WO1993000391A1 - Revetements polymeres - Google Patents

Revetements polymeres Download PDF

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Publication number
WO1993000391A1
WO1993000391A1 PCT/GB1992/000901 GB9200901W WO9300391A1 WO 1993000391 A1 WO1993000391 A1 WO 1993000391A1 GB 9200901 W GB9200901 W GB 9200901W WO 9300391 A1 WO9300391 A1 WO 9300391A1
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WO
WIPO (PCT)
Prior art keywords
polymer
peo
coating
groups
ppo
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Application number
PCT/GB1992/000901
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English (en)
Inventor
Ajay Kumar Luthra
Shivpal Singh Sandhu
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Biointeractions Limited
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Filing date
Publication date
Application filed by Biointeractions Limited filed Critical Biointeractions Limited
Priority to EP92909814A priority Critical patent/EP0591233A1/fr
Priority to JP4509265A priority patent/JPH06508645A/ja
Publication of WO1993000391A1 publication Critical patent/WO1993000391A1/fr
Priority to GB9325786A priority patent/GB2273102A/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses

Definitions

  • This invention relates to the field of polymer coatings. More specifically, it is concerned with coating polymers on to substrates, and embraces methods of coating substrates with polymers, substrates which have been coated by means of the invention, and such coated substrates in the form of contact lenses for the human (or indeed mammalian) eye. Furthermore, to the extent that classes of coating polymer disclosed herein are novel, they and the methods of making them are also within the.scope of the invention.
  • contact lenses can be made from a wide variety of materials, provided that they meet the necessary requirements for optical clarity, formability and shape stability, non-irritation to the eye, and so on.
  • contact lenses tend to be made from certain presently preferred materials, including polymers of hydroxyethylmethacrylate (HEMA) and N-vinylpyrrolidone. While these polymerised monomers may make up the bulk of the lens material, say 98%, small amounts of cross-linking agents, such as 2% of ethyl dimethacrylate and 2% of methacrylic acid, may be copolymerised.
  • the lens structure includes voids which are occupied with water, which may make up from typically 38%, up to 60 or 70%, of the total lens weight.
  • Hydrophilic contact lenses display an affinity for tear calcium and proteins, especially lysozyme, amino acids and glycoproteins, and these readily adhere to the lens surface. It is generally known and accepted that such deposits on contact lenses may cause a decrease in wearing comfort leading to a corresponding decrease in wearing time. Deposits may cause patient's eyes to become infected and it is not uncommon for a subsequent decrease in visual acuity to occur.
  • contact lens care systems have been devised and used for cleaning and disinfecting lenses. Contact lenses with deposits resulting from tear ingredients are usually cleaned with a surfactant cleaner on a daily basis. Soft contact lenses are cleaned additionally with an enzymatic cleaner to remove protein deposits thoroughly. However, even when contact lenses are repeatedly put on and taken off over a period of several months, tear components are sometimes absorbed/adsorbed on the contact lens surface despite use of cleaners.
  • Soft and hard contact lenses carrying an anionic charge can be co plexed with polymers bearing a cationic charge to form a polyelectrolyte complex which reduces the tendency for tear proteins to adhere to a lens surface.
  • the interaction between the cationic polymer and the anionic surface of the lens is generally weak, and dissipation of the cationic polymer occurs rapidly in most prior art constructions.
  • tear proteins are deposited on the lens, and the wearer begins to feel discomfort and must clean the contact lens before rewetting the lens surface with the cationic polymer to form another protective polyelectrolyte complex.
  • the invention provides a method of coating a polymeric substrate having functional groups in the substrate polymer chain at surface portions thereof which comprises reacting said functional groups with complementary functional groups on a hydrophilic coating polymer in a predominantly aqueous medium to form covalent linkages between the coating polymer and the substrate polymer.
  • the conditions should be such as to avoid degradation of either polymer.
  • the coating polymer may be in solution or dispersion in the aqueous reaction medium.
  • the substrate polymer may advantageously be a hydrogel, that is to say a gel in which the liquid is water.
  • the coating formed on the substrate polymer is also preferably a hydrogel.
  • the coating is desirably continuous. 5
  • the invention provides a method of rendering a contact lens that has functional groups (most suitably hydroxyl, carboxyl, amide, amino and sulphonate groups) more compatible with the eye by covalently bonding a polymer to the 0 surface of the lens, which enhances the hydrophilic character of the lens for a longer time relative to an untreated surface, and which reduces the tendency for tear proteins to adhere to the lens surface.
  • the preferred coating polymers are those that form a covalently bound hydrogel at the lens surface, which absorbs water, i 5 his good water retention and is compatible with the physiological structure of the eye.
  • a durable protective coating is formed which provides long lasting comfort to the eye.
  • the most suitable coatings are hydrophilic and are more resistant to protein deposition than the substrate polymer. Desirable coatings also 20 reduce the deposition of lipids and of ions, such as calcium ions.
  • the invention also extends, in another aspect, to a substrate polymer coated by the foregoing method, and in particular to a contact lens so coated.
