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1 2 ) Unlted States Patent 1 0 ) P a t e n t N 0 . : U S 8 , 2 6 2 , 9 4 7 B2Laredo ( 4 5 ) D a t e o f P a t e n t : * S e p . 1 1 , 2 0 1 2

( 5 4 ) UV/VISIBLE LIGHTABSORBERS FOR 5 , 3 3 1 , 0 7 3 A 7 / 1 9 9 4 W e i n s c h e n k , I I I e t a 1 .OPHTHALMIC LENS MATERIALS 5 , 4 7 0 , 9 3 2 A 1 1 / 1 9 9 5 J i n k e r s o n5 , 6 9 3 , 0 9 5 A 1 2 / 1 9 9 7 Freeman t a 1 .6 , 5 2 8 , 6 0 2 B1 3 / 2 0 0 3 Freeman t a 1 .( 7 5 ) I n v e n t o r : Walter R . L a r e d o , F o r t W o r t h , TX U S ) 6 , 8 0 6 , 3 3 7 B2 1 0 0 0 0 4 S c h l u e t e r e t a 1 6 , 8 4 6 , 8 9 7 B2 1 / 2 0 0 5 Salamone t a 1 .( 7 3 ) A s s i g n e e : N o v a r t i s AG, B a s e l (CH) 6 , 8 5 2 , 7 9 3 B2 2 / 2 0 0 5 S a l a m o n e e t a 1 .6 , 8 7 2 , 7 9 3 B1 3 / 2 0 0 5 S c h l u e t e r* ) N o t i c e : S u b j e c t t o a n y d i s c l a i m e r , t h e t e r m o f h i s g a b a 1 : 2 1 ?

- - , , enZ ap a t e n t i s e x l t e r t d e d 0 5 a d j u s t e d u n d e r 3 5 7 , 1 0 1 , 9 4 9 B 2 900 S a l a m O n e e t a 1 U - S - C - 1 5 4 ( ) Y 5 8 a y s - 7 , 6 9 1 , 9 1 8 B2 4 / 2 0 1 0 J i n k e r s o n e t a l .- ~ ~ ~ - 7,728,051 B2 6/2010 Weinschenk t a1.T 1 1 1 5 Patent 1 5 S u b l e c t t o a tenmnal d l s ' 2006/0197067 Al* 9 / 2 0 0 6 Xia e t a l . . . . . . . . . . . . . . . . . . . . . . . 252/582

C l a l m e r - 2007/0092830 A1 4 / 2 0 0 7 L a i e t a l .2007/0092831 A1 4/2007 L a i e t a 1 .( 2 1 ) A p p l . N o . : 1 2 / 8 3 0 , 0 8 7 2 0 0 8 / 0 2 4 2 8 1 8 A1 1 0 / 2 0 0 8 B e n z e t a l .2008/0266519 A1 1 0 / 2 0 0 8 S c h l u e t e r

( 2 2 ) F i l e d ; JUL 2 , 2010 2 0 0 9 / 0 0 4 3 1 0 5 A1 2 / 2 0 0 9 W e i n s c h e n k e t a 1 .2009/0088544 A1 4 / 2 0 0 9 Laredo. . . 2009/0093604 A1 4/2009 Schlueter( 6 5 ) Pm ubhcatlo Data 2 0 0 9 / 0 1 3 2 0 3 9 A1 5 / 2 0 0 9 C o r d o v a e t a l .

2009/0137745 A1 5 / 2 0 0 9 COrdOVa e t a l .US 011/0004301A1 J a n 6 2011 2 0 1 0 / 0 0 1 2 5 8 9 A1 l / 2 0 1 0 J i n k e r s o n, , 2010/0113641 A1 5 / 2 0 1 0 LaredoRelated U-s-APPlleatlon Data 2011/0266505 Al* 11/2011 Laredo e t a l . . . . . . . . . . . . . . . . . . 252/586

( 6 0 ) P r o v i s i o n a l a p p l i C a t i O n N O . 6 1 / 2 2 3 , 2 5 1 , ? l e d On u l . 6 , FOREIGN PATENT DOCUMENTS2009' CN 1727338 A 2 / 2 0 0 6

EP 0131468 A 2 l / l 9 8 5( 5 1 ) I n t - 0- EP 0 7 0 8 1 0 8 A1 1 2 / 1 9 9 7G02B / 2 3 ( 2 0 0 6 . 0 1 ) J P 2 0 0 5 0 5 3 0 5 8 A 3 / 2 0 0 5G O Z C 7 ( 2 0 0 6 0 1 ) 1 5 o W o 2 8 8 g 8 5 0 3 9 1 2 3 8 3

