Slippery, tenaciously adhering hydrogel coatings containing a polyurethane-urea polymer hydrogel commingled with a poly(N-vinylpyrrolidone) polymer hydrogel, coated polymer and metal substrate materials, and coated medical devices

A material bearing thereon a coating of a wet, slippery, tenaciously adhering, commingled hydrogel of a hydrophilic polyurethane-polyurea polymer hydrogel, and a poly(N-vinylpyrrolidone) polymer hydrogel, said material and coating comprising:

• a) a substrate, such that said substrate is a polymer selected from the group consisting of thermoplastic polyurethanes (TPU's), polyesters, nylon polymers, block copolymers of a polyether polymer and a polyester polymer, block copolymers of a polyether polymer and one selected from the group consisting of polyamides, polyimides, polyolefins, synthetic hydrocarbon elastomers, and natural rubber;
• or that said substrate is a metal selected from the group consisting of stainless steel, titanium, alloys of steel, nickel, titanium, molybdenum, cobalt, and chromium, and nitinol (nickel-titanium alloy), and vitallium (cobalt-chromium alloy);
• said polymer or metal substrate having a surface with reactive chemical functional groups thereon, said reactive chemical functional groups being selected from the group (i-v) consisting of (i) amine-containing groups, which are selected from the group consisting of amino groups, amido groups, urethane groups, urea groups, and combinations thereof, when said substrate is a polymer, and which are amino-silane groups when said substrate is a metal;
• (ii) hydroxyl groups, (iii) carboxyl groups, (iv) carbonyl groups, and (v) combinations thereof, such that there are at least some amine-containing groups on said substrate surface;
• b) a first coating, applied onto said substrate surface, said first coating containing a hydrophilic polyurethane-urea prepolymer intermediate, that is capable of forming a polyurethane-polyurea hydrogel-forming polymer, and that contains terminal isocyanate groups that are free to react with other species, said hydrophilic polyurethane-urea prepolymer intermediate being selected from the group consisting of a compound derived from a water-soluble polyether polyol or a copolyether polyol, and an organic polyisocyanate selected from the group consisting of aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates;
• such that at least some of said terminal isocyanate groups are reacted with and are covalently bonded to said reactive chemical functional groups on said substrate surface, forming covalent polyurea bonds therewith, resulting in the formation of a tie coat of a polyurethane-polyurea hydrogel-forming polymer, on said substrate surface, that tenaciously adheres to said substrate surface;
• wherein at least some of said terminal isocyanate groups of said polyurethane-urea prepolymer intermediate are present in said polyurethane-polyurea hydrogel-forming polymer of said tie coat, such that they remain free to react with other species;
• and
• c) a second coating, applied onto said tie coat, said second coating containing an aqueous solution of a poly(N-vinylpyrrolidone) hydrogel-forming polymer;
• wherein water of said aqueous solution of said poly(N-vinylpyrrolidone) hydrogel-forming polymer is bound with said polyurethane-polyurea hydrogel-forming polymer to form a first hydrogel of said commingled hydrogel, such that said first hydrogel of said commingled hydrogel is a polyurethane-polyurea polymer hydrogel;
• wherein water of said aqueous solution of said poly(N-vinylpyrrolidone) hydrogel-forming polymer is bound with said poly(N-vinylpyrrolidone) hydrogel-forming polymer to form a second hydrogel of said commingled hydrogel, such that said second hydrogel of said commingled hydrogel is a poly(N-vinylpyrrolidone) polymer hydrogel;
• and
• wherein said first hydrogel of said commingled hydrogel and said second hydrogel of said commingled hydrogel are commingled with one another, and form a composition selected from the group consisting of an interpolymer hydrogel network, a graft copolymer hydrogel, an association polymer hydrogel, and combinations thereof.

