CA2404522A1 - Fluorosulfone-silicone-hydrogel contact lenses, optical medical devices and compositions thereof - Google Patents
Fluorosulfone-silicone-hydrogel contact lenses, optical medical devices and compositions thereof Download PDFInfo
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- CA2404522A1 CA2404522A1 CA002404522A CA2404522A CA2404522A1 CA 2404522 A1 CA2404522 A1 CA 2404522A1 CA 002404522 A CA002404522 A CA 002404522A CA 2404522 A CA2404522 A CA 2404522A CA 2404522 A1 CA2404522 A1 CA 2404522A1
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- sulfone
- acrylic
- monomer
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- copolymer
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- 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
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- 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
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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
- G02B1/041—Lenses
- G02B1/043—Contact lenses
Abstract
Highly comfortable hydrophilic contact lenses that were made from a copolymer of an ethylenically unsaturated fluorosulfone ester monomer of acrylic and methacrylic acid and organosilicone monomer esters of acrylic and methacrylic acid, an ethylenically unsaturated ester of methacrylic acid having alkyl hydroxy groups and N-vinyl 2-pyrrolidinone, methacrylic acid and methods for manufacturing thereof.
Description
FLUOROSULFONE-SILICONE HYDROGEL CONTACT LENSES, OPTICAL MEDICAL DEVICES AND
COMPOSITIONS THEREOF
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to novel formulation of monomers, to produce polymers for the purpose of manufacturing hydrophilic contact lenses and other optical devices.
In particular, one important use of the materials made from the invention is the manufacture of corneal contact lenses.
COMPOSITIONS THEREOF
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to novel formulation of monomers, to produce polymers for the purpose of manufacturing hydrophilic contact lenses and other optical devices.
In particular, one important use of the materials made from the invention is the manufacture of corneal contact lenses.
2. Description of Related Art In recent years, hydrophilic corneal lenses have become more and more popular in the United States, Canada, and throughout the world. In an attempt to create contact lenses which are comfortable, oxygen permeable and essentially clean from deposits which requires the incorporation of fluorocarbon chain components in order to make the surface of the lens slick.
This permits easy movement of the Iens on the eyes without any friction along with the wettability component that allows the lens to be more hydrophilic, delivering the necessary comfort to the patient.
Previous hydrophilic contact lenses are based on 2-hydroxyethyl methacrylate (HEMA) or derivatives thereof which produce reasonable comfort to the patient while they are clean.
However, when worn for a longer period of time this type of lens has a tendency to accumulate deposits or debris on the surface of the lens which requires constant cleaning and in some cases, it becomes disposable. The patient then has to dispose of the contact lenses and get new ones.
While such materials accumulate proteinaceous matter as deposits on the lens surface, the lens is impaired to proper transparency. If the deposits on the lens are too large, the lens could cause abrasion to the wearer's eyes. In recent years Nicolson describes, in U.S. Patent No. 5,789,461 and related counterparts, extended wear hydrophilic contact lenses based on amido compounds. However, as practical experience shows a patient requires longer periods of time for adaptation to use such a lens.
In another silicone hydrogel contact lens, U.S. Patent No. 4,711,943, Harvey III describes amidosilicone methacrylates as his invention.
In Novicky's earlier patent, U.S. Patent No. 4,748,224, describes silicone-sulfone contact lenses as an RGP (rigid gas permeable) lens and semi-RGP's. However, it is desirable to invent contact lenses with superior comfort from initial placement of the lens on the human eye to achieve patient satisfaction and to encourage the patient's desire to use contact lenses.
SUMMARY OF THE INVENTION
The present invention, therefore, is intended to improve performance of a hydrophilic contact lens on human eyes. The copolymers of the present invention will give very good optical clarity when hydrated because the copolymers contain a fluorocarbon chain monomer which gives an extremely slick surface of the lens and remains free of debris or deposits - even when lenses are worn for longer periods of time. The copolymer plastic, when hydrated, will have increased strength over HEMA hydrophilic contact lenses. The copolymer plastic of the present invention can be prepared by polymerization in rod form and then processed into contact lens blanks which are ultimately machined into contact lenses. Secondly, the same copolymeric plastic can be directly cast molded in specific molds directly into the shape of contact lenses.
The said contact lenses when immersed in Alcon OPTI-FREE contact lens solution gives a hydrophilic contact lens polymer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A still further facet of the invention includes synthesis of the copolymer plastic which, when hydrated in saline solution, gives a water content between 15% to 50%
which can also be used for other medical devices, such as infra-ocular lenses, lenses for instruments used for body contact and health diagnostic instruments. The present invention includes the following monomers:
This permits easy movement of the Iens on the eyes without any friction along with the wettability component that allows the lens to be more hydrophilic, delivering the necessary comfort to the patient.
