EP1382229B1 - Article provided with surface antistatic properties and method for obtaining same - Google Patents

Article provided with surface antistatic properties and method for obtaining same Download PDF

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Publication number
EP1382229B1
EP1382229B1 EP02732838A EP02732838A EP1382229B1 EP 1382229 B1 EP1382229 B1 EP 1382229B1 EP 02732838 A EP02732838 A EP 02732838A EP 02732838 A EP02732838 A EP 02732838A EP 1382229 B1 EP1382229 B1 EP 1382229B1
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EP
European Patent Office
Prior art keywords
article
particles
electrically conducting
layer
process according
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German (de)
French (fr)
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EP1382229A1 (en
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Jean-Claude Guillaumon
Pascale Véronique NABARRA
Stéphanie REMAURY
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Centre National dEtudes Spatiales CNES
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Centre National dEtudes Spatiales CNES
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05F—STATIC ELECTRICITY; NATURALLY-OCCURRING ELECTRICITY
    • H05F3/00—Carrying-off electrostatic charges
    • H05F3/02—Carrying-off electrostatic charges by means of earthing connections

Definitions

  • the invention relates to an article having a surface electrical resistance of less than 10 9 ohms per square, especially for combating the effects of static electricity.
  • the accumulation of electrostatic charges on the surface of an article of dielectric material may be detrimental to the operation of electronic equipment or equipment by creating electrical discharges generating electromagnetic interference (parasites) or destructive electronic components.
  • a potential difference can generate an electric shock that can lead to disturbances or even the destruction of nearby electronic equipment.
  • thermo-optical characteristics such as the solar absorption coefficient or the infrared emissivity factor, well determined.
  • the outer or "superficial" layer of these coatings consists of a polymeric film in the case of SSM or a quartz plate in the case of OSR. To render this layer electrically conductive, a substantially transparent indium oxide doped with tin oxide coating is applied under vacuum.
  • the Applicant in the patent FR-B-2,770,230 proposes a solar reflector for the thermal control of a space vehicle whose coating is of less cost than the OSR or the SSM.
  • the surface layer of this coating is a polysiloxane layer about 50 microns thick applied to a metallized substrate.
  • This protective layer is however not electrically conductive so that the problem related to static electricity remains.
  • the conductive particles are applied on the cathode screen in the form of a homogeneous and stable aqueous suspension forming after drying a layer of about 50 to 400 nm thick.
  • the ATO and polypyrrole particles have average diameters of less than 30 nm and about 30 to 80 nm, respectively. The particles are therefore distributed in the volume of the surface layer and are therefore not arranged on the surface of the screen.
  • thermo-optical properties A means which would make it possible to confer antistatic properties on solar reflectors of FR-B-2,770,230 without substantially degrading their thermo-optical properties, would therefore be very useful.
  • electrostatic charges can be created on the surface of electrically insulating materials by friction of the air (trioelectric effect) or by friction with other insulating materials .
  • the accumulation of these electrostatic charges can create harmful electrical discharges for electronic equipment.
  • Various means for eliminating these charges are known, such as the use of conductive materials in the volume (for example polymer materials loaded with conductive particles) or the application of a layer of electrically conductive paint.
  • conductive materials for example polymer materials loaded with conductive particles
  • the application of a layer of electrically conductive paint there is no appropriate antistatic treatment.
  • the invention aims to satisfy these needs.
  • the invention is defined by the features of claim 1 and relates to an article whose surface has a surface electrical resistance less than or equal to 10 9 ohms per square, characterized in that it comprises a plurality of electrically conductive particles. adhering to its surface and spread over it.
  • a surface resistance of 10 9 ⁇ / ⁇ is considered the maximum permissible resistance for an acceptable antistatic effect.
  • the particles adhere to the surface of a cured layer of resin or varnish applied to the article.
  • the electrically conductive particles should have a size smaller than 0.4 ⁇ m. If transparency is not an essential criterion, larger particles can be used.
  • the precipitate is calcined at 500-600 ° C and then the whole is doped by calcination at a temperature depending on the type of oxide and dopant.
  • the quantity of the electroconductive particles adhering to the surface of the article is advantageously the smallest possible quantity which makes it possible to obtain a suitable surface electrical resistance, that is to say ⁇ 10 9 ⁇ / square, while not degrading not significantly the thermo-optical properties of the article, when the latter factor is important.
  • a suitable surface electrical resistance that is to say ⁇ 10 9 ⁇ / square
  • thermo-optical properties of the article when the latter factor is important.
  • This distribution of particles corresponds substantially to a surface concentration of 0.5 to 5 mg of particles per m 2 of surface area when the particles consist of a doped oxide, and from 2 to 20 mg of particles per m 2 of surface area when the particles consist of a metal.
  • the invention also relates to a process for imparting to an article a surface electrical resistance less than or equal to 10 9 ohms per square, characterized in that it comprises the application, on a soft and sticky surface of said article, of a plurality conductive particles electrically distributed on said surface, and then curing said surface.
  • a surface layer based on a hardenable resin is applied to said article prior to the application of said electrically conductive particles.
  • its thickness is between 5 and 50 microns.
  • the polymerizable or crosslinkable resin layer could be replaced by a varnish composition, for example constituted by a solution in a solvent of a polymeric material.
  • the surface of said article is treated with a solvent of the material constituting said surface in order to generate said soft and sticky surface.
  • the particles may be applied to the surface to be treated in the form of a dry powder using a pneumatic or electrostatic powder gun, such as those marketed by KREMLIN, or else in the form of a suspension in a medium. liquid, for example using a spray gun.
  • a pneumatic or electrostatic powder gun such as those marketed by KREMLIN
  • a suspension in a medium. liquid for example using a spray gun.
  • Other modes of particle application will be apparent to those skilled in the art.
  • the resin may be chosen, by way of illustration and without limitation, from polysiloxane, epoxide, polyurethane, polyester, acrylic resins, etc. .
  • FIG. 2 illustrates an article A consisting of a material 1 having the property of being able to be rendered, on the surface, soft and sticky. Electrically conductive particles 2 are applied and adhered to the surface of the article A.
  • the material 1 is transparent, for example if the article A is an aircraft window, for example polycarbonate, its thermo-optical properties are little changed by the application of particles 2 on its surface.
  • FIG. 3 illustrates an article A whose surface has been successively covered with a metallized film 3 and a layer 4 of transparent crosslinkable resin.
  • the combination of film 3 and layer 4 is intended to provide effective thermo-optical control.
  • the film 3 is not an indispensable element of the present invention and could be omitted, for example, if the surface layer 4 itself had the desired thermo-optical characteristics or in applications where these thermo-optical properties would be unimportant. .
  • Electrically conductive particles 2 cover the outer surface of the surface layer 4.
  • the embodiment of the invention illustrated in FIG. 3 is particularly adapted to the field of space. Indeed, under certain conditions indicated below, the electrically conductive particles 2 do not affect little or no the thermo-optical properties of the surface layer 4.
  • this surface is prepared in order to soften it.
  • the material 1 is a polymer, it can superficially dissolve its surface by means of a suitable solvent, as described above.
  • the particles 2 are applied to the surface of the resin prior to crosslinking or complete curing.
  • the viscosity of the surface of the substrate that is to say of the material 1 (FIG. 2) or of the surface layer 4 (FIG. 3), must allow, during the application of the electrically conductive particles 2, to maintain them. on the surface preventing them from penetrating deeply.
  • the surface is cured, for example by crosslinking or total polymerization of the polymer or by evaporation of the solvent.
  • the surface fixes the electrically conductive particles 2 and becomes electrically conductive or semiconductive.
  • the particles 2 are firmly fixed in the "gangue" that constitutes the substrate after curing.
  • the surface of the substrate comprising the electrically conductive particles 2 thus has good mechanical characteristics, which is an advantage over the SSM or OSR type coatings mentioned above.
  • This gangue also protects the electrically conductive particles 2 from moisture, which improves the stability of the surface electrical resistance over time.
  • ⁇ s denotes the solar absorption coefficient, ⁇ the infra-red emissivity factor and R s the surface electrical resistance of the surface of the article after the implementation of the present invention.
  • An antimony-doped tin powder with a particle size of less than 0.4 ⁇ m is sprayed into a 50/50 diacetate mixture using an air gun.
  • ethylene glycol / polyethylene glycol (MW 400) with a concentration of 5% by weight, on a 50 ⁇ m thick layer of polysilsesquioxane with non-crosslinked hydroxyl functional groups, previously applied to a polished aluminum support of 30 ⁇ m thick.
  • the amount of powder applied is 1 mg / m 2 of surface.
  • the layer is crosslinked at 225 ° C for 1 hour.
  • the layer is cured at 225 ° C for 1 hour.
  • An antimony-doped tin powder with a particle size of less than 0.4 ⁇ m is sprayed with a compressed air gun and suspended in a 50/50 diacetate mixture.
  • ethylene glycol / polyethylene glycol (MW 400) with a concentration of 10% by weight, on a layer 50 ⁇ m thick of an incompletely crosslinked mixture obtained from polydiethoxysiloxane (3 parts by weight), polydimethylsiloxane with silanol terminations (4 parts by weight), tetramethyldiethoxydisiloxane (4 parts by weight) and dibutyltin diacetate (0.014 parts by weight) previously applied to a polished aluminum support 30 microns thick.
  • the amount of powder applied is 1 mg / m 2 of surface.
  • silver powder is sprayed, the particles of which have nanometric dimensions and are suspended at a concentration of 10% by mass in a 50/50 diacetate mixture.
  • the quantity of powder applied is 2 mg / m 2 of surface.
  • the layer is cured at 225 ° C for 1 hour.
  • the Plexiglas ® thus treated has a surface electrical resistance of the order of 1 M ⁇ / ⁇ for a tin oxide deposit of about 2 mg / m 2 .
  • the Plexiglas ® thus treated has a surface electrical resistance of the order of 1M ⁇ / ⁇ for a tin oxide deposit of about 2 mg / m 2 .
  • the PVC thus treated has a surface electrical resistance of the order of 10 k ⁇ / ⁇ for a silver deposit of approximately 20 mg / m 2 .
  • An aluminized Kapton ® substrate is coated with a layer of a mixture of polysilsesquioxane (25 g) and antimony oxide doped tin oxide powder (0.22 g), the particles of which are inferior at 0.4 micrometers, obtained by grinding the ingredients for 30 minutes.
  • the layer thus applied is polymerized at 225 ° C. for 1 hour.
  • the layer thus applied is polymerized at 225 ° C. for 1 hour.
  • the invention is not limited to the embodiments described and shown, provided for illustrative and non-limiting.
  • the manufacture of powders of conductive particles 2, their nature, the techniques for applying the powder or the nature of the surface layer 4 or the material 1 of the article A may be different.

