# US 11,897,985 B2 · Water extractable ophthalmic devices

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- Number: US 11,897,985 B2
- Document ID: US11897985B2
- Status: Granted
- Kind: B2
- Application number: 17/729,181
- Filed: 2022-04-26
- Published: 2022-08-11
- Granted: 2024-02-13
- Earliest claimed: 2018-05-15
- Assignees: Bausch & Lomb Incorporated
- Applicants: Bausch & Lomb Incorporated
- Inventors: Ivan M. Nuñez; Lynn Coullard; Analuz Mark; Andrew J. Hoteling; Joseph W. Hoff
- Web page: https://patentgrep.com/patent/US11897985B2

## CPC

- C08F 226/10: N-Vinyl-pyrrolidone
- B29D 11/00134: {Curing of the contact lens material}
- C08J 3/075: Macromolecular gels
- C08J 3/24: Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K)
- G02B 1/043: {Contact lenses}
- B29K 2039/06: Polymers of N-vinyl-pyrrolidones
- C08F 2800/20: as weight or mass percentages
- C08F 2810/20: leading to a crosslinking, either explicitly or inherently
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B29D: PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE (making granules B29B9/00; making preforms B29B11/00)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

A water extractable ophthalmic device is disclosed which is a polymerization product of a monomeric mixture comprising: (a) one or more cyclic lactams; (b) one or more non-bulky organosilicon-containing monomers; (c) one or more bulky siloxane monomers; and (d) a crosslinking agent mixture comprising (i) one or more first crosslinking agents containing at least two ethylenically unsaturated reactive end groups, wherein the at least two ethylenically unsaturated reactive end groups are (meth)acrylate-containing reactive end groups and (ii) one or more second crosslinking agents containing at least two ethylenically unsaturated reactive end groups wherein at least one of the ethylenically unsaturated reactive end groups is a non-(meth)acrylate reactive end group. The water extractable ophthalmic device has an equilibrium water content of at least about 50 wt. %, a contact angle of less than about 50°, and an oxygen permeability of at least about 60 Barrers.

## Claims

### Claim 1

A method of preparing a water extractable ophthalmic device, the method comprising:
(a) curing a monomeric mixture in a mold, the monomeric mixture comprising (i) one or more cyclic lactams; (ii) one or more non-bulky organosilicon-containing monomers; (ii) one or more bulky siloxane monomers; and (iv) a crosslinking agent mixture comprising (1) one or more first crosslinking agents containing at least two ethylenically unsaturated reactive end groups, wherein the at least two ethylenically unsaturated reactive end groups are (meth)acrylate-containing reactive end groups and (2) one or more second crosslinking agents containing at least two ethylenically unsaturated reactive end groups wherein at least one of the ethylenically unsaturated reactive end groups is a non-(meth)acrylate reactive end group; and
(b) dry releasing the ophthalmic device from the mold to provide a water extractable ophthalmic device having an equilibrium water content of at least about 50 wt. %, a contact angle of less than about 50°, and an oxygen permeability of at least about 60 Barrers;
wherein the one or more second crosslinking agents are represented by the following structure:
wherein R is hydrogen or methyl; X is O; Y is O or NH; Z is NH; W is O and n is from 2 to 6.

### Claim 2 (depends on 1)

The method of claim 1, wherein the water extractable ophthalmic device further has a water extractable content of less than about 15 wt. %.

### Claim 3 (depends on 1)

The method of claim 1, wherein the one or more cyclic lactams are selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinyl caprolactam, N-vinyl-2-piperidone and mixtures thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein the one or more non-bulky organosilicon- containing monomers comprise a compound represented by the following structure:
wherein L is ethylenically unsaturated polymerizable group, V is a linker group or a bond; R1, R2, R3, R4, R5, R6, R7, R8, and R9 are independently hydrogen, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, alkenyl, haloalkenyl, and aromatic; R10 and R11 are independently hydrogen or an alkyl group wherein at least one of R10 and R11 is hydrogen; y is 2 to 7 and n is 1 to 100, or a compound represented by the following structure:
wherein R12 is H or methyl; X is O or NR16; wherein R16 is hydrogen or C1 to C4 alkyl, which may be further substituted with one or more hydroxyl groups; R13 is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R14 is independently a phenyl or a C1 to C4 alkyl group which may be substituted with fluorine, hydroxyl or ether; R15 is a C1 to C4 alkyl; and a is 2 to 50.

### Claim 5 (depends on 1)

The method of claim 1, wherein the one or more bulky siloxane monomers are selected from the group consisting of methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanyl methylmethacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, phenyltretramethyl-disloxanylethyl acrylate, methyldi(trimethylsiloxy)methacryloxymethyl silane, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyol allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate and mixtures thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the one or more first crosslinking agents are selected from the group consisting of an alkylene glycol-containing di(meth)acrylate crosslinking agent, an alkylene glycol-containing tri(meth)acrylate crosslinking agent, an alkylene glycol-containing tetra(meth)acrylate crosslinking agent and mixtures thereof.

### Claim 7 (depends on 1)

The method of claim 1, wherein the monomeric mixture comprises:
(i) about 42 wt. % to about 55 wt. %, based on the total weight of the monomeric mixture, of the one or more cyclic lactams;
(ii) about 5 to about 25 wt. %, based on the total weight of the monomeric mixture, of the one or more non-bulky organosilicon-containing monomers;
(iii) about 10 to about 45 wt. %, based on the total weight of the monomeric mixture, of the one or more bulky siloxane monomers; and
(iv) a crosslinking agent mixture comprising (i) about 0.05 to about 2 wt. %, based on the total weight of the monomeric mixture, of the one or more first crosslinking agents and (ii) about 0.05 to about 3 wt. %, based on the total weight of the monomeric mixture, of the one or more second crosslinking agents.

