CA2108682A1 - Novel composition for contact lenses - Google Patents
Novel composition for contact lensesInfo
- Publication number
- CA2108682A1 CA2108682A1 CA 2108682 CA2108682A CA2108682A1 CA 2108682 A1 CA2108682 A1 CA 2108682A1 CA 2108682 CA2108682 CA 2108682 CA 2108682 A CA2108682 A CA 2108682A CA 2108682 A1 CA2108682 A1 CA 2108682A1
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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
- C08F220/22—Esters containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Eyeglasses (AREA)
Abstract
NOVEL COMPOSITION FOR CONTACT LENSES
Abstract A hydrogel copolymer for making contact lenses comprises, by weight, about 5 to about 85 percent of .alpha.-methylene-N-methylpyrrolidone or glycidyl methacrylate and mixtures thereof from about 5 to about 35 percent of N,N-dimethylacrylamide, from about 5 to about 60 percent of a polymerizable fluoromonomer, and from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer. An initiator and a crosslinker are usually preferably also employed.
Abstract A hydrogel copolymer for making contact lenses comprises, by weight, about 5 to about 85 percent of .alpha.-methylene-N-methylpyrrolidone or glycidyl methacrylate and mixtures thereof from about 5 to about 35 percent of N,N-dimethylacrylamide, from about 5 to about 60 percent of a polymerizable fluoromonomer, and from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer. An initiator and a crosslinker are usually preferably also employed.
Description
2 ~ 2 NOVEL COMPOSmON FOR CONTACT IENSES
Background of ~e Invention This invention relates to contact lenses, and in particular to pliable or "soft" contact lens having - an exceptional combination of oxygen permeability, strength, and resistance to protein and mucus deposits.
There is a great need for a contact lens that has high oxygen permeability and wettability and resistance to protein and mucus deposits. These properties all contribute to an extension of the time during which a contact lens can be continuously worn by a wearer.
High oxygen permeability is needed because the pupil of the eye has no blood circulation and extracts the oxygen needed by its cells directly from the atmosphere. Wettability is essential for wearer comfort. Resistance to protein and mucus deposits from -. fluids that bathe the outer surface of the eye is ~ essential since without this feature the lens pores ¦ become clogged and both visual acuity and the oxygen permeability of the lens suffer.
Many types of contact lens compositions have been proposed. There are two general categories of contact lenses--rigid and hydrogel. For example, U.S. Patent Nos. 3,808,178 and 4,120,570 to Gaylord, 4,139,692 to Tanaka et al; 4,686,276 to Ellis et al;
u~
.','.,'. - ' -2- 210~82 4,743,106 to Novicky et al, and 4,812,598 to Chen propose the use of various copolymer compositions including silicon in contact lenses. The lenses are reasonably permeable to oxygen but are not of hydrogel or "soft" construction.
U.S. Patent No. 4,130,706 to Plambeck, Jr.
proposes a methacrylate-type fluoropolymer ("FMA") for making contact lenses. While the lenses are described as hydrophilic and oxygen permeable, it is believed that they are not wettable enough to be truly comfortable to persons wearing the lenses and are not sufficiently permeable to oxygen to be worn safely and continuously for extended periods.
U.S. Patent No. 3,940,207 to Barkdoll proposes contact lenses constructed of fluorine-containing polymers that are soft and have a low refractive index. It is believed that these contact lenses are not sufficiently oxygen permeable to be worn safely for extended periods.
s 20 U.S. Patent Nos. 4,954,587 and 5,011,275 to Mueller propose soft, extended wear contact lenses based on N,N-dimethylacrylamide ("DMA"). While the lenses have a high oxygen permeability, the use of higher amounts of the relatively soft polymer of N,N-dimethylacrylamide is limited in that the lenses could ` become too soft to be fabricated.
; It would be highly desirable to provide a hydrogel copolymer which can be used to form an easily fabricated pliable contact lens having the combination of oxygen permeability, wettability and resistance to protein and mucus deposits.
SummarY of the Invention The present invention relates to a hydrogel copolymer for making contact lenses, the copolymer comprising, by weight, about 10 percent to about 85 percent o~ ~-methylene-N-methylpyrrolidone or glycerdyl ~ - ~ . . - ,.. .. .
.'' . , , ~ '' ',- ' ' , ~ ' . .
,., , ' ' ',' ' ~ ~ --3- 2 1 a ~ ~ ~ 2 methacryla~e and mixtures thereof, from about 5 to about 25 percent of N,N-dimethylacrylamide, about 5 percent to about 80 percent of a polymerizable fluoromonomer, and about 1 percent to about 15 percent of a polymerizable hydrophophic, non-hydrolyzable - silicone monomer. Optionally, an initiator and a crosslinker are employed under circumstances disclosed below.
In one embodiment of the invention, the copolymer comprises, by weight, from about 10 to 85 percent a-methylene-N-methylpyrrolidone, from about 5 to about 85 percent of glycerdyl methacrylate, from about 5 to about 60 percent of a polymerizable fluoromonomer, and from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer.
In another embodiment, the copolymer comprises, by weight, from about 40 to about 90 percent of ~-methylene-N-methylpyrrolidone and from about 10 to about 60 percent of a polymerizable fluoromonomer such as fluoroacyrlates, styryl fluoromonomers and vinyl - fluoromonomers.
Detailed Descriotion of the Preferred Embodiments The present invention will now be described more fully hereinafter. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiment set forth herein; rather, this embodiment is provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those ; skilled in the art.
The present invention utilizes in various combinations, as described below ~-methylene~N-methylpyrrolidone ("~-MMP") or glycerdyl methacrylate ("GMA") and mixtures thereof, N,N-dimethyl methacrylamide, a polymerizable fluoromonomer, a ~. - : - .. . .
t`
:.. -. , : . . ;' :~
'' ' - , ~ ~, : - .
~4~ 210~6~2 polymerizable hydrophobic, non-hydrolyzable silicone monomer, an initiator, and a crosslinker.
Preferably, the hydrogel copolymer comprises, by weight, from about 5 to about 85 percent of -S methylene-N-methylpyrrolidone ox glycerdyl methacrylate and mixtures thereof, from about 10 to about 25 percent, and preferably from about 5 to about 20 percent of N,N-dimethylacrylamide, from about 5 to about 85 percent, and preferably from about 20 to about 40 percent by weight of a polymerizable fluoromonomer and from about l to about 15 percent, and preferably from about 2 to about 4 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer.
Preferably, from about 20 to about 30 percent of ~-methylene-N-methylpyrrolidone or from about 5 to about 30 percent of glycerdyl methacrylate is used.
If a mixture of ~-methylene-N-pyrrolidone and glyceridyl methacrylate is used, preferably from about 10 to about 85 percent of ~-methylene-N-pyrrolidone and from about 5 to about 85 percent of glycerdyl methacrylate are used.
