EP1382229A1 - Article provided with surface antistatic properties and method for obtaining same - Google Patents

Article provided with surface antistatic properties and method for obtaining same

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Publication number
EP1382229A1
EP1382229A1 EP02732838A EP02732838A EP1382229A1 EP 1382229 A1 EP1382229 A1 EP 1382229A1 EP 02732838 A EP02732838 A EP 02732838A EP 02732838 A EP02732838 A EP 02732838A EP 1382229 A1 EP1382229 A1 EP 1382229A1
Authority
EP
European Patent Office
Prior art keywords
article
electrically conductive
particles
conductive particles
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02732838A
Other languages
German (de)
French (fr)
Other versions
EP1382229B1 (en
Inventor
Jean-Claude Guillaumon
Pascale Véronique NABARRA
Stéphanie REMAURY
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National dEtudes Spatiales CNES
Original Assignee
Centre National dEtudes Spatiales CNES
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National dEtudes Spatiales CNES filed Critical Centre National dEtudes Spatiales CNES
Publication of EP1382229A1 publication Critical patent/EP1382229A1/en
Application granted granted Critical
Publication of EP1382229B1 publication Critical patent/EP1382229B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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, in particular for combating the effects of static electricity.
  • the accumulation of electrostatic charges on the surface of an article made of dielectric material can be detrimental to the functioning of electronic devices or equipment by creating electrical discharges generating electromagnetic disturbances (parasites) or destroying electronic components.
  • thermo-optical characteristics such as the solar absorption coefficient or the infrared emissivity factor, well determined.
  • the Applicant in patent FR-B-2 770 230, proposes a solar reflector for the thermal control of a spacecraft whose coating is of a lower cost than OSR or SSM.
  • the surface layer of this coating is a polysiloxane layer about 50 ⁇ m thick applied on a metallized substrate.
  • This protective layer is however not electrically conductive so that the problem associated with static electricity remains.
  • thermo-optical properties A means which would make it possible to confer antistatic properties to the solar reflectors of FR-B-2 770 230, without significantly 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 (trioboelectric effect) or by friction with other insulating materials . As in space, the accumulation of these electrostatic charges can create harmful electric discharges for electronic equipment.
  • Various means for eliminating these charges are known, such as the use of conductive materials in the volume (for example polymeric materials charged with conductive particles) or the application of a layer of electrically conductive paint.
  • conductive materials in the volume for example polymeric materials charged with conductive particles
  • a layer of electrically conductive paint for transparent articles, such as aircraft windows, there is no suitable antistatic treatment.
  • the invention aims to satisfy these needs. More specifically, the invention 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 distributed over the latter. A surface electrical resistance of 10 9 ⁇ / D is considered to be the maximum admissible resistance for an acceptable antistatic effect.
  • the particles adhere to the surface of a hardened layer of resin or varnish applied to the article.
  • the electrically conductive particles should be less than 0.4 ⁇ m. If transparency is not an essential criterion, larger particles can be used.
  • the electroconductive particles can 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, antimony oxide, bismuth oxide, titanium oxide or lead oxide; or
  • the salts of the oxide to be doped and of the dopant are dissolved in water or an appropriate solvent and then co-precipitated slowly by the action of an organic acid in solution.
  • organic acids are, for example, oxalic acid, citric acid, tartaric acid, malonic acid, maleic acid and the like.
  • the precipitate 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 which depends on the type of oxide and dopant.
