Grafted ophthalmic devices containing deactivated regions and processes for their preparation and use

Patent metadata

Field	Value
Publication number	US-2024325597-A1
Application number	US-202418426780-A
Country	US
Kind code	A1
Filing date	Jan 30, 2024
Priority date	Mar 28, 2023
Publication date	Oct 3, 2024
Grant date	—

Abstract

Disclosed are ophthalmic devices formed by a process comprising: (a) providing a reactive composition containing: (i) a polymerization initiator that is capable, upon a first activation, of forming two or more free radical groups, at least one of which is further activatable by subsequent activation; (ii) one or more ethylenically unsaturated compounds; and (iii) a crosslinker; (b) subjecting the reactive composition to a first activation step such that the reactive composition polymerizes therein to form a crosslinked substrate network containing a covalently bound activatable free radical initiator; (c) deactivating at least a portion of the covalently bound activatable free radical initiator at one or more selective regions of the crosslinked substrate network such that the crosslinked substrate network contains retained covalently bound activatable free radical initiator outside of the one or more selective regions and optionally within the one or more selective regions; (d) contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contacting is conducted under conditions such that the grafting composition penetrates into the crosslinked substrate network; and (e) activating the retained covalently bound activatable free radical initiator such that the grafting composition polymerizes with the crosslinked substrate network, thereby forming grafted polymeric networks, outside of the selective regions and optionally partially within the selective regions.

First claim

1 . An ophthalmic device formed by a process comprising:
a) providing a reactive composition containing: (i) a polymerization initiator that is capable, upon a first activation, of forming two or more free radical groups, at least one of which is further activatable by subsequent activation; (ii) one or more ethylenically unsaturated compounds; and (iii) a crosslinker; b) subjecting the reactive composition to a first activation step such that the reactive composition polymerizes therein to form a crosslinked substrate network containing a covalently bound activatable free radical initiator; c) deactivating at least a portion of the covalently bound activatable free radical initiator at one or more selective regions of the crosslinked substrate network such that the crosslinked substrate network contains retained covalently bound activatable free radical initiator outside of the one or more selective regions; d) contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contacting is conducted under conditions such that the grafting composition penetrates into the crosslinked substrate network; and e) activating the retained covalently bound activatable free radical initiator such that the grafting composition polymerizes with the crosslinked substrate network, thereby forming grafted polymeric networks outside of the selective regions.

2 . The ophthalmic device of claim 1 wherein the deactivating of step (c) varies spatially within the ophthalmic device.

3 . The ophthalmic device of claim 1 wherein the deactivating step (c) is achieved by irradiation at a wavelength capable of activating the initiator, wherein the initiation is conducted in an atmosphere containing oxygen gas.

4 . The ophthalmic device of claim 1 wherein the grafting composition of step (d) contains a crosslinker.

5 . The ophthalmic device of claim 1 wherein the grafting composition of step (d) is free of a crosslinker.

6 . The ophthalmic device of claim 1 wherein in step (c), only a portion of the covalently bound activatable free radical initiator is inactivated at the selective regions such that step (e) includes forming a grafted network partially within the selective regions.

7 . The ophthalmic device of claim 1 wherein the one or more ethylenically unsaturated compounds of step (a) comprise one or more polymerizable groups independently selected from: (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinylether, O-vinylcarbonate, O-vinylcarbamate, C 2-12 alkenyl, C 2-12 alkenylphenyl, C 2-12 alkenylnaphthyl, and C 2-6 alkenylphenyl-C 1-6 alkyl.

8 . The ophthalmic device of claim 1 wherein the one or more ethylenically unsaturated compounds of step (d) comprise one or more polymerizable groups independently selected from: (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinylether, O-vinylcarbonate, O-vinylcarbamate, C 2-12 alkenyl, C 2-12 alkenylphenyl, C 2-12 alkenylnaphthyl, and C 2-6 alkenylphenyl-C 1-6 alkyl.