In one embodiment of the invention, from about 50 to about 90 percent of ~-methylene-N-pyrrolidone can be blended with from about lO to about 50 percent of a polymerizable fluoromonomer to form the hydrogel copolymer. In this embodiment, the hydrogel copolymer can further include, by weight, from about 10 to about 25 percent of a polymerizable hydrophilic monomer selected from the group consisting of methacrylic acid ("MA"), 2-hydroxyethylmethacrylate ("HEMA"), N-vinyl-2-pyrrolidone ("NVP") and N,N-dimethylacrylamide ("DMA").
The polymerizable fluoromonomer useful herein can vary. An exemplary fluoromonomer is one based on a fluoroacrylate composition which includes the following fluorine-containing monomer:
.~ . ~... ..
.~ .
_5_ ~ 682 C= CH2 C=O
I
( CH2 ) m ( CFz ) n where R is H or CH3, m is an integer from 0 to 9, and n is an integer from 1 to 4. A similar monomer is disclosed in U.S. Patent No. 4,130,706 to Plambeck, Jr., the disclosure of which is incorporated herein by reference.
; Another exemplary fluoromonomer can be a fluoracrylate ~ R
.~ C= CH2 '. C=O
I -CH2 CHz C"~l F2 (m~
.
where R and m are defined as above. A similar monomer ~, is disclosed in U.S. Patent No. 3,282,905 to Fosick et i 10 al, the disclosure of which is incorporated herein by reference.
A particularly preferred composition is 2,2,2-trifluoroethyl methacrylate ("FMA").
CHz= Cl F
O=C-O -CH2-C-F
-6- ~ 1 08 ~ ~2 Alternatively, styryl fluoromonomers can be employed. The general formula of these monomers is CH-fH
~F, where r + s = 5 and r = 1 to 5 and s = 5 to 1.
A particularly preferred styryl fluoromonomer is pentafluorostyrene.
F ~ F
F
Other examples of fluoromonomers are p-vinyl benzyl trifluoroacetate and p-vinyl benzyl hexafluoroisopropyl ' ether.
Alternatively, vinyl fluoromonomers can be , 10 used. They have the general formula CH2=CH
( CH2 ) tCUF2U~l ~
where t = 1 to 4 and u = 1 to 9. A particularly ~-preferred vinyl fluoromonomer is 3,3,3 I trifluorovinylpropane CH2 = CH F
C8,C82-C-F
A
i i ~, . ' ., ', ' : " ': . . : ' ' _7_ 2108~2 Alternatively, perfluorocyclohexyl acrylates can be used having the general formula R F F
CH~-C ~
O-C-O~F
~ I
F F
where R = ~ or CH3. A particularly preferred pefluorocyclohexyl acrylate is perfluorocyclopentane.
It is no~ed that only ~-methylene-N-methylpyrrolidone and the polymerizable fluoromonomer can be used.
The polymerizable hydrophobic non-hydrolyzable silicone monomer useful herein can vary.
An exemplary silicone has the formula AtSI-O~SI-l CH2 )~ C=CH2 A a Y
where a is an integer from 1 to 5 and b is an integer from 0 to 6, A is selected from the group consisting Of ¦ Cl-C5 alkyl groups and phenyl groups, R is selected from the group consisting of a methyl group (CH~) and hydrogen, X and Y are selected from the group consisting of Cl to C5 alkyl groups, phenyl groups and Z
groups wherein Z is a group of the structure :~ A-¦~i - -¦
A a where a and A are as defined previously, and ~ is a 3 phenyl group. In the alkanol ester co-monomers, the ~ alkyl group contains from 1 to 20 carbon atoms.
20 Exemplary silicon-containing monomers are disclosed in J U.S. Patent Nos. 3,808,178 and 4,120,570 to Gaylord, ~;
i -8- 2 ~ ~ ~r;~ 2 the disclosures of which are incorporated herein by reference.
Alternatively, vinyl silicone monomers can be employed. The general formula can be represented as CH2=CH (I) Rl-s i -R
or ~1 (II) CH2 = CH R
(CH2)X- si -Rl where X = 1 to 6 and Rl is selected from the class consisting of Cl to C6 alkyl groups and phenyl groups or a mixture of alkyl and phenyl groups.
Particularly preferred examples of Class (I) ;
are CH2 = CH CH2 = CH : :
CH3 - si - CH3 CH3 -Si - CH3 CH3CH2 = CH <P
~-fi-C~3 where "~" represents a phenyl group.
Particularly preferred examples of Class (II) are ., :
.1 , J, ~ ,:
J .~ . . -:. . ~ , ' ' . ' . . , `.'. . :
. . .
~',: " ' ' , ' ' , , , . ' ',' ' :' - .
,: ' '' ~ . ' ' . ~ .' ' ' ' . - , ' , . ''' '' ' '',' ' ' . " ,. ' ' ' ' .. '. ' . ,' . " ' '~: " ';. ' .
",' ' ,~ ' '. . '' .. ' ', ' , ~ '"." . ' ', ' ' ' ", . ,. '' ' ', 2 1 ~
CH2= I H CIH3 CH2=CH CH, CH2 cH2 -si - CH3 Cf~z Cf~2 -SI-~>
CH3 CH, .
CH2 = CH
CH2 CH2 -Si -~
In both classes of vinyl silicone monomers, any methyl group (CH3 group) can be replaced by a benzene ring, as the preceding examples suggest.
Generally, vinyl silicone monomers are less reactive than acrylate silicone monomers. When vinyl silicone monomers are used, cobalt-60 ("Co-60"), radiation may be used as a source of polymerization energy. Co-60 may optionally be used as a source of polymerization energy even when vinyl silicone monomers are not employed.
. Exemplary non-hydrolyzable silicones include ~; methyldi(trimethylsiloxy)silylpropylglycerol methacrylate, methylidi(trimethylsiloxy)silylpropyl-glycerolethyl methacrylate, m,p-styrlethyltrimethyl-silane, m,p-styrylethyltris(trimethylisiloxy)silane, methylacryloxypropyltris(trimethylsiloxy)silane and 4-(3-trimethylsilylpropyl)benzylstyrene sulfonate.
Preferably a crosslinker is used. The crosslinker can constitute, by weight, about 0.01 percent to about 5 percent and more preferably about 0.5 percent to about 2 percent of the weight of the hydrogel copolymer. The crosslinker is preferably one of a mixture of ethyleneglycoldimethacrylate ("EGDMA"), ' a fluorine-containing compound, or a silicon-containing :~ .
~ .
~ -~.', . ' . ~ , '. ' ,' '- ' : " ' ' ' " :' :' .
-lo- 2 1 ~ 2 compound such as 1,3-bis[(p-acryloxymethyl) - phenethyl]tetramethyldisiloxane or bis(3-methacryloxypropyl)tetramethyldisiloxane.
A quantity of an initiator equal in weight to 0.05 percent to 2 about percent of the weight of the mixture of monomers is preferably added thereto, except when Co-60 is used as a source of polymerization energy. The initiator may be selected from the group consisting essentially of 2,2'-azobis(2,4-- 10 dimethylvaleronitrile) ("VAZ0 52"), azobisisobutyro-nitrile ("AIBN"), benzoinmethylether ("BME"), di(sec-butyl)peroxydicarbonate ("SBC"), and isopropylperoxydicarbonate ("Ipp"). The initiator may also be any of those disclosed in the U.S. Patent No. 4,120,570, to Gaylord, i.e., acetyl peroxide, lauroyl peroxide, decanoyl peroxide, caprylyl peroxide, b~nzoyl peroxide, tertiary-butyl peroxypivalate, diisopropyl peroxycarbonate, tertiary-butyl peroctoate, and ~ azobisisobutyronitrile.