Previous hydrophilic contact lenses are based on 2-hydroxyethyl methacrylate (HEMA) or derivatives thereof which produce reasonable comfort to the patient while they are clean.
However, when worn for a longer period of time this type of lens has a tendency to accumulate deposits or debris on the surface of the lens which requires constant cleaning and in some cases, it becomes disposable. The patient then has to dispose of the contact lenses and get new ones.
While such materials accumulate proteinaceous matter as deposits on the lens surface, the lens is impaired to proper transparency. If the deposits on the lens are too large, the lens could cause abrasion to the wearer's eyes. In recent years Nicolson describes, in U.S. Patent No. 5,789,461 and related counterparts, extended wear hydrophilic contact lenses based on amido compounds. However, as practical experience shows a patient requires longer periods of time for adaptation to use such a lens.
In another silicone hydrogel contact lens, U.S. Patent No. 4,711,943, Harvey III describes amidosilicone methacrylates as his invention.
In Novicky's earlier patent, U.S. Patent No. 4,748,224, describes silicone-sulfone contact lenses as an RGP (rigid gas permeable) lens and semi-RGP's. However, it is desirable to invent contact lenses with superior comfort from initial placement of the lens on the human eye to achieve patient satisfaction and to encourage the patient's desire to use contact lenses.
SUMMARY OF THE INVENTION
The present invention, therefore, is intended to improve performance of a hydrophilic contact lens on human eyes. The copolymers of the present invention will give very good optical clarity when hydrated because the copolymers contain a fluorocarbon chain monomer which gives an extremely slick surface of the lens and remains free of debris or deposits - even when lenses are worn for longer periods of time. The copolymer plastic, when hydrated, will have increased strength over HEMA hydrophilic contact lenses. The copolymer plastic of the present invention can be prepared by polymerization in rod form and then processed into contact lens blanks which are ultimately machined into contact lenses. Secondly, the same copolymeric plastic can be directly cast molded in specific molds directly into the shape of contact lenses.
The said contact lenses when immersed in Alcon OPTI-FREE contact lens solution gives a hydrophilic contact lens polymer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A still further facet of the invention includes synthesis of the copolymer plastic which, when hydrated in saline solution, gives a water content between 15% to 50%
which can also be used for other medical devices, such as infra-ocular lenses, lenses for instruments used for body contact and health diagnostic instruments. The present invention includes the following monomers:
[2-(N-ethylperfluoroalkylsulfonamido)ethylmethacrylate]
O O
\\ ~I
CHZ=C-C-O-(CHZ)n-N-S-CHz-CH2-(CFZ)m-CF3 R. Rz O
wherein R. and RZ, which may be the same or different, are hydrogen, alkyl, cyclic, or phenyl groups, n is an integer from 1 to 5 and m is an integer from 0 to 10. Typical monomers are:
2-(N-ethylperfluorobutylsulfonamido)ethylmethacrylate, 2-(N-ethylperfluorobutylsulfonamido)ethylacrylate, or mixtures thereof.
Representative of the hydroxyalkyl monomer of acrylic or methacrylic acid are those having the following general formula:
O O
CHZ=C-C-O-(CHz)n-OH and CHZ=C-C-O-(CHZ)n-OH
wherein n is an integer from 1 to 5 and 2,3 dihydroxypropyl acrylate and 2,3 dihydroxypropyl methacrylate or mixtures thereof.
Representative of heteroatom hydrophilic monomer are those having the following general formula:
~O
CH=CHZ
N-vinyl 2-pyrrolidinone Oxygen permeability monomer is represented by organosiloxanylalkyl ester monomers of acrylic and methacrylic acid have the structural formula:
A X O R
I t II
A Si Si-(CHz)n-O-C-C=CHZ (I) I
A Y
wherein X and Y are C~ to C6, alkyl, cyclic or phenyl groups and/or groups of the following structure:
A
I
A Si-0 I
A
m m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C. to Cb, alkyl or phenyl groups, and R is methyl group or hydrogen.
A second useful group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following formula:
A X O R
I ~ II i D Si-O Si-(CHZ)n-O-C-C=CHz (II) I I
A Y
m wherein X and Y are C~ to Cb, alkyl or phenyl groups or groups of the following structure:
A
I
D Si-O
A
m m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C. to Cb, alkyl or phenyl groups, R is methyl group or hydrogen, and D is hydrogen or hydroxy group.
A third useful group of oganosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following structural formula:
X O
CH3-Si-(CHZ)n-O-C-C=CHz I
Y R
wherein X and Y are groups of the following structure:
A
A Si-O
A
m m being an integer from 1 to 5, n is an integer from 1 to 3, wherein A is selected from C~ to Cb, alkyl, cyclic or phenyl groups and R is methyl group or hydrogen.