9 . The ophthalmic device of claim 1 wherein the polymerization initiator is a bisacylphosphine oxide, a bisacylphosphane oxide, a di-azo compound, a di-peroxide compound, an azo-bis(monoacylphosphine oxide), an azo-bis(monoacylphosphane oxide), a peroxy-bis(monoacylphosphine oxide), a peroxy-bis(monoacylphosphane oxide), an azo-bis(alpha-hydroxy ketone), a peroxy-bis(alpha-hydroxy ketone), an azo-bis(1,2-diketone), a peroxy-bis(1,2-diketone), a germanium based compound, tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate, or combinations thereof.

10 . The ophthalmic device of claim 1 wherein the polymerization initiator is a bisacylphosphine oxide or a bis(acyl)phosphane oxide.

11 . The ophthalmic device of claim 1 that is in the form of a hydrogel and wherein the reactive composition contains one or more silicone-containing components, and the grafting composition contains one or more hydrophilic reactive components.

12 . The ophthalmic device of claim 1 wherein the reactive composition, the grafting composition, or both the reactive composition and the grafting composition contain one or more additives selected from UV absorbers, photochromic compounds, pharmaceutical compounds, nutraceutical compounds, antimicrobial compounds, reactive tints, pigments, copolymerizable dyes, non-polymerizable dyes, release agents, wetting agents, and release agents.

13 . The ophthalmic device of claim 1 further comprising: following step (e), contacting the crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds and activating retained covalently bound activatable free radical initiator such that the second grafting composition polymerizes with the crosslinked substrate network outside of the selective regions and optionally partially within the selective regions.

14 . The ophthalmic device of claim 1 wherein steps (a) and (b) are performed in a mold assembly comprised of a front mold and a back mold, the front mold and the back mold defining and enclosing a cavity in the shape of the ophthalmic device therebetween, and process steps (c), (d), and (e) are performed in the mold assembly after the back mold has been removed.

15 . The ophthalmic device of claim 1 wherein the ophthalmic device is selected from the group consisting of a contact lens, an intraocular lens, a punctal plug, and an ocular insert.

16 . The ophthalmic device of claim 15 wherein the ophthalmic device is a contact lens or an intraocular lens.

17 . An ophthalmic device that is a reaction product of a composition comprising:
a) a crosslinked substrate network containing covalently bound activatable free radical initiators outside of one or more selective regions and optionally partially within the one or more selective regions; and b) a grafting composition containing one or more ethylenically unsaturated compounds, wherein the grafting composition is localized in the crosslinked substrate network where there are retained covalently bound activatable free radical initiators.

18 . The ophthalmic device of claim 17 wherein the concentration of the retained covalently bound activatable free radical initiators varies spatially within crosslinked substrate network.

19 . The ophthalmic device of claim 17 wherein the crosslinked substrate network is the reaction product of a reactive composition comprising: (i) a polymerization initiator that is capable, upon a first activation, of forming two or more free radical groups, at least one of which is further activatable by subsequent activation; (ii) one or more ethylenically unsaturated compounds; and (iii) a crosslinker.

20 . The ophthalmic device of claim 19 wherein the polymerization initiator is a bisacylphosphine oxide, a bisacylphosphane oxide, a di-azo compound, a di-peroxide compound, an azo-bis(monoacylphosphine oxide), an azo-bis(monoacylphosphane oxide), a peroxy-bis(monoacylphosphine oxide), a peroxy-bis(monoacylphosphane oxide), an azo-bis(alpha-hydroxy ketone), a peroxy-bis(alpha-hydroxy ketone), an azo-bis(1,2-diketone), a peroxy-bis(1,2-diketone), a germanium based compound, tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate, or combinations thereof.

21 . The ophthalmic device of claim 20 wherein the polymerization initiator is a bisacylphosphine oxide or a bis(acyl)phosphane oxide.

22 . The ophthalmic device of claim 17 w

Assignees

• Johnson & Johnson Vision Care

Inventors

• Widman Michael F
• Maharvi Ghulam

Classifications

• C08F271/02

  on to polymers of monomers containing heterocyclic nitrogen · CPC title

• C08F290/068

  Polysiloxanes · CPC title

• A61L27/52

  Hydrogels or hydrocolloids · CPC title

• G02B1/043

  Contact lenses · CPC title

• A61L27/16 Primary

  obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title