CA2347707C - Foldable ophthalmic and otorhinolaryngological device materials - Google Patents
Foldable ophthalmic and otorhinolaryngological device materials Download PDFInfo
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- CA2347707C CA2347707C CA002347707A CA2347707A CA2347707C CA 2347707 C CA2347707 C CA 2347707C CA 002347707 A CA002347707 A CA 002347707A CA 2347707 A CA2347707 A CA 2347707A CA 2347707 C CA2347707 C CA 2347707C
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- 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
-
- 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
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
- A61F2/145—Corneal inlays, onlays, or lenses for refractive correction
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
- A61F2/16—Intraocular lenses
Abstract
Disclosed are soft, high refractive index, acrylic materials having an elongation of at least 150 %. These materials, especially useful as intraocular lens materials, contain an aryl acrylic hydrophobic monomer as the single principal device-forming monomer. In addition to their use as intraocular lens materials, the present materials are also suitable for use in other ophthalmic or otorhinolaryngological devices, such as contact lenses, keratoprostheses, corneal inlays or rings; otological ventilation tubes and nasal implants.
Description
FOLDABLE OPHTHALMIC AND OTORHINOLARYNGOLOGICAL DEVICE
MATERIALS
Field of the Invention This invention is directed to acrylic device materials. In particular, this invention relates to soft, high refractive index acrylic device materials particularly suited for use as intraocular lens ("IOL") materials.
Background of the Invention With the recent advances in small-incision cataract surgery, increased emphasis has been placed on developing soft, foldable materials suitable for use in artificial lenses. In general, these materials fall into one of three categories: hydrogels, silicones, and acrylics.
In general, hydrogel materials have a relatively low refractive index, making them less desirable than other materials because of the thicker lens optic necessary to achieve a given refractive power. Silicone materials generally have a higher refractive index than hydrogels, but tend to unfold explosively after being placed in the eye in a folded position. Explosive unfolding can potentially damage the corneal endothelium and/or rupture the natural lens capsule. Acrylic materials are desirable because they typically have a high refractive index and unfold more slowly or controllably than silicone materials.
U.S. Patent No. 5,290,892 discloses high refractive index, acrylic materials suitable for use as an IOL material. These acrylic materials contain, as principal components, two aryl acrylic monomers. They also contain a cross-linking component. The IOLs made of these acrylic materials can be rolled or folded for insertion through small incisions.
U.S. Patent No. 5,331,073 also discloses soft acrylic IOL materials.
These materials contain as principal components, two acrylic monomers which are defined by the properties of their respective homopolymers. The first monomer is defined as one in which its homopolymer has a refractive index of at least about 1.50. The second monomer is defined as one in which its homopolymer has a glass transition temperature less than about 22 C.
These IOL materials also contain a cross-linking component. Additionally, these materials may optionally contain a fourth constituent, different from the first three constituents, which is derived from a hydrophilic monomer. These materials preferably have a total of less than about 15% by weight of a hydrophilic component.
U.S. Patent No. 5,693,095 discloses foldable ophthalmic lens materials comprising a total of at least 90% by weight of only two principal lens-forming monomers. One lens-forming monomer is an aryl acrylic hydrophobic monomer. The other lens-forming monomer is a hydrophilic monomer. The lens materials also comprise a cross-linking monomer and optionally comprise a UV absorber, polymerization initiators, reactive UV absorbers and reactive blue-light absorbers.
Summary of the Invention Improved soft, foldable acrylic materials which are particulariy suited for use as IOLs, but which are also useful as other ophthalmic or otorhinoloaryngological devices, such as contact lenses, keratoprostheses, corneal rings or inlays, otological ventilation tubes and nasal implants have now been discovered. These materials contain only one principal lens-forming component: an aryl acrylic hydrophobic monomer. The materials of the present invention comprise at least about 80% by weight of the principal monomeric component. The remainder of the material comprises a cross-linking monomer and optionally one or more additional components selected from the group consisting of UV-Iight absorbing compounds and blue-light absorbing compounds.
MATERIALS
Field of the Invention This invention is directed to acrylic device materials. In particular, this invention relates to soft, high refractive index acrylic device materials particularly suited for use as intraocular lens ("IOL") materials.
Background of the Invention With the recent advances in small-incision cataract surgery, increased emphasis has been placed on developing soft, foldable materials suitable for use in artificial lenses. In general, these materials fall into one of three categories: hydrogels, silicones, and acrylics.
In general, hydrogel materials have a relatively low refractive index, making them less desirable than other materials because of the thicker lens optic necessary to achieve a given refractive power. Silicone materials generally have a higher refractive index than hydrogels, but tend to unfold explosively after being placed in the eye in a folded position. Explosive unfolding can potentially damage the corneal endothelium and/or rupture the natural lens capsule. Acrylic materials are desirable because they typically have a high refractive index and unfold more slowly or controllably than silicone materials.
U.S. Patent No. 5,290,892 discloses high refractive index, acrylic materials suitable for use as an IOL material. These acrylic materials contain, as principal components, two aryl acrylic monomers. They also contain a cross-linking component. The IOLs made of these acrylic materials can be rolled or folded for insertion through small incisions.
U.S. Patent No. 5,331,073 also discloses soft acrylic IOL materials.
These materials contain as principal components, two acrylic monomers which are defined by the properties of their respective homopolymers. The first monomer is defined as one in which its homopolymer has a refractive index of at least about 1.50. The second monomer is defined as one in which its homopolymer has a glass transition temperature less than about 22 C.
These IOL materials also contain a cross-linking component. Additionally, these materials may optionally contain a fourth constituent, different from the first three constituents, which is derived from a hydrophilic monomer. These materials preferably have a total of less than about 15% by weight of a hydrophilic component.
U.S. Patent No. 5,693,095 discloses foldable ophthalmic lens materials comprising a total of at least 90% by weight of only two principal lens-forming monomers. One lens-forming monomer is an aryl acrylic hydrophobic monomer. The other lens-forming monomer is a hydrophilic monomer. The lens materials also comprise a cross-linking monomer and optionally comprise a UV absorber, polymerization initiators, reactive UV absorbers and reactive blue-light absorbers.
Summary of the Invention Improved soft, foldable acrylic materials which are particulariy suited for use as IOLs, but which are also useful as other ophthalmic or otorhinoloaryngological devices, such as contact lenses, keratoprostheses, corneal rings or inlays, otological ventilation tubes and nasal implants have now been discovered. These materials contain only one principal lens-forming component: an aryl acrylic hydrophobic monomer. The materials of the present invention comprise at least about 80% by weight of the principal monomeric component. The remainder of the material comprises a cross-linking monomer and optionally one or more additional components selected from the group consisting of UV-Iight absorbing compounds and blue-light absorbing compounds.
Among other factors, the present invention is based on the finding that acrylic copolymers suitable for use as foldable IOL materials can be synthesized using only one principal aryl acrylic hydrophobic monomer, reducing or eliminating difficulties, such as physico/chemical heterogeneity, associated with curing copolymers that contain two or more principal device-forming monomers.
According to one aspect of the present invention, there is provided a polymeric ophthalmic or otorhinolaryngological device material having an elongation of at least 150% and a glass transition temperature Tg of below 25 C, comprising a single device-forming monomer and a cross-linking monomer, wherein the single device-forming monomer is present in an amount of at least about 80% by weight and is an aryl acrylic hydrophobic monomer of the formula C~Y,B~O A
D
-J~ (I) wherein: A is H, CH3, CH2CH3, or CH2OH; B is (CH2)m or [0 (CH2) 2] n; C is (CHz) W; m is 2 - 6; n is 1 - 10; Y is nothing, 0, S, or NR, provided that if Y is 0, S, or NR, then B is (CH2)m; R is H, CH3, CnH2n+1(n=1-10) , iso-OC3H7, C6H5, or CH2C6H5i w is 0 - 6, provided that m + w<_ 8; and D is H, Cl-C4 alkyl, C1-C4 alkoxy, C6H5, CH2C6H5 or halogen; and wherein the cross-linking monomer is a terminally ethylenically unsaturated monomer having more than one unsaturated group.
According to another aspect of the present invention, there is provided an intraocular lens comprising the polymeric device material described herein.