Abstract

The invention concerns an article having a surface electrical resistance not more than 10<9> Ohms per square, characterised in that it comprises a plurality of electrically conductive particles (2) adhering to its surface.

Description

L'invention concerne un article ayant une résistance électrique superficielle inférieure à 109 Ohms par carré, notamment pour lutter contre les effets de l'électricité statique.The invention relates to an article having a surface electrical resistance of less than 10 9 ohms per square, especially for combating the effects of static electricity.

L'accumulation de charges électrostatiques à la surface d'un article en matériau diélectrique peut être nuisible au fonctionnement d'appareillages ou d'équipements électroniques par création de décharges électriques génératrices de perturbations électromagnétiques (parasites) ou destructrices de composants électroniques.The accumulation of electrostatic charges on the surface of an article of dielectric material may be detrimental to the operation of electronic equipment or equipment by creating electrical discharges generating electromagnetic interference (parasites) or destructive electronic components.

Un véhicule spatial soumis à l'environnement spatial d'orbites géostationnaires, hétiosynchrones ou plus généralement dans ou au-delà des ceintures de Van Allen, est soumis à des flux de particules, tels que des électrons et des protons, d'énergie variable. Ces flux chargent électriquement les revêtements externes des véhicules s'ils sont diélectriques, créant ainsi des différences de potentiel entre différentes parties du véhicule spatial.A spacecraft subjected to the space environment of geostationary orbitosynchronous or more generally in or beyond the Van Allen belts, is subjected to particle fluxes, such as electrons and protons, of variable energy. These flows electrically charge the outer coatings of the vehicles if they are dielectric, thereby creating potential differences between different parts of the spacecraft.

Au delà d'un certain seuil, une différence de potentiel peut générer une décharge électrique pouvant entraîner des perturbations ou même la destruction d'équipements électroniques se trouvant à proximité.Beyond a certain threshold, a potential difference can generate an electric shock that can lead to disturbances or even the destruction of nearby electronic equipment.

Une fonction essentielle du revêtement externe d'un véhicule spatial est d'assurer, au moins en partie, le contrôle thermique de ce véhicule. Le revêtement doit alors avoir des caractéristiques thermo-optiques, tels le coefficient d'absorption solaire ou le facteur d'émissivité infra-rouge, bien déterminées.An essential function of the outer coating of a spacecraft is to provide, at least in part, the thermal control of this vehicle. The coating must then have thermo-optical characteristics, such as the solar absorption coefficient or the infrared emissivity factor, well determined.

