# US 10,370,476 B2 · Silicone hydrogels comprising high levels of polyamides

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

- Number: US 10,370,476 B2
- Document ID: US10370476B2
- Status: Granted
- Kind: B2
- Application number: 15/609,079
- Filed: 2017-05-31
- Published: 2018-01-11
- Granted: 2019-08-06
- Earliest claimed: 2016-07-06
- Assignees: Johnson & Johnson Vision Care, Inc.
- Applicants: Johnson & Johnson Vision Care, Inc.
- Inventors: Azaam Alli; Alexander Guzman
- Web page: https://patentgrep.com/patent/US10370476B2

## CPC

- C08F 283/122: {on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-}
- B29D 11/00134: {Curing of the contact lens material}
- C08F 290/068: {Polysiloxanes}
- C08G 77/442: containing vinyl polymer sequences
- C08J 3/075: Macromolecular gels
- C08L 51/085: {on to polysiloxanes}
- C08L 83/10: Block- or graft-copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00)
- G02B 1/043: {Contact lenses}
- G02C 7/049: {Contact lenses having special fitting or structural features achieved by special materials or material structures}
- C08G 2210/00: Compositions for preparing hydrogels
- C08J 2383/04: Polysiloxanes
- C08J 2477/00: Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08L 39/00: Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L 2203/02: for biomedical use
- 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- 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)

## Abstract

Described are silicone hydrogels with high levels of polyamides exhibiting an excellent balance of physical, mechanical, and biological properties. The silicone hydrogels are formed from a reactive monomer mixture comprising: a hydroxylalkyl (meth)acrylate monomer; hydroxyl-containing silicone components; and a polyamide, wherein the polyamide is present in an amount greater than 15 weight percent, based on the total weight of reactive components in the reactive monomer mixture.

## Claims

### Claim 1

A silicone hydrogel formed from a reactive monomer mixture comprising:
a) at least one hydroxyalkyl (meth)acrylate monomer;
b) at least one first mono-functional hydroxyl-substituted poly(disubstituted siloxane) having 4 to 8 siloxane repeating units;
c) at least one second hydroxyl-substituted poly(disubstituted siloxane) that is a mono-functional hydroxyl-substituted poly(disubstituted siloxane) having 10 to 200 siloxane repeating units;
d) at least 15 wt % at least one polyamide, based on the total weight of reactive components in the reactive monomer mixture; and
e) optional further constituents.

### Claim 2 (depends on 1)

The silicone hydrogel of claim 1, wherein the polyamide is present in the reactive mixture in an amount between 15.1 weight percent and about 40 weight percent, based on the total weight of all reactive components in the reactive monomer mixture.

### Claim 3 (depends on 1)

The silicone hydrogel of claim 1, wherein the polyamide is selected from the group consisting of cyclic polyamides, acyclic polyamides, and mixtures thereof.

### Claim 4 (depends on 3)

The silicone hydrogel of claim 3, wherein the polyamide comprises repeating units selected from Formula I, Formula II and Formula IV
wherein
R1 is independently a hydrogen atom or methyl;
X is a direct bond, —(CO)—, or —(CO)—NH—Re—, wherein Re is a C1 to C3 alkyl group;
Ra is selected from H, straight or branched, substituted or unsubstituted C1 to C4 alkyl groups;
Rb is selected from H, straight or branched, substituted or unsubstituted C1 to C4 alkyl groups, amino groups having up to two carbon atoms, amide groups having up to four carbon atoms, and alkoxy groups having up to two carbon groups;
Rc is selected from H, straight or branched, substituted or unsubstituted C1 to C4 alkyl groups;
Rd is selected from H, straight or branched, substituted or unsubstituted C1 to C4 alkyl groups;
wherein the number of carbon atoms in Ra and Rb taken together is 8 or less, and wherein the number of carbon atoms in Rc and Rd taken together is 8 or less.

