EP1109846A1 - Matieres pour lentilles de contact - Google Patents

Matieres pour lentilles de contact

Info

Publication number
EP1109846A1
EP1109846A1 EP99930948A EP99930948A EP1109846A1 EP 1109846 A1 EP1109846 A1 EP 1109846A1 EP 99930948 A EP99930948 A EP 99930948A EP 99930948 A EP99930948 A EP 99930948A EP 1109846 A1 EP1109846 A1 EP 1109846A1
Authority
EP
European Patent Office
Prior art keywords
dma
polymer
tris
alkyl group
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99930948A
Other languages
German (de)
English (en)
Inventor
Thomas Paul Davis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unisearch Ltd
Original Assignee
Unisearch Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unisearch Ltd filed Critical Unisearch Ltd
Publication of EP1109846A1 publication Critical patent/EP1109846A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—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
    • C08F226/06—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 by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon

Definitions

  • the invention relates to a polymer having high oxygen permeability and to hydrated compositions including such polymer particularly in the form of a contact lens.
  • hydrogel contact lens materials must possess optical clarity, resistance to tear and high oxygen permeability.
  • Poly(2-hydroxyethylmethacrylate) is used for hydrogel contact lenses as it is hard enough to be easily fabricated by machining and polishing in the dry state yet soft and comfortable to wear in the water swollen state.
  • Other hydrophilic monomers are also used, such as dimethylacrylamide (DMA) polymers and N-vinylpyrrolidone (NVP) polymers with methacrylates.
  • DMA dimethylacrylamide
  • NDP N-vinylpyrrolidone
  • the oxygen permeability of such hydrogel contact lenses is determined by the water content and thickness of the lens and can be improved by increasing the water content or decreasing the thickness. Both strategies, however, can lead to lenses with insufficient strength which are easily damaged.
  • siloxane or fluorinated groups improves oxygen permeability without loss of good mechanical properties. While siloxane groups give slightly higher oxygen permeability, fluorinated groups are especially desirable as they allow the manufacture of polymers with higher dry hardness and therefore better machineability while at the same time reducing lipophilicity and deposit formation on the hydrated polymer.
  • the fluorine has been introduced into polymeric materials by polymerising hydrophilic monomers such as N-vinylpyrrolidone (NVP) and 2-hydroxyethyl methacrylate (HEMA) with fluorinated styrenes and methacrylates.
  • hydrophilic monomers such as N-vinylpyrrolidone (NVP) and 2-hydroxyethyl methacrylate (HEMA)
  • NVP N-vinylpyrrolidone
  • HEMA 2-hydroxyethyl methacrylate
  • TS Patent No 5011275 by Mueller discloses a hydrogel based on a polymer of 15 - 85% dimethylacrylamide and 15 - 85% fluorine containing monomer and optionally other acrylates or methacrylates and a polyviny ⁇ functional cross-linking agent.
  • the polymers form clear hydrogels with about 25 - 75% water content.
  • Ri is hydrogen or methyl
  • n is an integer from 1 - 4
  • in is an integer from 0 - 11
  • X is hydrogen or fluorine with the proviso that, when m is 0.
  • X is fluorine; hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, undecafluoro cyclohexyl-methyl methacrylate and 2, 3, 4, 5, 6- pentafluorostyrene.
  • the present inventors have found a group of fluorine-containing sulfanomido monomers which when polymerised with dimethylacrylamide give high water content and unexpectedly high oxygen permeability.
  • the present invention consists in a polymer including the polymerisation product of (a) N. N-dimethylacrylamide, and (b) a monomer of the formula (I) :
  • n F 2lJ+ 1 S0 2 N(CH 2 ) 2 COOC CH 2 wherein n is an integer from 1 to 8. preferably 4 to 8.
  • R' is an alkyl group, preferably a lower alkyl group containing up to 4 carbon atoms, more preferably ethyl or butyl, and
  • R" is hydrogen or an alkyl group which may be the same as or different from R'. preferably hydrogen or a lower alkyl group containing up to 4 carbon atoms, more preferably hydrogen or methyl.