WO W O 2 0 0 8 0 4 8 8 8 0 A 2 4/2008C 0 7 1 ) 2 4 9 / 1 6 ( 2 0 0 6 . 0 1 ) OTHER UBLICATIONS

3 1 / 0 0 3 6 0 0 2 , 4 - D i - t e 1 t - b u t y l - 6 - 5 - c h l 0 r 0 - 2 H - b e n Z 0 t r i a Z 0 l - 2 - y l ) p h e n 0 l , 9 8 % ,_ _ _ Sigma-Aldrich C o . , Catalog #423327.( 5 2 ) us. l . . . . . . . . . . . . . . . . . . . . 252/586, 252/183.11, 351/159, I n t e r n a t i o n a l S e a r c h R e p o r t d a t e d D e c 2 2 , 2010 f o r P a t e n t coopm4 2 4 / 7 8 0 4 ; 2 : 5 3 ; ; g i g g g g 2 2 3 3 2 ? 2 3 1 2 4 3 7 1 ; t i o n T r e a t y A p p l i c a t i o n N o . P C T ? J S 2 0 l 0 / 0 4 0 9 7 2 .

( 5 8 ) Field of Classi?cation Search . . . . . . . . . . . . . . . . . 252/586, * C i t e d by examiner2 5 2/183.11; 52 3/10 5, 106, 107; 5 26/320; . . . . .5 3 4 / 8 4 3 , 8 5 2 ; 5 4 8 / 2 5 9 , 2 6 1 , 26 0 , 2 5 5 , 2 5 7 ; Prmry ExamlwT 1 1 2 ? A h V a Z l _

6 2 3 / 6 1 1 ; 3 5 1 / 1 5 9 ; 4 2 4 / 7 8 0 4 ; 5 1 4 / 9 1 2 ( 7 4 ) A i m / 9 1 4 8 6 1 1 1 1 o r Fm * amckMyanS e e a p p l i c a t i o n ? l e f o r c o m p l e t e s e a r c h h i s t o r y . ( 5 7 ) ABSTRACT

( 5 6 ) References Cited B e n Z o t r i a Z o l e U V / V 1 s i b l e l i g h t - a b s o r b i n g monomers r e d i sU . S . PATENTDOCUMENTS

4,611,061 A * 9/1986 Beardetal. . . . . . . . . . . . . . . . . . . . 548/2605 , 2 8 0 , 8 9 2 A 1 / 1 9 9 4 S m i t h

c l o s e d . The UV/V s a b s o r b e r s a r e p a r t i c u l a r l y s u i t a b l e f o r u s ei n i n t r a o c u l a r l e n s m a t e r i a l s .

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UV/VISIBLE LIGHTABSORBERS FOROPHTHALMIC LENS MATERIALST h i s a p p l i c a t i o n c l a i m s p r i o r i t y f r o m US. P a t e n t A p p l i c a

t i o n S e r . N o . 6 1 / 2 2 3 , 2 5 1 ? l e d J u l . 6 , 2 0 0 9 .FIELD OFTHE INVENTION

T h i s i n v e n t i o n i s d i r e c t e d t o u l t r a v i o l e t / v i s i b l e l i g h ta b s o r b e r s . I n p a r t i c u l a r , t h i s i n v e n t i o n r e l a t e s t o n o v e l benZot r i a Z o l e monomers e s p e c i a l l y s u i t a b l e f o r u s e i n i m p l a n t a b l eo p h t h a l m i c l e n s m a t e r i a l s .

BACKGROUND OFTHE INVENTIONMany l t r a v i o l e t and v i s i b l e l i g h t a b s o r b e r s a r e knoWn s