### Claim 5 (depends on 4)

The silicone hydrogel of claim 4, wherein the number of carbon atoms in Ra and Rb taken together is 6 or less.

### Claim 6 (depends on 3)

The silicone hydrogel of claim 3, wherein the cyclic polyamide is prepared from at least one of α-lactam, β-lactam, γ-lactam, δ-lactam, and ε-lactam.

### Claim 7 (depends on 3)

The silicone hydrogel of claim 3, wherein the cyclic polyamide comprises repeating units of Formula IV
wherein
R1 is independently a hydrogen atom or methyl; f is a number from 1 to 10, and
X is a direct bond, —(CO)—, or —(CO)—NH—Re—, wherein Re is a C1 to C3 alkyl group.

### Claim 8 (depends on 7)

The silicone hydrogel of claim 7, wherein f is 8 or less.

### Claim 9 (depends on 8)

The silicone hydrogel of claim 8, wherein f is 6 or less.

### Claim 10 (depends on 7)

The silicone hydrogel of claim 7, wherein f is 2 to 6.

### Claim 11 (depends on 10)

The silicone hydrogel of claim 10, wherein f is 3.

### Claim 12 (depends on 10)

The silicone hydrogel of claim 10, wherein f is 2.

### Claim 13 (depends on 3)

The silicone hydrogel of claim 3, wherein the polyamide is a copolymer.

### Claim 14 (depends on 1)

The silicone hydrogel of claim 1, wherein the polyamide is selected from polyvinylpyrrolidone (PVP), polyvinylmethyacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof.

### Claim 15 (depends on 14)

The silicone hydrogel of claim 14, wherein the polyamide is PVP.

### Claim 16 (depends on 14)

The silicone hydrogel of claim 14, wherein the polyamide is PVMA.

### Claim 17 (depends on 13)

The silicone hydrogel of claim 13, wherein the copolymer comprises at least 80 mole percent of the repeating units selected from NVP, VMA, DMA, NVA, and mixtures thereof.

### Claim 18 (depends on 13)

The silicone hydrogel of claim 13, wherein the copolymer further comprises at least one repeating unit selected from the group consisting of N-vinyl amides, acrylamides, hydroxyalkyl (meth)acrylates, alkyl(meth)acrylates, N-vinylpyrrolidone, N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, vinyl acetate, acrylonitrile, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, methacryloxypropoyl tristrimethylsiloxysilane, siloxane substituted acrylates or methacrylates, and mixtures thereof.

### Claim 19 (depends on 1)

The silicone hydrogel of claim 1 further comprising at least one additional hydrophilic monomer.

### Claim 20 (depends on 1)

The silicone hydrogel of claim 1 wherein said hydroxyalkyl (meth)acrylate monomer is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 1-hydroxypropyl-2-(meth)acrylate, 2-hydroxy-2-methyl-propyl (meth)acrylate, 3-hydroxy-2,2-dimethyl-propyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, polyethylene glycol monomethacrylate, and mixtures thereof.

### Claim 21 (depends on 1)

The silicone hydrogel of claim 1 wherein said hydroxyalkyl (meth)acrylate monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethyl-propyl methacrylate, and mixtures thereof or 2-hydroxyethyl methacrylate, 3-hydroxy-2,2-dimethyl-propyl methacrylate, hydroxybutyl methacrylate or glycerol methacrylate and mixtures thereof.

### Claim 22 (depends on 19)

The silicone hydrogel of claim 19, wherein the additional hydrophilic monomer is selected from the group consisting of ethylene glycol vinyl ether (EGVE), di(ethylene glycol) vinyl ether (DEGVE), N-vinyl pyrrolidone (NVP), 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone; 1-ethyl-5-methylene-2-pyrrolidone, N-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, N-vinyl-N-methyl acetamide (VMA), N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, allyl alcohol, N-vinyl caprolactam, N-2-hydroxyethyl vinyl carbamate, N-carboxy-ß-alanine N-vinyl ester; N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine and mixtures thereof.

