 52', 53 ', 54', 55 ', 56') rotating on themselves at certain stations (52, 53, 54, 55) around axis rotation (520, 530, 540, 550).
- the blanks Downstream of this device (5), the blanks have also been subjected to different types of finishing: formation of a relief, typically on the head (11), but possibly on the skirt (12) of the blank (2, 3) or the final capsule, or formation of means for facilitating a first opening, means comprising at least one weakening line.
- This device (6) has been used to manufacture caps and caps closure caps closure caps having a seal or a threaded insert.
- the surface tension was measured and observed that it ranged from 34 dynes / cm to 36 dynes / cm, the starting blanks (1) having a surface tension ranging from 30 to 32 dynes / cm.
- Lacquered blanks (3) were subjected to abrasion tests and tear-off tests on adhesive tape.
- the invention has great advantages.
- the method according to the invention avoids expensive treatments in investment and operating costs, particularly with regard to the energy consumed.
- this process avoids any softening of the metal constituting the initial metal blank and any loss of its mechanical characteristics.
- the invention makes it possible to avoid bulky equipment, so that the treatment according to the invention corresponds to both an investment cost, and to a minimal occupied volume, which makes it possible to have a very large production workshop. compact, besides said processing can be performed in masked time and continuously, so that it does not introduce specific production costs, the cost of energy consumed being negligible.
Abstract
Description
L'invention concerne le domaine des capsules de bouchage ou des capsules de surbouchage, et typiquement des capsules métalliques à base d'aluminium ou d'étain.The invention relates to the field of closure capsules or overcap capsules, and typically metal capsules based on aluminum or tin.
L'invention concerne plus particulièrement un procédé de fabrication de ces capsules, selon le préambule de la revendication 1.The invention relates more particularly to a method of manufacturing these capsules, according to the preamble of
Un procédé avec les étapes (a), (b) et (e) de la revendication 1 est décrit dans le document
Les capsules de bouchage métalliques, typiquement en aluminium, sont fabriquées typiquement de la manière suivante :
- une presse d'emboutissage forme des ébauches de capsules à partir de métal en bande vernis sur ses deux faces, d'épaisseur typique allant de 0,21 à 0,25 mm,
- ces ébauches sont dégraissées en étuve à haute température, typiquement de 180° à 210°C, pendant un temps allant de 3 à 5 minutes, afin d'éliminer le lubrifiant d'emboutissage,
- ces ébauches sont ensuite laquées sur toute leur surface extérieure et sont passées en étuve afin de cuire la laque,
- ces ébauches laquées sont imprimées sur la jupe, typiquement en offset, avec un séchage final des encres en étuve,
- un vernis de surimpression est enfin appliqué sur l'impression afin de la protéger, ledit vernis étant séché lors d'un passage en étuve,
- l'ébauche ainsi obtenue est dotée d'un joint et/ou d'un insert plastique intérieur fileté.
- a stamping press forms blanks of capsules from metal strip on both sides, with a typical thickness ranging from 0.21 to 0.25 mm,
- these blanks are defatted in an oven at high temperature, typically from 180 ° to 210 ° C, for a time ranging from 3 to 5 minutes, in order to eliminate the drawing lubricant,
- these blanks are then lacquered on their entire outer surface and are passed in an oven in order to cook the lacquer,
- these lacquered blanks are printed on the skirt, typically in offset, with a final drying of the inks in an oven,
- an overprint varnish is finally applied to the printing to protect it, said varnish being dried during a passage in an oven,
- the blank thus obtained is provided with a seal and / or a threaded inner plastic insert.
En ce qui concerne les capsules métalliques, qu'elles soient de bouchage ou de surbouchage, il y a une demande permanente à la fois pour réduire les coûts de production, sous peine de voir ces capsules remplacées par d'autres capsules plus économiques relevant d'une autre technologie et d'un autre matériau, et pour améliorer les décors et leur tenue d'usage.Regarding metal caps, whether capping or overcapping, there is a permanent demand both to reduce production costs, under penalty of seeing these capsules replaced by other capsules more economical under the same conditions. 'another technology and another material, and to improve the sets and their wear of use.
L'invention vise à résoudre simultanément ces deux problèmes.The invention aims to solve both problems simultaneously.
