Method of forming a hydrophilic coating on a substrate

• US 4,373,009 A
• Filed: 05/18/1981
• Issued: 02/08/1983
• Est. Priority Date: 05/18/1981
• Status: Expired due to Term

• Current Assignee: Astra Meditec AB
• Original Assignee: International Silicone Corporation
• Inventors: Winn, R. Alastair
• Primary Examiner(s): Silverberg, Sam
• Application Number:
  US06/264,957
• Time in Patent Office: 631 Days
• Field of Search: 428/424.2, 428/424.4, 428/224.8, 428/423.5, 428/424.7, 428/424.6, 427/412.1, 427/2, 128/348, 128/349 R
• US Class Current: 428/424.2
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 33/0088 by grafting of a monomer onto the substrate
• CPC Class Codes: A61L 33/064 obtained by reactions only involving carbon-to-carbon unsaturated bonds A61L33/062 takes precedence
• CPC Class Codes: A61L 33/066 Rubbers
• CPC Class Codes: B05D 7/02 to macromolecular substances, e.g. rubber treatment or coating of shaped articles made of macromolecular substances C08J7/00
• CPC Class Codes: C08G 18/6283 Polymers of nitrogen containing compounds having carbon-to-carbon double bonds C08G18/6262, C08G18/6266 take precedence
• CPC Class Codes: C08J 2439/00 Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
• 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 7/043 Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/056 Forming hydrophilic coatings
• CPC Class Codes: C08J 7/12 Chemical modification
• CPC Class Codes: C08L 29/10 Homopolymers or copolymers of unsaturated ethers C08L35/08 takes precedence
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C08L 33/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08L 33/26 Homopolymers or copolymers of acrylamide or methacrylamide
• CPC Class Codes: C08L 39/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08L 39/08 Homopolymers or copolymers of vinyl-pyridine
• CPC Class Codes: C09K 3/18 for application to surfaces to minimize adherence of ice, mist or water thereto rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30; Thawing or antifreeze materials for application to surfaces used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00
• CPC Class Codes: G01N 33/544 : the carrier being organic
• CPC Class Codes: Y10T 428/31562 : Next to polyamide [nylon, etc.]
• CPC Class Codes: Y10T 428/31573 : Next to addition polymer of ethylenically unsaturated monomer
• CPC Class Codes: Y10T 428/31576 : Ester monomer type [polyvinylacetate, etc.]
• CPC Class Codes: Y10T 428/3158 : Halide monomer type [polyvinyl chloride, etc.]

Abstract

A method of forming a hydrophlic coating on a substrate comprised of applying a hydrophilic copolymer capable of chemically reacting with a coupling agent which will promote adhesion to the substrate. A polyisocyanate coupling agent is applied to the surface from a solvent solution followed by applying the hydrophilic copolymer from solvent solution. In certain instances, the copolymer and isocyanate can be simultaneously applied from a solvent solution. The resulting hydrophilic coating is thrombo resistant, biocompatable and stable.

Claims

1. The method of bonding a hydrophilic coating to the surface of a biomedical substrate comprising:

applying a coating from a solvent solution comprised of a polyisocyanate to the surface of said substrate to form a coupling coating with unreacted isocyanates;

applying a solvent solution comprised of a hydrophilic copolymer made from monomers of vinylpyrollidone and monomers containing active hydrogen which will react with isocyanate to form a covalent bond between said coupling coating and said hydrophilic copolymer;

evaporating the solvent and reacting said isocyanates.

2. The method according to claim 1 in which said substrate is a polymer substrate.

3. The method according to claim 2 in which said polymer substrate is selected from the group consisting of a polyurethane resin, a vinyl resin, a polyacrylate, a polycarbonate, a polyester and rubber.

4. The method according to claim 3 in which said rubber is selected from the group consisting of latex rubber, polyisoprene and butadiene styrene copolymer.

5. The method according to claim 1 in which said polyisocyanate is selected from the group consisting of polymethylenepolyphenyl isocyanate, 4,4'"'"'-diphenylmethane diisocyanate and position isomers thereof, 3,4-dichlorophenyl diisocyanate and isoferrone isocyanate.

6. The method according to claim 1 in which said polyisocyanate is a blocked isocyanate.

7. The method according to claim 6 in which said polyisocyanate is selected from the group consisting of phenol blocked diphenyl methane 4,4'"'"'-diisocyanate, and ketoxime blocked tetraisocyanate (E-320 Mobay).

8. The method according to claim 1 in which said copolymer has an average of at least two active hydrogen atom sites per molecule.

9. The method according to claim 8 in which said copolymer is swellable in an aqueous media.

10. The method according to claim 9 in which said copolymer is also soluble in non-aqueous solvents which do not react with isocyanate.

11. The method according to claim 8 in which said copolymer consists primarily of repeating units containing no reactive hydrogen atoms.

12. The method according to claim 8 in which said copolymer is selected from the groups consisting of vinyl methyl ether, vinyl pyridine, N-vinyl-2-pyrrolidone, acrylamide, hydroxy acrylate, acrylic acid hydroxy propyl methacrylate and hydroxy ethyl methacrylate.

13. The method according to claim 1 in which said polyisocyanate is at least about 0.1% W/V.

14. The method according to claim 13 in which said polyisocyanate is from about 0.3% to about 15% W/V.

15. The method according to claim 2 in which said polyisocyanate solution is in contact with said substrate less than about 120 minutes.

