CA1251882A - Highly oxygen permeable contact lens materials and compositions thereof - Google Patents
Highly oxygen permeable contact lens materials and compositions thereofInfo
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- CA1251882A CA1251882A CA000512768A CA512768A CA1251882A CA 1251882 A CA1251882 A CA 1251882A CA 000512768 A CA000512768 A CA 000512768A CA 512768 A CA512768 A CA 512768A CA 1251882 A CA1251882 A CA 1251882A
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Abstract
HIGHLY OXYGEN PERMEABLE CONTACT LENS
MATERIALS AND COMPOSITIONS THEREOF
ABSTRACT
Highly oxygen permeable hard and semi-hard contact lenses are made from the copolymer of an ethylenically unsaturated siloxanylalkoxy ester monomer, ethylenically unsaturated fluorocarbon ester monomer and/or ethylenically unsaturated sulfone monomer; the copolymer plastic can be modified by the incorporation of hardening, stability and/or wettability agents.
Also disclosed herein are methods for manufacture of such contact lenses.
MATERIALS AND COMPOSITIONS THEREOF
ABSTRACT
Highly oxygen permeable hard and semi-hard contact lenses are made from the copolymer of an ethylenically unsaturated siloxanylalkoxy ester monomer, ethylenically unsaturated fluorocarbon ester monomer and/or ethylenically unsaturated sulfone monomer; the copolymer plastic can be modified by the incorporation of hardening, stability and/or wettability agents.
Also disclosed herein are methods for manufacture of such contact lenses.
Description
:~25~
- 2 -ACKGROUND OF ~'HE INVENTION
Oxygen permeable contact lenses in the prior art are essentially made from a E;iloxane nono~r and me~yl methacrylate.
These lenses are permeable to oxygen; hence, allowing oxygen from the air to pass through the lenses and reach the cornea which allows such lenses to be worn for longer periods of 'cime as compared to non-oxygen permeable contact lenses such as PMMA
which were available previously.
Such contact lenses are disclosed in the prior art by Gaylord, U.S. Patents Nos. 3,8Q8,178 and 4,120,570. Later, Ellis disclosed in his patents, U.S. Patents Nos. 4,152,508 and 4,330,383, the partial replacement oE the methyl methacrylate monomer with dimethyl itaconateO The Novicky patents, V.S.
Patents Nos. 4,216,303, 4,242,483, 4,248,989, 4,303,772 and 4,365,074, disclose contact lenses comprising high molecular weight polysiloxanylalkyl esters of acrylic and methacrylic acids. The Chang patent, U.S. Patent No. 4,182,822, discloses contact lenses comprised of a copolymer from polysiloxanylalkyl ester of acrylic and ~ethacrylic acid essentially the same as disclosed in the Gaylord patents, supra., that were copolymer-ized with N-vinyl pyrrolidinone or N,N-dimethyl methacrylamide.
Ichinoche, et al., Canadian Patent No. 1,184,341, teaches the use of an organosiloxanyl ester monomer oE acrylic and methacrylic-acid copolymerized with Eluorocarbon ester monomers of acrylic and methacrylic acids and copolymerized to produce oxygen permeable contact lenses. The LeBoeuf patent U.S. Patent No. 4,2461389, disclose, acrylic siloxane based.
1L8~.2 polymers which also ~ontain HEMA and/or polyvinyl 2-pyrrolidinone which are suitable for use in forming water~containing oxygen permeable contact lenses.
¦ All siloxane ester monomers in the prior art employ ¦essentially the same alkyl bridge between the methacryloxy group and ¦siloxanyl part of the structure; wherein, neither one used an ethoxy group or 2~3-dioxypropyl groups. The organosilicone monomers of the present invention can be copolymerized with perfluoroalkyl ¦ester monomer~ and/or with sulfone monomers.
i SUMMARY OF THE INVENTION
~ I
The present invention relates to a novel generation of contact lenses comprising copolymers made from siloxanylalkoxy ester monomers of acrylic, methacrylic and/or itaconic acids and mixtures thereof and perfluoroalkyl ester .7 ¦ monomers of acrylicl methacrylic and/or itaconic acids and ¦ mixtures thereof,which are copolymerized with ethylenically ¦ unsaturated sulfone alkyl monomers and/or ethylenically ¦ unsaturated sulfone ester monomers of acrylic, methacrylic and/or ¦ itaconic acids and mixtures thereof, to produce highly oxygen ¦ permeable an~ improved materials for contact lenses.
¦ The first representative siloxanylalkoxy es~er monomer of acrylic or methacrylic acid of the present invention has the eneral ~tructural formula:
CHz=C-C-O-C~z-CH-CH 2 -O-S i to-s i ~-A
X~ Y
A-Si-A
A m wherein X and Y are Cl to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure:
m being an integer from 1 to S,and R is c~ méthyl group or hydrogen.
The second useful organosiloxanylalkoxy ester monomer of acrylic or methacrylic acid is represented by the following structural formula CHz=C-C-O-(CH~) -o-si~-o-si~-A
n being an integer Erom 1 to 3; wherein, X and Y are Cl to C6 alkyl, cyclic or phenyl group~3 and/or groups of the following stru re: A~-Si-O~-m being an integer from 1 to 5,and R is a methyl group or hydrogen.
The above disclosed new organosilicone monomers can be partially substituted by additional organosiloxanylalkyl ester monomers ~rom the prior art. The first representative partially ¦substituted organosiloxanylalkyl ester monomer of acrylic and ¦methacrylic acid from the prior art has the structural formula:
At si-o t~ cHz)n~~C~c=c~:Z
wherein, X and Y are C~ to C6 alkyl, cyclic or phenyl groups ¦and/or groups of the following structure:
l,tlli_ol; ~
¦ m being an integer fro~ 1 to 6, n being an integer from 1 to 33 ¦ and R is a methyl yroup or hydrogen.
I
¦ The second useful partially substitutedorganosiloxanyl-¦ alkyl ester monomer of acrylic and methacrylic acids is ¦ represented by the following formula:
Dtsi-o!-si-(c8~)n-o-c-c=
¦ wherein, X and Y are Cl to C6 alkyl, cyclic or phenyl groups or ¦ groups of the ~ollowing structure:
D ~ i-O~-m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C~ to C6 alkyl or phenyl groups, R is a methyl group or hydrogen, and D is hydrogen or a hydroxy group, The third useful partially substituted organosiloxanyl-alkyl ester monomer of acrylic and methacrylic acids is represented by the follow'ng structural formula:
X O R
CH3-li-(CH 2 ) ~ O-c-l=cH 2 ¦ wherein, X and Y are groups of the ollowing structure:
¦ wherein m is an integer from 1 to 5, n is an integer from ¦ 1 to 3; A is selected from Cl to C6 alkyI, cyclic or phenyl ¦ groups and R is a methyl group or hydrogen.
The fourth useful pa~lally substituted organosiloxanyl-alkyl ester monomer of itaconic acid is represented by the ¦ following formula:
~-O-(CH2)n-Si-~O-Si 0 (CH2~n-li-tO-Si~-~
.~
.~ 2 wherein, X and Y are Cl to C6, alkyl, cyclic or phenyl groups or groups of the following structure.
BtAi--X
m being an integer from 1 to 5, n being an integer from 1 to 3;
wherein, A is selected from Cl to C6 alkyl, cyclic or phenyl groups and B is a methyl group, hydrogen or a hydroxy group~
The perfluoroalkyl ester monomers of acrylic and methacrylic acid are represented by the following formula-o ~O(CH2)m-(CFz~CF2)a~CF2z . CH2=f-C-O(CH2)n-S ~ OtCH2~m-(CF~-CF2)a-CF2Z
R o(cH2)m-~cF2-cF2)a-cFzz n being an integer from 1 to 3, R is a methyl group or hydrogen, m being an inteqer from 1 to 4, a being an integer from 1 to 10 and Z is fluorine or hydrogen.
Another useful perfluoroalkyl ester monomer of the present invention is represented by the following formula:
CF 3- t CF 2-CF 2 ) rl~ ( CH 2 ) m-O-C-C=CH 2 and telomer alcohol methacrylates or acrylates of the following formula:
!l I
H-(CF2-CF~ )n~(CH2 )m~~C~C=CHZ
and mixtures thereof; wherein, n is an integer from 1 to 10, m is an integer ~rom 1 to 5 and R is a methyl group or hydrogen, Particularly useful in the manufacture of the lenses of the present invention are those fluoroalkyl esters selected from the group con~i~ting of per1uoroalkyl ethyl acrylates and methacrylates of the following formula:
CF 3 -CF 2 - ( CF2-CF 2 ) n-CH 2 -CH2-O-C C=CH 2 wherein, n is an integer from 1 to 10 and R is a methyl group or hydrogen.