  • the invention accordingly provides a contact lens, which may comprise a soft or hard contact lens polymer, synthetic or natural, forming the corrective optical element of the lens, having a coating suitable for use in the human eye, wherein the coating 0 comprises a polymer that is covalently bonded to the surface of the lens polymer, thus forming a thin protective layer or coating covalently linked to the lens surface.
  • a soft or hard contact lens comprises a 5 polymer containing functional groups such as hydroxyl, carboxyl, amide, amino or sulphonic acid, on to which the polymer coating can be chemically bonded.
  • the functional groups may carry an ionic charge or may have the potential of carrying an ionic charge, for example ions formally derivable by the gain or loss of a proton or electron, or equivalent. Accordingly, references to carboxyl • groups and to sulphonic acid groups include carboxylate and sulphonate anions, for example.
  • suitable substrate materials include the following polymers with surface functional groups.
  • Soft hydrophilic contact lens polymer substrates may be crosslinked hydroxyethylmethacrylate (HEMA), crosslinked HEMA and methacrylic acid, and crosslinked HEMA and N-vinylpyrrolidone.
  • HEMA hydroxyethylmethacrylate
  • methacrylic acid crosslinked HEMA and methacrylic acid
  • N-vinylpyrrolidone crosslinked HEMA and N-vinylpyrrolidone
  • Contact lenses made from natural polymers include cellulose acetate butyrate polymers (retaining free hydroxyl groups).
  • Contact lenses made from synthetic polymers include polyvinyl alcohol (retaining free hydroxyl groups).
  • oxygen permeable hard contact lens polymer substrates include polyfluoroacrylate, polysiloxanyl acrylate and methacrylate polymers, which carry an ionic charge, or retain free hydroxyl groups.
  • the invention does however extend to the coating of many other polymer substrates with suitable surface functional groups, including those used as contact lens materials, as are well known in the art.
  • water soluble hydrophilic polymers when covalently bonded to the surface of soft or hard contact lenses provide a hydrophilic surface which reduces the tendency for tear proteins to adhere to a lens surface.
  • These water soluble hydrophilic polymers can be non-ionic and cationic synthetic or natural polymers.
  • Preferred types of covalent bonding between the respective functional groups on the substrate polymer and the coating polymer include, but are not limited to, carbonate bonding with hydroxyl functional groups on the substrate, ester bonding with carboxyl groups, urethane bonding with amino groups, sulphonic ester bonding with sulphonic acid groups, ether or ester linkages with epoxide groups, urea with hydroxyl groups to form carbamate ester and urea with lens surface carboxyl groups to form acyl carbamate, and amide bonding between an amine and lens carboxyl groups.
  • the reactions between the respective functional groups have as a comnon feature that they all take place in aqueous media under relatively mild conditions to bind the coating polymer to the substrate surface without degrading either polymer.
  • covalent bonding between functional groups on the respective polymers include amide, urea, allophanate, biuret, acyl urea and carbodiimide linkages.
  • Hydrophilic synthetic non-ionic polymers useful as the covalently bound coating polymer include homopolymers, copolymers and graft copolymers of polyvinylalcohol (PVA), homopolymers of polyethylene oxide (PEO) and polypropylene oxide (PPO), copolymers of poly ⁇ ethylene oxide and polypropylene oxide, and graft copolymers of siloxanes and polyethylene oxide or polypropylene oxide.
  • Hydro ⁇ philic natural polymers useful as the covalently bound coating polymer include homopolymers, copolymers and graft copolymers of cellulose and its derivatives, chitin and chitosan. The following examples of different kinds of polymer are suitable as the coating agent to be covalently bound to the substrate.
  • Polyvinyl alcohol can be covalently bonded to the surface of soft and oxygen permeable hard contact lens to provide a permanent hydrophilic coating which reduces the tendency for tear proteins to adhere to the lens surface.
  • PVA can be covalently bonded to the surface of a contact lens using conventional water soluble coupling agents or by linking epoxide functionalities on PVA by which it can then be linked to the lens surface.
  • PVA can be grafted with polyethylene oxide (PEO) or polypropylene oxide (PPO) or a mixture of the two.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • the graft copolymers can then be covalently bonded to the lens surface using conventional chemistry.
  • PEO and PPO may have the structures shown in Formulae (1) and (2) below :
  • Compounds in which at least o e of X and Y is -0-C0-(CH2) n -NH2 are novel.
  • Molecular weights of (1) and (2) can vary from less than 100 up to 20,000.
  • Suitable graft copolymers of PVA and PEO, and of PVA and PPO can also be achieved by reacting PVA with ethylene oxide and propylene oxide respectively, or with a mixture of ethylene oxide and propylene oxide to obtain PVA graft copolymer containing both PEO and PPO.
  • ethylene oxide and propylene oxide instead of ethylene oxide and propylene oxide, ethylene carbonate and propylene carbonate can be used to achieve the same result.
  • the above graft copolymers can then be covalently bonded to the lens surface using conventional chemistry.
  • Polydimethylsiloxanes can be grafted with (1) or (2) or both through a hydrosilation reaction to form a coating polymer.
