EP0362137A2
Expired / Lapsed
EP
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Molded polymers with hydrophilic surfaces, and process for making them
Assignee: Novartis AG
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Filing: 1989-09-20
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Granted: —
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Expires: 2009-09-20
Abstract
Abstract Polymer composites are described which consist of a 0.1-500 micron thick film of a preshaped, surface-forming hydrophilic first polymer A covalently grafted onto an underlaying bulk and structural second polymer B and which are prepared by polymerizing said second polymer B on a substrate which is coated with the hydrophilic first polymer A, said first polymer being able to co-react with the monomers used to prepare the second polymer B. Because of their continuous nature and covalent bonding, the hydrophilic surface films of polymer A adhere tightly to the underlaying polymer B and also conform exactly to the configuration of the substrate or mold; polymers with such permanently modified surfaces are useful as biocompatible materials, for instance as contact lenses or as low-friction or non-blocking elastomers, as well as non-fogging, washable and printable polymers. The instant process can also be adopted to prepare the reverse type of polymer composite comprising a hydrophilic polymer with a thin hydrophobic or lipophobic surface. Such composites can be used as membranes, release-rate controlling devices and solvent and soil-resistant polymers.
Inventors
- 👤 Karl F. Mueller
- 👤 Paul Harisiades
- 👤 Sonia J. Heiber
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-01 21:49
CPC Classifications
C; C08; C08J; C08J5/00; B; B29; B29C; B29C41/00; B29C41/003; C08B; C08B15/00; C08B15/05; C08B15/06; C08F; C08F290/00; C08F290/08; C08F290/10; C08F299/00; G; G02; G02B; G02B1/00; G02B1/04; G02B1/041; G02B1/043
Claims Analysis
Total Claims: 42
Claim 1
Independent Claim
55 words
A product which comprises (a) a preformed, optically true, thin, conforming, continuous, integral, wettable hydrophilic polymeric surface of hydrophilic polymer (A) intimately bonded through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface on (b) a polymer substrate which is reaction cast and is an essentially hydrophobic polymer (B).
Claim 2
Dependent Claim
55 words
A product which comprises (a) a preformed, optically true, thin, conforming, continuous, integral, wettable hydrophilic polymeric surface of hydrophilic polymer (A) intimately bonded through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface on (b) a polymer substrate which is reaction cast and is an essentially hydrophobic polymer (B).
Claim 3
Dependent Claim
11 words
A product according to claim 1, which is a contact lens.
Claim 4
Dependent Claim
24 words
A product according to claim 1 or 2 wherein the hydrophilic polymeric surface of hydrophilic polymer (A) is 0.1 to 500 microns in thickness.
Claim 5
Dependent Claim
65 words
A product according to claim 1 wherein the hydrophilic polymer (A) is either a polymer (A-1) which contains a plurality of "step-growth reactive" functional groups and is selected from the group consisting of water soluble vinyl polymers, carbohydrate polymers, polyethylene oxide or polyethylene oxide-containing polymers, and polyamines, or is an essentially water soluble polymer (A-2) bearing a plurality of "chain-growth (free radical) reactive" functional groups.
Claim 6
Dependent Claim
46 words
A product according to claim 4 wherein the hydrophilic polymer (A) is a polymer (A-1) which contains a plurality of "step-growth reactive" functional groups and is selected from the group consisting of water soluble vinyl polymers, carbohydrate polymers, polyethylene oxide or polyethylene oxide-containing polymers and polyamines.
Claim 7
Dependent Claim
35 words
A product according to claim 5 wherein the hydrophilic polymer (A-1) is poly(vinyl alcohol), ethoxylated poly(vinyl alcohol), hydroxyalkyl cellulose or a copolymer of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or an aminoalkyl methacrylate with N,N-dimethacrylamide or N-vinylpyrrolidone.
Claim 8
Dependent Claim
20 words
A product according to claim 6, wherein the hydrophilic polymer (A-1) is poly(vinyl alcohol), ethoxylated poly(vinyl alcohol) or hydroxethyl cellulose.
Claim 9
Dependent Claim
28 words
A product according to claim 4 wherein the hydrophilic polymer (A) is an essentially water soluble polymer (A-2) bearing a plurality of "chain-growth (free radical) reactive" functional groups.
