Surface modified surgical instruments, devices, implants, contact lenses and the like

• US 5,100,689 A
• Filed: 10/05/1990
• Issued: 03/31/1992
• Est. Priority Date: 04/10/1987
• Status: Expired due to Term

• Current Assignee: University of Florida Research Incorporated
• Original Assignee: University of Florida (State University System of Florida)
• Inventors: Robinson, Richard, Sheets, John W., Larson, Jeffrey A., Kumar, G. Sudesh, Osborn, David C., Yahiaoui, Ali, Burns, James W., Goldberg, Eugene P.
• Primary Examiner(s): LUSIGNAN, MICHAEL R
• Application Number:
  US07/592,482
• Time in Patent Office: 543 Days
• Field of Search: 427/2, 427/36, 522/84, 522/85, 522/167, 604/96, 606/107, 623/1, 623/3, 623/66
• US Class Current: 600/36
• CPC Class Codes: A61F 2/145 Corneal inlays, onlays, or lenses for refractive correction
• CPC Class Codes: A61F 2/16 Intraocular lenses
• CPC Class Codes: A61F 2002/009 for hindering or preventing attachment of biological tissue of bone tissue onto implantable joints A61F2002/30932
• CPC Class Codes: A61L 2300/236 Glycosaminoglycans, e.g. heparin, hyaluronic acid, chondroitin
• CPC Class Codes: A61L 2400/18 Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
• CPC Class Codes: A61L 2430/16 for reconstruction of eye parts, e.g. intraocular lens, cornea
• CPC Class Codes: A61L 27/16 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 33/0076 Chemical modification of the substrate
• CPC Class Codes: A61L 33/0088 by grafting of a monomer onto the substrate
• CPC Class Codes: C08J 7/18 using wave energy or particle radiation
• CPC Class Codes: C08L 33/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08L 39/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08L 51/06 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: Y10S 623/921 Blood vessel

Abstract

Improved medical devices and instruments prepared by an improved method of producing hydrophilic, gamma-irradiation or electron beam-irradiation induced polymerized and chemically grafted coatings or plastic surfaces of articles adapted for contacting living tissue,the improvement comprising carrying out the graft polymerization in an aqueous solution under specific combinations of the following conditions:

1) monomer concentration in the range of from about 0.1% to about 50%, by weight;

2) total gamma or electron beam irradiation dose in the range of from about 0.001 to less than about 0.50 Mrad; and

3) gamma dose rate in the range of from about 10 to about 2500 rads/min or electron beam-irradiation dose rate in the range of from about 10 to about 10⁸ rads/min.

Claims

1. In a method for modifying a plastic surface of an article, said surface adapted for contact with living tissue of a human or non-human animal, by the gamma-irradiation induced polymerized chemically grafted coating thereon of:

1) a monomer comprising N-vinylpyrrolidone (NVP),

2) a monomer comprising 2-hydroxyethylmethacrylate (HEMA),

3) a mixture of (NVP) and (HEMA), (NVP-HEMA), or

4) a mixture of

     1),

     2) or

     3) with up to about 50 wt. %, based on the total monomer weight, of an ionic monomer, salt of an ionic monomer or mixture thereof;

so as to form a hydrophilic graft polymer coating of;

I. polyvinylpyrrolidone (PVP),

II. poly-2-hydroxyethylmethacrylate (PHEMA),

III. a copolymer of (NVP) and (HEMA), or

IV. a copolymer of (NVP), (HEMA) or (NVP-HEMA) and said ionic monomer, on said surface, the improvement comprising;

conducting said gamma-irradiation induced graft polymerization in an aqueous solution under the following conditions;

a) monomer concentration in the range of from about 0.1% to about 50%, by weight;

b) total gamma dose in the range of from about 0.001 to less than about 0.50 Mrad; and

c) gamma dose rate in the range of from about 10 to about 2500 rads/min.

2. The method of claim 1 further including one or more of the following conditions:

d) substantially excluding free oxygen from said graft polymerization solution;

e) maintaining the thickness of said polymer coating in the range of from about 100 Å

to about 100 microns;

f) including a free radical scavenger in said aqueous graft polymerization solution; and

g) including in said aqueous graft polymerization solution a swelling solvent for said plastic surface.

3. The method of claim 1 wherein said article is a surgical instrument.

4. The method of claim 1 wherein said article is a medical device.

5. The method of claim 1 wherein said article is a prosthetic implant.

6. The method of claim 1 wherein said article is a soft or hard contact lens.

7. The method of claim 1 wherein said ionic monomer is a vinylsulfonic acid, a vinylcarboxylic acid or a salt thereof.

8. The method of claim 7 wherein said vinyl-carboxylic acid is acrylic, methacrylic or crotonic acid.

9. The method of claim 7 wherein said vinylsulfonic acid is sulfoethylmethacrylate, sulfopropylmethacrylate, styrene sulfonic acid or vinylsulfonic acid.

10. The method of claim 1 wherein said ionic monomer is an amino-functional monomer.

11. The method of claim 10 wherein said amino-functional monomer is a vinylpyridine, an amino-styrene, an aminoacrylate or an aminomthacrylate.

12. The method of claim 1 wherein said plastic is selected from the group consisting of polyacrylates, polymethacrylates, polyolefins, ethylene-propylene copolymers, polybutadiene, styrene-butadiene copolymers, styrene-ethylene-butadiene copolymers, polycarbonates, fluorocarbon polymers, polysiloxanes, polyurethanes, polyvinylchloride, polyesters and mixtures thereof.

14. An article prepared according to the method of claim 1 or 13.

15. An article according to claim 14 comprising a surgical instrument, medical device, prosthetic implant or contact lens.

13. A method for modifying a plastic surface of an article, said surface adapted for contact with living tissue of a human or non-human animal, by electron beam-irradiation induced polymerized chemically grafted coating thereon of:

1) a monomer comprising N-vinylpyrrolidone (NVP),

2) a monomer comprising 2-hydroxyethylmethacrylate (HEMA),

3) a mixture of (NVP) and (HEMA), (NVP-HEMA), or

4) a mixture of

     1),

     2) or

     3) with up to about 50 wt. %, based on the total monomer weight, of an ionic monomer, salt of an ionic monomer or mixture thereof;

so as to form a hydrophilic graft polymer coating of;

I. polyvinylpyrrolidone (PVP),

II. poly-2-hydroxyethylmethacrylate (PHEMA),

III. a copolymer of (NVP) and (HEMA), or

IV. a copolymer of (NVP), (HEMA) or (NVP-HEMA) and said ionic monomer, on said surface comprising;

conducting said electron beam-irradiation induced graft polymerization in an aqueous solution under the following conditions;

a) monomer concentration in the range of from about 0.1% to about 50%, by weight;

b) total electron beam irradiation dose in the range of from about 0.001 to less than about 0.50 Mrad; and

c) an electron beam irradiation dose rate in the a range of from about 10 to about 10⁸ rads/min.