VAZ0 52 or AIBN may be used as an initiator when polymerization is aided by ultraviolet or thermal radiation, BME may be used as the initiator when polymerization is aided by the ultraviolet radiation, and SBC or Ipp may be used as the initiator when polymerization is aided by thermal radiation. Co-60 or another radioactive source may also be used to promote polymerization, particularly when vinyl silicone monomers or other monomers that are not highly reactive are employed. When Co-60 or another radioactive source is not used, polymerization energy is supplied in the form of thermal energy or in the form of ultraviolet radiation, as may be appropriate in view of the -initiator employed. When Co-60 radiation is employed, 3 no initiators are needed.
After curing, the resulting polymer is formed in any conventional or otherwise suitable process into contact lenses. The lenses have a shore hardness (D
.
: : " . : ~ . .: . . , scale) within atherange of 82 to 89. Oxygen permeability in DK units (ml cm/cm2 sec cmHg X 10-10) at 35°C is within the range of 10°-34°, light transmission is greater than 95%, refractive index is close to that of HEMA, and the coefficient of expansion is within the range of 1.1 to 1.6.
The following examples set forth representative formulas for the materials used in making contact lenses according to the invention:
Example 1 The following are mixed at room temperature in a 100ml beaker:
The initiator is added to the mixture, and the mixture is poured into a test tube and polymerized by thermal polymerization (i.e., application of heat) 1.alpha.-methylene-N-methylpyrrolidone 22,2,2-trifluoroethylmethacrylate available from Aldrich Chemical Company of Milwaukee, Wisconson 3N,N-dimethylacrylamide available from Aldrich Chemical Company 4methylacryloxypropyltris(trimethylsiloxy)silane available from Huls America, Inc, of Newark, New Jersey 5etheyleneglycoldimethacrylate available from Rohm Tech, Inc. of Marden, Massachuseets 6isopropylperoxydicarbonate available from Polyscience, Inc. of Warrington, Pennsylvania 21'~8f;82 This is accomplished by placing the test tube in a hot water bath at a temperature of 30C. The polymerized material is a colorless, solid, transparent polymer.
The polymer is lathe-cut into buttons of conventional shape and size. The buttons are ground to the shape of contact lenses having respective center thicknesses of O.lmm to 0.2mm, and then polished. The lenses are highly transparent (light transmission i8 greater than 95%) and have uniform optical properties. They have an oxygen permeability of 35 DK units at 35 C (normal eye temperature), a contact angle of less than 18-, and a refractive index of 1.40S.
The following examples are similar to Example 1 but illustrate variations of the materials and quantities thereof employed and of the method of polymerization.
ExamPle2 Percent 8y Inaredients Weiaht ~-MMP
FMA 19.94 DMA 39.38 ; MDC 29.90 EGDMA .50 BME7 0.02 25 The mixture is molded in the form of shells and polymerized by ultraviolet radiation in accordance with U. S. Patent No. 4,812,598 to Chen, the disclosure of which is incorporated herein by reference. The shells ~-are lathe-cut to form contact lenses in accordance therewith.
. ~ .
7bcn~oinmethylefher iniliator available from Polyscience, rnc ,, .
::
. - ` : ' ' , . -.. . : :: : : :, .- -: ' ' . ; -.- :: . :
.: . ' ` ' ' '' . ' '`~ `' ' ' ', ., :
:: .: ' : ' - ;
.
2~0'~2 ExamPle3 Percent By In~redients Weiaht ~-MMP 64.74 MDC 9.96 FMA 24.90 BME
The mixture is molded in the form of shells and polymerized by W polymerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
Example 4 Percent By Inqredients _ Weiqht ~-MMP 10.00 ; DMA 29.50 ~-~ 20 MDC 30.00 EDGMA 0.50 BME 0.02 The mixture ls molded in the form of shells - and polymerized by W polymerization in accordance with Example 2. The shells are lathe-cut to form contact -~ lenses in accordance therewith.
~.
-` ExamPle 5 Percent By Inaredients Weiqht GMA ~10;00 MDC 11.40 FMA 25.00 DMA 53.50 EGDMA 0.10 VAZ0-52 0.20 X
.
,~ . .
-: . .
,. : - ~ . . ~ . :. :
., -: , - , . . ..
21~86~2 The mixture is molded in the form of shells and polymerized by thermal polymerization in accordance with Example 1. The shells are lathe-cut to form contact lenses in accordance therewith.
The lenses are highly transparent (light transmission is greater than 95%~ and have uniform optical properties. They have an oxygen permeability of 46.7 DK units at 35-C (normal eye temperature), an expansion factor of 1.39, and a water content of about 54 percent.
ExamPle6 Percent By Ingredients Weiaht ~-MMP
NVp8 20.00 FMA 15.00 :
MDC 7.00 EGDMA 0.
VAZ0-52 0.02 -The mixture is molded in the form of shells and polymerized by W polmerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
, The lenses are highly transparent (light transmission is greater than 95%) and have uniform optical properties. They hav~ an oxygen permeability of 47.4 DK units at 35-C, an expansion factor of 1.4, and a water content of about 65 percent.
... .
~.
.
... .
:~ .
~ 8N-vinyl-2-~qrolidone '~
, - - - .
", ~ - . . ..
~ . .... `' .' '',' ' ' .. ~' ~ , .
.. . ., - . . : . . :
., . , . . --15- 21~8682 Example 7 Percent By Ingredients Weiaht ~-MMP 75.00 FMA 24.70 EGDMA 0.30 VAZO-52 0.30 The mixture is molded in the form of shells and polymerized by W polymerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
The lenses are highly transparent (light transmission is greater than 95%) and have uniform optical properties. They have an oxygen permeability of 25 DK units at 35 C, an expansion factor of 1.32, and a water content of about 54.4 percent.
Example 8 Percent By - Inqredients Weiqht ~-MMP 80.00 FMA 19.20 EGDMA 0.30 ; BME 0.30 The mixture is molded in the form of shells and polymerized by UV polymerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
The lenses are highly transparent (light , transmission is greater than 95%) and have uniform optical properties. They have an oxygen permeability of 62.7 DK units at 35-C, an expansion factor of 1.69, and a water content of 77.3 percent.
' .
:, ,j .
' 2lQ~r;~
Example 9 Percent By Inaredients Weiaht ~-MMP 67.95 GMA 17.00 FMA 10.00 EGDMA o.05 VAZO-52 0.02 The mixture is molded in the form of shells and polymerized by W polymerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
The lenses are highly transparent (light lS transmission is greater than 95%) and have uniform optical properties. They have an oxygen permeability of 45.5 DK units at 35 C, an expansion factor of 1.38, and a water content of 62.5 percent.