16. The method according to claim 2 in which said polyisocyanate solution is in contact with said substrate 5-20 minutes.

17. The method according to claim 16 in which said polyisocyanate solution is in contact with said substrate approximately 10 minutes.

18. A method of forming a hydrophilic layer on a substrate comprising:

forming unreacted isocyanate groups on the surface of the substrate;

treating the surface of the substrate with a hydrophilic copolymer made from monomers of vinylpyrollidone and monomers containing active hydrogen adapted to form covalent bonds with the unreacted isocyanate.

19. The method of forming a hydrophilic coating according to claim 18 comprising simultaneously applying solvent solution containing polyisocyanate and hydrophilic copolymer which will form covalent bonds when reacted with isocyanates, eliminating the solvent and reacting said polyisocyanate and reactive copolymer.

20. The method according to claim 19 in which said solvent solution includes a reactive diluent which is subsequently polymerized in situ.

21. The method according to claim 20 in which a solvent is selected which will not react with isocyanates.

22. The method according to claim 20 in which said diluent in said solution is up to about 100%.

23. The method according to claim 22 in which said reactive diluent is a UV cured vinyl containing monomer, dimer or trimer.

24. The method according to claim 20 in which said reactive diluent is a UV cured, vinyl containing monomer, dimer or trimer.

25. The method according to claim 24 wherein said reactive diluent is selected from the group consisting of hydroxyl methyl methacrylate, N-vinyl-2-pyrollidone, hydroxy propylmethacrylate, acrylic, methacrylic acid and acrylamide.

26. The method according to claim 21 in which the substrate is selected from the group consisting of a vinyl or butadiene styrene rubber.

27. The method according to claim 26 including treating the substrate with chemical modifiers from the group consisting of gamma amino propyl functional silanes and ozone.

28. The method according to claim 26 including treating the substrate with a plasma discharge or high radiation energy.

29. The method according to claim 25 in which the substrate is selected from the group consisting of polyethylene and polypropylene.

30. The method according to claim 29 including treating the substrate with chemical modifiers from the group consisting of gamma amino propyl functional silanes and ozonolysis.

31. The method according to claim 30 including treating the substrate with a plasma discharge or high radiation energy.

32. The method according to claim 18 in which the copolymer has a molecular weight average of at least 100,000.

33. The method according to claim 32 in which said copolymer has at least two active hydrogen atom sites per molecule.

34. The method according to claim 33 in which said copolymer is swellable in an aqueous media.

35. The method according to claim 34 in which said copolymer is also soluble in non-aqueous solvents which do not react with isocyanates.

36. The method according to claim 18 in which said copolymer is swellable in an aqueous media.

37. The method according to claim 33 in which said copolymer is selected from the groups consisting of vinyl methyl ether, vinyl pyridine, N-vinyl-2-pyrrolidone, acrylamide, hydroxy acrylate, acrylic acid, hydroxy propylmethacrylate, and hydroxy ethyl methacrylate.

38. The method according to claim 18 in which said polyisocyanate is applied from solvent solution containing at least about 0.1% W/V polyisocyanate.

39. The method according to claim 38 in which said polyisocyanate is from about 0.3% to about 15% W/V.

40. The method according to claim 19 in which said substrate is a polymer substrate.

41. The method according to claim 40 in which said polymer substrate is selected from the group consisting of a polyurethane resin, a vinyl resin, a polyacrylate, a polycarbonate and rubber.

42. The method according to claim 41 in which copolymer has a molecular weight average of at least 100,000.

43. The method according to claim 42 in which said copolymer has an average of at least two active hydrogen atom sites per molecule.

44. The method according to claim 43 in which said copolymer is swellable in an aqueous media.

45. The method according to claim 44 in which said copolymer is also soluble in non-aqueous solvents which do not react with isocyanates.

46. The method according to claim 19 in which said copolymer is swellable.

47. The method according to claim 45 in which said copolymer is selected from the groups consisting of vinyl methyl ether, vinyl pyridine, N-vinyl-2-pyrrolidone, acrylamide, hydroxy acrylate, acrylic acid, hydroxy propyl methacrylate, and hydroxy ethyl methacrylate.

48. A biomedical product having a hydrophilic coating comprising;

a substrate;

a polyisocyanate coupling coating;

a hydrophilic copolymer coating made from monomers of vinylpyrollidone and monomers containing active hydrogen;

coating retention means for retaining said hydrophilic copolymer coating on said substrate by a covalent bond, said hydrophilic copolymer having an average of at least two or more sites capable of covalently bonding to said polyisocyanate coupling coating.

49. The product according to claim 48 in which said substrate is a polymer substrate.

50. The product according to claim 49 in which polymer substrate is selected from the group consisting of a polyurethane resin, a vinyl resin, a polyacrylate, a polycarbonate, a polyester and rubber.

51. The product according to claim 50 in which said rubber is a latex rubber, polyisoprene, or styrene butadiene.

52. A product according to claim 48 in which said substrate comprises a medical instrument adapted for blood or subcutaneous tissue contact.

53. A product according to claim 52 in which said medical instrument is an intravenous tube.

54. A product according to claim 52 in which said medical instrument is a surgical tool.

55. A product according to claim 54 in which said medical instrument is a stainless steel surgical tool.

56. A product according to claim 52 in which said medical instrument is a wound drain.