UV cure topcoatings for medical devices

Abstract

The invention concerns coating compositions for medical devices or medical implants comprising a polymer which is soluble in water or water-alcohol solutions, the polymer made from monomers comprising: (a) at least one monomer that is a photo radical generator, and (b) at least one monomer comprising one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides; wherein the molar ratio of one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to photo radical generator group is 20:1 to 500:1.

Claims

1. A coating composition for medical devices or medical implants comprising a random polymer which is soluble in water or water-alcohol solutions, the polymer made from monomers consisting essentially of: (a) at least one monomer that is a photo radical generator comprising one or more of 4-methacryloxy-2-hydroxybenzophenone, 4-acryloxybenzophenone, 4-methacryloxybenzophenone, acrylamidobenzophenone, methacrylamidobenzophenone, 2-hydroxy-4-acryloxyethoxybenzophenone, and 2-hydroxy-4-methacryloxyethoxybenzophenone, and (b) (i) at least one monomer comprising ethylenic monomers comprising at least one acidic group; and (ii) at least one monomer comprising one or more of acrylates or acrylamides, provided one monomer is N-(2-hydroxyethyl)acrylamide; wherein the ethylenic monomers comprise acrylic acid; wherein the acrylates or acrylamides comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, or any mixture of the foregoing; wherein the molar ratio of both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to (a) monomers comprising a photo radical generator is 20:1 to 500:1.

2. The coating composition of claim 1, wherein the polymer is made from monomers consisting of: (a) at least one monomer that is a photo radical generator comprising one or more of 4-methacryloxy-2-hydroxybenzophenone, 4-acryloxybenzophenone, 4-methacryloxybenzophenone, acrylamidobenzophenone, methacrylamidobenzophenone, 2-hydroxy-4-acryloxyethoxybenzophenone, and 2-hydroxy-4-methacryloxyethoxybenzophenone, and (b) (i) at least one monomer comprising ethylenic monomers comprising at least one acidic group; and (ii) at least one monomer comprising one or more of acrylates or acrylamides, provided one monomer is N-(2-hydroxyethyl)acrylamide; wherein the ethylenic monomers comprise and acrylic acid; wherein the acrylates or acrylamides comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, or any mixture of the foregoing; wherein the molar ratio of both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to (a) monomers comprising a photo radical generator is 20:1 to 500:1.

3. The coating composition of claim 1, wherein the photo radical generator comprises 4-methacryloxy-2-hydroxybenzophenone.

4. The coating composition of claim 1, wherein the molar ratio of N-(2-hydroxyethyl)acrylamide to acrylic acid is 2:1 to 5:1.

5. The coating composition of claim 1, wherein the molar ratio of both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to photo radical generator comprising at least one photopolymerizable group is 40:1 to 200:1.

6. A coating composition for medical devices or medical implants comprising a random polymer which is soluble in water or water-alcohol solutions, the polymer made from monomers consisting essentially of: (a) at least one monomer that is a photo radical generator comprising one or more of 4-methacryloxy-2-hydroxybenzophenone, 4-acryloxybenzophenone, 4-methacryloxybenzophenone, acrylamidobenzophenone, methacrylamidobenzophenone, 2-hydroxy-4-acryloxyethoxybenzophenone, and 2-hydroxy-4-methacryloxyethoxybenzophenone, and (b) (i) at least one monomer comprising ethylenic monomers comprising at least one acidic group; and (ii) at least one monomer comprising one or more of acrylates or acrylamides; wherein the ethylenic monomers comprising at least one acidic group comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid and itaconic acid, and mixtures thereof; wherein the acrylates or acrylamides comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and N-(2-hydroxyethyl) methacrylamide, N-acryloylamido ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, or any mixture of the foregoing; wherein the molar ratio of both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to (a) monomers comprising a photo radical generator is 20:1 to 500:1; wherein the polymer has a weight-average molecular weight (Mw) of between 20,000 and 800,000.

7. The coating composition of claim 1, additionally comprising a second polymer which is soluble in water or water-alcohol solutions.

8. The coating composition of claim 7, wherein the ethylenic monomers of the second polymer comprise at least one acidic group, the ethylenic monomers of the second polymer comprising the at least one acidic group comprise one or more of acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid, itaconic acid, and any combination thereof.