Thus there is provided in accordance with the 20 invention a novel and highly-effective contact lens that has an exceptional combination of oxygen permeability, wettability and resistance to protein and mucus deposits. A novel material for manufacturing the lens is also provided, and it is noted that the 25 material may be used for other medical articles needing the combination of oxygen permeability, wettability and resistance to protein and mucus deposits.
Many modifications of the preferred embodiments of the invention disclosed above will 30 readily occur to those skilled in the art upon consideration of this disclosure. For example, initiators other than the ones disclosed may be employed, the contact lens may be tinted or clear, the temperature and times of polymerization may vary, etc.
~, 35 Accordingly, the invention is not limited except by the appended claims.
:~
:~, ';.,: -- .,,- . ; . .. . ~ .
, . . . , : . : .
.. . ..
'' ' '; "' ' ~
Background of ~e Invention This invention relates to contact lenses, and in particular to pliable or "soft" contact lens having - an exceptional combination of oxygen permeability, strength, and resistance to protein and mucus deposits.
There is a great need for a contact lens that has high oxygen permeability and wettability and resistance to protein and mucus deposits. These properties all contribute to an extension of the time during which a contact lens can be continuously worn by a wearer.
High oxygen permeability is needed because the pupil of the eye has no blood circulation and extracts the oxygen needed by its cells directly from the atmosphere. Wettability is essential for wearer comfort. Resistance to protein and mucus deposits from -. fluids that bathe the outer surface of the eye is ~ essential since without this feature the lens pores ¦ become clogged and both visual acuity and the oxygen permeability of the lens suffer.
Many types of contact lens compositions have been proposed. There are two general categories of contact lenses--rigid and hydrogel. For example, U.S. Patent Nos. 3,808,178 and 4,120,570 to Gaylord, 4,139,692 to Tanaka et al; 4,686,276 to Ellis et al;
u~
.','.,'. - ' -2- 210~82 4,743,106 to Novicky et al, and 4,812,598 to Chen propose the use of various copolymer compositions including silicon in contact lenses. The lenses are reasonably permeable to oxygen but are not of hydrogel or "soft" construction.
U.S. Patent No. 4,130,706 to Plambeck, Jr.
proposes a methacrylate-type fluoropolymer ("FMA") for making contact lenses. While the lenses are described as hydrophilic and oxygen permeable, it is believed that they are not wettable enough to be truly comfortable to persons wearing the lenses and are not sufficiently permeable to oxygen to be worn safely and continuously for extended periods.
U.S. Patent No. 3,940,207 to Barkdoll proposes contact lenses constructed of fluorine-containing polymers that are soft and have a low refractive index. It is believed that these contact lenses are not sufficiently oxygen permeable to be worn safely for extended periods.
s 20 U.S. Patent Nos. 4,954,587 and 5,011,275 to Mueller propose soft, extended wear contact lenses based on N,N-dimethylacrylamide ("DMA"). While the lenses have a high oxygen permeability, the use of higher amounts of the relatively soft polymer of N,N-dimethylacrylamide is limited in that the lenses could ` become too soft to be fabricated.
; It would be highly desirable to provide a hydrogel copolymer which can be used to form an easily fabricated pliable contact lens having the combination of oxygen permeability, wettability and resistance to protein and mucus deposits.
SummarY of the Invention The present invention relates to a hydrogel copolymer for making contact lenses, the copolymer comprising, by weight, about 10 percent to about 85 percent o~ ~-methylene-N-methylpyrrolidone or glycerdyl ~ - ~ . . - ,.. .. .
.'' . , , ~ '' ',- ' ' , ~ ' . .
,., , ' ' ',' ' ~ ~ --3- 2 1 a ~ ~ ~ 2 methacryla~e and mixtures thereof, from about 5 to about 25 percent of N,N-dimethylacrylamide, about 5 percent to about 80 percent of a polymerizable fluoromonomer, and about 1 percent to about 15 percent of a polymerizable hydrophophic, non-hydrolyzable - silicone monomer. Optionally, an initiator and a crosslinker are employed under circumstances disclosed below.
In one embodiment of the invention, the copolymer comprises, by weight, from about 10 to 85 percent a-methylene-N-methylpyrrolidone, from about 5 to about 85 percent of glycerdyl methacrylate, from about 5 to about 60 percent of a polymerizable fluoromonomer, and from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer.
In another embodiment, the copolymer comprises, by weight, from about 40 to about 90 percent of ~-methylene-N-methylpyrrolidone and from about 10 to about 60 percent of a polymerizable fluoromonomer such as fluoroacyrlates, styryl fluoromonomers and vinyl - fluoromonomers.
Detailed Descriotion of the Preferred Embodiments The present invention will now be described more fully hereinafter. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiment set forth herein; rather, this embodiment is provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those ; skilled in the art.
The present invention utilizes in various combinations, as described below ~-methylene~N-methylpyrrolidone ("~-MMP") or glycerdyl methacrylate ("GMA") and mixtures thereof, N,N-dimethyl methacrylamide, a polymerizable fluoromonomer, a ~. - : - .. . .
t`
:.. -. , : . . ;' :~
'' ' - , ~ ~, : - .
~4~ 210~6~2 polymerizable hydrophobic, non-hydrolyzable silicone monomer, an initiator, and a crosslinker.
Preferably, the hydrogel copolymer comprises, by weight, from about 5 to about 85 percent of -S methylene-N-methylpyrrolidone ox glycerdyl methacrylate and mixtures thereof, from about 10 to about 25 percent, and preferably from about 5 to about 20 percent of N,N-dimethylacrylamide, from about 5 to about 85 percent, and preferably from about 20 to about 40 percent by weight of a polymerizable fluoromonomer and from about l to about 15 percent, and preferably from about 2 to about 4 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer.
Preferably, from about 20 to about 30 percent of ~-methylene-N-methylpyrrolidone or from about 5 to about 30 percent of glycerdyl methacrylate is used.
If a mixture of ~-methylene-N-pyrrolidone and glyceridyl methacrylate is used, preferably from about 10 to about 85 percent of ~-methylene-N-pyrrolidone and from about 5 to about 85 percent of glycerdyl methacrylate are used.
In one embodiment of the invention, from about 50 to about 90 percent of ~-methylene-N-pyrrolidone can be blended with from about lO to about 50 percent of a polymerizable fluoromonomer to form the hydrogel copolymer. In this embodiment, the hydrogel copolymer can further include, by weight, from about 10 to about 25 percent of a polymerizable hydrophilic monomer selected from the group consisting of methacrylic acid ("MA"), 2-hydroxyethylmethacrylate ("HEMA"), N-vinyl-2-pyrrolidone ("NVP") and N,N-dimethylacrylamide ("DMA").
The polymerizable fluoromonomer useful herein can vary. An exemplary fluoromonomer is one based on a fluoroacrylate composition which includes the following fluorine-containing monomer:
.~ . ~... ..
.~ .