Selon l'invention, le procédé de fabrication de capsules métalliques, typiquement en aluminium, comprend :
- a) un approvisionnement de métal en bande ou en format, typiquement revêtu sur ses deux faces d'une couche de vernis d'emboutissage,
- b) une étape d'emboutissage, en une ou plusieurs passes, dudit métal en bande ou en format, typiquement à l'aide d'un lubrifiant d'emboutissage, de manière à former une ébauche emboutie comprenant une tête et une jupe, typiquement axi-symétrique selon une direction axiale (10),
- c) une étape de dégraissage de ladite ébauche emboutie, destinée à éliminer typiquement les restes de lubrifiant d'emboutissage, pour former une ébauche dégraissée apte à être laquée,
- d) une étape de laquage de ladite ébauche dégraissée, ladite ébauche laquée ainsi obtenue étant ensuite éventuellement décorée,
- e) une étape éventuelle de finition,
- a) a supply of metal strip or format, typically coated on both sides with a layer of stamping varnish,
- b) a step of stamping, in one or more passes, said metal strip or format, typically using a stamping lubricant, so as to form a stamped blank comprising a head and a skirt, typically axi-symmetric in an axial direction (10),
- c) a step of degreasing said stamped blank, intended to typically eliminate the residues of stamping lubricant, to form a defatted preform capable of being lacquered,
- d) a step of lacquering said degreased blank, said lacquered blank thus obtained being then optionally decorated,
- e) a possible finishing step,
Généralement, d'une part, ledit traitement est réalisé à la température ambiante, ce qui est extrêmement avantageux tant en ce qui concerne les économies d'énergie qu'en ce qui concerne les inconvénients d'un adoucissement du métal, et d'autre part, il est réalisé en temps masqué dans la mesure où il peut être mis en oeuvre en étant associé à tout ou partie d'une étape de décoration, et cela sans ralentir la cadence de ladite étape de décoration, de sorte que ladite étape de dégraissage ne constitue pas en elle-même une étape, de sorte qu'il s'agit d'une opération de mise en oeuvre très économique.Generally, on the one hand, said treatment is carried out at ambient temperature, which is extremely advantageous both with regard to energy savings and with regard to the disadvantages of softening the metal, and other on the other hand, it is produced in masked time insofar as it can be implemented while being associated with all or part of a decoration step, and this without slowing down the rate of said decorating step, so that said step of degreasing is not in itself a step, so it is a very economical implementation operation.
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La
figure 1a est une vue en perspective représentant schématiquement un dispositif pour la mise en oeuvre du procédé selon l'invention.Thefigure 1a is a perspective view schematically showing a device for implementing the method according to the invention. -
La
figure 1b est une vue en coupe axiale d'une électrode utilisée dans le procédé selon l'invention.Thefigure 1b is an axial sectional view of an electrode used in the method according to the invention. -
Les
figures 2a et 2b illustrent de manière schématique et partielle le poste (53) de dégraissage de la jupe (12) de l'ébauche (1) de lafigure 1a .
Lafigure 2a est une coupe selon l'axe de rotation (530) du support (53') de l'ébauche (1).
Lafigure 2b est une coupe dans un plan perpendiculaire à l'axe de rotation (530).TheFigures 2a and 2b illustrate diagrammatically and partially the degreasing station (53) of the skirt (12) of the blank (1) of thefigure 1a .
Thefigure 2a is a section along the axis of rotation (530) of the support (53 ') of the blank (1).
Thefigure 2b is a section in a plane perpendicular to the axis of rotation (530). -
Les
figures 3a et 3b illustrent de manière schématique et partielle le poste (52) de dégraissage de la tête (11) de l'ébauche (1) de lafigure 1a .
Lafigure 3a est une coupe selon l'axe de rotation (520) du support (52') de l'ébauche (1).
Lafigure 3b est une vue de dessus de la tête (11), l'électrode (40, 40') ayant été représentée en pointillés .
Sur lesfigures 2a à 3b , les flèches entre les électrodes (40, 40', 40") et l'ébauche (1) représentent le plasma (58) formé, la distance d entre les électrodes et l'ébauche ayant été exagérée de manière à pouvoir représenter le plasma (58).TheFigures 3a and 3b illustrate diagrammatically and partially the station (52) for degreasing the head (11) of the blank (1) of thefigure 1a .
Thefigure 3a is a section along the axis of rotation (520) of the support (52 ') of the blank (1).
Thefigure 3b is a top view of the head (11), the electrode (40, 40 ') having been shown in dashed lines.
On theFigures 2a to 3b , the arrows between the electrodes (40, 40 ', 40 ") and the blank (1) represent the plasma (58) formed, the distance d between the electrodes and the blank having been exaggerated so as to be able to represent the plasma (58).
Selon l'invention, ledit traitement par rayonnement énergétique peut être un traitement comprenant la formation d'un plasma ou d'un effluve ionique ou électronique.According to the invention, said energy radiation treatment may be a treatment comprising the formation of a plasma or an ionic or electronic efflux.
Ledit traitement peut être un traitement utilisant typiquement un champ électrique élevé, typiquement au moins égal à 5 kV, et un courant à haute fréquence, typiquement au moins égal à 10 kHz.Said treatment may be a treatment typically using a high electric field, typically at least 5 kV, and a high frequency current, typically at least 10 kHz.
De préférence, et comme illustré sur la
Comme illustré sur la
Il a été trouvé que ce type d'électrode (40) était particulièrement adapté pour traiter la surface métallique extérieure des ébauches embouties (1), pour la débarrasser de ses résidus de lubrifiant de mise en forme, et pour permettre ensuite l'accrochage d'une laque.It has been found that this type of electrode (40) is particularly adapted to treat the outer metal surface of the stamped blanks (1), to remove its residues of shaping lubricant, and then to allow the attachment of a lacquer.