i n g r e d i e n t s f o r p o l y m e r i c m a t e r i a l s u s e d t o make p h t h a l m i cl e n s e s . Such b s o r b e r s a r e p r e f e r a b l y c o v a l e n t l y bound o t h ep o l y m e r i c n e t W o r k o f t h e l e n s m a t e r i a l i n s t e a d o f s i m p l yp h y s i c a l l y e n t r a p p e d i n t h e m a t e r i a l t o p r e v e n t t h e m f r o mm i g r a t i n g , p h a s e s e p a r a t i n g o r l e a c h i n g o u t o f t h e l e n s m a t er i a l . S u c h s t a b i l i t y i s p a r t i c u l a r l y i m p o r t a n t f o r i m p l a n t a b l eo p h t h a l m i c l e n s e s W h e r e t h e l e a c h i n g o f t h e a b s o r b e r mayp r e s e n t b o t h t o x i c o l o g i c a l i s s u e s a n d l e a d t o t h e l o s s o fU V / v i si b l e b l o c k i n g a c t i v i t y i n t h e i m p l a n t .N u m e r o u s c o p o l y m e r i Z a b l e b e n Z a t r i a Z o l e , b e n Z o p h e n o n eand t r i a Z i n e a b s o r b e r s a r e knoWn. Most o f t h e s e compoundsa r e knoWn a s UV b s o r b e r s , though some may e knoWn oa l s o a b s o r b some p o r t i o n o f v i s i b l e l i g h t . Many a b s o r b e r sc o n t a i n c o n v e n t i o n a l o l e ? n i c p o l y m e r i Z a b l e g r o u p s , s u c h a sm e t h a c r y l a t e , a c r y l a t e , m e t h a c r y l a m i d e , a c r y l a m i d e o r s t yr e n e g r o u p s . C o p o l y m e r i Z a t i o n W i t h o t h e r i n g r e d i e n t s i n t h el e n s m a t e r i a l s , t y p i c a l l y W i t h a r a d i c a l i n i t i a t o r , i n c o r p o r a t e st h e a b s o r b e r s i n t o t h e r e s u l t i n g p o l y m e r c h a i n . I n c o r p o r a t i o nof d d i t i o n a l f u n c t i o n a l groups on an absorber may n?uenceone o r more of t h e a b s o r b e r s l i g h t - a b s o r b i n g p r o p e r t i e s ,s o l u b i l i t y o r r e a c t i v i t y . I f h e a b s o r b e r d o e s n o t h a v e s u ? i c i e n ts o l u b i l i t y i n t h e r e m a i n d e r o f t h e o p h t h a l m i c l e n s m a t e r i a li n g r e d i e n t s o r p o l y m e r i c l e n s m a t e r i a l , t h e a b s o r b e r may o al e s c e i n t o d o m a i n s t h a t c o u l d i n t e r a c t W i t h l i g h t a n d r e s u l t i nd e c r e a s e d o p t i c a l c l a r i t y o f t h e l e n s .

E x a m p l e s o f p o l y m e r i c o p h t h a l m i c l e n s m a t e r i a l s t h a ti n c o r p o r a t e UV b s o r b e r s can be found i n U S . P a t . N o s .5 , 2 9 0 , 8 9 2 ; 5 , 3 3 1 , 0 7 3 a n d 5 , 6 9 3 , 0 9 5 .

SUMMARYOFTHE INVENTIONT h e p r e s e n t i n v e n t i o n p r o v i d e s b e n Z o t r i a Z o l e l i g h t a b s o r b

i n g monomers h a t a b s o r b b o t h u l t r a v i o l e t l i g h t a n d a p o r t i o no f v i s i b l e l i g h t ( U V / V i s a b s o r b e r s ) . T h e s e a b s o r b e r s a r es u i t a b l e f o r u s e i n o p h t h a l m i c l e n s e s , i n c l u d i n g c o n t a c tl e n s e s . T h e y a r e p a r t i c u l a r l y u s e f u l i n i m p l a n t a b l e l e n s e s ,s u c h a s i n t r a o c u l a r l e n s e s ( I O L s ) .The a b s o r b e r compounds o f t h e p r e s e n t i n v e n t i o n a b s o r bW a v e l e n g t h s o f l i g h t betWeen 400-45 0 nm n a d d i t i o n t oh i g h e r e n e r g y UVA a y s betWeen 400-320 nm, UVB a y sbetWeen 32 0-280 nm, and UVC a y s beloW 280 nm. Theyc o n t a i n r e a c t i v e g r o u p s , Which l l o W f o r c o v a l e n t a t t a c h m e n to f t h e a b s o r b e r s t o o c u l a r l e n s m a t e r i a l s. A d d i t i o n a l l y , t h ea b s o r b e r s o f t h e pr e s e n t i n v e n t i o n c a n b e s y n t h e s i z e d i na p p r o x i m a t e l y 4 - 6 s t e p s f r o m r e a d i l y a v a i l a b l e s t a r t i n g m a t er i a l s .

The p r e s e n t i n v e n t i o n a l s o r e l a t e s t o o p h t h a l m i c d e v i c em a t e r i a l s c o n t a i n i n g s u c h UV/Vis a b s o r b e r s .

BRIEF DESCRIPTIONOFTHE DRAWINGSF I G . 1 shoWs p e r c e n t t r a n s m i t t a n c e c u r v e s f o r t h e UV/Vis

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F I G . 3 shoWs t h e a b s o r b a n c e c u r v e f o r Co mpound .DETAILED DESCRIPTIONOFTHE INVENTION

U n l e s s i n d i c a t e d o t h e r w i s e , a l l i n g r e d i e n t a m o u n t se x p r e s s e d i n p e r c e n t a g e t e r m s a r e p r e s e n t e d a s % /W.