A material bearing thereon a coating of a dried, tenaciously adhering, commingled hydrogel of a hydrophilic polyurethane-polyurea polymer hydrogel, and a poly(N-vinylpyrrolidone) polymer hydrogel, said dried hydrogel coating being reactivateable to a wet, slippery hydrogel, said material and said dried hydrogel coating comprising:

• a) a hydrophilic or hydrophilicized hydrophobic polymer substrate or a metal substrate, having a surface with reactive chemical functional groups thereon, at least some of which are amine-containing groups;
• b) a first coating, applied onto said substrate surface, said first coating containing a hydrophilic polyurethane-urea prepolymer intermediate, that is capable of forming a polyurethane-polyurea hydrogel-forming polymer, and that contains terminal isocyanate groups that are free to react with other species, such that at least some of said terminal isocyanate groups are reacted with and are covalently bonded to said reactive chemical functional groups on said substrate surface, forming covalent polyurea bonds therewith, resulting in the formation of a tie coat of a polyurethane-polyurea hydrogel-forming polymer, on said substrate surface, such that said polyurethane-polyurea hydrogel-forming polymer tenaciously adheres to said substrate surface;
• and
• wherein at least some of said terminal isocyanate groups of said polyurethane-urea prepolymer intermediate are present in said polyurethane-polyurea hydrogel-forming polymer such that they remain free to react with other species;
• and
• c) a second coating, applied onto said tie coat, said second coating containing an aqueous solution of a poly(N-vinylpyrrolidone) hydrogel-forming polymer;
• such that a wet, slippery, tenaciously adhering, commingled hydrogel is formed on said tie coat upon the application of said second coating to said tie coat;
• wherein water of said aqueous solution of said poly(N-vinylpyrrolidone) hydrogel-forming polymer is bound with said polyurethane-polyurea hydrogel-forming polymer to form a first hydrogel of said commingled hydrogel, such that said first hydrogel of said commingled hydrogel barrier coat is a polyurethane-polyurea polymer hydrogel;
• wherein water of said aqueous solution of said poly(N-vinylpyrrolidone) hydrogel-forming polymer is bound with said poly(N-vinylpyrrolidone) hydrogel-forming polymer to form a second hydrogel of said commingled hydrogel, such that said second hydrogel of said commingled hydrogel is a poly(N-vinylpyrrolidone) polymer hydrogel;
• wherein said polyurethane-polyurea polymer hydrogel of said commingled hydrogel and said poly(N-vinylpyrrolidone) polymer hydrogel of said commingled hydrogel are commingled with one another;
• and
• wherein said wet, slippery, tenaciously adhering, commingled hydrogel is then dried to remove moisture therefrom, forming a dried, tenaciously adhering, commingled hydrogel coating on said substrate surface, such that said dried hydrogel coating is reactivateable to a wet, slippery, hydrogel coating by the re-exposure of said dried hydrogel coating to an aqueous fluid.

A two-part coating composition for a wet, slippery, tenaciously adhering, commingled hydrogel coating of a hydrophilic polyurethane-polyurea polymer hydrogel and a poly(N-vinylpyrrolidone) polymer hydrogel, for a hydrophilic or hydrophilicized hydrophobic polymer substrate or a metal substrate, that has a surface bearing reactive chemical functional groups thereon, said reactive chemical functional groups including at least some amine-containing groups, said composition comprising:

• a) a first coating composition comprising a hydrophilic polyurethane-urea prepolymer intermediate, that is capable of forming a polyurethane-polyurea hydrogel-forming polymer, and that contains terminal isocyanate groups that are free to react with other species, such that at least some of said terminal isocyanate groups are capable of reacting with and covalently bonding to said reactive chemical functional groups on said substrate surface, to form covalent polyurea bonds therewith, resulting in the formation of a tie coat of a polyurethane-polyurea hydrogel-forming polymer, on said substrate surface, that tenaciously adheres to said substrate surface, to which said first coating composition is applied, with said hydrophilic polyurethane-urea prepolymer intermediate being derived from:
• a compound selected from the group consisting of a water-soluble polyether polyol and a water-soluble copolyether polyol;
• and
• an organic polyisocyanate selected from the group consisting of aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates;
• and
• b) a second coating composition, for application onto said tie coat, said second coating composition comprising a poly(N-vinylpyrrolidone) hydrogel-forming polymer;
• with said second coating composition further comprising a moisture-containing, hydrogel-forming compound, that contains isocyanate-reactive functional groups, such that a barrier coat of a wet, slippery, tenaciously adhering, commingled hydrogel is formed upon the application of said second coating composition to said tie coat;
• wherein said moisture of said hydrogel-forming compound is bound with said polyurethane-polyurea hydrogel-forming polymer of said tie coat to form a first hydrogel of said commingled hydrogel barrier coat, on said tie coat, such that said first hydrogel of said commingled hydrogel barrier coat is a polyurethane-polyurea polymer hydrogel;
• wherein said isocyanate-reactive functional groups of said hydrogel-forming compound are reacted with and are covalently bonded to at least some of said terminal isocyanate groups of said polyurethane-polyurea hydrogel-forming polymer of said tie coat, which were free to react therewith, thereby rendering said polyurethane-polyurea polymer hydrogel tenaciously adhering to said tie coat, and thus also tenaciously adhering to said substrate surface;
• wherein said moisture of said hydrogel-forming compound is bound with said poly(N-vinylpyrrolidone) hydrogel-forming polymer to form a second hydrogel of said commingled hydrogel barrier coat, such that said second hydrogel of said commingled hydrogel barrier coat is a poly(N-vinylpyrrolidone) polymer hydrogel;
• wherein said first hydrogel of said commingled hydrogel barrier coat and said second hydrogel of said commingled hydrogel barrier coat are commingled with one another, forming a composition selected from the group consisting of an interpolymer hydrogel network, a graft copolymer hydrogel, an association polymer hydrogel, and combinations thereof, such that said second hydrogel is thereby also rendered tenaciously adhering to said tie coat and thus also tenaciously adhering to said substrate surface;
• and
• wherein said commingled hydrogel barrier coat has a water content of at least 70% by weight.

An intermediate composition for forming a coating of a wet, slippery, tenaciously adhering, commingled hydrogel of a hydrophilic polyurethane-polyurea hydrogel and a poly(N-vinylpyrrolidone) polymer hydrogel, on a polymer or metal substrate material, said intermediate composition comprising:

• a) a hydrophilic or hydrophilicized hydrophobic polymer substrate or a metal substrate, having a surface with reactive chemical functional groups thereon, said reactive chemical functional groups being selected from the group (i-v) consisting of (i) amine-containing groups, such that in the case of a polymer substrate, said amine-containing groups are selected from the group consisting of amino groups, amido groups, urethane groups, urea groups, and combinations thereof;
• and such that in the case of a metal substrate, said amine-containing groups are amino-silane groups;
• (ii) hydroxyl groups, (iii) carboxyl groups, (iv) carbonyl groups, and (v) combinations thereof, such that there are at least some amine-containing groups on said substrate surface;
• and
• b) a tie-coat, on said substrate surface, said tie coat comprising a hydrophilic prepolymer intermediate of a polyurethane-urea polymer or copolymer, containing terminal isocyanate groups that are free to react with other species, such that at least some of said terminal isocyanate groups are reacted with and are covalently bonded to said reactive chemical functional groups on said substrate surface, forming covalent polyurea bonds therewith, resulting in the formation of a polyurethane-polyurea hydrogel-forming polymer or copolymer, with said tie coat tenaciously adhering to said substrate surface;
• further such that at least some of said terminal isocyanate groups of said polyurethane polymer or copolymer are present in said polyurethane-polyurea hydrogel-forming polymer or copolymer, such that they remain available for reaction with a hydrogel-forming compound, that is applied to said tie coat and that contains isocyanate-reactive functional groups, said hydrogel-forming compound being selected from the group consisting of water, water-soluble amines, and combinations thereof, to form a barrier coat of a commingled hydrogel on said tie coat, which commingled hydrogel barrier coat tenaciously adheres to said tie coat;
• and
• still further such that said polyurethane-polyurea polymer or copolymer is capable of commingling with a poly(N-vinylpyrrolidone) polymer, which is applied to said tie coat, such that said polyurethane-polyurea polymer or copolymer hydrogel of said commingled hydrogel barrier coat and said poly(N-vinylpyrrolidone) polymer hydrogel form a composition selected from the group consisting of an interpolymer hydrogel network, a graft copolymer hydrogel, an association polymer hydrogel, and combinations thereof, with said commingled hydrogel barrier coat tenaciously adhering to said tie coat and thus also tenaciously adhering to said substrate surface.