La demanderesse a pu observer que le traitement selon l'invention, à la fois sous une haute tension et à une fréquence élevée, réalisé à la température ambiante et à l'air ambiant, était à la fois, économique par la faible énergie consommée, la puissance installée étant d'environ 500 W, fiable, peu dangereux dans sa mise en oeuvre, et peu agressif pour le métal parce que, avec les électrodes utilisés, l'effluve émis est régulièrement réparti sur toute la longueur de l'électrode en regard de la capsule (1), de sorte qu'il n'y a pas de risque de "claquage" avec un point de passage d'un courant localisé qui pourrait endommager ponctuellement ladite ébauche (1).The Applicant has been able to observe that the treatment according to the invention, both under high voltage and at a high frequency, carried out at ambient temperature and at ambient air, was both economical with the low energy consumed, the installed power being about 500 W, reliable, not very dangerous in its implementation, and not very aggressive for the metal because, with the electrodes used, the emitted discharge is regularly distributed over the whole length of the electrode in view of the capsule (1), so that there is no risk of "breakdown" with a point of passage of a localized current that could punctually damage said blank (1).
Typiquement, ledit traitement peut être effectué grâce à une différence de potentiel entre lesdites électrodes (40, 40', 40") et ladite ébauche emboutie (1), allant typiquement de 10 à 30 kV, de manière à former ledit champ électrique élevé, lesdites électrodes (40, 40', 40") étant portées à un potentiel de 10-30 kV et ladite ébauche (1) étant à la terre ou à un potentiel nul, ladite différence de potentiel servant à réguler ladite intensité dudit traitement, lesdites électrodes (40, 40', 40") étant à une distance d des surfaces de ladite ébauche (1) à traiter inférieure à 4 mm.Typically, said treatment can be performed by virtue of a potential difference between said electrodes (40, 40 ', 40 ") and said stamped blank (1), typically ranging from 10 at 30 kV, so as to form said high electric field, said electrodes (40, 40 ', 40 ") being brought to a potential of 10-30 kV and said blank (1) being grounded or at a zero potential, said potential difference serving to regulate said intensity of said treatment, said electrodes (40, 40 ', 40 ") being at a distance d from the surfaces of said blank (1) to be treated less than 4 mm.
Comme illustré sur la
Ladite rotation de ladite ébauche (1) peut s'étendre sur 1 à 2 tours, pendant un temps au plus égal à 1 seconde, ladite ébauche tournant sur elle-même, ayant été placée sur un bras ou plot (52', 53') tournant sur lui-même selon un axe de rotation (520, 530).Said rotation of said blank (1) can extend over 1 to 2 turns, for a time at most equal to 1 second, said blank rotating on itself, having been placed on an arm or stud (52 ', 53' ) rotating on itself along an axis of rotation (520, 530).
Selon l'invention, ledit traitement peut aussi être un traitement par plasma dit "froid", réalisé typiquement à la pression atmosphérique.According to the invention, said treatment can also be a so-called "cold" plasma treatment, typically carried out at atmospheric pressure.
Il est avantageux en effet, que le traitement puisse être effectué à la température ambiante, typiquement au défilé, et sans nécessiter d'atmosphère gazeuse particulière, de manière à limiter les coûts d'investissement et les coûts de fonctionnement.It is indeed advantageous that the treatment can be carried out at ambient temperature, typically on the run, and without requiring a particular gaseous atmosphere, so as to limit investment costs and operating costs.
Ledit lubrifiant peut comprendre un solvant organique volatil et un composé de lubrification apte à se dégrader rapidement sous l'action dudit traitement.Said lubricant may comprise a volatile organic solvent and a lubricating compound capable of rapidly degrading under the action of said treatment.
Ledit composé peut être une huile de paraffine.Said compound may be a paraffin oil.
Comme illustré sur la
Ladite étape de pistolage peut être suivie d'un premier séchage dit de "mise hors poussière", à une température inférieure à 100°C, et typiquement à une température de 80°C, pendant un temps typiquement inférieur à 2 minutes, de manière à ce que ladite ébauche laquée (3) puisse être ensuite directement décorée ou imprimée.Said spraying step may be followed by a first so-called "dust-off" drying, at a temperature below 100 ° C., and typically at a temperature of 80 ° C, for a time typically less than 2 minutes, so that said lacquered blank (3) can then be directly decorated or printed.
Entre ladite étape de dégraissage et ladite étape de pistolage, il peut s'être écoulé un temps Δt inférieur à 15 minutes, typiquement inférieur à une minute, et éventuellement inférieur à 10 secondes.Between said degreasing step and said spraying step, a time Δt shorter than 15 minutes, typically less than one minute, and possibly less than 10 seconds, may have elapsed.