_5_ ~ 682 C= CH2 C=O
I
( CH2 ) m ( CFz ) n where R is H or CH3, m is an integer from 0 to 9, and n is an integer from 1 to 4. A similar monomer is disclosed in U.S. Patent No. 4,130,706 to Plambeck, Jr., the disclosure of which is incorporated herein by reference.
; Another exemplary fluoromonomer can be a fluoracrylate ~ R
.~ C= CH2 '. C=O
I -CH2 CHz C"~l F2 (m~
.
where R and m are defined as above. A similar monomer ~, is disclosed in U.S. Patent No. 3,282,905 to Fosick et i 10 al, the disclosure of which is incorporated herein by reference.
A particularly preferred composition is 2,2,2-trifluoroethyl methacrylate ("FMA").
CHz= Cl F
O=C-O -CH2-C-F
-6- ~ 1 08 ~ ~2 Alternatively, styryl fluoromonomers can be employed. The general formula of these monomers is CH-fH
~F, where r + s = 5 and r = 1 to 5 and s = 5 to 1.
A particularly preferred styryl fluoromonomer is pentafluorostyrene.
F ~ F
F
Other examples of fluoromonomers are p-vinyl benzyl trifluoroacetate and p-vinyl benzyl hexafluoroisopropyl ' ether.
Alternatively, vinyl fluoromonomers can be , 10 used. They have the general formula CH2=CH
( CH2 ) tCUF2U~l ~
where t = 1 to 4 and u = 1 to 9. A particularly ~-preferred vinyl fluoromonomer is 3,3,3 I trifluorovinylpropane CH2 = CH F
C8,C82-C-F
A
i i ~, . ' ., ', ' : " ': . . : ' ' _7_ 2108~2 Alternatively, perfluorocyclohexyl acrylates can be used having the general formula R F F
CH~-C ~
O-C-O~F
~ I
F F
where R = ~ or CH3. A particularly preferred pefluorocyclohexyl acrylate is perfluorocyclopentane.
It is no~ed that only ~-methylene-N-methylpyrrolidone and the polymerizable fluoromonomer can be used.
The polymerizable hydrophobic non-hydrolyzable silicone monomer useful herein can vary.
An exemplary silicone has the formula AtSI-O~SI-l CH2 )~ C=CH2 A a Y
where a is an integer from 1 to 5 and b is an integer from 0 to 6, A is selected from the group consisting Of ¦ Cl-C5 alkyl groups and phenyl groups, R is selected from the group consisting of a methyl group (CH~) and hydrogen, X and Y are selected from the group consisting of Cl to C5 alkyl groups, phenyl groups and Z
groups wherein Z is a group of the structure :~ A-¦~i - -¦
A a where a and A are as defined previously, and ~ is a 3 phenyl group. In the alkanol ester co-monomers, the ~ alkyl group contains from 1 to 20 carbon atoms.
20 Exemplary silicon-containing monomers are disclosed in J U.S. Patent Nos. 3,808,178 and 4,120,570 to Gaylord, ~;
i -8- 2 ~ ~ ~r;~ 2 the disclosures of which are incorporated herein by reference.
Alternatively, vinyl silicone monomers can be employed. The general formula can be represented as CH2=CH (I) Rl-s i -R
or ~1 (II) CH2 = CH R
(CH2)X- si -Rl where X = 1 to 6 and Rl is selected from the class consisting of Cl to C6 alkyl groups and phenyl groups or a mixture of alkyl and phenyl groups.
Particularly preferred examples of Class (I) ;
are CH2 = CH CH2 = CH : :
CH3 - si - CH3 CH3 -Si - CH3 CH3CH2 = CH <P
~-fi-C~3 where "~" represents a phenyl group.
Particularly preferred examples of Class (II) are ., :
.1 , J, ~ ,:
J .~ . . -:. . ~ , ' ' . ' . . , `.'. . :
. . .
~',: " ' ' , ' ' , , , . ' ',' ' :' - .
,: ' '' ~ . ' ' . ~ .' ' ' ' . - , ' , . ''' '' ' '',' ' ' . " ,. ' ' ' ' .. '. ' . ,' . " ' '~: " ';. ' .
",' ' ,~ ' '. . '' .. ' ', ' , ~ '"." . ' ', ' ' ' ", . ,. '' ' ', 2 1 ~
CH2= I H CIH3 CH2=CH CH, CH2 cH2 -si - CH3 Cf~z Cf~2 -SI-~>
CH3 CH, .
CH2 = CH
CH2 CH2 -Si -~
In both classes of vinyl silicone monomers, any methyl group (CH3 group) can be replaced by a benzene ring, as the preceding examples suggest.
Generally, vinyl silicone monomers are less reactive than acrylate silicone monomers. When vinyl silicone monomers are used, cobalt-60 ("Co-60"), radiation may be used as a source of polymerization energy. Co-60 may optionally be used as a source of polymerization energy even when vinyl silicone monomers are not employed.
. Exemplary non-hydrolyzable silicones include ~; methyldi(trimethylsiloxy)silylpropylglycerol methacrylate, methylidi(trimethylsiloxy)silylpropyl-glycerolethyl methacrylate, m,p-styrlethyltrimethyl-silane, m,p-styrylethyltris(trimethylisiloxy)silane, methylacryloxypropyltris(trimethylsiloxy)silane and 4-(3-trimethylsilylpropyl)benzylstyrene sulfonate.
Preferably a crosslinker is used. The crosslinker can constitute, by weight, about 0.01 percent to about 5 percent and more preferably about 0.5 percent to about 2 percent of the weight of the hydrogel copolymer. The crosslinker is preferably one of a mixture of ethyleneglycoldimethacrylate ("EGDMA"), ' a fluorine-containing compound, or a silicon-containing :~ .
~ .
~ -~.', . ' . ~ , '. ' ,' '- ' : " ' ' ' " :' :' .
-lo- 2 1 ~ 2 compound such as 1,3-bis[(p-acryloxymethyl) - phenethyl]tetramethyldisiloxane or bis(3-methacryloxypropyl)tetramethyldisiloxane.
A quantity of an initiator equal in weight to 0.05 percent to 2 about percent of the weight of the mixture of monomers is preferably added thereto, except when Co-60 is used as a source of polymerization energy. The initiator may be selected from the group consisting essentially of 2,2'-azobis(2,4-- 10 dimethylvaleronitrile) ("VAZ0 52"), azobisisobutyro-nitrile ("AIBN"), benzoinmethylether ("BME"), di(sec-butyl)peroxydicarbonate ("SBC"), and isopropylperoxydicarbonate ("Ipp"). The initiator may also be any of those disclosed in the U.S. Patent No. 4,120,570, to Gaylord, i.e., acetyl peroxide, lauroyl peroxide, decanoyl peroxide, caprylyl peroxide, b~nzoyl peroxide, tertiary-butyl peroxypivalate, diisopropyl peroxycarbonate, tertiary-butyl peroctoate, and ~ azobisisobutyronitrile.