Claim 10
Dependent Claim
112 words
A product according to claim 8, wherein the hydrophilic polymer (A-2) is poly-N-vinylpyrrolidone, poly-N,N-dimethylacrylamide, a copolymer of N,N-dimethylacrylamide with acrylic acid, methacrylic acid, sodium styrene sulfonate, 2-methacrylamido-2-methylpropane sulfonic acid or 2-hydroxyethyl methacrylate; a copolymer of 2-hydroxyethyl methacrylate or N-tert.-butylaminoethyl methacrylate in which at least 1 mol % of the mer units are reacted with an isocyanato or oxirane functional vinyl compound; poly(vinylalcohol), ethoxylated poly(vinyl alcohol) or hydroxyethyl cellulose in which 0 to 5 mol % of the OH groups are reacted with an isocyanato or oxirane functional vinyl compound; poly(ethylene oxide) of 1000-10000 MW, bis-(aminopropyl)-poly(ethylene oxide) or a block copolyurethane of poly(ethylene oxide) and polydimethylsiloxane dialkanol, with or without terminal methacrylate groups.
Claim 11
Dependent Claim
68 words
A product according to claim 9 wherein the hydrophilic polymer (A-2) is poly-N,N-dimethylacrylamide, a copolymer of N,N-dimethylacrylamide with acrylic acid, methacrylic acid, sodium styrene sulfonate, 2-methacrylamido-2-methyl-propane-sulfonic acid or 2-hydroxyethyl methacrylate; ethoxylated poly(vinyl alcohol) or hydroxyethyl cellulose with 1-4 mol % of OH groups reacted with 2-isocyanatoethyl methacrylate, m-isopropenyl-α,α-dimethylbenzyl isocyanate or glycidyl methacrylate; poly(ethylene oxide) or bis-aminopropyl)polyethylene oxide of 900-8000 MW endcapped with2-isocyanatoethyl methacrylate, m-isopropenyl-α,α-dimethylbenzyl isocyanate or glycidyl methacrylate.
Claim 12
Dependent Claim
41 words
A product according to claim 1, wherein the essentially hydrophobic polymer (B) is either a step-growth polymer (B-1) which is a polyester, polyamide, polyimide, polyether, polyurethane, polyurea, epoxy resin, polythioether, silicone rubber or polyionene, or is a chain-growth vinyl polymer (B-2).
Claim 13
Dependent Claim
30 words
A product according to claim 11 wherein the hydrophobic polymer is a polymer (B-1) which is a polyester, polyamide, polyimide, polyether, polyurethane, polyurea, epoxy resin, polythioether, silicone rubber or polyionene.
Claim 14
Dependent Claim
16 words
A product according to claim 12 wherein the hydrophobic polymer (B-1) is a polyurethane or polyurea.
Claim 15
Dependent Claim
14 words
A product according to claim 13 wherein the hydrophobic polymer (B-1) is a polyurethane.
Claim 16
Dependent Claim
21 words
A product according to claim 14 wherein the polyurethane contains polydimethylsiloxane chains of 500-10000 MW or is a fluorine containing polyurethane.
Claim 17
Dependent Claim
15 words
A product according to claim 12 wherein the hydrophobic polymer (B-1) is a silicone rubber.
Claim 18
Dependent Claim
20 words
A product according to claim 11 wherein the hydrophobic polymer is a polymer (B-2) which is a chain-growth vinyl polymer.
Claim 19
Dependent Claim
54 words
A product according to claim 17 wherein the hydrophobic polymer (B-2) is a linear or crosslinked vinyl polymer having recurring structural units of the formula I: wherein R₁ is hydrogen or methyl, R₂ is an ester, amide, carboxy, ether, lactam or aromatic group, and R₃ is hydrogen or has the same meaning as R₂.
Claim 20
Dependent Claim
48 words
A product according to claim 18 wherein the hydrophobic polymer (B-2) is a linear or crosslinked homopolymer or copolymer of a monomer or monomers selected from the group consisting of mono- or polyfunctional acrylates, methacrylates, acrylamides, methacrylamides, fumarates, maleates, itaconates, vinyl ethers, vinyl esters, vinyl lactams or styrenes.