Selon l'invention, ladite ébauche laquée (3) peut être imprimée, typiquement par sérigraphie mais éventuellement par offset ou par flexographie, sur sa jupe (12) et éventuellement sur tête (11), puis soumise à un second séchage, typiquement à une température de 140°C, pendant un temps typiquement inférieur à quatre minutes, de manière à obtenir une capsule imprimée.According to the invention, said lacquered blank (3) can be printed, typically by screen printing but possibly by offset or flexography, on its skirt (12) and possibly on the head (11), then subjected to a second drying, typically at a temperature of 140 ° C, for a time typically less than four minutes, so as to obtain a printed capsule.
Avantageusement, pour augmenter la richesse du décor de la capsule finale, un motif en relief peut être formé sur ladite tête (11) de ladite ébauche (1, 2 , 3) ou de ladite capsule imprimée, ledit motif en relief étant typiquement formé à l'aide d'un jeu de poinçon et de matrice portant ledit motif.Advantageously, to increase the richness of the decor of the final capsule, a raised pattern can be formed on said head (11) of said blank (1, 2, 3) or said printed capsule, said relief pattern being typically formed in using a punch and die set bearing said pattern.
Ledit métal en bande ou en format peut être de l'aluminium, typiquement de la série 8000, à un état allant typiquement de l'état 1/4 dur jusqu'à un état 3/4 dur, et à une épaisseur allant de 0,18 mm à 0,30 mm, et de préférence de 0,21 mm à 0,25 mm.Said strip or format metal may be aluminum, typically of the 8000 series, in a state typically ranging from the 1/4 hard state to a 3/4 hard state, and at a thickness of 0 , 18 mm to 0.30 mm, and preferably from 0.21 mm to 0.25 mm.
Ladite étape de finition peut comprendre notamment, typiquement dans le cas où ladite capsule est une capsule de bouchage, au moins un des moyens complémentaires qui suivent :
- l'incorporation d'un joint d'étanchéité,
- l'incorporation d'un insert de vissage,
- la formation de moyens pour faciliter une première ouverture, comprenant typiquement au moins une ligne d'affaiblissement.
- the incorporation of a seal,
- the incorporation of a screwing insert,
- forming means for facilitating a first opening, typically comprising at least one line of weakness.
Comme illustré sur les
Selon l'invention, ladite électrode (40, 40', 40") peut être placée à ladite distance d de ladite ébauche (1), c'est-à-dire, soit de ladite tête (11), soit d'une génératrice de ladite jupe (12), ladite distance d allant de 0,2 à 4 mm, et typiquement de 1 mm à 2 mm. Les essais ont été généralement réalisés avec d = 1,5 mm.According to the invention, said electrode (40, 40 ', 40 ") can be placed at said distance d from said blank (1), that is to say, either of said head (11), or of a generatrix of said skirt (12), said distance d ranging from 0.2 to 4 mm, and typically from 1 mm to 2 mm The tests were generally carried out with d = 1.5 mm.
Un autre objet de l'invention est formé par des capsules de bouchage formées par le procédé selon l'invention.Another object of the invention is formed by capping capsules formed by the process according to the invention.
Un autre objet de l'invention est formé par des capsules de surbouchage formées par le procédé selon l'invention.Another object of the invention is formed by overcap capsules formed by the process according to the invention.
Un autre objet de l'invention est constitué par une utilisation du procédé selon l'invention pour former des capsules de bouchage ou des capsules de surbouchage, selon la revendication 21.Another object of the invention is constituted by a use of the method according to the invention for forming capping capsules or overcaping capsules, according to claim 21.
Un autre objet de l'invention est formé par un dispositif (5) pour mettre en oeuvre, en continu, le procédé de dégraissage d'ébauches (1) qui est mis en oeuvre dans la procédé de l'invention.Another object of the invention is formed by a device (5) for implementing, continuously, the degreasing process of blanks (1) which is implemented in the method of the invention.
Comme illustré sur la
- une station de chargement (51) en aval d'un dispositif d'alimentation (8) en ébauches (1) à dégraisser,
- une station de dégraissage (51, 52) desdites ébauches (1), lesdites ébauches (1) étant mises en rotation sur elles-mêmes en regard d'électrodes de dégraissage fixes (40, 40', 40") à une distance d prédéterminée, lesdites électrodes (40, 40', 40") étant alimentées en un courant de fréquence et tension prédéterminées apte à générer un effluve destructeur des restes ou résidus de lubrifiant, lesdites ébauches (1) étant mises à la terre, de manière à obtenir des ébauches embouties et dégraissées (2),
- une station d'éjection ou de déchargement (56) desdites ébauches dégraissées (2).
- a loading station (51) downstream of a feed device (8) in blanks (1) to be degreased,
- a degreasing station (51, 52) of said blanks (1), said blanks (1) being rotated on themselves facing fixed degreasing electrodes (40, 40 ', 40 ") at a predetermined distance d said electrodes (40, 40 ', 40 ") being supplied with a current of predetermined frequency and voltage capable of generating a destructive emanation of the residues or residues of lubricant, said blanks (1) being grounded, so as to obtain stamped and degreased blanks (2),
- an ejection or unloading station (56) of said defatted blanks (2).
