Method of Coating a Polymer Surface with a Polymer Containing Coating and an Item Comprising a Polymer Coated Polymer

• US 20080213460A1
• Filed: 01/17/2006
• Published: 09/04/2008
• Est. Priority Date: 01/17/2005
• Status: Abandoned Application

• Current Assignee: Biomodics ApS
• Original Assignee: Biomodics ApS
• Inventors: Alm, Martin, Benter, Maike
• Application Number:
  US11/814,017
• Publication Number:
  US 20080213460A1
• Time in Patent Office: Days
• US Class Current: 427/2.1
• CPC Class Codes: A61L 2420/02 Methods for coating medical devices
• CPC Class Codes: A61L 31/048 obtained by reactions only involving carbon-to-carbon unsaturated bonds A61L31/041 takes precedence
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/14 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: B05D 1/18 performed by dipping
• CPC Class Codes: B05D 2401/90 at least one component of the composition being in supercritical state or close to supercritical state
• CPC Class Codes: C08J 7/0427 with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/056 Forming hydrophilic coatings
• CPC Class Codes: C08L 25/06 Polystyrene
• CPC Class Codes: C08L 85/02 containing phosphorus

Abstract

A method of coating a surface of a solid polymer substrate, e.g. comprising silicone, thermoplast, thermoset and/or elastomers, with a coating comprising a coat polymer.

The method includes providing a coat polymer, such as a polymer polymer comprises one or more polymer having metacrylate backbone, for the coating, and dissolving said coat polymer in a first solvent, such as water, carbon dioxide and/or organic solvents, placing said solid polymer substrate in a reaction chamber introducing said polymer coat solution into the reaction chamber, introducing carbon dioxide into the reaction chamber, and depositing the coating onto the solid polymer substrate surface, wherein the carbon dioxide during at least a part of the deposition step is in its liquid state at a pressure of 7.4 Mpa or less. Optionally the carbon dioxide is subjected to turbulence, e.g. by mechanical stirring during at least a part of the deposition step.

Claims

1. A method of coating a surface of a solid polymer substrate with a coating comprising a coat polymer, said method comprising:

providing a coat polymer for the coating, and dissolving said coat polymer in a first solvent,

placing said solid polymer substrate in a reaction chamber,

introducing said polymer coat solution into the reaction chamber,

introducing carbon dioxide into the reaction chamber, and

depositing the coating onto the solid polymer substrate surface,

wherein the carbon dioxide during at least a part of the deposition step is in its liquid state at a pressure up to 7.4 MPa.

2. A method according to claim 1 wherein the solid polymer substrate is of a polymer composition comprising at least 10% by weight of thermoplastic and/or thermosets selected from the group consisting of silicone polymers, thermoplastic elastomers, rubbers, polyolefins, polyesters, polystyrene, polyacrylates, polyethers, polyurethane, polycarbonate, thermoplastic vulcanisates, polyurethane, epoxy polymers, thermoset polyimide and mixtures thereof.

3. A method according to claim 1 wherein the solid polymer substrate is of a polymer composition comprising at least 10% by weight of a thermoplastic elastomer selected from the group consisting of a random copolymer and a block copolymer.

4. A method according to claim 1 wherein the solid polymer substrate is of a polymer composition comprising at least 10% by weight of a rubber selected from the group consisting of butadiene rubber, isoprene rubber, nitril rubber, styrene-butadiene rubber, latex and urethane rubber.

5. A method according to claim 1 wherein the solid polymer substrate is of a polymer composition comprising at least 10% by weight of an polyolefin selected from the group consisting of polyvinyls.

6. A method according to claim 1 wherein the solid polymer substrate is of a polymer composition comprising at least 10% by weight of silicone polymers selected from the group consisting of dimethyl polysiloxane, methylphenyl polysiloxane, fluorosilicone rubber, silicone esters, polysiloxanes, polysilanes, chlorosilanes, alkoxysilanes, aminosilanes, polysilanes polydialkylsiloxanes, polysiloxanes containing phenyl substituents, said polymers of the silicone polymer composition optionally being vinyl-functionalized and/or optionally being partially or fully fluorinated.