VAZ0 52 or AIBN may be used as an initiator when polymerization is aided by ultraviolet or thermal radiation, BME may be used as the initiator when polymerization is aided by the ultraviolet radiation, and SBC or Ipp may be used as the initiator when polymerization is aided by thermal radiation. Co-60 or another radioactive source may also be used to promote polymerization, particularly when vinyl silicone monomers or other monomers that are not highly reactive are employed. When Co-60 or another radioactive source is not used, polymerization energy is supplied in the form of thermal energy or in the form of ultraviolet radiation, as may be appropriate in view of the -initiator employed. When Co-60 radiation is employed, 3 no initiators are needed.
After curing, the resulting polymer is formed in any conventional or otherwise suitable process into contact lenses. The lenses have a shore hardness (D
.
: : " . : ~ . .: . . , scale) within atherange of 82 to 89. Oxygen permeability in DK units (ml cm/cm2 sec cmHg X 10-10) at 35°C is within the range of 10°-34°, light transmission is greater than 95%, refractive index is close to that of HEMA, and the coefficient of expansion is within the range of 1.1 to 1.6.
The following examples set forth representative formulas for the materials used in making contact lenses according to the invention:
Example 1 The following are mixed at room temperature in a 100ml beaker:
The initiator is added to the mixture, and the mixture is poured into a test tube and polymerized by thermal polymerization (i.e., application of heat) 1.alpha.-methylene-N-methylpyrrolidone 22,2,2-trifluoroethylmethacrylate available from Aldrich Chemical Company of Milwaukee, Wisconson 3N,N-dimethylacrylamide available from Aldrich Chemical Company 4methylacryloxypropyltris(trimethylsiloxy)silane available from Huls America, Inc, of Newark, New Jersey 5etheyleneglycoldimethacrylate available from Rohm Tech, Inc. of Marden, Massachuseets 6isopropylperoxydicarbonate available from Polyscience, Inc. of Warrington, Pennsylvania 21'~8f;82 This is accomplished by placing the test tube in a hot water bath at a temperature of 30C. The polymerized material is a colorless, solid, transparent polymer.
The polymer is lathe-cut into buttons of conventional shape and size. The buttons are ground to the shape of contact lenses having respective center thicknesses of O.lmm to 0.2mm, and then polished. The lenses are highly transparent (light transmission i8 greater than 95%) and have uniform optical properties. They have an oxygen permeability of 35 DK units at 35 C (normal eye temperature), a contact angle of less than 18-, and a refractive index of 1.40S.
The following examples are similar to Example 1 but illustrate variations of the materials and quantities thereof employed and of the method of polymerization.
ExamPle2 Percent 8y Inaredients Weiaht ~-MMP
FMA 19.94 DMA 39.38 ; MDC 29.90 EGDMA .50 BME7 0.02 25 The mixture is molded in the form of shells and polymerized by ultraviolet radiation in accordance with U. S. Patent No. 4,812,598 to Chen, the disclosure of which is incorporated herein by reference. The shells ~-are lathe-cut to form contact lenses in accordance therewith.
. ~ .
7bcn~oinmethylefher iniliator available from Polyscience, rnc ,, .
::
. - ` : ' ' , . -.. . : :: : : :, .- -: ' ' . ; -.- :: . :
.: . ' ` ' ' '' . ' '`~ `' ' ' ', ., :
:: .: ' : ' - ;
.
2~0'~2 ExamPle3 Percent By In~redients Weiaht ~-MMP 64.74 MDC 9.96 FMA 24.90 BME
The mixture is molded in the form of shells and polymerized by W polymerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
Example 4 Percent By Inqredients _ Weiqht ~-MMP 10.00 ; DMA 29.50 ~-~ 20 MDC 30.00 EDGMA 0.50 BME 0.02 The mixture ls molded in the form of shells - and polymerized by W polymerization in accordance with Example 2. The shells are lathe-cut to form contact -~ lenses in accordance therewith.
~.
-` ExamPle 5 Percent By Inaredients Weiqht GMA ~10;00 MDC 11.40 FMA 25.00 DMA 53.50 EGDMA 0.10 VAZ0-52 0.20 X
.
,~ . .
-: . .
,. : - ~ . . ~ . :. :
., -: , - , . . ..
21~86~2 The mixture is molded in the form of shells and polymerized by thermal polymerization in accordance with Example 1. The shells are lathe-cut to form contact lenses in accordance therewith.
The lenses are highly transparent (light transmission is greater than 95%~ and have uniform optical properties. They have an oxygen permeability of 46.7 DK units at 35-C (normal eye temperature), an expansion factor of 1.39, and a water content of about 54 percent.
ExamPle6 Percent By Ingredients Weiaht ~-MMP
NVp8 20.00 FMA 15.00 :
MDC 7.00 EGDMA 0.
VAZ0-52 0.02 -The mixture is molded in the form of shells and polymerized by W polmerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
, The lenses are highly transparent (light transmission is greater than 95%) and have uniform optical properties. They hav~ an oxygen permeability of 47.4 DK units at 35-C, an expansion factor of 1.4, and a water content of about 65 percent.
... .
~.
.
... .
:~ .
~ 8N-vinyl-2-~qrolidone '~
, - - - .
", ~ - . . ..
~ . .... `' .' '',' ' ' .. ~' ~ , .
.. . ., - . . : . . :
., . , . . --15- 21~8682 Example 7 Percent By Ingredients Weiaht ~-MMP 75.00 FMA 24.70 EGDMA 0.30 VAZO-52 0.30 The mixture is molded in the form of shells and polymerized by W polymerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
The lenses are highly transparent (light transmission is greater than 95%) and have uniform optical properties. They have an oxygen permeability of 25 DK units at 35 C, an expansion factor of 1.32, and a water content of about 54.4 percent.
Example 8 Percent By - Inqredients Weiqht ~-MMP 80.00 FMA 19.20 EGDMA 0.30 ; BME 0.30 The mixture is molded in the form of shells and polymerized by UV polymerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
The lenses are highly transparent (light , transmission is greater than 95%) and have uniform optical properties. They have an oxygen permeability of 62.7 DK units at 35-C, an expansion factor of 1.69, and a water content of 77.3 percent.
' .
:, ,j .
' 2lQ~r;~
Example 9 Percent By Inaredients Weiaht ~-MMP 67.95 GMA 17.00 FMA 10.00 EGDMA o.05 VAZO-52 0.02 The mixture is molded in the form of shells and polymerized by W polymerization in accordance with Example 2. The shells are lathe-cut to form contact lenses in accordance therewith.
The lenses are highly transparent (light lS transmission is greater than 95%) and have uniform optical properties. They have an oxygen permeability of 45.5 DK units at 35 C, an expansion factor of 1.38, and a water content of 62.5 percent.
Thus there is provided in accordance with the 20 invention a novel and highly-effective contact lens that has an exceptional combination of oxygen permeability, wettability and resistance to protein and mucus deposits. A novel material for manufacturing the lens is also provided, and it is noted that the 25 material may be used for other medical articles needing the combination of oxygen permeability, wettability and resistance to protein and mucus deposits.
Many modifications of the preferred embodiments of the invention disclosed above will 30 readily occur to those skilled in the art upon consideration of this disclosure. For example, initiators other than the ones disclosed may be employed, the contact lens may be tinted or clear, the temperature and times of polymerization may vary, etc.