Des revêtements actuels utilisés pour le contrôle thermique sont, par exemple, des SSM, de l'anglais Second Surface Mirrors, ou Miroirs à double Surface, ou des OSR, de l'anglais Optical Surface Reflectors, ou Surfaces Optiques Réfléchissantes. La couche externe ou « superficielle » de ces revêtements est constituée d'un film polymérique dans le cas des SSM ou d'une plaque de quartz dans le cas des OSR. Pour rendre conductrice électriquement cette couche, on y applique sous vide un dépôt sensiblement transparent à base d'oxyde d'indium dopé à l'oxyde d'étain.Current coatings used for thermal control are, for example, SSM, English Second Surface Mirrors, or Double Surface Mirrors, or OSR, Optical Surface Reflectors, or Reflective Optical Surfaces. The outer or "superficial" layer of these coatings consists of a polymeric film in the case of SSM or a quartz plate in the case of OSR. To render this layer electrically conductive, a substantially transparent indium oxide doped with tin oxide coating is applied under vacuum.

Si ce dépôt conducteur électriquement remplit bien sa fonction d'élimination des décharges électrostatiques, il est fragile, sensible à l'humidité et coûteux.If this electrically conductive deposit performs its function of elimination of electrostatic discharges, it is fragile, sensitive to moisture and expensive.

La Demanderesse, dans le brevet FR-B-2 770 230 , propose un réflecteur solaire pour le contrôle thermique d'un véhicule spatial dont le revêtement est d'un coût moins élevé que les OSR ou les SSM. La couche superficielle de ce revêtement est une couche en polysiloxane d'environ 50 µm d'épaisseur appliquée sur un substrat métallisé. Cette couche protectrice n'est cependant pas conductrice électriquement de sorte que le problème lié à l'électricité statique subsiste.The Applicant in the patent FR-B-2,770,230 , proposes a solar reflector for the thermal control of a space vehicle whose coating is of less cost than the OSR or the SSM. The surface layer of this coating is a polysiloxane layer about 50 microns thick applied to a metallized substrate. This protective layer is however not electrically conductive so that the problem related to static electricity remains.

Pour limiter l'accumulation de charges à la surface d'une telle couche non conductrice électriquement, on pourrait penser à mélanger au matériau de la couche superficielle des particules conductrices électriquement afin de la rendre électriquement conductrice dans le volume.To limit the accumulation of charges on the surface of such an electrically non-conductive layer, one could think of mixing electrically conductive particles with the material of the surface layer in order to make it electrically conductive in the volume.

Cette solution a l'inconvénient cependant de dégrader les qualités thermo-optiques du réflecteur et n'est donc pas satisfaisante pour une utilisation où il faut assurer un contrôle thermique d'un véhicule spatial.This solution has the disadvantage, however, of degrading the thermo-optical qualities of the reflector and is therefore not satisfactory for use where it is necessary to provide a thermal control of a spacecraft.

Dans EP A 0649 161 , les particules conductrices sont appliquées sur l'écran cathodique sous la forme d'une suspension aqueuse homogène et stable formant après séchage une couche d'environ 50 à 400 nm d'épaisseur. Les particules d'ATO et de polypyrrole ont des diamètres moyens inférieurs à 30 nm et d'environ 30 à 80 nm, respectivement. Les particules sont donc réparties dans le volume de la couche superficielle et ne sont donc pas disposées à la surface de l'écran.In EP 0649161 , the conductive particles are applied on the cathode screen in the form of a homogeneous and stable aqueous suspension forming after drying a layer of about 50 to 400 nm thick. The ATO and polypyrrole particles have average diameters of less than 30 nm and about 30 to 80 nm, respectively. The particles are therefore distributed in the volume of the surface layer and are therefore not arranged on the surface of the screen.

Un moyen qui permettrait de conférer des propriétés antistatiques aux réflecteurs solaires de FR-B-2 770 230 , sans dégrader sensiblement leurs propriétés thermo-optiques, serait donc très utile.A means which would make it possible to confer antistatic properties on solar reflectors of FR-B-2,770,230 without substantially degrading their thermo-optical properties, would therefore be very useful.

Dans le domaine de l'aéronautique, de l'électronique ou de l'informatique, des charges électrostatiques peuvent être créées à la surface de matériaux électriquement isolants par frottement de l'air (effet trioboélectrique) ou par frottement avec d'autres matériaux isolants. Comme dans le domaine spatial, l'accumulation de ces charges électrostatiques peut créer des décharges électriques nocives pour les équipements électroniques. Divers moyens pour éliminer ces charges sont connus, tels que l'utilisation de matériaux conducteurs dans le volume (par exemple des matériaux polymères chargés de particules conductrices) ou l'application d'une couche de peinture conductrice de l'électricité. Cependant, pour des articles transparents, tels que des hublots d'avions, il n'existe pas de traitement antistatique approprié.In the field of aeronautics, electronics or computer science, electrostatic charges can be created on the surface of electrically insulating materials by friction of the air (trioelectric effect) or by friction with other insulating materials . As in the space field, the accumulation of these electrostatic charges can create harmful electrical discharges for electronic equipment. Various means for eliminating these charges are known, such as the use of conductive materials in the volume (for example polymer materials loaded with conductive particles) or the application of a layer of electrically conductive paint. However, for transparent articles, such as aircraft portholes, there is no appropriate antistatic treatment.

Un moyen qui permettrait de conférer des propriétés antistatiques à des articles transparents sans altérer sensiblement leur transparence serait donc très utile.A means which makes it possible to confer antistatic properties on transparent articles without substantially altering their transparency would therefore be very useful.

L'invention vise à satisfaire ces besoins.The invention aims to satisfy these needs.

Plus précisément, l'invention est définie par les caractéristiques de la revendication 1 et concerne un article dont la surface présente une résistance électrique superficielle inférieure ou égale à 109 Ohms par carré, caractérisé en ce qu'il comporte une pluralité de particules conductrices électriquement adhérant à sa surface et réparties sur cette dernière.More specifically, the invention is defined by the features of claim 1 and relates to an article whose surface has a surface electrical resistance less than or equal to 10 9 ohms per square, characterized in that it comprises a plurality of electrically conductive particles. adhering to its surface and spread over it.

Une résistance électrique superficielle de 109Ω/□ est considérée comme la résistance maximale admissible pour un effet antistatique acceptable.A surface resistance of 10 9 Ω / □ is considered the maximum permissible resistance for an acceptable antistatic effect.