  • the quantity of electroconductive particles adhering to the surface of the article is advantageously the lowest possible quantity which makes it possible to obtain an appropriate surface electrical resistance, that is to say ⁇ 10 9 ⁇ / square, while not degrading not notably the thermo-optical properties of the article, when the latter factor is important. For information and not limitation, it has been found that quantity of particles distributed over the surface of the article with an interparticle distance of the order of 10 to 20 ⁇ m usually gives satisfactory results.
  • This distribution of the particles corresponds substantially to a surface concentration of 0.5 to 5 mg of particles per m 2 of surface when the particles consist of a doped oxide, and of 2 to 20 mg of particles per m 2 of surface when the particles are made of a metal.
  • the invention also relates to a method 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 electrically conductive particles distributed over said surface, followed by hardening of said surface.
  • a surface layer based on a hardenable resin is applied to said article, incompletely hardened so as to be soft and sticky, prior to the application of said electrically conductive particles.
  • its thickness is between 5 and 50 ⁇ m.
  • the layer of polymerizable or crosslinkable resin could be replaced by a varnish composition, for example consisting of a solution in a solvent of a polymeric material.
  • the surface of said article is treated with a solvent for the material constituting said surface in order to generate said soft and sticky surface.
  • the particles can be applied to the surface to be treated in the dry powder state using a pneumatic or electrostatic powder gun, like those sold by the company KREMLIN, or else in the form of a suspension in a medium. liquid, for example using a paint spray gun.
  • a pneumatic or electrostatic powder gun like those sold by the company KREMLIN
  • a suspension in a medium. liquid for example using a paint spray gun.
  • Other modes of application of the particles will be obvious to a person skilled in the art.
  • the resin can be chosen, by way of illustration and without limitation, from polysiloxane, epoxy, polyurethane, polyesters, acrylic resins, etc.
  • the softening must be carried out using an appropriate solvent chosen according to the material to be softened.
  • To soften methacrylate resins use is made, for example, of benzene, toluene, xylene, methylene chloride, chloroform, ethylene chloride, chlorobenzene, dioxane , methyl ethyl ketone, diisopropyl ketone, cyclohexanone, methyl formate or ethyl acetate.
  • To soften polycarbonate resins for example, benzene, chloroform, acetone, methylene chloride, m-cresol, dioxane, cyclohexanone, pyridine or DMF are used.
  • chloroform formic acid or dichloroethylene
  • methyl ethyl ketone cyclopentanone
  • cyclohexanone DMF
  • nitrobenzene or DMSO are used, for example.
  • FIG. 1 is a schematic view, in section, of an article made 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, to the surface of which a surface layer of resin has been applied.
  • identical notations are used for analogous or identical elements.
  • FIG. 1 shows, in section, an article A made of a material 1 charged, in its volume, with electrically conductive particles 2.
  • the material 1 is thus made electrically conductive and does not accumulate electrostatic charges.
  • FIG. 2 illustrates an article A made of a material 1 having the property of being able to be made, on the surface, soft and sticky. Electrically conductive particles 2 are applied and adhered to the surface of article A.
  • the material 1 is transparent, for example if the article A is an airplane window, for example made of polycarbonate, its thermo-optical properties are little modified by the application of the particles 2 to its surface.
  • FIG. 3 illustrates an article A, the surface of which has been successively covered with a metallized film 3 and then with a layer 4 of transparent crosslinkable resin.
  • the combination of film 3 and layer 4 is intended to ensure effective thermooptic control.
  • the film 3 is not an essential element of the present invention and could be omitted, for example, if the surface layer 4 itself possessed the desired thermo-optical characteristics or in applications where these thermo-optical properties would be unimportant .
