# US 11,029,447 B2 · Method for producing MPS-compatible water gradient contact lenses

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- Number: US 11,029,447 B2
- Document ID: US11029447B2
- Status: Granted
- Kind: B2
- Application number: 16/204,705
- Filed: 2018-11-29
- Published: 2019-06-13
- Granted: 2021-06-08
- Earliest claimed: 2017-12-13
- Assignees: Alcon Inc.
- Applicants: Novartis AG
- Inventors: Yongxing Qiu; John Dallas Pruitt; Newton T. Samuel; Chung-Yuan Chiang; Angela Driver-Scott; Ciara Dauenhauer; Rita Anand
- Web page: https://patentgrep.com/patent/US11029447B2

## CPC

- G02B 1/043: {Contact lenses}
- B05D 5/00: Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B29D 11/00038: {Production of contact lenses}
- B29D 11/00125: {Auxiliary operations, e.g. removing oxygen from the mould, conveying moulds from a storage to the production line in an inert atmosphere}
- B29D 11/00865: {Applying coatings; tinting; colouring (printing, marking or copying processes B41M; identification in general G09F3/00; producing decorative effects in general B44C; positioning or marking of lenses B24B13/0055)}
- B65B 55/22: Immersing contents in protective liquids
- C08L 33/02: Homopolymers or copolymers of acids; Metal or ammonium salts thereof
- C08L 79/04: Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L 83/04: Polysiloxanes
- C09D 133/02: Homopolymers or copolymers of acids; Metal or ammonium salts thereof
- G02B 1/18: Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films (G02B1/16 takes precedence)
- G02C 7/049: {Contact lenses having special fitting or structural features achieved by special materials or material structures}
- B05D 1/18: performed by dipping
- B05D 1/38: with intermediate treatment (intermediate treatment per se B05D3/00)
- B05D 3/002: {Pretreatement}
- B05D 3/02: by baking {(B05D3/04 takes precedence)}
- B05D 5/10: to obtain an adhesive surface
- B29K 2083/00: Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
- B29K 2105/0061: {Gel or sol}
- C08L 2201/10: Transparent films; Clear coatings; Transparent materials
- C08L 2201/54: Aqueous solutions or dispersions
- G02B 2207/109: Sols, gels, sol-gel materials
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- B29D: PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE (making granules B29B9/00; making preforms B29B11/00)
- B65B: MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING (bundling and pressing devices for cigars A24C1/44; devices for tensioning and securing binders adapted to be supported by the article or articles to be bound B25B25/00; applying closure members to bottles, jars or similar containers B67B1/00-B67B6/00; concurrent cleaning, filling and closing of bottles B67C7/00; emptying bottles, jars, cans, casks, barrels or similar containers B67C9/00)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- 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)
- 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

The invention is related to a process for producing contact lenses that not only comprise a water gradient structural configurations, but also have a minimized uptakes of polyquaternium-1 and a long-lasting surface hydrophilicity and wettability even after being undergone a simulated 30-days lens care regime.

## Claims

### Claim 1

A process for producing a contact lens, comprising the steps of:
(a) obtaining a contact lens precursor which is a coated contact lens which comprises a lens bulk material completely covered with an anchor layer of a polyanionic polymer which comprises at least 60% by mole of repeating units of at least one carboxyl-containing vinylic monomer; and
(b) heating, in the presence of at least one first polyaziridine which has a number average molecular weight of about 2000 Dalton or less and at least two aziridine groups, the contact lens precursor in a first aqueous solution which comprises a thermally-crosslinkable hydrophilic polymeric material which has thermally-crosslinkable groups, to and at a temperature from about 30° C. to about 140° C. for a period of time sufficient to obtain the contact lens,
wherein the contact lens comprise (i) a crosslink anchor layer thereon and (2) an outer surface hydrogel layer which is covalently attached to the crosslinked anchor layer, wherein the crosslinked anchor layer is obtained crosslinking the polyanionic polymer in the anchor layer via crosslinkers derived from said at least one polyaziridine in coupling reaction between at least two pair of aziridine and carboxyl groups, wherein the outer surface hydrogel layer is formed by crosslinking the thermally-crosslinked hydrophilic polymeric material, wherein the contact lens has a polyquaternium-1 uptake (“PUpz”) of about 0.6 μg/lens or less.