9. The coating composition of claim 7, wherein the acrylates or acrylamides of the second polymer comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, and any mixture of the foregoing.

10. A coating composition for medical devices or medical implants comprising a random polymer which is soluble in water or water-alcohol solutions, the polymer made from monomers consisting essentially of: (a) at least one monomer that is a photo radical generator comprising one or more of 4-methacryloxy-2-hydroxybenzophenone, 4-acryloxybenzophenone, 4-methacryloxybenzophenone, acrylamidobenzophenone, methacrylamidobenzophenone, 2-hydroxy-4-acryloxyethoxybenzophenone, and 2-hydroxy-4-methacryloxyethoxybenzophenone, and (b) (i) at least one monomer comprising ethylenic monomers comprising at least one acidic group; and (ii) at least one monomer comprising one or more of acrylates or acrylamides; wherein the ethylenic monomers comprising at least one acidic group comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid and itaconic acid, and mixtures thereof; wherein the acrylates or acrylamides comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, or any mixture of the foregoing; wherein the molar ratio of both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to (a) monomers comprising a photo radical generator is 20:1 to 500:1; additionally comprising a second polymer which is soluble in water or water-alcohol solutions; wherein the second polymer has a weight-average molecular weight (Mw) of between 50,000 and 800,000.

11. The coating composition of claim 6, wherein the photo radical generator comprises 4-methacryloxy-2-hydroxybenzophenone.

12. The coating composition of claim 6, wherein the molar ratio of both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to photo radical generator comprising at least one photopolymerizable group is 40:1 to 200:1.

13. The coating composition of claim 6, additionally comprising a second polymer which is soluble in water or water-alcohol solutions.

14. The coating composition of claim 13, wherein the ethylenic monomers of the second polymer comprise at least one acidic group, the ethylenic monomers of the second polymer comprising the at least one acidic group comprise one or more of acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid, itaconic acid, and any combination thereof.

15. The coating composition of claim 13, wherein the acrylates or acrylamides of the second polymer comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, and any mixture of the foregoing.

16. The coating composition of claim 10, wherein the photo radical generator comprises 4-methacryloxy-2-hydroxybenzophenone.

17. The coating composition of claim 10, wherein the molar ratio of both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to photo radical generator comprising at least one photopolymerizable group is 40:1 to 200:1.

18. The coating composition of claim 10, wherein the ethylenic monomers of the second polymer comprise at least one acidic group, the ethylenic monomers of the second polymer comprising the at least one acidic group comprise one or more of acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid, itaconic acid, and any combination thereof.

19. The coating composition of claim 10, wherein the acrylates or acrylamides of the second polymer comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, and any mixture of the foregoing.

Description

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

(1) The requirements for any coating intended for use on medical devices will be set forth and explained first. The specification will then show how the present invention fulfills these requirements.

(2) The coatings of the instant invention are suitable for use in medical devices. The coatings of the present invention have the following properties: (1) the coating must be able, on drying, to form a continuous, adherent film of good integrity on the surface of the material to be coated. This means that the minimum film-forming temperature of the coating solution must be lower than the expected drying temperature to be used during device fabrication; (2) the formed polymer film must be flexible and adherent enough to conform without rupture to the bending and twisting of the coated device under the expected conditions of use; (3) when the coated device is immersed for long periods in aqueous media such as human blood, the film must not weaken or lose its integrity; (4) the coating must present a non-cytotoxic and blood compatible surface. When contacted with human blood the coating must not initiate blood coagulation and the complement pathways; (5) the coating must be firmly and securely bound to the substrate so that no particles or fragments or leachable components can contaminate an aqueous medium such as human blood; and (6) the coating must withstand some acceptable form of sterilization without loss of integrity, durability, biocompatibility or lubricity.

(3) In some embodiments, the invention concerns coating compositions for medical devices or medical implants comprising a polymer which is soluble in water or water-alcohol solutions, the polymer made from monomers comprising: (a) at least one monomer that is a photo radical generator, and (b) at least one monomer comprising one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides; wherein the molar ratio of one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to photo radical generator group is 20:1 to 500:1.

(4) The polymer may be packaged in a water or water-alcohol mixture. The alcohol is typically a C.sub.1-C.sub.6 alcohol. Preferred alcohols include methanol, ethanol and iso-propanol. The ratio of water to alcohol can be 100:0 to 50:50.