According to one aspect of the present invention, there is provided a polymeric ophthalmic or otorhinolaryngological device material having an elongation of at least 150% and a glass transition temperature Tg of below 25 C, comprising a single device-forming monomer and a cross-linking monomer, wherein the single device-forming monomer is present in an amount of at least about 80% by weight and is an aryl acrylic hydrophobic monomer of the formula C~Y,B~O A
D
-J~ (I) wherein: A is H, CH3, CH2CH3, or CH2OH; B is (CH2)m or [0 (CH2) 2] n; C is (CHz) W; m is 2 - 6; n is 1 - 10; Y is nothing, 0, S, or NR, provided that if Y is 0, S, or NR, then B is (CH2)m; R is H, CH3, CnH2n+1(n=1-10) , iso-OC3H7, C6H5, or CH2C6H5i w is 0 - 6, provided that m + w<_ 8; and D is H, Cl-C4 alkyl, C1-C4 alkoxy, C6H5, CH2C6H5 or halogen; and wherein the cross-linking monomer is a terminally ethylenically unsaturated monomer having more than one unsaturated group.
According to another aspect of the present invention, there is provided an intraocular lens comprising the polymeric device material described herein.
73498=89 Detailed Description of the Invention The ophthalmic or otorhinolaryngological device materials of the present invention comprise only one principal device-forming monomer. For convenience, the device-forming monomer may be referred to as a lens-forming monomer, particularly with reference to an IOL. The materials of the present invention, however, are also suitable for use as other ophthalmic or otorhinolaryngological devices such as contact lenses, keratoprostheses, comeal inlays or rings, otological ventilation tubes and nasal implants.
The aryl acrylic hydrophobic monomers suitable for use as the sole lens-forming monomer in the materials of the present invention have the formula O
B~O A
D
(~) wherein: A is H, CH3, CH2CH3, or CH2OH;
B is (CH2)m or [O(CH2)2]1;
C is (CH2),N;
mis2-6;
n is 1 - 10;
Y is nothing, 0, S, or NR, provided that if Y is 0, S, or NR, then B
is (CH2)m;
3a R is H, CH3, CnH2n+1 (n=1-10), iso-OC3H7, C6H5, or CH2C6H5;
w is 0 - 6, provided that m + w_8; and D is H, C, - C4 alkyl, Cl - C4 alkoxy, C6H5, CH2C6H5 or halogen.
Preferred aryl acrylic hydrophobic monomers for use in the materials of the present invention are those wherein A is CH3, B is (CH2)m, m is 2 - 5, Y
is nothing or 0, w is 0 - 1, and D is H. Most preferred are 4-phenylbutyl methacrylate, 5-phenylpentyl methacrylate, 2-benzyloxyethyl methacrylate, and 3-benzyloxypropyl methacrylate.
Monomers of structure I can be made by known methods. For example, the conjugate alcohol of the desired monomer can be combined in a reaction vessel with methyl methacrylate, tetrabutyl titanate (catalyst), and a polymerization inhibitor such as 4-benzyloxy phenol. The vessel can then be heated to facilitate the reaction and distill off the reaction by-products to drive the reaction to completion. Alternative synthesis schemes involve adding methacrylic acid to the conjugate alcohol and catalyzing with a carbodiimide or mixing the conjugate alcohol with methacryloyl chloride and a base such as pyridine or triethylamine.
The materials of the present invention comprise a total of at least about 80%, preferably at least about 85%, by weight or more of the principal lens-forming monomer.
The copolymer materials of the present invention are cross-linked. The copolymerizable cross-linking agent used in the copolymers of this invention may be any terminally ethylenically unsaturated compound having more than one unsaturated group. Suitable cross-linking agents include, for example:
ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; allyl methacrylate; 1,3-propanediol dimethacrylate; 2,3-propanediol dimethacrylate; 1,6-hexanediol dimethacrylate; 1,4-butanediol dimethacrylate;
CH2=C(CH3)C(=O)O-(CH2CH20)n-C(=O)C(CH3)=CH2 where n = 1 50; and CH2=C(CH3)C(=O)O(CH2)tO-C(=O)C(CH3)=CH2 where t = 3 - 20; and their corresponding acrylates. The most preferred cross-linking monomer is CH2=C(CH3)C(=O)O-(CH2CH2O)r,-C(=O)C(CH3)=CH2 where n is such that the number-average molecular weight is about 400, about 600, or, most preferably, about 1000.
The chosen cross-linking agent should be soluble in the chosen monomer of structure I to minimize curing problems. When n approaches the upper end of the range of 1 - 50, the CH2=C(CH3)C(=O)O-(CH2CH2O)n-1o C(=O)C(CH3)=CH2 cross-linker may not be soluble at desired levels in some monomers of structure l, even with the aid of heat or sonication.
Generally, only one cross-linking monomer will be present in the device materials of the present invention. In some cases, however, combinations of cross-linking monomers may be desirable. If combinations of two or more types of cross-linking agents are used, none of the cross-linking agents may be CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2 wherein n = 2-50.
Generally, the total amount of the cross-linking component is at least 0.1% by weight and, depending on the identity and concentration of the remaining components and the desired physical properties, can range to about 20% by weight. The preferred concentration range for the cross-linking component is 0.1 - 15% by weight.
In addition to the aryl acrylic hydrophobic lens-forming monomer and the cross-linking component, the lens material of the present invention may also contain a total of up to about 10% by weight of additional components which serve other purposes, such as reactive UV and/or blue-light absorbers.
A preferred reactive UV absorber is 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, commercially available as o-Methallyl Tinuvin P
The aryl acrylic hydrophobic monomers suitable for use as the sole lens-forming monomer in the materials of the present invention have the formula O
B~O A
D
(~) wherein: A is H, CH3, CH2CH3, or CH2OH;
B is (CH2)m or [O(CH2)2]1;
C is (CH2),N;
mis2-6;
n is 1 - 10;
Y is nothing, 0, S, or NR, provided that if Y is 0, S, or NR, then B
is (CH2)m;
3a R is H, CH3, CnH2n+1 (n=1-10), iso-OC3H7, C6H5, or CH2C6H5;
w is 0 - 6, provided that m + w_8; and D is H, C, - C4 alkyl, Cl - C4 alkoxy, C6H5, CH2C6H5 or halogen.
Preferred aryl acrylic hydrophobic monomers for use in the materials of the present invention are those wherein A is CH3, B is (CH2)m, m is 2 - 5, Y
is nothing or 0, w is 0 - 1, and D is H. Most preferred are 4-phenylbutyl methacrylate, 5-phenylpentyl methacrylate, 2-benzyloxyethyl methacrylate, and 3-benzyloxypropyl methacrylate.
Monomers of structure I can be made by known methods. For example, the conjugate alcohol of the desired monomer can be combined in a reaction vessel with methyl methacrylate, tetrabutyl titanate (catalyst), and a polymerization inhibitor such as 4-benzyloxy phenol. The vessel can then be heated to facilitate the reaction and distill off the reaction by-products to drive the reaction to completion. Alternative synthesis schemes involve adding methacrylic acid to the conjugate alcohol and catalyzing with a carbodiimide or mixing the conjugate alcohol with methacryloyl chloride and a base such as pyridine or triethylamine.
The materials of the present invention comprise a total of at least about 80%, preferably at least about 85%, by weight or more of the principal lens-forming monomer.
The copolymer materials of the present invention are cross-linked. The copolymerizable cross-linking agent used in the copolymers of this invention may be any terminally ethylenically unsaturated compound having more than one unsaturated group. Suitable cross-linking agents include, for example:
ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; allyl methacrylate; 1,3-propanediol dimethacrylate; 2,3-propanediol dimethacrylate; 1,6-hexanediol dimethacrylate; 1,4-butanediol dimethacrylate;
CH2=C(CH3)C(=O)O-(CH2CH20)n-C(=O)C(CH3)=CH2 where n = 1 50; and CH2=C(CH3)C(=O)O(CH2)tO-C(=O)C(CH3)=CH2 where t = 3 - 20; and their corresponding acrylates. The most preferred cross-linking monomer is CH2=C(CH3)C(=O)O-(CH2CH2O)r,-C(=O)C(CH3)=CH2 where n is such that the number-average molecular weight is about 400, about 600, or, most preferably, about 1000.
The chosen cross-linking agent should be soluble in the chosen monomer of structure I to minimize curing problems. When n approaches the upper end of the range of 1 - 50, the CH2=C(CH3)C(=O)O-(CH2CH2O)n-1o C(=O)C(CH3)=CH2 cross-linker may not be soluble at desired levels in some monomers of structure l, even with the aid of heat or sonication.
