Coated articles

• US 20020006493A1
• Filed: 05/30/2001
• Published: 01/17/2002
• Est. Priority Date: 05/30/2000
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Lally, John Martin, Winterton, Lynn Cook, Lohmann, Dieter, Qiu, Yongxing, Chabrecek, Peter, Leukel, Jorg
• Granted Patent: US 6,589,665 B2
• Time in Patent Office: Days
• US Class Current: 428/64.1
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: C08J 7/16 with polymerisable compounds
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: Y10T 428/21 Circular sheet or circular blank
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

The invention relates to novel composite materials comprising (a) an inorganic or organic bulk material having attached to its surface at least one polyionic material that comprises covalently bound initiator moieties for radical polymerization; and (b) a hydrophilic surface coating obtainable by applying one or more different ethylenically unsaturated hydrophilic monomers or macromonomers to the bulk material surface provided with the initiator radicals and polymerizing said monomers or macromonomers.

The composite materials of the invention have desirable characteristics regarding adherence to the substrate, durability, hydrophilicity, wettability, biocompatibility and permeability and are thus useful for the manufacture of biomedical articles such as ophthalmic devices.

Claims

1. A composite material comprising

(a) an inorganic or organic bulk material having attached to its surface a polyionic material that comprises covalently bound initiator moieties for radical polymerization;

and

(b) a hydrophilic surface coating obtainable by applying one or more different ethylenically unsaturated hydrophilic monomers or macromonomers to the bulk material surface provided with the initiator radicals and polymerizing said monomers or macromonomers.

2. A composite material according to claim 1, which is a biomedical device.

3. A composite material according to claim 1, wherein the bulk material comprises an organic polymer selected from a polyacrylate, polymethacrylate, polyacrylamide, poly(N,N-dimethylacrylamide), polymethacrylamide, polyvinyl acetate, polysiloxane, perfluoroalkyl polyether, fluorinated polyacrylate and -methacrylate and an amphiphilic segmented copolymer comprising at least one hydrophobic segment and at least one hydrophilic segment.

4. A composite material according to claim 1, wherein the polyionic material consists of one ionic polymer.

5. A composite material according to claim 1, wherein the polyionic material includes at least one bilayer, the bilayer comprising a first ionic polymer and a second ionic polymer having charges opposite of the charges of the first ionic polymer.

6. A composite material according to claim 5, wherein the bilayer(s) comprise(s) an anionic polymer selected from a linear polyacrylic acid, a branched polyacrylic acid, a polymethacrylic acid, a polyacrylic acid or polymethacrylic acid copolymer, a maleic or fumaric acid copolymer, a poly(styrenesulfonic acid), a polyamido acid, a poly(2-acrylamido-2-methylpropanesulfonic acid), and an alkylene polyphosphate, alkylene polyphosphonate, carbohydrate polyphosphate or carbohydrate polyphosphonate;

and a cationic polymer selected from a polyallylamine (PAH);

a polyethyleneimine (PEI);

a polyvinylamine homo- or copolymer;

a poly(vinylbenzyl-tri-C₁-C₄-alkylammonium salt);

a polymer of an aliphatic or araliphatic dihalide and an aliphatic N,N,N′

,N′

-tetra-C₁-C₄-alkyl-alkylenediamine;

a poly(vinylpyridin) or poly(vinylpyridinium salt);

a poly (N,N-diallyl-N,N-di-C₁-C₄-alkyl-ammoniumhalide);

a homo- or copolymer of a quaternized di-C₁-C₄-alkyl-aminoethyl acrylate or methacrylate;

POLYQUAD®

; and

a polyaminoamide.

7. A composite material according to claim 5, wherein the bilayer(s) comprise(s) an anionic polymer selected from a linear or branched polyacrylic acid and an acrylic acid copolymer;

and a cationic polymer selected from a polyallylamine homopolymer;

a polyallylamine comprising modifier units of the formula

8. A composite material according to claim 5, wherein the bilayer(s) comprise(s) a first anionic polymer and a second cationic polymer.

9. A composite material according to claim 5, wherein the bilayer(s) are formed on the bulk material surface by a dip method involving the steps of

(i) applying a coating of a first ionic polymer to the bulk material by immersing the bulk material in a solution of the first ionic polymer;

and

(ii) applying a coating of a second ionic polymer having charges opposite of the charges of the first ionic polymer to the bulk material by immersing the bulk material in a solution of the second ionic polymer.

10. A composite material according to claim 5, wherein the bulk material comprises one or more bilayers having —

NH₂ and/or —

NH—

groups attached to its surface, some of whose H atoms have been substituted by radicals of the formulae

11. A composite material according to claim 1, wherein according to (b) a hydrophilic macromonomer of the formula

12. A composite material according to claim 11, wherein the hydrophilic macromonomer is a compound of formula (1), wherein R is hydrogen or methyl, R₁ is hydrogen, methyl or carboxyl, R₁′

is hydrogen, A is a radical of the formula (2a) or (2b), and (oligomer) is the radical of a telomer of formula (3a).

13. A composite material according to claim 11, wherein (oligomer) denotes a radical of formula (3a), and the radical -(alk)-S-[B]_p-[B′

]_q-Q is a radical of formula

14. A composite material according to claim 11, wherein the hydrophilic macromonomer applied according to (b) is of the formula

15. A composite material according to claim 1, wherein the polymerization of the monomers or macromonomers on the modified bulk material surface is initiated by the action of irradiation.

16. A composite material according to claim 15, wherein the polymerization is initiated by the action of UV radiation for a time period of 0.5 to 5 minutes.

17. A composite material according to claim 1, wherein the hydrophilic surface coating (b) is obtainable by grafting at least one macromonomer to the bulk material surface with formation of a bottle-brush-type structure composed of tethered chains.

18. A composite material according to claim 1, wherein the hydrophilic surface coating has a coating thickness of from 0.01 to 5 0 μ

m.

24. Biomedical device comprising a composite material according to claim 1.

25. Biomedical device according to claim 24, wherein the biomedical device is a contact lens, intraocular lens or artificial cornea.

26. A composite material according to claim 1, which is a contact lens, intraocular lens or artificial cornea.

19. A process for the manufacture of a composite material, which comprises the steps:

(a) providing an inorganic or organic bulk material having attached to its surface a polyionic material that comprises covalently bound initiator moieties for radical polymerization;

(b) applying a coating of one or more different ethylenically unsaturated hydrophilic monomers or macromonomers to the bulk material surface provided with the initiator radicals, and

(c) polymerizing the coating of unsaturated hydrophilic macromonomers thermally or by irradiation, preferably by UV radiation.

20. A process according to claim 19, wherein the polyionic material includes at least one bilayer, the bilayer comprising a first ionic polymer and a second ionic polymer having charges opposite of the charges of the first ionic polymer, said bilayer being applied to the bulk material surface by a dip method comprising the steps of (i) immersing the bulk material in a solution of the first ionic polymer;

and then (ii) immersing the bulk material in a solution of the second ionic polymer having charges opposite to the charges of the first ionic polymer.

21. A process according to claim 20, wherein the first ionic polymer is an anionic polymer comprising carboxy groups or a salt thereof, and the second ionic polymer is a cationic polymer comprising primary or secondary amino groups or a salt thereof.

22. A process according to claim 19, wherein the initiator moieties for radical polymerization are bound to the polyionic material by reaction of amino groups of the polyionic material with isocyanato groups of the initiator moiety.

23. A process according to claim 19, wherein the inorganic or organic bulk material is a contact lens, intraocular lens or artificial cornea.