(5) Some preferred photo radical generators are benzophenone compounds. In some embodiments, the photo radical generator is selected from one or more of comprises one or more of 4-methacryloxy-2-hydroxybenzophenone, 4-acryloxybenzophenone, 4-methacryloxybenzophenone, acrylamidobenzophenone, methacrylamidobenzophenone, 2-hydroxy-4-acryloxyethoxybenzophenone, 2,4-dihydroxy-4-vinyl benzophenone, and 2-hydroxy-4-methacryloxyethoxybenzophenone. One preferred photo radical generator group comprises 4-methacryloxy-2-hydroxybenzophenone.

(6) A variety of ethylenic monomers may be used. In some embodiments the monomers comprise at least one acidic group comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid and itaconic acid, and mixtures thereof. In some embodiments, the ethylenic monomers comprise N-(2-hydroxyethyl)acrylamide and acrylic acid. In certain embodiments, the molar ratio of N-(2-hydroxyethyl)acrylamide to acrylic acid is 2:1 to 5:1.

(7) Preferred acrylates and acrylamides include acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyOmethyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, or any mixture of the foregoing.

(8) In some embodiments, the molar ratio of one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to photo radical generator comprising at least one photopolymerizable group is 40:1 to 200:1.

(9) In certain embodiments, the polymer has a weight-average molecular weight (Mw) of between 20,000 and 800,000 or 20,000 to 400,000 or 50,000 and 400,000.

(10) Some coating compositions additionally comprise a second polymer which is soluble in water or water-alcohol solutions. In some embodiments, the second polymer comprises one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides. In the second polymer, the ethylenic monomers of the second polymer comprise at least one acidic group, the ethylenic monomers of the second polymer comprising the at least one acidic group comprise one or more of acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid, itaconic acid, and any combination thereof. Additionally, in the second polymer the acrylates or acrylamides comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, and any mixture of the foregoing.

(11) In some embodiments, the second polymer has a weight-average molecular weight (Mw) of between 50,000 and 800,000.

(12) The invention also concerns coated substrates comprising a substrate and a lubricious coating made using a coating composition described herein. Preferred embodiments, additionally comprise a basecoat that contacts both the substrate and the lubricious coating composition. Preferred basecoats are hydrophobic.

(13) The coatings may be used on any medical device or implant suitable for the coating's application. In some embodiments, the substrate is plastic or metallic.

(14) Preferred coated substrates have a lubricity of less than 25 gf friction and a durability of less than 50 gf friction as measured by a pinch test.

(15) The invention also concerns medical devices and medical implants comprising a coated substrate described herein. In some embodiments, the medical device or medical implant is sterilized by at least one of gamma-ray, E-beam, and ethylene oxide.

(16) In additional embodiments, the coatings described herein contain a pharmaceutical or antimicrobial agent blended with the coating composition.

(17) 4-Methacryloxy-2-hydroxy benzophenone (MHB) can be copolymerized with polar acrylates such as Acrylic Acid and N-(2-Hydroxyethyl)acrylamide to produce a hydrophilic, photoactive polymer. Upon ultraviolet (UV) cure this polymer functions as a lubricious topcoat. It can also be used as an additive to other hydrophilic (non-photoactive) polymers to form a lubricious coating after UV Cure.

(18) ##STR00001##

(19) The invention relates to at least the following aspects.

(20) Aspect 1. A coating composition for medical devices or medical implants comprising a polymer which is soluble in water or water-alcohol solutions, the polymer made from monomers comprising: (a) at least one monomer that is a photo radical generator comprising one or more of 4-methacryloxy-2-hydroxybenzophenone, 4-acryloxybenzophenone, 4-methacryloxybenzophenone, acrylamidobenzophenone, methacrylamidobenzophenone, 2-hydroxy-4-acryloxyethoxybenzophenone, 2,4-dihydroxy-4-vinyl benzophenone, and 2-hydroxy-4-methacryloxyethoxybenzophenone, and (b) at least one monomer comprising one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides; wherein the ethylenic monomers comprise at least one acidic group comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid and itaconic acid, and mixtures thereof; wherein the acrylates or acrylamides comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyOmethyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, or any mixture of the foregoing; wherein the molar ratio of one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to photo radical generator group is 20:1 to 500:1.