Generally, only one cross-linking monomer will be present in the device materials of the present invention. In some cases, however, combinations of cross-linking monomers may be desirable. If combinations of two or more types of cross-linking agents are used, none of the cross-linking agents may be CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2 wherein n = 2-50.
Generally, the total amount of the cross-linking component is at least 0.1% by weight and, depending on the identity and concentration of the remaining components and the desired physical properties, can range to about 20% by weight. The preferred concentration range for the cross-linking component is 0.1 - 15% by weight.
In addition to the aryl acrylic hydrophobic lens-forming monomer and the cross-linking component, the lens material of the present invention may also contain a total of up to about 10% by weight of additional components which serve other purposes, such as reactive UV and/or blue-light absorbers.
A preferred reactive UV absorber is 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, commercially available as o-Methallyl Tinuvin P
("oMTP") from Polysciences, Inc., Warrington, Pennsyivania. UV absorbers are typically present in an amount from about 0.1 - 5 % (weight).
Suitable reactive blue-light absorbing compounds are those described in U.S. Patent No. 5,470,932. Blue-light absorbers are typically present in an amount from about 0.01 - 0.5 % (weight).
Suitable polymerization initiators include thermal initiators and photoinitiators. Preferred thermal initiators include peroxy free-radical initiators, sucti as t-butyl (peroxy-2-ethyl)hexanoate and di-(tert-butyicyclohexyl) peroxydicarbonate (commercially available as Perkadox 16 from Akzo 'Chemicals Inc., Chicago, Illinois). Particularly in cases where the lens material does not contain a blue-light absorbing chromophore, preferred photoinitiators 1s include benzoylphosphine oxide photoinitiators, such as the blue-light initiator 2,4,6-trimethyl-benzoyldiphenylphosphine oxide, commercially available as Lucirin TPO from BASF Corporation (Charlotte, North Carolina). Initiators are typically present in an amount of about 5% (weight) or less.
The identity and amount of the principal lens-forming monomer described above and the identity and amount of any additional components are determined by the desired properties of the finished ophthalmic lens.
Preferably, the ingredients and their proportion are selected so that the acrylic lens materials of the present invention possess the following properties, which make the materials of the present invention particularly suitable for use in {OLs which are to be inserted through incisions of 5 mm or less.
The lens material preferably has a refractive index in the dry state of at least about 1.50 as measured by an Abbe' refractometer at 589 nm (Na light source). For a given optic diameter, optics made from materials having a refractive index lower than 1.50 are necessarily thicker than optics of the same power which are made from materials having a higher refractive index. As such, IOL optics made from materials having a refractive index lower than about 1.50 generally require relatively larger incisions for IOL implantation.
The glass-transition temperature ("Tg") of the lens material, which affects the material's folding and unfolding characteristics, is preferably below about 25 C, and more preferably below about 15 C. Tg is measured by differential scanning calorimetry at 10 C/min., and is determined at the midpoint of the transition of the heat flux curve.
The lens material will have an elongation of at least 150%, preferably at least 200%, and most preferably at least 300%. This property indicates that the lens generally will not crack, tear or split when folded. Elongation of polymer samples is determined on dumbbell shaped tension test specimens with a 20 mm total length, length in the grip area of 4.88 mm, overall width of 2.49 mm, 0.833 mm width of the narrow section, a fillet radius of 8.83 mm, and a thickness of 0.9 mm. Testing is performed on samples at standard laboratory conditions of 23 2 oC and 50 5 % relative humidity using a tensile tester.
The grip distance is set at 14 mm and a crosshead speed is set at 500 mm/minute and the sample is pulled to failure. The elongation (strain) is reported as a fraction of the displacement at failure to the original grip distance. The modulus is calculated as the instantaneous slope of the stress-strain curve at a selected strain. Stress is calculated at the maximum load for the sample, typically the load when the sample breaks, assuming that the initial area remains constant. This stress is recorded as "tensile strength"
in the examples below.
IOLs constructed of the materials of the present invention can be of any design capable of being rolled or folded into a small cross section that can fit through a relatively smaller incision. For example, the IOLs can be of what is known as a one piece or multipiece design, and comprise optic and haptic components. The optic is that portion which serves as the lens. The haptics are attached to the optic and hold the optic in its proper place in the eye.
The optic and haptic(s) can be of the same or different material. A multipiece lens is so called because the optic and the haptic(s) are made separately and then the haptics are attached to the optic. In a single piece lens, the optic and the haptics are formed out of one piece of material. Depending on the material, the haptics are then cut, or lathed, out of the material to produce the IOL.
The invention will be further illustrated by the following examples, which are intended to be illustrative, but not limiting.
)o Example 1: Synthesis of 4-phenylbutyl methacrylate.
/ O T(OCaHe)4 ~ O
I + ~ ~ ~ + CH3OH
~ OH 0-1-r 4-BOP O1~-A
41) (2) 43) A three neck round bottom flask containing a teflon coated magnetic stirring bar was successively charged with 120 mL (1.09 mol) of methyl methacrylate (2), 5.35 g (0.015 mol) of titanium tetrabutoxide (Ti(OC4H9)4), 60 mL (0.39 )s mol) of 4-phenyl-l-butanol (1), and 14.6 g (0.073 mol) of 4-benzyloxyphenol (4-BOP). An addition funnel, thermometer, and a short path still head with thermometer and receiver flask were placed in the flask necks. The flask was placed in an oil bath and the temperature was increased until distillation began. Methyl methacrylate (2) was placed in the addition funnel and was 20 added dropwise at the same rate as the distillate. The reaction mixture was heated for 4 hours and then cooled to room temperature. The crude product was vacuum distilled to isolate 62.8 g (0.29 mol, 74%) of 4-phenylbutyl methacrylate (3) as a clear, colorless liquid.
Example 2: Synthesis of 3-benzyloxypropyl methacrylate.
O
O Ti(OCaHs)4 OOH + , J ' ~ 0---0 + CH3OH
~' ~II( 4-BOP
A
(~) (2) (3) A three neck round bottom flask containing a teflon coated magnetic stirring )o bar was successively charged with 95 mL (0.884 mol) of methyl methacrylate (2), 4.22 g (0.012 mol) of titanium tetrabutoxide (Ti(OC4H9)4), 50 mL (0.316 mol) of 3-benzyloxy-l-propanol (1), and 14.6 g (0.073 mol) of 4-benzyloxyphenol (4-BOP). An addition funnel, thermometer, and a short path still head with thermometer and receiver flask were placed in the flask necks.
The flask was placed in an oil bath and the temperature was increased until distillation began. Methyl methacrylate (2) was placed in the addition funnel and was added dropwise at the same rate as the distillate. The reaction mixture was heated for 4 hours and then cooled to room temperature. The crude product was vacuum distilled to isolate 36.5 g(0.156 mol, 49%) of 3-benzyloxypropyl methacrylate (3) as a clear, colorless liquid.
Examples 3 - 29, shown below in Tables 1- 4, illustrate of the materials of the present invention. Each of the formulations of Examples 3 - 29 are prepared as follows. After combining the formulation components as listed in Tables 1-4, each formulation is mixed by agitation and then injected into a polypropylene 25 x 12 x 1 mm slab mold. To make slabs, the cavity in the bottom portion of the slab mold is filled to capacity with the formulation and then the top is placed on strictly as a seal. The molds can either be filled under an inert nitrogen or standard laboratory atmosphere. To maintain the mold geometry during curing, spring clamps are used on the molds. The clamped molds are placed in a forced air oven and cured by heating to 70 -80 C, holding at 70 - 80 C for one hour, then heating to approximately 100 -110 C and holding at approximately 100 - 110 C for two hours. At the end of polymerization period, the molds are opened and the cured intraocular lenses or polymer slabs are removed and extracted in acetone to remove any materials not bound to the cross-linked network.