The perfluoroalkyl ester monomers of itaconic acid useful in the present invention for the manufacturing of contact lenses are represented by the following formula:
I-o-'CHZ'ntCF2-CF2l-F
C-O-(CHz)n-~CF2-CF2~-F
n being an integer from 1 to 4 and m is an integer from 1 to 10.
Additional perfluorocarbon monomers useful in the present invention to form copolymers are found in published European ¦Patent Application No. 0084406 by David ~. Rice, et al., such ¦monomers havin~ the following general structural formula:
l A-CF 2-0- t CF2-CF 2-0 )m-(CF2-O~n-CF a-Z
¦wherein, m is an integer from 2 to 20, n is an integer from 2 to 130, A is selected from CF9-, C~3-/ CH2F-, and CF2 H-, and Z has ,,"-' 5 ~8 ~Z
~he formula which includes one of the following:
l l l H2C=f-; H2C=C-C-O-; H2C=C-CNH-; and -C-C-R R O R O O
~r mixtures thereof.
¦ The principal sulfone monomers embodied in the present ¦invention which contribute to the increased oxygen permeability ¦and strength o the copolymer for contact lenses are represented ~by the following general structural formula:
¦ A--S--B
I , ¦wherein, A is selected from one of the following:
CH2=CH-; CH2 GCH-C 6 H4-;
~2 =C-~l -O- ( CH2)n~; CH2=C-C-O-t C~2 ) n~;
I O O
¦B is C1 to C20 alkyl, cyclic or phenyl groups and n is ¦~n inteyer ~rom 1 to 5~
The preferable sulfone monomers which are useful in the pr~sent invention are:
methyl vinyl sulfone, methyl styrene sulfone, ethyl vinyl sulfone, ethyl styrene sulfone, propyl vinyl sulfone, propyl styrene sulfone, phenyl vinyl sulfone, phenyl styrene sulEone, cyclohexyl vinyl sulfone, cyclohexyl styrene sulfone, pentyl vinyl sulfone, pentyl styrene sulfone, butyl vinyl sulfone, butyl styrene sulfone, phenoxyethyl vinyl sulfone, phenoxye-thyl 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.
The copolymer plastic material of the present invention also incorporates hardening agen-ts such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, phenyl metha-crylate, tetrahydrofurfuryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, phenyl acrylate, tetrahydrofurfuryl acrylate, dimethyl itaconate, diethyl itaconate, dipropyl itaconate, dicyclohexyl itaconate, diphenyl itaconate, vinyl ben~ene (styrene), divinyl benzene and equivalents.
The contact lens material is further modified by the incorporation of wettability and cross-linking agents to improve overall performance of the contact lens on the human eye. Such representative monomers of wettability agents are acrylic acid, methacrylic acid, ~-hydroxyethyl acrylate, 2-hydroxyethyl metha-crylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, and/or N-vinyl 2-pyrrolidinone or mixtures thereof.
Representative cross-linking agents are ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethylene-glycol dimethacrylate~ tetraethyleneglycol dimethacrylate, dimethacrylate siloxanyl ester monomer SPSX-563A), ethylene-glycol diacrylate, diethyleneglycol diacrylate, triethylene-glycol diacrylate, tetraethyleneglycol diacrylate, divinyl benzene, divinyl sulfone and/or trimethylolpropane trimethac-rylate or mixtures thereof.
A variety of other ingredi~nts may be included in the polymerization mixture 50 aS either to ~nce properties or provide specific properties, For example, wettability of the surface of the lens is a very important characteristic for contact lenses ¦to possess in order to provide comfort and good visual acuity.
¦In addition to already disclosed wettability agents named herein, ¦additional ethylenically unsaturated monomers can also be incor-¦porated th~ have a hydrophilic group such as hydroxy, carboxy, ¦carbo~do sul~onyl, and sulfonanido groups. As an ~le, such additional ¦monomer can be 2-car~oxyethyl acrylate, 2-carbonamidoethyl methacrylate, . I ... . .
~%~
2-sulfoethyl methacrylate, 2 sulfonamidoethyl acrylate, vinyl sulfonic acid, and mixtures thereof~
The preferred composition of the present invention comprises:
(a) from about 5 to 6S weight percent of an ethylenically unsaturated organosiloxanylalkoxy ester monom~r of acrylic and/or methacrylic acids and siloxanylalkyl ester monomers of itaconic acid or mixtures thereof;
~b) from about 2 to 30 weight percent of an ethylenically unsaturated perfluoralkyl ester monomer or mixtures thereof;
(c) from about 1 to 25 weight percent of an ethylenically unsaturated sulfone monomer or mixtures thereof;
td) from about 10 to 70 weight percent of a hardening agent monomer (preferably, methyl methacrylate, cyclohexyl methacrylate and/or dimethyl itaconate) or mixtures thereof;
~e) from about 1 to 18 weight percent of a difunctional cross-linking monomer (preferably triethylene-glycol dimethacrylate, tetraethyleneglycol dimethacrylate) or mixtures thereof; and tf) from about 1 to 15 weight percent of a wetting agent monomer (preferably methacrylic acid or N-vinyl 2-pyrrolidinone) or mixtures thereoE.
The copolymer plastic can also be prepared without a perfluora ~ 1 ester monom~r and/or sulfone monomer and the material would still possess high oxygen permeability and good wettability.
The polymerization of the oxygen permeable material for the manufacture of contact lenses disclosed in the present invention is accomplished by using free-radical polymerization;
such techniques are disclosed in the prior art.
Example 1:
This example illustrates the preparation of tris(tri-methylsiloxy)methacryloxyethoxysilane, an organosilicone monomer useful in the present invention. To a three-necked, round bottom, 12 liter flask eguipped with mechanical stirrer and ¦cooling system is added 5 liters of dry toluene, 2 moles of 2-hydroxyethylmethacrylate and ~ moles plus 10% excess of triethylamine. The flask content is cooled down to about 5C.
When the temperature is reached, start addition of 2 equivalent ¦moles of tristtrimethylsiloxy)chlorosilane; all addition takes about one hour. Then the temperature is raised to 30C and the stirring is continued for 6 hour~. After the reaction is completed, the white precipitate of triethylamine hydrochloride is filtered off: distillation of toulene proceeds at about 45C
under aspirator vacuum. The crude product is washed twice with cold water and then 2 times with 5~ sodium bicarbonate solution;
then the crude product is washed again 2 times with cold water.
The crude prod~ct is dried over anhydrous MgSO4 for 3 hours;
the MgSO4 is removed by filtration and the product is stripped under high vacuum at 75C. The refractive index n2DSis 1.4112 + 0.001 the infrared spectrum confirmed the structure. The I
:: i - - ~
same procedure is used for the preparation of tris(pentamethyl-disiloxanyl)methacryloxyethoxysilane, bistpentamethyldisilox-anyl)trimethylsiloxanylmethacryloxyethoxysilane, and bis(tri-ethylsiloxy)pentamethyldisiloxanylmethacryloxyethoxysilane if the starting material tris(trimethylsiloxy)chlorosilane is replaced with pentamethylchlorosilane and trimethylchlorosilane in the desired molar ratio.
Example 2:
This example illustrates the preparation o~ the representative perfluoroalkyl ester monomer useful in the present invention. A 12 liter, 3-necked, round bottom flask equipped with a mechanical stirrer and cooling system is charged wi-th 5 liters of toluene, 3 moles of 1,1',2,2'-tetrahydroperfluoro-hexanol and 3 moles plus 10~ excess of triethylamine. q'he flask content while stirring is cooled down to about 5-10C until the temperature is reached, then start addition of 1 mole of trichloromethacryloxypropylsilane; all addition takes about one hour. When all addition is completed the temperature of the reaction mixture is raised to 30C and stirxing is continued for 10 hours. AEtex the reaction is completedr the white pre~pitate of triethylamine hydrochloride is filtered off; distillatlon of toluene proceeds at about 45 C under aspixator vacuum. The crude product is washed twice with cold water, then 2 times with 5% sodium bicarbonate solution and then the crude product is washed again 2 times with cold water. The crude product is dried over anhydrous MgSO" for 3 hours; the MgSO4 is removed by ~iltration and the product is stripped under high vacuum at 75C. The monomer is then ready to be used in the polymer-ization process.
Example 3~
This example is an illustration o the preparation of ~,3-di~tris(trimethylsiloxy)siloxarlyl]methacryloxypropane. The 12 liter flask equipment with a mechanical stirrer, additional funnel and cooling system is charged with 5 liters of toluene, 2 moles of 2,3-dihydroxypropylmethacrylate and 2 moles plu5 10%
excess of triethylamine. The contents of the flask is cooled down to 5C, then addition of 2 moles of tris(trimethylsiloxy)-chlorosilane proceeds in about a period of one hour. When all addition is completed the temperature of the reaction mixture is elevated to 30C and stirring is con-tinued for abou-t 8 hours.