(21) Aspect 2. The coating composition of claim 1, wherein the photo radical generator group comprises 4-methacryloxy-2-hydroxybenzophenone.

(22) Aspect 3. The coating composition of claim 1, wherein the ethylenic monomers comprise N-(2-hydroxyethyl)acrylamide and acrylic acid.

(23) Aspect 4. The coating composition of claim 3, wherein the molar ratio of N-(2-hydroxyethyl)acrylamide to acrylic acid is 2:1 to 5:1.

(24) Aspect 5. The coating composition of claim 1, wherein the molar ratio of one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides to photo radical generator comprising at least one photopolymerizable group is 40:1 to 200:1.

(25) Aspect 6. The coating composition of claim 1, wherein the polymer has a weight-average molecular weight (Mw) of between 20,000 and 800,000.

(26) Aspect 7. The coating composition of claim 1, additionally comprising a second polymer which is soluble in water or water-alcohol solutions.

(27) Aspect 8. The coating composition of claim 7, comprising one or both of (i) ethylenic monomers comprising at least one acidic group and (ii) one or more of acrylates or acrylamides.

(28) Aspect 9. The coating composition of claim 8, wherein the ethylenic monomers of the second polymer comprise at least one acidic group, the ethylenic monomers of the second polymer comprising the at least one acidic group comprise one or more of acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, acryloxypropionic acid, isocrotonic acid, maleic anhydride, maleic acid and half esters, half amides and half thioesters of maleic acid, fumaric acid, itaconic acid, and any combination thereof.

(29) Aspect 10. The coating composition of claim 8, wherein the acrylates or acrylamides of the second polymer comprise acrylamide, N-(2-hydroxyethyl)acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and N-(2-hydroxyethyl) methacrylamide, N-acryloylamido-ethoxyethanol, N-(hydroxymethyl) acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 4-hydroxybutyl acrylate, hydroxypropyl acrylate, methyl 3-hydroxy-2-methylenebutyrate, hydroxypropyl methacrylate, 2-allyloxyethanol, 3-allyloxy-1,2-propanediol, 1,4-butanediol vinyl ether, di(ethylene glycol)vinyl ether, ethylene glycol vinyl ether, N,N-1,2-dihydroxyethylene-bis-acrylamide, N,N-1,2-dihydroxyethylene-bis-methyacrylamide, N-hydroxymethyl methacrylamide, N-tri(hydroxymethyl)-methyl-methacrylamide, and any mixture of the foregoing.

(30) Aspect 11. The coating composition of claim 8, wherein the second polymer has a weight-average molecular weight (Mw) of between 50,000 and 800,000.

(31) Aspect 12. The coating composition of claim 1, additionally comprising water or a water/alcohol mixture.

(32) Aspect 13. A coated substrate comprising: a substrate and a lubricious coating made using a coating composition of any one of claims 1-12.

(33) Aspect 14. The coated substrate of claim 13, additionally comprising a base coat that contacts both the substrate and the lubricious coating composition.

(34) Aspect 15. The coated substrate of claim 14, wherein the base coat is hydrophobic.

(35) Aspect 16. The coated substrate of claim 13, wherein the substrate is plastic.

(36) Aspect 17. The coated substrate of claim 13, wherein the substrate is metallic.

(37) Aspect 18. The coated substrate of any one of claims 13-17, wherein the coated substrate has a lubricity of less than 25 gf friction and a durability of less than 50 gf friction as measured by a pinch test.

(38) Aspect 19. A medical device or medical implant comprising a coated substrate of any one of claims 13-18.

(39) Aspect 20. The medical device or medical implant of claim 19 where the medical device or medical implant is sterilized by at least one of gamma-ray, E-beam, and ethylene oxide.

(40) Aspect 21. The medical device or medical implant of claim 19 or 20, where the lubricious coating contains a pharmaceutical or antimicrobial agent blended with the coating composition.

EXAMPLES

(41) The invention is illustrated by the following non-limiting examples.