  • Preferred polymers are those containing 40 - 90% by weight of component (a) and 10 - 60% by weight of component (b). based on the total weight of the monomers (a) and (b).
  • a second aspect of the present invention consists in a hydrated composition in the form of a contact lens which includes a polymer including the polymerisation product of (a) N. N-dimethylacrylamide, and
  • the hydrated composition in the form of a contact lens has an oxygen permeability of at least 30 Dk.
  • a third aspect of the present invention consists in a hydrated composition in the form of an ophthalmic prosthetic device, a drug deliveiy device or bandage which includes a polymer, said polymer including the polymerisation product of:
  • the polymer may include additional monomers, preferably in an amount of from 2 to 50% by weight based on the total weight of the polymer.
  • additional monomers may be included selected from the group consisting of: styrene and styrene derivatives, methacrylates - especially 3- [tris(trimethylsilyloxy)silyl] propyl methacrylate (TRIS).
  • styrene and styrene derivatives methacrylates - especially 3- [tris(trimethylsilyloxy)silyl] propyl methacrylate (TRIS).
  • vinyl pyrrolidone vinyl monomers containing phosphoryl choline functional groups, and partly or fully fluorinated derivatives of the foregoing.
  • the polymer may be formed in the presence or absence of crosslinking agents.
  • crosslinking agents may be multi-functional vinyl compounds such as ethylene glycol dimethacrylate or 1,1.1- trimethylolpropane trimethacrylate. although a wide range of commercial crosslinkers are available and any polymerizable crosslinker is suitable for use in these compositions.
  • Crosslinking agents are preferably included in an amount of up to 8% by weight based on the total weight of the polymer.
  • a fourth aspect of the present invention consists in a hydrogel having an equilibrium water content in the range of from 30 to 90% by weight, the hydrogel being suitable for use as a contact lens and including a polymer having a fluorine and/or siloxane rich hydrophobic phase separated from a hydrophilic phase.
  • the equilibrium water content of the hydrogel is in the range of from 40 to 80% by weight.
  • the fluorine and/or siloxane rich hydrophobic phase preferably includes units of the monomer of formula
  • the hydrophobic phase preferably includes units of DMA.
  • the hydrophilic phase may include other monomers known to those skilled in the art. for example, methacrylic/acrylic acids and their ester derivatives. N-Vinyl-2- pyrrolidone. acrylamides, methacrylamides and functional zwitterionic monomers introduced to confer biocompatibility such as phosphoryl choline derivatives.
  • the polymers are prepared by free radical polymerization, either in bulk, solution, suspension or emulsion using heat- or UV activated initiators or redox systems. Alternatively gamma radiation can be used to initiate polymerisation.
  • initiators can be used based on azo-or peroxy compounds for thermally initiated systems or photoinitiators based on benzoin derivatives or other compounds capable of generating radicals which absorb in the UV or visible regions.
  • the polymers can be produced in sheet form or films by casting monomer solutions and subsequently carrying out the polymerization or by casting polymer solutions into moulds.
  • the polymers can also be fabricated in a spin-casting process. For contact lens manufacture, the polymer may be formed as a rod. button or sheet and subsequently machined, cut and polished to the finished article. For use as a hydrogel material the polymer is often made as a crosslinked material.
  • Any organic solvent may be used for the polymerization process provided it prevents polymer precipitation and inhomogeneity of the polymer product.
  • Figure 1 Structure of fluorine sulphonamide acrylic monomers used in the examples.