After the reaction i9 comple~ed,the white precipitate of triethyl-amine hydrochloride is filtered off; distillation o toluene proceeds at about 45C under aspirator vacuum. The crude product is ~ashed twice with cold water arld 2 ~imes with 5~
sodium bicarbonate solution and then the crude product is washed again 2 times with cold water. The crude product is dried over anhydrous MgSO" for 3 hours; the MgSO4 is removed by filtration and the product is stripped under high vacuum at 75C. The re~ractive index of the product is 1.4083 + 0.002. The same procedure is used for the preparation of 2,3-di(pentamethyldi-siloxanyl)methacryloxypropane if the starting material tris~tri-methylsiloxy)chlorosilane is replaced with pentamethylchlorodi-siloxane.
Example 4:
This example illustrates the preparation of representa-tive copolymer material for contact lenses. To a 200 ml Elask is added 3S grams,of the organosilicone monomer previously prepared in Example 1, =~trimethyl9iloxy)methacryloxyethoxysilane, 15 grams of 2,3-di~tris(trimethylsiloxy)siloxanyl]methacryloxy-propane, 2 ~rams of methacrylate dimer tPSX-563A), 10 grams of cyclohexyl methacrylate, 5 grams of methacrylic acid, 2.5 grams of N-vinyl 2-pyrrolidinone, 5 grams of the perfluoro mDnomer prepared in Example 2, 10 grams of triethyleneglycol dimethacrylate, 14 grams of methyl methacrylate, 5 drops of D&C #6 color dyer 0O5 ml of t-butyl peroxypivalate and 0.2 grams of benzoyl peroxide. All contents are mixed thoroughly and poured into polypropylene tubes, molds or silylated glass tubes, closed and polymerized in water bath at 40C for a period of about 18 hours. The rods are then put into a thermostated oven for at least 24 hours, having a temperature of about 100C. The copolymer plastic is transparent, hard and suitable for the machining of highly permeable contact lenses.
Example 5O
This example illustrates the preparation of representa-tive copolymer plastic material for contact lenses made only from siloxanyl monomer as a source of oxygen permeability. To the 200 ml flask is added 41 grams of 2,3t-di[tris~trimethylsiloxy)-¦siloxanyl]methacryloxypropane, 10 gxams of cyclohexyl methac-¦rylate, 4.5 grams of methacrylic acid, 5 grams of diethylene-¦glycol dimethacrylate, 39 grams of methyl methacrylate, 0.4 grams ¦of t-butyl peroxyoctoate and 0.1 grams of benzoyl peroxide, all ¦components are mixed thoroughly and poured into polypropylene ¦ tubes, molds or silylated glass tubes closed with stoppers and ¦ polymerized in a water bath or thermostated oven set at 45C
¦ for a period of about 20 hours. The rods or blanks are then put into a thermostated oven preheated at 105C for a period of 24 hours. The copolymer plastic is transparent, hard, oxygen . * Trademark permeable, wettable and suitable for manufacturing oxygen permeable contact lenses.
E~les 6-13:
This example illustrates the preparation of optically clear plastic prepared in accordance with the polymeri~ation procedure described in Example 5, except that the amounts and kinds o~ monomers may be different as shown in thP following table:
T A B L E
.. . ... ~ , ... . . . ~ _ . _ B x~ _N u m b e r onents (Parts) _ 2,3-diltris(trimethylsiloxy)-siloxanyl]methacryloxypropane 35 30 2010 0 15 2020 tris(trimethylsiloxy1-methacryloxyethoxysilane 0_ 10 2030 40 0 1515 tris(dimethylhydrosiloxy)-methacryloxy~ropx_silane 5 0 5 010 _15 510 methacryloxymethylpenta-methyldisiloxane 0 5 _0 0 0 15 5 0 cy~lohexyl methacrylate 12 10 5 0 10 610 0 dimethyl itaconate 10 5 2020 0 10 030 triethyleneglycol dimethacxylate _ 6 8 7 5 4 10 6 8 methyl methacrylate 25 28 3030 25 _30 40_0 methacr lic acid 5 45 0 54 6 0 4 , Y _ _ _ N-vinyl 2-pyrrolidinone 3 0 6 03 0 5 2 vinyl benzene 0 5 ~0 34 10 010 ~ Y
Example 14:
¦ This example illustrates the preparation of oxygen ¦permeable copolymer plastic for contact lenses made from ¦siloxanylalkoxy ester monomer and perfluoroalkyl ester monomer ¦as a source of oxygen permeability. To a 200 ml flask is added 35 parts of bistpentamethyldisiloxanyl)trimethylsiloxymethacry-loxyethoxysilane, 15 parts of cyclohexyl methacrylate, 10 parts of tris(l,l'-dihydroper1uorohexyloxy)methacryloxypropylsilane,
Oxygen permeable contact lenses in the prior art are essentially made from a E;iloxane nono~r and me~yl methacrylate.
These lenses are permeable to oxygen; hence, allowing oxygen from the air to pass through the lenses and reach the cornea which allows such lenses to be worn for longer periods of 'cime as compared to non-oxygen permeable contact lenses such as PMMA
which were available previously.
Such contact lenses are disclosed in the prior art by Gaylord, U.S. Patents Nos. 3,8Q8,178 and 4,120,570. Later, Ellis disclosed in his patents, U.S. Patents Nos. 4,152,508 and 4,330,383, the partial replacement oE the methyl methacrylate monomer with dimethyl itaconateO The Novicky patents, V.S.
Patents Nos. 4,216,303, 4,242,483, 4,248,989, 4,303,772 and 4,365,074, disclose contact lenses comprising high molecular weight polysiloxanylalkyl esters of acrylic and methacrylic acids. The Chang patent, U.S. Patent No. 4,182,822, discloses contact lenses comprised of a copolymer from polysiloxanylalkyl ester of acrylic and ~ethacrylic acid essentially the same as disclosed in the Gaylord patents, supra., that were copolymer-ized with N-vinyl pyrrolidinone or N,N-dimethyl methacrylamide.
Ichinoche, et al., Canadian Patent No. 1,184,341, teaches the use of an organosiloxanyl ester monomer oE acrylic and methacrylic-acid copolymerized with Eluorocarbon ester monomers of acrylic and methacrylic acids and copolymerized to produce oxygen permeable contact lenses. The LeBoeuf patent U.S. Patent No. 4,2461389, disclose, acrylic siloxane based.
1L8~.2 polymers which also ~ontain HEMA and/or polyvinyl 2-pyrrolidinone which are suitable for use in forming water~containing oxygen permeable contact lenses.
¦ All siloxane ester monomers in the prior art employ ¦essentially the same alkyl bridge between the methacryloxy group and ¦siloxanyl part of the structure; wherein, neither one used an ethoxy group or 2~3-dioxypropyl groups. The organosilicone monomers of the present invention can be copolymerized with perfluoroalkyl ¦ester monomer~ and/or with sulfone monomers.
i SUMMARY OF THE INVENTION
~ I
The present invention relates to a novel generation of contact lenses comprising copolymers made from siloxanylalkoxy ester monomers of acrylic, methacrylic and/or itaconic acids and mixtures thereof and perfluoroalkyl ester .7 ¦ monomers of acrylicl methacrylic and/or itaconic acids and ¦ mixtures thereof,which are copolymerized with ethylenically ¦ unsaturated sulfone alkyl monomers and/or ethylenically ¦ unsaturated sulfone ester monomers of acrylic, methacrylic and/or ¦ itaconic acids and mixtures thereof, to produce highly oxygen ¦ permeable an~ improved materials for contact lenses.
¦ The first representative siloxanylalkoxy es~er monomer of acrylic or methacrylic acid of the present invention has the eneral ~tructural formula:
CHz=C-C-O-C~z-CH-CH 2 -O-S i to-s i ~-A
X~ Y
A-Si-A
A m wherein X and Y are Cl to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure:
m being an integer from 1 to S,and R is c~ méthyl group or hydrogen.
The second useful organosiloxanylalkoxy ester monomer of acrylic or methacrylic acid is represented by the following structural formula CHz=C-C-O-(CH~) -o-si~-o-si~-A
n being an integer Erom 1 to 3; wherein, X and Y are Cl to C6 alkyl, cyclic or phenyl group~3 and/or groups of the following stru re: A~-Si-O~-m being an integer from 1 to 5,and R is a methyl group or hydrogen.
The above disclosed new organosilicone monomers can be partially substituted by additional organosiloxanylalkyl ester monomers ~rom the prior art. The first representative partially ¦substituted organosiloxanylalkyl ester monomer of acrylic and ¦methacrylic acid from the prior art has the structural formula:
At si-o t~ cHz)n~~C~c=c~:Z
wherein, X and Y are C~ to C6 alkyl, cyclic or phenyl groups ¦and/or groups of the following structure:
l,tlli_ol; ~
¦ m being an integer fro~ 1 to 6, n being an integer from 1 to 33 ¦ and R is a methyl yroup or hydrogen.
