Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units and use thereof
First Claim
1. A macromer comprising a segment, Seg, of the formula
whereinR14 is a bond or --N(R1)--, or if R14 is not attached to a silicon atom, then R14 may also be --O--;
R15 is --O-- or --N(R1)--;
R1 is H, C1 -C4 -alkyl or phenyl;
n is 0-3;
m is 0-3;
h is 1, or h may be 0 when the atom Sil to which it would otherwise be attached is carbon;
each Sil is independently of the formula ##STR63## each L is independently of the formula
space="preserve" listing-type="equation">--L.sup.1 --R.sup.6 --L.sup.2 --each A is independently of the formula ##STR64## each R2 and R5 are independently C1 -C4 -alkylene, carbonyl, C1 -C6 -alkylene-carbonyl, C1 -C4 -alkylene-(oxy-C1 -C4 -alkylene)g or C1 -C4 -alkylene-OCH2 -(hydroxy C1 -C4 alkylene)-CH2 --;
with g being an integer from 1 to 10;
each b and each f is independently 0 or 1;
each y is independently 1 to 200;
each R3 and each R4 are independently selected from C1 -C18 -alkyl or aryl of up to 12 carbon atoms;
each L1 and each L2 are independently --COO-- or --CONH-- in which the oxygen or nitrogen is bound to R6, --CO-- or a bond;
each R6 is independently(i) --(C1 -C25 -aliphatic)-- or (ii) of the formula
space="preserve" listing-type="equation">--(C.sub.1-20 aliphatic).sub.j --Q.sub.k --[(5-7 membered cycloaliphatic or aryl of up to 25 carbon atoms)-Q.sub.(k.sbsb.1.sub.) -(C.sub.1-20 aliphatic).sub.(j.sbsb.1.sub.) ].sub.D in whicheach q is independently 0-3;
each j, each k, each (j1) and each (k1) are 0 or 1, but if j is 0, k is 0; and
if (j1) is 0, (k1) is 0;
each D is 1 to 3;
each aliphatic group in R6 (i) or (ii) above is uninterrupted at any point by Q;
each aliphatic, cycloaliphatic or aryl group within R6 (i) or (ii) above is unsubstituted or substituted by one or more substituents which substituents are halogen, hydroxy, C1 -C4 alkyl. carboxy or C1 -C12 -perhaloalkyl;
each Q is independently selected from --O--, --COO--, --OCO--, --N(R1)--, --N(R1)CO--, --CON(R1)--, --OOCN(R1)--, --N(R1)COO--, --OCOO-- or --N(R1)CON(R1)--;
each r is independently 0-4;
each t is independently 3-200;
each R7 is independently selected from groups (a) or (c) and each R8 is independently selected from the groups (a), (b), (c) or (d);
(a) hydrogen, halogen, C1 -C16 -alkyl, C2 -C16 -alkenyl, or said alkyl or said alkenyl substituted by fluoro, by C1 -C16 -alkoxy, by C2 -C16 -alkanoyloxy, by C1 -C16 -alkoxy-CC-C2 -C16 -alkenyloxy-CO-, by C3 -C16 -alkenoyloxy, by aryl of up to 10 carbon atoms, by aroyl of up to 11 carbon atoms, by aroyloxy of up to 11 carbon atoms, by aryl of up to 10 carbon atoms-oxycarbonyl, by C3 -C8 -cycloalkyl, by C3 -C8 -cycloalkoxy, by C3 -C8 -cycloalkylcarbonyloxy, by C3 -C8 -cycloalkoxycarbonyl, by oxacycloalkyl of up to 7 carbon atoms, by oxacycloalkoxy of up to 7 carbon atoms, by oxacycloalkoxy of up to 7 carbon atoms-carbonyl or by oxacycloalkyl of up to 7 carbon atoms-carbonyloxy;
with the proviso that the alkoxy substituent in (a) is not bound to a carbon atom already single bound to another oxygen atom;
(b) C1 -C16 -alkoxy, C2 -C16 -alkanoyloxy, C1 -C16 -alkoxy-CO-, C2 -C16 -alkenyloxy-CO- or C3 -C16 -alkenoyloxy, or any of said groups substituted by fluoro, by aryl of up to 10 carbon atoms or by C1 -C6 -alkoxy provided said alkoxy is not bound to a carbon atom which is singly bound to another oxygen atom;