Ladite station de dégraissage peut comprendre deux stations de traitement, une première station (51) de traitement de ladite tête (11) de ladite ébauche (1) à dégraisser (1) et une seconde station (52) de traitement de ladite jupe (12) avec typiquement un traitement séparé de ladite tête (11) et de ladite jupe (12) de ladite ébauche (1) à dégraisser (1).Said degreasing station may comprise two treatment stations, a first station (51) for treating said head (11) of said preform (1) to be degreased (1) and a second station (52) for treating said skirt (12). ) with typically a separate treatment of said head (11) and said skirt (12) of said blank (1) to degrease (1).
Ladite pluralité de postes ou stations comprend en outre, après ladite station de dégraissage ou lesdites stations de dégraissage, une station de laquage (54) et une station de séchage (55).Said plurality of stations or stations further comprises, after said degreasing station or said degreasing stations, a lacquering station (54) and a drying station (55).
On a mis au point le dispositif (5) de traitement en continu selon les
En amont, ce dispositif a été alimenté, au poste (51), en ébauches (1) telles que sorties de la presse à emboutir. Ces ébauches embouties (1) ont été formées à partir de bande d'aluminium verni sur ses deux faces, l'emboutissage ayant été réalisé avec un lubrifiant formant une solution d'une huile minérale en milieu alcoolique.Upstream, this device was fed, at the station (51), blanks (1) such as outputs of the stamping press. These stamped blanks (1) were formed from aluminum strip varnished on both sides, the stamping having been made with a lubricant forming a solution of a mineral oil in an alcoholic medium.
Le traitement de dégraissage a été réalisé soit avec un appareil de marque STT (type SG2) à fréquence fixe (40 kHz) et à puissance variable de 0 à 715 W, soit avec un appareil de marque Softal (type 3003) à fréquence variable entre 16 kHz et 40 kHz, et à 4 positions de puissance (366 W, 426 W, 493 W et 500W).The degreasing treatment was carried out either with STT (type SG2) fixed frequency (40 kHz) and variable power from 0 to 715 W, or with a Softal (type 3003) device with a variable frequency between 16 kHz and 40 kHz, and 4 power positions (366 W, 426 W, 493 W and 500W).
L'appareil STT a été utilisé à 50% de sa puissance soit 350W, alors que l'appareil Softal a été utilisé avec une puissance de 500 W.The STT device was used at 50% of its power, ie 350W, while the Softal device was used with a power of 500 W.
On a utilisé une électrode (40, 40', 40") de 70 mm de longueur utile, comme illustré sur la
Le dispositif de dégraissage (4) comprend, comme illustré sur la
Typiquement, la durée de traitement de dégraissage a été de 0,55 seconde, l'ébauche (1) faisant de 1 à 2 tours sur elle-même.Typically, the degreasing treatment time was 0.55 seconds, the blank (1) making from 1 to 2 turns on itself.
Dans ces essais, la distance d a été fixée à 1,5 mm.In these tests, the distance d was set at 1.5 mm.
Comme illustré sur les
Les ébauches (1) sont placées sur des plots (51', 52', 53', 54', 55', 56') tournants sur eux-mêmes à certaines stations (52, 53, 54, 55) autour d'axe de rotation (520, 530, 540, 550).The blanks (1) are placed on studs (51 ', 52', 53 ', 54', 55 ', 56') rotating on themselves at certain stations (52, 53, 54, 55) around axis rotation (520, 530, 540, 550).
Compte tenu des paramètres expérimentaux, il a été calculé que l'énergie électrique reçue par les ébauches (1) s'élevait à 7,8 J/cm2 avec le dispositif STT et à 4 J/cm2 avec le dispositif Softal.Given the experimental parameters, it was calculated that the electrical energy received by the blanks (1) amounted to 7.8 J / cm 2 with the STT device and 4 J / cm 2 with the Softal device.
En aval de ce dispositif (5), les ébauches dégraissées et laquées (3) éjectées du poste (55), ont été dirigées vers une machine à imprimer par sérigraphie, de manière à obtenir des capsules imprimées.Downstream of this device (5), the degreased and lacquered blanks (3) ejected from the station (55), were directed to a screen printing machine, so as to obtain printed capsules.
En aval de ce dispositif (5), on a également soumis les ébauches à différents types de parachèvement : formation d'un relief, typiquement sur la tête (11), mais éventuellement sur la jupe (12) de l'ébauche (2, 3) ou dé la capsule finale, ou encore formation de moyens destinés à faciliter une première ouverture, moyens comprenant au moins une ligne d'affaiblissement.Downstream of this device (5), the blanks have also been subjected to different types of finishing: formation of a relief, typically on the head (11), but possibly on the skirt (12) of the blank (2, 3) or the final capsule, or formation of means for facilitating a first opening, means comprising at least one weakening line.