I
¦ The second useful partially substitutedorganosiloxanyl-¦ alkyl ester monomer of acrylic and methacrylic acids is ¦ represented by the following formula:
Dtsi-o!-si-(c8~)n-o-c-c=
¦ wherein, X and Y are Cl to C6 alkyl, cyclic or phenyl groups or ¦ groups of the ~ollowing structure:
D ~ i-O~-m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C~ to C6 alkyl or phenyl groups, R is a methyl group or hydrogen, and D is hydrogen or a hydroxy group, The third useful partially substituted organosiloxanyl-alkyl ester monomer of acrylic and methacrylic acids is represented by the follow'ng structural formula:
X O R
CH3-li-(CH 2 ) ~ O-c-l=cH 2 ¦ wherein, X and Y are groups of the ollowing structure:
¦ wherein m is an integer from 1 to 5, n is an integer from ¦ 1 to 3; A is selected from Cl to C6 alkyI, cyclic or phenyl ¦ groups and R is a methyl group or hydrogen.
The fourth useful pa~lally substituted organosiloxanyl-alkyl ester monomer of itaconic acid is represented by the ¦ following formula:
~-O-(CH2)n-Si-~O-Si 0 (CH2~n-li-tO-Si~-~
.~
.~ 2 wherein, X and Y are Cl to C6, alkyl, cyclic or phenyl groups or groups of the following structure.
BtAi--X
m being an integer from 1 to 5, n being an integer from 1 to 3;
wherein, A is selected from Cl to C6 alkyl, cyclic or phenyl groups and B is a methyl group, hydrogen or a hydroxy group~
The perfluoroalkyl ester monomers of acrylic and methacrylic acid are represented by the following formula-o ~O(CH2)m-(CFz~CF2)a~CF2z . CH2=f-C-O(CH2)n-S ~ OtCH2~m-(CF~-CF2)a-CF2Z
R o(cH2)m-~cF2-cF2)a-cFzz n being an integer from 1 to 3, R is a methyl group or hydrogen, m being an inteqer from 1 to 4, a being an integer from 1 to 10 and Z is fluorine or hydrogen.
Another useful perfluoroalkyl ester monomer of the present invention is represented by the following formula:
CF 3- t CF 2-CF 2 ) rl~ ( CH 2 ) m-O-C-C=CH 2 and telomer alcohol methacrylates or acrylates of the following formula:
!l I
H-(CF2-CF~ )n~(CH2 )m~~C~C=CHZ
and mixtures thereof; wherein, n is an integer from 1 to 10, m is an integer ~rom 1 to 5 and R is a methyl group or hydrogen, Particularly useful in the manufacture of the lenses of the present invention are those fluoroalkyl esters selected from the group con~i~ting of per1uoroalkyl ethyl acrylates and methacrylates of the following formula:
CF 3 -CF 2 - ( CF2-CF 2 ) n-CH 2 -CH2-O-C C=CH 2 wherein, n is an integer from 1 to 10 and R is a methyl group or hydrogen.
The perfluoroalkyl ester monomers of itaconic acid useful in the present invention for the manufacturing of contact lenses are represented by the following formula:
I-o-'CHZ'ntCF2-CF2l-F
C-O-(CHz)n-~CF2-CF2~-F
n being an integer from 1 to 4 and m is an integer from 1 to 10.
Additional perfluorocarbon monomers useful in the present invention to form copolymers are found in published European ¦Patent Application No. 0084406 by David ~. Rice, et al., such ¦monomers havin~ the following general structural formula:
l A-CF 2-0- t CF2-CF 2-0 )m-(CF2-O~n-CF a-Z
¦wherein, m is an integer from 2 to 20, n is an integer from 2 to 130, A is selected from CF9-, C~3-/ CH2F-, and CF2 H-, and Z has ,,"-' 5 ~8 ~Z
~he formula which includes one of the following:
l l l H2C=f-; H2C=C-C-O-; H2C=C-CNH-; and -C-C-R R O R O O
~r mixtures thereof.
¦ The principal sulfone monomers embodied in the present ¦invention which contribute to the increased oxygen permeability ¦and strength o the copolymer for contact lenses are represented ~by the following general structural formula:
¦ A--S--B
I , ¦wherein, A is selected from one of the following:
CH2=CH-; CH2 GCH-C 6 H4-;
~2 =C-~l -O- ( CH2)n~; CH2=C-C-O-t C~2 ) n~;
I O O
¦B is C1 to C20 alkyl, cyclic or phenyl groups and n is ¦~n inteyer ~rom 1 to 5~
The preferable sulfone monomers which are useful in the pr~sent invention are:
methyl vinyl sulfone, methyl styrene sulfone, ethyl vinyl sulfone, ethyl styrene sulfone, propyl vinyl sulfone, propyl styrene sulfone, phenyl vinyl sulfone, phenyl styrene sulEone, cyclohexyl vinyl sulfone, cyclohexyl styrene sulfone, pentyl vinyl sulfone, pentyl styrene sulfone, butyl vinyl sulfone, butyl styrene sulfone, phenoxyethyl vinyl sulfone, phenoxye-thyl 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.
The copolymer plastic material of the present invention also incorporates hardening agen-ts such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, phenyl metha-crylate, tetrahydrofurfuryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, phenyl acrylate, tetrahydrofurfuryl acrylate, dimethyl itaconate, diethyl itaconate, dipropyl itaconate, dicyclohexyl itaconate, diphenyl itaconate, vinyl ben~ene (styrene), divinyl benzene and equivalents.
The contact lens material is further modified by the incorporation of wettability and cross-linking agents to improve overall performance of the contact lens on the human eye. Such representative monomers of wettability agents are acrylic acid, methacrylic acid, ~-hydroxyethyl acrylate, 2-hydroxyethyl metha-crylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, and/or N-vinyl 2-pyrrolidinone or mixtures thereof.
Representative cross-linking agents are ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethylene-glycol dimethacrylate~ tetraethyleneglycol dimethacrylate, dimethacrylate siloxanyl ester monomer SPSX-563A), ethylene-glycol diacrylate, diethyleneglycol diacrylate, triethylene-glycol diacrylate, tetraethyleneglycol diacrylate, divinyl benzene, divinyl sulfone and/or trimethylolpropane trimethac-rylate or mixtures thereof.
A variety of other ingredi~nts may be included in the polymerization mixture 50 aS either to ~nce properties or provide specific properties, For example, wettability of the surface of the lens is a very important characteristic for contact lenses ¦to possess in order to provide comfort and good visual acuity.
¦In addition to already disclosed wettability agents named herein, ¦additional ethylenically unsaturated monomers can also be incor-¦porated th~ have a hydrophilic group such as hydroxy, carboxy, ¦carbo~do sul~onyl, and sulfonanido groups. As an ~le, such additional ¦monomer can be 2-car~oxyethyl acrylate, 2-carbonamidoethyl methacrylate, . I ... . .
~%~
2-sulfoethyl methacrylate, 2 sulfonamidoethyl acrylate, vinyl sulfonic acid, and mixtures thereof~
The preferred composition of the present invention comprises:
(a) from about 5 to 6S weight percent of an ethylenically unsaturated organosiloxanylalkoxy ester monom~r of acrylic and/or methacrylic acids and siloxanylalkyl ester monomers of itaconic acid or mixtures thereof;
~b) from about 2 to 30 weight percent of an ethylenically unsaturated perfluoralkyl ester monomer or mixtures thereof;
(c) from about 1 to 25 weight percent of an ethylenically unsaturated sulfone monomer or mixtures thereof;
td) from about 10 to 70 weight percent of a hardening agent monomer (preferably, methyl methacrylate, cyclohexyl methacrylate and/or dimethyl itaconate) or mixtures thereof;
~e) from about 1 to 18 weight percent of a difunctional cross-linking monomer (preferably triethylene-glycol dimethacrylate, tetraethyleneglycol dimethacrylate) or mixtures thereof; and tf) from about 1 to 15 weight percent of a wetting agent monomer (preferably methacrylic acid or N-vinyl 2-pyrrolidinone) or mixtures thereoE.
The copolymer plastic can also be prepared without a perfluora ~ 1 ester monom~r and/or sulfone monomer and the material would still possess high oxygen permeability and good wettability.
The polymerization of the oxygen permeable material for the manufacture of contact lenses disclosed in the present invention is accomplished by using free-radical polymerization;
such techniques are disclosed in the prior art.