  • Figure 2 Photographs of uncrosslinked xerogels where A is N.N- Dimethylacrylamide (DMA) homopolymer and (a) B-G are 2-(N- butyl perfluoro octane sulfonamido) ethyl acrylate (BFA) /DMA copolymers containing (sequentially), 10, 20, 30. 40. 50 and 60wt% BFA (b) H-M are 2- (N- ethyl perfluoro octane sulfonamido) ethyl acrylate (EFA) /DMA copolymers containing (sequentially). 10. 20. 30. 40.
  • DMA N.N- Dimethylacrylamide
  • BFA 2-(N- butyl perfluoro octane sulfonamido) ethyl acrylate
  • BFA butyl perfluoro octane sulfonamid
  • N-S are 2-(N- ethyl perfluoro octane sulfonamido) ethyl methacrylate (EFMA) /DMA copolymers containing (sequentially). 10, 20. 30. 40. 50 and 60wt% EFMA.
  • Figure 3 Thermograms for uncrosslinked BFA/DMA xerogels.
  • the solid vertical lines indicate the T g values for the two glass transition homopolymers where A is DMA homopolymer.
  • B is
  • BFA-20/DMA-80 C is BFA-40/DMA-60
  • D is BFA-60/DMA-40
  • E is BFA homopolymer.
  • Figure 4 Structure of BFA DMA copolymer showing the origin of the two distinct regions giving rise to the two glass transition temperatures. MODES FOR CARRYING OUT THE INVENTION
  • N.N-Dimethylacrylamide (supplied by Sigma-Aldrich Pty. Ltd) was purified by passing over a short column of basic alumina to remove the inhibitor.
  • Fluorinated monomers were selected as follows:
  • Monomer mixtures were made up gravimetrically. deoxygenated with nitrogen for lOmins and irradiated in sealed polypropylene ampoules.
  • the ⁇ -irradiation dose was 1 Mrad obtained from a o ⁇ Co source , the dose rate being 0.01 Mrad If 1 as determined by Fricke dosimetry.
  • the resultant solid rods of xerogel were post-cured at 90°C for 24 firs and then lathe cut to produce thin discs (diameter 10mm: thickness 1mm) for swelling measurements and thin discs (diameter 10mm: thickness 0.1-0.5mm) for oxygen permeability measurements.
  • hydrogels are referred to on the basis of the corresponding xerogels.
  • compositions are expressed percentage by weight.
  • BFA-20 / DMA-80 means that crosslinker is absent and that BFA/DMA is 20/80 (w/w).
  • BFA-20 / DMA-80 / EDMA-5 a terpolymer designated BFA-20 / DMA-80 / EDMA-5.
  • EDMA comprises 5wt% of the total monomers (BFA + DMA + EDMA). As conversion in these polymerizations is close to 100%. the compositions of xerogels are virtually identical to those of the feed mixtures.
  • the equilibrium water content (EWC) of the hydrogels is defined as:
  • the volume fraction of polymer within a hydrogel is given as
  • D and D 0 are the diameters of the hydrogel and xerogel respectively.
  • Measurements were made on swollen samples over a range of thicknesses (at least three) on a JDF DklOOO I M coulometric oxygen permeation instrument under wet cell conditions.
  • T g glass transition temperatures
  • the xerogel rods were lathe cut into discs: the visual appearance of the discs is shown in Figure (2a-c).
  • the polymers containing EFMA. the methacrylate derivative proved to be either hazy or opaque indicating that this copolymer may be unsuitable for contact lens applications.
  • a crosslinker (l%wt. EDMA, for example) enabled the production of transparent materials. All of the xerogels maintained their transparency on swelling.
  • the xerogel rods often appeared to contain residual stresses (clearly shown via observation between cross- polarising lenses) which may be due to either inhomogeneities in the original monomer mixing and/or a substantial gel effect observed in these reactions. It was found that the dominant cause of the residual stresses was the gel (or
  • the T g values for the xerogels were determined and are shown in Table 1. In all three copolymer systems, two T g s were observed. The thermograms for the BFA/ DMA series are shown in Figure 3. The higher T g is assumed to originate from the DMA component and the lower T g from the BFA side-chain. Random copolymers usually exhibit only one T g . given by the weighted average of the T g s of the two polymeric components. The T g behaviour observed is relatively unusual for random copolymers and is normally associated with graft copolymers, where the grafted chain is incompatible with the backbone polymer, or with incompatible polymer blends.
  • the long perfluorinated side-chains are sufficiently long and flexible to form domains with a sub-ambient glass transition.
