Low particulate lubricious coating with vinyl pyrrolidone and acidic polymer-containing layers

1. A lubricious coating comprising:

a first coated layer comprising a vinyl pyrrolidone polymer and photoreactive groups, wherein the photoreactive groups are pendent from the vinyl pyrrolidone polymer or on a first cross-linking agent comprising at least two photoreactive groups, or both; and

a second coated layer that is different in composition than the first coated layer and is a top coating comprising an acid polymer, wherein the second coated layer is in direct contact with the first coated layer, wherein the first coated layer is between the second coated layer and a substrate surface,

wherein (a) the acid polymer is formed from a composition comprising one or more of the following monomers: acrylic acid, methacrylic acid, itaconic acid, monomethyl itaconic acid, maleic anhydride, fumaric acid, crotonic acid, acrylamido-2-methylpropanesulfonic acid (AMPS), 2-(meth)acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, 2-sulfoethyl methacrylate, and salts thereof, or (b) the acid polymer is a sulfonic acid polymer, a carboxylic acid polymer, or a phosphonic acid polymer.

2. The coating of claim 1 wherein the second coated layer further comprises an acrylamide polymer comprising at least one photo reactive group, optionally wherein the acrylamide polymer comprises acrylamide-, sulfonate-, and alkylene oxide-containing subunits.

3. The coating of claim 2 , wherein the vinyl pyrrolidone polymer and the acrylamide polymer are present in the coating at a weight ratio in the range of approximately 3:1 to 1:3 (wt./wt.), respectively.

4. The coating of claim 2 , wherein the acid polymer and the acrylamide polymer are present in the coating at a weight ratio in the range of approximately 2:1 to 1:2 (wt./wt.), respectively.

5. The coating of claim 1 comprising a first or second cross-linking reagent, wherein at least one of the first and second cross-linking agent(s) is a compound of formula Photo 1 -LG-Photo 2 , wherein Photo 1 and Photo 2 , independently represent at least one photoreactive group and LG represents a linking group comprising at least one silicon or at least one phosphorus atom, there is a covalent linkage between at least one photoreactive group and the linking group, wherein the covalent linkage between at least one photoreactive group and the linking group is interrupted by at least one heteroatom, optionally wherein at least one of the first and second cross-linking agents is a compound of formula selected from:

wherein R 1 , R 2 , R 8 and R 9 are any substitution; R 3 , R 4 , R 6 and R 7 are alkyl, aryl, or a combination thereof; R 5 is any substitution; and each X, independently, is O, N, Se, S, or alkyl, or a combination thereof;

wherein R 1 and R 5 are any substitution; R 2 and R 4 can be any substitution, except OH; R 3 can be alkyl, aryl, or a combination thereof; and each X, independently, is O, N, Se, S, alkyl or a combination thereof;

wherein R 1 , R 2 , R 4 and R 5 are any substitution; R 3 is any substitution; R 6 and R 7 are alkyl, aryl, or a combination thereof, and each X, independently, is O, N, Se, S, alkyl, or a combination thereof; and

6. The coating of claim 1 , wherein the acid polymer is an acrylic acid polymer that has an average molecular weight of 150 kDa or greater.

7. The coating of claim 1 , wherein:

(I) the coating releasing particulates of less than 3,000 particles greater than 10 microns; or

(II) (a) the coating exhibits a lubricity when wetted of between 0 and 30 grams of force for at least 10 consecutive testing cycles, or wherein (b) the coating exhibits a durability of lubricity such there is less than a 30 percent increase in measured friction between the average of cycles 1-5 of testing and cycles 10-15 of testing, or both (a) and (b).

8. The coating of claim 1 , wherein the thickness of the first and second coated layers combined is in the range of about 100 to 1000 nm when dry.

9. The coating of claim 1 , wherein the first coated layer does not include the acid polymer of the second coated layer, and the second coated layer does not include the vinyl pyrrolidone polymer of the first coated layer.

10. A medical device comprising the coating of claim 1 .

11. The medical device of claim 10 , wherein the substrate comprises polyamide, polyimide, polyether block amide (PEBAX), polyether ether ketone (PEEK), high density polyethylene (HDPE), polyethylene, polyurethane, or polyethylene vinyl acetate.

12. The medical device of claim 10 , the medical device comprising a catheter.

13. The medical device of claim 10 , wherein the catheter is selected from the group consisting of venous access catheters, vascular access catheters, angioplasty catheters, cardiac catheters, balloon catheters, drug infusion catheters, intravenous catheters, stroke therapy catheters, and stent graft catheters.

14. A method making a coating according to claim 1 on a medical device comprising:

applying a first coating solution directly or indirectly on a medical device surface, the first coating solution comprising a vinyl pyrrolidone polymer and photoreactive groups, wherein the photoreactive groups are pendent from the vinyl pyrrolidone polymer or present on a first cross-linking agent comprising at least two photoreactive groups; and a first solvent, and drying the first coating solution;

exposing the first coating solution to actinic radiation to form a first layer;

applying a second coating solution onto the first layer, wherein the second coating solution is different in composition than the first coating solution, the second coating solution comprising an acid polymer wherein (a) the acid polymer is formed from a composition comprising one or more of the following monomers: acrylic acid, methacrylic acid, itaconic acid, monomethyl itaconic acid, maleic anhydride, fumaric acid, crotonic acid, acrylamido-2-methylpropanesulfonic acid (AMPS), 2-(meth)acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, 2-sulfoethyl methacrylate, and salts thereof, or (b) the acid polymer is a sulfonic acid polymer, a carboxylic acid polymer, or a phosphonic acid polymer, and a second solvent, and optionally a second cross-linking agent comprising at least two photoreactive groups, and drying the second coating solution; and

exposing the second coating solution to actinic radiation to form a second layer.

15. The coating of claim 1 wherein the acid polymer is a copolymer made from two or more different acid-group containing monomers, or is a copolymer made from one or more acid-group containing monomer(s) and one or more non-acid group containing monomer(s), wherein optionally the copolymer is a random copolymer, a block copolymers, a graft copolymer, or a blends thereof.

16. The lubricious coating of claim 1 where, in the first coated layer the vinyl pyrrolidone polymer is the sole polymeric component, and in the second coated layer the acid polymer is the sole polymeric component.

17. The lubricious coating of claim 1 wherein the first coated layer consists essentially of the vinyl pyrrolidone polymer and the photoreactive groups, and the second coated layer consists essentially of the acid polymer.