Ce dispositif (6) a servi à fabriquer des capsules de surbouchage et des capsules de bouchage, les capsules de bouchage étant dotées d'un joint ou d'un insert fileté.This device (6) has been used to manufacture caps and caps closure caps closure caps having a seal or a threaded insert.
Sur les ébauches dégraissées (2), on a mesuré la tension de surface et observé qu'elle allait de 34 dynes/cm à 36 dynes/cm, les ébauches (1) de départ ayant une tension de surface allant de 30 à 32 dynes/cm.On the defatted blanks (2), the surface tension was measured and observed that it ranged from 34 dynes / cm to 36 dynes / cm, the starting blanks (1) having a surface tension ranging from 30 to 32 dynes / cm.
Sur les ébauches laquées (3), on a fait des tests d'abrasion et des tests d'arrachage de laques au ruban adhésif.Lacquered blanks (3) were subjected to abrasion tests and tear-off tests on adhesive tape.
Tous ces tests ont montré l'excellente adhérence de la laque sur le métal dégraissé selon l'invention.All these tests showed the excellent adhesion of the lacquer on the degreased metal according to the invention.
L'invention présente de grands avantages.The invention has great advantages.
En effet, d'une part, le procédé selon l'invention permet d'éviter des traitements coûteux en investissement et en coûts de fonctionnement, notamment en ce qui concerne l'énergie consommée.Indeed, firstly, the method according to the invention avoids expensive treatments in investment and operating costs, particularly with regard to the energy consumed.
D'autre part, ce procédé évite tout adoucissement du métal constituant l'ébauche métallique de départ et toute perte de ses caractéristiques mécaniques.On the other hand, this process avoids any softening of the metal constituting the initial metal blank and any loss of its mechanical characteristics.
Compte tenu de cela, il a ainsi été possible de réduire de 5 à 10 % l'épaisseur de l'ébauche métallique.In view of this, it has thus been possible to reduce the thickness of the metal blank by 5 to 10%.
Enfin, l'invention permet d'éviter des équipements volumineux, de sorte que le traitement selon l'invention correspond à la fois un coût d'investissement, et à un volume occupé minimes, ce qui permet d'avoir un atelier de production très compact, sans compter que ledit traitement peut être réalisé en temps masqué et en continu, de sorte qu'il n'introduit pas de coûts de production spécifiques, le coût de l'énergie consommée étant négligeable.Finally, the invention makes it possible to avoid bulky equipment, so that the treatment according to the invention corresponds to both an investment cost, and to a minimal occupied volume, which makes it possible to have a very large production workshop. compact, besides said processing can be performed in masked time and continuously, so that it does not introduce specific production costs, the cost of energy consumed being negligible.
Claims (24)
- Method for producing metal caps, typically of aluminium, including:a) providing strip or format metal, typically coated on its two sides with a layer of drawing varnish,b) drawing, in one or two stages, said strip or format metal, typically using a drawing lubricant, so as to form a deep-drawn blank (1) including a head (11) and a skirt (12), typically axisymmetrical according to an axial direction (10),c) degreasing said deep-drawn blank (1), so as typically to remove the remainder of the drawing lubricant, in order to form a degreased blank (2) capable of being lacquered,d) lacquering said degreased blank (2), said lacquered blank (3) thus obtained then optionally being decorated,e) performing an optional finishing step,characterised in that, during said degreasing step c), said deep-drawn blank (1) is subjected to an energy radiation emission treatment of selected intensity and duration so as to eliminate or break down said remaining lubricant, said treatment being carried out entirely at a metal temperature of less than 150 °C, and for a time typically less than 1 s, so as to obtain, after said treatment, a surface tension equal to at least 33 dynes/cm, and typically equal to at least 34 dynes/cm.
- Method according to claim 1, in which said energy radiation treatment is a treatment including the formation of a plasma or an ionic or electronic discharge.
- Method according to claim 2, in which said treatment is a treatment typically using a high electric field, typically equal to at least 5 kV, and a high-frequency current, typically equal to at least 10 kHz.
- Method according to claim 3, in which said treatment is performed using two bars or electrodes (40) for emission of said discharge, a lateral electrode (40''), typically parallel to said skirt (12), intended to reach and treat said skirt (12), and a frontal electrode (40'), substantially perpendicular to said lateral electrode (40") and parallel to said head (11), intended to reach and treat said head (11).
- Method according to claim 4 in which said electrodes (40, 40', 40'') include an electrically-conductive metal core (41) covered with a dielectric ceramic layer (42).
- Method according to any one of claims 4 to 5, in which said treatment is carried out with a difference in potential between said electrodes (40, 40', 40") and said deep-drawn blank (1), typically ranging from 10 to 30 kV, so as to form said high electric field, said electrodes (40, 40', 40") being brought to a potential of 10 to 30 kV and said blank (1) being at the ground or at a zero potential, said difference in potential serving to regulate said intensity of said treatment, said electrodes (40, 40', 40") being at a distance d from the surfaces of said blank (1) to be treated of less than 4 mm.