Physical property data shown for the cured materials in Tables 1- 4 were assessed (according to the methods referred to above). Unless indicated otherwise, all ingredient amounts shown below are listed as % by weight. The following abbreviations are used in Tables 1-4:
PEMA: 2-phenylethyi methacrylate PPrMA: 3-phenylpropylmethacrylate PBMA: 4-phenylbutylmethacrylate BEEMA: benzyloxyethoxyethyl methacrylate BEMA: 2-benzyloxyethyl methacrylate BPMA: 3-benzyloxypropyl methacrylate PPMA: 5-phenylpentyl methacrylate BBMA: 4-benzyloxybutyi methacrylate PEO 1000: polyethylene glycol 1000 dimethacrylate PEO 600: polyethylene glycol 600 dimethacrylate PEO 400: polyethylene glyclo 400 dimethacrylate EGDMA: ethylene glycoldimethacrylate t-BPO: t-butyl (peroxy-2-ethyl)hexanoate BPO: benzoyl peroxide TABLE I
Example PEMA PPrMA PBMA PEO 1000 EGDMA t-BPO %Elongation Tg No. ( C) Examples Component 8 9 10 11 12 13 14 BEMA - - - - - 89.9 -PBMA - - - - - - 90.0 BPMA 94.7 90 - 99.6 - - -PPMA - - 89.7 - - - -BBMA - - - - 89.9 - -PEO 1000 5.3 10 10.3 - 10.1 10.1 10.1 EGDMA - - - 0.4 - - -t-BPO 1.4 1.5 1.4 1.6 1.6 1.3 1.4 Tensile strength (MPa) 3.37 2.83 2.02 3.07 1.11 6.46 4.195 % Strain 900 659 515 974 440 815 696 Young's modulus (MPa) 0.67 0.62 0.76 1.02 0.33 1.89 2.00 100% modulus (MPa) 0.45 0.42 0.51 0.59 0.22 1.07 0.99 RI (dry) 1.539 1.534 1.533 1.543 1.531 1.541 1.535 Examples Component 15 16 17 18 19 20 21 22 23 PBMA 89.75 85.02 79.97 94.95 89.82 85.03 94.99 89.89 84.96 PEO 400 10.25 14.98 20.03 --- --- --- --- ___ ---PEO 600 --- --- --- 5.05 10.18 14.97 --- --- ___ PEO1000 --- --- --- --- --- --- 5.01 10.11 15.04 BPO 0.98 0.96 0.95 0.98 0.95 0.96 1.04 0.95 0.97 Tensile Strength (MPA) 8.23 8.6 8.74 6.55 6.33 514 6.17 5.62 4.35 % Strain 444 378 325 881 707 562 1051 875 699 Young's 6.59 5.78 modulus (MPA) 5.56 3.85 2.82 1.77 4.05 1.92 1.24 100% modulus 3.47 3.34 (MPA) 3.32 2.28 1.55 1.12 2.06 1.12 0.77 T C 5 4 -1 -1 -5 --- --- --- ___ Examples (Ingredients shown in % w/w) Component 24 25 26 27 28 29 30 31 BEEMA --- --- --- --- --- --- 99.6 90.0 PPrMA 85.03 --- --- 85.00 --- --- ___ ---PBMA --- 85.02 --- --- 84.94 --- --- ---PPMA --- --- 85.06 --- --- 85.00 --- PEO 600 14.97 14.98 14.94 --- --- ___ ___ ___ PEO1000 --- --- --- 15.00 15.06 15.00 --- 10.0 EGDMA --- --- ------ --- --- 0.6 BPO 1.00 1.01 0.99 1.01 1.01 1.01 --- ---t-BPO --- --- --- --- --- --- 1.1 1.2 Tensile Strength (MPA) 8.34 4.24 2.67 6.15 3.35 2.05 1.56 1.22 % Strain 502 486 390 662 582 402 468 294 Youngs (MPA) 5.48 1.38 0.85 2.41 0.88 0.67 0.32 0.51 100% (MPA) 3.09 0.96 0.57 1.41 0.63 0.48 0.24 0.36 Tg C --- --- --- --- --- --- -23.2 -26.7
Suitable reactive blue-light absorbing compounds are those described in U.S. Patent No. 5,470,932. Blue-light absorbers are typically present in an amount from about 0.01 - 0.5 % (weight).
Suitable polymerization initiators include thermal initiators and photoinitiators. Preferred thermal initiators include peroxy free-radical initiators, sucti as t-butyl (peroxy-2-ethyl)hexanoate and di-(tert-butyicyclohexyl) peroxydicarbonate (commercially available as Perkadox 16 from Akzo 'Chemicals Inc., Chicago, Illinois). Particularly in cases where the lens material does not contain a blue-light absorbing chromophore, preferred photoinitiators 1s include benzoylphosphine oxide photoinitiators, such as the blue-light initiator 2,4,6-trimethyl-benzoyldiphenylphosphine oxide, commercially available as Lucirin TPO from BASF Corporation (Charlotte, North Carolina). Initiators are typically present in an amount of about 5% (weight) or less.
The identity and amount of the principal lens-forming monomer described above and the identity and amount of any additional components are determined by the desired properties of the finished ophthalmic lens.
Preferably, the ingredients and their proportion are selected so that the acrylic lens materials of the present invention possess the following properties, which make the materials of the present invention particularly suitable for use in {OLs which are to be inserted through incisions of 5 mm or less.
The lens material preferably has a refractive index in the dry state of at least about 1.50 as measured by an Abbe' refractometer at 589 nm (Na light source). For a given optic diameter, optics made from materials having a refractive index lower than 1.50 are necessarily thicker than optics of the same power which are made from materials having a higher refractive index. As such, IOL optics made from materials having a refractive index lower than about 1.50 generally require relatively larger incisions for IOL implantation.
The glass-transition temperature ("Tg") of the lens material, which affects the material's folding and unfolding characteristics, is preferably below about 25 C, and more preferably below about 15 C. Tg is measured by differential scanning calorimetry at 10 C/min., and is determined at the midpoint of the transition of the heat flux curve.
The lens material will have an elongation of at least 150%, preferably at least 200%, and most preferably at least 300%. This property indicates that the lens generally will not crack, tear or split when folded. Elongation of polymer samples is determined on dumbbell shaped tension test specimens with a 20 mm total length, length in the grip area of 4.88 mm, overall width of 2.49 mm, 0.833 mm width of the narrow section, a fillet radius of 8.83 mm, and a thickness of 0.9 mm. Testing is performed on samples at standard laboratory conditions of 23 2 oC and 50 5 % relative humidity using a tensile tester.
The grip distance is set at 14 mm and a crosshead speed is set at 500 mm/minute and the sample is pulled to failure. The elongation (strain) is reported as a fraction of the displacement at failure to the original grip distance. The modulus is calculated as the instantaneous slope of the stress-strain curve at a selected strain. Stress is calculated at the maximum load for the sample, typically the load when the sample breaks, assuming that the initial area remains constant. This stress is recorded as "tensile strength"
in the examples below.
IOLs constructed of the materials of the present invention can be of any design capable of being rolled or folded into a small cross section that can fit through a relatively smaller incision. For example, the IOLs can be of what is known as a one piece or multipiece design, and comprise optic and haptic components. The optic is that portion which serves as the lens. The haptics are attached to the optic and hold the optic in its proper place in the eye.
The optic and haptic(s) can be of the same or different material. A multipiece lens is so called because the optic and the haptic(s) are made separately and then the haptics are attached to the optic. In a single piece lens, the optic and the haptics are formed out of one piece of material. Depending on the material, the haptics are then cut, or lathed, out of the material to produce the IOL.
The invention will be further illustrated by the following examples, which are intended to be illustrative, but not limiting.
)o Example 1: Synthesis of 4-phenylbutyl methacrylate.
/ O T(OCaHe)4 ~ O
I + ~ ~ ~ + CH3OH
~ OH 0-1-r 4-BOP O1~-A
41) (2) 43) A three neck round bottom flask containing a teflon coated magnetic stirring bar was successively charged with 120 mL (1.09 mol) of methyl methacrylate (2), 5.35 g (0.015 mol) of titanium tetrabutoxide (Ti(OC4H9)4), 60 mL (0.39 )s mol) of 4-phenyl-l-butanol (1), and 14.6 g (0.073 mol) of 4-benzyloxyphenol (4-BOP). An addition funnel, thermometer, and a short path still head with thermometer and receiver flask were placed in the flask necks. The flask was placed in an oil bath and the temperature was increased until distillation began. Methyl methacrylate (2) was placed in the addition funnel and was 20 added dropwise at the same rate as the distillate. The reaction mixture was heated for 4 hours and then cooled to room temperature. The crude product was vacuum distilled to isolate 62.8 g (0.29 mol, 74%) of 4-phenylbutyl methacrylate (3) as a clear, colorless liquid.
Example 2: Synthesis of 3-benzyloxypropyl methacrylate.