### Claim 2 (depends on 1)

The process of claim 1, further comprising a step of soaking the contact lens precursor in a second aqueous solution comprising at least one second polyaziridine having a number average molecular weight of about 2000 Dalton or less and at least two aziridine groups.

### Claim 3 (depends on 2)

The process of claim 2, wherein the first aqueous solution further comprises said at least one first polyaziridine.

### Claim 4 (depends on 3)

The process of claim 3, wherein the first and second polyaziridines independent of each other are selected from a group consisting of trimethylolpropane tris(2-methyl-1-aziridinepropionate), pentaerythritol tris[3-(1-aziridinyl)propionate], trimethylolpropane tris(3-aziridinopropionate), a Michael reaction product of a vinylic crosslinker having at least three (meth)acryloyl groups and 2-methylaziridine, a Michael reaction product of a vinylic crosslinker having at least three (meth)acryloyl groups and aziridine, or a combination thereof.

### Claim 5 (depends on 4)

The process of claim 4, wherein the vinylic crosslinker is selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane ethoxylate triacrylates, glyceryl propoxylate triacrylate, trimethylolpropane propoxylate triacrylates, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol ethoxylate tetraacrylate, dipentaerythritol pentaacrylate, caprolactone modified dipentaerythritol hexaacrylates, caprolactone modified dipentaerythritol pentaacrylate, ethoxylated glycerol triacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, ethoxylated pentaerythritol trimethacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol trimethacrylate, ethoxylated dipentaerythritol tetramethacrylate, ethoxylated dipentaerythritol pentamethacrylate, ethoxylated dipentaerythritol hexamethacrylate, ethoxylated dipentaerythritol triacrylate, ethoxylated dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol pentaacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated pentaerythritol trimethacrylate, propoxylated pentaerythritol triacrylate, propoxylated pentaerythritol tetramethacrylate, propoxylated pentaerythritol tetraacrylate, propoxylated dipentaerythritol trimethacrylate, propoxylated dipentaerythritol tetramethacrylate, propoxylated dipentaerythritol pentamethacrylate, propoxylated dipentaerythritol hexamethacrylate, propoxylated dipentaerythritol triacrylate, propoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol pentaacrylate and propoxylated dipentaerythritol hexaacrylate, ethoxylated trimethyloylpropane triacrylamide, and combinations thereof.

### Claim 6 (depends on 5)

The process of claim 5, wherein the first and second aqueous solutions independent of each other comprise two polyaziridines, a first polyaziridine having at least two aziridine groups of
and a second polyaziridine having at least two aziridine groups of
and at least one hydrophilic moiety selected from the group consisting of —OH, —[OC2H4O]n1—. —CONHR1, —CONR1—, and combinations thereof, wherein n1 is an integer of 1 to 10 and R1 is hydrogen, methyl or ethyl.

### Claim 7 (depends on 6)

The process of claim 6, wherein the first and second aqueous solutions independent of each other comprise from about 0.01% to about 2.5% by weight of said at least one first or second polyaziridine.

### Claim 8 (depends on 6)

The process of claim 6, wherein the first aqueous solution is a lens packaging solution, wherein the step of heating is performed by autoclaving the contact lens precursor immersed in the lens packaging solution in a sealed lens package at a temperature of from about 115° C. to about 125° C. for approximately 20-90 minutes.

### Claim 9 (depends on 8)

The process of claim 8, wherein the lens packaging solution further comprises a partially hydrolyzed polyvinyl alcohol having a hydrolysis degree of hydrolysis of from about 80% to about 98%.

### Claim 10 (depends on 8)

The process of claim 8, wherein the lens packaging solution has a pH of from about 7.0 to about 9.0 before autoclaving and a pH of from about 6.5 to about 7.7 after autoclaving.

### Claim 11 (depends on 8)

The process of claim 8, wherein the first aqueous solution is obtained directly in the lens package by mixing a third aqueous solution and a fourth aqueous, wherein the third aqueous solution comprises the thermally-crosslinkable hydrophilic polymeric material.