O O
\\ ~I
CHZ=C-C-O-(CHZ)n-N-S-CHz-CH2-(CFZ)m-CF3 R. Rz O
wherein R. and RZ, which may be the same or different, are hydrogen, alkyl, cyclic, or phenyl groups, n is an integer from 1 to 5 and m is an integer from 0 to 10. Typical monomers are:
2-(N-ethylperfluorobutylsulfonamido)ethylmethacrylate, 2-(N-ethylperfluorobutylsulfonamido)ethylacrylate, or mixtures thereof.
Representative of the hydroxyalkyl monomer of acrylic or methacrylic acid are those having the following general formula:
O O
CHZ=C-C-O-(CHz)n-OH and CHZ=C-C-O-(CHZ)n-OH
wherein n is an integer from 1 to 5 and 2,3 dihydroxypropyl acrylate and 2,3 dihydroxypropyl methacrylate or mixtures thereof.
Representative of heteroatom hydrophilic monomer are those having the following general formula:
~O
CH=CHZ
N-vinyl 2-pyrrolidinone Oxygen permeability monomer is represented by organosiloxanylalkyl ester monomers of acrylic and methacrylic acid have the structural formula:
A X O R
I t II
A Si Si-(CHz)n-O-C-C=CHZ (I) I
A Y
wherein X and Y are C~ to C6, alkyl, cyclic or phenyl groups and/or groups of the following structure:
A
I
A Si-0 I
A
m m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C. to Cb, alkyl or phenyl groups, and R is methyl group or hydrogen.
A second useful group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following formula:
A X O R
I ~ II i D Si-O Si-(CHZ)n-O-C-C=CHz (II) I I
A Y
m wherein X and Y are C~ to Cb, alkyl or phenyl groups or groups of the following structure:
A
I
D Si-O
A
m m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C. to Cb, alkyl or phenyl groups, R is methyl group or hydrogen, and D is hydrogen or hydroxy group.
A third useful group of oganosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following structural formula:
X O
CH3-Si-(CHZ)n-O-C-C=CHz I
Y R
wherein X and Y are groups of the following structure:
A
A Si-O
A
m m being an integer from 1 to 5, n is an integer from 1 to 3, wherein A is selected from C~ to Cb, alkyl, cyclic or phenyl groups and R is methyl group or hydrogen.
An additional sulfone monomer can be incorporated into copolymer plastic of the present invention. The preferable monomers are: methyl vinyl sulfone, methyl styrene sulfone, ethyl vinyl sulfone, ethyl styrene sulfone, propyl vinyl sulfone, propyl styrene sulfone, phenyl vinyl sulfone, phenyl styrene sulfone, cyclohexyl vinyl sulfone, cyclohexyl styrene sulfone, pentyl vinyl sulfone, pentyl styrene sulfone, butyl vinyl sulfone, butyl styrene sulfone, phenoxyethyl vinyl sulfone. phenoxyethyl styrene sulfone, divinyl sulfone, methacryloxyethyl methyl sulfone, methacryloxyethyl ethyl sulfone, methacryloxyethyl propyl sulfone, methacryloxyethyl butyl sulfone, methacryloxyethyl phenyl sulfone, methacryloxyethyl pentyl sulfone, methacryloxyethyl styrene sulfone, or mixtures thereof.
The said copolymer plastic material can also be modified by adding small amounts of from about 1 to 20 weight percent of alkyl or cyclic ester monomer of acrylic or methacrylic acids; preferably, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, cyclohexyl methacrylate, 2-hydroxycyclohexyl methacrylate, propyl methacrylate, and propyl acrylate.
The hydrophilic contact lens material can be further modified to achieve better hydration of the lens by the addition of methacrylic acid or acrylic acid and a small amount of cross-linking agent to improve overall performance of the contact lenses. Representative cross-linking agents are ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, triethyleneglycol diacrylate, tetraethyleneglycol diacrylate, divinyl benzene, divinyl sulfone, trimethylolpropane trimethacrylate, and mixtures thereof.
The preferred composition of the present invention comprises o~
( a ) from about 1 to 60 weight percent of ethylenically unsaturated perfluoroalkylsulfonamidoethyl ester monomer of acrylic or methacrylic acid or mixtures thereof;
( b ) from about 1 to 50 weight percent of ethylenically unsaturated hydroxyalkyl monomer of acrylic or methacrylic acid or mixtures thereof;
( c ) from about 5 to 65 weight percent organosilicone monomer;
( d ) from 2 to 40 weight percent of N-Vinyl 2-pyrrolidinone;
( a ) from about 0.1 to 8 weight percent of acrylic or methacrylic acid or mixtures thereof;
( f ) from about 0.1 to 7 weight percent of cross-linking agent monomer, preferably ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate and tetraethyleneglycol dimethacrylate or mixtures thereof; and ( g ) from about 1 to 20 weight percent of alkyl or cyclic esters monomer of methacrylic acid and acrylic acid; preferably, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, cyclohexyl methacrylate, 2-hydroxycyclohexyl methacrylate and mixtures thereof.