### Claim 23 (depends on 19)

The silicone hydrogel of claim 19, wherein the additional hydrophilic monomer is selected from N,N-dimethylacrylamide, N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, N-vinyl acetamide, and 1-methyl-5-methylene-2-pyrrolidone.

### Claim 24 (depends on 19)

The silicone hydrogel of claim 19, wherein the additional hydrophilic monomer comprises N-vinylpyrrolidone, N,N-dimethylacrylamide, and mixtures thereof.

### Claim 25 (depends on 1)

The silicone hydrogel of claim 1, wherein the first mono-functional hydroxyl-substituted poly(disubstituted siloxane) and the second hydroxyl-substituted poly(disubstituted siloxane) are present in the reactive monomer mixture in concentrations that provide a weight ratio, of the first mono-functional hydroxyl-substituted poly(disubstituted siloxane) to the second hydroxyl-substituted poly(disubstituted siloxane) of between 0.1 to 1.3.

### Claim 26 (depends on 1)

The silicone hydrogel of claim 1, wherein the first mono-functional hydroxyl-substituted poly(disubstituted siloxane) has the structure shown Formula VI-1
wherein
Z is selected from O, N, S or NCH2CH2O, when Z is O or S R2 is not present;
R1 is independently H or methyl;
R2 is H or is a linear, branched, or cyclic alkyl group containing one to eight carbon atoms, any of which may be further substituted with at least one hydroxy group, and which may be optionally substituted with amide, ether, and combinations thereof;
R3 and R4 are independently a linear, branched, or cyclic alkyl group containing one to eight carbon atoms, any of which may be further substituted with at least one hydroxy group, amide, ether, and combinations thereof; or R3 and R4 may be independently phenyl;
n is 4-8, and
R5 is selected from straight or branched C1 to C8 alkyl groups, which may be optionally substituted with one or more hydroxyl, amide, ether, and combinations thereof.

### Claim 27 (depends on 1)

The silicone hydrogel of claim 1, wherein the second hydroxyl-substituted poly(disubstituted siloxane) comprises a compound of Formula VI-2
wherein Z is selected from O, N, S or NCH2CH2O, when Z is O or S R2 is not present;
R1 is independently H or methyl;
R2 is H or is a linear, branched, or cyclic alkyl group containing one to eight carbon atoms, any of which may be further substituted with at least one hydroxy group, and which may be optionally substituted with amide, ether, and combinations thereof;
R3 and R4 are independently a linear, branched, or cyclic alkyl group containing one to eight carbon atoms, any of which may be further substituted with at least one hydroxy group, and which may be optionally substituted with amide, ether, and combinations thereof; or R3 and R4 may be independently phenyl;
n is the number of siloxane units and is from 10 to 200; and
R5 is selected from straight or branched C1 to C8 alkyl groups, which may be optionally substituted with one or more hydroxyl, amide, ether, and combinations thereof.

### Claim 28 (depends on 1)

The silicone hydrogel of claim 1 wherein the total weight percent of the first mono-functional hydroxyl-substituted poly(disubstituted siloxane) and the second hydroxyl-substituted poly(disubstituted siloxane) is between about 40 and about 70 wt %.

### Claim 29 (depends on 1)

The silicone hydrogel of claim 1, further comprising at least one additional silicone-containing component selected from the group consisting of non-hydroxyl silicone-containing monomers, macromers, cross-linking agents.

### Claim 30 (depends on 1)

The silicone hydrogel of claim 1, wherein the weight ratio of the first mono-functional hydroxyl-substituted poly(disubstituted siloxane) to the second hydroxyl-substituted poly(disubstituted siloxane) is between 0.1 and 1.

### Claim 31 (depends on 2)

The silicone hydrogel of claim 2, wherein the average number of siloxane repeating units of the first mono-functional hydroxyl-substituted poly(disubstituted siloxane) is 4 and the average number of siloxane repeating units of the second hydroxyl-substituted poly(disubstituted siloxane) is between 10 and 20.