  • Electrically conductive particles 2 cover the external surface of the surface layer 4.
  • the embodiment of the invention illustrated in Figure 3 is particularly suited to the field of space.
  • the electrically conductive particles 2 have little or no effect on the thermo-optical properties of the surface layer 4.
  • the embodiment according to FIG. 2 before application of the particles
  • the material 1 is a polymer
  • its surface can be dissolved superficially by means of an appropriate solvent, as described above.
  • the particles 2 are applied to the surface of the resin before it is cross-linked or completely cured.
  • 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 make it possible, when applying the electrically conductive particles 2, to maintain them on the surface by preventing them from penetrating deep.
  • the surface is hardened, 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 semi-conductive.
  • the particles 2 are firmly fixed in the "gangue" that constitutes the substrate after it has hardened.
  • the surface of the substrate comprising the electrically conductive particles 2 thus exhibits good mechanical characteristics, which is an advantage compared to the coatings of the SSM or OSR type mentioned above.
  • This gangue also protects the electrically conductive particles 2 from humidity, which improves the stability of the surface electrical resistance over time.
  • tin powder doped with antimony oxide the particles of which are less than 0.4 ⁇ m, suspended in a 50/50 diacetate mixture.
  • ethylene glycol / polyethylene glycol (PM 400) with a concentration of 5% by mass, on a 50 ⁇ m thick layer of polysilsesquioxane with non-crosslinked hydroxyl functional groups, previously applied on 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 amount of powder applied is 1 mg / m 2 of surface.
  • the layer is cured at 225 ° C for 1 hour.
  • tin powder doped with antimony oxide whose particles are less than 0.4 ⁇ m, suspended in a 50/50 diacetate mixture.
  • ethylene glycol / polyethylene glycol (MW 400) with a concentration of 10% by mass, on a 50 ⁇ m thick layer of an incompletely crosslinked mixture obtained from polydiethoxysiloxane (3 parts by weight), polydimethylsiloxane with silanol endings (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 micrometers thick.
  • the amount of powder applied is 1 mg / m 2 of surface.
  • Silver powder is sprayed with an air pistol, the particles of which have nanometric dimensions and are suspended with a concentration of 10% by mass in a 50/50 diacetate mixture.
  • the amount of powder applied is 2 mg / m 2 of surface.
  • the layer is cured at 225 ° C for 1 hour.
  • EXAMPLE 5 Using an air pistol, sprayed tin oxide powder doped with antimony oxide suspended in a 50/50 mixture of ethylene glycol diacetate / polyethylene glycol ( PM ⁇ 400) with a concentration of 5% by mass, the particles of which are less than 0.4 ⁇ m on Plexiglas 8 , the surface of which has been previously softened under the action of trichlorethylene.
  • the Plexiglas 8 thus treated has a surface electrical resistance of the order of 1 M ⁇ / D for a deposit of tin oxide of approximately 2 mg / m 2 .
  • Silver powder the particles 2 of which have nanometric dimensions, is sprayed using a compressed air gun, suspended in a mixture
  • the PVC thus treated has a surface electrical resistance of the order of 10 k ⁇ / Q for a silver deposit of approximately 20 mg / m 2 .
  • the layer thus applied is polymerized at 225 ° C for 1 hour.
  • the invention is not limited to the embodiments described and shown, provided by way of illustration and not limitation. In particular the manufacture of powders of conductive particles 2, their nature, the manufacture of powders of conductive particles 2, their nature, the manufacture of powders of conductive particles 2, their nature, the manufacture of powders of conductive particles 2, their nature, the manufacture of powders of conductive particles 2, their nature, the manufacture of powders of conductive particles 2, their nature, the manufacture of powders of conductive particles 2, their nature, the manufacture of powders of conductive particles 2, their nature, 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 of the material 1 of article A may be different.

