HIGHLY OXYGEN PERMEABLE CONTACT LENS MATERIALS AND COMPOSITIONS THEREOF

PRODUITS TRES PERMEABLES A L'OXYGENE POUR VERRES DE CONTACT; COMPOSITIONS A BASE DE CES PRODUITS

English 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.

Claims

- 22 -
The embodiments of the invention which are claimed as
an exclusive property or priviledge are defined as follows:
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:
<IMG>
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups
and/or groups of the following structure:
<IMG>
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:
<IMG>
wherein n is an integer from 1 to 3, X and Y are C1 to C6

- 23 -
alkyl, cyclic or phenyl groups and/or groups of the following
structure:
<IMG>
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:
<IMG>
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.

- 24 -
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:
<IMG>
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups
and/or groups of the following structure:
<IMG>
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:
<IMG>
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:

- 25 -
<IMG>
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:
<IMG>
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,

- 26 -
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:
<IMG>

- 27 -
wherein X and Y are C1 to C6, alkyl, cyclic or phenyl groups
and/or groups of the following structure:
<IMG>
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:
<IMG>
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:
<IMG>
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:
<IMG>

- 28 -
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups
and/or groups of the following structure:
<IMG>
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:
<IMG>
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups or
groups of the following structure:
<IMG>
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:
<IMG>
wherein X and Y are groups of the following structure:
<IMG>

- 29 -
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:
<IMG>
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups or
groups of the following structure:
<IMG>
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:
<IMG>

- 30 -
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:
<IMG>
and telomer alcohol methacrylates or acrylates of the following
formula:
<IMG>
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:
<IMG>
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

- 31 -
30, A is selected from CF3-, CH3-, CH2F-, CF2H-,and Z has the
formula which includes one of the following:
<IMG>
or mixtures thereof.
CLAIM 9:
An oxygen permeable contact lens material comprising
organosiloxanylalkoxy ester monomers having the following
formulas:
<IMG>
wherein X and Y are C1 to C6 alkyl, cyclic or phenyl groups
and/or groups of the following structure
<IMG>
m being an integer from 1 to 5 and R is a methyl group or hydrogen;
and/or the following formula:

- 32 -
<IMG>
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:
<IMG>
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:
<IMG>
wherein A is selected from one of the following:
CH2=CH-; CH2=CH-C6H4-;
<IMG>
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,

- 33 -
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.

- 34 -
CLAIM 12
A contact lens material according to claim 1 wherein
said organosiloxanyl ester monomer of acrylic and methacrylic
acid is tris(trimethylsiloxy) methacryloxyethoxysilane.
CLAIM 13
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.
CLAIM 14
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.
CLAIM 15
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,

- 35 -
4 parts methacrylic acid,
3 parts of N-vinyl 2-pyrrolidinone, and
25 parts of methyl methacrylate.
CLAIM 16
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.
CLAIM 17
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.

- 36 -
CLAIM 18
A contact lens device which is manufactured from the
oxygen-permeable contact lens material defined in claim 14.
CLAIM 19
A contact lens device manufactured from the
interpolymer of claim 13.
CLAIM 20
A contact lens device manufactured from the contact
lens material defined in claim 15.
CLAIM 21
A contact lens device manufactured from the contact
lens material defined in claim 16.

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:

- 4 --
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.

- 5 -
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-;
CH3 H
~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,

-- 10 --
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
- 19 -
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