  • X may be acrylate or methacrylate and Y can be OH, epoxide, -0-CH 2 -CH(NH 2 )-CH 3 , or -0-C0-(CH 2 ) n -NH 2 (where n is from 0 5 to 6).
  • glycidyl acrylates (GA), glycidyl methacylates (GM), epoxypropyl acrylate (EPA) and epoxypropyl methacrylate (EPM) may 10 also be grafted, to form a range of novel coating polymers.
  • GA glycidyl acrylates
  • GM glycidyl methacylates
  • EPA epoxypropyl acrylate
  • EPM epoxypropyl methacrylate
  • novel polydimethylsiloxane graft copolymers have the following general formula:
  • the coefficients x, y and n can vary to give molecular weights in a broad range of 3000 to 100,000.
  • the above water soluble hydrophilic polymers may be covalently bonded to the lens surface using conventional chemistry.
  • Ethylene oxide and propylene oxide can react with cellulose to 25 produce graft copolymers of PEO-cellulose and PPO-cellulose, or a mixture of ethylene oxide and propylene oxide may be used to give PEO/PPO-cellulose graft copolymer.
  • the same result can also be achieved by using ethylene carbonate and propylene carbonate.
  • Analo ⁇ ous results are achieved with hydroxyethyl cellulose in place 30 of c € lose
  • (1) and (2) can be grafted on to hydroxyethyl- cellulose and then covalently bonded to the surface of the contact lens.
  • Hydroxyethyl cellulose can also have epoxide functionalities through which it can be covalently bonded using conventional water soluble coupling agents.
  • Chitin and chitosan can also be grafted with PEO and PPO using ethylene oxide and propylene oxide or a mixture of both to form a further range of novel coating polymers.
  • the graft copolymers may then be covalently bonded to the lens surface.
  • Soft and oxygen permeable hard contact lenses can also be made more resistant to tear protein deposition by directly polymerising ethylene oxide or propylene oxide or a mixture of the two on to the contact lens.
  • PEO and/or PPO may be grafted directly on to the lens surface.
  • the same results can be achieved 5 by using ethylene carbonate and/or propylene carbonate instead of ethylene and propylene oxides.
  • Homopolymers of (1) and (2) can also be used to covalently bond to the contact lens surface to provide a hydrophilic coating which 0 reduces the tendency of tear proteins to deposit on to the lens surface.
  • X can be either acrylate or methacrylate and Y can be OH, COOH, epoxide, 0CH , OC2H5, propoxy, 5 butoxy, allyloxy, -0-CH 2 -CH(NH 2 )-CH 3 , or -0-C0-(CH 2 ) n -NH 2 (where n is from 0 to 6).
  • the presence of the vinyl double bond when X is acrylate or methacrylate enables the molecule to be homopolymerised ® to produce polymers with pendant OH, COOH, epoxide, 0CH 3 , OC2H5, propoxy, butoxy, allyloxy, -0-CH 2 -CH(NH 2 )-CH 3 , or -0-C0-(CH 2 ) n -NH 2 , or a mixture of pendant groups.
  • X is acrylate and Y is OH is polymerised then all pendant groups will be OH.
  • a mixture of two pendant groups is achieved.
  • the mixture need not be limited to a mixture of two pendant groups, but can be more than two.
  • (1) and (2) can be copolymerised when X is either methacrylate or acrylate and Y for both (1) and (2) can be the same or different groups.
  • Both (1) and (2) can also be copolymerised with a variety of unsaturated monomers when X for (1) and (2) is either methacrylate or acrylate and Y can be any of OH, COOH, epoxide, 0CH 3 , OC2H5, propoxy, butoxy, allyloxy, -0-CH2-CH(NH )-CH 3 , and -0-C0-(CH ) n -NH2.
  • Suitable unsaturated monomers for co- polymerisation include vinylene carbonate, hydroxyethylmethacry ⁇ late, hydroxypropylmethacrylate, hydroxyethyl acrylate, hydroxypropylacryl te, n-vinylpyrrolidone, acrylamide, hydroxybutylacrylate, hydroxybutylmethacrylate, butylacrylamide, dihydroxypropylacrylate, dihydroxypropylmethacrylate, epoxypropyl- acrylate, epoxypropylmethacrylate, glycidyl acrylate, glycidyl methacrylate, and hydroxypropylmethacrylamide.
  • Synthetic cationic polymers which can be covalently bonded to the lens surface include cationic PVA, and copolymers of polyethylene oxide and polypropylene oxide.
  • X may be acrylate or methacrylate and Y can be OH, epoxide, -0-CH 2 -CH(NH 2 )-CH 3 , or -0-C0-(CH 2 ) n -NH 2 (where n is from 0 to 6).
  • (1) and (2) can then be copolymerised with :
  • (b) other cationic polymerisable monomers which include : dimethylaminoethyl acrylate and methacrylate, 2-methacryloyl- oxyethyltrimethylammonium chloride, 3-methac ⁇ ylamidopropyl di ethylamine, 3-methacrylamidopropyl trimethylammonium chloride, 1-vinyl and 2-methyl 1-vinylimidazole, 3-acrylamido-3-methylbutyl- dimethylamine, 3-acrylamido-3-methylbutyl trimethylammonium chloride, N-(3-methacryloyloxy-2-hydroxypropyl) trimethylammonium chloride, diallyldimethylammonium chloride and methylsulphate, vinylbenzyltrimethylammonium chloride.