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P r e f e r a b l y , t h e UV/ 1 5 i s a b s o r b e r s o f h e p r e s e n t i n v e n t i o na r e those Wherein

X : C 3 - C 4 a l k e n y l , a l k y l ,C H 2 C H 2 C H 2 S C H 2 C H 2 ;Y : n o t h i n g i f X : C 3 C 4 a l k e n y l , o t h e r W i s e Y:iO4C( : O ) * C ( R l ) : C H 2 ;Rl:H r CH3;R 2 : C l - C 2 a l k y l ; a n dR3:CH3, C H 3 O , F , C 1 , o r C F 3 .T h r e e p r e f e r r e d a b s o r b e r s o f t h e p r e s e n t i n v e n t i o n a r e :2 - ( 3 - ( 3 - ( 5 - c h l o r o - 2 H - b e n Z o [ d ] [ 1 , 2 , 3 ] t r i a Z o l - 2 - y l ) - 4 - h yd r o x y - 5 - m e t h o x y - p h e n y l ) p r o p y l t h i o ) e t h y l m e t h a c r y l a t e( C o m p o u n d 1 ) ;4 - a l l y l - 2 - ( 5 - c h l o r o - 2 H - b e n Z o [ d ] [ 1 , 2 , 3 ] t r i a Z o l - 2 - y l ) - 6 - m e t ho x y p h e n o l ( C o m p o u n d 2 ) ;3 - ( 3 - ( 5 - c h l o r o - 2 H - b e n Z o d ] [ 1 , 2 , 3 ] t r i a Z o l - 2 - y l ) - 4 - h y d r o x y5 - m e t h o x y - p h e n y l ) p r o p y l m e t h a c r y l a t e ( C o m p o u n d 3 ) ;4 - a l l y l - 2 - m e t h o x y - 6 - ( 5 ( t r i ? u o r o m e t h y l ) - 2 H - b e n Z o d ] 1 , 2 ,3 ] t r i a Z o l - 2 - y l ) p h e n o l ( C o m p o u n d 4 ) ; a n d3 - ( 4 - h y d r o x y - 3 - m e t h o x y - 5 - ( 5 - ( t r i ? u o r o m e t h y l ) - 2 H - b e n Z o[ d ] [ 1 , 2 , 3 ] t r i a Z o l - 2 - y l ) p h e n y l ) p r o p y l m e t h a c r y l a t e ( C o mp o u n d 5 ) .

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d e r i v e d from e s s e n t i a l o i l s s u c h a s c l o v e i s o i l , n u t m e g ,c i n n a m o n , a n d b a y l e a f .

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The UV/V s i s a b s o r b e r s of h e p r e s e n t i n v e n t i o n a r e p a rt i c u l a r l y s u i t a b l e f o r u s e i n I O L s . IOL a t e r i a l s W i l l g e n e r a l l yc o n t a i n from 0 . 1 t o 5% W / W ) ofa UV/Vis s a b s o r b e r o f t h ep r e s e n t i n v e n t i o n . P r e f e r a b l y , IOL m a t e r i a l s W i l l c o n t a i nfrom 0 . 5 t o 4% W/W) o f a n a b s o r b e r o f t h e p r e s e n t i n v e n t i o n .Most p r e f e r a b l y , IOL m a t e r i a l s W i l l c o n t a i n from 1 t o 3%( W / W ) o f a n a b s o r b e r o f t h e p r e s e n t i n v e n t i o n . Such d e v i c em a t e r i a l s a r e p r e p a r e d by o p o l y m e r i Z i n g t h e a b s o r b e r s o f h ep r e s e n t i n v e n t i o n W i t h o t h e r i n g r e d i e n t s , s u c h a s d e v i c ef o r m i n g m a t e r i a l s , c r o s s - l i n k i n g a g e n t s , a n d o p t i o n a l l y b l u el i g h t b l o c k i n g c h r o m o p h o r e s .