Landscapes

  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Elimination Of Static Electricity (AREA)

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

Article doué de propriétés antistatiques superficielles et procédé d'obtention. Article endowed with surface antistatic properties and process for obtaining it.
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, in particular 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 made of dielectric material can be detrimental to the functioning of electronic devices or equipment by creating electrical discharges generating electromagnetic disturbances (parasites) or destroying electronic components.
Un véhicule spatial soumis à l'environnement spatial d'orbites géostationnaires, héliosynchrones 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. 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.A space vehicle subjected to the space environment of geostationary orbit, heliosynchronous or more generally in or beyond the Van Allen belts, is subjected to fluxes of particles, such as electrons and protons, of variable energy. These fluxes electrically charge the external coatings of vehicles if they are dielectric, thus creating potential differences between different parts of the spacecraft. Beyond a certain threshold, a potential difference can generate an electric shock which can cause disturbances or even the destruction of electronic equipment located nearby.
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 ensure, 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. Si ce dépôt conducteur électriquement remplit bien sa fonction d'élimination des décharges électrostatiques, il est fragile, sensible à l'humidité et coûteux. 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.Current coatings used for thermal control are, for example, SSM, from the English Second Surface Mirrors, or Double Surface Mirrors, or OSR, from the English Optical Surface Reflectors, or Optical Reflective Surfaces. The outer or "surface" layer of these coatings consists of a polymer film in the case of SSM or a quartz plate in the case of OSR. To make this layer electrically conductive, there is applied under vacuum a substantially transparent deposit based on indium oxide doped with tin oxide. If this electrically conductive deposit fulfills its function of eliminating electrostatic discharges, it is fragile, sensitive to humidity and costly. The Applicant, in patent FR-B-2 770 230, proposes a solar reflector for the thermal control of a spacecraft whose coating is of a lower cost than OSR or SSM. The surface layer of this coating is a polysiloxane layer about 50 μm thick applied on a metallized substrate. This protective layer is however not electrically conductive so that the problem associated with 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 thermooptiques 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 drawback, however, of degrading the thermooptical qualities of the reflector and is therefore not satisfactory for use where it is necessary to provide thermal control of a spacecraft.
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 to the solar reflectors of FR-B-2 770 230, without significantly 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 data processing, electrostatic charges can be created on the surface of electrically insulating materials by friction of the air (trioboelectric effect) or by friction with other insulating materials . As in space, the accumulation of these electrostatic charges can create harmful electric discharges for electronic equipment. Various means for eliminating these charges are known, such as the use of conductive materials in the volume (for example polymeric materials charged with conductive particles) or the application of a layer of electrically conductive paint. However, for transparent articles, such as aircraft windows, there is no suitable antistatic treatment.
Un moyen qui permettrait de conférer des propriétés antistatiques à des articles transparents sans altérer sensiblement leur transparence serait donc très utile. L'invention vise à satisfaire ces besoins. Plus précisément, l'invention 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. Une résistance électrique superficielle de 109Ω/D est considérée comme la résistance maximale admissible pour un effet antistatique acceptable.A means which would make it possible to confer antistatic properties on transparent articles without appreciably altering their transparency would therefore be very useful. The invention aims to satisfy these needs. More specifically, the invention 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 distributed over the latter. A surface electrical resistance of 10 9 Ω / D is considered to be the maximum admissible 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. Les particules électroconductrices peuvent être des oxydes métalliques dopés tels queAccording to one embodiment, the particles adhere to the surface of a hardened layer of resin or varnish applied to the article. When transparency in the wavelength range of 200 to 1000 nm is an essential factor, such as for example a space solar reflector or an aircraft window, the electrically conductive particles should be less than 0.4 μm. If transparency is not an essential criterion, larger particles can be used. The electroconductive particles can be doped metal oxides such as