  • all grafting monomers given in (a) and (b) above may also be used to provide cationic graft copolymers of polydimethylsiloxanes.
  • Cationic natural polymers which may be covalently bonded to a substrate such as a lens surface include cationic cellulose and chitosan.
  • the copolymer was dissolved in anhydrous dimethylsulphoxide (DMSO).
  • DMSO dimethylsulphoxide
  • 5 CDI 3.3g was dissolved in DMSO and added dropwise over a period of one hour. The solution was further stirred for one hour before the DMSO was distilled off under reduced pressure.
  • lysozyme comprises only 18 per cent of the total tear proteins, it appears to be selectively absorbed and denatured on 5 the surfaces of soft hydrophilic lenses.
  • Lysozyme absorption studies were carried out by incubating the lens in 5ml of lysozyme solution for approximately twenty-four hours. 0.05% w/v lysozyme was dissolved in PBS. After twenty-four hours 0 the lysozyme solution was measured spectrophotometrically at 281.6nm. Control solutions contained untreated contact lenses.
  • X is OH and Y -0CH 3 .
  • PEO molecular weight ranged from 300 to 5000.
  • Example 2 the PEO was activated with CDI (mole ratio 1:1) in acetone and reacted with PVA in 40mM potassium bicarbonate buffer (pH 8.5) for twenty-four hours. The solution was next dialysed for twenty-four hours, then the resultant PVA-PEO graft copolymer was freeze dried.
  • CDI mole ratio 1:1
  • 40mM potassium bicarbonate buffer pH 8.5
  • copolymer was dissolved in anhydrous acetone.
  • CDI (3.3g) was dissolved in acetone and added dropwise over a period of one hour. The solution was further stirred for one hour before the acetone was distilled off under reduced pressure.
  • Example 2 three high water content polyHEMA contact lenses were treated with 150mg of the CDI-activated PVA-PEO graft copolymer.
  • the graft copolymer was linked to surface OH groups via a carbonate linkage and to surface COOH groups via an ester linkage.
  • Lysozyme absorption studies showed that after treatment there was a 90% reduction in lysozyme absorption relative to the control untreated lens.
  • PV0-PE0 graft copolymers were synthesised as in Example 2.
  • the graft copolymer was linked to the lens surface using a water soluble carbodiimide (l-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride) (EDC).
  • EDC water soluble carbodiimide
  • Lysozyme absorption studies showed that after treatment there was a 90% reduction in lysozyme absorption relative to the control.
  • the resultant graft copolymer of PVA-PEO was either dissolved in 100ml anhydrous acetone or anhydrous DMSO to which was added 3.3g CDI dissolved in either acetone or DMSO over a period of one hour. The solution was left stirring for another hour and then the solvent was removed under reduced pressure.
  • Example 2 three high water content polyHEMA contact lenses were treated with 150mg of the CDI-activated PVA-PEO graft copolymer.
  • the graft copolymer was linked to surface OH groups via a carbonate bond and to surface COOH groups via an ester linkage.
  • Soft high water content polyHEMA lenses (as in Example 1) were incubated with 150mg of the polymer.
  • the graft copolymer was 5 covalently bonded to the lens surface.
  • the graft copolymer formed a carbonate bond with surface OH groups and an ester linkage with surface COOH.
  • Protein absorption studies showed a 95% reduction in lysozyme 20 absorption relative to untreated contact lenses.
  • PEO molecular weights ranged from 350-2500 and the overall graft copolymer molecular weight of polydimethylsiloxanes and PEO ranged from 4000-30,000. All or half PEO hydroxyl groups were activated on the polymers with CDI in acetone, before linking to the lens surface took place in potassium bicarbonate buffer. The PEO n hydroxyl groups which were activated with CDI reacted with the lens surface hydroxyl groups to form a carbonate bond and also formed ester l inkages with surface COOH groups.
  • the cocktail contained one contact lens in 5ml distilled water with 250mg graft copolymer and 0.5ml Lewis acid. The solution was left at room temperature for twenty-four hours.
  • the graft copolymer was covalently bound to the lens surface via the epoxide group on the glycidylacrylate.
  • the epoxide formed an ether linkage with surface OH groups and an ester linkage with surface COOH groups.
  • the lenses were washed and assayed for protein absorption. There was an 85% reduction in protein absorption relative to the untreated lens.
  • Hydroxyethylcellulose was reacted with ethylene oxide (as in Example 3).
  • the reactior of ethylene oxide with hydroxyethyl- cellulose was stopped wht.i the polymer completely dissolved in acetone.
  • the polymer was activated with CDI in acetone and the acetone was removed under reduced pressure.
  • 200mg of the CDI activated PEO-cellulose was incubated with high water content polyHEMA contact lenses (as in Example 1) and oxygen permeable hard contact lenses (polysiloxanyl methacrylate copolymerised with methacrylic add) for twenty-four hours.
  • the coating polymer formed a hydrophilic coating chemically bonded to the lens surface.