Selon un mode de réalisation, les particules adhèrent à la surface d'une couche durcie de résine ou vernis appliquée sur l'article. Lorsque la transparence dans le domaine des longueur d'onde de 200 à 1000 nm est un facteur essentiel, comme par exemple pour un réflecteur solaire spatial ou un hublot d'avion, il convient que les particules électro-conductrices, aient une grosseur inférieure à 0,4 µm. Si la transparence n'est pas un critère essentiel, des particules plus grosses peuvent être utilisées.In one embodiment, the particles adhere to the surface of a cured layer of resin or varnish applied to the article. When the transparency in the wavelength range from 200 nm to 1000 nm is an essential factor, as for example for a spatial solar reflector or a plane porthole, the electrically conductive particles should have a size smaller than 0.4 μm. If transparency is not an essential criterion, larger particles can be used.

Les particules électroconductrices peuvent être des oxydes métalliques dopés tels que

  • l'oxyde d'étain dopé, par exemple au chlore, au fluor, à l'oxyde d'antimoine, à l'oxyde d'indium ou à l'oxyde de bismuth,
  • l'oxyde d'indium dopé, par exemple à l'oxyde d'étain, à l'oxyde d'antimoine, à l'oxyde de bismuth, à l'oxyde de titane ou à l'oxyde de plomb ; ou bien
  • des métaux finement divisés tels que : l'argent, le zinc, le cuivre, l'aluminium, le platine, l'or, le palladium ou similaires.
The electroconductive particles may be doped metal oxides such as
  • doped tin oxide, for example with chlorine, fluorine, antimony oxide, indium oxide or bismuth oxide,
  • doped indium oxide, for example with tin oxide, with antimony oxide, with bismuth oxide, with titanium oxide or with lead oxide; or
  • finely divided metals such as: silver, zinc, copper, aluminum, platinum, gold, palladium or the like.

Pour obtenir des particules d'oxydes dopés les plus fines possible, on procède par exemple de la façon suivante:

  • Les sels de l'oxyde à doper et du dopant sont mis en solution dans de l'eau ou un solvant approprié puis co-précipités lentement par action d'un acide organique en solution.
  • Les acides organiques utilisables sont, par exemple, l'acide oxalique, l'acide citrique, l'acide tartrique, l'acide malonique, l'acide maléique et similaires.
In order to obtain the finest doped oxide particles possible, one proceeds, for example, as follows:
  • The salts of the oxide to be doped and the dopant are dissolved in water or an appropriate solvent and then co-precipitated slowly by the action of an organic acid in solution.
  • Useful organic acids are, for example, oxalic acid, citric acid, tartaric acid, malonic acid, maleic acid and the like.

Après filtration et séchage en étuve, le précipité est calciné à 500-600°C puis l'ensemble est dopé par calcination à une température qui dépend du type d'oxyde et de dopant.After filtration and drying in an oven, the precipitate is calcined at 500-600 ° C and then the whole is doped by calcination at a temperature depending on the type of oxide and dopant.

La quantité des particules électroconductrices adhérant à la surface de l'article est avantageusement la quantité la plus faible possible qui permet d'obtenir une résistance électrique superficielle appropriée, c'est-à-dire ≤ 109 Ω/carré, tout en ne dégradant pas notablement les propriétés thermo-optiques de l'article, lorsque ce dernier facteur est important. A titre indicatif et non limitatif, on a trouvé qu'une quantité de particules réparties sur la surface de l'article avec une distance interparticules de l'ordre de 10 à 20 µm donne habituellement des résultats satisfaisants.The quantity of the electroconductive particles adhering to the surface of the article is advantageously the smallest possible quantity which makes it possible to obtain a suitable surface electrical resistance, that is to say ≤ 10 9 Ω / square, while not degrading not significantly the thermo-optical properties of the article, when the latter factor is important. As an indication and not limiting, we found that quantity of particles distributed over the surface of the article with an interparticle distance of the order of 10 to 20 μm usually gives satisfactory results.

Cette répartition des particules correspond sensiblement à une concentration surfacique de 0,5 à 5 mg de particules par m2 de surface lorsque les particules sont constituées d'un oxyde dopé, et de 2 à 20 mg de particules par m2 de surface lorsque les particules sont constituées d'un métal.This distribution of particles corresponds substantially to a surface concentration of 0.5 to 5 mg of particles per m 2 of surface area when the particles consist of a doped oxide, and from 2 to 20 mg of particles per m 2 of surface area when the particles consist of a metal.

L'invention concerne également un procédé pour conférer à un article une résistance électrique superficielle inférieure ou égale à 109 Ohms par carré, caractérisé en ce qu'il comprend l'application, sur une surface molle et collante dudit article, d'une pluralité de particules conductrices électriquement réparties sur ladite surface, puis un durcissement de ladite surface.The invention also relates to a process for imparting to an article a surface electrical resistance less than or equal to 10 9 ohms per square, characterized in that it comprises the application, on a soft and sticky surface of said article, of a plurality conductive particles electrically distributed on said surface, and then curing said surface.

Selon un mode de mise en oeuvre, on applique sur ledit article une couche superficielle à base d'une résine durcissable, incomplètement durcie de façon à être molle et collante, préalablement à l'application desdites particules conductrices électriquement.According to one embodiment, a surface layer based on a hardenable resin, incompletely hardened so as to be soft and sticky, is applied to said article prior to the application of said electrically conductive particles.

De manière avantageuse pour la transparence de la couche de résine durcissable, son épaisseur est comprise entre 5 et 50 µm.Advantageously for the transparency of the curable resin layer, its thickness is between 5 and 50 microns.

Selon une variante de ce mode de mise en oeuvre, on pourrait remplacer la couche de résine polymérisable ou réticulable par une composition de vernis, par exemple constituée d'une solution dans un solvant d'une matière polymère.According to a variant of this embodiment, the polymerizable or crosslinkable resin layer could be replaced by a varnish composition, for example constituted by a solution in a solvent of a polymeric material.

Selon un autre mode de mise en oeuvre, préalablement à l'application desdites particules conductrices électriquement, on traite la surface dudit article au moyen d'un solvant de la matière constituant ladite surface afin de générer ladite surface molle et collante.According to another embodiment, prior to the application of said electrically conductive particles, the surface of said article is treated with a solvent of the material constituting said surface in order to generate said soft and sticky surface.

Les particules peuvent être appliquées sur la surface à traiter à l'état de poudre sèche à l'aide d'un pistolet à poudre pneumatique ou électrostatique, comme ceux commercialisés par la société KREMLIN, ou bien sous forme d'une suspension dans un milieu liquide, par exemple à l'aide d'un pistolet à peinture. D'autres modes d'application des particules seront évidents pour l'homme du métier.The particles may be applied to the surface to be treated in the form of a dry powder using a pneumatic or electrostatic powder gun, such as those marketed by KREMLIN, or else in the form of a suspension in a medium. liquid, for example using a spray gun. Other modes of particle application will be apparent to those skilled in the art.

