Hydrophilic coating and substrates coated therewith having enhanced durablity and lubricity

• US 6,709,706 B2
• Filed: 03/14/2003
• Issued: 03/23/2004
• Est. Priority Date: 02/22/1995
• Status: Expired due to Fees

• Current Assignee: Boston Scientific Scimed (Boston Scientific Corporation)
• Original Assignee: Scimed Life Systems Incorporated (Boston Scientific Corporation)
• Inventors: Welch, Eric, Nunez, George, Zhong, Shengping
• Primary Examiner(s): Dixon, Merrick
• Application Number:
  US10/387,380
• Publication Number:
  US 20030162032A1
• Time in Patent Office: 375 Days
• Field of Search: 427/412.1, 427/393.5, 427/2.1, 427/2.3, 427/333, 427/355, 427/337, 427/340
• US Class Current: 427/333
• CPC Class Codes: A61L 2300/452 Lubricants
• CPC Class Codes: A61L 2300/608 having two or more layers
• CPC Class Codes: A61L 2400/10 Materials for lubricating medical devices
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 29/14 Materials characterised by their function or physical properties , e.g. lubricating compositions
• CPC Class Codes: A61L 29/16 Biologically active materials, e.g. therapeutic substances A61L29/048 takes precedence
• CPC Class Codes: A61L 31/16 Biologically active materials, e.g. therapeutic substances A61L31/047 takes precedence
• CPC Class Codes: C08J 2367/00 Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08J2377/12; of polyester-imides C08J2379/08; Derivatives of such polymers
• CPC Class Codes: C08J 2433/26 Homopolymers or copolymers of acrylamide or methacrylamide
• CPC Class Codes: C08J 2475/06 from polyesters
• 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 7/043 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: C08L 75/04 Polyurethanes
• CPC Class Codes: C09D 133/24 Homopolymers or copolymers of amides or imides
• CPC Class Codes: C09D 175/06 from polyesters
• CPC Class Codes: C09D 175/08 from polyethers
• CPC Class Codes: Y10T 428/1393 Multilayer [continuous layer]
• CPC Class Codes: Y10T 428/24793 Comprising discontinuous or differential impregnation or bond
• CPC Class Codes: Y10T 428/24802 : Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/31536 : Including interfacial reaction product of adjacent layers
• CPC Class Codes: Y10T 428/31576 : Ester monomer type [polyvinylacetate, etc.]

Abstract

A substrate, such as a catheter or a guide wire, or a portion of the substrate is provided with a lubricous, hydrophilic abrasion-resistant coating by: (a) coating the substrate with a first aqueous coating composition having an aqueous dispersion or emulsion of a polymer having organic acid functional groups and a polyfunctional crosslinking agent having functional groups capable of reacting with organic acid groups, and drying the coating to obtain a substantially water-insoluble coating layer having excess polyfunctional including functional groups being reactive with organic acid groups remaining; and (b) contacting the dried water-insoluble coating layer with a second aqueous coating composition having an aqueous solution or dispersion of a hydrophilic polymer having organic acid functional groups, a polymer having organic acid functional groups and a polyfunctional crosslinking agent having functional groups capable of reacting with organic acid groups, and drying the combined coating to form an intermediate coating, whereby the polymer and the hydrophilic polymer of the second composition become bonded to the polymer of the first coating composition through the excess crosslinking agent; and (c) contacting the dried intermediate coating with a third aqueous coating composition having an aqueous solution or dispersion of a hydrophilic polymer having organic acid functional groups, and drying the combined coatings, the hydrophilic polymer of the third coating composition thereby becoming bonded to the polymers of the second coating composition through the excess crosslinking agent. The dryings can be carried out at ambient (room) temperature.

Claims

1. A method of providing a substrate with a hydrophilic coating which becomes lubricous when contacted with an aqueous fluid, comprising:

a) coating said substrate with a first aqueous coating composition comprising an aqueous dispersion or emulsion of a first polymer having organic acid functional groups and a first polyfunctional crosslinking agent having functional groups being capable of reacting with organic acid groups, and drying said first coating composition to obtain a substantially water-insoluble coating layer still including functional groups being reactive with organic acid groups; and

b) contacting said dried coating layer with a second aqueous coating composition comprising an aqueous solution or dispersion of a hydrophilic polymer having organic acid functional groups, a second polymer having organic acid functional groups, and a second polyfunctional crosslinking agent having functional groups being capable of reacting with organic acid groups, and drying to effectuate covalent bonding of said hydrophilic polymer and said second polymer to said first polymer of the first coating composition through said first or said second crosslinking agents to form a hydrophilic coating;

wherein said first polymer and said second polymer may be the same or different, and further wherein said first crosslinking agent and said second crosslinking agent may be the same or different.