~, 35 Accordingly, the invention is not limited except by the appended claims.
:~
:~, ';.,: -- .,,- . ; . .. . ~ .
, . . . , : . : .
.. . ..
'' ' '; "' ' ~
Claims (28)
1. A hydrogel copolymer useful for making pliable contact lenses, said copolymer comprising, by weight:
(a) from about 5 to about 35 percent of .alpha.-methylene-N-methylpyrrolidone or glycerdyl methacrylate and mixtures thereof;
(b) from about 5 to about 35 percent of N,N-dimethylacrylamide;
(c) from about 5 to about 60 percent of a polymerizable fluoromonomer; and (d) from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer.
(a) from about 5 to about 35 percent of .alpha.-methylene-N-methylpyrrolidone or glycerdyl methacrylate and mixtures thereof;
(b) from about 5 to about 35 percent of N,N-dimethylacrylamide;
(c) from about 5 to about 60 percent of a polymerizable fluoromonomer; and (d) from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer.
2. A hydrogel copolymer according to Claim 1 wherein the weight of the .alpha.-methylene-N-methylpyrrolidone is about 20 to about 30 percent by weight.
3. A hydrogel copolymer according to Claim 1 wherein the weight of the glycerdyl methacrylate is about 5 to about 30 percent by weight.
4. A hydrogel copolymer according to Claim 1 wherein the weight of said fluoromonomer is from about 20 percent to about 40 percent by weight.
5. A hydrogel copolymer according to Claim 1 wherein the weight of said silicone monomer is from about 2 percent to about 4 percent of the weight of said copolymer.
6. A hydrogel copolymer according to Claim 1 wherein said fluoromonomer is selected from the group consisting of fluoroacrylates, styryl fluoromonomers, and vinyl fluoromonomers.
7. A hydrogel copoloymer according to Claim 1 wherein said silicone monomer is where a is an integer from 1 to 5 and b is an integer from 0 to 6, A is selected from the group consisting of C1-C5 alkyl groups and phenyl groups, R is selected from the group consisting of a methyl group (CH3) and hydrogen, X and Y are selected from the group consisting of C1 to C5 alkyl groups, phenyl groups and Z
groups wherein Z is a group of the structure where a and A are as defined previously, and ? is a phenyl group.
groups wherein Z is a group of the structure where a and A are as defined previously, and ? is a phenyl group.
8. A hydrogel copolymer according to Claim 1 wherein said silicone monomer is selected from the group consisting of methyldi(trimethylsiloxy)silyl-propylglycerol methacrylate, methylidi(trimethyl-siloxy)silylpropylglycerolethyl methacrylate, m,p-styrlethyltrimethylsilane, m,p-styrylethyltris-(trimethylisiloxy)silane, methylacryloxypropyltris-(trimethylsiloxy)silane and 4-(3-trimethylsilylpropyl)-benzylstyrene sulfonate.
9. A hydrogel copolymer according to Claim 1 further comprising, by weight, about 0.01 to about 5 percent, of an initiator selected from the group consisting of 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, benzoinmethylether, di(sec-butyl)peroxydicarbonate, and isopropylperoxydicarbonate.
10. A hydrogel copolymer according to Claim 1 further comprising, by weight, about 0.05 to about 2 percent of a crosslinker selected from the group consisting of a silicon-containing crosslinker, a fluorine-containing crosslinker, ethyleneglycoldi-methacrylate and mixtures thereof.
11. A hydrogel copolymer useful for making pliable contact lenses, said copolymer comprising, by weight:
(a) from about 10 to about 85 percent of a-methylene-N-methylpyrrolidone;
(b) from about 5 to about 85 percent of glycerdyl methacrylate;
(c) from about 5 to about 60 percent of a polymerizable fluoromonomer; and (d) from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer.
(a) from about 10 to about 85 percent of a-methylene-N-methylpyrrolidone;
(b) from about 5 to about 85 percent of glycerdyl methacrylate;
(c) from about 5 to about 60 percent of a polymerizable fluoromonomer; and (d) from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer.
12. A hydrogel copolymer according to Claim 11 wherein the weight of the .alpha.-methylene-N-methylpyrrolidone is about 20 to about 30 percent by weight.
13. A hydrogel copolymer according to Claim 11 wherein the weight of the glycerdyl methacrylate is about 5 to about 30 percent by weight.
14. A hydrogel copolymer according to Claim 11 wherein the weight of said fluoromonomer is about 20 percent to about 40 percent of the weight of said copolymer.
15. A hydrogel copolymer according to Claim 11 wherein the weight of said silicone monomer is about 2 percent to about 4 percent of the weight of said copolymer.
16. A hydrogel copoloymer according to Claim 11 wherein said silicone monomer is where a is an integer from 1 to 5 and b is an integer from 0 to 6, A is selected from the group consisting of C1-C5 alkyl groups and phenyl groups, R is selected from the group consisting of a methyl group (CH3) and hydrogen, X and Y are selected from the group consisting of C1 to C5 alkyl groups, phenyl groups and Z
groups wherein Z is a group of the structure where a and A are as defined previously, and is a phenyl group.
groups wherein Z is a group of the structure where a and A are as defined previously, and is a phenyl group.
17. A hydrogel copolymer according to Claim 11 wherein said silicone monomer is selected from the group consisting of methyldi(trimethylsiloxy)silyl-propylglycerol methacrylate, methylidi(trimethyl-siloxy)silylpropylglycerolethyl methacrylate, m,p-styrlethyltrimethylsilane, m,p-styrylethyltris-(trimethylisiloxy)silane, methylacryloxypropyltris-(trimethylsiloxy)silane and 4-(3-trimethylsilylpropyl)-benzylstyrene sulfonate.
18. A hydrogel copolymer according to Claim 11 further comprising, by weight, about 0.01 to about 5 percent, of an initiator selected from the group consisting of 2,2'-azobis(2,4-dimethylvalero-nitrile), azobisisobutyronitrile, benzoinmethylether, di(sec-butyl)peroxydicarbonate, and isopropylperoxydicarbonate.
19. A hydrogel copolymer according to Claim 11 further comprising, by weight, about 0.05 to about 2 percent of a crosslinker selected from the group consisting of a silicon-containing crosslinker, a fluorine-containing crosslinker, ethyleneglycoldi-methacrylate and mixtures thereof.
20. A hydrogel copolymer useful for making pliable contact lenses, said copolymer comprising, by weight:
(a) from about 40 to about 90 percent of .alpha.-methylene-N-methylpyrrolidone and (b) from about 10 to about 60 percent of a polymerizable fluoromonomer selected from the group consisting of fluoroacrylates, styryl fluoromonomers and vinyl fluoromonomers.
(a) from about 40 to about 90 percent of .alpha.-methylene-N-methylpyrrolidone and (b) from about 10 to about 60 percent of a polymerizable fluoromonomer selected from the group consisting of fluoroacrylates, styryl fluoromonomers and vinyl fluoromonomers.