Dans les modes de mise en oeuvre où on applique les particules sur une couche superficielle de résine incomplètement durcie, on peut choisir la résine, à titre illustratif et non limitatif, parmi les résines polysiloxanes, époxydes, polyuréthanes, polyesters, acryliques, etc...In the embodiments in which the particles are applied to an incompletely hardened resin surface layer, the resin may be chosen, by way of illustration and without limitation, from polysiloxane, epoxide, polyurethane, polyester, acrylic resins, etc. .

Dans le mode de mise en oeuvre où on applique des particules sur une surface préalablement ramollie de l'article, le ramollissement doit être effectué à l'aide d'un solvant approprié choisi en fonction du matériau à ramollir. Ainsi, à titre d'exemples illustratifs et non limitatifs :

  • Pour ramollir des résines méthacrylates, on utilise par exemple du benzène, du toluène, du xylène, du chlorure de méthylène, du chloroforme, du chlorure d'éthylène, du chlorobenzène, du dioxane, de la méthyléthylcétone, de la diisopropylcétone, de la cyclohexanone, du formiate de méthyle ou de l'acétate d'éthyle.
  • Pour ramollir des résines polycarbonates, on utilise par exemple du benzène, du chloroforme, de l'acétone, du chlorure de méthylène, du m-crésol, du dioxane, de la cyclohexanone, de la pyridine ou du DMF.
  • Pour ramollir des résines polyesters, on utilise par exemple du chloroforme, de l'acide formique ou du dichloroéthylène.
  • Pour ramollir du chlorure de vinyle, on utilise par exemple du THF, de la méthyléthylcétone, de la cyclopentanone, de la cyclohexanone, du DMF, du nitrobenzène ou du DMSO.
  • Sur le dessin annexé:
    • La figure 1 est une vue schématique, en coupe, d'un article rendu conducteur électriquement par incorporation de particules conductrices électriquement dans son volume, selon la technique antérieure.
    • La figure 2 est une vue schématique, en coupe, d'un article, selon la présente invention, dont la surface a été ramollie avant application des particules conductrices électriquement.
    • La figure 3 est une vue schématique, en coupe, d'un autre article, selon la présente invention, à la surface duquel une couche superficielle de résine a été appliquée.
  • Dans les différentes figures, des notations identiques sont utilisées pour des éléments analogues ou identiques.
  • La figure 1 représente, en coupe, un article A constitué d'un matériau 1 chargé, dans son volume, de particules 2 conductrices électriquement. Le matériau 1 est ainsi rendu conducteur électriquement et n'accumule pas les charges électrostatiques.
  • L'incorporation de particules 2 conductrices électriquement dans le volume du matériau 1 n'est pas toujours techniquement possible. De plus, quand le matériau 1 est transparent, ses propriétés thermo-optiques sont fortement modifiées par l'incorporation, dans le volume, des particules 2 conductrices électriquement.
In the embodiment in which particles are applied to a previously softened surface of the article, the softening must be carried out using a suitable solvent chosen as a function of the material to be softened. Thus, by way of illustrative and non-limiting examples:
  • To soften methacrylate resins, benzene, toluene, xylene, methylene chloride, chloroform, ethylene chloride, chlorobenzene, dioxane, methyl ethyl ketone, diisopropyl ketone, cyclohexanone are used, for example. methyl formate or ethyl acetate.
  • For softening polycarbonate resins, for example, benzene, chloroform, acetone, methylene chloride, m-cresol, dioxane, cyclohexanone, pyridine or DMF are used.
  • To soften polyester resins, chloroform, formic acid or dichloroethylene is used, for example.
  • To soften vinyl chloride, for example THF, methyl ethyl ketone, cyclopentanone, cyclohexanone, DMF, nitrobenzene or DMSO are used.
  • In the attached drawing:
    • Figure 1 is a schematic sectional view of an article rendered electrically conductive by incorporation of electrically conductive particles in its volume, according to the prior art.
    • Figure 2 is a schematic sectional view of an article according to the present invention, the surface of which has been softened before application of the electrically conductive particles.
    • Figure 3 is a schematic sectional view of another article according to the present invention, on the surface of which a surface layer of resin has been applied.
  • In the different figures, identical notations are used for similar or identical elements.
  • Figure 1 shows, in section, an article A consisting of a material 1 loaded, in its volume, electrically conductive particles 2. The material 1 is thus rendered electrically conductive and does not accumulate electrostatic charges.
  • The incorporation of electrically conductive particles 2 into the volume of the material 1 is not always technically possible. Moreover, when the material 1 is transparent, its thermo-optical properties are strongly modified by the incorporation, in the volume, electrically conductive particles 2.

La figure 2 illustre un article A constitué d'un matériau 1 possédant la propriété de pouvoir être rendu, en surface, mou et collant. Des particules 2 conductrices électriquement sont appliquées et rendues adhérentes à la surface de l'article A.FIG. 2 illustrates an article A consisting of a material 1 having the property of being able to be rendered, on the surface, soft and sticky. Electrically conductive particles 2 are applied and adhered to the surface of the article A.

Si le matériau 1 est transparent, par exemple si l'article A est un hublot d'avion, par exemple en polycarbonate, ses propriétés thermo-optiques sont peu modifiées par l'application des particules 2 à sa surface.If the material 1 is transparent, for example if the article A is an aircraft window, for example polycarbonate, its thermo-optical properties are little changed by the application of particles 2 on its surface.

La figure 3 illustre un article A dont la surface a été successivement couverte d'un film métallisé 3 puis d'une couche 4 de résine réticulable transparente. L'association du film 3 et de la couche 4 est destinée à assurer un contrôle thermo-optique efficace.3 illustrates an article A whose surface has been successively covered with a metallized film 3 and a layer 4 of transparent crosslinkable resin. The combination of film 3 and layer 4 is intended to provide effective thermo-optical control.

Le film 3 n'est pas un élément indispensable de la présente invention et pourrait être omis, par exemple, si la couche superficielle 4 possédait elle-même les caractéristiques thermo-optiques recherchées ou dans des applications où ces propriétés thermo-optiques seraient sans importance.The film 3 is not an indispensable element of the present invention and could be omitted, for example, if the surface layer 4 itself had the desired thermo-optical characteristics or in applications where these thermo-optical properties would be unimportant. .