O
O Ti(OCaHs)4 OOH + , J ' ~ 0---0 + CH3OH
~' ~II( 4-BOP
A
(~) (2) (3) A three neck round bottom flask containing a teflon coated magnetic stirring )o bar was successively charged with 95 mL (0.884 mol) of methyl methacrylate (2), 4.22 g (0.012 mol) of titanium tetrabutoxide (Ti(OC4H9)4), 50 mL (0.316 mol) of 3-benzyloxy-l-propanol (1), and 14.6 g (0.073 mol) of 4-benzyloxyphenol (4-BOP). An addition funnel, thermometer, and a short path still head with thermometer and receiver flask were placed in the flask necks.
The flask was placed in an oil bath and the temperature was increased until distillation began. Methyl methacrylate (2) was placed in the addition funnel and was added dropwise at the same rate as the distillate. The reaction mixture was heated for 4 hours and then cooled to room temperature. The crude product was vacuum distilled to isolate 36.5 g(0.156 mol, 49%) of 3-benzyloxypropyl methacrylate (3) as a clear, colorless liquid.
Examples 3 - 29, shown below in Tables 1- 4, illustrate of the materials of the present invention. Each of the formulations of Examples 3 - 29 are prepared as follows. After combining the formulation components as listed in Tables 1-4, each formulation is mixed by agitation and then injected into a polypropylene 25 x 12 x 1 mm slab mold. To make slabs, the cavity in the bottom portion of the slab mold is filled to capacity with the formulation and then the top is placed on strictly as a seal. The molds can either be filled under an inert nitrogen or standard laboratory atmosphere. To maintain the mold geometry during curing, spring clamps are used on the molds. The clamped molds are placed in a forced air oven and cured by heating to 70 -80 C, holding at 70 - 80 C for one hour, then heating to approximately 100 -110 C and holding at approximately 100 - 110 C for two hours. At the end of polymerization period, the molds are opened and the cured intraocular lenses or polymer slabs are removed and extracted in acetone to remove any materials not bound to the cross-linked network.
Physical property data shown for the cured materials in Tables 1- 4 were assessed (according to the methods referred to above). Unless indicated otherwise, all ingredient amounts shown below are listed as % by weight. The following abbreviations are used in Tables 1-4:
PEMA: 2-phenylethyi methacrylate PPrMA: 3-phenylpropylmethacrylate PBMA: 4-phenylbutylmethacrylate BEEMA: benzyloxyethoxyethyl methacrylate BEMA: 2-benzyloxyethyl methacrylate BPMA: 3-benzyloxypropyl methacrylate PPMA: 5-phenylpentyl methacrylate BBMA: 4-benzyloxybutyi methacrylate PEO 1000: polyethylene glycol 1000 dimethacrylate PEO 600: polyethylene glycol 600 dimethacrylate PEO 400: polyethylene glyclo 400 dimethacrylate EGDMA: ethylene glycoldimethacrylate t-BPO: t-butyl (peroxy-2-ethyl)hexanoate BPO: benzoyl peroxide TABLE I
Example PEMA PPrMA PBMA PEO 1000 EGDMA t-BPO %Elongation Tg No. ( C) Examples Component 8 9 10 11 12 13 14 BEMA - - - - - 89.9 -PBMA - - - - - - 90.0 BPMA 94.7 90 - 99.6 - - -PPMA - - 89.7 - - - -BBMA - - - - 89.9 - -PEO 1000 5.3 10 10.3 - 10.1 10.1 10.1 EGDMA - - - 0.4 - - -t-BPO 1.4 1.5 1.4 1.6 1.6 1.3 1.4 Tensile strength (MPa) 3.37 2.83 2.02 3.07 1.11 6.46 4.195 % Strain 900 659 515 974 440 815 696 Young's modulus (MPa) 0.67 0.62 0.76 1.02 0.33 1.89 2.00 100% modulus (MPa) 0.45 0.42 0.51 0.59 0.22 1.07 0.99 RI (dry) 1.539 1.534 1.533 1.543 1.531 1.541 1.535 Examples Component 15 16 17 18 19 20 21 22 23 PBMA 89.75 85.02 79.97 94.95 89.82 85.03 94.99 89.89 84.96 PEO 400 10.25 14.98 20.03 --- --- --- --- ___ ---PEO 600 --- --- --- 5.05 10.18 14.97 --- --- ___ PEO1000 --- --- --- --- --- --- 5.01 10.11 15.04 BPO 0.98 0.96 0.95 0.98 0.95 0.96 1.04 0.95 0.97 Tensile Strength (MPA) 8.23 8.6 8.74 6.55 6.33 514 6.17 5.62 4.35 % Strain 444 378 325 881 707 562 1051 875 699 Young's 6.59 5.78 modulus (MPA) 5.56 3.85 2.82 1.77 4.05 1.92 1.24 100% modulus 3.47 3.34 (MPA) 3.32 2.28 1.55 1.12 2.06 1.12 0.77 T C 5 4 -1 -1 -5 --- --- --- ___ Examples (Ingredients shown in % w/w) Component 24 25 26 27 28 29 30 31 BEEMA --- --- --- --- --- --- 99.6 90.0 PPrMA 85.03 --- --- 85.00 --- --- ___ ---PBMA --- 85.02 --- --- 84.94 --- --- ---PPMA --- --- 85.06 --- --- 85.00 --- PEO 600 14.97 14.98 14.94 --- --- ___ ___ ___ PEO1000 --- --- --- 15.00 15.06 15.00 --- 10.0 EGDMA --- --- ------ --- --- 0.6 BPO 1.00 1.01 0.99 1.01 1.01 1.01 --- ---t-BPO --- --- --- --- --- --- 1.1 1.2 Tensile Strength (MPA) 8.34 4.24 2.67 6.15 3.35 2.05 1.56 1.22 % Strain 502 486 390 662 582 402 468 294 Youngs (MPA) 5.48 1.38 0.85 2.41 0.88 0.67 0.32 0.51 100% (MPA) 3.09 0.96 0.57 1.41 0.63 0.48 0.24 0.36 Tg C --- --- --- --- --- --- -23.2 -26.7
Claims (14)
1. A polymeric ophthalmic or otorhinolaryngological device material having an elongation of at least 150% and a glass transition temperature Tg of below 25°C, comprising a single device-forming monomer and a cross-linking monomer, wherein the single device-forming monomer is present in an amount of at least about 80% by weight and is an aryl acrylic hydrophobic monomer of the formula wherein: A is H, CH3, CH2CH3, or CH2OH;
B is (CH2)m or [O(CH2)2]n;
C is (CH2)w;
m is 2 - 6;
n is 1 - 10;
Y is nothing, O, S, or NR, provided that if Y is O, S, or NR, then B is (CH2)m;
R is H, CH3, C n H2n+1 (n=1-10), iso-OC3H7, C6H5, or CH2C6H5;
w is 0 - 6, provided that m + w <= 8; and D is H, C1-C4 alkyl, C1-C4 alkoxy, C6H5, CH2C6H5 or halogen; and wherein the cross-linking monomer is a terminally ethylenically unsaturated monomer having more than one unsaturated group.
B is (CH2)m or [O(CH2)2]n;
C is (CH2)w;
m is 2 - 6;
n is 1 - 10;
Y is nothing, O, S, or NR, provided that if Y is O, S, or NR, then B is (CH2)m;
R is H, CH3, C n H2n+1 (n=1-10), iso-OC3H7, C6H5, or CH2C6H5;
w is 0 - 6, provided that m + w <= 8; and D is H, C1-C4 alkyl, C1-C4 alkoxy, C6H5, CH2C6H5 or halogen; and wherein the cross-linking monomer is a terminally ethylenically unsaturated monomer having more than one unsaturated group.
2. The polymeric ophthalmic or otorhinolaryngological device material of claim 1, wherein A is CH3, B is (CH2)m, m is 2 - 5, Y is nothing or O, w is 0 - 1, and D is H.
3. The polymeric ophthalmic or otorhinolaryngological device material of claim 2, wherein the aryl acrylic hydrophobic monomer is selected from the group consisting of 4-phenylbutyl methacrylate; 5-phenylpentyl methacrylate;
2-benzyloxyethyl methacrylate; and 3-benzyloxypropyl methacrylate.
2-benzyloxyethyl methacrylate; and 3-benzyloxypropyl methacrylate.
4. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 3 further comprising one or more components selected from the group consisting of reactive W absorbers and reactive blue-light absorbers.
5. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 4, wherein the material is an ophthalmic device material and has a refractive index of at least 1.50.
6. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 5, wherein the material has a Tg less than about +15°C.
7. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 6, wherein the material has an elongation of at least 200%.
8. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 6, wherein the material has an elongation of at least 300%.
9. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 8, wherein the device is selected from the group consisting of contact lenses; keratoprostheses; corneal inlays or rings;
otological ventilation tubes; and nasal implants.
otological ventilation tubes; and nasal implants.
10. The polymeric ophthalmic or otorhinolaryngological device material of claim 1 wherein the cross-linking monomer comprises one or more cross-linking agents selected from the group consisting of ethylene glycol dimethacrylate;
diethylene glycol dimethacrylate; allyl methacrylate;
1,3-propanediol dimethacrylate; 2,3-propanediol dimethacrylate; 1,6-hexanediol dimethacrylate;
1,4-butanediol dimethacrylate; CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2 where n = 1 - 50; CH2=C(CH3)C(=O)O(CH2)t-OC(=O)C(CH3)=CH2 where t = 3 - 20; and their corresponding acrylates, provided that if the device material comprises two or more cross-linking agents, none of the cross-linking agents is CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2 wherein n = 2 - 50.
diethylene glycol dimethacrylate; allyl methacrylate;
1,3-propanediol dimethacrylate; 2,3-propanediol dimethacrylate; 1,6-hexanediol dimethacrylate;
1,4-butanediol dimethacrylate; CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2 where n = 1 - 50; CH2=C(CH3)C(=O)O(CH2)t-OC(=O)C(CH3)=CH2 where t = 3 - 20; and their corresponding acrylates, provided that if the device material comprises two or more cross-linking agents, none of the cross-linking agents is CH2=C(CH3)C(=O)O-(CH2CH2O)n-C(=O)C(CH3)=CH2 wherein n = 2 - 50.
11. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 10, wherein the single device-forming monomer is present in an amount of at least about 85% by weight.
12. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 11, wherein the cross-linking monomer is present in an amount of about 0.01 - 15% by weight.
13. The polymeric ophthalmic or otorhinolaryngological device material of any one of claims 1 to 12, wherein the aryl acrylic hydrophobic monomer is selected from the group consisting of 4-phenylbutyl methacrylate; 5-phenylpentyl methacrylate; 2-benzyloxyethyl methacrylate; and 3-benzyloxypropyl methacrylate; and the cross-linking monomer is CH2=C(CH3)C(=O)O(CH2CH2O)n-C(=O)C(CH3)=CH2, where n is such that the number average molecular weight of the cross-linking monomer is about 1000.
14. An intraocular lens optic comprising the polymeric device material defined in any one of claims 1 to 13.
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US60/152,622 | 1999-09-07 | ||
PCT/US2000/023283 WO2001018078A1 (en) | 1999-09-07 | 2000-08-23 | Foldable ophthalmic and otorhinolaryngological device materials |
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EP (1) | EP1210380B1 (en) |
JP (3) | JP5459816B2 (en) |
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Families Citing this family (78)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8247511B2 (en) | 1999-04-12 | 2012-08-21 | Advanced Vision Science, Inc. | Water plasticized high refractive index polymer for ophthalmic applications |
US6281319B1 (en) | 1999-04-12 | 2001-08-28 | Surgidev Corporation | Water plasticized high refractive index polymer for ophthalmic applications |
US6723815B2 (en) | 1999-09-02 | 2004-04-20 | Alcon, Inc. | Covalently-bound, hydrophilic coating compositions for surgical implants |
BR0007069B1 (en) * | 1999-09-07 | 2010-02-09 | collapsible ophthalmic and ENT device materials. | |
US8048155B2 (en) | 2002-02-02 | 2011-11-01 | Powervision, Inc. | Intraocular implant devices |
JP4260742B2 (en) * | 2002-07-16 | 2009-04-30 | アルコン,インコーポレイテッド | Ophthalmic and ENT device materials |
US10835373B2 (en) | 2002-12-12 | 2020-11-17 | Alcon Inc. | Accommodating intraocular lenses and methods of use |
US8361145B2 (en) | 2002-12-12 | 2013-01-29 | Powervision, Inc. | Accommodating intraocular lens system having circumferential haptic support and method |
US8328869B2 (en) | 2002-12-12 | 2012-12-11 | Powervision, Inc. | Accommodating intraocular lenses and methods of use |
US7354980B1 (en) | 2004-03-12 | 2008-04-08 | Key Medical Technologies, Inc. | High refractive index polymers for ophthalmic applications |
US8166299B2 (en) * | 2004-07-06 | 2012-04-24 | Andrew Christopher Kemshall | Secure messaging |
US7157538B2 (en) * | 2004-08-13 | 2007-01-02 | Alcon, Inc. | Covalently-bound, hydrophilic coating compositions for surgical implants |
CN101142499A (en) * | 2004-09-28 | 2008-03-12 | 布鲁尔科技公司 | Curable high refractive index resins for optoelectronic applications |
US7446157B2 (en) | 2004-12-07 | 2008-11-04 | Key Medical Technologies, Inc. | Nanohybrid polymers for ophthalmic applications |
JP2009526894A (en) * | 2006-02-14 | 2009-07-23 | プロコルニア ホールディング ビー.ブイ. | High refractive index monomer and (co) polymer prepared therefrom |
EP1818690A1 (en) * | 2006-02-14 | 2007-08-15 | Procornea Holding B.V. | Intraocular lenses essentially free from glistenings |
US8058323B2 (en) * | 2006-07-21 | 2011-11-15 | Novartis Ag | Low-tack ophthalmic and otorhinolaryngological device materials |
TW200816966A (en) * | 2006-07-21 | 2008-04-16 | Alcon Mfg Ltd | Low-tack ophthalmic and otorhinolaryngological device materials |
US7714039B2 (en) * | 2006-07-21 | 2010-05-11 | Alcon, Inc. | Low-tack ophthalmic and otorhinolaryngological device materials |
TWI399228B (en) * | 2006-07-21 | 2013-06-21 | Alcon Inc | Low-tack ophthalmic and otorhinolaryngological device materials |
EP2081612B1 (en) * | 2006-10-13 | 2012-11-21 | Novartis AG | Intraocular lenses with unique blue-violet cutoff and blue light transmission characteristics |
EP2139871B1 (en) * | 2007-04-30 | 2010-09-01 | Alcon, Inc. | Uv-absorbers for ophthalmic lens materials |
US20090001372A1 (en) * | 2007-06-29 | 2009-01-01 | Lumination Llc | Efficient cooling of lasers, LEDs and photonics devices |
US8668734B2 (en) | 2010-07-09 | 2014-03-11 | Powervision, Inc. | Intraocular lens delivery devices and methods of use |
EP2178462B1 (en) | 2007-07-23 | 2014-04-02 | PowerVision, Inc. | Post-implant lens power modification |
US8968396B2 (en) | 2007-07-23 | 2015-03-03 | Powervision, Inc. | Intraocular lens delivery systems and methods of use |
EP2671541B1 (en) | 2007-07-23 | 2019-04-17 | PowerVision, Inc. | Accommodating intraocular lenses |
ATE511530T1 (en) * | 2007-07-25 | 2011-06-15 | Alcon Inc | HIGH REFRACTIVE INDEX MATERIALS FOR OPHTHALMIC DEVICES |
TWI435915B (en) * | 2007-08-09 | 2014-05-01 | Alcon Inc | Ophthalmic lens materials containing chromophores that absorb both uv and short wavelength visible light |
US7858672B1 (en) | 2007-10-02 | 2010-12-28 | Alcon, Inc. | Methacrylic materials suitable for ophthalmic and otorhinolaryngological devices |
TW200916130A (en) | 2007-10-02 | 2009-04-16 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials containing an alkylphenol ethoxylate |