2. A method of claim 1, wherein said second polymer is present in said second coating composition in an amount of up to 10 weight percent of said second coating composition.

3. A method of claim 1 wherein said second polymer in the second aqueous coating composition is the same as said first polymer in the first aqueous coating composition.

4. A method of claim 1 wherein said second crosslinking agent in the second aqueous coating composition is the same as said first crosslinking agent in the first aqueous coating composition.

5. A method of claim 1 further comprising:

providing a quantity of said second polyfunctional crosslinking agent in said second aqueous coating composition so that said hydrophilic coating still includes functional groups being reactive with organic acid groups.

6. A method of claim 5 further comprising:

contacting said hydrophilic coating with a third aqueous coating composition comprising an aqueous solution or dispersion of a second hydrophilic polymer having organic acid functional groups, and drying the combined coatings to effectuate covalent bonding of the second hydrophilic polymer to said first hydrophilic polymer or said second polymer of said hydrophilic coating through said second crosslinking agent;

wherein said second hydrophilic polymer in the third aqueous coating composition and said hydrophilic polymer in the second aqueous coating composition may be the same or different.

7. A method of claim 6, wherein said second hydrophilic polymer in the third aqueous coating composition is the same as said hydrophilic polymer in the second aqueous coating composition.

8. A method of claim 1, wherein the organic acid functional groups are selected from free carboxylic or sulfonic acid groups, metal salts of such acid groups, particularly alkali metal salts, and quaternary amine salts of such acid groups.

9. A method of claim 1, wherein said first or said second polyfunctional crosslinking agent is selected from polyfunctional aziridines, polyfunctional carboimides and combinations thereof.

10. A method of claim 1, wherein said first or said second polyfunctional crosslinking agent is a crosslinking agent having more than two functional groups per molecule.

11. A method of claim 1, wherein said first or said second polymer is selected from homo- and copolymers having a substantial amount of organic acid functional groups in their structure.

12. A method of claim 1, wherein said first or said second polymer is selected from the group consisting of polyurethanes, polyacrylates, polymethacrylates, polyisocrotonates, epoxy resins, acrylate-urethane copolymers and combinations thereof.

13. A method according to claim 12, wherein said first or said second polymer comprises an acrylate-urethane copolymer and/or a polyurethane.

14. A method of claim 6, wherein said hydrophilic polymer in said second coating composition or said second hydrophilic polymer in said third coating composition comprises monomer units from at least one monomer having organic acid functional groups.

15. A method according to claim 14, wherein said hydrophilic polymer in said second coating composition or said second hydrophilic polymer in said third coating composition is selected from the group consisting of acrylic acid, methacrylic acid, isocrotonic acid and combinations thereof.

16. A method according to claim 14, wherein said hydrophilic polymer in said second coating composition or said second hydrophilic polymer in said third coating composition further comprises monomer units without any organic acid functional groups.

17. A method according to claim 14, wherein said hydrophilic polymer in said second coating composition or said second hydrophilic polymer in said third coating composition comprises an acrylamide-acrylic acid copolymer.

18. A method of claim 6, wherein the hydrophilic polymer in said second coating composition or said second hydrophilic polymer in said third coating composition have a molecular weight in the range from about 100,000 to about 15 million.

19. A method of claim 6, wherein the concentration of said hydrophilic polymer in said second coating composition or the concentration of said second hydrophilic polymer in said third coating composition is from about 0.1 to about 5% by weight solids content.

20. A method of claim 1, wherein the concentration of said first polymer in said first coating composition is from about 2 to about 60% by weight solids content.

21. A method of claim 1, wherein the concentration of said first crosslinking agent in said first coating composition is in the range from about 0.2 to about 30% by weight of said first coating composition and the concentration of said second crosslinking agent in the second coating composition is in the range from about 0.01 to about 10% by weight of said second coating composition.

22. A method of claim 6, wherein the functional groups of said first crosslinking agent and of said second crosslinking agent are capable of reacting with the organic acid functional groups of said first polymer, said second polymer, said hydrophilic polymer and said second hydrophilic polymer at a temperature below 120°

C.