- Method according to claim 6, in which said lateral electrode (40") is arranged so that it is parallel to a generator of said skirt (12), so that, by rotation of said blank (1), the entirety of said skirt (12) is subjected to the energy radiation emitted by said lateral electrode (40"), uniformly over the entire height of said skirt (12).
- Method according to claim 7, in which said rotation of said blank (1) involves 1 to 2 rotations, during a time equal to at least 1 second.
- Method according to claim 1, in which said treatment is a so-called "cold" plasma treatment, typically performed at atmospheric pressure.
- Method according to any one of claims 1 to 8, in which said lubricant includes a volatile organic solvent and a lubrication compound capable of breaking down rapidly under the action of said treatment.
- Method according to claim 10, in which said compound is a paraffin oil.
- Method according to any one of claims 1 to 11, in which said lacquering step includes a so-called spray-painting step in which typically the entirety of an external surface of said degreased blank is covered with a lacquer by spraying or by application with a spray-paint gun, so as to form a lacquered blank (3).
- Method according to claim 12, in which said spray-painting step is followed by a first so-called "dust-free" drying step at a temperature below 100 °C and typically at a temperature of 80 °C, for a time of less than 2 minutes, so that said lacquered blank (3) can then be directly decorated or printed.
- Method according to either one of claims 12 or 13, in which, between said degreasing step and said spray-painting step, a time Δt of less than 15 minutes, typically less than one minute, and possibly less than 10 seconds can pass.
- Method according to any one of claims 1 to 14, in which said lacquered blank (3) is printed, typically by screen printing, on its skirt (12) and possibly on its head (11), then subjected to a second drying operation, typically at a temperature of 140 °C, for a time typically less than four minutes, so as to obtain a printed capsule.
- Method according to any one of claims 1 to 15, in which a relief pattern is formed on said head (11) of said blank (1, 2, 3) or of said printed cap, said relief pattern typically being formed with a punch-and-die set having said pattern.
- Method according to any one of claims 1 to 16, in which said strip or format metal is aluminium, typically of the 8000 series, with a temper typically ranging from 1/4 hard temper to 3/4 hard temper, and with a thickness ranging from 0.18 mm to 0.30 mm, and preferably from 0.21 mm to 0.25 mm.
- Method according to any one of claims 1 to 17, in which said finishing step includes in particular, typically if said cap is a sealing cap, at least one of the additional means, which include:- the incorporation of a seal ring,- the incorporation of a screw insert,- the formation of means for facilitating a first opening, typically including at least one break-off line.
- Method according to any one of claims 4 to 18, in which said electrode (40, 40', 40") can be a cylindrical electrode with an exterior diameter typically ranging from 15 mm to 20 mm, and with a length ranging from 100 to 150 mm, with a metal core (41) having a length ranging from 50 to 90 mm, said electrode (40, 40', 40'') including an external dielectric ceramic layer or sheath (42) having a thickness ranging from 0.5 to 3 mm.
- Method according to any one of claims 1 to 19, in which said electrode (40, 40', 40'') is placed at said distance d from said blank (1), that is, either from said head (11) or from a generator of said skirt (12), said distance d ranging from 0.2 to 4 mm, and typically from 1 mm to 2 mm.
- Use of the method according to any one of claims 1 to 20, in order to form sealing caps or oversealing caps.
- Device (5) for continuously implementing the degreasing blanks (1) step of the method according to any one of claims 1 to 20, including a mobile support for said blanks, typically a plate (50) rotating about an axis of rotation 50, typically in stepper mode, and equipped with a plurality of stations with means or arms for supporting (51', 52', 53', 54', 55') said blanks (1), said plurality of stations including:- a loading station (51) downstream of a device (8) for supplying blanks (1) to be degreased,- a station for degreasing (51, 52) said blanks (1), said blanks (1) being rotated about themselves opposite stationary degreasing electrodes (40, 40', 40") at a predetermined distance d, said electrodes (40, 40', 40'') being powered by a current at a predetermined frequency and voltage capable of generating a discharge to destroy the lubricant remains or residue, said blanks (1) being grounded so as to obtain deep-drawn and degreased blanks (2),- a station for ejection or discharge (56) of said degreased blanks (2).
- Device according to claim 22 in which said degreasing station includes two treatment stations, a first station (51) for treatment of said head (11) of said blank (1) to be degreased (1) and a second station (52) for treatment of said skirt (12), typically with a separate treatment of said head (11) and said skirt (12) of said blank (1) to be degreased (1).