### Claim 32 (depends on 19)

The silicone hydrogel of claim 19, wherein the total weight percent of additional hydrophilic monomer is between about 5 and about 30 wt. %.

### Claim 33 (depends on 1)

The silicone hydrogel of claim 1, further comprising at least one cross-linking agent selected from the group consisting of bifunctional crosslinkers, trifunctional crosslinkers, tetrafunctional crosslinkers, multifunctional crosslinkers, and mixtures thereof.

### Claim 34 (depends on 27)

The silicone hydrogel of claim 27, wherein n is from 10 to 20.

### Claim 35 (depends on 1)

The silicone hydrogel of claim 1, wherein the monofunctional hydroxyl substituted, poly(disubstituted siloxane)s are selected from the group consisting of monofunctional hydroxyl substituted, poly(dimethylsiloxane) of Formula VIIa-IXb
wherein R1 is methyl or H; n is between 4 and 30;
R2 is independently selected from the group consisting of H or a linear, branched, or cyclic alkyl group containing one to eight carbon atoms, any of which may be further substituted with at least one hydroxy group, and which may be optionally substituted with amide, ether, and combinations thereof;
n1 n2 are independently between 4 to 100;
n3 is 1-50;
R5 is selected from straight or branched C1 to C8 alkyl groups, which may be optionally substituted with one or more hydroxyl, amide, ether, polyhydroxyl groups selected from straight or branched C1 to C8 groups having a formula of CfHg(OH)h wherein f=1-8 and g+h=2f+1 and cyclic C1 to C8 groups having a formula of CfHg(OH)h wherein f=1-8 and g+h=2f−1, and combinations thereof;
a is 4-8 for the first hydroxyl-containing silicone component and between 4-100 for the second hydroxyl-containing silicone component.

### Claim 36 (depends on 1)

The silicone hydrogel of claim 1, wherein the further constituent is selected from a diluent, a UV absorbing compound, a medicinal agent, an antimicrobial compound, a pharmaceutical compound, a nutraceutical compound, a photochromic compound, a reactive tint, a pigment, a copolymerizable dye, a nonpolymerizable dye, a release agent, a copolymer, and combinations thereof.

### Claim 37 (depends on 36)

The silicone hydrogel of claim 36, wherein the UV absorbing compound is selected from the group consisting of reactive 2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, 2-hydroxyphenyltriazines, oxanilides, cyanoacrylates, salicylates, 4-hydroxybenzoates, and mixtures thereof.

### Claim 38 (depends on 36)

The silicone hydrogel of claim 36, wherein the UV absorbing compound is selected from the group consisting of 2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, 5-vinyl and 5-isopropenyl derivatives of 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and 4-acrylates or 4-methacrylates of 2-(2,4-dihydroxyphenyl)-2H-benzotriazole or 2-(2,4-dihydroxyphenyl)-1,3-2H-dibenzotriazole, and mixtures thereof.

### Claim 39 (depends on 1)

The silicone hydrogel of claim 1, wherein the silicone hydrogel has an oxygen permeability (Dk) of at least about 80 barrers.

### Claim 40 (depends on 1)

The silicone hydrogel of claim 1, further comprising at least one charged monomer comprises at least one ionic moiety selected from the group consisting of anions, cations, zwitterions, betaines, and mixtures thereof.

### Claim 41 (depends on 1)

A contact lens comprising the silicone hydrogel of claim 1.

### Claim 42 (depends on 41)

The contact lens of claim 41, wherein the lysozyme uptake is at least 50 μg.

### Claim 43 (depends on 41)

The contact lens of claim 41, wherein the lipid uptake is less than 15 μg.

### Claim 44 (depends on 41)

The contact lens of claim 41, wherein the dynamic contact angle is less than about 95°.