(c) aryl of up to 10 carbon atoms, C3 -C8 -cycloalkyl or oxacycloalkyl of up to 7 carbon atoms, each of which is unsubstituted or substituted by a substituent selected from those indicated in (a) and (b) above;
or(d) aryloxy of up to 10 carbon atoms, cycloalkoxy of up to 8 carbon atoms, cycloalkyl of up to 8 carbon atoms-COO--, cycloalkoxy of up to 8 carbon atoms-carbonyl, aroyloxy of up to 11 carbon atoms, oxacycloalkoxy of up to 7 carbon atoms, oxacycloalkenyloxy of up to 7 carbon atoms, oxacycloalkoxy of up to 7 carbon atoms-carbonyl, oxacycloalkyl of up to 7 carbon atoms-carbonyloxy, aryloxy of up to 11 carbon atoms or aroyloxy of up to 11 carbon atoms, or any of said groups substituted by fluoro, by C1 -C6 -alkyl or by C1 -C6 -alkoxy provided said alkoxy substituent is not bound to a carbon atom which is singly bound to another oxygen atom;
ortwo adjacent R7 and R8 groups together with the atoms to which they are attached may form a 5-8 membered cycloalkyl, cycloalkenyl or oxacycloalkyl ring;
or a 6-14 membered bicyclo-ring; and
with the proviso that at least 30% of the A groups contain no subblock in excess of 15 repeating units and where the A groups are copolymeric groups of the --E--X--E-- type where the X subblock has approximately twice the number of repeating units as either subblock E has.
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Accused Products
Abstract
Contact lenses which are optically clear, wettable, flexible, and of high oxygen permeability in the aqueous ocular environment of use, of a block copolymer containing polysiloxane and polyoxyalkylene oxide units are disclosed, as well as the preparation thereof and methods of treating vision defects therewith.
172 Citations
3 Claims
- 1. A macromer comprising a segment, Seg, of the formula
- space="preserve" listing-type="equation">--(R.sup.14 --Sil--[(L).sub.h --R.sup.14 Sil--].sub.n --(L).sub.h --R.sup.15 --A--[L--R.sup.15 --A].sub.m)-- (I)
wherein R14 is a bond or --N(R1)--, or if R14 is not attached to a silicon atom, then R14 may also be --O--; R15 is --O-- or --N(R1)--; R1 is H, C1 -C4 -alkyl or phenyl; n is 0-3; m is 0-3; h is 1, or h may be 0 when the atom Sil to which it would otherwise be attached is carbon; each Sil is independently of the formula ##STR63## each L is independently of the formula
space="preserve" listing-type="equation">--L.sup.1 --R.sup.6 --L.sup.2 --each A is independently of the formula ##STR64## each R2 and R5 are independently C1 -C4 -alkylene, carbonyl, C1 -C6 -alkylene-carbonyl, C1 -C4 -alkylene-(oxy-C1 -C4 -alkylene)g or C1 -C4 -alkylene-OCH2 -(hydroxy C1 -C4 alkylene)-CH2 --; with g being an integer from 1 to 10; each b and each f is independently 0 or 1; each y is independently 1 to 200; each R3 and each R4 are independently selected from C1 -C18 -alkyl or aryl of up to 12 carbon atoms; each L1 and each L2 are independently --COO-- or --CONH-- in which the oxygen or nitrogen is bound to R6, --CO-- or a bond; each R6 is independently (i) --(C1 -C25 -aliphatic)-- or (ii) of the formula
space="preserve" listing-type="equation">--(C.sub.1-20 aliphatic).sub.j --Q.sub.k --[(5-7 membered cycloaliphatic or aryl of up to 25 carbon atoms)-Q.sub.(k.sbsb.1.sub.) -(C.sub.1-20 aliphatic).sub.(j.sbsb.1.sub.) ].sub.Din which each q is independently 0-3; each j, each k, each (j1) and each (k1) are 0 or 1, but if j is 0, k is 0; and