  • the high T g (corresponding to DMA) is seen to reduce as the concentration of fluoro-monomer increases, there is also a concomitant reduction in the lower glass transition.
  • the reduction in both T g s is possibly explicable as follows.
  • the structure of the copolymer is shown in Figure 4.
  • the high T g corresponds to the backbone polymer chain region which comprises both DMA and fluoro-monomer segments.
  • the high DMA T g is mediated by a contribution from the fluoro-monomer component.
  • the low T g originates solely from the flexible side-chain most distant from the polymer backbone forming icrodomains this value is lower than the T g obtained for the pure fluoropolymer as it excludes contributions from the fixed polymer backbone.
  • these copolymers manifest transparency, as it is evident that the materials are inhomogeneous. It may be conjectured that some compatibility may be introduced from two sources.
  • the pure fluoro-monomers used in this current study are in fact a mixture of monomers with different length side-chains and thus the extent of incompatibility of the perfluoro sidechains with DMA rich areas may be tempered by a contribution from the smaller side-chains acting as compatibilisers. It is also conceivable that the sulphonamide group in the perfluoro side-chains acts to some extent as a compatibilizer via favourable interactions with the tertiary amide group in DMA.
  • Table 2 shows the swelling data obtained for the three different copolymer systems at selected compositions, prepared in the absence of a crosslinker. As expected the presence of higher fluorine concentrations induces a decrease in the equilibrium swelling. Despite this, it is possible to achieve high water contents whilst maintaining a reasonable fluorine content. This is clearly demonstrated by comparison of these new materials with PHEMA with an EWC of about 40wt% - a similar water content is achieved with 60%wt of the fluoro- monomers in these new materials. The sol fractions are all fairly low indicating that most of the DMA has copolymerized. There appears to be no significant differences among the swelling behaviours of the three different copolymer sets.
  • Table 3 shows the swelling characteristics of the same copolymer systems prepared with 1. 2 and 5wt% EDMA crosslinker. Increasing concentrations of crosslinker lead to lower EWC values and (generally) lower sol fractions consistent with previous observations made on hydrogel materials.
  • the oxygen permeabilities obtained on the uncrosslinked hydrogels are given in Table 4. Each reported value is an average of at least three independent measurements. The important factor is the large oxygen permeability of these hydrogel materials compared with non-fluorinated materials. This can be clearly demonstrated by comparing those hydrogels with about 60wt% fluoro-monomer that have water contents around 40wt% (similar to PHEMA). The oxygen permeability is about five times higher than PHEMA. This indicates that oxygen transmission in these hydrogels occurs not only via the dissolved oxygen in the aqueous phase but also by another route (which predominates) and which is assumed to be via a co-continuous polymeric phase, which is rich in fluorine.
  • Table 1 Glass transition temperatures for uncrosslinked xerogels.
  • Table 2 Swelling properties of uncrosslinked hydrogels at 296K.
  • Table 3 Swelling properties of crosslinked hydrogels at 296K.
  • BFA-20/DMA-80/EDMA-1 71 0.28 6.94
  • BFA-40/DMA-60/EDMA- 1 55 0.40 1.61
  • BFA-60/DMA-40/EDMA-1 37 0.60 1.02
  • EFA-20/DMA-80/EDMA-1 66 0.31 2.19
  • EFA-40/DMA-60/EDMA-1 52 0.44 1.47
  • EFA-60/DMA-40 EDMA-1 34 0.64 0.85
  • EFMA-20/DMA-80/EDMA-1 72 0.26 2.79 EFMA-40/DMA-60/EDMA-1 57 0.39 2.97 EFMA-60/DMA-40/EDMA-1 43 0.53 2.86
  • EFA-20/DMA-80/EDMA-2 64 0.39 8.75 EFA-40/DMA-60/EDMA-2 51 0.51 4.90 EFA-60 DMA-40/EDMA-2 34 0.67 2.63
  • N,N-Dimethylacrylamide (DMA) supplied by Sigma-Aldrich Pty. Ltd
  • 3- [tris (trimethylsilyloxy)] propyl methacrylate (TRIS) also supplied by Sigma- Aldrich Pty. Ltd
  • Fluorinated monomers were selected as follows:
  • Monomer mixtures were made up gravimetrically, deoxygenated with nitrogen for lOmins and irradiated in sealed polypropylene ampoules.
  • the ⁇ -irradiation dose was 1 Mrad obtained from a 60 Co source, the dose rate being O.OlMrad h "1 as determined by Fricke dosimetry.
  • the resultant solid rods of xerogel were post-cured at 90°C for 24 hrs and then lathe cut to produce thin discs (diameter 10mm; thickness 1mm) for swelling measurements and thin discs (diameter 10mm; thickness 0.1-0.5mm) for oxygen permeability measurements.
  • hydrogels are referred to on the basis of the corresponding xerogels.
  • conversion in these polymerizations is close to 100%, the compositions of xerogels are virtually identical to those of the feed mixtures.
  • the equilibrium water content (EWC) of the hydrogels is defined as:
  • volume fraction of polymer within a hydrogel is given as ⁇ 2 J ⁇ [6]
  • D and D 0 are the diameters of the hydrogel and xerogel respectively
  • the terpolymer compositions in Tables (5) and (6) are expressed on a mole percentage basis, relative to the total moles of (EFA or BFA + DMA) for the principal monomers and to the total moles of the whole for TRIS.
  • DMA-96/BFA-4/TRIS-1.4 means that DMA comprises 96 mol.-% of (DMA + BFA), BFA comprises 4 mol wt.-% of (DMA + BFA) and TRIS is present at a concentration of 1.4 mol.-% of (MMA + BFA
  • Table (5) shows the swelling data obtained for the different copolymer systems at selected compositions, prepared in the absence of a crosslinker with ⁇ 5, 10 and 20 wt.-% TRIS.
  • higher concentrations of TRIS increase the total amount of hydrophobic monomer in the terpolymer compositions causing lower EWC values.
  • 20wt.-% 5.3 mol.-%
  • TRIS has a similar impact on the EWC as the inclusion of only lwt.-% ethylene glycol dimathacrylate (EDMA).
  • EDMA ethylene glycol dimathacrylate
  • TRIS is often used as a monomer to increase the oxygen permeability of polymeric materials. Consequently, it was assumed that the incorporation of
  • TRIS would ameliorate the oxygen permeability of these hydrogels.
  • the high oxygen permeability of these hydrogels (without TRIS) was attributed to two mechanisms for oxygen transmission: via the aqueous phase and through a fluorine-rich co-continuous polymeric phase.
  • the oxygen permeability results for the current TRIS-containing terpolymers are given in Table 6. Each reported value is an average of at least three independent measurements. It is evident from these results that when the fluorinated monomer (BFA or EFA) is present at 4 mol.-% (20 wt-%) the addition of TRIS induces a decrease in the Dk value. This is consistent with a decrease in oxygen transmission that can be attributed solely to a decrease in the EWC.
  • the oxygen permeability result for BFA-96/DMA-4/TRIS-1.4 appears to be veiy low in comparison with the other data and may simply be an anomalous result.
  • Overall this oxygen permeability data may indicate that the TRIS is having no influence on the secondaiy transmission route via the F-rich polymeric phase and is simply acting as a hydrophobic comonomer.
  • the fluorinated monomer BFA or EFA
  • BFA or EFA fluorinated monomer
  • DMA-96/BFA-3/TRIS-1 now means that DMA comprises 96 mol.-% of (DMA + BFA + TRIS), BFA comprises 3 mol.-% of (DMA + BFA + TRIS) and TRIS is present at a concentration of 1 mol.-% of (MMA + BFA + TRIS). It is also pertinent to note that compositions containing 96 mol.-% and 90 mol.-% DMA correspond to compositions of 80 wt.-% and 60 wt.-% DMA respectively.
  • Table 5 Swelling properties of hydrogels with added TRIS at 296K.
  • Table 7 Swelling properties of hydrogels with constant DMA at 296K.
  • the polymers of this invention are useful for ophthalmic devices such as soft contact lenses. They are also useful for a variety of other applications which benefit from the hydrophilic nature and high oxygen permeability of the polymer, such as oxygen permeable wound dressings or bandages, carriers for controlled delivery of drugs either as dermal patches, orally taken beads, body implants or eye inserts and gas separation membranes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Eyeglasses (AREA)