Example 1:
This example illustrates the preparation of tris(tri-methylsiloxy)methacryloxyethoxysilane, an organosilicone monomer useful in the present invention. To a three-necked, round bottom, 12 liter flask eguipped with mechanical stirrer and ¦cooling system is added 5 liters of dry toluene, 2 moles of 2-hydroxyethylmethacrylate and ~ moles plus 10% excess of triethylamine. The flask content is cooled down to about 5C.
When the temperature is reached, start addition of 2 equivalent ¦moles of tristtrimethylsiloxy)chlorosilane; all addition takes about one hour. Then the temperature is raised to 30C and the stirring is continued for 6 hour~. After the reaction is completed, the white precipitate of triethylamine hydrochloride is filtered off: distillation of toulene proceeds at about 45C
under aspirator vacuum. The crude product is washed twice with cold water and then 2 times with 5~ sodium bicarbonate solution;
then the crude product is washed again 2 times with cold water.
The crude prod~ct is dried over anhydrous MgSO4 for 3 hours;
the MgSO4 is removed by filtration and the product is stripped under high vacuum at 75C. The refractive index n2DSis 1.4112 + 0.001 the infrared spectrum confirmed the structure. The I
:: i - - ~
same procedure is used for the preparation of tris(pentamethyl-disiloxanyl)methacryloxyethoxysilane, bistpentamethyldisilox-anyl)trimethylsiloxanylmethacryloxyethoxysilane, and bis(tri-ethylsiloxy)pentamethyldisiloxanylmethacryloxyethoxysilane if the starting material tris(trimethylsiloxy)chlorosilane is replaced with pentamethylchlorosilane and trimethylchlorosilane in the desired molar ratio.
Example 2:
This example illustrates the preparation o~ the representative perfluoroalkyl ester monomer useful in the present invention. A 12 liter, 3-necked, round bottom flask equipped with a mechanical stirrer and cooling system is charged wi-th 5 liters of toluene, 3 moles of 1,1',2,2'-tetrahydroperfluoro-hexanol and 3 moles plus 10~ excess of triethylamine. q'he flask content while stirring is cooled down to about 5-10C until the temperature is reached, then start addition of 1 mole of trichloromethacryloxypropylsilane; all addition takes about one hour. When all addition is completed the temperature of the reaction mixture is raised to 30C and stirxing is continued for 10 hours. AEtex the reaction is completedr the white pre~pitate of triethylamine hydrochloride is filtered off; distillatlon of toluene proceeds at about 45 C under aspixator vacuum. The crude product is washed twice with cold water, then 2 times with 5% sodium bicarbonate solution and then the crude product is washed again 2 times with cold water. The crude product is dried over anhydrous MgSO" for 3 hours; the MgSO4 is removed by ~iltration and the product is stripped under high vacuum at 75C. The monomer is then ready to be used in the polymer-ization process.
Example 3~
This example is an illustration o the preparation of ~,3-di~tris(trimethylsiloxy)siloxarlyl]methacryloxypropane. The 12 liter flask equipment with a mechanical stirrer, additional funnel and cooling system is charged with 5 liters of toluene, 2 moles of 2,3-dihydroxypropylmethacrylate and 2 moles plu5 10%
excess of triethylamine. The contents of the flask is cooled down to 5C, then addition of 2 moles of tris(trimethylsiloxy)-chlorosilane proceeds in about a period of one hour. When all addition is completed the temperature of the reaction mixture is elevated to 30C and stirring is con-tinued for abou-t 8 hours.
After the reaction i9 comple~ed,the white precipitate of triethyl-amine hydrochloride is filtered off; distillation o toluene proceeds at about 45C under aspirator vacuum. The crude product is ~ashed twice with cold water arld 2 ~imes with 5~
sodium bicarbonate solution and then the crude product is washed again 2 times with cold water. The crude product is dried over anhydrous MgSO" for 3 hours; the MgSO4 is removed by filtration and the product is stripped under high vacuum at 75C. The re~ractive index of the product is 1.4083 + 0.002. The same procedure is used for the preparation of 2,3-di(pentamethyldi-siloxanyl)methacryloxypropane if the starting material tris~tri-methylsiloxy)chlorosilane is replaced with pentamethylchlorodi-siloxane.
Example 4:
This example illustrates the preparation of representa-tive copolymer material for contact lenses. To a 200 ml Elask is added 3S grams,of the organosilicone monomer previously prepared in Example 1, =~trimethyl9iloxy)methacryloxyethoxysilane, 15 grams of 2,3-di~tris(trimethylsiloxy)siloxanyl]methacryloxy-propane, 2 ~rams of methacrylate dimer tPSX-563A), 10 grams of cyclohexyl methacrylate, 5 grams of methacrylic acid, 2.5 grams of N-vinyl 2-pyrrolidinone, 5 grams of the perfluoro mDnomer prepared in Example 2, 10 grams of triethyleneglycol dimethacrylate, 14 grams of methyl methacrylate, 5 drops of D&C #6 color dyer 0O5 ml of t-butyl peroxypivalate and 0.2 grams of benzoyl peroxide. All contents are mixed thoroughly and poured into polypropylene tubes, molds or silylated glass tubes, closed and polymerized in water bath at 40C for a period of about 18 hours. The rods are then put into a thermostated oven for at least 24 hours, having a temperature of about 100C. The copolymer plastic is transparent, hard and suitable for the machining of highly permeable contact lenses.
Example 5O
This example illustrates the preparation of representa-tive copolymer plastic material for contact lenses made only from siloxanyl monomer as a source of oxygen permeability. To the 200 ml flask is added 41 grams of 2,3t-di[tris~trimethylsiloxy)-¦siloxanyl]methacryloxypropane, 10 gxams of cyclohexyl methac-¦rylate, 4.5 grams of methacrylic acid, 5 grams of diethylene-¦glycol dimethacrylate, 39 grams of methyl methacrylate, 0.4 grams ¦of t-butyl peroxyoctoate and 0.1 grams of benzoyl peroxide, all ¦components are mixed thoroughly and poured into polypropylene ¦ tubes, molds or silylated glass tubes closed with stoppers and ¦ polymerized in a water bath or thermostated oven set at 45C
¦ for a period of about 20 hours. The rods or blanks are then put into a thermostated oven preheated at 105C for a period of 24 hours. The copolymer plastic is transparent, hard, oxygen . * Trademark permeable, wettable and suitable for manufacturing oxygen permeable contact lenses.
E~les 6-13:
This example illustrates the preparation of optically clear plastic prepared in accordance with the polymeri~ation procedure described in Example 5, except that the amounts and kinds o~ monomers may be different as shown in thP following table:
T A B L E
.. . ... ~ , ... . . . ~ _ . _ B x~ _N u m b e r onents (Parts) _ 2,3-diltris(trimethylsiloxy)-siloxanyl]methacryloxypropane 35 30 2010 0 15 2020 tris(trimethylsiloxy1-methacryloxyethoxysilane 0_ 10 2030 40 0 1515 tris(dimethylhydrosiloxy)-methacryloxy~ropx_silane 5 0 5 010 _15 510 methacryloxymethylpenta-methyldisiloxane 0 5 _0 0 0 15 5 0 cy~lohexyl methacrylate 12 10 5 0 10 610 0 dimethyl itaconate 10 5 2020 0 10 030 triethyleneglycol dimethacxylate _ 6 8 7 5 4 10 6 8 methyl methacrylate 25 28 3030 25 _30 40_0 methacr lic acid 5 45 0 54 6 0 4 , Y _ _ _ N-vinyl 2-pyrrolidinone 3 0 6 03 0 5 2 vinyl benzene 0 5 ~0 34 10 010 ~ Y
Example 14:
¦ This example illustrates the preparation of oxygen ¦permeable copolymer plastic for contact lenses made from ¦siloxanylalkoxy ester monomer and perfluoroalkyl ester monomer ¦as a source of oxygen permeability. To a 200 ml flask is added 35 parts of bistpentamethyldisiloxanyl)trimethylsiloxymethacry-loxyethoxysilane, 15 parts of cyclohexyl methacrylate, 10 parts of tris(l,l'-dihydroper1uorohexyloxy)methacryloxypropylsilane,
3 parts of N-vinyl 2-pyrrolidinone, 7 parts of t~traethylene-¦glycol dimethacrylate, 5 parts of methacrylic acid, 25 parts ofmethyl methacrylate, 0~5 parts of t-butyl peroxypivalate and 0~2 parts of benzoyl peroxide; the polymerization i5 carried out by the same procedure as described in Example 5. The resulting plastic i~ transparent, hard, stable, wettable and suitable for machining of highly permeable contact lenses~
¦E~les 15-22:
I Samples of optically clear plastic are prepared in ¦accordance with the polymeri~ation procedure described in Example 14, except that the amDunts and kinds of o~onents may be different, as shown in the following tableo j~ ~5 T~ B L E
E x a m v 1 e N u m b e r Components (Parts) ~15 16 17 18 ~1920 21 22 tris(l,l'-dihydroperfluoro-hexyloxy)methacryloxypropyl-silane 10 0 520 40 0 20 15 bis(l,l',2,2'-tetrahydro-perfluorobutyl)itaconate 0 15 5 0 0 5 3 5 2,3-di[tri6(trimethylsiloxy)-sllo~anyl3methacryloxypropane _ 3025_ 10 20 20 5 0 10 tris(trimethylsiloxy)meth-acryloxyethoxysilane 10 lS 25 5 0 30 40 20 di(pentamethyldisiloxanyl-ethy~)itaconate _ 5__ 0 510_ 5 5 5 dimethyl itaconate _10 0 610 30 15 0 _12 methyl methacrylate 20 30 1810 10 20 18 20 cyclohexyl methacr~late _10 15 820 0 0 15 0 N-vinyl 2-p~rrolldinone _0_ 3 2 6 ? 0 4 0 vinyl benzene _0 2 6 0 3 _ 8 0 0 diethyleneglycol dimethacrylate _ _ 6 0 _ 2 4 6 0 0 triethyleneglycol dimethacrylate ~ . ~ 0 6 1 4 ~ _L~ 6 All samples of the above copolymer plastic are clear, transparent and gas permeable.