  • the chemical bond was a carbonate bond with lens surface OH groups and an ester linkage with surface COOH for both polyHEMA and the oxygen permeable hard lenses.
  • the lenses were tested for lysozyme absorption. Greater than 90% reduction in lysozyme absorption was observed for both types of lenses.
  • High water content polyHEMA and oxygen permeable hard contact lenses were placed in vials.
  • 5ml distilled water was added and 250mg ethylene carbonate.
  • Potassium carbonate (50mg) was added and the solution warmed to ca. 60°C for two hours.
  • Ethylene carbonate reacted with the lens surface to form polyethylene oxide polymer on both lens types.
  • the initial bond with the lens surface is dependent on the functional group present. If OH is present, the initial bond is an ether linkage, and if COOH is present, then an initial ester bond is formed.
  • the lenses were washed and tested for lysozyme absorption. Greater than 90% reduction in protein absorption was observed for the treated lenses when compared to control untreated lenses,
  • X is OH and Y -0CH 3 .
  • PEO polymers of molecular weights between 200 and 5000 were used, including molecular weights of 200, 350, 550, 750, 1000, 2000 and 5000.
  • CDI was dissolved in anhydrous acetone.
  • PEO was also dissolved in anhydrous acetone and placed in a dry dropping funnel. The PEO was added dropwise to the CDI over a period of one hour. The solution was left to stir for a further one hour, after which the acetone was evaporated off under reduced pressure. Mole ratio 1:1 was used to obtain CDI-activated PEO polymer.
  • Example 2 three high water content polyHEMA contact lenses were treated with 200mg of the CDI-activated PEO polymer.
  • the polymer was linked to surface OH groups via a carbonate linkage and to surface COOH groups via an ester linkage.
  • Lysozyme and albumin absorption studies showed that after treatment there was 90% reduction in lysozyme and albumin absorption relative to the control untreated lens.
  • X is OH and Y is (a) OH and (b) -0CH 3 .
  • PEO polymers with molecular weights of between 200 and 20000 were used, including 200, 550, 750, 1000, 2000, 5000, 10000 and 20000.
  • Example 3 three high water content contact lenses were each placed in 5ml distilled water (pH 6) containing 20mg EDC and incubated at room temperature for six hours. To this solution 400mg PEO polymer was added and the temperature of the solution was gradually raised to 80°C over a period of one hour and maintained at 80°C for two hours.
  • the polymer was linked to the lens surface COOH groups via an e er linkage.
  • Molecular weights of the PEO polymer varied from 200 to 10000.
  • Example 10 the PEO polymer was activated with CDI and reacted with three high water content polyHEMA contact lenses and three oxygen permeable hard contact lenses (as in Example 8).
  • the chemical bond was a urethane linkage with lens surface OH groups and an amide linkage with surface COOH for both polyHEMA and the oxygen permeable hard lens.
  • the lenses were tested for both lysozyme and albumin absorption. Greater than 90% reduction in lysozyme and albumin was observed for both types of lenses.
  • EDC was used to couple the PEO polymer to the lens COOH groups, but instead of forming an ester linkage (as in Example 3) an amide bond was formed.
  • Y is (a) OH, (b) -0CH 3 and (c) -0-C-NH 2
  • Molecular weights of the PEO polymer varied from 200 to 20000.
  • the above polymer is formed by reacting a PEO polymer (Formula 1) where X is OH and Y is OH or -0CH 3 with urea. PEO polymer and urea are refluxed for six hours in an organic solvent (dioxane or toluene).
  • the organic solvent is removed under reduced pressure.
  • the resultant PEO polymer is then linked to the surface of the contact lens either by using CDI (as in Example 10) or by using EDC (as in Example 3).
  • CDI the chemical bond formed with lens surface OH groups was a carbamate ester and an acyl carbamate with lens COOH groups.
  • EDC the bond formed is also a carbamate ester with lens COOH groups.
  • Lysozyme studies showed that after treatment there was a 90% reduction in lysozyme absorption relative to the control untreated lens.
  • X is methacrylate and Y is OH.
  • Molecular weight of PEO polymer can vary between 200 and 2000.
  • PEO polymer was homo-polymerised in water. 90 wt% distilled water was de-gassed and purged with nitrogen for half an hour and then heated to 80°C. PEO polymer (10 wt%) containing 230mg potassium persulphate (dissolved in 2ml distilled water) was added slowly to the heated water (under nitrogen) over a period of fifteen minutes. The reaction was allowed to continue for one hour. The polymer was then dialysed for twenty-four hours and freeze dried.
  • X is methacrylate and Y is -0CH 3 .
  • Molecular weight of PEO polymer can vary between 200 and 5000.
  • the polymers were then linked to the surface of polyHEMA high water content contact lenses either by using CDI (as in Example 10) or by using EDC (as in Example 3).
  • CDI the chemical bond was a carbamate ester with lens surface OH groups and an acyl carbamate with surface COOH groups.
  • EDC the chemical bond was also an acyl carbamate with surface COOH groups.
  • the mole % of acrylamide varied between 10 and 90 mol% in the above polymerisation mixtures.
