Covering a substrate with a polymer film that is stable in a liquid medium

• US 8,889,253 B2
• Filed: 04/10/2009
• Issued: 11/18/2014
• Est. Priority Date: 04/10/2008
• Status: Expired due to Fees

• Current Assignee: Centre National De La Recherche Scientifique
• Original Assignee: Centre National De La Recherche Scientifique
• Inventors: Kekicheff, Patrick, Clauzel, Maryline
• Primary Examiner(s): FLETCHER III, WILLIAM P
• Application Number:
  US12/937,201
• Publication Number:
  US 20110027567A1
• Time in Patent Office: 2,048 Days
• Field of Search: 427/203, 428/220
• US Class Current: 428/220
• CPC Class Codes: B05D 1/36 Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• CPC Class Codes: B05D 3/00 Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials successively applying liquids or other fluent materials B05D1/36; drying ovens F26B
• CPC Class Codes: B05D 3/02 by baking B05D3/04 takes precedence
• CPC Class Codes: B05D 3/06 by exposure to radiation B05D3/02 takes precedence ; plasma treatment B05D3/141
• CPC Class Codes: B32B 3/00 Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form

Abstract

The present invention relates to a process for covering a substrate with a polymer film characterized in that, prior to the deposition of said polymer film, nanoparticles are adsorbed electrostatically onto the surface of said substrate to be covered.

Claims

1. Process for covering a substrate, at least one dimension of which is greater than one millimeter, with a polymer film, wherein, prior to the deposition of said polymer film, nanoparticles are adsorbed electrostatically onto the surface of said substrate to be covered, wherein the polymer film is not a polyelectrolyte.

2. Process according to claim 1, wherein the substrate comprises a metallic and/or mineral and/or polymer and/or organometallic and/or organic and/or ceramic surface which is intended to be covered by the polymer film.

3. Process according to claim 2, wherein

the metallic surface to be covered is in steel, stainless steel, or a metal chosen from aluminium, gold, silver, iron, lead, copper, zinc, nickel, titanium, tungsten, chromium, platinum, cobalt, zirconium, molybdenum, tin, gallium, ruthenium, yttrium and manganese, an alloy or a mixture thereof;

the mineral surface to be covered is in pozzolana, clays, sand, gravels, perlite, vermiculite, mineral wools, graphite, an aluminosilicate, silicon, glass, a metal oxide, or a mixture thereof;

the polymer surface to be covered is in polytetrafluoroethylene, polydimethylsiloxane, polycarbonate, epoxy resin or polyvinyl chloride; and

the organic surface to be covered is in cellulose, wood and derivatives thereof, or fruit shells and skins.

4. Process according to claim 3, wherein the alloy is brass or bronze, the aluminosilicate is mica, the metal oxide is sapphire, the derivative of wood is fibres or bark, and the fruit shell is coconut shell.

5. Process according to claim 1, wherein the surface of the substrate to be covered is in a single area of the surface which is optionally perforated;

or is in a set of several separate areas.

6. Process according to claim 1, wherein the substrate is an optical instrument, a sensor, a pipe, a plate, or a cylinder.

7. Process according to claim 6, wherein the optical instrument is a mirror, a lens or an attenuator;

the sensor is a biosensor or an organic field-effect transistor; and

the plate and cylinder is for printing.

8. Process according to claim 1, wherein the mean size of the nanoparticles is between 1 and 200 nm.

9. Process according to claim 8, wherein the mean size of the nanoparticles is between 3 and 50 nm.

10. Process according to claim 9, wherein the mean size of the nanoparticles is between 3 and 20 nm.

11. Process according to claim 1, wherein the nanoparticles are selected from nanoparticles based on carbon;

and/or nanoparticles based on silicon; and

/or nanoparticles based on metal; and

/or nanoparticles based on a mineral;

organometallic nanoparticles;

polymer nanoparticles;

nanoparticles based on ceramics;

nanoparticles based on clays; and

/or nanoparticles based on nanotubes.

12. Process according to claim 11, wherein

the carbon is carbon black or graphite;

the metal is selected from the group consisting of aluminium, silver, cadmium, cerium, chromium, cobalt, copper, tin, iron, gallium, manganese, nickel, gold, palladium, platinum, lead, ruthenium, selenium, sulphur, titanium, thorium, tungsten, yttrium, zinc, zirconium, and mixtures and alloys thereof;

the mineral is a metal, oxide, hydroxide or carbonate;

the polymer is natural or synthetic latex, a coordination polymer or a biopolymer;

the ceramics is silicon nitride;

the clay is selected from the group consisting of smectites, kaolins, illites, chlorites and attapulgites; and

the nanotubes are based on carbon, boron nitride, molybdenum sulphide, tungsten sulphide, copper sulphide, nickel chloride, cadmium chloride and cadmium iodide.

