Process for surface modifying substrates and modified substrates resulting therefrom
View Patent ↗The invention relates to a process for coating a material surface, comprising the steps of: (a) applying to the material surface a tie layer comprising a polyionic material; (b) covalently binding a bifunctional compound comprising an ethylenically unsaturated double b 3 nd to the tie layer; and (c) graft polymerizing a hydrophilic monomer onto the compound comprising the ethylenically unsaturated double bond. The coated articles that are obtainable by the process of the invention have desirable characteristics regarding adherences to the substrate, durability, hydrophilicity, wettability, biocompatibility and permeability and are thus useful for the manufacture of biomedical articles such as ophthalmic devices.
1. A process for coating a material surface, comprising the steps of:
(a) applying to the material surface a tie layer comprising a polyionic material;
(b) covalently binding a bifunctional compound comprising an ethylenically unsaturated double bond to the tie layer; and
(c) graft polymerizing a hydrophilic monomer onto the compound comprising the ethylenically unsaturated double bond.
2. A process according to claim 1 , wherein the material surface is the surface of an organic bulk material, in particular the surface of a biomedical device comprising an organic bulk material.
3. A process according to claim 1 or 2 , wherein the tie layer of step (a) consists of one single polyionic material.
4. A process according to claim 1 or 2 , wherein the tie layer of step (a) includes at least one bilayer comprising a polycationic material and a polyanionic material.
5. A process according to any one of claim 1 , wherein the polyionic material of the tie layer comprises one or more polymers selected from the group consisting of a poly(allylamine hydrochloride), a poly(ethyleneimine), a poly(acrylic acid), and a poly(methacrylic acid).
6. A process according to any one of the claim 1 , wherein the covalent bonding between the tie layer and the bifunctional compound comprising an ethylenically unsaturated double bond occurs via reaction of a hydroxy, amino, alkylamine, thiol or carboxy group, of the tie layer with an isocyanato, azlactone, epoxy, carboxy anhydride, carboxy or hydroxy group, of the ethylenically unsaturated compound.
7. A process according to any one of claim 1 , wherein the ethylenically unsaturated compound is of formula:
wherein
R 1 is hydrogen, C 1 -C 4 -alkyl or halogen;
R 2 is hydrogen, unsubstituted or hydroxy-substituted C 1 -C 6 -alkyl or phenyl;
R 3 and R 3 ′ are each an ethylenically unsaturated radical having from 2 to 6 C-atoms, or R 3 and R 3 ′ together form a bivalent radical —C(R 4 )═C(R 4 ′)— wherein R 4 and R 4 ′ are each independently hydrogen, C 1 -C 4 -alkyl or halogen and
(Alk*) is C 1 -C 6 -alkylene, and (Alk**) is C 2 -C 12 -alkylene.
8. A process according to claim 7 , wherein, in step (b), the compound comprising an ethylenically unsaturated double bond is of formula (2a).
9. A process according to any one of the claim 1 , wherein, in step c), the hydrophilic monomer is selected from the group consisting of acrylamide, acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, methacrylamide, N,N-dimethylacrylamide, allylalcohol, N-vinylpyrrolidone and N,N-dimethylaminoethyl acrylate.
10. A process according to any one of claim 1 , wherein in step (c), the monomer comprises one or more different monomers at least one of them comprising a reactive group.
11. A process according to any one of the claim 1 , wherein in step (c), the monomer comprises a reactive group,
(i) said reactive groups are reacted with a further compound comprising an ethylenically unsaturated double bond,
(ii) a hydrophilic monomer and optionally a co-monomer having a crosslinkable group are graft-polymerized to said ethylenically unsaturated double bond, and
(iii) in case crosslinkable groups being present in step (ii), crosslinking of said groups is initiated.
12. A process according to claim 11 , wherein, in step (i), the further compound comprising an ethylenically unsaturated double bond is a compound of formula (2a)-(2e) according to claim 7 .
13. A process according to claim 12 , wherein, in step (ii) the hydrophilic monomer is selected from the group consisting of acrylic acid, acrylamide, N,N-dimethylacrylamide and N-vinylpyrrolidone and no co-monomer having a crosslinking group is present.
14. A coated material that is obtainable by the process of any one of the claim 1 .
15. A coated material according to claim 14 , which is a biomedical device.
16. A coated material according to claim 15 , which is an ophthalmic device.
17. A coated material according to claim 16 , which is a contact lens, intraocular lens or artificial cornea.