-g_ The polymerization of the oxygen permeable wettable contact lens material is disclosed in prior art using free-radical polymerization techniques such as that disclosed in Novicky U.S.
Patent No. 4,861,850.
This example illustrates the preparation of representative copolymer plastic material for hydrophilic contact lenses:
To a 200 ml flask was added 20 grams of HEMA (2-hydroxyethylmethacrylate), 15 grams of N-vinyl 2-pyrrolidinone, 25 g of [2-(N-ethylperfluorobutanesulfonamido)ethylmethacrylate], 30 grams of organosilicone monomer I, 10 grams of methyl methacrylate, 5 grams of methacrylic acid and 0.5 grams of t-butylperoxyoctoate. All components were mixed thoroughly and poured into polypropylene tubes, molds closed with stoppers and polymerized in a water bath or thermostated oven set at 65°C for a period of about 20 hours. The rods or blanks were then put into a thermostated oven preheated at 105°C for a period of 24 hours.
The copolymer plastic is hard and suitable for the manufacturing of contact lenses. Then, when immersed in a saline solution (such as Alcon OPTI-FREE) it becomes an hydrophilic lens having a water content about 24.2 weight percent.
This example illustrates preparation for direct casting of contact lenses. To a 200 ml flask was added 20 grams of [2-(N-ethylperfluorobutanesulfonamido)ethylmethacylate], 20 grams of 2-hydroxyethyl methacrylate, 15 grams of N-vinyl-pyrrolidinone, 30 grams of organosilcone monomer II, 15 grams of methyl methacrylate, 8 grams of methacrylic acid, 3 grams of TEGDMA, and 0.5 grams of free radical catalyst VAZO 67. All components were thoroughly mixed and poured to the cast contact lens molds (such as described in the Travnicek U.S. Patent No. 4,165,158). Polymerization was carried out at room temperature (21 °C) gradually increasing to 115°C over a period of 3 hours and then for an additional 2 hours the temperature was held at constant to finish polymerization. The oven was turned off and the temperature was gradually brought down to room temperature. The casting molds were removed from the oven, and separated. The contact lenses were removed from the concave portion of the mold, then hydrated in Alcon OPTI-FREE mufti-purpose solution. The expansion factor was 1.15 and the water content of the lens was 23 weight percent. The power of the lens on hydration changed 0.75 diopters. The hydrated lens was very clear, slippery, wettable and suitable for hydrophilic contact lens.
This example illustrates preparation of the representative copolymer plastic material for hydrophilic contact lenses. To a 200 ml flask was added 30 grams of distilled HEMA, 15 grams of N-vinyl 2-pyrrolidinone, 1.5 grams of diethyleneglycol dimethacrylate, 4.5 grams of methacrylic acid, 20 grams of 2-(N-ethylperfluoroethylsulfonamido)ethylmethacrylate, 20 grams of organosilicone monomer I and 10 grams of methyl methacrylate. The mixture was stirred together thoroughly and 0.5 grams fo IABN catalyst was added, then stirred again until all catalyst was dissolved. The mixture was poured into contact lens mold cavities, the molds were closed with the convex part of the mold, then polymerized in a thermostated oven at a program-mabel temperature starting from 30°C to 118°C over a 2 hour period. They were slowly cooled down in the oven at room temperature, the molds removed from the oven and the lenses were removed from the casting molds. The lenses were hydrated for a 2-3 day period in Alcon OPTI-FREE solution.
This example illustrates the preparation of copolymer plastic material with an additional polysulfone monomer. To a 200 ml flask was added 15 grams of distilled HEMA, 5 grams of vinylmethyl sulfone, 10 grams of N-vinyl 2-pyrrolidinone, 35 grams of 2-(N-ethylperfluorobutyl-sulfonamido)ehtylmethacryalte, 25 grams of organosilicone monomer II and 10 grams of methyl methacrylate. The mixture was stirred thoroughly and 0.5 grams of IABN
catalyst was added then stirred again until all the catalyst was dissolved. The mixture was poured into suitable polypropylene molds, then polymerized in a thermostated oven starting from 30° C to 127°C, programmable over a 3 hour period of time. The lenses were processed in the same way as in EXAMPLE 3 using the Alcon OPTI-FREE solution for hydration of the lenses.