Claim 21
Dependent Claim
87 words
A product according to claim 19 wherein the hydrophobic polymer (B-2) contains 30-100 mol % of mer-units of a linear or branched alkyl acrylate or methacrylate with 1 to 18 carbon atoms in the alkyl group; a cycloalkyl acrylate or methacrylate with 6 to 12 carbon atoms in the cycloalkyl group; phenyl- and benzyl acrylate or methacrylate; styrene; a fluorine containing acrylate, methacrylate or styrenic monomer with 3 to 21 fluorine atoms; a Si atoms containing acrylate, methacrylate or styrenic monomer with 2 to 10 Si atoms.
Claim 22
Dependent Claim
43 words
A product according to claim 17, wherein the hydrophobic polymer (B-2) is the polymerization product of 20-100 % (by weight) of a heat- or radiation curable poly-vinyl substituted polyester, polyurethane, polyurea or polyether of 500-10,000 MW with 0-80 % (by weight) vinyl monomers.
Claim 23
Dependent Claim
40 words
A product according to claim 21, wherein the hydrophobic polymer (B-2) is the polymerization product of 50-100 % (by weight) of a divinyl substituted polyethylene-, polypropylene- or poly-tetramethylene oxide of 500-10,000 MW, and 0-50 % (by weight) of vinyl monomers.
Claim 24
Dependent Claim
28 words
A product according to claim 17, wherein the hydrophobic polymer (B-2) is the polymerization product of a di-, tri- or tetravinyl substituted poly-dimethylsiloxane or poly-dimethylsiloxane-polyurethane of 500-10,000 MW.
Claim 25
Dependent Claim
38 words
A product according to claim 23, wherein the hydrophobic polymer (B-2) is the copolymerization product of 20-80 % (by weight) of a di-, tri- or tetravinyl substituted polydimethyl siloxane or polyurethane with 80-20 % (by weight) vinyl monomers.
Claim 26
Dependent Claim
29 words
A product according to claim 17, wherein the hydrophobic polymer (B-2) is the polymerization product of a divinyl derivative of a fluorinated polyether diol or a perfluoroalkyl substituted diol.
Claim 27
Dependent Claim
14 words
A product according to any of the preceding claims which is a contact lens.
Claim 28
Dependent Claim
21 words
A product according to any of claims 6, 7, 9, 10, 15, 16, 20 or 22-25, which is a contact lens.
Claim 29
Dependent Claim
136 words
A process for making a product having a preformed, optically true, thin, conforming, continuous, integral, wettable hydrophilic polymeric surface on an essentially hydrophobic polymer form, said surface being intimately bonded and copolymerized through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface, which comprises (a) coating a mold with a film-forming first hydrophilic polymer (A), said polymer containing sites capable of undergoing subsequent copolymerization with a monomer or monomer mixture required to form a hydrophobic polymer (B), (b) polymerizing the monomer or monomer mixture required to form the hydrophobic polymer (B) in contact with the coated mold whereby effecting copolymerization with the reactive sites present in the mold coating to achieve intimate bonding therewith by way of a multiplicity of covalent bonds, and (c) releasing the product from the mold.
Claim 30
Dependent Claim
136 words
A process for making a product having a preformed, optically true, thin, conforming, continuous, integral, wettable hydrophilic polymeric surface on an essentially hydrophobic polymer form, said surface being intimately bonded and copolymerized through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface, which comprises (a) coating a mold with a film-forming first hydrophilic polymer (A), said polymer containing sites capable of undergoing subsequent copolymerization with a monomer or monomer mixture required to form a hydrophobic polymer (B), (b) polymerizing the monomer or monomer mixture required to form the hydrophobic polymer (B) in contact with the coated mold whereby effecting copolymerization with the reactive sites present in the mold coating to achieve intimate bonding therewith by way of a multiplicity of covalent bonds, and (c) releasing the product from the mold.
Claim 31
Dependent Claim
100 words
A process according to claim 28 wherein the hydrophilic polymer (A) is either a polymer (A-1) which contains a plurality of "step-growth reactive" functional groups and is selected from the group consisting of water soluble vinyl polymers, carbohydrate polymers, polyethylene oxide or polyethylene oxide-containing polymers, and polyamines, or is an essentially water soluble polymer (A-2) bearing a plurality of "chain-growth (free radical) reactive" functional groups and the essentially hydrophobic polymer (B) is either a step-growth polymer (B-1) which is a polyester, polyamide, polyimide, polyether, polyurethane, polyurea, epoxy resin, polythioether, silicone rubber or polyionene, or is a chain-growth vinyl polymer (B-2).