Des particules électriquement conductrices 2 couvrent la surface externe de la couche superficielle 4.Electrically conductive particles 2 cover the outer surface of the surface layer 4.

Le mode de réalisation de l'invention illustré sur la figure 3 est particulièrement adapté au domaine du spatial. En effet, sous certaines conditions indiquées ci-dessous, les particules 2 conductrices électriquement n'affectent pas ou peu les propriétés thermo-optiques de la couche superficielle 4.The embodiment of the invention illustrated in FIG. 3 is particularly adapted to the field of space. Indeed, under certain conditions indicated below, the electrically conductive particles 2 do not affect little or no the thermo-optical properties of the surface layer 4.

Dans le mode de réalisation selon la figure 2, avant application des particules 2 conductrices sur la surface de l'article A, on prépare cette surface afin de la ramollir.In the embodiment according to Figure 2, before application of the conductive particles 2 on the surface of the article A, this surface is prepared in order to soften it.

Dans le cas où le matériau 1 est un polymère, on peut dissoudre superficiellement sa surface au moyen d'un solvant approprié, comme décrit plus haut.In the case where the material 1 is a polymer, it can superficially dissolve its surface by means of a suitable solvent, as described above.

Dans le mode de réalisation selon la figure 3, les particules 2 sont appliquées à la surface de la résine avant sa réticulation ou son durcissement complet.In the embodiment according to Figure 3, the particles 2 are applied to the surface of the resin prior to crosslinking or complete curing.

La viscosité de la surface du substrat, c'est-à-dire du matériau 1 (figure 2) ou de la couche superficielle 4 (figure 3), doit permettre, lors de l'application des particules 2 conductrices électriquement, de les maintenir en surface en les empêchant de pénétrer en profondeur.The viscosity of the surface of the substrate, that is to say of the material 1 (FIG. 2) or of the surface layer 4 (FIG. 3), must allow, during the application of the electrically conductive particles 2, to maintain them. on the surface preventing them from penetrating deeply.

Après application des particules 2 conductrices électriquement, on procède au durcissement de la surface, par exemple par réticulation ou polymérisation totale du polymère ou par évaporation du solvant.After application of the electrically conductive particles 2, the surface is cured, for example by crosslinking or total polymerization of the polymer or by evaporation of the solvent.

En durcissant complètement, la surface fixe les particules 2 conductrices électriquement et devient conductrice ou semi-conductrice électriquement.By completely hardening, the surface fixes the electrically conductive particles 2 and becomes electrically conductive or semiconductive.

Les particules 2 sont solidement fixées dans la « gangue » que constitue le substrat après son durcissement. La surface du substrat comportant les particules 2 conductrices électriquement présente ainsi de bonnes caractéristiques mécaniques, ce qui est un avantage par rapport aux revêtements du type SSM ou OSR mentionnés ci-dessus.The particles 2 are firmly fixed in the "gangue" that constitutes the substrate after curing. The surface of the substrate comprising the electrically conductive particles 2 thus has good mechanical characteristics, which is an advantage over the SSM or OSR type coatings mentioned above.

Cette gangue protège également de l'humidité les particules 2 conductrices électriquement, ce qui améliore la stabilité de la résistance électrique superficielle dans le temps.This gangue also protects the electrically conductive particles 2 from moisture, which improves the stability of the surface electrical resistance over time.

Les exemples non limitatifs suivants illustrent l'invention.The following nonlimiting examples illustrate the invention.

αs désigne le coefficient d'absorption solaire, ε le facteur d'émissivité infra-rouge et Rs la résistance électrique superficielle de la surface de l'article après la mise en oeuvre de la présente invention.α s denotes the solar absorption coefficient, ε the infra-red emissivity factor and R s the surface electrical resistance of the surface of the article after the implementation of the present invention.

EXEMPLE 1EXAMPLE 1

On projette, à l'aide d'un pistolet à air comprimé de la poudre d'étain dopé à l'oxyde d'antimoine dont les particules sont inférieures à 0,4 µm, mise en suspension dans un mélange 50/50 diacétate d'éthylène-glycol/polyéthylène-glycol (PM = 400) avec une concentration de 5 % en masse, sur une couche de 50 µm d'épaisseur de polysilsesquioxane à groupements fonctionnels hydroxyles non réticulé, préalablement appliquée sur un support en aluminium poli de 30 µm d'épaisseur. La quantité de poudre appliquée est de 1 mg/m2 de surface.An antimony-doped tin powder with a particle size of less than 0.4 μm is sprayed into a 50/50 diacetate mixture using an air gun. ethylene glycol / polyethylene glycol (MW = 400) with a concentration of 5% by weight, on a 50 μm thick layer of polysilsesquioxane with non-crosslinked hydroxyl functional groups, previously applied to a polished aluminum support of 30 μm thick. The amount of powder applied is 1 mg / m 2 of surface.

La couche est réticulée à 225°C pendant 1 heure.The layer is crosslinked at 225 ° C for 1 hour.

Les propriétés thermo-optiques de l'article sont :
αs = 0,15 ε = 0,82 Rs = 1MΩ/□The thermo-optical properties of the article are:
α s = 0.15 ε = 0.82 R s = 1MΩ / □

EXEMPLE 2EXAMPLE 2

On projette, à l'aide d'un pistolet à air comprimé de la poudre d'oxyde d'étain dopé à l'oxyde d'antimoine, dont les particules sont inférieures à 0,4µm, mise en suspension dans un mélange 50/50 diacétate d'éthylène-glycol/polyéthylène-glycol (PM = 400) avec une concentration de 5 % en masse, sur une couche composée d'un mélange de polysilsesquioxane à groupements fonctionnels hydroxyle (90%) et de polysilanol (10%) de 50 µm d'épaisseur préalablement appliquée sur un support en aluminium poli de 30 micromètres d'épaisseur. La quantité de poudre appliquée est de 1 mg/m2 de surface.An antimony oxide-doped tin oxide powder having a particle size of less than 0.4 μm is sprayed with a compressed air gun and suspended in a mixture. 50/50 diacetate ethylene glycol / polyethylene glycol (MW = 400) with a concentration of 5% by weight, on a layer composed of a mixture of polysilsesquioxane hydroxyl functional groups (90%) and polysilanol (10%) 50 microns thick previously applied to a polished aluminum support 30 microns thick. The amount of powder applied is 1 mg / m 2 of surface.

La couche est durcie à 225°C pendant 1 heure.The layer is cured at 225 ° C for 1 hour.