### Claim 45

A silicone hydrogel formed from a reactive monomer mixture comprising:
a) At least one hydroxyalkyl (meth)acrylate;
b) a hydroxyl-containing silicone component that comprises a mixture of a first hydroxyl substituted, linear poly(dialkylsiloxane) of Formula VI,
wherein
Z is selected from O, N, S or NCH2CH2O, when Z is O or S R2 is not present;
R1 is independently H or methyl;
R2 is H or is a linear, branched, or cyclic alkyl group containing one to eight carbon atoms, any of which may be further substituted with at least one hydroxy group, and which may be optionally substituted with amide, ether, and combinations thereof;
R3 and R4 are independently a linear, branched, or cyclic alkyl group containing one to eight carbon atoms, any of which may be further substituted with at least one hydroxy group, amide, ether, and combinations thereof; or R3 and R4 may be independently phenyl;
n is 4-8 for the first monofunctional hydroxyl substituted, poly(disubstituted siloxane),
R5 is selected from straight or branched C1 to C8 alkyl groups, optionally substituted with one or more hydroxyl, amide, ether, and combinations thereof; and,
a second hydroxyl substituted, linear poly(dialkylsiloxane) that is a monofunctional hydroxyl substituted, linear poly(dialkylsiloxane) of Formula VI, wherein n is 10 to 20;
wherein a ratio of the second hydroxyl substituted, linear poly(dialkylsiloxane) to the first hydroxyl substituted, linear poly(dialkylsiloxane) is in a range of 0.1 to 1.3;
greater than 15 weight percent, based on the total weight of the reactive monomer mixture, of at least one polyamide selected from the group consisting of PVP, PVMA, PDMA, PNVA, polyacrylamide, and copolymers and mixtures thereof; and
optionally, methacrylic acid.

### Claim 46 (depends on 45)

The silicone hydrogel of claim 45, further comprising at least one additional hydrophilic monomer is selected from the group consisting of N-vinyl amides, N-vinylimides, N-vinyl lactams, hydrophilic (meth)acrylates, (meth)acrylamides, hydrophilic styrenes, vinyl ethers, O-vinyl carbonates, O-vinyl carbamates, N-vinyl ureas, other hydrophilic vinyl compounds and mixtures thereof.

### Claim 47 (depends on 1)

A method of making the silicone hydrogel of claim 1, the method comprising:
preparing the reactive monomer mixture comprising the hydroxyalkyl (meth)acrylate monomer; the first and second hydroxyl-substituted poly(disubstituted siloxane) components; the polyamide; and any optional further constituents, wherein the polyamide is present in the reactive monomer mixture in an amount greater than 15 weight percent, based on the total weight of the reactive monomer mixture; and
curing the reactive monomer mixture to form a silicone hydrogel.

### Claim 48

A silicone hydrogel formed from a reactive monomer mixture comprising:
a) between 15 and about 40 wt % at least one polyamide;
b) at least one hydroxyl silicone-containing monomer;
c) at least one hydroxyl substituted poly(disubstituted siloxane) selected from the group consisting of monofunctional poly(disubstituted siloxane) having 4 to 8 siloxane repeating units, and monofunctional hydroxyl substituted poly(disubstituted siloxane)s having 10 to 200 siloxane repeating units;
d) at least one hydrophilic monomer.

### Claim 49 (depends on 1)

A contact lens comprising the silicone hydrogel of claim 1.

### Claim 50 (depends on 49)

The contact lens of claim 49, wherein the lipid uptake is less than about 15 μg/lens.

### Claim 51 (depends on 49)

The contact lens of claim 49, wherein the lipid uptake is less than 10 μg/lens.

### Claim 52 (depends on 49)

The contact lens of claim 49, wherein the PQ1 uptake is less than about 20%.

### Claim 53 (depends on 49)

The contact lens of claim 49, wherein the dynamic contact angle is less than about 60°.