  • the polymers were linked to the surface of polyHEMA high water content contact lenses either by using CDI (as in Example 10) or by using EDC (as in Example 3).
  • CDI the chemical bond was a carbonate bond between polymer OH groups and lens surface OH groups or a carbamate ester with acrylamide or methacrylamide.
  • An ester bond was formed between polymer OH groups and lens surface COOH groups or an acyl carbamate with acrylamide or methacrylamide.
  • EDC the chemical bond was either an ester between polymer OH groups and lens surface COOH groups or an acyl carbamate with acrylamide or methacrylamide with lens surface COOH groups.
  • Lysozyme and albumin studies showed that after treatment there was a 95% reduction in lysozyme and albumin absorption relative to the control untreated lens.
  • Vinylene carbonate (mol% 20, 40 and 60) was copolymerised (as in Example 15) with PEO polymer Formula (1), where X is methacrylate and Y is -0CH 3 , molecular weight 350.
  • vinylene carbonate (mol% 20, 40 and 60) was copolymerised with other molecular weight PEO polymers of the above structure (eg 550, 750, 1000 and 2000).
  • Vinylene carbonate (mol% 20, 40 and 60) was also copolymerised with PEO polymer Formula (1), where X is methacrylate and Y is OH, molecular weight 350.
  • the above polymers were dialysed for twenty-four hours and freeze dried.
  • the polymers were linked to the lens surface OH groups via an ether linkage and to the lens COOH groups via an ester linkage,
  • Lysozyme and albumin studies showed that after treatment there was an 85% reduction in lysozyme and albumin absorption relative to the control untreated lens
  • Glycidyl methacrylate (mol% 20, 40 and 60) was copolymerised (as 1n Example 15) with PEO polymer Formula (1), where X is methacrylate and Y is -0CH 3 , molecular weight 350.
  • glycidyl methacrylate (mol% 20, 40 and 60) was copolymerised with other molecular weight PEO polymers of the above structure (eg molecular weights 550, 750, 1000 and 2000).
  • Glycidyl methacrylate (mol% 20, 40 and 60) was also copolymerised with PEO polymer Formula (1), where X is methacrylate and Y is OH molecular weights 350 and 550.
  • the above polymers were dialysed for twenty-four hours and freeze dried. Polymerisation reactions of the above copolymers were also carried out in organic solvents such as toluene under nitrogen using VAZ0 67 (du Pont) as catalyst. The mixtures were allowed to reflux for twenty-four hours, after which the solvent was removed under reduced pressure.
  • Lysozyme studies showed that after treatment there was an 85% reduction in lysozyme absorption relative to the control untreated lens.
  • N-vinyl pyrrolidone (mol% 20, 40 and 60) was copolymerised (as in Example 15) with PEO polymer - Formula (1), where X is methacrylate and Y is -0CH 3 , molecular weight 350.
  • N-vinyl pyrrolidone (mol% 20, 40 and 60) was copolymerised with other molecular weight PEO polymers of the above structure (eg molecular weights 550 and 750).
  • the above polymers were dialysed for twenty-four hours and freeze dried.
  • the polymers were then linked to the surface of polyHEMA high water content contact lenses either by using CDI (as in Example 10) or by using EDC (as in Example 3).
  • CDI the chemical bond was a carbonate with lens surface OH groups and an ester with surface COOH groups.
  • EDC the chemical bond was an ester with surface COOH groups.
  • Lysozyme studies showed that after treatment there was an 80% reduction in lysozyme absorption relative to the control untreated lens.
  • HEMA Hydroxyethylmethacrylate
  • polymers were then linked to the surface of polyHEMA high water content contact lenses either by using CDI (as in Example 10) or by using EDC (as in Example 3).
  • CDI the chemical bond was a carbonate with lens surface OH groups and an ester with surface COOH groups.
  • EDC the chemical bond was an ester with surface COOH groups. Lysozy e studies showed that after treatment there was an 85% reduction in lysozyme absorption relative to the control untreated lens.
  • 2-methacryloyloxyethyltrimethylammonium chloride (mol% 10, 20 and 30) was copolymerised (as in Example 15) with PEO polymer - Formula 0 (1), where X is methacrylate and Y is OH (molecular weight 350).
  • the above cationic monomer was copolymerised with other molecular weight PEO polymers of the above structure (eg molecular weights 550 and 750).
  • the cationic monomer was also copolymerised with 40mol% PEO polymer - Formula (1), where X is methacrylate and Y is OH (molecular weight 350) and 30mol% PEO polymer - Formula (1), where X is methacrylate and Y is -0CH (molecular weight 2000).
  • the above copolymers were dialysed for twenty-four hours and freeze dried.
  • the polymers were then linked to the surface of polyHEMA high water content contact lenses by using EDC (as in Example 3).
  • the chemical bond was an ester with surface COOH groups.
  • Cationic PVA molecular weight 25000 (200mg) was linked to the surface of a polyHEMA high water content contact lens by using EDC (as in Example 3).
  • the chemical bond was an ester with surface COOH groups.
  • Lysozyme studies showed that after treatment there was an 80% reduction in lysozyme absorption relative to the control untreated lens.
