Wettable, rigid gas permeable, substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof

• US 5,070,170 A
• Filed: 04/24/1989
• Issued: 12/03/1991
• Est. Priority Date: 02/26/1988
• Status: Expired due to Fees

• Current Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Su, Kai C., Robertson, J. Richard
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US07/342,849
• Time in Patent Office: 953 Days
• Field of Search: 528/28, 528/26, 528/25, 528/29, 556/421, 556/414, 556/437, 556/442, 556/438
• US Class Current: 528/25
• CPC Class Codes: C08G 18/8108 having only one isocyanate or isothiocyanate group
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 83/12 containing polyether sequences
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02C 7/04 Contact lenses for the eyes disinfection or sterilisation of contact lenses A61L12/00

Abstract

Contact lenses which are optically clear, wettable, of high oxygen permeability and substantially non-swellable in the aqueous ocular envionment 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.

Claims

1. A macromer comprising a segment, Seg, of the formula

--R¹⁴ --Sil--[(L)_h --R¹⁴ --Sil]_n (L)_h --R¹⁵ --A--L--R¹⁵ --A]_m (I)

wherein

R¹⁴ is a bond or --N(R¹)--, or --O--, provided that it may not be an oxygen if it is attached directly to a silicon atom or another oxygen atom, and may not be --N(R¹)-- if R¹⁴ is attached directly to an oxygen atom or to a nitrogen atom;

R¹⁵ is --O-- or --N(R¹)--;

R¹ is H, C_1-4 alkyl, or phenyl;

n is 0-3;

m is 0-3;

h is 1, or h may be 0 when the atom of Sil to which it would otherwise be attached is carbon;

each Sil is independently of the formula ##STR82## wherein (x1) and (x3) are independently an integer of from 0 to 25;

(x2) is an integer of from 1 to 25;

each (Sil²), (Sil³), (Sil⁴), and (Sil⁵) is independently selected from

cyclic siloxanes of the formula (IV²) ##STR83## provided that Sil² is not the same as Sil³, Sil⁵ is not the same as Sil⁴, and Sil³ and Sil⁴ are the same or different;

in which each R³ may be the same or different;

each R⁴ may be the same or different;

each of (x10) is independently zero to 25;

each of x11, and x12 is independently 1 to 25;

each or x8 and x9 is independently zero or one;

each R³ and R⁴ is independently selected from

a) C_1-18 alkyl or aryl of up to 12 carbon atoms, each of which is unsubstituted or substituted by halogen or by C_1-4 alkyl,

b) halogen;

or

c) a group of the formula ##STR84## wherein (x13) is an integer of from 1 to 3;

each R³⁸ may be the same or different and is selected from C_1-4 alkyl, ##STR85## or C_6-12 aryl, with each R³⁹ and each R⁴⁰ being independently selected from C_1-4 alkyl, C_6-12 aryl, epoxy, halogen, hydroxy C_1-4 alkyl, amino, amino-C_1-4 alkyl, hydroxy, isocyanto, or isothiocyanato;

each L⁸, and each L⁹ is, when linking two Si atoms, independently a linking group of the formula

space="preserve" listing-type="equation">--L.sup.10 --(G--L.sup.10).sub.(a3) (XII)

wherein a3 is zero or one;

each L¹⁰ is independently selected from ##STR86## or --O-- when (a3) is zero or one or further selected from --OC--(O)-- and --OC(O)NR-- when (a3) is one, and in which the atom of L¹⁰ bonded to a silicon atom is either a saturated carbon atom or an oxygen atom;

each R⁴¹ is independently hydrogen or lower alkyl; and

when not linking 2 silicon atoms, and L⁸ is independently further selected from a linking group of the formula

space="preserve" listing-type="equation">--L.sup.10 --(G--L.sup.11).sub.(a4) (XIII)

wherein (a4) is zero or one;

L¹⁰, when (a4) is zero or one, is selected from ##STR87## or oxygen; and

when (a4) is one, L¹⁰ is further selected from --OC(O)-- or OC(O)NR¹ --, in which the atom of L¹⁰ which is bound to a silicon atom is either a saturated carbon or an oxygen;