(42) Materials. 4-methacryloxy-2-hydroxy benzophenone (MHB) was purchased from Polysciences and Bimax. Purity of MHB was confirmed with nuclear magnetic resonance NMR. All other chemicals were purchased from approved suppliers and IR spectra were taken on Perkin Elmer Frontier FT-IR Spectrometer with a Universal ATR Sampling Accessory. NMRs were done at USciences with a Bruker 400 MHz NMR.

(43) Poly(HEAA-co-AA) in Table 1. The polymer was made by reacting 29.79 g of N-(2-hydroxyethyl)acrylamide (HEAA), 6.21 g of acrylic acid (AA) in 263 milliliters (mL) of water. The initiator for the polymerization was ammonium persulfate and sodium hydroxymethansulfinate hydrate. 0.015 mL of a 1% solution of iron(II) sulfate FeSO.sub.4 was added to catalyze the reaction. The polymerization was done under N.sub.2 at 40? C. The polymer was purified by dialysis or precipitation with acetone (similar to Example 1 of US2013/0323291 A1).

(44) Poly(HEAA-co-AA-co-MHB) 1-4 in Table 1. The photo-active polymer was made by reacting 15.29 g of HEAA, 3.19 g of AA and 1.00 g, 0.50 g, or 0.25 g of MHB in 40 mL of IPA and 30 mL of water. 0.59 mL of a 50 milligrams per milliliter (mg/mL) solution of Azobisisobutyronitrile (AiBN) in THF was added to the monomer solution. The solution was sparged for 30 minutes to remove the oxygen, then heated to 60? C. for 24 hours. After the reaction was complete the polymer was precipitate with 150 mL of ethyl acetate. The solvent was decanted off and the polymer then dried in an oven at 60? C. with any remaining solvent being removed under vacuum. The polymer was dissolved in a 50:50 mixture of IPA and water.

(45) Poly(HEAA-co-AA-co-MHB) 5-7 in Table 1. The photo-active polymer was made by reacting 15.29 grams (g) of HEAA, 3.19 g of AA and 1.00 g, 0.50 g or 0.25 g of MHB in 40 mL of ethanol and 30 mL of water. 0.245 mL of a 20 mg/mL solution of (AiBN) in THF was added to the monomer solution. The solution was sparged for 30 minutes to remove the oxygen then heated to 60? C. for 24 hours. After the reaction was complete the polymer was precipitate with 150 mL of ethyl acetate. The solvent was decanted off and the polymer then dried in an oven at 60? C. with any remaining solvent removed under vacuum. The polymers were dissolved in a 50:50 mixture of ethanol and water.

(46) The molecular weights were determined through SEC using a Waters 1515 isocratic high performance liquid chromatography HPLC pump, Waters 2489 UV/Visible detector set to 276 nanometers (nm) and 290 nm, Waters 2414 Refractive Index Detector, and 3 columns (2 Waters Ultrahydrogel 2000 and 1 Waters Ultrahydrogel 250). The molecular weights were calculated by comparing to poly (acrylic acid) standards using Empower 3 software.

(47) The coating was applied to a Pebax? 55D plastic tubing using the dip-coating method. The Pebax? tubing had an outer diameter of 0.079 inches and a wall thickness of 0.005 inches. The tubing was placed over stainless steel rod for stability. The tubing was first dipped into the basecoat and extracted at 0.2 inches per second and was rotated in UV chamber for 5 minutes set to the desired intensity. Then the tubing was dipped into the topcoat and extracted at 0.2 inches per second and was rotated in UV chamber for 5 minutes set to the desired intensity.

(48) UV cure was performed in an Uvitron IntelliRay model UV0832 UV Cure unit equipped with a UVA 600 Watt metal halide lamp. Irradiance was measured with an EIT Uvicure Plus II radiometer purchased from INPRO Technologies. This one channel UVA radiometer measures the radiation between 320 and 390 nm.

(49) The friction of the coating was pinch tested on a Tinius Olsen 5ST Electromechanical Testing Machine with a 10N load cell and the data was collected with Horizon software. The Tinius Olsen is equipped with a heated water bath and pinch pads that pressed together at a constant force. The water bath is filled with PBS solution and heated to 37? C. The pinch pads are submerged in the water and pressed together with 450 g of force. The friction is measured as the grams of force required to push and pull the sample through the pads. The lubricity and durability are determined by averaging the grams of force when the samples are pulled through the pads. Lubricity is the average from cycle 2-4 and durability is the average from cycle 28-30.