Samples of optically clear plastic hydrophilic contact lenses were prepared in accordance with EXAMPLE 3; however, component compositions were different as described in the following table:
TABLE
Example Number Components~Part~ 5 6 7 8 9 10 2-(N-ethylperfluorobutylsulfonamido)-20 20 10 15 30 14 ethylemthacrylate N-vinyl2-pyrrolidinone 15 10 12 15 20 18 2-hydroxyethylmethacrylate 20 25 30 14.5 20 18 methacrylic acid 5 3 6 5 5 ethyleneglycol dimethacrylate - - 0.5 - - -diethyleneglycol dimethacrylate - - - 1.5 - -organosilicone monomer I 30 25 20 23 20 30 organosilicone monomer II - - - 11 - -methylvinyl sulfone _ 5 _ _ _ _ phenyl styrene sulfone - - g _ _ _ methyl methacrylate 5 5 8 10 10 10 methacryloxyethyl methyl sulfone - - _ 5 _ _ 2-(N-ethylperfluorooctylsulfonamido)ethyl-5 7 5.5 - - 5 methacrylate *Note: All samples of the above copolymer plastics are clear after hydration.
This example illustrates preparation of the copolymer plastic for hydrophilic contact lenses with the additional handling of tint to it. The copolymer plastic was prepared in accordance with EXAMPLE 3 and 0.02% of D&C #6 green dye was added to the mixture and polymerized the same way as described in the above-referenced example. The resulting contact lenses after hydration had a slight bluish tint to it for easy use for the wearer.
Although I have described my invention in connection with specific examples and preferred embodiments thereof, it is readily apparent to those skilled in the art that the invention may be modified without departing from the scope of the claims.
The said copolymer plastic material can also be modified by adding small amounts of from about 1 to 20 weight percent of alkyl or cyclic ester monomer of acrylic or methacrylic acids; preferably, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, cyclohexyl methacrylate, 2-hydroxycyclohexyl methacrylate, propyl methacrylate, and propyl acrylate.
The hydrophilic contact lens material can be further modified to achieve better hydration of the lens by the addition of methacrylic acid or acrylic acid and a small amount of cross-linking agent to improve overall performance of the contact lenses. Representative cross-linking agents are ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, triethyleneglycol diacrylate, tetraethyleneglycol diacrylate, divinyl benzene, divinyl sulfone, trimethylolpropane trimethacrylate, and mixtures thereof.
The preferred composition of the present invention comprises o~
( a ) from about 1 to 60 weight percent of ethylenically unsaturated perfluoroalkylsulfonamidoethyl ester monomer of acrylic or methacrylic acid or mixtures thereof;
( b ) from about 1 to 50 weight percent of ethylenically unsaturated hydroxyalkyl monomer of acrylic or methacrylic acid or mixtures thereof;
( c ) from about 5 to 65 weight percent organosilicone monomer;
( d ) from 2 to 40 weight percent of N-Vinyl 2-pyrrolidinone;
( a ) from about 0.1 to 8 weight percent of acrylic or methacrylic acid or mixtures thereof;
( f ) from about 0.1 to 7 weight percent of cross-linking agent monomer, preferably ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate and tetraethyleneglycol dimethacrylate or mixtures thereof; and ( g ) from about 1 to 20 weight percent of alkyl or cyclic esters monomer of methacrylic acid and acrylic acid; preferably, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, cyclohexyl methacrylate, 2-hydroxycyclohexyl methacrylate and mixtures thereof.
-g_ The polymerization of the oxygen permeable wettable contact lens material is disclosed in prior art using free-radical polymerization techniques such as that disclosed in Novicky U.S.
Patent No. 4,861,850.
This example illustrates the preparation of representative copolymer plastic material for hydrophilic contact lenses:
To a 200 ml flask was added 20 grams of HEMA (2-hydroxyethylmethacrylate), 15 grams of N-vinyl 2-pyrrolidinone, 25 g of [2-(N-ethylperfluorobutanesulfonamido)ethylmethacrylate], 30 grams of organosilicone monomer I, 10 grams of methyl methacrylate, 5 grams of methacrylic acid and 0.5 grams of t-butylperoxyoctoate. All components were mixed thoroughly and poured into polypropylene tubes, molds closed with stoppers and polymerized in a water bath or thermostated oven set at 65°C for a period of about 20 hours. The rods or blanks were then put into a thermostated oven preheated at 105°C for a period of 24 hours.
The copolymer plastic is hard and suitable for the manufacturing of contact lenses. Then, when immersed in a saline solution (such as Alcon OPTI-FREE) it becomes an hydrophilic lens having a water content about 24.2 weight percent.
This example illustrates preparation for direct casting of contact lenses. To a 200 ml flask was added 20 grams of [2-(N-ethylperfluorobutanesulfonamido)ethylmethacylate], 20 grams of 2-hydroxyethyl methacrylate, 15 grams of N-vinyl-pyrrolidinone, 30 grams of organosilcone monomer II, 15 grams of methyl methacrylate, 8 grams of methacrylic acid, 3 grams of TEGDMA, and 0.5 grams of free radical catalyst VAZO 67. All components were thoroughly mixed and poured to the cast contact lens molds (such as described in the Travnicek U.S. Patent No. 4,165,158). Polymerization was carried out at room temperature (21 °C) gradually increasing to 115°C over a period of 3 hours and then for an additional 2 hours the temperature was held at constant to finish polymerization. The oven was turned off and the temperature was gradually brought down to room temperature. The casting molds were removed from the oven, and separated. The contact lenses were removed from the concave portion of the mold, then hydrated in Alcon OPTI-FREE mufti-purpose solution. The expansion factor was 1.15 and the water content of the lens was 23 weight percent. The power of the lens on hydration changed 0.75 diopters. The hydrated lens was very clear, slippery, wettable and suitable for hydrophilic contact lens.