- 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,- doped tin oxide, for example with chlorine, fluorine, antimony oxide, indium oxide or bismuth oxide,
- 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- doped indium oxide, for example with tin oxide, antimony oxide, bismuth oxide, titanium oxide or lead oxide; or
- des métaux finement divisés tels que : l'argent, le zinc, le cuivre, l'aluminium, le platine, l'or, le palladium ou similaires.- 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 :To obtain the finest possible doped oxide particles, for example, proceed as follows:
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.The salts of the oxide to be doped and of 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. 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.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 which depends on the type of oxide and dopant. The quantity of electroconductive particles adhering to the surface of the article is advantageously the lowest possible quantity which makes it possible to obtain an appropriate surface electrical resistance, that is to say <10 9 Ω / square, while not degrading not notably the thermo-optical properties of the article, when the latter factor is important. For information and not limitation, it has been 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 the particles corresponds substantially to a surface concentration of 0.5 to 5 mg of particles per m 2 of surface when the particles consist of a doped oxide, and of 2 to 20 mg of particles per m 2 of surface when the particles are made 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 method 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 electrically conductive particles distributed over said surface, followed by hardening of 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 is applied to said article, incompletely hardened so as to be soft and sticky, 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 μm.
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 layer of polymerizable or crosslinkable resin could be replaced by a varnish composition, for example consisting of 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 for 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 can be applied to the surface to be treated in the dry powder state using a pneumatic or electrostatic powder gun, like those sold by the company KREMLIN, or else in the form of a suspension in a medium. liquid, for example using a paint spray gun. Other modes of application of the particles will be obvious to a person 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.. 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.In the embodiments in which the particles are applied to a surface layer of incompletely hardened resin, the resin can be chosen, by way of illustration and without limitation, from polysiloxane, epoxy, polyurethane, polyesters, acrylic resins, etc. In the embodiment where particles are applied to a previously softened surface of the article, the softening must be carried out using an appropriate solvent chosen according to the material to be softened. Thus, by way of illustrative and nonlimiting examples: To soften methacrylate resins, use is made, for example, of benzene, toluene, xylene, methylene chloride, chloroform, ethylene chloride, chlorobenzene, dioxane , methyl ethyl ketone, diisopropyl ketone, cyclohexanone, methyl formate or ethyl acetate. To soften polycarbonate resins, for example, benzene, chloroform, acetone, methylene chloride, m-cresol, dioxane, cyclohexanone, pyridine or DMF are used.
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.To soften polyester resins, chloroform, formic acid or dichloroethylene are used, for example. To soften vinyl chloride, THF, methyl ethyl ketone, cyclopentanone, cyclohexanone, DMF, nitrobenzene or DMSO are used, for example.
Sur le dessin annexé :In the attached drawing:
- 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.- Figure 1 is a schematic view, in section, of an article made electrically conductive by incorporation of electrically conductive particles in its volume, according to the prior art.
- 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.- 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, to the surface of which a surface layer of resin has been applied. In the various figures, identical notations are used for analogous or identical elements.
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.FIG. 1 shows, in section, an article A made of a material 1 charged, in its volume, with electrically conductive particles 2. The material 1 is thus made electrically conductive and does not accumulate electrostatic charges.