- Device according to either one of claims 22 or 23, in which said plurality of stations also includes, after said degreasing station(s), a lacquering station (54) and a drying station (55).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PL05763703T PL1755804T3 (en) | 2004-05-06 | 2005-05-02 | Method for making decorated bottle caps with improved mechanical strength and device for implementing said method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0404885A FR2869820B1 (en) | 2004-05-06 | 2004-05-06 | PROCESS FOR MANUFACTURING DECORATED CAPSULES WITH IMPROVED MECHANICAL RESISTANCE |
PCT/FR2005/001091 WO2005120743A1 (en) | 2004-05-06 | 2005-05-02 | Method for making decorated bottle caps with improved mechanical strength and device for implementing said method |
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EP1755804A1 EP1755804A1 (en) | 2007-02-28 |
EP1755804B1 true EP1755804B1 (en) | 2008-02-13 |
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EP05763703A Active EP1755804B1 (en) | 2004-05-06 | 2005-05-02 | Method for making decorated bottle caps with improved mechanical strength and device for implementing said method |
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US (1) | US7832075B2 (en) |
EP (1) | EP1755804B1 (en) |
AT (1) | ATE385864T1 (en) |
AU (1) | AU2005251969B2 (en) |
CA (1) | CA2564640C (en) |
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PL (1) | PL1755804T3 (en) |
WO (1) | WO2005120743A1 (en) |
ZA (1) | ZA200609232B (en) |
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AR090422A1 (en) | 2012-02-18 | 2014-11-12 | Anheuser Busch Llc | CONTAINER CLOSURE |
GB201205243D0 (en) | 2012-03-26 | 2012-05-09 | Kraft Foods R & D Inc | Packaging and method of opening |
GB2511559B (en) | 2013-03-07 | 2018-11-14 | Mondelez Uk R&D Ltd | Improved Packaging and Method of Forming Packaging |
GB2511560B (en) | 2013-03-07 | 2018-11-14 | Mondelez Uk R&D Ltd | Improved Packaging and Method of Forming Packaging |
FR3025505B1 (en) * | 2014-09-05 | 2019-03-22 | Constellium Neuf-Brisach | PROCESS FOR MANUFACTURING TEXTURED-SMOOTH MIXED METAL CAPSULE CAPSULES |
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GB203976A (en) * | 1922-12-21 | 1923-09-20 | Bernardin Bottle Cap Company | Improvements in bottle caps and the method of making the same |
WO1989012801A1 (en) * | 1988-06-15 | 1989-12-28 | Toyo Seikan Kaisha, Ltd. | Drawn printed can and production method thereof |
JPH04501246A (en) * | 1988-10-05 | 1992-03-05 | アルコア ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング フェルパックングスヴェルケ | screw lid |
FR2665887B1 (en) * | 1990-08-14 | 1992-10-16 | Cebal | CAPPING CAPSULE THAT CAN BE CUT WITHOUT RISK OF INJURY AND ITS MANUFACTURING METHOD. |
FR2702754B1 (en) * | 1993-03-18 | 1995-06-16 | Alsacienne Aluminium | CAP OF CAP OF A BOTTLE COLLAR. |
FR2803827B1 (en) * | 2000-01-13 | 2002-03-08 | Pechiney Emballage Alimentaire | CAPPING CAP FOR STANDARD GLASS RING |
US20040045806A1 (en) * | 2000-11-29 | 2004-03-11 | Willi Neff | Method and device for treating the surfaces of items |
FR2836158B1 (en) * | 2002-02-19 | 2005-01-07 | Usinor | PROCESS FOR PLASMA CLEANING OF THE SURFACE OF A MATERIAL COATED WITH AN ORGANIC SUBSTANCE, AND IMPLEMENTATION INSTALLATION |
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2004
- 2004-05-06 FR FR0404885A patent/FR2869820B1/en not_active Expired - Lifetime
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2005
- 2005-05-02 AT AT05763703T patent/ATE385864T1/en active
- 2005-05-02 NZ NZ550928A patent/NZ550928A/en unknown
- 2005-05-02 WO PCT/FR2005/001091 patent/WO2005120743A1/en active IP Right Grant
- 2005-05-02 ZA ZA200609232A patent/ZA200609232B/en unknown
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DE602005004783D1 (en) | 2008-03-27 |
FR2869820B1 (en) | 2007-06-22 |
DE602005004783T2 (en) | 2009-02-12 |
CA2564640A1 (en) | 2005-12-22 |
AU2005251969B2 (en) | 2010-06-10 |
AU2005251969A1 (en) | 2005-12-22 |
ZA200609232B (en) | 2008-07-30 |
PL1755804T3 (en) | 2008-07-31 |
CA2564640C (en) | 2013-07-02 |
MXPA06012814A (en) | 2007-01-26 |
US20070107190A1 (en) | 2007-05-17 |
WO2005120743A1 (en) | 2005-12-22 |
EP1755804A1 (en) | 2007-02-28 |
ATE385864T1 (en) | 2008-03-15 |
FR2869820A1 (en) | 2005-11-11 |
US7832075B2 (en) | 2010-11-16 |
NZ550928A (en) | 2009-12-24 |
ES2301034T3 (en) | 2008-06-16 |
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