(50) Basecoat solutions were made using two different photo-active basecoat polymers. The Basecoat polymer can be diluted with a variety of different solvents including Isopropanol (IPA) and Ethanol. Basecoat A: 10 wt % solution of a copolymer of 2-ethylhexyl methacrylate (EHMA), N-vinylpyrrolidone (NVP), (hydroxyethyl)methacrylate (HEMA), and MHB in propylene glycol methyl ether acetatePMA with a polyaziridine crosslinker. Basecoat B: 10 wt % solution of a copolymer of butyl acrylate (BA), methyl methacrylate (MMA), NVP, HEMA, and MHB in PMA with a polyaziridine crosslinker.

(51) TABLE-US-00001 TABLE 1 Lists the composition and M.sub.w and M.sub.n for the polymers made and tested. Poly(HEAA-co- Mole % AA-co-MHB) MHB M.sub.w M.sub.n M.sub.w/M.sub.n 1 2 72417 19150 3.78 2 1 58864 12757 4.61 3 1 191290 55687 3.44 4 0.5 216586 74642 2.94 5 2 218178 79888 2.73 6 1 254733 69063 3.69 7 0.5 231294 75766 3.05 Poly(HEAA-co-AA) 0 649456 301998 2.15

(52) TABLE-US-00002 TABLE 2 Shows the results of the friction test of the different topcoats and UV light intensity using A as the Basecoat. The photo-active topcoat contained a Poly(HEAA-co-AA- co-MHB) described in table 1, Poly(HEAA-co-AA), and surfactants in water. Poly(HEAA-co- Poly(HEAA- AA-co-MHB) co-AA) Intensity Lubricity Durability Basecoat (Wt %) (Wt %) (mW/cm.sup.2) (gf) (gf) Pads 1 A 1% (19 kMn/2% 2% 130 14 ? 0.8 14 ? 1.0 Silicone MHB) 2 A 1% (19 kMn/2% 2% 90 10 ? 0.9 13 ? 0.2 Silicone MHB) 3 A 1% (19 kMn/2% 2% 90 12 ? 0.2 17 ? 6.1 Delrin MHB) 4 A 0.5% (19 kMn/2% 2% 90 12 ? 0.6 14 ? 2.6 Delrin MHB) 5 A 1% (13 kMn/1% 2% 90 12 ? 4.0 25 ? 13 Delrin MHB) 6 A 1% (56 kMn/1% 2% 90 19 ? 3.7 45 ? 20 Delrin MHB) 7 A 0.5% (56 kMn/1% 2% 90 15 ? 1.6 41 ? 3.1 Delrin MHB) 8 A 1% (75 kMn/0.5% 2% 90 18 ? 8.3 116 ? 105 Delrin MHB) 9 A 1% (69 kMn/1% 2% 90 14 ? 1.2 16 ? 6.4 Delrin MHB) 10 A 0.5% (69 kMn/1% 2% 90 16 ? 2.8 44 ? 32 Delrin MHB) 11 A 1% (69 kMn/1% 2% 130 12 ? 0.8 26 ? 7.6 Delrin MHB) 12 A 0.5% (69 kMn/1% 2% 130 14 ? 2.3 31 ? 11 Delrin MHB) 13 A 1% (80 kMn/2% 2% 90 11 ? 1.6 85 ? 9.2 Delrin MHB) 14 A 0.5% (80 kMn/2% 2% 90 13 ? 4.0 111 ? 25.sup. Delrin MHB) 15 A 1% (80 kMn/2% 2% 130 16 ? 5.4 105 ? 34.sup. Delrin MHB) 16 A 0.5% (80 kMn/2% 2% 130 13 ? 5.8 75 ? 33 Delrin MHB) 17 A 1% (76 kMn/0.5% 2% 90 13 ? 4.0 144 ? 69.sup. Delrin MHB) 18 A 1% (76 kMn/0.5% 2% 130 12 ? 2.2 16 ? 10 Delrin MHB)