Abstract

L'invention concerne, d'une part un polymère très perméable à l'oxygène, et d'autre part des compositions hydratées pour lentilles de contact à base de ce polymère. L'invention concerne plus particulièrement un produit de polymérisation issu (a) du N,N-diméthylacrylamide et (b) d'un monomère représenté par la formule (I). Dans cette formule, n est un entier valant de 1 à 8, de préférence de 4 à 8. R' est groupe alkyle, de préférence groupe alkyle inférieur portant jusqu'à 4 atomes de carbone, et de préférence encore groupe éthyle ou butyle. R'' est hydrogène ou groupe alkyle identique ou différent de R', mais de préférence hydrogène ou groupe alkyle inférieur portant jusqu'à 4 atomes de carbone, et de préférence encore hydrogène ou méthyle. Le monomère de diméthylamine ou les monomères de la formule (I) peuvent être combinés à un ou plusieurs monomères supplémentaires sélectionnés dans le groupe des styrène et dérivés de styrène, méthacrylate, et plus particulièrement 3-[tris(triméthylsilyloxy)silyl]propylméthacrylate (TRIS), acrylates, acrylamides, méthacrylamides, vinyl-pyrrolidone, monomères vinyliques contenant des groupes fonctionnels phosphoryle choline, ainsi que leurs dérivés partiellement ou totalement fluorés.
EP99930948A 1998-07-13 1999-07-13 Matieres pour lentilles de contact Withdrawn EP1109846A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPP463998 1998-07-13
AUPP4639A AUPP463998A0 (en) 1998-07-13 1998-07-13 Contact lens material
PCT/AU1999/000575 WO2000004065A1 (fr) 1998-07-13 1999-07-13 Matieres pour lentilles de contact

Publications (1)

Publication Number Publication Date
EP1109846A1 true EP1109846A1 (fr) 2001-06-27

Family

ID=3808877

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99930948A Withdrawn EP1109846A1 (fr) 1998-07-13 1999-07-13 Matieres pour lentilles de contact

Country Status (6)

Country Link
EP (1) EP1109846A1 (fr)
JP (1) JP2002520456A (fr)
KR (1) KR20010074704A (fr)
AU (1) AUPP463998A0 (fr)
CA (1) CA2337173A1 (fr)
WO (1) WO2000004065A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110243852A1 (en) * 2008-12-17 2011-10-06 Koninklijke Philips Electronics N.V. Method for the production of labelled scaffolds, comprising at least one reactive fluorinated surfactant, and scaffold produced therewith

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU618817B2 (en) * 1988-07-05 1992-01-09 Novartis Ag Dimethylacrylamide-copolymer hydrogels with high oxygen permeability
JPH0580278A (ja) * 1991-09-24 1993-04-02 Seiko Epson Corp ソフトコンタクトレンズ
JP3453224B2 (ja) * 1995-09-12 2003-10-06 株式会社メニコン 含水性ソフトコンタクトレンズ材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0004065A1 *

Also Published As

Publication number Publication date
AUPP463998A0 (en) 1998-08-06
KR20010074704A (ko) 2001-08-09
CA2337173A1 (fr) 2000-01-27
JP2002520456A (ja) 2002-07-09
WO2000004065A1 (fr) 2000-01-27

Similar Documents

Publication Publication Date Title
EP1197782B1 (fr) Matiere pour lentille oculaire
WO2002050144A2 (fr) Biomateriaux polymeriques contenant des monomeres de silsesquioxane
JP2008001905A (ja) フルオロシリコーンヒドロゲル
EP0524557B1 (fr) Composition pour lentille oculaire
JP5668062B2 (ja) イオン性化合物、組成物、硬化物、ハイドロゲル及び眼用レンズ
US6262208B1 (en) Ocular lens material and process for producing the same
EP1109846A1 (fr) Matieres pour lentilles de contact
JP6974633B2 (ja) ポリマー材料
JP6857784B2 (ja) ポリマー材料
GB2129005A (en) Multifunctional organopolysil resin systems and contact lenses made therefrom
US5391591A (en) Oxygen permeable hard contact lens materials comprising a fluoroalkyl(silicon-containing alkyl) fumarate copolymer
AU4764199A (en) Contact lens material
JP3063877B2 (ja) 含水性ソフトコンタクトレンズ
JP3974673B2 (ja) 含水性ソフトコンタクトレンズ
KR20190066563A (ko) 우수한 물성을 가지는 실리콘 하이드로겔 렌즈
EP2807198A1 (fr) Hydrogels de silicone et leurs procédés de fabrication
JP3084180B2 (ja) コンタクトレンズ
JP3453226B2 (ja) 酸素透過性硬質眼用レンズ材料およびその製法
JPH04168415A (ja) コンタクトレンズ
WO2022118697A1 (fr) Modificateur pour dispositif d'ophtalmologie
JPH10170874A (ja) プラスチック成形品
JPH11171929A (ja) プラスチック成形品
JPS62209512A (ja) 眼用レンズ材料
JPH04264421A (ja) コンタクトレンズ
JPH04159319A (ja) 酸素透過性高分子材料の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010213

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 20010912