### Claim 12 (depends on 11)

The process of claim 11, wherein the third aqueous solution is free of any polyaziridine.

### Claim 13 (depends on 11)

The process of claim 11, wherein the third aqueous solution further comprises said at least one polyaziridine.

### Claim 14 (depends on 11)

The process of claim 11, wherein the fourth aqueous solution comprises said at least one first polyaziridine.

### Claim 15 (depends on 11)

The process of claim 11, wherein the fourth aqueous solution is free of any polyaziridine.

### Claim 16 (depends on 11)

The process of claim 11, wherein said at least one carboxyl-containing vinylic monomer is acrylic acid, methacrylic acid, ethylacrylic acid, 2-(meth)acrylamidoglycolic acid, and combinations thereof.

### Claim 17 (depends on 11)

The process of claim 11, wherein the polyanionic polymer is polyacrylic acid, polymethacrylic acid, poly(ethylacrylic acid), poly(acrylic acid-co-methacrylic acid), poly[ethylacrylic acid-co-(meth)acrylic acid], poly(N,N-2-acrylamidoglycolic acid), poly[(meth)acrylic acid-co-acrylamide], poly[(meth)acrylic acid-co-vinylpyrrolidone], poly[ethylacrylic acid-co-acrylamide], poly[ethylacrylic acid-co-vinylpyrrolidone], poly[(meth)acrylic acid-co-vinylacetate], poly[ethylacrylic acid-co-vinylacetate], or combinations thereof.

### Claim 18 (depends on 11)

The process of claim 11, wherein the polyanionic polymer is a graft polymer which is grafted onto the inner layer or the lens bulk material, wherein the graft polymer comprises repeating units of at least one carboxyl-containing vinylic monomer which is acrylic acid, methacrylic acid, ethylacrylic acid, 2-(meth)acrylamidoglycolic acid, and combinations thereof.

### Claim 19 (depends on 11)

The process of claim 11, wherein the thermally-crosslinkable hydrophilic polymeric material is a partially-crosslinked polymeric material that comprises a three-dimensional network and thermally-crosslinkable groups within the network or being attached to the network.

### Claim 20 (depends on 19)

The process of claim 19, wherein the thermally-crosslinkable hydrophilic polymeric material comprises azetidinium groups and is a partial reaction product of at least one azetidinium-containing polymer with at least one hydrophilicity-enhancing agent having at least one carboxyl, primary amine, secondary amine, or thiol group.

### Claim 21 (depends on 11)

The process of claim 11, wherein the lens bulk material is a silicone hydrogel material, wherein the silicone hydrogel bulk material comprises: (1) repeating units of at least one polysiloxane vinylic monomer; (2) repeating units of at least one hydrophilic vinylic monomer; (3) repeating units of at least one polysiloxane vinylic crosslinker; (4) repeating units of at least one hydrophilic N-vinyl amide monomer; (5) repeating units of at least one polycarbosiloxane vinylic monomer; (6) repeating units of at least one polycarbosiloxane vinylic crosslinker; (7) repeating units of at least one silicone-containing vinylic monomer having a bis(trialkylsilyloxy)alkylsilyl or tris(trialkylsilyloxy)silyl group; (8) repeating units of one or more blending vinylic monomers; (9) repeating units of one or more non-silicone vinylic crosslinking agents; or (10) combinations thereof.

### Claim 22 (depends on 11)

The process of claim 11, wherein the lens bulk material is a non-silicone hydrogel material comprising repeating units of at least one hydroxyl-containing vinylic monomer selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, vinyl alcohol, allyl alcohol, and combinations thereof.

### Claim 23 (depends on 11)

The process of claim 11, wherein the lens bulk material comprise a central circular portion composed of a rigid gas permeable lens material and an annular portion composed of a non-silicone hydrogel material surrounding the central circular portion, wherein the non-silicone hydrogel material comprises repeating units of at least one hydroxyl-containing vinylic monomer selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, vinyl alcohol, allyl alcohol, and combinations thereof.