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

• US 5,290,548 A
• Filed: 03/30/1992
• Issued: 03/01/1994
• Est. Priority Date: 04/10/1987
• Status: Expired due to Term

• Current Assignee: University of Florida Research Foundation, Incorporated (State University System of Florida)
• Original Assignee: University of Florida (State University System of Florida)
• Inventors: Mentak, Khalid, Yahiaoui, Ali, Goldberg, Eugene P.
• Primary Examiner(s): WEBMAN, EDWARD J
• Application Number:
  US07/859,016
• Time in Patent Office: 701 Days
• Field of Search: 522/84, 522/85, 522/167, 522/153, 522/149, 522/912, 522/915, 525/937, 424/78.18, 424/78.24, 264/1.4, 264/2.2, 427/2, 427/42, 427/35, 427/36, 427/495, 427/496, 427/506, 427/498, 427/595
• US Class Current: 424/78.18
• CPC Class Codes: A61F 2/0077 Special surfaces of prostheses, e.g. for improving ingrowth A61F2/30767 takes precedence
• CPC Class Codes: A61F 2/16 Intraocular lenses
• CPC Class Codes: A61F 2/1613 having special lens configurations, e.g. multipart lenses; having particular optical properties, e.g. pseudo-accommodative lenses, lenses having aberration corrections, diffractive lenses, lenses for variably absorbing electromagnetic radiation, lenses having variable focus
• CPC Class Codes: A61F 2002/0086 for preferentially controlling or promoting the growth of specific types of cells or tissues of bone tissue onto implantable joints A61F2002/3093
• 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: A61K 31/727 Heparin; Heparan
• CPC Class Codes: A61K 31/728 Hyaluronic acid
• CPC Class Codes: A61K 31/79 Polymers of vinyl pyrrolidone
• 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 27/34 Macromolecular materials
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61L 33/0088 by grafting of a monomer onto the substrate
• CPC Class Codes: B05D 3/068 using ionising radiations (gamma, X, electrons)
• 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: 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 5/08 Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
• 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 522/912 : Polymer derived from ethylenic monomers only
• CPC Class Codes: Y10S 522/915 : involving inert gas, steam, nitrogen gas, or carbon dioxide
• CPC Class Codes: Y10S 525/937 : Utility as body contact e.g. implant, contact lens or I.U.D.
• CPC Class Codes: Y10S 623/92 : Method or apparatus for preparing or treating prosthetic

Abstract

A method for modifying the plastic surface of an article adapted for contacting living tissue by the gamma or electron beam irradiation induced chemical graft coating thereon of:

(1) a neutral or ionic water-soluble, hydrophilic vinylic monomer or salt thereof;

(2) a mixture of at least two of said monomers, or

(3) a mixture of (1) or (2) with up to about 50%, by weight, based on the total monomer weight, of a member selected from the group consisting of N-vinylpyrrolidone, 2-hydroxyethyl-methacrylate, and mixtures thereof; so as to form a hydrophilic graft polymer coating on the surface.

Claims

1. 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 neutral or ionic water-soluble, hydrophilic, vinylic monomer or salt thereof;

(2) a mixture of at least two of said monomers, or

(3) a mixture of (1) or (2) with up to about 50%, by weight, based on the total monomer weight, of a member selected from the group consisting of N-vinylpyrrolidone, 2-hydroxyethyl-methacrylate, and mixtures thereof;

so as to form a hydrophilic graft polymer coating on said surface comprising;

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

a) total 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 2,500 rads/min.

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

d) degassing 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 or 2 wherein said monomer is selected from the group consisting of acrylamide, dimethylacrylamide, polyethylene glycol monomethacrylate, hydroxypropylacrylamide, methacrylic acid, sulfopropylacrylate, styrene-sulfonic acid, 2-acrylamide-2-methyl-1-propane sulfonic acid, vinylsulfonic acid, dimethylaminoethylmethacrylate, mixtures and salts thereof.

4. The method of claim 1 or 2 further including, prior to said step of polymerization, the step comprising pre-soaking said plastic surface in at least one of said monomers (1) or (3) or in a first aqueous solution of at least one of said monomers (1) or (3), having a concentration of monomer therein of from about 5 to about 95%, by weight;

said pre-soaking being conducted for a period of time and at a temperature sufficient to facilitate diffusion of said monomer into said plastic surface.

5. The method of claim 4 wherein said pre-soaking step is conducted at a temperature in the range of from about 25°

to about 90°

C. and for a period of time of from about 0.5 to about 48 hours.

6. The method of claim 1 wherein said article is an ocular implant material.

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

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

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

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

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

12. The method of claim 11 wherein said polyolefin is an ethylene-propylene copolymer or polybutadiene.

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

17. An article according to claim 16 comprising a surgical instrument, medical device, prosthetic implant, contact lens or ocular implant.

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 the one-step electron beam-irradiation induced polymerized chemically grafted coating thereon of:

(1) a neutral or ionic water-soluble, hydrophilic, vinylic monomer or salt thereof;

(2) a mixture of at least two of said monomers, or

(3) a mixture of (1) or (2) with up to about 50%, by weight, based on the total monomer weight, of a member selected from the group consisting of N-vinylpyrrolidone, 2-hydroxyethyl-methacrylate, and mixtures thereof;

so as to form a hydrophilic graft polymer coating on said surface comprising;

conducting said electron beam-irradiation induced graft polymerization in an aqueous solution of at least one of said monomers 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 equivalent to a gamma 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 equivalent to a gamma irradiation dose rate in the range of from about 10 to about 10⁸ rads/min.

14. The method of claim 13 further including, prior to said step of polymerization, the step comprising:

pre-soaking said plastic surface in at least one of said monomers (1) or (3) or in a first aqueous solution of at least one of said monomers (1) or (3), having a concentration of monomer therein of from about 5 to about 95%, by weight, said pre-soaking being conducted for a period of time and at a temperature sufficient to facilitate diffusion of said monomer into said plastic surface.

15. The method of claim 13 or 14 wherein said monomer is selected from the group consisting of acrylamide, dimethylacrylamide, polyethylene glycol monomethacrylate, hydroxypropylacrylamide, methacrylic acid, sulfopropylacrylate, styrene-sulfonic acid, 2-acrylamide-2-methyl-1-propane sulfonic acid, vinylsulfonic acid, dimethylaminoethylmethacrylate, mixtures and salts thereof.