Example 23:
This example illustrates the preparation of oxygen permeable copolymer plastic for contact lenses from siloxanyl-alkoxy ester of methacrylic acid and sulfone monomer as a source of oxygen permeability; consisting of 40 parts of tris~trimethyl-siloxy)methacryloxyethoxysilane, 10 parts of cyclohexyl methac-rylate, 8 parts of methyl vinyl sulfone, 20 parts o tetrahydro-furfuryl methacryla~e, 5 parts of ~-hydroxyethyl methacrylate, 7 parts of ~-vinyl 2-pyrrolidinone, 7 parts of methyl methacry-late and 0.4 parts o t-butyl peroxypivalate are polymerized.
The resulting copolymer plastic has a hardness of 86 ~ 2 as measured on the Shore D (ASTM-2240) hardness tester.
~ r~
Example 24:
A contact lens has been manufactured from the oxygen permeable material of the present invention using standard, conventional manufacturing techniques known in the art. The base curve of the lens was cut at 7.80 mm, the front curve of the lens was cut at 8.21 mm, the center thickness of the lens was 0.19 mm. The contact lens was then polished using a tech-nique widely known in the contact lens industry. The base curve of the lens was 7.81 mm; after the lens was polished the base curve remained at 7.81 mm. The lens was soaked over 72 hours in Soaclens solution and the base curve remained at 7.81 mm.
Examples 25-32 Samples of optically clear plastic are prepared in accordance with the polymerization procedure described in Example 4, except that the amounts and kinds of components may be different as shown in the following table:
~ p = _ Components (Parts) 25 ~26,~ 27 28 2930 31 32 tris~trimethylsiloxy) methacryloxyethoxysilane 25 40 30 40 3045 lU 0 tristtrimethylsiloxy)-methacryloxypropylsilane 10 0 10 5 10 0 20 _30 1,1',2,2'-tetrahydroper-fluorohexyl methacrylate _ 10 5 0 10 2 0 5 0 tris(l,l'-dihydroperfluoro-butyloxy)methacryloxy-propylsilane 5 0 5 0 210 0 20 methyl vinyl sul~one _ 0 5 6 010 0 10 10 me~thyl methacrylate 30 30 29 30 2135 30 15 cyclohexyl methacr,ylate _ _1010 11 1010 0 10 15 methacrylic acid 5 5 4 2 5 5 5 4 di~thyleneglycol dimethacrylate _ _ _ _ 5 5 5 3 10 5 10 6 * All samples of the above copolymer plastlc are hard, transparent and easily machinable~
, ,,, ~*Trademark ~ ~2~
E`.xa~
Thc~ polymerization oE a mixture oE 2U parts of ¦2,3-~i[~ri~trimethylsiloxy)siloxanyl~mcthacryloxypropane, 20 ¦~ar~ o~ trls~trimethylsiloxy)methacryloxypropylsilane, lQ parts ~ b1s(1,11,$-trihydroperEluoropentyl)itaconate, 10 parts of cyclohexyl methacrylate, 8 parts of ethyleneglyc~l dimethac-¦rylate, 4 ~art~ ~ methacrylic acid, 3 parts oE N-vinyl ¦2-pyrrolidinone an~ 25 parts of methyl methacrylate are poly-¦meri~d by u~lng ~ree-radical cataly~t~, a~ shown in Example 5, ¦in polypropylen~ base curv~ premQlded caps~ The re~ultin~
¦pla~tic giv~ a tran~parent/ concave plug.
¦Exc!m~ s l Tho uolymerization prQcedure oE Example 5 is repec~ted, ¦~xc~pt ~at ~lac~unts and kinds of compon~nts in the polvmerization ¦ar~ changed as Eollows: 45 part~ o tris(trlme~hylsiloxy)-¦~iloxanyLmethacryloxy~thoxy~ilane, 10 part~ oE tris~l,l',2,2'-¦t~trahydroper~luoropentyloxy)metllacrylo~ypropylsilane, 10 parts of cyclohexyl meth~crylate, 9 part~ oE triathyleneglycol dim~thacryl~te, ~ part~ of rmethacrylic acid, 3 parts of N-vinyl 2-pyrrolidinone and L8 parts of methyl methacrylate are polymer-lted by u~lnc~ free radical initiator ~t ~7C. Th~ plastic i~ th~n removed frolll the molds, trans~erred into a ~hermostated ov~n which is ~et at 108C and the copolymer plastic i9 cured for an Addlt~o~l~l 24 hours. The resulting plastic has an o~ygen permeability ~ a~out 91 x lO ll(csn2/sec3(m1 O~/ml x rnrn Hg) at ¦35CI a~ analy~.ed on the Schellla-Versatae"Model ~20 instrument ¦(an ~nalytic~l t~chniclue widely u~3~d in the industry).
~Trac~ellla rk
¦E~les 15-22:
I Samples of optically clear plastic are prepared in ¦accordance with the polymeri~ation procedure described in Example 14, except that the amDunts and kinds of o~onents may be different, as shown in the following tableo j~ ~5 T~ B L E
E x a m v 1 e N u m b e r Components (Parts) ~15 16 17 18 ~1920 21 22 tris(l,l'-dihydroperfluoro-hexyloxy)methacryloxypropyl-silane 10 0 520 40 0 20 15 bis(l,l',2,2'-tetrahydro-perfluorobutyl)itaconate 0 15 5 0 0 5 3 5 2,3-di[tri6(trimethylsiloxy)-sllo~anyl3methacryloxypropane _ 3025_ 10 20 20 5 0 10 tris(trimethylsiloxy)meth-acryloxyethoxysilane 10 lS 25 5 0 30 40 20 di(pentamethyldisiloxanyl-ethy~)itaconate _ 5__ 0 510_ 5 5 5 dimethyl itaconate _10 0 610 30 15 0 _12 methyl methacrylate 20 30 1810 10 20 18 20 cyclohexyl methacr~late _10 15 820 0 0 15 0 N-vinyl 2-p~rrolldinone _0_ 3 2 6 ? 0 4 0 vinyl benzene _0 2 6 0 3 _ 8 0 0 diethyleneglycol dimethacrylate _ _ 6 0 _ 2 4 6 0 0 triethyleneglycol dimethacrylate ~ . ~ 0 6 1 4 ~ _L~ 6 All samples of the above copolymer plastic are clear, transparent and gas permeable.
Example 23:
This example illustrates the preparation of oxygen permeable copolymer plastic for contact lenses from siloxanyl-alkoxy ester of methacrylic acid and sulfone monomer as a source of oxygen permeability; consisting of 40 parts of tris~trimethyl-siloxy)methacryloxyethoxysilane, 10 parts of cyclohexyl methac-rylate, 8 parts of methyl vinyl sulfone, 20 parts o tetrahydro-furfuryl methacryla~e, 5 parts of ~-hydroxyethyl methacrylate, 7 parts of ~-vinyl 2-pyrrolidinone, 7 parts of methyl methacry-late and 0.4 parts o t-butyl peroxypivalate are polymerized.
The resulting copolymer plastic has a hardness of 86 ~ 2 as measured on the Shore D (ASTM-2240) hardness tester.
~ r~
Example 24:
A contact lens has been manufactured from the oxygen permeable material of the present invention using standard, conventional manufacturing techniques known in the art. The base curve of the lens was cut at 7.80 mm, the front curve of the lens was cut at 8.21 mm, the center thickness of the lens was 0.19 mm. The contact lens was then polished using a tech-nique widely known in the contact lens industry. The base curve of the lens was 7.81 mm; after the lens was polished the base curve remained at 7.81 mm. The lens was soaked over 72 hours in Soaclens solution and the base curve remained at 7.81 mm.