Les propriétés thermo-optiques de l'article sont :
αs =0,16 ε = 0,83 Rs = 200kΩ/□The thermo-optical properties of the article are:
α s = 0.16 ε = 0.83 R s = 200kΩ / □

EXEMPLE 3EXAMPLE 3

On projette à l'aide d'un pistolet à air comprimé de la poudre d'étain dopé à l'oxyde d'antimoine dont les particules sont inférieures à 0,4 µm, mise en suspension dans un mélange 50/50 diacétate d'éthylène-glycol/polyéthylène-glycol (PM = 400) avec une concentration de 10 % en masse, sur une couche de 50 µm d'épaisseur d'un mélange incomplètement réticulé obtenu à partir de polydiéthoxysiloxane (3 parties en poids), de polydiméthylsiloxane avec terminaisons silanols (4 parties en poids), de tétraméthyldiéthoxydisiloxane (4 parties en poids) et de diacétate de dibutyl-étain (0,014 partie en poids) préalablement appliquée sur un support en aluminium poli de 30 micromètres d'épaisseur. La quantité de poudre appliquée est de 1 mg/m2 de surface.An antimony-doped tin powder with a particle size of less than 0.4 μm is sprayed with a compressed air gun and suspended in a 50/50 diacetate mixture. ethylene glycol / polyethylene glycol (MW = 400) with a concentration of 10% by weight, on a layer 50 μm thick of an incompletely crosslinked mixture obtained from polydiethoxysiloxane (3 parts by weight), polydimethylsiloxane with silanol terminations (4 parts by weight), tetramethyldiethoxydisiloxane (4 parts by weight) and dibutyltin diacetate (0.014 parts by weight) previously applied to a polished aluminum support 30 microns thick. The amount of powder applied is 1 mg / m 2 of surface.

La couche est réticulée à température ambiante pendant 24 heures. Les propriétés thermo-optiques de l'article sont :
αs = 0,16 ε = 0,85 Rs = 200 kΩ/□The layer is crosslinked at room temperature for 24 hours. The thermo-optical properties of the article are:
α s = 0.16 ε = 0.85 R s = 200 kΩ / □

EXEMPLE 4EXAMPLE 4

On projette, à l'aide d'un pistolet à air comprimé de la poudre d'argent, dont les particules ont des dimensions nanométriques et sont mises en suspension avec une concentration de 10 % en masse dans un mélange 50/50 diacétate d'éthylène-glycol/polyéthylène-glycol (PM = 400), sur une couche de 50 µm d'épaisseur de polysilsesquioxane à groupes fonctionnels hydroxyle non réticulée préalablement appliquée sur un support en aluminium poli de 30 micromètres d'épaisseur. La quantité de poudre appliquée est de 2 mg/m2 de surface.With the aid of a compressed air gun, silver powder is sprayed, the particles of which have nanometric dimensions and are suspended at a concentration of 10% by mass in a 50/50 diacetate mixture. ethylene glycol / polyethylene glycol (MW = 400), on a 50 μm thick layer of polysilsesquioxane with non-crosslinked hydroxyl functional groups previously applied to a polished aluminum support 30 microns thick. The quantity of powder applied is 2 mg / m 2 of surface.

La couche est durcie à 225°C pendant 1 heure.The layer is cured at 225 ° C for 1 hour.

Les propriétés thermo-optiques de l'article obtenu sont :
αs = 0,16 ε = 0,82 Rs = 100Ω/□The thermo-optical properties of the article obtained are:
α s = 0.16 ε = 0.82 R s = 100Ω / □

EXEMPLE 5EXAMPLE 5

On projette, à l'aide d'un pistolet à air comprimé de la poudre d'oxyde d'étain dopé à l'oxyde d'antimoine en suspension dans un mélange 50/50 diacétate d'éthylène-glycol/polyéthylène-glycol (PM = 400) avec une concentration de 5 % en masse, dont les particules sont inférieures à 0,4 µm sur du Plexiglas® dont la surface a été préalablement ramollie sous l'action de trichloroéthylène.An antimony oxide-doped tin oxide powder is sprayed into a 50/50 ethylene glycol diacetate / polyethylene glycol MW = 400) with a concentration of 5% by weight, the particles of which are less than 0.4 μm on Plexiglas ® whose surface has been softened beforehand by the action of trichlorethylene.

Après évaporation des solvants, le Plexiglas® ainsi traité a une résistance électrique superficielle de l'ordre de 1 MΩ/□ pour un dépôt d'oxyde d'étain d'environ 2 mg/m2.After evaporation of the solvents, the Plexiglas ® thus treated has a surface electrical resistance of the order of 1 MΩ / □ for a tin oxide deposit of about 2 mg / m 2 .

EXEMPLE 6EXAMPLE 6

On projette, à l'aide d'un pistolet à air comprimé de la poudre d'oxyde d'antimoine en suspension dans un mélange 50/50 diacétate d'éthylène-glycol/polyéthylène-glycol (PM = 400) avec une concentration de 5 % en masse, dont les particules sont inférieures à 0,4 µm, sur du Plexiglas® ayant été revêtu préalablement d'une couche de solution de Plexiglas® dissous dans du trichloréthylène.An antimony oxide powder suspended in a 50/50 ethylene glycol diacetate / polyethylene glycol mixture (MW = 400) is sprayed with an air gun to a concentration of 5% by mass, the particles are less than 0.4 μ m, on the Plexiglas ® having been previously coated with a layer of Plexiglas ® dissolved solution in trichlorethylene.

Après évaporation des solvants, le Plexiglas® ainsi traité a une résistance électrique superficielle de l'ordre de 1MΩ/□ pour un dépôt d'oxyde d'étain d'environ 2mg/m2.After evaporation of the solvents, the Plexiglas ® thus treated has a surface electrical resistance of the order of 1MΩ / □ for a tin oxide deposit of about 2 mg / m 2 .

EXEMPLE 7EXAMPLE 7

On projette, à l'aide d'un pistolet à air comprimé de la poudre d'argent, dont les particules 2 ont des dimensions nanométriques, en suspension dans un mélange 50/50 diacétate d'éthylène-glycol/polyéthylène-glycol (PM = 400) avec une concentration de 5 % en masse, sur une plaque de PVC dont la surface a été ramollie sous l'action de cyclohexanone.With the aid of a compressed air gun, silver powder, the particles 2 of which are nanometrically dimensioned, is suspended in a 50/50 mixture of ethylene glycol diacetate and polyethylene glycol (PM). = 400) with a concentration of 5% by mass, on a PVC plate whose surface was softened under the action of cyclohexanone.

Après évaporation des solvants, le PVC ainsi traité a une résistance électrique superficielle de l'ordre de 10 kΩ/□ pour un dépôt d'argent d'environ 20 mg/m2.After evaporation of the solvents, the PVC thus treated has a surface electrical resistance of the order of 10 kΩ / □ for a silver deposit of approximately 20 mg / m 2 .

