# US 10,502,978 B2 · Polymers and nanogel materials and methods for making and using the same

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,502,978 B2
- Document ID: US10502978B2
- Status: Granted
- Kind: B2
- Application number: 15/638,557
- Filed: 2017-06-30
- Published: 2017-10-19
- Granted: 2019-12-10
- Earliest claimed: 2012-05-25
- Assignees: Johnson & Johnson Vision Care, Inc.
- Applicants: Johnson & Johnson Vision Care, Inc.
- Inventors: Charles W. Scales; Kevin P. McCabe; Brent Matthew Healy
- Web page: https://patentgrep.com/patent/US10502978B2

## CPC

- G02C 7/049: {Contact lenses having special fitting or structural features achieved by special materials or material structures}
- G02B 1/043: {Contact lenses}
- G02C 2202/16: Laminated or compound lenses
- G02C: SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES (trial frames for testing the eyes A61B3/04; goggles or eyeshields not having the same features as spectacles A61F9/00)
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

## Abstract

Provided are articles such as medical devices which comprise at least one water soluble, crosslinked copolymer. The primary polymer chains of the copolymer are hydrophilic and independently have a degree of polymerization in the range of about 10 to about 10,000. The water soluble, crosslinked copolymers of the present invention are free from terminal substrate associating segments. The copolymers may be incorporated into a formulation from which the article is made or may be contacted with the article post-formation.

## Claims

### Claim 1

An ophthalmic solution comprising at least one water soluble, cross-linked copolymer comprising a plurality of primary polymer chains each having a degree of polymerization in the range of about 10 to about 10,000, wherein said copolymer is present in an amount effective to inhibit lipid uptake in a contact lens which is soaked in said solution and said ophthalmic solution is transparent, and wherein said water soluble, crosslinked polymers has primary chains, ζ, represented by the formula
wherein R1 is a divalent group selected from the group consisting of optionally substituted alkylene; optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic rings; optionally substituted alkylthio; optionally substituted alkoxy; or optionally substituted dialkylamino;
U is independently selected from the group consisting of hydrogen, halogen, C1-C4 alkyl which may be optionally substituted with hydroxyl, alkoxy, aryloxy (OR″), carboxy, acyloxy, aroyloxy (O2CR″), alkoxy-carbonyl, aryloxy-carbonyl (CO2R″) and combinations thereof,
V is independently selected from the group consisting of R″, —CO2R″, —COR″, —CN, —CONH2, —CONHR″, —CONR″2, —O2CR″, —OR″, cyclic and acyclic N-vinyl amides and combinations thereof;
R′ is independently selected from the group consisting of optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, alkaryl wherein the substituents are independently selected from the group that consists of epoxy, hydroxyl, alkoxy, acyl, acyloxy, carboxy, carboxylate, sulfonic acid, and sulfonate, alkoxy- or aryloxy-carbonyl, isocyanato, cyano, silyl, halo, dialkylamino; phosphoric acids, phosphates, phosphonic acids, phosphonates and combinations thereof;
R15′ and R15 are residues of hydrophilic, free radical reactive cross-linking agents;
R18 is a controlled radical polymerization agent;
ζl is another primary chain, are mole fractions, and α is equal to about 0.85 to about 0.999, β is not 0, and the mole fractions of β and γ combined are about 0.15 to about 0.001.

### Claim 2 (depends on 1)

The ophthalmic solution of claim 1 wherein said copolymer has a cross-linker to primary chain molar ratio in the range of about 0.01 to about 3.

### Claim 3 (depends on 1)

The ophthalmic solution of claim 1 wherein said at least one copolymer is present in an amount in the range of about 0.005 and about 2 weight %.

### Claim 4 (depends on 1)

The ophthalmic solution of claim 1 wherein said at least one copolymer is present in an amount in the range of about 0.01 and about 0.5 weight %.

### Claim 5 (depends on 1)

The ophthalmic solution of claim 1 wherein said primary polymer chains each have a degree of polymerization in the range of about 50 to about 1,000.

### Claim 6 (depends on 1)

The ophthalmic solution of claim 1 wherein said primary polymer chains each have a degree of polymerization in the range of about 100 to about 500.

### Claim 7 (depends on 1)

The ophthalmic solution of claim 1 wherein said water soluble, crosslinked polymers has primary chains, ζ, represented by the formula
Wherein R1, U, V, R15, R15′, α, β, γ and m are as defined in claim 1.

### Claim 8 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R1 is selected from the group consisting of optionally substituted benzyl, optionally substituted phenyl, ethanoate, optionally substituted propionate, 4-cyanopentanoate, or isobutyroate functionalities.

### Claim 9 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R1 is selected from the group consisting of 4-cyanopentanoate, isobutanoic, or a benzylic group.

### Claim 10 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R1 is selected from the group consisting of a cyano-methy or cumyl group.

