Medical device coated with interpenetrating network of hydrogel polymers

• US 6,120,904 A
• Filed: 05/24/1999
• Issued: 09/19/2000
• Est. Priority Date: 02/01/1995
• Status: Expired due to Term

• Current Assignee: Schneider Electric SE
• Original Assignee: Schneider Electric SE
• Inventors: Helmus, Michael N., Ding, Ni, Forman, Michael R., Hostettler, Fritz, Rhum, David
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): AYLWARD, DAVID E
• Application Number:
  US09/317,531
• Time in Patent Office: 484 Days
• Field of Search: 428/423.1, 428/423.3, 428/423.5, 428/423.7, 428/424.8, 428/425.8, 604/96, 525/452, 525/453
• US Class Current: 428/423.3
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: A61L 29/145 Hydrogels or hydrocolloids
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/145 Hydrogels or hydrocolloids
• CPC Class Codes: B05D 7/02 to macromolecular substances, e.g. rubber treatment or coating of shaped articles made of macromolecular substances C08J7/00
• CPC Class Codes: B05D 7/16 using synthetic lacquers or varnishes
• CPC Class Codes: B05D 7/52 Two layers
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/2865 Compounds having only one primary or secondary amino group; Ammonia
• CPC Class Codes: C08G 18/4833 Polyethers containing oxyethylene units
• CPC Class Codes: C08G 18/755 and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08G 2270/00 Compositions for creating interpenetrating networks
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 39/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08L 75/00 Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 175/12 from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31554 Next to second layer of polyamidoester
• CPC Class Codes: Y10T 428/31562 : Next to polyamide [nylon, etc.]
• CPC Class Codes: Y10T 428/31565 : Next to polyester [polyethylene terephthalate, etc.]
• CPC Class Codes: Y10T 428/31587 : Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• CPC Class Codes: Y10T 428/31605 : Next to free metal

Abstract

A medical device comprising an organic polymer substrate material having a coating thereon, the coating comprising an interpenetrating network of two different hydrogel polymers, one of which is a polyurethane/polyurea hydrogel polymer, the polyurethane/polyurea hydrogel polymer being linked to the substrate material by covalent urea linkages.

Claims

1. A medical device comprising an organic polymer substrate material having a coating thereon, the coating comprising an interpenetrating network of two different hydrogel polymers, one of which is a polyurethane/polyurea hydrogel polymer, the polyurethane/polyurea hydrogel polymer being linked to the substrate material by covalent urea linkages.

2. A device as in claim 1 wherein the second of said two hydrogel polymers is selected from the group consisting of polysaccharide polymers, metal salts of polysaccharide polymers, poly(ethylene oxide)homopolymers and poly(N-vinylpyrrolidone)polymers.

3. A device as in claim 1 wherein said substrate material is selected from the group consisting of polyethylene terephthalate, polyether-polyester block copolymers, polyether-polyamide block copolymers, polyamide, polyimides, polyurethanes, polyofin polymers, hydrocarbon elastomers, nitrile rubbers, ethylene/alkyl acrylate copolymers and natural rubber.

4. A device as in claim 1 formed by a process comprising the steps of:

a) providing the substrate material with isocyanate-reactive chemical groups on the surface thereof, at least some of which are amine groups;

b) forming a tie-coat layer by applying a first formulation to the substrate surface, the first formulation comprising an isocyanate functional hydrogel-forming prepolymer formed by reaction of a polyether and a polyisocyanate compound,

whereby some of the isocyanate groups of the prepolymer react with said amine groups to form urea linkages between the substrate material and the prepolymer and some of the isocyanate groups of the prepolymer remain unreacted; and

c) applying a second formulation to the tie-coat layer, the second formulation having therein at least one isocyanate-reactive component and comprising an aqueous solution of a second hydrogel polymer different from said polyurethane/polyurea hydrogel polymer,

whereby water in the second formulation forms a hydrogel with tie-coat layer prepolymer;

the second hydrogel polymer penetrates into the tie-coat layer; and

the free isocyanate groups of the tie-coat layer prepolymer react with said isocyanate-reactive component in the second formulation to form said polyurethane/polyurea hydrogel polymer, such that at least a portion of the tie-coat layer and the barrier layer are commingled and form said interpenetrating network of polyurethane/urea and second hydrogel polymers.

5. A device as in claim 4 wherein said amine groups were provided on substrate material surface by treatment thereof with a plasma of a nitrogen-containing gas.

6. A device as in claim 4 wherein said second hydrogel polymer is a poly(N-vinylpyrrolidone)polymer.

7. A device as in claim 1, the device being a catheter, a catheter balloon or a stent.