  • Cationic cellulose (molecular weight 50000) was linked to the surface of a polyHEMA contact lens in an identical fashion to that in Example 23, and similar reductions in lysozyme absorption were observed relative to the untreated control.

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Abstract

Procédé de revêtement de substrats polymères,principalement de lentilles de contact, mettant en réaction des groupes fonctionnels sur la surface polymère d'un substrat avec des groupes fonctionnels complémentaires sur un polymère de revêtement hydrophile dans un milieu aqueux pour former des liaisons covalentes entre les deux polymères. Les deux polymères sont de préférence des hydrogels. Des groupes fonctionnels adaptés présentent des groupes hydroxyle, carboxyle, amino et sulphonate. Le revêtement améliore le caractère hydrophile de la lentille sur une durée plus longue par rapport à une surface non traitée, et réduit la tendance des protéines des larmes à adhérer à la surface de la lentille. Les polymères de revêtement comprennent principalement, parmi d'autres, des polymères d'oxyde de polyéthylène et d'oxyde de polypropylène à fonctionnalité libre, des copolymères greffés de polydiméthylsiloxane présentant des fractions copolymères d'oxyde de polyéthylène, d'oxyde de polypropylène, d'acrylate de glycidyle, de méthacylate de glycidyle, d'acrylate d'époxypropyle, ou de méthacrylate d'époxypropyle, et des copolymères greffés de chitine et de chitosan avec des polymères d'oxyde de polyéthylène et de polypropylène.
PCT/GB1992/000901 1991-06-27 1992-05-18 Revetements polymeres WO1993000391A1 (fr)

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EP92909814A EP0591233A1 (fr) 1991-06-27 1992-05-18 Revetements polymeres
JP4509265A JPH06508645A (ja) 1991-06-27 1992-05-18 ポリマー被覆物
GB9325786A GB2273102A (en) 1991-06-27 1993-12-16 Polymer coating

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GB919113875A GB9113875D0 (en) 1991-06-27 1991-06-27 Polymer coatings

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EP1566398A1 (fr) * 2004-02-19 2005-08-24 Dai-Ichi Kogyo Seiyaku Co., Ltd. Séchage de résines non-ioniques, solubles dans l'eau de type alkylene oxide, leur emballage et leur transport
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WO2013001096A1 (fr) 2011-06-30 2013-01-03 Dsm Ip Assets B.V. Monomère contenant de la silicone
US8480227B2 (en) 2010-07-30 2013-07-09 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
WO2014177871A1 (fr) 2013-04-30 2014-11-06 Coopervision International Holding Company, Lp Lentilles de contact en hydrogel de silicone aminé primaire et compositions et procédés apparentés
US9005700B2 (en) 2011-10-12 2015-04-14 Novartis Ag Method for making UV-absorbing ophthalmic lenses
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US9377562B2 (en) 2011-08-17 2016-06-28 Toray Industries, Inc. Medical device, and method for producing same
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US9511089B2 (en) 2004-11-22 2016-12-06 Johnson & Johnson Vision Care, Inc. Ophthalmic compositions comprising polyether substituted polymers
US9708087B2 (en) 2013-12-17 2017-07-18 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
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US7160953B2 (en) 1991-07-05 2007-01-09 Biocompatibles Uk Limited Polymeric surface coatings
US5783650A (en) * 1991-07-05 1998-07-21 Biocompatibles Limited Polymeric surface coatings
US5648442A (en) * 1991-07-05 1997-07-15 Biocompatibles Limited Polymeric surface coatings
US5705583A (en) * 1991-07-05 1998-01-06 Biocompatibles Limited Polymeric surface coatings
US5453467A (en) * 1991-08-30 1995-09-26 Biocompatibles Limited Polymer treatments
WO1994028443A1 (fr) * 1993-05-21 1994-12-08 Allergan, Inc. Amelioration des proprietes hydrophiles de polymeres de silicone
WO1995016475A1 (fr) * 1993-12-14 1995-06-22 University Of Washington Lentilles intraoculaires recouvertes d'oxyde de polyethylene
US5618316A (en) * 1993-12-14 1997-04-08 Hoffman; Allan S. Polyethylene oxide coated intraocular lens
EP0699926A1 (fr) * 1994-03-18 1996-03-06 Nikon Corporation Lentille en matiere plastique et composition pour couche de base
EP0699926B1 (fr) * 1994-03-18 2002-12-04 Nikon Corporation Lentille en matiere plastique avc une couche de base
WO1996014887A1 (fr) * 1994-11-16 1996-05-23 Alcon Laboratories, Inc. Revetements a base d'oxyde de polyethylene reticule destines a ameliorer la compatibilite biologique d'appareils medicaux destines a etre implantes
EP0713106A1 (fr) * 1994-11-17 1996-05-22 Menicon Co., Ltd. Lentilles de contact perméables à l'oxygène ayant une surface hydrophile et procédé de fabrication
US5708050A (en) * 1994-11-17 1998-01-13 Menicon Co., Ltd. Oxygen permeable contact lens having high durable hydrophilic surface and method for producing the same