### Claim 8 (depends on 1)

The method of claim 1, wherein the monomeric mixture further comprises a minor amount of 2-hydroxyethyl methacrylate (HEMA).

### Claim 9 (depends on 1)

The method of claim 1, wherein the monomeric mixture further comprises an ultraviolet (UV) blocker.

### Claim 10 (depends on 1)

The method of claim 1, wherein the water extractable ophthalmic device is one of a contact lens and a hydrogel.

### Claim 11 (depends on 1)

The method of claim 1, wherein the step of curing comprises one of thermal curing or infrared curing.

### Claim 12 (depends on 1)

The method of claim 1, wherein the water extractable ophthalmic device has an equilibrium water content of from about 50 wt. % to about 70 wt. %, a contact angle of from about 30° to about 50° , and an oxygen permeability of at least about 70 Barrers.

### Claim 13

A method of preparing a water extractable ophthalmic device, the method comprising:
(a) curing a monomeric mixture in a mold, the monomeric mixture comprising (i) one or more cyclic lactams; (ii) one or more non-bulky organosilicon-containing monomers; (ii) one or more bulky siloxane monomers; and (iv) a crosslinking agent mixture comprising (1) one or more first crosslinking agents containing at least two ethylenically unsaturated reactive end groups, wherein the at least two ethylenically unsaturated reactive end groups are (meth)acrylate-containing reactive end groups and (2) about 0.01 to about 3 wt. %, based on the total weight of the monomeric mixture, of one or more second crosslinking agents containing at least two ethylenically unsaturated reactive end groups, wherein at least one of the ethylenically unsaturated reactive end groups is a non-(meth)acrylate reactive end group; and wherein at least one of the one or more second crosslinking agents are represented by the following structure:
wherein x is from 2 to 10; and
(b) dry releasing the ophthalmic device from the mold to provide the water extractable ophthalmic device.

### Claim 14 (depends on 13)

The method of claim 13, wherein the one or more cyclic lactams are selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinyl caprolactam, N-vinyl-2-piperidone and mixtures thereof.

### Claim 15 (depends on 13)

The method of claim 13, wherein the one or more non-bulky organosilicon-containing monomers comprise a compound represented by the following structure:
wherein L is ethylenically unsaturated polymerizable group, V is a linker group or a bond; R1, R2, R3, R4, R5, R6, R7, R8, and R9 are independently hydrogen, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, alkenyl, haloalkenyl, and aromatic; R10 and R11 are independently hydrogen or an alkyl group wherein at least one of R10 and R11 is hydrogen; y is 2 to 7 and n is 1 to 100, or a compound represented by the following structure:
wherein R12 is H or methyl; X is O or NR16; wherein R16 is hydrogen or C1 to C4 alkyl, which may be further substituted with one or more hydroxyl groups; R13 is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R14 is independently a phenyl or a C1 to C4 alkyl group which may be substituted with fluorine, hydroxyl or ether; R15 is a C1 to C4 alkyl; and a is 2 to 50.

### Claim 16 (depends on 13)

The method of claim 13, wherein the one or more bulky siloxane monomers are selected from the group consisting of methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanyl methylmethacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, phenyltretramethyl-disloxanylethyl acrylate, methyldi(trimethylsiloxy)methacryloxymethyl silane, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyol allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate and mixtures thereof.

### Claim 17 (depends on 13)

The method of claim 13, wherein the one or more first crosslinking agents are selected from the group consisting of an alkylene glycol-containing di(meth)acrylate crosslinking agent, an alkylene glycol-containing tri(meth)acrylate crosslinking agent, an alkylene glycol-containing tetra(meth)acrylate crosslinking agent and mixtures thereof.

### Claim 18 (depends on 13)

The method of claim 13, wherein the monomeric mixture comprises:
(i) about 42 wt. % to about 55 wt. %, based on the total weight of the monomeric mixture, of the one or more cyclic lactams;
(ii) about 5 to about 25 wt. %, based on the total weight of the monomeric mixture, of the one or more non-bulky organosilicon-containing monomers;
(iii) about 10 to about 45 wt. %, based on the total weight of the monomeric mixture, of the one or more bulky siloxane monomers; and
(iv) (1) about 0.05 to about 2 wt. %, based on the total weight of the monomeric mixture, of the one or more first crosslinking agents.

### Claim 19 (depends on 13)

The method of claim 13, wherein the monomeric mixture further comprises one or more of a minor amount of 2-hydroxyethyl methacrylate (HEMA) and an ultraviolet (UV) blocker.

### Claim 20 (depends on 13)

The method of claim 13, wherein the water extractable ophthalmic device is one of a contact lens and a hydrogel.

### Claim 21 (depends on 13)

The method of claim 13, wherein the step of curing comprises one of thermal curing or infrared curing.

### Claim 22 (depends on 13)

The method of claim 13, wherein the water extractable ophthalmic device has an equilibrium water content of from about 50 wt. % to about 70 wt. %, a contact angle of from about 30° to about 50° , an oxygen permeability of at least about 70 Barrers and a water extractable content of less than about 15 wt. %.