if (j1) is 0, (k1) is 0;each D is 1 to 3; each aliphatic group in R6 (i) or (ii) above is uninterrupted at any point by Q; each aliphatic, cycloaliphatic or aryl group within R6 (i) or (ii) above is unsubstituted or substituted by one or more substituents which substituents are halogen, hydroxy, C1 -C4 alkyl. carboxy or C1 -C12 -perhaloalkyl; each Q is independently selected from --O--, --COO--, --OCO--, --N(R1)--, --N(R1)CO--, --CON(R1)--, --OOCN(R1)--, --N(R1)COO--, --OCOO-- or --N(R1)CON(R1)--; each r is independently 0-4; each t is independently 3-200; each R7 is independently selected from groups (a) or (c) and each R8 is independently selected from the groups (a), (b), (c) or (d); (a) hydrogen, halogen, C1 -C16 -alkyl, C2 -C16 -alkenyl, or said alkyl or said alkenyl substituted by fluoro, by C1 -C16 -alkoxy, by C2 -C16 -alkanoyloxy, by C1 -C16 -alkoxy-CC-C2 -C16 -alkenyloxy-CO-, by C3 -C16 -alkenoyloxy, by aryl of up to 10 carbon atoms, by aroyl of up to 11 carbon atoms, by aroyloxy of up to 11 carbon atoms, by aryl of up to 10 carbon atoms-oxycarbonyl, by C3 -C8 -cycloalkyl, by C3 -C8 -cycloalkoxy, by C3 -C8 -cycloalkylcarbonyloxy, by C3 -C8 -cycloalkoxycarbonyl, by oxacycloalkyl of up to 7 carbon atoms, by oxacycloalkoxy of up to 7 carbon atoms, by oxacycloalkoxy of up to 7 carbon atoms-carbonyl or by oxacycloalkyl of up to 7 carbon atoms-carbonyloxy;
with the proviso that the alkoxy substituent in (a) is not bound to a carbon atom already single bound to another oxygen atom;(b) C1 -C16 -alkoxy, C2 -C16 -alkanoyloxy, C1 -C16 -alkoxy-CO-, C2 -C16 -alkenyloxy-CO- or C3 -C16 -alkenoyloxy, or any of said groups substituted by fluoro, by aryl of up to 10 carbon atoms or by C1 -C6 -alkoxy provided said alkoxy is not bound to a carbon atom which is singly bound to another oxygen atom; (c) aryl of up to 10 carbon atoms, C3 -C8 -cycloalkyl or oxacycloalkyl of up to 7 carbon atoms, each of which is unsubstituted or substituted by a substituent selected from those indicated in (a) and (b) above;
or(d) aryloxy of up to 10 carbon atoms, cycloalkoxy of up to 8 carbon atoms, cycloalkyl of up to 8 carbon atoms-COO--, cycloalkoxy of up to 8 carbon atoms-carbonyl, aroyloxy of up to 11 carbon atoms, oxacycloalkoxy of up to 7 carbon atoms, oxacycloalkenyloxy of up to 7 carbon atoms, oxacycloalkoxy of up to 7 carbon atoms-carbonyl, oxacycloalkyl of up to 7 carbon atoms-carbonyloxy, aryloxy of up to 11 carbon atoms or aroyloxy of up to 11 carbon atoms, or any of said groups substituted by fluoro, by C1 -C6 -alkyl or by C1 -C6 -alkoxy provided said alkoxy substituent is not bound to a carbon atom which is singly bound to another oxygen atom;
ortwo adjacent R7 and R8 groups together with the atoms to which they are attached may form a 5-8 membered cycloalkyl, cycloalkenyl or oxacycloalkyl ring;
or a 6-14 membered bicyclo-ring; andwith the proviso that at least 30% of the A groups contain no subblock in excess of 15 repeating units and where the A groups are copolymeric groups of the --E--X--E-- type where the X subblock has approximately twice the number of repeating units as either subblock E has. - View Dependent Claims (2, 3)
- 3. The macromer of claim 2 of the formula
- space="preserve" listing-type="equation">Cap--Grp--Cap III
wherein Grp is as defined in claim 2; each Cap is independently selected from formula VI or VII below provided at least one Cap per macromer is of formula VI;