Examples 25-32 Samples of optically clear plastic are prepared in accordance with the polymerization procedure described in Example 4, except that the amounts and kinds of components may be different as shown in the following table:
~ p = _ Components (Parts) 25 ~26,~ 27 28 2930 31 32 tris~trimethylsiloxy) methacryloxyethoxysilane 25 40 30 40 3045 lU 0 tristtrimethylsiloxy)-methacryloxypropylsilane 10 0 10 5 10 0 20 _30 1,1',2,2'-tetrahydroper-fluorohexyl methacrylate _ 10 5 0 10 2 0 5 0 tris(l,l'-dihydroperfluoro-butyloxy)methacryloxy-propylsilane 5 0 5 0 210 0 20 methyl vinyl sul~one _ 0 5 6 010 0 10 10 me~thyl methacrylate 30 30 29 30 2135 30 15 cyclohexyl methacr,ylate _ _1010 11 1010 0 10 15 methacrylic acid 5 5 4 2 5 5 5 4 di~thyleneglycol dimethacrylate _ _ _ _ 5 5 5 3 10 5 10 6 * All samples of the above copolymer plastlc are hard, transparent and easily machinable~
, ,,, ~*Trademark ~ ~2~
E`.xa~
Thc~ polymerization oE a mixture oE 2U parts of ¦2,3-~i[~ri~trimethylsiloxy)siloxanyl~mcthacryloxypropane, 20 ¦~ar~ o~ trls~trimethylsiloxy)methacryloxypropylsilane, lQ parts ~ b1s(1,11,$-trihydroperEluoropentyl)itaconate, 10 parts of cyclohexyl methacrylate, 8 parts of ethyleneglyc~l dimethac-¦rylate, 4 ~art~ ~ methacrylic acid, 3 parts oE N-vinyl ¦2-pyrrolidinone an~ 25 parts of methyl methacrylate are poly-¦meri~d by u~lng ~ree-radical cataly~t~, a~ shown in Example 5, ¦in polypropylen~ base curv~ premQlded caps~ The re~ultin~
¦pla~tic giv~ a tran~parent/ concave plug.
¦Exc!m~ s l Tho uolymerization prQcedure oE Example 5 is repec~ted, ¦~xc~pt ~at ~lac~unts and kinds of compon~nts in the polvmerization ¦ar~ changed as Eollows: 45 part~ o tris(trlme~hylsiloxy)-¦~iloxanyLmethacryloxy~thoxy~ilane, 10 part~ oE tris~l,l',2,2'-¦t~trahydroper~luoropentyloxy)metllacrylo~ypropylsilane, 10 parts of cyclohexyl meth~crylate, 9 part~ oE triathyleneglycol dim~thacryl~te, ~ part~ of rmethacrylic acid, 3 parts of N-vinyl 2-pyrrolidinone and L8 parts of methyl methacrylate are polymer-lted by u~lnc~ free radical initiator ~t ~7C. Th~ plastic i~ th~n removed frolll the molds, trans~erred into a ~hermostated ov~n which is ~et at 108C and the copolymer plastic i9 cured for an Addlt~o~l~l 24 hours. The resulting plastic has an o~ygen permeability ~ a~out 91 x lO ll(csn2/sec3(m1 O~/ml x rnrn Hg) at ¦35CI a~ analy~.ed on the Schellla-Versatae"Model ~20 instrument ¦(an ~nalytic~l t~chniclue widely u~3~d in the industry).
~Trac~ellla rk
Claims (11)
- CLAIM 1:
A contact lens material comprising an organic polymer which consists of an organosiloxanylalkoxy ester monomer of acrylic and methacxylic acid which has the structural formula:
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure:
where m is an integer from 1 to 5 and R is a methyl group or hydrogen;
and an organosiloxanylalkoxy ester monomer of acrylic or methacrylic acid having the following structural formula:
wherein n is an integer from 1 to 3, X and Y are C1 to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure:
in which m is an integer from 1 to 5 and R is a methyl group or hydrogen. - CLAIM 2:
A contact lens device which is manufactured from oxygen permeable copolymer plastic material which comprises organosiloxanylalkoxy ester monomers of acrylic and methacrylic acid of Claim l; said monomers being partially substituted with organosiloxanylalkyl ester monomers of the prior art. - CLAIM 3:
An ophthalmic device which is manufactured from oxygen permeable copolymer plastic material which contains perfluoro-alkyl ester monomers of acrylic and methacrylic acids, said perfluoroalkyl ester monomers having the following formula:
n being an integer from 1 to 3, R is a methyl group or hydrogen, m being an integer from 1 to 4, a being an integer from 1 to 10 and Z is fluorine or hydrogen. - CLAIM 4:
An ophthalmic device which is manufactured from oxygen permeable copolymer plastic material, said plastic material comprising an organosiloxanylalkoxy ester monomer of acrylic and methacrylic acids which is represented by the following formula:
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure:
wherein m is an integer from 1 to 5 and R is a methyl group or hydrogen;
and an organosiloxanylalkoxy ester monomer of acrylic or methacrylic acid represented by the following structural formula:
wherein n is an integer from 1 to 3, X and Y are C1 to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure:
n being an integer from 1 to 5 and R is a methyl group or hydrogen;
and perfluoroalkyl ester monomers of acrylic and methacrylic acids, said perfluoxoalkyl ester monomers having the following formula:
n being an integer from 1 to 3, R is a methyl group or hydrogen, m being an integer from 1 to 4, a being an integer from 1 to 10 and Z is fluorine or hydrogen. - CLAIM 5 A contact lens material comprising from about 5 to 65 weight percent of organosiloxanylalkoxy ester mononers of acrylic and methacrylic acids selected from the group consisting of 2,3-di[tris(trimethylsiloxy)-siloxanyl]methacryloxypropane, tris(trimethylsiloxy)methacryloxy-ethoxysilane, 2,3-di[tris(trimethylsiloxy)siloxanyl]acryloxy-propane, tris(trimethylsiloxy)acryloxyethoxysilane, 2,3-di(penta-methyldisiloxanyl)methacryloxypropane, tris(pentamethyldisilox-anyl)methacryloxyethoxysilane, bis(pentamethyldisiloxanyl)tri-methylsiloxanylmethacryloxyethoxysilane, bis(trimethylsiloxy)-pentamethyldisiloxanylmethacryloxyethoxysilane and from about 2 to 30 weight percent of a perfluoroalkyl monomer of methacrylic, acrylic and/or itaconic acids and mixtures thereof and from about 10 to 60 weight percent of a hardening agent selected from the group consisting of methyl, methacrylate, ethyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, phenyl methacrylate, tetrahydrofurfuryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, phenyl acrylate, tetrahydrofurfuryl acrylate, dimethyl itaconate, diethyl itaconate, dipropyl itaconate, dicyclohexyl itaconate, diphenyl itaconate, vinyl benzene (styrene), divinyl benzene and equivalents; said contact lens material being modified to be wettable by incorporation of one or more wettability agents selected from the group consisting of acrylic acid, metha-crylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, and/or N-vinyl 2-pyrrolidinone and mixtures thereof; said contact lens material also including a cross-linking agent selected from the group consisting of ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, tetraethylene glycol dimethac-rylate, dimethacrylate siloxanyl ester monomer (PSX-563A)?(trademark) ethyleneglycol diacrylate, tetraethyleneglycol diacrylate, divinyl benzene, divinyl sulfone and/or trimethylolpropane trimethacrylate or mixtures thereof.