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.The incorporation of electrically conductive particles 2 into the volume of the material 1 is not always technically possible. In addition, when the material 1 is transparent, its thermo-optical properties are strongly modified by the incorporation, in the volume, of the 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 made of a material 1 having the property of being able to be made, on the surface, soft and sticky. Electrically conductive particles 2 are applied and adhered to the surface of 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 airplane window, for example made of polycarbonate, its thermo-optical properties are little modified by the application of the particles 2 to 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 thermooptique efficace. 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.FIG. 3 illustrates an article A, the surface of which has been successively covered with a metallized film 3 and then with a layer 4 of transparent crosslinkable resin. The combination of film 3 and layer 4 is intended to ensure effective thermooptic control. The film 3 is not an essential element of the present invention and could be omitted, for example, if the surface layer 4 itself possessed 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 external 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. Dans le mode de réalisation selon la figure 2, avant application des particulesThe embodiment of the invention illustrated in Figure 3 is particularly suited to the field of space. In fact, under certain conditions indicated below, the electrically conductive particles 2 have little or no effect on the thermo-optical properties of the surface layer 4. In the embodiment according to FIG. 2, before application of the particles
2 conductrices sur la surface de l'article A, on prépare cette surface afin de la ramollir.2 conductors on the surface of 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. 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 case where the material 1 is a polymer, its surface can be dissolved superficially by means of an appropriate solvent, as described above. In the embodiment according to FIG. 3, the particles 2 are applied to the surface of the resin before it is cross-linked or completely cured.
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. 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.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 make it possible, when applying the electrically conductive particles 2, to maintain them on the surface by preventing them from penetrating deep. After application of the electrically conductive particles 2, the surface is hardened, 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 semi-conductive.
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 it has hardened. The surface of the substrate comprising the electrically conductive particles 2 thus exhibits good mechanical characteristics, which is an advantage compared to the coatings of the SSM or OSR type 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 humidity, which improves the stability of the surface electrical resistance over time.
Les exemples non limitatifs suivants illustrent l'invention. as désigne le coefficient d'absorption solaire, ε le facteur d'émissivité infrarouge et Rs la résistance électrique superficielle de la surface de l'article après la mise en oeuvre de la présente invention.The following nonlimiting examples illustrate the invention. as denotes the solar absorption coefficient, ε the infrared emissivity factor and Rs 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.Using a compressed air gun, we project tin powder doped with antimony oxide, the particles of which are less than 0.4 μm, suspended in a 50/50 diacetate mixture. ethylene glycol / polyethylene glycol (PM = 400) with a concentration of 5% by mass, on a 50 μm thick layer of polysilsesquioxane with non-crosslinked hydroxyl functional groups, previously applied on 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 : as = 0,15 ε = 0,82 Rs = 1 MΩ/DThe thermo-optical properties of the article are: as = 0.15 ε = 0.82 Rs = 1 MΩ / D
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. La couche est durcie à 225°C pendant 1 heure.Using a compressed air gun, we spray tin oxide powder doped with antimony oxide, whose particles are less than 0.4 μm, suspended in a mixture 50 / 50 ethylene glycol diacetate / polyethylene glycol (MW = 400) with a concentration of 5% by mass, on a layer composed of a mixture of polysilsesquioxane with hydroxyl functional groups (90%) and polysilanol (10%) 50 μm thick previously applied to a polished aluminum support 30 micrometers thick. The amount of powder applied is 1 mg / m 2 of surface. The layer is cured at 225 ° C for 1 hour.
Les propriétés thermo-optiques de l'article sont : as = 0,16 ε = 0,83 Rs - 200kΩ/DThe thermo-optical properties of the article are: as = 0.16 ε = 0.83 Rs - 200kΩ / D
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.Using a compressed air gun, we spray tin powder doped with antimony oxide whose particles are less than 0.4 μm, suspended in a 50/50 diacetate mixture. ethylene glycol / polyethylene glycol (MW = 400) with a concentration of 10% by mass, on a 50 μm thick layer of an incompletely crosslinked mixture obtained from polydiethoxysiloxane (3 parts by weight), polydimethylsiloxane with silanol endings (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 micrometers 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 : as = 0,16 ε = 0,85 Rs = 200 kΩ/DThe layer is crosslinked at room temperature for 24 hours. The thermo-optical properties of the article are: as = 0.16 ε = 0.85 Rs = 200 kΩ / D