TW200920330A (en) * | 2007-10-02 | 2009-05-16 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials containing an alkyl ethoxylate |
TWI426931B (en) * | 2007-10-03 | 2014-02-21 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials |
TWI426932B (en) * | 2007-10-05 | 2014-02-21 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials |
TWI461186B (en) * | 2007-10-05 | 2014-11-21 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials |
EP2247976B1 (en) * | 2008-02-12 | 2012-08-08 | Aaren Scientific Inc. | Ophthalmic lens having a yellow dye light blocking component |
TW201000155A (en) | 2008-05-06 | 2010-01-01 | Alcon Inc | High refractive index ophthalmic device materials |
US7884228B1 (en) * | 2008-05-06 | 2011-02-08 | Alcon, Inc. | UV-absorbers for ophthalmic lens materials |
US7803359B1 (en) | 2008-05-06 | 2010-09-28 | Alcon, Inc. | UV-absorbers for ophthalmic lens materials |
US8043607B2 (en) * | 2008-07-15 | 2011-10-25 | Novartis Ag | UV-absorbers for ophthalmic lens materials |
WO2010022108A2 (en) * | 2008-08-18 | 2010-02-25 | Envisionier Medical Technologies, Inc. | Fluid delivery catheter apparatus |
EP2334361A4 (en) * | 2008-08-27 | 2011-10-26 | Patrick C Melder | Nasal ventilation system and method of using same |
US8945142B2 (en) | 2008-08-27 | 2015-02-03 | Cook Medical Technologies Llc | Delivery system for implanting nasal ventilation tube |
US8236053B1 (en) | 2008-10-08 | 2012-08-07 | Novartis Ag | 2-amino benzophenone UV-absorbers for ophthalmic lens materials |
TWI453199B (en) | 2008-11-04 | 2014-09-21 | Alcon Inc | Uv/visible light absorbers for ophthalmic lens materials |
US10299913B2 (en) | 2009-01-09 | 2019-05-28 | Powervision, Inc. | Accommodating intraocular lenses and methods of use |
US8293858B1 (en) | 2009-01-14 | 2012-10-23 | Novartis Ag | Ophthalmic and otorhinolaryngological device materials containing a reactive NVP macromer |
US8148445B1 (en) | 2009-01-14 | 2012-04-03 | Novartis Ag | Ophthalmic and otorhinolaryngological device materials containing a multi-arm PEG macromer |
TWI464151B (en) * | 2009-07-06 | 2014-12-11 | Alcon Inc | Uv/visible light absorbers for ophthalmic lens materials |
TWI487690B (en) | 2009-07-06 | 2015-06-11 | Alcon Inc | Visible light absorbers for ophthalmic lens materials |
AU2010289896B2 (en) | 2009-08-24 | 2013-08-29 | Alcon Inc. | Ophthalmic and otorhinolaryngological device materials |
TWI473629B (en) | 2010-01-18 | 2015-02-21 | Alcon Inc | Visible light absorbers for ophthalmic lens materials |
JP2013520291A (en) | 2010-02-23 | 2013-06-06 | パワーヴィジョン・インコーポレーテッド | Liquid for accommodation type intraocular lens |
JP5882302B2 (en) | 2010-04-29 | 2016-03-09 | ノバルティス アーゲー | Intraocular lens having a combination of UV absorber and blue light chromophore |
US8362177B1 (en) | 2010-05-05 | 2013-01-29 | Novartis Ag | High refractive index ophthalmic device materials with reduced tack |
TWI473823B (en) | 2010-06-21 | 2015-02-21 | Novartis Ag | High refractive index, acrylic ophthalmic device materials with reduced glistenings |
US9622853B2 (en) | 2010-07-05 | 2017-04-18 | Jagrat Natavar DAVE | Polymeric composition for ocular devices |
TWI517861B (en) | 2011-02-08 | 2016-01-21 | 諾華公司 | Low-tack, hydrophobic ophthalmic device materials |
TWI513768B (en) | 2011-06-01 | 2015-12-21 | Novartis Ag | Hydrophobic acrylic intraocular lens materials |
TWI551646B (en) * | 2011-06-03 | 2016-10-01 | 諾華公司 | Hydrophobic acrylic intraocular lens materials |
JP5799634B2 (en) | 2011-07-22 | 2015-10-28 | 株式会社リコー | Image processing apparatus and image processing system |
TW201311621A (en) | 2011-08-15 | 2013-03-16 | Novartis Ag | UV-absorbers for ophthalmic lens materials |
KR101982897B1 (en) | 2011-09-16 | 2019-05-27 | 벤즈리써치앤드디벨롭먼트코오포레이숀 | Hydrophobic intraocular lens |
US10433949B2 (en) | 2011-11-08 | 2019-10-08 | Powervision, Inc. | Accommodating intraocular lenses |
AU2012369994B2 (en) | 2012-02-15 | 2014-12-04 | Alcon Inc. | Ophthalmic and otorhinolaryngological device materials containing a multi-arm PEG macromer |
US8585938B1 (en) | 2012-03-30 | 2013-11-19 | Novartis Ag | UV-absorbers for ophthalmic lens materials |
MX2014015344A (en) | 2012-06-26 | 2015-03-05 | Novartis Ag | 2-amino benzophenone uv-absorbers for ophthalmic lens materials. |
EP2941445B1 (en) | 2013-01-07 | 2017-03-22 | Council of Scientific & Industrial Research | Flexible, high refractive index hydrophobic copolymer |
JP6717740B2 (en) | 2013-03-15 | 2020-07-01 | パワーヴィジョン・インコーポレーテッド | Device for accommodating and placing intraocular lens and method of using the same |
EP3077016B1 (en) * | 2013-12-04 | 2018-05-16 | Novartis AG | Soft acrylic materials with high refractive index and minimized glistening |
US9956384B2 (en) | 2014-01-24 | 2018-05-01 | Cook Medical Technologies Llc | Articulating balloon catheter and method for using the same |
JP6371480B2 (en) | 2014-12-16 | 2018-08-08 | ノバルティス アーゲー | Low water content acrylate-acrylamide copolymers for ophthalmic appliances |
CN106999628A (en) | 2014-12-16 | 2017-08-01 | 诺华股份有限公司 | Hydrophobic acrylic acid's ester acrylamide copolymer for Ophthalmoligic instrument |
WO2016133656A1 (en) | 2015-02-16 | 2016-08-25 | Novartis Ag | Wet-pack intraocular lens materials with high refractive index |
CN108348328B (en) | 2015-11-06 | 2020-04-10 | 力景公司 | Accommodating intraocular lens and method of manufacture |
KR102309508B1 (en) | 2017-06-05 | 2021-10-06 | 알콘 인코포레이티드 | Intraocular lens material with high refractive index and high Abbe number |
KR20220074943A (en) | 2019-10-04 | 2022-06-03 | 알콘 인코포레이티드 | Adjustable Intraocular Lenses and Methods of Postoperative Adjustment of Intraocular Lenses |
CN111154028A (en) * | 2020-01-06 | 2020-05-15 | 东南大学 | High-refractive-index corneal contact lens material and application thereof |
Family Cites Families (55)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3850892A (en) | 1972-01-03 | 1974-11-26 | Biocontacts | Physiologically compatible plastic contact lenses and a method for their production |
US4304895A (en) | 1973-06-20 | 1981-12-08 | Wesley-Jessen, Inc. | Ultraviolet absorbing corneal contact lenses |
AR207867A1 (en) | 1974-07-04 | 1976-11-08 | Smith & Nephew Res | A LIGHTLY INTERLACED HYDROGEL COPOLYMER |
US4260954A (en) | 1979-01-26 | 1981-04-07 | Barcus-Berry, Inc. | Amplifier load correction system |
US4267295A (en) | 1979-02-09 | 1981-05-12 | Syntex (U.S.A.) Inc. | Polymeric compositions and hydrogels formed therefrom |
US4452776A (en) | 1979-08-20 | 1984-06-05 | Eye Research Institute Of Retina Foundation | Hydrogel implant article and method |
JPS6017404B2 (en) | 1980-12-15 | 1985-05-02 | ホ−ヤ株式会社 | Low dispersion high refractive index lens |
US4405773A (en) | 1982-02-05 | 1983-09-20 | Schering Corporation | Hydrophylic contact lenses and methods for making same |
US5507805A (en) | 1982-05-03 | 1996-04-16 | American Cyanamid Company | Intraocular lens and method of retaining in place |
DE3376267D1 (en) | 1982-11-11 | 1988-05-19 | Showa Denko Kk | POLYMERIZABLE COMPOSITIONS |
JPS59195621A (en) | 1983-04-22 | 1984-11-06 | Toyo Contact Lens Co Ltd | Soft contact lens |