EXEMPLE 8EXAMPLE 8

Cet exemple et le suivant sont donnés en vue d'illustrer la perte des propriétés thermo-optiques de réflecteurs solaires conducteurs électriques dans le volume (hors invention) par rapport à des réflecteurs conducteurs électriques en surface (selon l'invention).This example and the following are given with a view to illustrating the loss of the thermo-optical properties of electrically conductive solar reflectors in the volume (excluding the invention) with respect to surface-conducting electrical reflectors (according to the invention).

On applique sur un substrat en Kapton® aluminisé, une couche d'un mélange de polysilsesquioxane (25 g) et de poudre d'oxyde d'étain dopé à l'oxyde d'antimoine (0,22 g) dont les particules sont inférieures à 0,4 micromètres, obtenu par broyage des ingrédients pendant 30 minutes.An aluminized Kapton ® substrate is coated with a layer of a mixture of polysilsesquioxane (25 g) and antimony oxide doped tin oxide powder (0.22 g), the particles of which are inferior at 0.4 micrometers, obtained by grinding the ingredients for 30 minutes.

La couche ainsi appliquée est polymérisée à 225°C pendant 1 heure.The layer thus applied is polymerized at 225 ° C. for 1 hour.

Les propriétés thermo-optiques de l'article sont :

  • αs = 0,20
  • ε = 0,83 et la résistance électrique volumique est supérieure à 1 GΩ.
The thermo-optical properties of the article are:
  • α s = 0.20
  • ε = 0.83 and the electrical resistance volume is greater than 1 GΩ.

EXEMPLE 9EXAMPLE 9

On applique sur un substrat d'aluminium poli, une couche d'un mélange de polysesquioxane (25 g) et de poudre d'argent dont les particules ont des dimensions nanométriques (0,22 g), obtenu par broyage des ingrédients pendant 30 minutes.A layer of a mixture of polysesquioxane (25 g) and silver powder whose particles have nanometric dimensions (0.22 g), obtained by grinding the ingredients for 30 minutes, is applied to a polished aluminum substrate. .

La couche ainsi appliquée est polymérisée à 225°C pendant 1 heure.The layer thus applied is polymerized at 225 ° C. for 1 hour.

Les propriétés thermo-optiques de l'article obtenu sont :

  • αs = 0,30
  • ε = 0,83 et la résistance électrique volumique est supérieure à 1 GΩ.
The thermo-optical properties of the article obtained are:
  • α s = 0.30
  • ε = 0.83 and the electrical resistance volume is greater than 1 GΩ.

Bien entendu, l'invention n'est pas limitée aux modes de réalisation décrits et représentés, fournis à titre illustratif et non limitatif. En particulier la fabrication de poudres de particules 2 conductrices, leur nature, les techniques d'application de la poudre ou la nature de la couche superficielle 4 ou du matériau 1 de l'article A peuvent être différents.Of course, the invention is not limited to the embodiments described and shown, provided for illustrative and non-limiting. In particular, the manufacture of powders of conductive particles 2, their nature, the techniques for applying the powder or the nature of the surface layer 4 or the material 1 of the article A may be different.

Claims (14)

  1. Article having a superficial electrical resistance of less than or equal to 109 ohms per square, characterised in that it comprises on its surface a plurality of electrically conducting particles (2) fixed to the surface of the said article by cross-linking of the said surface.
  2. Article according to claim 1, characterised in that the said electrically conducting particles (2) have a size less than 0.4 µm.
  3. Article according to any one of claims 1 and 2, characterised in that the distance between the said electrically conducting particles (2) is of the order of 10 to 20 µm.
  4. Article according to any one of claims 1 to 3, characterised in that the said article (A) comprises a cross-linked superficial layer (4) consisting of a resin or varnish.
  5. Article according to claim 4, characterised in that the layer (4) is transparent.
  6. Process for conferring on an article (A) a superficial electrical resistance less than or equal to 109 ohms per square, characterised in that it comprises applying a plurality of electrically conducting particles (2) to a soft and adhesive surface of the said article (A), followed by a cross-linking of the said surface.
  7. Process according to claim 6, characterised in that a superficial layer (4) based on a cross-linkable resin, incompletely cross-linked so as to be soft and adhesive, is applied to the said article (A) prior to the application of the said electrically conducting particles (2).
  8. Process according to claim 7, characterised in that the thickness of the said cross-linkable layer of resin is between 5 and 50 µm.
  9. Process according to claim 6, characterised in that prior to the application of the said electrically conducting particles (2), the surface of the said article (A) is treated with a solvent for the material constituting the said surface, so as to make the said surface soft and adhesive.
  10. Process according to any one of claims 6 to 9, characterised in that the said electrically conducting particles (2) have a size less than 0.4 µm.
  11. Process according to any one of claims 6 to 10, characterised in that the said electrically conducting particles (2) consist of particles (2) of doped oxide.
  12. Process according to claim 11, characterised in that an amount of the said particles (2) of doped oxide is applied that is within the range from 0.5 to 5 mg per square metre of the said soft and adhesive surface.
  13. Process according to any one of claims 6 to 10, characterised in that the said electrically conducting particles (2) consist of metallic particles (2).
  14. Process according to claim 13, characterised in that an amount of the said metallic particles (2) is applied that is within the range from 2 to 20 mg per square metre of the said soft and adhesive surface.
EP02732838A 2001-04-27 2002-04-25 Article provided with surface antistatic properties and method for obtaining same Expired - Lifetime EP1382229B1 (en)

Applications Claiming Priority (3)

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FR0105712 2001-04-27
FR0105712A FR2824230B1 (en) 2001-04-27 2001-04-27 DUTY ARTICLE OF SUPERFICIAL ANTISTATIC PROPERTIES AND METHOD OF OBTAINING
PCT/FR2002/001420 WO2002089535A1 (en) 2001-04-27 2002-04-25 Article provided with surface antistatic properties and method for obtaining same

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CN101321426B (en) * 2007-06-06 2013-02-27 3M创新有限公司 Electrostatic resistant film and product including the same
ES2320839B1 (en) * 2007-11-27 2010-03-11 Cosentino S.A. PROCEDURE FOR THE MANUFACTURE OF AN ANTI-STATIC ARTICLE OF AGLOMERATED STONE AND ARTICLE OBTAINED BY MEANS OF THIS PROCEDURE.

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DE60222758T2 (en) 2008-07-17
DE60222758D1 (en) 2007-11-15
ES2294135T3 (en) 2008-04-01
FR2824230A1 (en) 2002-10-31

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