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.Silver powder is sprayed with an air pistol, the particles of which have nanometric dimensions and are suspended with a concentration of 10% by mass in a 50/50 diacetate mixture. ethylene glycol / polyethylene glycol (PM = 400), on a 50 μm thick layer of polysilsesquioxane with non-crosslinked hydroxyl functional groups previously applied on a polished aluminum support 30 micrometers thick. The amount 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 : s = 0,16 ε = 0,82 Rs = 100Ω/DThe thermo-optical properties of the article obtained are: s = 0.16 ε = 0.82 Rs = 100Ω / D
EXEMPLE 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 Plexiglas8 dont la surface a été préalablement ramollie sous l'action de trichloroéthylène.EXAMPLE 5 Using an air pistol, sprayed tin oxide powder doped with antimony oxide suspended in a 50/50 mixture of ethylene glycol diacetate / polyethylene glycol ( PM ≈ 400) with a concentration of 5% by mass, the particles of which are less than 0.4 μm on Plexiglas 8 , the surface of which has been previously softened under the action of trichlorethylene.
Après évaporation des solvants, le Plexiglas8 ainsi traité a une résistance électrique superficielle de l'ordre de 1 MΩ/D pour un dépôt d'oxyde d'étain d'environ 2 mg/m2.After evaporation of the solvents, the Plexiglas 8 thus treated has a surface electrical resistance of the order of 1 MΩ / D for a deposit of tin oxide of approximately 2 mg / m 2 .
EXEMPLE 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. Après évaporation des solvants, le Plexiglas* ainsi traité a une résistance électrique superficielle de l'ordre de 1 MΩ/D pour un dépôt d'oxyde d'étain d'environ 2mg/m2.EXAMPLE 6 Antimony oxide powder suspended in a 50/50 mixture of ethylene glycol diacetate / polyethylene glycol (PM = 400) is sprayed using an air gun. concentration of 5% by mass, the particles of which are less than 0.4 μm, on Plexiglas "having been previously coated with a layer of Plexiglas * solution dissolved in trichlorethylene. After evaporation of the solvents, the Plexiglas * thus treated has a surface electrical resistance of the order of 1 MΩ / D for a deposit of tin oxide of approximately 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 mélangeSilver powder, the particles 2 of which have nanometric dimensions, is sprayed using a compressed air gun, suspended in a mixture
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.50/50 ethylene glycol diacetate / polyethylene glycol (MW = 400) with a concentration of 5% by mass, on a PVC plate whose surface has been 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/Q pour un dépôt d'argent d'environ 20 mg/m2. EXEMPLE 8After evaporation of the solvents, the PVC thus treated has a surface electrical resistance of the order of 10 kΩ / Q for a silver deposit of approximately 20 mg / m 2 . EXAMPLE 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 in order to illustrate the loss of the thermo-optical properties of electrically conductive solar reflectors in the volume (outside the invention) compared to electrically conductive surface 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. La couche ainsi appliquée est polymérisée à 225°C pendant 1 heure. Les propriétés thermo-optiques de l'article sont : αs = 0,20 ε = 0,83 et la résistance électrique volumique est supérieure à 1 GΩ. EXEMPLE 9A layer of a mixture of polysilsesquioxane (25 g) and tin oxide powder doped with antimony oxide (0.22 g), the particles of which are smaller, is applied to an aluminized Kapton® substrate. 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 thermo-optical properties of the article are: α s = 0.20 ε = 0.83 and the electrical volume resistance is greater than 1 GΩ. EXAMPLE 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. La couche ainsi appliquée est polymérisée à 225°C pendant 1 heure. Les propriétés thermo-optiques de l'article obtenu sont : as = 0,30 ε = 0,83 et la résistance électrique volumique est supérieure à 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, lesA layer of a mixture of polysesquioxane (25 g) and silver powder, the particles of which have nanometric dimensions (0.22 g), is obtained on a polished aluminum substrate, obtained by grinding the ingredients for 30 minutes. . The layer thus applied is polymerized at 225 ° C for 1 hour. The thermo-optical properties of the article obtained are: as = 0.30 ε = 0.83 and the electrical volume resistance is greater than 1 GΩ. Of course, the invention is not limited to the embodiments described and shown, provided by way of illustration and not limitation. In particular the manufacture of powders of conductive particles 2, their nature, the
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. The techniques for applying the powder or the nature of the surface layer 4 or of the material 1 of article A may be different.