L¹¹ is selected from a bond, ##STR88## --O--, --C(O)--, --OC(O)--, --C(O)0--, --OC(O)0--, --NR¹ --C(O)--, --C(O)NR¹ --, --OC(O)NR¹ --, --NR¹ C(O)O--, or --NR¹ C(O)NR¹ --,

R⁴¹ and R¹ being as defined above;

G is a linking group selected from

a) a divalent aliphatic group having up to 25 carbon atoms, which may be interrupted by an interrupting unit selected from --O--, --COO--, --OOC--, --NRl--, --NR¹ CO--, OCNR¹ --, --OOCNR¹ --, --NR¹ COO--, --OOCO--, or --NR¹ C(O)NR¹ --;

each of said divalent aliphatic groups whether interrupted or not being unsubstituted or substituted by lower alkyl;

b) a divalent 5-7 membered cycloaliphatic,,a divalent 5-7 membered cycloaliphatic-C_1-18 aliphatic, and a divalent C_1-18 aliphatic-5-7 membered cycloaliphatic-C_1-18 -aliphatic, each of which may be interrupted in the non-cyclic portion or between the cyclic and non-cyclic portion as in a) above or be unsubstituted or substituted as in a) above, or both interrupted and substituted as in a) above;

c) a divalent C_6-25 arylene which is unsubstituted or substituted by a subsituent selected from halogen, C_1-4 alkyl, C_1-12 perhaloalkyl, amino, carboxy, C_1-4 alkoxy carbonyl, amino carbonyl, C_1-4 alkylamino carbonyl di(C_1-4 -alkyl) amino carbonyl, or a polyglycol of the formula ##STR89## wherein (a5) is zero or one;

one of R⁴² and R⁴³ is H and the other is hydrogen or methyl when (a5) is zero and both R⁴² and R⁴³ are hydrogen when (a5) is one; and

(a6) is an integer of up to 60;

or

d) a divalent -(aliphatiyl).sub.(a

     7)- aryl(aliphatyl).sub.(a

     8)- wherein one of (a7) and (a8) is one and the other is independently zero or 1, each aliphatyl having up to 40 carbon atoms, the aryl portion being 6-14 carbon atoms, the aliphatyl portions being uninterrupted or interrupted as in a) above, the (aliphatyl).sub.(a

     7) aryl-(aliphatyl).sub.(a

     8) group further being uninterrupted or interrupted between either or both of the aliphatyl portions and the aryl portions by an interrupting group set out in a) above, the aliphatyl portions being independently unsubstituted or substituted by a substituent set forth in a) above, and the aryl portion being unsubstituted or substituted by a substituent set forth in c) above;

each R³⁶ and each R³⁷ is independently selected from a bond, or the same group from which L⁸ is selected;

each L is independently of the formula

each A is independently of the formula

space="preserve" listing-type="equation">--L.sup.1 R.sup.6 L.sup.2--

and

each A is independently of the formula ##STR90## and within formula IV;

each R² and each R⁵ are independently C_1-7 alkylene, carbonyl, C_1-6 alkylene carbonyl, C_1-4 alkylene-(oxy-C_1-4 -alkylene)_g or C_1-4 alkylene--OCH₂ -(hydroxy C_1-4 alkylene)-CH₂ ; and

with g being an integer of from 1 to 10;

each y is independently 1 to 200;

and each R³ and each R⁴ is independently selected from C_1-18 alkyl or aryl of up to 12 carbon atoms; and

within L;

each L¹ and each L² is independently ##STR91## in which the oxygen or nitrogen is bound to R⁶, or ##STR92## or a bond; and

each R⁶ is independently

(i) --(C_1-25 aliphatic)--

(ii) of the formula ##STR93## in which each q is independently 0-3;

each j, each k, each (j₁) and each (k₁) and each d is independently 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 the R⁶ (i) or (ii) above is uninterrupted or interrupted at any point by Q;