7. A method according to claim 1 wherein the solid polymer substrate is of a polymer composition comprising up to 40% by weight of fillers and/or additives, said fillers being particles or fibres in the form of minerals or organic fillers.

8. A method according to claim 1 wherein the coat polymer comprises a polymer which is more oleophobic than the solid polymer substrate.

9. A method according to claim 1 wherein the coat polymer comprises a polymer which is more hydrophilic than the solid polymer substrate.

10. A method according to claim 1 wherein the coat polymer comprises one or more polymers with anti oxidizing and/or electrical conductive properties.

11. A method according to claim 1 wherein the coat polymer has an average number molecular weight of at least 5,000.

12. A method according to claim 1 wherein the coat polymer comprises one or more of the polymers selected from the group consisting of PTFE, phospholipid containing polymers, such as 2-methacryloyloxyethylphosphorylcholine (MPC) containing polymers;

butyl metacrylate containing polymers (PBMA);

poly(2-hydroxyethyl metacrylate) (PHEMA) containing polymers;

polydimethylsiloxane (PDMS);

poly(ethylene glycol) (PEG); and

vinylpyrrolidone containing polymer.

13. A method according to claim 1 wherein the coat polymer comprises one or more polymers having a metacrylate backbone.

14. A method according to claim 1 wherein said first solvent is selected from the group consisting of water, carbon dioxide, cyclohexanones;

alcohols;

acids of alcohols; and

mixtures thereof.

15. A method according to claim 1 wherein said first solvent comprises an organic solvent, at least 50 by weight.

16. A method according to claim 1 wherein said first solvent comprises a mixture of water and one or more organic solvents.

17. A method according to claim 1 wherein said first solvent comprises a mixture of carbon dioxide and one or more organic solvents.

18. A method according to claim 1 wherein the method further includes dissolving or dispersing at least one additional component in the first solvent, the additional component being selected from the group consisting of pigments;

anti-thrombotic agents;

anti-microbial agents; and

antioxidants.

19. A method according to claim 1 wherein when the solid polymer substrate is placed in the reaction chamber, carbon dioxide is introduced into the reaction chamber to raise the pressure to at least 0.2 MPa, where after the polymer coat solution is injected into the reaction chamber.

20. A method according to claim 19 wherein the pressure within the reaction chamber is raised to at least 0.5 MPa prior to injecting the polymer coat solution into the reaction chamber.

21. A method according to claim 19 wherein the reaction chamber at the time of introducing the polymer coat solution into the reaction chamber comprises carbon dioxide in its liquid and state.

22. A method according to claim 1 wherein the polymer coat solution is injected into the reaction chamber together with carbon dioxide.

23. A method according to claim 1 further comprising the steps of dissolving the coat polymer in a first solvent, followed by mixing said polymer coat solution with carbon dioxide in gas form where after the polymer coat solution carbon dioxide mixture is injected into the reaction chamber.

24. A method according to claim 1 further comprising the steps of dissolving the coat polymer in a first solvent, followed by mixing said polymer coat solution with carbon dioxide in liquid form where after the polymer coat solution carbon dioxide mixture being is injected into the reaction chamber.

25. A method according to claim 23 wherein the step of dissolving the coat polymer in a first solvent is performed at a temperature of between 10 and 100°

C.

26. A method according to claim 23 wherein the step of dissolving the coat polymer in a first solvent is performed at a pressure of at least 0.1.

27. A method according to claim 23 wherein the step of dissolving the coat polymer in a first solvent is performed prior to its introduction into the reactor chamber.

28. A method according to claim 23 wherein the step of dissolving the coat polymer in a first solvent is performed prior to bringing it into contact with the solid polymer substrate.

