Hydrophilic lubricious coatings

• US 5,091,205 A
• Filed: 12/22/1989
• Issued: 02/25/1992
• Est. Priority Date: 01/17/1989
• Status: Expired due to Term

• Current Assignee: Union Carbide Chemicals And Plastics Company, Inc.
• Original Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Inventors: Fan, You-Ling
• Primary Examiner(s): Lusignan, Michael
• Assistant Examiner(s): Dudash, Diana L.
• Application Number:
  US07/449,777
• Time in Patent Office: 795 Days
• Field of Search: 427/412.1, 427/393.5, 427/2, 604/265, 604/266
• US Class Current: 427/2.28
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: B05D 2201/00 Polymeric substrate or laminate
• CPC Class Codes: B05D 3/10 by other chemical means
• CPC Class Codes: B05D 3/101 Pretreatment of polymeric substrate
• CPC Class Codes: B05D 5/04 to obtain a surface receptive to ink or other liquid B05D5/02, B41M5/52 take precedence
• CPC Class Codes: B05D 5/08 to obtain an anti-friction or anti-adhesive surface rendering particulate materials free-flowing in general, e.g. making them hydrophobic B01J2/30
• CPC Class Codes: C08G 18/625 Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
• CPC Class Codes: C08G 18/705 Dispersions of isocyanates or isothiocyanates in a liquid medium C08G18/702 takes precedence
• CPC Class Codes: C08J 2375/12 from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• CPC Class Codes: C08J 2433/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C08J 7/042 with two or more layers, where at least one layer of a composition contains a polymer binder
• 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 7/046 Forming abrasion-resistant coatings; Forming surface-hardening coatings
• CPC Class Codes: C08J 7/056 Forming hydrophilic coatings
• CPC Class Codes: C08J 7/065 Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Abstract

A new method is provided to impart a hydrophilic lubriciious coating onto articles such as medical devices. A device, for example a catheter, is first contacted with a polyisocyanate solution, to provide coupling, then contacted with a poly(carboxylic acid) solution to give a coating, and is then finally oven dried. These coatings have lubricity that only becomes manifest upon exposure to water ro body fluids, and moreover, are also long lasting and have good abrasion resistance. This combination of properties is not available from other currently used or proposed coatings.

Claims

1. A method of covering at least a portion of a substrate with a hydrophilic coating which coating exhibits good abrasion resistance and an increased lubricity when contacted with an aqueous-containing fluid, said method comprising the steps of:

(1) contacting said substrate with polyisocyanate contained in at least one first inert solvent to provide at least a partially coated substrate;

(2) contacting said coated substrate with a poly(acrylic acid) polymer of the formula;

##STR2## where n=0-0.95 mole fraction of neutralized acid moieties,

m=0.05-1.0 mole fraction of acid moieties with the proviso that n+m=1,

X₁, X₂, X₃ are each a hydrogen atom or a monovalent organic radical,

Y is a single bond or a divalent organic radical,

Z is a metallic ion or a tertiary ammonium ion,

and

p is a number such that the polymer has a molecular weight between about 200,000 and about 5,000,000, said poly(acrylic acid) polymer contained in at least one second solvent to provide a multiple coated substrate; and

(3) thereafter drying said multiple coated substrate to provide a hydrophillic, lubricious coating which contains free carboxylic acid groups or partially neutralized carboxylic acid groups.

2. The method of claim 1 wherein said substrate is a medical device.

3. The method of claim 2 wherein said medical device is a catheter.

4. The method of claim 1 wherein said substrate coated with said polyisocyanate is dried at a temperature of up to about 150°

C. before step (2).

5. The method of claim 4 wherein said multiple coated substrate is dried at a temperature of from about 25°

to about 150°

C.

6. The method of claim 1 wherein said first solvent is methyl ethyl ketone.

7. The method of claim 1 wherein said first solvent is ethyl acetate.

8. The method of claim 1 wherein said first solvent is a mixture of at least two solvents.

9. The method of claim 8 wherein said mixture contains mineral oil.

10. The method of claim 8 wherein said mixture contains at least one surfactant.

11. The method of claim 1 wherein said second solvent is at least one organic solvent inert to said poly(acrylic acid) polymer.

12. The method of claim 1 wherein said second solvent is dimethylformamide.

13. The method of claim 1 wherein said second solvent is dimethylsulfoxide.

14. The method of claim 1 wherein said second solvent is a mixture of dimethylformamide and methyl ethyl ketone.

15. The method of claim 1 wherein said second solvent is a mixture of dimethylformamide, methyl ethyl ketone and t-butyl alcohol.

16. The method of claim 1 wherein said polyisocyanate is a diisocyanate.

17. The method of claim 16 wherein said diisocyanate is a mixture of toluene 2,4- and 2,6-diisocyanate.

18. The method of claim 16 wherein said diisocyanate is a diphenylmethane diisocyanate.

19. The method of claim 16 wherein said diisocyanate is an adduct of diphenylmethane diisocyanate and a polyol.

20. The method of claim 1 wherein said polyisocyanate is an isocyanate end-capped polyfunctional aliphatic adduct.

21. The method of claim 1 wherein said polyisocyanate is an isocyanate end-capped polyfunctional aromatic adduct.

22. The method of claim 1 wherein said coated substrate is thermoformed to different shapes.

23. The method of claim 22 wherein said coated substrate is first treated with an alkaline bath before thermoforming.

24. The method of claim 22 wherein said coated substrate is first treated with an alkali metal salt bath before thermoforming.

25. The method of claim 22 wherein said coated substrate is first treated with an alkali metal phosphate bath before thermoforming.