This example illustrates preparation of the representative copolymer plastic material for hydrophilic contact lenses. To a 200 ml flask was added 30 grams of distilled HEMA, 15 grams of N-vinyl 2-pyrrolidinone, 1.5 grams of diethyleneglycol dimethacrylate, 4.5 grams of methacrylic acid, 20 grams of 2-(N-ethylperfluoroethylsulfonamido)ethylmethacrylate, 20 grams of organosilicone monomer I and 10 grams of methyl methacrylate. The mixture was stirred together thoroughly and 0.5 grams fo IABN catalyst was added, then stirred again until all catalyst was dissolved. The mixture was poured into contact lens mold cavities, the molds were closed with the convex part of the mold, then polymerized in a thermostated oven at a program-mabel temperature starting from 30°C to 118°C over a 2 hour period. They were slowly cooled down in the oven at room temperature, the molds removed from the oven and the lenses were removed from the casting molds. The lenses were hydrated for a 2-3 day period in Alcon OPTI-FREE solution.
This example illustrates the preparation of copolymer plastic material with an additional polysulfone monomer. To a 200 ml flask was added 15 grams of distilled HEMA, 5 grams of vinylmethyl sulfone, 10 grams of N-vinyl 2-pyrrolidinone, 35 grams of 2-(N-ethylperfluorobutyl-sulfonamido)ehtylmethacryalte, 25 grams of organosilicone monomer II and 10 grams of methyl methacrylate. The mixture was stirred thoroughly and 0.5 grams of IABN
catalyst was added then stirred again until all the catalyst was dissolved. The mixture was poured into suitable polypropylene molds, then polymerized in a thermostated oven starting from 30° C to 127°C, programmable over a 3 hour period of time. The lenses were processed in the same way as in EXAMPLE 3 using the Alcon OPTI-FREE solution for hydration of the lenses.
Samples of optically clear plastic hydrophilic contact lenses were prepared in accordance with EXAMPLE 3; however, component compositions were different as described in the following table:
TABLE
Example Number Components~Part~ 5 6 7 8 9 10 2-(N-ethylperfluorobutylsulfonamido)-20 20 10 15 30 14 ethylemthacrylate N-vinyl2-pyrrolidinone 15 10 12 15 20 18 2-hydroxyethylmethacrylate 20 25 30 14.5 20 18 methacrylic acid 5 3 6 5 5 ethyleneglycol dimethacrylate - - 0.5 - - -diethyleneglycol dimethacrylate - - - 1.5 - -organosilicone monomer I 30 25 20 23 20 30 organosilicone monomer II - - - 11 - -methylvinyl sulfone _ 5 _ _ _ _ phenyl styrene sulfone - - g _ _ _ methyl methacrylate 5 5 8 10 10 10 methacryloxyethyl methyl sulfone - - _ 5 _ _ 2-(N-ethylperfluorooctylsulfonamido)ethyl-5 7 5.5 - - 5 methacrylate *Note: All samples of the above copolymer plastics are clear after hydration.
This example illustrates preparation of the copolymer plastic for hydrophilic contact lenses with the additional handling of tint to it. The copolymer plastic was prepared in accordance with EXAMPLE 3 and 0.02% of D&C #6 green dye was added to the mixture and polymerized the same way as described in the above-referenced example. The resulting contact lenses after hydration had a slight bluish tint to it for easy use for the wearer.
Although I have described my invention in connection with specific examples and preferred embodiments thereof, it is readily apparent to those skilled in the art that the invention may be modified without departing from the scope of the claims.