### Claim 11 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R1 is polyvalent.

### Claim 12 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein U is selected from H or methyl.

### Claim 13 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R″ is selected from the group consisting of methyl, —CH2OH, —CH2CH2OH, —CH2CH2CH2OH, CH2—CO2−, —CH2CH2—CO2−, —CH2CH2CH2—CO2−, —CH2CH2CH2CH2—CO2−, —CH2CH2CH2CH2CH2—CO2−, —CH2—SO3−, —CH2CH2—SO3−, —CH2CH2CH2−SO3−, —CH2CH2CH2CH2—SO3−, —CH2CH2CH2CH2CH2—SO3−, —(CH3)2—CH2—CO2−, —(CH3)2−CH2−SO3H, —CH2CH2CH2—+N(CH3)2—CH2CH2—CO2−, —CH2CH2—+N(CH3)2—CH2CH2—CO2−, —CH2CH2CH2—+N(CH3)2—CH2CH2CH2—SO3−, —CH2CH2—+N(CH3)2—CH2CH2CH2—SO3−, —CH2CH2CH2—+N(CH3)2—CH2CH2CH2—PO3−2, —CH2CH2—+N(CH3)2—CH2CH2CH2—PO3−2, —CH2CH2CH2—+N(CH3)2—CH2CH2—PO3−2—CH2CH2—+N(CH3)2—CH2CH2—PO3−2, and combinations thereof.

### Claim 14 (depends on 12)

The ophthalmic solution of claim 12 wherein V is selected from the group consisting of pyrrolidonyl, piperidonyl, 2-caprolactam, 3-methyl-2-caprolactam, 3-methyl-2-piperidonyl, 4-methyl-2-piperidonyl, 4-methyl-2-caprolactam, 3-ethyl-2-pyrrolidonyl, 4,5-dimethyl-2-pyrrolidonyl, imidazolyl, N—N-dimethylamido, amido, N,N-bis(2-hydroxyethyl)amido, -cyano, N-isopropyl amido, acetate, carboxypolyethylene glycol, N-(2-hydroxypropyl) amido, N-(2-hydroxyethyl) amido, carboxyethyl phosphorylcholine, 3-(dimethyl(4-benzyl)ammonio)propane-1-sulfonate 3-((3-amidopropyl)dimethylammonio)propane-1-sulfonate 3-((3-(carboxy)propyl)dimethylammonio)propane-1-sulfonate N-methylacetamide, -acetamide, N-methylpropionamide, N-methyl-2-methylpropionamide, 2-methylpropionamide, N,N′-dimethylurea, and the like, and mixtures thereof.

### Claim 15 (depends on 12)

The ophthalmic solution of claim 12 wherein V is selected from the group consisting of —N—(CH3)2, pyrrolidonyl, —CON(CH3)2, N-(2-hydroxyethyl) amido or —N(CH3)COCH3.

### Claim 16 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R15 and R15′cross-linking agents are free of dimethylsiloxane groups.

### Claim 17 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R15 and R15′ are polymerization residues of at least one crosslinking agent selected from the group consisting of N,N′-alkylenebis(meth)acrylamides; polyalkyleneglycoldi(meth)acrylates, polyalkyleneglycoldi(meth)acrylamides, triallyl cyanurate, 1,3-divinylimidazolidin-2-one, and 3,3″ alkylenebis(1-vinylpyrrolidin-2-one), wherein the alkylene has 1-12 carbons, and mixtures thereof.

### Claim 18 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R15 and R15′ are polymerization residues of at least one crosslinking agent selected from the group consisting of N,N′-methylenebis(meth)acrylamide; N,N′-ethylenebis(meth)acrylamide; N,N′-propylenebis(meth)acrylamide; N,N′-butylenebis(meth)acrylamide; N,N′-pentamethylenebis(meth)acrylamide; N,N′-hexamethylenebis(meth)acrylamide; ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetra-ethylene glycol di(meth)acrylate; N,N′-(oxybis(ethane-2,1-diyl))diacrylamide N,N′-(((oxybis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))diacrylamide, triallyl cyanurate, 1,3-divinylimidazolidin-2-one and mixtures thereof.

### Claim 19 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein R18 is a RAFT or ATRP control agent.

### Claim 20 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein α is about 0.92 to about 0.999, and the combined mole fraction of β and γ is about 0.08 to about 0.001.

### Claim 21 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein α is about 0.95 to about 0.999, and the combined mole fraction of β and γ is about 0.05 to about 0.001.

### Claim 22 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein α is about 0.97 to about 0.999, and the combined mole fraction of β and γ is about 0.025 to about 0.001.

### Claim 23 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein said water soluble, crosslinked polymer has a degree of polymerization in the range of about 25 to about 5,000.

### Claim 24 (depends on 1)

The ophthalmic solution of claim 1 wherein said water soluble, crosslinked polymer has a degree of polymerization in the range of about 100 to about 1000.

### Claim 25 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein said water soluble, crosslinked polymer has a degree of polymerization in the range of about 100 to about 500.

### Claim 26 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein said water soluble, crosslinked polymer has a degree of polymerization in the range of about 100 to about 300.

### Claim 27 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein said water soluble, crosslinked polymer is free of substrate associative blocks.

### Claim 28 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein said primary chain, ζl has a PDI of less than about 1.5.

### Claim 29 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein at least about 20% of V are derived from N-(2-hydroxypropyl) (meth)acrylamide.

### Claim 30 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein V comprises repeating units derived from comonomers.

### Claim 31 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein V is substantially free of anionic groups.

### Claim 32 (depends on 1, 7)

The ophthalmic solution of claim 1 or 7 wherein V is free of anionic groups.

### Claim 33 (depends on 30)

The ophthalmic solution of claim 30 wherein said comonomers are selected from the group consisting of hydrophilic monomers, hydrophobic monomers, anionic monomers, cationic monomers, zwitterionic monomers, stimuli responsive monomers and combinations thereof.

### Claim 34 (depends on 30)

The ophthalmic solution of claim 30 wherein said comonomers are selected from the group consisting of anionic monomers, zwitterionic monomers and combinations thereof.