Claim 32
Dependent Claim
11 words
A contact lens prepared by the process according to claim 28.
Claim 33
Dependent Claim
11 words
A contact lens prepared by the process according to claim 29.
Claim 34
Dependent Claim
56 words
A product which comprises a) a preformed, thin, conforming, continuous, integral polymeric surface of a hydrophobic and/or lipophobic polymer (C) intimately bonded through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface on b) a polymer substrate which is reaction cast and is a more hydrophilic and/or liphophilic polymer (D).
Claim 35
Dependent Claim
56 words
A product which comprises a) a preformed, thin, conforming, continuous, integral polymeric surface of a hydrophobic and/or lipophobic polymer (C) intimately bonded through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface on b) a polymer substrate which is reaction cast and is a more hydrophilic and/or liphophilic polymer (D).
Claim 36
Dependent Claim
23 words
A product according to claim 32 wherein the polymeric surface of hydrophobic and/or lipophobic polymer (C) is 0.1 to 500 microns in thickness.
Claim 37
Dependent Claim
49 words
A product according to claim 32, wherein the hydrophobic and/or lipophobic polymer (C) is selected from the group consisting of water insoluble vinyl polymers, polydienes, polyesters, polyethers, polyamides, polyurethanes, or polyureas and contain either a plurality of "step-growth-reactive" functional groups (C-1) or a plurality of "chain-growth-reactive" functional groups (C-2).
Claim 38
Dependent Claim
39 words
A product according to claim 32 wherein the more hydrophilic and/or lipophilic polymer (D) is either a step-growth polymer (D-1), which is a polyester, polyamide, polyimide, polyurethane, polyurea, epoxy resin or polyionene, or is a chain-growth vinyl polymer (D-2).
Claim 39
Dependent Claim
145 words
A process for making a product having a preformed, thin, conforming, continuous, integral hydrophobic and/or lipophobic polymeric surface on a more hydrophilic and/or lipophilic polymer form, said surface being intimately bonded and copolymerized through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface, which comprises a) coating a mold with a film-forming first hydrophobic and/or lipophobic polymer (C) said polymer containing sites capable of undergoing subsequent copolymerization with a monomer or monomer mixture required to form a more hydrophilic and/or lipophilic polymer (D), b) polymerizing the monomer or monomer mixture required to form the more hydrophilic and/or lipophilic polymer (D) in contact with the coated mold whereby effecting copolymerization with the reactive sites present in the mold coating to achieve intimate bonding therewith by way of a multiplicity of covalent bonds, and c) releasing the product from the mold.
Claim 40
Dependent Claim
145 words
A process for making a product having a preformed, thin, conforming, continuous, integral hydrophobic and/or lipophobic polymeric surface on a more hydrophilic and/or lipophilic polymer form, said surface being intimately bonded and copolymerized through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface, which comprises a) coating a mold with a film-forming first hydrophobic and/or lipophobic polymer (C) said polymer containing sites capable of undergoing subsequent copolymerization with a monomer or monomer mixture required to form a more hydrophilic and/or lipophilic polymer (D), b) polymerizing the monomer or monomer mixture required to form the more hydrophilic and/or lipophilic polymer (D) in contact with the coated mold whereby effecting copolymerization with the reactive sites present in the mold coating to achieve intimate bonding therewith by way of a multiplicity of covalent bonds, and c) releasing the product from the mold.
Claim 41
Dependent Claim
84 words
A process according to claim 36 wherein the hydrophobic and/or lipophobic polymer (C) is selected from the group consisting of water insoluble vinyl polymers, polydienes, polyesters, polyethers, polyamides, polyurethanes or polyureas containing either a plurality of "step-growth-reactive" functional groups (C-1) or a plurality of "chain-growth (free radical) reactive" functional groups, (C-2), and the more hydrophilic and/or lipophilic polymer (D) is either a step-growth polymer (D-1), which is a polyester, polyamide, polyimide, polyurethane, polyurea, epoxy resin, or polyionene, or is a chain-growth vinyl polymer (D-2).
Claim 42
Dependent Claim
21 words
A product according to claim 34, wherein the hydrophobic and/or lipophobic polymer (C) contains at least 20 % by weight fluorine.
References Cited (Backward Citations)
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