US5910518A (en) * 1994-11-17 1999-06-08 Menicon Co., Ltd. Oxygen permeable contact lens having high durable hydrophilic surface and method for producing the same
EP1154287A3 (fr) * 1994-11-17 2002-02-13 Menicon Co., Ltd. Lentilles de contact perméables à l'oxygène ayant une surface hydrophile et procédé de fabrication
EP1154287A2 (fr) * 1994-11-17 2001-11-14 Menicon Co., Ltd. Lentilles de contact perméables à l'oxygène ayant une surface hydrophile et procédé de fabrication
US6500481B1 (en) 1998-06-11 2002-12-31 Johnson & Johnson Vision Care, Inc. Biomedical devices with amid-containing coatings
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US6838491B1 (en) 1998-06-11 2005-01-04 Johnson & Johnson Vision Care, Inc. Biomedical devices with hydrophilic coatings
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WO2001027662A1 (fr) * 1999-10-12 2001-04-19 Johnson & Johnson Vision Care, Inc. Procede de fabrication et de selection d'un revetement de lentille de contact
CN1313842C (zh) * 1999-10-12 2007-05-02 庄臣及庄臣视力保护公司 接触透镜涂层选择及其制造工艺
US6858310B2 (en) 2000-04-03 2005-02-22 Bausch & Lomb Incorporated Renewable surface treatment of silicone medical devices with reactive hydrophilic polymers
US6599559B1 (en) * 2000-04-03 2003-07-29 Bausch & Lomb Incorporated Renewable surface treatment of silicone medical devices with reactive hydrophilic polymers
JP2002047365A (ja) * 2000-05-10 2002-02-12 Toray Ind Inc 表面処理プラスチック成形品の製造方法
US6638563B2 (en) * 2000-09-19 2003-10-28 Bausch & Lomb Incorporated Method for applying renewable polymeric lens coating
GB2371304A (en) * 2001-01-16 2002-07-24 Suisse Electronique Microtech Surface passivation of organic polymers and elastomers
US8017665B2 (en) 2002-01-14 2011-09-13 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing heterocyclic compounds and methods for their production
US7173073B2 (en) 2002-01-14 2007-02-06 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing heterocyclic compounds and methods for their production
US7767730B2 (en) 2002-01-14 2010-08-03 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing heterocyclic compounds and methods for their production
WO2003095171A1 (fr) * 2002-05-13 2003-11-20 Novartis Ag Pretraitement de moules de lentilles de contact
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EP1566398A1 (fr) * 2004-02-19 2005-08-24 Dai-Ichi Kogyo Seiyaku Co., Ltd. Séchage de résines non-ioniques, solubles dans l'eau de type alkylene oxide, leur emballage et leur transport
US10441533B2 (en) 2004-11-22 2019-10-15 Johnson & Johnson Vision Care, Inc. Ophthalmic compositions comprising polyether substituted polymers
US9849081B2 (en) 2004-11-22 2017-12-26 Johnson & Johnson Vision Care, Inc. Ophthalmic compositions comprising polyether substituted polymers
US9606263B2 (en) 2004-11-22 2017-03-28 Johnson & Johnson Vision Care, Inc. Ophthalmic compositions comprising polyether substituted polymers
US9511089B2 (en) 2004-11-22 2016-12-06 Johnson & Johnson Vision Care, Inc. Ophthalmic compositions comprising polyether substituted polymers
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US8944592B2 (en) 2010-07-30 2015-02-03 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
US10920102B2 (en) 2010-07-30 2021-02-16 Alcon Inc. Silicone hydrogel lens with a crosslinked hydrophilic coating
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US9244200B2 (en) 2010-07-30 2016-01-26 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
US8939577B2 (en) 2010-07-30 2015-01-27 Novartis Ag Silicone hydrogel lenses with water-rich surfaces
US10781340B2 (en) 2010-07-30 2020-09-22 Alcon Inc. Silicone hydrogel lenses with water-rich surfaces
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US9507173B2 (en) 2010-07-30 2016-11-29 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
US9738813B2 (en) 2010-07-30 2017-08-22 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
US8529057B2 (en) 2010-07-30 2013-09-10 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
WO2013001096A1 (fr) 2011-06-30 2013-01-03 Dsm Ip Assets B.V. Monomère contenant de la silicone
US9377562B2 (en) 2011-08-17 2016-06-28 Toray Industries, Inc. Medical device, and method for producing same
US9778488B2 (en) 2011-08-17 2017-10-03 Toray Industries, Inc. Medical device and method for producing the same
US9005700B2 (en) 2011-10-12 2015-04-14 Novartis Ag Method for making UV-absorbing ophthalmic lenses
US10222509B2 (en) 2011-11-15 2019-03-05 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
US9395468B2 (en) 2012-08-27 2016-07-19 Ocular Dynamics, Llc Contact lens with a hydrophilic layer
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GB2273102A (en) 1994-06-08
GB9325786D0 (en) 1994-03-02
EP0591233A1 (fr) 1994-04-13
JPH06508645A (ja) 1994-09-29
GB9113875D0 (en) 1991-08-14
AU1740792A (en) 1993-01-25

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