Lubricious hydrophilic composite coated on substrates

• US 5,001,009 A
• Filed: 09/02/1987
• Issued: 03/19/1991
• Est. Priority Date: 09/02/1987
• Status: Expired due to Term

• Current Assignee: Angiotech Pharmaceuticals Incorporated
• Original Assignee: Sterilization Technical Services, Inc.
• Inventors: Whitbourne, Richard J.
• Primary Examiner(s): P. C. Sluby
• Application Number:
  US07/092,077
• Time in Patent Office: 1,294 Days
• Field of Search: 428/412, 428/421, 428/423.3, 428/480, 428/423.5, 428/423.7, 428/424.6, 428/424.8, 428/424.4, 428/425.5, 428/425.6, 428/425.8, 428/480, 428/435 , 428/441, 428/442, 428/451, 428/458, 428/461, 428/462, 428/463, 428/483, 428/474.9, 428/516, 428/475.8, 428/476.1, 428/517, 428/476.3, 428/476.9, 525/303
• US Class Current: 428/412
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 27/50 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• 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 31/10 Macromolecular materials
• CPC Class Codes: A61L 31/14 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: C08J 2339/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08J 2401/02 Cellulose; Modified cellulose
• CPC Class Codes: C08L 39/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• 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 428/31576 Ester monomer type [polyvinylacetate, etc.]
• CPC Class Codes: Y10T 428/3158 Halide monomer type [polyvinyl chloride, etc.]
• CPC Class Codes: Y10T 428/31587 Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• CPC Class Codes: Y10T 428/31598 Next to silicon-containing [silicone, cement, etc.] layer
• CPC Class Codes: Y10T 428/31601 Quartz or glass
• CPC Class Codes: Y10T 428/31605 Next to free metal
• CPC Class Codes: Y10T 428/31616 : Next to polyester [e.g., alkyd]
• CPC Class Codes: Y10T 428/31623 : Next to polyamide or polyimide
• CPC Class Codes: Y10T 428/31645 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31649 : Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31667 : Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
• CPC Class Codes: Y10T 428/31681 : Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
• CPC Class Codes: Y10T 428/31692 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31699 : Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31732 : At least one layer is nylon type
• CPC Class Codes: Y10T 428/31743 : Next to addition polymer from unsaturated monomer[s]
• CPC Class Codes: Y10T 428/31746 : Polymer of monoethylenically unsaturated hydrocarbon
• CPC Class Codes: Y10T 428/3175 : Next to addition polymer from unsaturated monomer[s]
• CPC Class Codes: Y10T 428/31757 : Polymer of monoethylenically unsaturated hydrocarbon
• CPC Class Codes: Y10T 428/31786 : Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31797 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31913 : Monoolefin polymer
• CPC Class Codes: Y10T 428/31917 : Next to polyene polymer

Abstract

The lubricious hydrophilic coatings of the invention include a hydrophilic polyolefin such as polyvinyl-pyrrolidone and a water-insoluble stabilizing polymer such as a cellulose ester. The coatings may also include an adherent polymer and a plasticizing agent. The coatings are significantly more lubricious when wet than when dry, are adherent to a variety of substrates, and are resistant to removal by wet abrasion. The coating method of the invention involves preparing a solution of the stabilizing polymer and a solution of the hydrophilic polyolefin, and coating the substrate first in one then the other. Alternatively, both the insolubilizing and hydrophilic polymers may be dissolved in a single solvent system and applied to the substrate in a single step. The solutions of the invention are stable, non-reactive, and non-hazardous. The coatings of the invention may be applied to biomedical devices and implants such as catheters, condoms, and nasogastric and endotracheal tubes.

Claims

1. A lubricious composite, comprising

an outer layer having an exposed outer surface, said outer layer comprising a hydrophilic polymer selected from the group consisting of polyvinylpyrollidone, polyvinylpyrollidone-polyvinyl acetate copolymer, a mixture of the above, and the like,

an inner layer comprising a water-insoluble stabilizing polymer selected from the group consisting of a cellulose ester, a copolymer of polymethyl vinyl ether and maleic anhydride, an ester of the copolymer, and nylon,

said composite being substantially more slippery when wet than when dry, resistant to removal by wet abrasion, and essentially insoluble in aqueous solution, the ratio of said hydrophilic polymer to said stabilizing polymer altering the degree of wet lubricity, resistance to removal, and insolubility of said composite.

2. The coating of claim 1, wherein said inner layer includes a hydrophilic polymer.

3. The coating of claim 1, wherein said outer layer includes a stabilizing polymer.

4. The coating of claim 1 which is applied to a metallic substrate.

5. The coating of claim 1 which is applied to glass.

6. The coating of claim 1 which is applied to a polymeric substrate selected from the group consisting of polyurethane, polyvinylchloride, polyacrylate, polycarbonate, polystryrene, polyester resins, polybutadiene-styrene copolymers, nylon, polypropylene, polybutylene, teflon, silicon, and polyvinyl acetal.

14. The coating of claim 1 in which the stabilizing polymer is selected from the group consisting of cellulose acetate, cellulose acetate butyrate, cellulose acetate proprionate, cellulose nitrate, ethyl cellulose, and hydroxyethyl cellulose.

15. The coating of claim 1 which further comprising an adherent polymer.

16. The coating of claim 1, further comprising an adherent polymer selected from the group consisting of polyester, polyurethane, styrene polybutadiene, acrylic resin, polyvinylidene chloride, polycarbonate, and polyvinylchloride,

17. The coating of claim 1, further comprising a plasticizing agent.

18. The coating of claim 1, further comprising a plasticizing agent selected from the group consisting of camphor, polyvinyl butyral, dibutylphthalate, castor oil, dioctyl phthalate, acetyl tributyl citrate, dibutyl sebacate, sebacic acid, and alkyl resin.

7. An article having a lubricious composite coating, comprising

an outer layer having an exposed outer surface, said outer layer comprising a hydrophilic polymer selected from the group consisting of polyvinylpyrollidone, polyvinylpyrollidone-polyvinyl acetate copolymer;

a mixture of the above, and the like,

an inner layer comprising a water-insoluble stabilizing polymer selected from the group consisting of a cellulose ester, a copolymer of polymethyl vinyl ether and maleic anhydride, an ester of the copolymer, and nylon,

a substrate to which said inner layer adheres,

said composite being substantially more slippery when wet than when dry, resistant to removal by wet abrasion, and essentially insoluble in aqueous solution, the ratio of said hydrophilic polymer to said stabilizing polymer altering the degree of wet lubricity, resistance to removal, and insolubility of said composite.

8. The article of claim 7, wherein said hydrophilic polymer is selected from the group consisting of polyvinylpyrrolidone and polyvinylpyrrolidone-vinyl acetate, and said stabilizing polymer is selected from the group consisting of cellulose acetate, cellulose acetate butyrate, cellulose acetate proprionate, cellulose nitrate, ethyl cellulose, and hydroxyethyl cellulose.

9. The article of claim 8, wherein said inner layer includes a plasticizing agent.

10. The article of claim 8, wherein said inner layer includes an adherent polymer for promoting bonding between said substrate and said inner layer.

11. The article of claim 7, wherein said substrate is metal.

12. The article of claim 7, wherein said substrate is glass.

13. The article of claim 7, wherein said substrate is selected from the group consisting of polyurethane, polyvinylchloride, polyacrylate, polycarbonate, polystryrene, polyester resins, polybutadiene-styrene copolymers, nylon, polypropylene, polybutylene, teflon, silicon, and polyvinyl acetal.