13. Process according to claim 12, wherein the mineral is selected from the group consisting of cerium oxide, titanium oxide, silicon oxide, aluminium oxide, yttrium oxide, aluminium hydroxide, zirconium oxide, yttrium oxide, yttrium carbonate, iron oxide, gold oxide, silver oxide, palladium oxide, sulphur oxide, selenium oxide, cadmium oxide, thorium oxide and chromium oxide;

the coordination polymer is Prussian blue and the like; and

the biopolymer is chitin.

14. Process according to claim 1, wherein the nanoparticles cover at least 2% of the surface of the substrate to be covered.

15. Process according to claim 14, wherein the nanoparticles cover between 5 and 70% of the surface of the substrate to be covered.

16. Process according to claim 15, wherein the nanoparticles cover between 20 and 40% of the surface of the substrate to be covered.

17. Process according to claim 1, wherein the adsorption of the nanoparticles is carried out by immersing the substrate in a dispersion of said nanoparticles in a solvent or by spraying the nanoparticles onto the free surface of the substrate to be covered.

18. Process according to claim 17, further comprising a step of washing the substrate and by a drying step.

19. Process according to claim 1, wherein the polymer is selected from the group consisting of thermoplastic polymers;

thermosetting polymers;

elastomers;

natural polymers;

polyesters;

polyketones, polyamides;

polyacrylonitriles;

polycyanoacrylates;

polyethersulphones;

fluoropolymers and fluorocopolymers;

polystyrene;

polyethylene;

polyvinylpyrrolidone;

polyvinyl acetate;

crosslinked, branched or star polymers;

copolymers;

dendrimers; and

mixtures thereof.

20. Process according to claim 19, wherein

the thermoplastic polymer is selected from the group consisting of polymethacrylates, polyphenylene oxide, polyphenylene sulphide, polypropylene and polyvinyl chloride;

the thermosetting polymer is chosen from epoxy resins, polycarbonates, polyimides and polydicyclopentadiene;

the elastomer is chosen from silicones, polyurethanes, polyisobutylene, polychloroprene, polybutadiene and polyisoprene;

the natural polymer is chosen from cellulose, latex and starch;

the polyester is polyethylene terephthalate;

the polyketone is a poly(aryl ether ketone);

the polyamide is a polyaramide; and

the fluoropolymers and fluorocopolymers are selected from the group consisting of polytetrafluoroethylene, ethylene-tetrafluoroethylene polymer, polychlorotrifluoroethylene, perfluoropropylene, poly(heptafluorobutyl acetate), the copolymer of vinylidene fluoride and chlorotrifluoroethylene, the copolymer of vinylidene fluoride and perfluoropropene, the poly(ester of 2,2,3,3,4,4-hexafluoropentanediol and adipic acid), and 3,3,3-trifluoropropylmethylsilicone.

21. Process according to claim 20, wherein the polymethacrylate is polymethyl methacrylate or polyethyl methacrylate;

and the silicone is polydimethylsiloxane.

22. Process according to claim 1, wherein the polymer film comprises metal or polymer particles of nanometric or micrometric size, pigments, or nanoparticles selected from nanoparticles based on carbon;

and/or nanoparticles based on silicon; and

/or nanoparticles based on metal; and

/or nanoparticles based on a mineral;

organometallic nanoparticles;

polymer nanoparticles;

nanoparticles based on ceramics;

nanoparticles based on clays; and

/or nanoparticles based on nanotubes.

23. Process according to claim 1, wherein the polymer film is deposited by centrifugation, by dipping, by droplets, by laminar flow or by spraying.

24. Process according to claim 1, further comprising, prior to the deposition of the polymer film, an additional step of treating the surface of the substrate to be covered which is intended to improve the adhesion of the polymer film onto the substrate.

25. Process according to claim 24, wherein the additional step is a treatment by silanisation, by cold plasma or by UV under ozone.

26. Process according to claim 1, further comprising a heat treatment step after the polymer film has been deposited.

27. Process according to claim 26, wherein the heat treatment step is a postcure of the polymer film at a temperature above the glass transition temperature of the polymer.

28. Process according to claim 1, wherein the substrate is covered with a treatment for an anticorrosive and/or antibacterial surface treatment, and/or for adhesive bonding.

29. Substrate coated with a polymer film obtainable by a process according to claim 1.