US4528311A (en) | 1983-07-11 | 1985-07-09 | Iolab Corporation | Ultraviolet absorbing polymers comprising 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazoles |
US4664666A (en) | 1983-08-30 | 1987-05-12 | Ezekiel Nominees Pty. Ltd. | Intraocular lens implants |
EP0391452B1 (en) | 1983-08-30 | 1994-01-05 | Ezekiel Nominees Pty.Ltd. | Intraocular lens implants |
CA1252249A (en) * | 1983-09-24 | 1989-04-04 | Teruo Sakagami | Halogen-containing resin lens material |
JPS60200011A (en) | 1984-03-21 | 1985-10-09 | Matsushita Electric Ind Co Ltd | Liquid fuel burner |
US4620954A (en) | 1985-06-07 | 1986-11-04 | Ciba Vision Care Corp. | Hydrogel from ultraviolet-initiated copolymerization |
JPS62111229A (en) | 1985-11-11 | 1987-05-22 | Hoya Corp | Soft contact lens |
US4676792A (en) | 1986-08-26 | 1987-06-30 | Donald Praeger | Method and artificial intraocular lens device for the phakic treatment of myopia |
JPH0622565B2 (en) | 1986-10-28 | 1994-03-30 | 株式会社メニコン | Intraocular lens material |
EP0273710B2 (en) | 1986-12-26 | 1996-10-16 | Nippon Shokubai Kagaku Kogyo Co., Ltd | Resin having high refractive index, process for producing said resin and optical materials composed of said resin |
NL8701548A (en) | 1987-07-01 | 1989-02-01 | Tno | POLYMER NETWORK, METHOD FOR THE PREPARATION THEREOF, THE USE THEREOF FOR CLADING AND / OR IMPREGNATING OR FOR MANUFACTURING EYE LENSES, AND FORMED PROPERTIES, WHOLLY OR FROM AN EXISTINGLY PROVEN POLISH. |
US4834750A (en) | 1987-09-17 | 1989-05-30 | Ioptex Research, Inc. | Deformable-elastic intraocular lens |
US5269813A (en) | 1990-06-12 | 1993-12-14 | Menicon Co., Ltd. | Material for one-piece intraocular lenses |
ATE143677T1 (en) * | 1990-11-07 | 1996-10-15 | Nestle Sa | POLYMERS AND THEIR USE FOR OPTHALMIC LENSES |
US5290892A (en) * | 1990-11-07 | 1994-03-01 | Nestle S.A. | Flexible intraocular lenses made from high refractive index polymers |
JPH05310A (en) | 1991-06-26 | 1993-01-08 | Kobe Steel Ltd | Wiper device for hot rolling mill and method for controlling the same |
US5341974A (en) | 1992-06-19 | 1994-08-30 | Mont-Bell Co., Ltd. | Back bag |
US5331073A (en) | 1992-11-09 | 1994-07-19 | Allergan, Inc. | Polymeric compositions and intraocular lenses made from same |
JP3108550B2 (en) | 1992-11-11 | 2000-11-13 | 株式会社メニコン | Soft ophthalmic lens material |
US5470932A (en) | 1993-10-18 | 1995-11-28 | Alcon Laboratories, Inc. | Polymerizable yellow dyes and their use in opthalmic lenses |
US5451651A (en) | 1993-12-17 | 1995-09-19 | Bausch & Lomb Incorporated | Urea and urethane monomers for contact lens materials |
SE9403392D0 (en) | 1994-10-06 | 1994-10-06 | Pharmacia Ab | Intraocular lens materials |
US5654350A (en) | 1995-06-07 | 1997-08-05 | Johnson & Johnson Vision Products, Inc. | Contact lenses with hydrophilic crosslinkers |
KR100331456B1 (en) * | 1995-06-07 | 2002-10-25 | 알콘 래보레이토리스, 인코퍼레이티드 | Improved high refractive index ophthalmic lens materials |
SE9600006D0 (en) | 1996-01-02 | 1996-01-02 | Pharmacia Ab | Foldable intraocular lens materials |
US5922821A (en) * | 1996-08-09 | 1999-07-13 | Alcon Laboratories, Inc. | Ophthalmic lens polymers |
DK0914169T3 (en) * | 1997-05-29 | 2003-11-03 | Alcon Mfg Ltd | Materials for use in glaucoma filtration devices |
US5891931A (en) | 1997-08-07 | 1999-04-06 | Alcon Laboratories, Inc. | Method of preparing foldable high refractive index acrylic ophthalmic device materials |
AU727484B2 (en) * | 1997-08-12 | 2000-12-14 | Alcon Laboratories, Inc. | Ophthalmic lens polymers |
JP3641110B2 (en) | 1997-08-20 | 2005-04-20 | 株式会社メニコン | Materials for soft intraocular lenses |
JP4144920B2 (en) | 1997-08-20 | 2008-09-03 | 興和株式会社 | Soft intraocular lens material |
DE19738345C1 (en) | 1997-09-02 | 1999-05-06 | Mdp Medical Device Polymers Gm | intraocular lens |
CN1213671A (en) | 1997-10-07 | 1999-04-14 | 参天制药株式会社 | Four-component copolymer and eye lens formed by same |
ES2243053T3 (en) * | 1998-04-15 | 2005-11-16 | Alcon Manufacturing Ltd. | MATERIALS OF OPTALMIC DEVICES OF HIGH REFRACTION INDEX, PREPARED USING A METHOD OF RETICULATION AFTER POLYMERIZATION. |
AU739750B2 (en) * | 1998-04-15 | 2001-10-18 | Alcon Laboratories, Inc. | Bicomposite intraocular lens and method for its preparation |
EP1080382B1 (en) * | 1998-04-15 | 2009-07-08 | Alcon, Inc. | High refractive index ophthalmic device materials |
WO2000026698A1 (en) | 1998-10-29 | 2000-05-11 | Allergan Sales, Inc. | Intraocular lenses made from polymeric compositions |
US6245106B1 (en) | 1998-10-29 | 2001-06-12 | Allergan Sales, Inc. | Intraocular lenses made from polymeric compositions and monomers useful in said compositions |
US6329485B1 (en) | 1998-12-11 | 2001-12-11 | Bausch & Lomb Incorporated | High refractive index hydrogel compositions for ophthalmic implants |
US6281319B1 (en) | 1999-04-12 | 2001-08-28 | Surgidev Corporation | Water plasticized high refractive index polymer for ophthalmic applications |
WO2000079312A1 (en) | 1999-06-17 | 2000-12-28 | Bausch & Lomb Surgical, Inc. | High refractive index compositions for ophthalmic implants |
US6271281B1 (en) | 1999-08-26 | 2001-08-07 | Medennium, Inc. | Homopolymers containing stable elasticity inducing crosslinkers and ocular implants made therefrom |
JP2003508605A (en) * | 1999-09-07 | 2003-03-04 | アルコン,インコーポレイテッド | Equipment materials for ophthalmology and otorhinolaryngology |
BR0007069B1 (en) * | 1999-09-07 | 2010-02-09 | collapsible ophthalmic and ENT device materials. |
-
2000
- 2000-08-23 BR BRPI0007069-6A patent/BR0007069B1/en not_active IP Right Cessation
- 2000-08-23 ES ES00957779T patent/ES2235935T3/en not_active Expired - Lifetime
- 2000-08-23 CN CNB008085501A patent/CN1151186C/en not_active Expired - Fee Related
- 2000-08-23 WO PCT/US2000/023283 patent/WO2001018078A1/en active IP Right Grant
- 2000-08-23 JP JP2001522299A patent/JP5459816B2/en not_active Expired - Fee Related
- 2000-08-23 DE DE60018766T patent/DE60018766T2/en not_active Expired - Lifetime
- 2000-08-23 DK DK00957779T patent/DK1210380T3/en active
- 2000-08-23 US US09/645,669 patent/US6528602B1/en not_active Expired - Lifetime
- 2000-08-23 AU AU69347/00A patent/AU766276B2/en not_active Ceased
- 2000-08-23 CA CA002347707A patent/CA2347707C/en not_active Expired - Fee Related
- 2000-08-23 AT AT00957779T patent/ATE291045T1/en active
- 2000-08-23 PT PT00957779T patent/PT1210380E/en unknown
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2003
- 2003-01-24 US US10/350,993 patent/US6653422B2/en not_active Expired - Lifetime
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2011
- 2011-05-19 JP JP2011112886A patent/JP2011161261A/en not_active Withdrawn
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- 2013-12-02 JP JP2013248836A patent/JP2014042846A/en not_active Withdrawn
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AU6934700A (en) | 2001-04-10 |
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US6653422B2 (en) | 2003-11-25 |
JP2003508187A (en) | 2003-03-04 |
WO2001018078A1 (en) | 2001-03-15 |
JP2014042846A (en) | 2014-03-13 |
BR0007069A (en) | 2001-07-31 |
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