26. The method of claim 1 wherein said polyisocyanate is a reaction product of a polyfunctional isocyanate with an aliphatic polyester polyol.

27. The method of claim 1 wherein said polyisocyanate is a reaction product of a polyfunctional isocyanate with an aromatic polyester polyol.

28. The method of claim 1 wherein said polyisocyanate is a mixture of a diisocyanate and an isocyanate end-capped polyfunctional adduct.

29. The method of claim 1 wherein said poly(acrylic acid) polymer is a colloidal dispersion of a homopolymer.

30. The method of claim 1 wherein said poly(acrylic acid) polymer has a molecular weight of from about 200,000 to about 5,000,000.

31. The method of claim 30 wherein said poly(acrylic acid) polymer has a molecular weight of about 3,000,000.

32. The method of claim 1 wherein said carboxylic acid-containing polymer is a copolymer.

33. The method of claim 1 wherein said carboxylic acid containing polymer is partially cross-linked, and contains at least some water insoluble units.

34. The method of claim 1 wherein said polyisocyanate applied as a dispersion.

35. The method of claim 1 wherein said poly(isocyanate) is applied as an oil-in-water emulsion.

36. The method of claim 1 wherein said poly(acrylic acid) polymer is applied as an emulsion.

37. The method of claim 1 wherein said poly(acrylic acid) polymer is applied as a dispersion.

44. The method of claim 1 wherein at least one additive is incorporated into said coating.

46. The method of claim 44 wherein said additive is an antithrombogenic.

47. The method of claim 44 wherein said additive is heparin.

38. A method of covering at least a portion of a substrate with a hydrophilic coating having good abrasion resistance, and which exhibits an increased lubricity when contacted with an aqueous-containing fluid, said method comprising the steps of:

(1) contacting said substrate with a polyisocyanate contained in at least one first inert organic solvent to provide at least a partially coated substrate;

(2) contacting said coated substrate with a poly(acrylic acid) polymer of the formula;

##STR3## where n=0-0.95 mole fraction of neutralized acid moieties;

m=0.05-1.0 mole fraction of acid moieties with the proviso that n+m=1;

X₁, X₂, X₃ are each a hydrogen atom or a monovalent organic radical;

Y is a single bond or a divalent organic radical;

Z is a metallic ion or a tertiary ammonium ion; and

p is a number such that the polymer has a molecular weight between about 200,000 and about 5,000,000;

said carboxylic acid-containing polymer contained in at least one second inert organic solvent to provide a multiple coated substrate; and

(3) thereafter drying said multiple coated substrate to provide a hydrophilic, lubricious coating.

39. The method of claim 38 wherein the first solvent is methyl ethyl ketone.

40. The method of claim 38 wherein the second solvent is dimethylformamide.

41. The method of claim 38 wherein said second solvent is a mixture of dimethylformamide and methyl ethyl ketone.

42. The method of claim 38 wherein said substrate coated with said polyisocyanate is dried at a temperature of up to about 150°

C. before step (2).

43. The method of claim 38 wherein at least one of said first or second solvents contains a surfactant.

45. The method of claim 38 wherein at least one additive is incorporated into said coating.

48. A method of covering at least a portion of a substrate with a hydrophilic coating which coating exhibits good abrasion resistance and an increased lubricity when contacted with an aqueous-containing fluid, said method comprising the steps of:

(1) contacting said substrate with polyisocyanate contained in at least one first inert solvent to provide at least a partially coated substrate;

(2) drying said coated substrate to provide a primer coat of the polyisocyanate on the substrate;

(3) contacting said coated substrate with a poly(acrylic acid) polymer of the formula;

##STR4## where n=0-0.95 mole fraction of neutralized acid moieties,

m=0.05-1.0 mole fraction of acid moieties with the proviso that n+m=1,

X₁, X₂, X₃ are each a hydrogen atom or a monovalent organic radical,

Y is a single bond or a divalent organic radical,

Z is a metallic ion or a tertiary ammonium ion,

and

p is a number such that the polymer has a molecular weight between about 200,000 and about 5,000,000, said poly(acrylic acid) polymer contained in at least one second solvent to provide a multiple coated substrate;

(4) thereafter drying said multiple coated substrate to provide a hydrophillic, lubricious coating which contains free carboxylic acid groups or partially neutralized carboxylic acid groups; and

(5) optionally neutralizing the multiple coated substrate.

49. The method of claim 48 wherein the polyisocyanate is diphenylmethane diisocyanate or an adduct thereof, wherein the first inert solvent is either methyl ethyl ketone or toluene, wherein the second inert solvent is a mixture of methyl ethyl ketone, dimethylformamide and t-butyl alcohol.

50. The method of claim 49 wherein the polyisocyanate is diphenylmethane diioscyanate or an adduct thereof in the first inert solvent is present in a concentration of from about 0.5 to about 20 percent by weight and the poly(acrylic acid) in the second inert solvent is present in a concentration of from about 0.1 to about 10 percent by weight.

51. The method of claim 50 wherein the polyisocyanate is diphenylmethane diisocyanate or an adduct thereof in the first inert solvent is present in a concentration of from about 1 to about 5 percent by weight and the poly(acrylic acid) in the second inert solvent is present in a concentration of from about 0.5 to about 2 percent by weight.

52. The method of claim 48 wherein the polyisocyanate is a mixture of different polyisocyanates, wherein the first inert solvent is either methyl ethyl ketone or toluene, wherein the second inert solvent is a mixture of methyl ethyl ketone, dimethylformamide and t-butyl alcohol.