21. A hydrogel copolymer according to Claim 20 further comprising, by weight:
(c) from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer;
(d) from about 0.01 to about 5 percent of an initiator selected from the group consisting of claim 1 further comprising, by weight, about 0.01 to about 5 percent, of an initiator selected from the group consisting of 2,2'-azobis(2,4-dimethylvalero- nitrile), azobisisobutyronitrile, benzoinmethylether, di(sec-butyl)peroxydicarbonate, and isopropylperoxydicarbonate; and (e) from about 0.05 to about 2 percent of a crosslinker selected from the group consisting of claim 1 further comprising, by weight, 0.05 to about 2 percent of a crosslinker selected from the group consisting of a silicon-containing crosslinker, a fluorine-containing crosslinker, and ethyleneglycol-dimethacrylate mixtures thereof.
(c) from about 1 to about 15 percent of a polymerizable hydrophobic non-hydrolyzable silicone monomer;
(d) from about 0.01 to about 5 percent of an initiator selected from the group consisting of claim 1 further comprising, by weight, about 0.01 to about 5 percent, of an initiator selected from the group consisting of 2,2'-azobis(2,4-dimethylvalero- nitrile), azobisisobutyronitrile, benzoinmethylether, di(sec-butyl)peroxydicarbonate, and isopropylperoxydicarbonate; and (e) from about 0.05 to about 2 percent of a crosslinker selected from the group consisting of claim 1 further comprising, by weight, 0.05 to about 2 percent of a crosslinker selected from the group consisting of a silicon-containing crosslinker, a fluorine-containing crosslinker, and ethyleneglycol-dimethacrylate mixtures thereof.
22. A hydrogel copolymer according to Claim 20 or 21 further comprising, by weight, from about 10 to about 25 percent of a polymerizable hydrophilic monomer selected from the group consisting of methacrylic acid, 2-hydroxyethylmethacrylate, N-vinyl-2-pyrrolidone and N,N-dimethylacrylamide.
23. A hydrogel copolymer according to Claim 20 wherein the weight of the .alpha.-methylene-N-methylpyrrolidine is about 60 to about 80 percent by weight.
24. A hydrogel copolymer according to claim 20 wherein the weight of said fluoromonomer is about 20 percent to about 40 percent of the weight of said copolymer.
25. A hydrogel copolymer according to claim 20 wherein said styryl fluoromonomer is selected from the group consisting of pentafluorostyrene, p-vinyl benzyltrifluoroacetate and p-vinyl benzyl hexafluoroisopropylether.
26. A hydrogel copoloymer according to claim 20 wherein said silicone monomer is where a is an integer from 1 to 5 and b is an integer from 0 to 6, A is selected from the group consisting of C1-C5 alkyl groups and phenyl groups, R is selected from the group consisting of a methyl group (CH3) and hydrogen, X and Y are selected from the group consisting of C1 to C5 alkyl groups, phenyl groups and Z
groups wherein Z is a group of the structure where a and A are as defined previously, and ? is a phenyl group.
groups wherein Z is a group of the structure where a and A are as defined previously, and ? is a phenyl group.
27. A hydrogel copolymer according to Claim 20 wherein said silicone monomer is selected from the group consisting of methyldi(trimethylsiloxy)silyl-propylglycerol methacrylate, methylidi(trimethyl-siloxy)silylpropylglycerolethyl methacrylate, m,p-styrlethyltrimethylsilane, m,p-styrylethyltris-(trimethylisiloxy)silane, methylacryloxypropyltris-(trimethylsiloxy)silane and 4-(3-trimethylsilylpropyl)-benzylstyrene sulfonate.
28. A contact lens made from the hydrogel copolymer of Claims 1, 11 or 20.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68738591A | 1991-04-18 | 1991-04-18 | |
| US687,385 | 1991-04-18 | ||
| US78613091A | 1991-10-31 | 1991-10-31 | |
| US786,130 | 1991-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2108682A1 true CA2108682A1 (en) | 1992-10-19 |
Family
ID=27103999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2108682 Abandoned CA2108682A1 (en) | 1991-04-18 | 1992-04-16 | Novel composition for contact lenses |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2108682A1 (en) |
| WO (1) | WO1992018548A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5741830A (en) * | 1995-02-15 | 1998-04-21 | Menicon Co., Ltd. | Water-absorptive soft contact lens |
| US6822016B2 (en) | 2001-09-10 | 2004-11-23 | Johnson & Johnson Vision Care, Inc. | Biomedical devices containing internal wetting agents |
| US7052131B2 (en) * | 2001-09-10 | 2006-05-30 | J&J Vision Care, Inc. | Biomedical devices containing internal wetting agents |
| CA2401865C (en) * | 2000-03-24 | 2010-01-12 | Novartis Ag | Crosslinkable or polymerizable prepolymers |
| JP5669396B2 (en) | 2006-12-13 | 2015-02-12 | ノバルティス アーゲー | Actinic radiation curable silicone hydrogel copolymers and uses thereof |
| JP5484916B2 (en) * | 2007-03-22 | 2014-05-07 | ノバルティス アーゲー | Prepolymer having dangling polysiloxane-containing polymer chain |
| WO2008116132A2 (en) | 2007-03-22 | 2008-09-25 | Novartis Ag | Silicone-containing prepolymers with hydrophilic polymeric chains |
| US8044111B2 (en) | 2007-11-30 | 2011-10-25 | Novartis Ag | Actinically-crosslinkable silicone-containing block copolymers |
| MY154718A (en) | 2007-12-10 | 2015-07-15 | Novartis Ag | Method for making silicone hydrogel contact lenses |
| MX349540B (en) | 2010-07-30 | 2017-08-02 | Novartis Ag * | Amphiphilic polysiloxane prepolymers and uses thereof. |
| JP5784131B2 (en) | 2010-10-06 | 2015-09-24 | ノバルティス アーゲー | Polymerizable chain-extended polysiloxane with pendant hydrophilic groups |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2256932A1 (en) * | 1973-07-10 | 1975-08-01 | Union Optics Corp | Unsatd heterocyclic copolymers - form hydrogels suitable for contact lens |
| US4182822A (en) * | 1976-11-08 | 1980-01-08 | Chang Sing Hsiung | Hydrophilic, soft and oxygen permeable copolymer composition |
| GB2152064B (en) * | 1983-12-27 | 1986-12-03 | Toyo Contact Lens Co Ltd | Water-absorptive contact lenses |
| US4990582A (en) * | 1986-07-18 | 1991-02-05 | Salamone Joseph C | Fluorine containing soft contact lens hydrogels |
| US4812598A (en) * | 1987-06-18 | 1989-03-14 | Ocular Technologies, Inc. | Gas permeable contact lens and method and materials for its manufacture |
| WO1991004283A1 (en) * | 1989-09-14 | 1991-04-04 | Chang Sing Hsiung | Soft gas permeable contact lens having improved clinical performance |
-
1992
- 1992-04-16 CA CA 2108682 patent/CA2108682A1/en not_active Abandoned
- 1992-04-16 WO PCT/US1992/003128 patent/WO1992018548A1/en active Application Filing
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|---|---|
| WO1992018548A1 (en) | 1992-10-29 |
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