Claims

REVENDICATIONS
1 . Article ayant une résistance électrique superficielle inférieure ou égale à 109 Ohms par carré, caractérisé en ce qu'il comporte à sa surface une pluralité de particules (2) conductrices électriquement, enrobées, au moins en partie, par un matériau dudit article.1. Article having a surface electrical resistance less than or equal to 10 9 Ohms per square, characterized in that it comprises on its surface a plurality of electrically conductive particles (2), coated, at least in part, with a material of said article.
2. Article selon la revendication 1 , caractérisé en ce que lesdites particules (2) conductrices électriquement ont une grosseur inférieure à 0,4 μm.2. Article according to claim 1, characterized in that said electrically conductive particles (2) have a size less than 0.4 μm.
3. Article selon l'une quelconque des revendications 1 et 2, caractérisé en ce que la distance entre lesdites particules (2) conductrices électriquement est de l'ordre de 10 à 20 μm.3. Article according to any one of claims 1 and 2, characterized in that the distance between said particles (2) electrically conductive is of the order of 10 to 20 microns.
4. Article selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ledit article (A) comporte une couche superficielle durcie (4) constituée d'une résine ou vernis.4. Article according to any one of claims 1 to 3, characterized in that said article (A) comprises a hardened surface layer (4) consisting of a resin or varnish.
5. Article selon la revendication 4, caractérisé en ce que la couche (4) est transparente.5. Article according to claim 4, characterized in that the layer (4) is transparent.
6. Procédé pour conférer à un article (A) 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 (A), d'une pluralité de particules (2) conductrices électriquement, puis un durcissement de ladite surface.6. Method for imparting to an article (A) 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 (A), a plurality of electrically conductive particles (2), followed by hardening of said surface.
7. Procédé selon la revendication 6, caractérisé en ce qu'on applique sur ledit article (A) une couche superficielle (4) à base d'une résine durcissable, incomplètement durcie de façon à être molle et collante, préalablement à l'application desdites particules (2) conductrices électriquement.7. Method according to claim 6, characterized in that there is applied to said article (A) a surface layer (4) based on a hardenable resin, incompletely hardened so as to be soft and sticky, prior to application said electrically conductive particles (2).
8. Procédé selon la revendication 7, caractérisé en ce que l'épaisseur de ladite couche de résine durcissable est comprise entre 5 et 50 μm.8. Method according to claim 7, characterized in that the thickness of said layer of curable resin is between 5 and 50 microns.
9. Procédé selon la revendication 6, caractérisé en ce que, préalablement à l'application desdites particules (2) conductrices électriquement, on traite la surface dudit article (A) au moyen d'un solvant de la matière constituant ladite surface afin de générer ladite surface molle et collante. 9. Method according to claim 6, characterized in that, prior to the application of said electrically conductive particles (2), the surface of said article (A) is treated with a solvent for the material constituting said surface in order to generate said soft and sticky surface.
10. Procédé selon l'une quelconque des revendications 6 à 9, caractérisé en ce que lesdites particules (2) conductrices électriquement ont une grosseur inférieure à 0,4 μm.10. Method according to any one of claims 6 to 9, characterized in that said electrically conductive particles (2) have a size less than 0.4 μm.
1 1. Procédé selon l'une quelconque des revendications 6 à 10, caractérisé en ce que lesdites particules (2) conductrices électriquement sont constituées de particules (2) en oxyde dopé.1 1. Method according to any one of claims 6 to 10, characterized in that said electrically conductive particles (2) consist of particles (2) of doped oxide.
12. Procédé selon la revendication 1 1, caractérisé en ce qu'on applique une quantité desdites particules (2) en oxyde dopé comprise dans la gamme de 0,5 à 5 mg par mètre carré de ladite surface molle et collante.12. The method of claim 1 1, characterized in that an amount of said particles (2) of doped oxide is applied in the range of 0.5 to 5 mg per square meter of said soft and sticky surface.
13. Procédé selon l'une quelconque des revendications 6 à 10, caractérisé en ce que lesdites particules (2) conductrices électriquement sont constituées de particules (2) métalliques.13. Method according to any one of claims 6 to 10, characterized in that said electrically conductive particles (2) consist of metal particles (2).
14. Procédé selon la revendication 13, caractérisé en ce qu'on applique une quantité desdites particules (2) métalliques comprise dans la gamme de 2 à 20 mg par mètre carré de ladite surface molle et collante. 14. The method of claim 13, characterized in that an amount of said metal particles (2) is applied in the range of 2 to 20 mg per square meter of said soft and sticky 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)

Application Number Priority Date Filing Date Title
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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EP1382229A1 true EP1382229A1 (en) 2004-01-21
EP1382229B1 EP1382229B1 (en) 2007-10-03

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EP (1) EP1382229B1 (en)
AT (1) ATE375075T1 (en)
DE (1) DE60222758T2 (en)
ES (1) ES2294135T3 (en)
FR (1) FR2824230B1 (en)
WO (1) WO2002089535A1 (en)

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Publication number Priority date Publication date Assignee Title
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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Publication number Priority date Publication date Assignee Title
US2592601A (en) * 1948-02-05 1952-04-15 Pittsburgh Plate Glass Co Transparent electroconductive article and method for producing the same
JPH088080B2 (en) * 1986-12-24 1996-01-29 株式会社東芝 Cathode ray tube and method of manufacturing cathode ray tube
BE1007662A3 (en) * 1993-10-18 1995-09-05 Philips Electronics Nv A picture display device having a display screen having an antistatic and light absorbing coating layer.

Non-Patent Citations (1)

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Title
See references of WO02089535A1 *

Also Published As

Publication number Publication date
ES2294135T3 (en) 2008-04-01
FR2824230A1 (en) 2002-10-31
DE60222758D1 (en) 2007-11-15
EP1382229B1 (en) 2007-10-03
FR2824230B1 (en) 2006-12-29
ATE375075T1 (en) 2007-10-15
WO2002089535A1 (en) 2002-11-07
DE60222758T2 (en) 2008-07-17

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