(53) TABLE-US-00003 TABLE 3 Show the results of the friction test of the different topcoats. Coated two times with topcoat and no basecoat. The photo-active topcoat contained a Poly(HEAA-co- AA-co-MHB) described in table 1, Poly(HEAA-co-AA), and surfactants in water. Poly(HEAA-co- Poly(HEAA- AA-co-MHB) co-AA) Intensity Lubricity Durability (Wt %) Wt % (mW/cnf) (gf) (gf) Pads 1 1% (19 kMn/2% 2% 130 12 ? 1.4 .sup.15 ? 1.8 Silicone MHB) 2 1% (19 kMn/2% 2% 90 9 ? 2.3 100 ? 74 Silicone MHB) 3 1% (19 kMn/2% 2% 130 52 ? 6.8 158 ? 3.7 Delrin MHB) 4 1% (19 kMn/2% 2% 90 51 ? 6.4 132 ? 14 Delrin MHB) 5 1% (69 kMn/1% 2% 130 6 ? 4.5 76 ? 57 Silicone MHB) 6 1% (69 kMn/1% 2% 90 5 ? 1.1 29 ? 36 Silicone MHB) 7 1% (69 kMn/1% 2% 130 29 ? 8.3 104 ? 20 Delrin MHB) 8 1% (69 kMn/1% 2% 90 51 ? 6.6 108 ? 3.2 Delrin MHB)

(54) TABLE-US-00004 TABLE 4 Show the results of the friction test of the different topcoats using Basecoat B. The photo-active topcoat contained a Poly(HEAA-co-AA-co-MHB) described in table 1, Poly(HEAA-co-AA), and in water. Poly(HEAA-co- Poly(HEAA- AA-co-MHB) co-AA) IPA Intensity Lubricity Durability Basecoat (Wt %) (Wt %) (Wt %) (mW/cm.sup.2) (gf) (gf) Pads 1 B 1% (19 kMn/2% 2% none 90 36 ? 9.8 50 ? 26 Delrin MHB) 2 B 1% (19 kMn/2% 2% 10 90 9.6 ? 1.4 10 ? 0.2 Delrin MHB) 3 B 0.5% (19kMn/2% 2% none 90 38 ? 2.3 83 ? 67 Delrin MHB) 4 B 0.5% (19 kMn/2% 2% 10 90 14 ? 1.3 15 ? 1.3 Delrin MHB) 5 B 1% (80 kMn/2% 2% 10 90 16 ? 5.9 20 ? 12 Delrin MHB)

(55) Throughout this specification, words are to be afforded their normal meaning, as would be understood by those skilled in the relevant art, unless otherwise indicated. However, so as to avoid misunderstanding, the meanings of certain terms will be specifically defined or clarified.

(56) In the present disclosure the singular forms a, an, and the include the plural reference, and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to a material is a reference to at least one of such materials and equivalents thereof known to those skilled in the art, and so forth.

(57) When a value is expressed as an approximation by use of the descriptor about, it will be understood that the particular value forms another embodiment. In general, use of the term about indicates approximations that can vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the specific context in which it is used, based on its function. The person skilled in the art will be able to interpret this as a matter of routine. In some cases, the number of significant figures used for a particular value may be one non-limiting method of determining the extent of the word about. In other cases, the gradations used in a series of values may be used to determine the intended range available to the term about for each value.

(58) Where present, all ranges are inclusive and combinable. That is, references to values stated in ranges include every value within that range including the endpoint values.

(59) When a list is presented, unless stated otherwise, it is to be understood that each individual element of that list and every combination of that list is to be interpreted as a separate embodiment. For example, a list of embodiments presented as A, B, or C is to be interpreted as including the embodiments, A, B, C, A and B, A and C, B and C, or A, B, and C.

(60) It is to be appreciated that certain features of the invention which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. That is, unless obviously incompatible or specifically excluded, each individual embodiment is deemed to be combinable with any other possible embodiment(s) and such a combination is considered to be another embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. Further, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step or part may also be considered an independent embodiment in itself.

(61) As used herein, the terms article and substrate are not limited to any shape or size, as it may be a layer of material, multiple layers or a block having at least one surface of which is modified by a coating composition described herein.

(62) As used herein the term hydrophobic is characterized by the lack of solubility of the non-crosslinked polymer in water.

(63) The term hydrophilic refers to a substrate surface made of a polymer where the uncured or non-crosslinked polymer is soluble in water or in a water alcohol solution that is more than 50% water.

(64) Unless otherwise specified, all molecular weights are weight-average molecular weights (Mw).