- CLAIM 6:
An oxygen permeable copolymer plastic for contact lenses comprising from about 5 to 70 weight percent of an organo-siloxanylalkoxy ester monomer of acrylic and methacrylic acids having the following formula:
wherein X and Y are C1 to C6, alkyl, cyclic or phenyl groups and/or groups of the following structure:
m being an integer from 1 to 5 and R is a methyl group or hydrogen;
and/or an organosiloxanylalkoxy ester monomer of acrylic or methacrylic acid having the following structural formula:
wherein n is an integer from 1 to 3, X and Y are C1 to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure:
m being an integer from 1 to 5 and R is a methyl group or hydrogen;
said organosiloxanylalkoxy ester monomers of acrylic or methac-rylic acid can be partially substituted with organosiloxanyl-alkyl ester monomers from the prior art having the following structural formula:
wherein X and Y 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 and R is a methyl group or hydrogen; and/or the 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 a methyl group or hydrogen,and D is hydrogen or a hydroxy group; and or the formula:
wherein X and Y are groups of the following structure:
wherein m is an integer from 1 to 5, n is an integer from 1 to 3, A is selected from C1 to C6 alkyl, cyclic or phenyl groups and R is a methyl group or hydrogen; and/or the following formula:
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups or groups of the following structure:
wherein m is an integer from 1 to 5, n is an integer from 1 to 3, A is selected from C1 to C6 alkyl, cyclic or phenyl groups and B is a methyl group, hydrogen or a hydroxy group. - CLAIM 7:
An oxygen permeable copolymer plastic for contact lenses according to Claim 6, said copolymer plastic containing additional oxygen permeability monomers selected from perfluoroalkyl esters of methacrylic, acrylic and itaconic acids and mixtures thereof having the following formulas:
n being an integer from 1 to 3, R is a methyl group or hydrogen, m being an integer from 1 to 4, a being an integer from 1 to 10 and Z is fluorine or hydrogen; and/or the following formula:
and telomer alcohol methacrylates or acrylates of the following formula:
and mixtures thereof, wherein n is an integer from 1 to 10, m is an integer from 1 to 5 and R is a methyl group or hydrogen;
and/or the following formula:
wherein n is an integer from 1 to 4 and m is an integer from 1 to 10. - CLAIM 8:
An oxygen permeable copolymer plastic for contact lenses according to Claim 6, comprising about 2 to 30 weight percent of additional perfluorocarbon monomers having the following structural formula:
A-CF2-O-(CF2-CF2-O)m-(CF2-O)n-CF2-Z
wherein n is an integer from 2 to 20, n is an integer from 2 to 30, A is selected from CF3-, CH3-, CH2F-, CF2H-,and Z has the formula which includes one of the following:
or mixtures thereof. - CLAIM 9:
An oxygen permeable contact lens material comprising organosiloxanylalkoxy ester monomers having the following formulas:
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure m being an integer from 1 to 5 and R is a methyl group or hydrogen;
and/or the following formula:
wherein n is an integer from 1 to 3, and X and Y are C1 to C6 alkyl, cyclic or phenyl groups and/or groups of the following structure:
m being an integer from 1 to 5 and R is a methyl group or hydrogen:
and an organosulfone monomer for the purpose of increasing oxygen permeability having the following structural formula:
wherein A is selected from one of the following:
CH2=CH-; CH2=CH-C6H4-;
wherein B is C1 to C20 alkyl, cyclic or phenyl groups and n is an integer from 1 to 5; said copolymer plastic also including a hardening agent selected from the group consisting of alkyl ester monomers or acrylic, methacrylic and/or itaconic acids or mixtures thereof, and is further modified by the incorporation of a nettability agent selected from the group consisting of acrylic acid, methacrylic acid, 2-hydroxyethyl acetylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropy1 acrylate, 2,3-dihydroxypropyl methacrylate, and/or N-vinyl 2-pyrrolidinone or mixtures thereof, and a cross-linking agent selected from the group consisting of ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, tetraethyleneglycol dimethac-rylate, dimethacrylate siloxanyl ester monomer("PSX-563A")(trademark) ethyleneglycol diacrylate, diethyleneglycol diacrylate, triethyleneglycol diacrylate, tetraethyleneglycol diacrylate, divinyl benzene, divinyl sulfone and/or trimethylolpropane trimethacrylate or mixtures thereof. - CLAIM 10:
An oxygen permeable contact lens material according to Claim 9 wherein said material is modified by incorporation from about 2 to 30 weight percent of perfluoroalkyl ester monomers of acrylic, methacrylic and/or itaconic acids or mixtures thereof. - CLAIM 11:
An ophthalmic device which is manufactured from an oxygen permeable copolymer plastic made from organosiloxanylalkoxy ester of acrylic, methacrylic and/or itaconic acids or mixtures thereof, and from perfluoroalkyl ester monomers of acrylic, methacrylic and/or itaconic acids or mixtures thereof, and from sulfone monomers: wherein said device is modified by the incorporation of a hardening agent selected from the group consisting of alkyl ester monomers of acrylic, nethacrylic, and/or itaconic acids or mixtures thereof; said device being additionally modified by the incorpora-tion of wettability and cross-linking agents.
A contact lens material according to claim 1 wherein said organosiloxanyl ester monomer of acrylic and methacrylic acid is tris(trimethylsiloxy) methacryloxyethoxysilane.
A contact lens material according to claim 5 which consists essentially of an interpolymer of bis(pentamethyl-disiloxanyl)trimethylsiloxymethacryloxy-ethoxysilane, tris(1,1'-dihydroperfluorohexyloxy)methacryloxypropylsilane, cyclohexyl methacrylate, N-vinyl 2-pyrrolidinone, and tetraethylene glycol dimethacrylate.
An oxygen permeable contact lens material according to claim 9 which consists essentially of an interpolymer of the following monomers, in parts by weight:
parts of tris(trimethylsiloxy)methacryloxyethoxy-silane, 10 parts of cyclohexyl methacrylate, 8 parts of methyl vinyl sulfone, 20 parts of tetrahydrofurfuryl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, 7 parts of methyl methacrylate, and 7 parts of n-vinyl 2-pyrrolidinone.
A contact lens material according to claim 5 which consists essentially of an interpolymer of the following, in parts by weight:
parts of 2,3-di[tris(trimethylsiloxy)siloxanyl]-methacryloxypropane, 20 parts tris(trimethylsiloxy)methacryloxypropylsilane, 10 parts of cyclohexyl methacrylate, 8 parts of ethylene glycol dimethacrylate, 4 parts methacrylic acid, 3 parts of N-vinyl 2-pyrrolidinone, and 25 parts of methyl methacrylate.
A contact lens material according to claim 5 which consists essentially of an interpolymer of the following, in parts by weight:
parts of tris(trimethylsiloxy)siloxanyl methacryloxyethoxysilane, parts of tris(1,1', 2,2' tetrahydro-perfluoropentyloxy)-methacryloxypropylsilane, 10 parts of cyclohexyl methacrylate, 9 parts of triethylene glycol dimethacrylate, 5 parts of methacrylic acid, 3 parts of N-vinyl 2-pyrrolidinone, and 18 parts of methyl methacrylate.
A contact lens material according to claim 5 which consists essentially of an interpolymer of the following, in parts by weight:
parts of 2,3-diltris(trimethylsiloxy)siloxanyl]-methacryloxypropane, parts of tris(1,1'-dihydroperfIuorohexyloxy)-methacryloxypropylsilane, parts of tris(trimethylsiloxy)-methacryloxyethoxysilane, 5 parts of di(pentamethyldisiloxanylethyl)-itaconate, 10 parts of dimethyl itaconate, 20 parts of methyl methacrylate, 10 parts of cyclohexyl methacrylate, 3 parts of methacrylic acid, and 6 parts of diethylene glycol dimethacrylate.
A contact lens device which is manufactured from the oxygen-permeable contact lens material defined in claim 14.
A contact lens device manufactured from the interpolymer of claim 13.
A contact lens device manufactured from the contact lens material defined in claim 15.
A contact lens device manufactured from the contact lens material defined in claim 16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000512768A CA1251882A (en) | 1986-06-30 | 1986-06-30 | Highly oxygen permeable contact lens materials and compositions thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000512768A CA1251882A (en) | 1986-06-30 | 1986-06-30 | Highly oxygen permeable contact lens materials and compositions thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1251882A true CA1251882A (en) | 1989-03-28 |
Family
ID=4133464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000512768A Expired CA1251882A (en) | 1986-06-30 | 1986-06-30 | Highly oxygen permeable contact lens materials and compositions thereof |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1251882A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5777052A (en) * | 1996-06-28 | 1998-07-07 | Dow Corning Toray Slicone Co., Ltd. | Silicone modified vinyl polymers and method for the preparation thereof |
| EP2138889A1 (en) * | 2008-06-26 | 2009-12-30 | Lachezar Komitov | Alignment layer for LCD |
| CN114516942A (en) * | 2020-11-18 | 2022-05-20 | 亨泰光学股份有限公司 | Hard oxygen-permeable contact lens polymer material and polymerization method thereof |
-
1986
- 1986-06-30 CA CA000512768A patent/CA1251882A/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5777052A (en) * | 1996-06-28 | 1998-07-07 | Dow Corning Toray Slicone Co., Ltd. | Silicone modified vinyl polymers and method for the preparation thereof |
| EP2138889A1 (en) * | 2008-06-26 | 2009-12-30 | Lachezar Komitov | Alignment layer for LCD |
| WO2009156483A1 (en) * | 2008-06-26 | 2009-12-30 | Lachezar Komitov | Alignment layer for lcd |
| TWI493261B (en) * | 2008-06-26 | 2015-07-21 | Lachezar Komitov | A polymer for usr in an alignment layer for a liquid crystal material, a surface director alignment layer material, and a liquid crystal device and a method for the manufacture the same |
| CN114516942A (en) * | 2020-11-18 | 2022-05-20 | 亨泰光学股份有限公司 | Hard oxygen-permeable contact lens polymer material and polymerization method thereof |
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