29. A method according to claim 1 wherein the solid polymer substrate is treated with the polymer coat solution in the presence of carbon dioxide in the deposition step for a deposition step time of at least 2 minutes, the deposition step time being defined as the point in time where the solid polymer substrate and at least some of the polymer coat solution and at least some carbon dioxide are present in the reaction chamber and the pressure is at least 0.2 MPa until the pressure in the reactor is reduced to 0.2 MPa or less.

30. A method according to claim 29 wherein the deposition time is sufficiently long to apply a continuous coating onto the solid polymer substrate.

31. A method according to claim 1 wherein the carbon dioxide for at least 1 minute during the deposition step is in its liquid state.

32. A method according to claim 1 wherein the carbon dioxide is in its liquid state and is subjected to a turbulent movement during at least a part of the deposition step for at least 2 minutes.

33. A method according to claim 1 wherein the temperature during the deposition step is at least 0°

C.

34. A method according to claim 1 wherein the pressure in the reactor during at least 10% of the deposition step time is at least 1.0 MPa.

35. A method according to claim 1 wherein the pressure in the reactor during at least 10%, of the deposition step time is between 0.5 and 3.0 MPa.

36. A method according to claim 34 wherein the pressure in the reactor during the deposition step may be pulsed with one or more pulses, wherein one pulse includes raising the pressure by at least 0.1 MPa, followed by lowering the pressure by at least 0.1 MPa, followed by increasing the pressure by at least 0.1 MPa.

37. A method according to claim 36 wherein the pressure variation during at least 10% of the deposition step time is less than 1.0 MPa/minute.

38. A method according to claim 37 wherein the pressure reduction half-life (t_1/2P) during at least 50% of the deposition step time is substantially constant (within +−

10%).

39. A method according to claim 38 wherein the pressure reduction at the last 10% of the deposition step time is less than 2.0 MPa/minute.

40. A method according to claim 39 wherein the pressure in the reactor is reduced from 2 to 1 bar as slowly as or even slower than the reduction from 3 to 2 bars.

41. A method according to claim 1 wherein the solid polymer substrate is subjected to a pretreatment prior to the step of applying the coating, the pretreatment comprises an extraction step, the extraction step preferably includes extraction of oils and water from the solid polymer substrate.

42. A method according to claim 41 wherein the extraction step is performed by subjecting the solid polymer substrate to one or more of the treatments, a heat treatment, a vacuum treatment, a treatment with a supercritical solvent and at treatment with liquid carbon dioxide.

43. A method according claim 41 wherein at least 0.05% by weight of the solid polymer substrate is extracted during the extraction step.

44. A method according to claim 1 wherein the solid polymer substrate is subjected to a post heat treatment at a temperature of between T_g and T_g—

40°

C. of the coat polymer, the post heat treatment being performed after termination of the deposition step.

45. A method according to claim 44 wherein the post heat treatment is performed for at least 30 minutes.

46. A method according to claim 1 wherein the deposited coating has a thickness of between 10⁻

5 μ

g/cm² and 1 mg/cm².

47. A method according to claim 1 wherein the deposited coating has an essentially even thickness over the treated surface of the solid polymer substrate.

48. An item obtainable using the method as defined in claim 1.

49. An item according to claim 48, wherein the item is a medical device for use in contact with the human body.

50. An item according to claim 48, wherein the item is a laboratory utensil.

51. A method according to claim 1 wherein the solid polymer substrate is of a polymer composition comprising at least 10% by weight of a thermoplastic elastomer selected from the group consisting of TPE, SEBS, SBS, SIS, TPE-polyether-amide, TPE-polyether-ester, TPE-urethanes, TPE PP/NBR, TPE-PP/EPDM, TPE-vulcanisates and TPE-PP/IIR.

52. A method according to claim 1 wherein the solid polymer substrate is of a polymer composition comprising up to 40% by weight of fillers and/or additives, said fillers being particles or fibres in the form of minerals or organic fillers.

53. A method according to claim 1 wherein the coat polymer comprises butyl metacrylate containing polymers (PBMA) and poly(2-hydroxyethyl metacrylate) (PHEMA) containing polymers.