Claims (12)
1. A copolymer plastic contact lens material consisting of principle monomers as follows:
(a) from about 1 to 60 weight percent of perfluoroalkylsulfonylamideoethyl ester monomer of acrylic and methacrylic acid having the following formula:
wherein, R1 and R2, which may be the same or different, are hydrogen, alkyl, cyclic or phenyl groups, n is an integer from 1 to 5 and m is an integer from 0 to 10. Typical monomers are
(a) from about 1 to 60 weight percent of perfluoroalkylsulfonylamideoethyl ester monomer of acrylic and methacrylic acid having the following formula:
wherein, R1 and R2, which may be the same or different, are hydrogen, alkyl, cyclic or phenyl groups, n is an integer from 1 to 5 and m is an integer from 0 to 10. Typical monomers are
2-(N-ethylperfluorobutylsulfonamido)ethylmethacrylate, 2-(N-ethylperfluorobutylsulfoneamido)-ethylacrylate or mixtures thereof; and 2-(N-ethylperfluorooctylsulfoneamido)ethylmethacrylate, 2(N-ethylperfluorooctylsulfoneamido)ethylacrylate and mixtures thereof;
(b) from 5 to 40 weight percent of hydrophilic monomer which is hydroxyalkyl monomer of acrylic and methacrylic acids that are represented by having the general formula:
wherein, n is an integer from 1 to 5 and 2,3 dihydroxypropylacrylate and 2,3 dihydroxypropyl-methacrylate. Another wettability agent monomer incorporated into the copolymer plastic material can be N-vinyl 2-pyrrolidinone which has the following formula:
(c) from about 5 to 40 weight percent of at least one organosilicone monomer;
wherein, typical organosiloxanyl ester monomers of acrylic and methacrylic acid having the following structural formula:
wherein, X and & are C1 to C6, alkyl, cyclic or phenyl groups and/or groups of the following structure:
m being an integer from 1 to 6, n being an integer from 1 to 3; wherein, A is selected from C1 to C6, alkyl or phenyl groups and R is methyl group or hydrogen.
A second useful group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following formula:
wherein, X and Y are C1 to C6, alkyl, cyclic or phenyl groups or groups of the following structure:
m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C1 to C6, alkyl or phenyl groups, R is methyl group or hydrogen and D is hydrogen or hydroxy group.
A third useful group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following structural formula:
wherein, X and Y are groups of the following structure:
m being an integer from 1 to 5, n is an integer from 1 to 3; wherein, A is selected from C1 to C6, alkyl, cyclic or phenyl groups and R is methyl group or hydrogen.
(d) from about 1 to 20 weight percent said copolymer plastic material can also be modified by adding small amounts of from about 1 to 20 weight percent of alkyl or cyclic ester monomer of acrylic or methacrylic acids; preferably, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, cyclohexyl methacrylate, 2-hydroxycyclohexyl methacrylate, propyl methacrylate, and propyl acrylate.
2. The copolymer of Claim 1; wherein, a perfluoroalkylorganosulfone monomer is typically 2-(N-ethylperfuorobutylsulfoneamido)ethylmethacrylate, 2(N-ethylperfluorobutylsulfone-amido)ethylacrylate, 2-(N-ethylperfluorooctylsulfoneamido)ethylmethacrylate, 2-(N-ethyl-perfluorooctylsulfoneamido)ethylacylate and mixtures thereof.
(b) from 5 to 40 weight percent of hydrophilic monomer which is hydroxyalkyl monomer of acrylic and methacrylic acids that are represented by having the general formula:
wherein, n is an integer from 1 to 5 and 2,3 dihydroxypropylacrylate and 2,3 dihydroxypropyl-methacrylate. Another wettability agent monomer incorporated into the copolymer plastic material can be N-vinyl 2-pyrrolidinone which has the following formula:
(c) from about 5 to 40 weight percent of at least one organosilicone monomer;
wherein, typical organosiloxanyl ester monomers of acrylic and methacrylic acid having the following structural formula:
wherein, X and & are C1 to C6, alkyl, cyclic or phenyl groups and/or groups of the following structure:
m being an integer from 1 to 6, n being an integer from 1 to 3; wherein, A is selected from C1 to C6, alkyl or phenyl groups and R is methyl group or hydrogen.
A second useful group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following formula:
wherein, X and Y are C1 to C6, alkyl, cyclic or phenyl groups or groups of the following structure:
m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C1 to C6, alkyl or phenyl groups, R is methyl group or hydrogen and D is hydrogen or hydroxy group.
A third useful group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following structural formula:
wherein, X and Y are groups of the following structure:
m being an integer from 1 to 5, n is an integer from 1 to 3; wherein, A is selected from C1 to C6, alkyl, cyclic or phenyl groups and R is methyl group or hydrogen.
(d) from about 1 to 20 weight percent said copolymer plastic material can also be modified by adding small amounts of from about 1 to 20 weight percent of alkyl or cyclic ester monomer of acrylic or methacrylic acids; preferably, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, cyclohexyl methacrylate, 2-hydroxycyclohexyl methacrylate, propyl methacrylate, and propyl acrylate.
2. The copolymer of Claim 1; wherein, a perfluoroalkylorganosulfone monomer is typically 2-(N-ethylperfuorobutylsulfoneamido)ethylmethacrylate, 2(N-ethylperfluorobutylsulfone-amido)ethylacrylate, 2-(N-ethylperfluorooctylsulfoneamido)ethylmethacrylate, 2-(N-ethyl-perfluorooctylsulfoneamido)ethylacylate and mixtures thereof.