each aliphatic, cycloaliphatic, and aryl group within the R⁶ (i) or (ii) above is unsubstituted or substituted by one or more substituents which substituents are halogen, hydroxy, C_1-4 alkyl, carboxy or C_1-12 perhaloalkyl;

each Q is independently selected from --O--, ##STR94## --N(R¹)--, --N(R¹)C(O)--, --C(O)N(R¹)--, --OOCN(R¹)--, --N(R¹)COO--, ##STR95## and within formula V;

each r is independently 0-4;

each t is independently 3-200; and

each R⁷ is independently selected from groups i) or iii) below and each R⁸ is independently selected from groups i)-iv) below;

i) hydrogen, halogen, unsubstituted C_1-16 alkyl, substituted C_1-16 alkyl, unsubstituted C_2-16 alkenyl, or substituted C_2-16 alkenyl, wherein a) the substituents on the alkyl and alkenyl groups in i) are independently selected from fluoro, C_1-16 alkoxy, C_2-16 alkanoyloxy, C_1-16 alkoxy-C(O)-C_2-16 alkenyloxy-C(O)-, C_3-16 alkenoyloxy, aryl of up to 10 carbon atoms, aryloxy of up to 10 carbon atoms, aroyl of up to 11 carbon atoms, aroyloxy of up to 11 carbon atoms, aryl (of up to 10 carbon atoms)-oxycarbonyl, C_3-8 cycloalkyl, C_3-8 cycloalkoxy, (C_3-8 cycloalkyl)-carbonyloxy, (C_3-8 cycloalkoxy)carbonyl, oxacycloalkyl of up to 7 carbon atoms, oxacycloalkoxy of up to 7 carbon atoms, oxacycloalkoxy (of up to 7 carbon atoms)-carbonyl, and oxacycloalkyl (of up to 7 carbon atoms)-carbonyloxy; and

b) each alkyl or alkenyl group in a) being unsubstituted or further substituted by fluoro, C_1-6 alkyl, or C_1-6 alkoxy provide that said last mentioned alkoxy is not bound to a carbon already singly bound to another oxygen atom;

ii) C_1-16 alkoxy, C_2-16 alkanoyloxy, C_1-16 alkoxy--C(O)--, C_2-16 alkenyloxy--C(O)-- and C_3-16 alkenoyloxy, each of which may be further substituted by fluoro, aryl of up to 10 carbon atoms, or C_1-6 alkoxy provided that the last mentioned alkoxy is not bound to a carbon atom which is singly bound to another oxygen;

iii) aryl of up to 10 carbon atoms, C_3-8 cycloalkyl, and oxacycloalkyl of up to 7 carbon atoms, each of which is unsubstituted or substituted by a substituent selected from those indicated in i)a) or b) above;

or

iv) aryloxy of up to 10 carbon atoms, cycloalkoxy of up to 8 carbons, cycloalkyl (of up to 8 carbons)--C(O)0--, cycloalkoxy (of up to 8 carbons)-carbonyl, aroyloxy of up to 11 carbons, oxacycloalkoxy of up to 7 carbons, oxacycloalkenyloxy of up to 7 carbons, oxacycloalkoxy (of up to 7 carbon atoms)-carbonyl, oxacycloalkyl (of up to 7 carbon atoms)-carbonyloxy, aryloxy of up to 11 carbon atoms, and aroyloxy of up to 11 carbon atoms, each of which is unsubstituted or substituted by fluoro, C_1-6 alkyl, or C_1-6 alkoxy, provided said last mentioned alkoxy is not bound to a carbon atom which is singly bound to another oxygen; and

2 adjacent groups R⁷ and R⁸, together with the atoms to which they are attached may define a 5-8 membered cycloalkyl, cycloalkenyl, or oxacycloalkyl ring or a 6-14 membered bicyclo-ring.

2. The macromer of claim 1 comprising a segment, Seg, in a group, Grp, of the formula

3. The macromer of claim 2 of the formula