wherein formula VI is
space="preserve" listing-type="equation">R.sup.16 (L.sup.4).sub.z (R.sup.6).sub.w (A.sup.1).sub.V (L.sup.3).sub.x [J(R.sup.9).sub.M (L.sup.5).sub.G (R.sup.6).sub.Y (L.sup.6).sub.T ].sub.z (VI)and formula VII is
space="preserve" listing-type="equation">R.sup.17 (L.sup.4).sub.z (R.sup.6).sub.w (A.sup.1).sub.V (L.sup.3).sub.x [J(R.sup.9).sub.M (L.sup.5).sub.G (R.sup.6).sub.Y (L.sup.6).sub.T ].sub.z (VII)in which each R6 is as defined in claim 2; each w, x and z are independently 0 or 1, but if w is 0, then one of x and z must be 0; each G, M, T, V, Y and Z is independently 0 or 1, but if Y is 0, then G must be zero and M must be one; each J is --O-- or --NH--; each A1 and R9 is independently of the formula ##STR65## each L3 is independently ##STR66## with the right hand portion attached to Grp provided that the atom of Grp to which L3 is attached is not a carbonyl carbon an amido nitrogen or a carboxy oxygen and L3 is --O-- or --NR1 -- when the atom of Grp to which it is attached is a carbonyl carbon; each L4 is independently ##STR67## when w is one, and selected from the same group as L3 when w is zero; each L5 is ##STR68## with the carbonyl attached to R9 or J;
each L6 is ##STR69## with the nitrogen attached to R6 or R9 ;
each R16 is independently of the formula ##STR70## in which R12 is hydrogen or C1-7 alkyl and each of R10 and R11 is independently H, C1-7 alkyl, or --COOR13 with R13 being H or C1-4 alkyl;and R17 is selected from a) H, NH2, OH, --NCO, --NCS, ##STR71## or COOR12 when the non-R17 atom to which it is attached is-a non-carbonyl saturated carbon or the non-R17 atom to which it is attached is a carbon which is part of a ring; b) H, ##STR72## and R12 when the non-R17 atom to which it is attached is an oxygen other than a carboxy oxygen; c) H and R12, when the non-R17 atom to which it is attached is a carboxy oxygen; d) ##STR73## and R12 when the non-R17 atom to which it is attached is an amino nitrogen, or R12 when the non-R17 atom to which it is attached is an amido nitrogen; e) OH, R12, ##STR74## NH2, --NHR12 when the non-R17 atom to which it is attached is a carboxy carbon;
orf) H, OH, hal, --OR12 when the non-R17 atom to which it is attached is silicon.
Specification
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- Resources
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Current AssigneeCIBA Vision Corporation (Bayer AG)
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Original AssigneeCiba-Geigy Corporation (Novartis Ag)
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InventorsSu, Kai C., Mueller, Karl F., Goldenberg, Merrill S., Robertson, J. Richard
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Primary Examiner(s)Marquis, Melvyn I.
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Application NumberUS07/342,848Time in Patent Office953 DaysField of Search528/26, 528/28, 528/25, 528/29, 556/421, 556/414, 556/437, 556/438US Class Current528/25CPC Class CodesC08F 283/12 on to polysiloxanesC08F 290/068 PolysiloxanesC08F 299/08 from polysiloxanesC08F 30/08 containing siliconC08G 18/61 PolysiloxanesC08G 18/672 Esters of acrylic or alkyl ...C08G 77/46 containing polyether sequencesC08L 51/085 on to polysiloxanesC08L 83/12 containing polyether sequencesG02B 1/043 Contact lensesG02C 7/04 Contact lenses for the eyes...