3. A composition consisting essentially of a copolymer of an ethylenically unsaturated perfluoroalkylsulfonamidoalkyl ester monomer of acrylic or methacrylic acid, an ethylenically unsaturated ester monomer of methacrylic acid having alkylhydroxy groups, organosilicone ester monomer of acrylic and methacrylic acid and N-vinyl 2-pyrrolidinone and optionally a crosslinking agent.
4. A copolymer plastic contact lens material consisting essentially of from about 1 to 60 weight percent of an ethylenically unsaturated fluorosulfone ester monomer having the general formula (I) of:
wherein, R1 and R2, which may be the same or different, are hydrogen, alkyl, cyclic or phenyl groups, n is an integer from 1 to 5 and m is an integer from 0 to 10. The balance consisting of at least one comonomer selected from the group consisting of an hydroxyalkyl monomer of acrylic or methacrylic acid, sulfone monomer, pyrrolidinone and optionally a crosslinking agent, a wettability agent, an hardening agent, a dye or pigment and mixtures thereof.
wherein, R1 and R2, which may be the same or different, are hydrogen, alkyl, cyclic or phenyl groups, n is an integer from 1 to 5 and m is an integer from 0 to 10. The balance consisting of at least one comonomer selected from the group consisting of an hydroxyalkyl monomer of acrylic or methacrylic acid, sulfone monomer, pyrrolidinone and optionally a crosslinking agent, a wettability agent, an hardening agent, a dye or pigment and mixtures thereof.
5. A copolymer plastic of Claim 1; wherein, is included additional hydrophilic monomers 2,3-dihydroxypropyl acrylate and 2,3-dihydroxypropyl methacrylate or mixtures thereof.
6. A copolymer plastic hydrophilic contact lens material consisting of perfluoroamidoalkyl-sulfone monomers of acrylic and methacrylic acid and pyrrolidinones.
7. A contact lens material consisting of the monomers in Claim 1; wherein, additional sulfone monomers are included from the group as follows: methyl vinyl sulfone, methyl styrene sulfone, ethyl vinyl sulfone, ethyl styrene sulfone, propyl vinyl sulfone, propyl styrene sulfone, phenyl vinyl sulfone, phenyl styrene sulfone, cyclohexyl vinyl sulfone, cyclohexyl styrene sulfone, pentyl vinyl sulfone, pentyl styrene sulfone, butyl vinyl sulfone, butyl styrene sulfone, phenoxyethyl vinyl sulfone, phenoxyethyl styrene sulfone, divinyl sulfone, methacryloxyethyl methyl sulfone, methacryloxyethyl ethyl sulfone, methacryloxyethyl propyl sulfone, methacryloxyethyl butyl sulfone, methacryloxyethyl phenyl sulfone, methacryloxyethyl pentyl sulfone, methacryloxyethyl styrene sulfone and mixtures thereof.
8. A composition made up of a copolymer of an ethylenically unsaturated perfluoroalkyl-sulfonamidoalkyl ester monomer of acrylic acid and an ethylenically unsaturated ester monomer of methacrylic acid having alkyl hydroxy groups and N-vinyl 2-pyrrolidinone.
9. An hydrophilic contact lens comprising the copolymer of Claim 5.
10. A contact lens copolymer plastic of Claim 1; wherein, said plastic is immersed in saline solution and produces an hydrophilic polymer having between 15 to 50 weight percent water content.
11. The copolymer plastic material according to Claim 3; wherein, the copolymer is further modified by an incorporation of a small amount of 0.1 to 6 weight percent of an additional wettability agent such as acrylic acid, methacrylic acid, 2,3 dihydroxypropyl methacrylate, N-vinyl 2-pyrrolidinone and mixtures thereof.
12. The copolymer plastic contact lens material of Claim 1; wherein, further steps are required for hydrating copolymer plastic to create an hydrophilic contact lens.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002404522A CA2404522A1 (en) | 2002-09-19 | 2002-09-19 | Fluorosulfone-silicone-hydrogel contact lenses, optical medical devices and compositions thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002404522A CA2404522A1 (en) | 2002-09-19 | 2002-09-19 | Fluorosulfone-silicone-hydrogel contact lenses, optical medical devices and compositions thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2404522A1 true CA2404522A1 (en) | 2004-03-19 |
Family
ID=32075098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002404522A Abandoned CA2404522A1 (en) | 2002-09-19 | 2002-09-19 | Fluorosulfone-silicone-hydrogel contact lenses, optical medical devices and compositions thereof |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2404522A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007147599A1 (en) * | 2006-06-21 | 2007-12-27 | Acri.Tec Ag Gesellschaft Für Ophtalmotologische Producte | Ophthalmological composition and use thereof |
-
2002
- 2002-09-19 CA CA002404522A patent/CA2404522A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007147599A1 (en) * | 2006-06-21 | 2007-12-27 | Acri.Tec Ag Gesellschaft Für Ophtalmotologische Producte | Ophthalmological composition and use thereof |
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