Many d e v i c e - f o r m i n g monomers a r e knoWn i n t h e a r t andi n c l u d e b o t h i s a c r y l i c a n d s i l i c o n e - c o n t a i n i n g monomersamong o t h e r s . S e e , f o r e x a m p l e , US. P a t . N o s . 7 , 1 0 1 , 9 4 9 ;7 , 0 6 7 , 6 0 2 ; 7 , 0 3 7 , 9 5 4 ; 6 , 8 7 2 , 7 9 3 6 , 8 5 2 , 7 9 3 ; 6 , 8 4 6 , 8 9 7 ;6 , 8 0 6 , 3 3 7 ; 6 , 5 2 8 , 6 0 2 ; a n d 5 , 6 9 3 , 0 9 5 . I n t h e c a s e o f I O L s , a n yknoWn IOL d e v i c e m a t e r i a l i s s u i t a b l e f o r u s e i n t h e c o m pos i t i o n s o f t h e p r e s e n t i n v e n t i o n . P r e f e r a b l y , t h e o p h t h a l m i cd e v i c e m a t e r i a l s c o m p r i s e a n a c r y l i c o r m e t h a c r y l i c d e v i c ef o r m i n g m o n o m e r . More p r e f e r a b l y , t h e d e v i c e - f o r m i n gm ono mer s comprise a monomer f formula I V :

Where i n f o r m u l a I V :A s H , C H 3 , CH2CH3, o r CHZOH;B s (CH2)m o r [ O ( C H 2 ) 2 l Z ;C s ( C H 2 ) W ;m s 2 - 6 ;Z s 1 - 1 0 ;Y s n o t h i n g , 0 , S , o r N R ' , p r o v i d e d t h a t i f Y i s O , S , o r N R ' ,

t h e n B s ( C H 2 ) m ;

1 0

1 5

30

35

40

45

50

60

6 5

W s 0 - 6 , p r o v i d e d t h a t m+W8; a n dD s H , C l - C 4 a l k y l , C l - C 4 a l k o x y , C 6 H 5 , CH2C6H5 o rh a l o g e n .P r e f e r r e d monomers of form ula IV a r e t h o s e WhereinA s

H r CH3, B s ( C H 2 ) m , m s 2 - 5 , Y s n o t h i n g o r O , W s 0 - 1 ,a n d D s H . Most p r e f e r r e d a r e 2 - p h e n y l e t h y l m e t h a c r y l a t e ;4 - p h e n y l b u t y l m e t h a c r y l a t e ; 5 - p h e n y l p e n t y l m e t h a c r y l a t e ;2 - b e n Z y l o x y e t h y l m e t h a c r y l a t e ; a n d 3 - b e n Z y l o x y p r o p y lm e t h a c r y l a t e ; a n d t h e i r c o r r e s p o n d i n g a c r y l a t e s .Monomers of formula IV a r e knoWn and can be made byknoWn m e t h o d s . F o r e x a m p l e , t h e c o n j u g a t e a l c o h o l o f t h e

d e s i r e d monomer an be combined i n a r e a c t i o n v e s s e l Withm e t h y l m e t h a c r y l a t e , t e t r a b u t y l t i t a n a t e ( c a t a l y s t ) , a n d a p o l ym e r i Z a t i o n i n h i b i t o r s u c h a s 4 - b e n Z y l o x y p h e n o l . The e s s e lcan t h e n be h e a t e d t o f a c i l i t a t e t h e r e a c t i o n and i s t i l l o f f t h er e a c t i o n b y - p r o d u c t s t o d r i v e t h e r e a c t i o n t o c o m p l e t i o n .A l t e r n a t i v e s y n t h e s i s s c h e m e s i n v o l v a d d i n g m e t h a c r y l i ca c i d t o t h e c o n j u g a t e a l c o h o l and c a t a l y z i n g W i t h a c a r b o d ii m i d e o r m i x i n g t h e c o n j u g a t e a l c o h o l W i t h m e t h a c r y l o y lc h l o r i d e and a b a s e such a s p y r i d in e o r t r i e t h y l a m i n e .

D e v i c e m a t e r i a l s g e n e r a l l y c o m p r i s e a t o t a l o f a t l e a s ta b o u t 7 5 % , p r e f e r a b l y a t l e a s t a b o u t 8 0 % , o f d e v i c e - f o r m i n gmonomers.

I n a d d it i o n t o an a b s o r b e r of h e p r e s e n t i n v e n t i o n and ad e v i c e - f o r m i n g monomer, t h e d e v i c e m a t e r i a l s o f t h e p r e s e n ti n v e n t i o n g e n e r a l l y c o m p r i s e a c r o s s - l i n k i n g a g e n t . T h ec r o s s - l i n k i n g a g e n t u s e d i n t h e d e v i c e m a t e r i a l s o f h i s i n v e nt i o n may b e a n y t e r m i n a l l y e t h y l e n i c a l l y u n s a t u r a t e d compound h a v i n g more t h a n one u n s a t u r a t e d g r o u p . S u i t a b l ec r o s s - l i n k i n g a g e n t s i n c l u d e , f o r e x a m p l e : e t h y l e n e g l y c o ld i m e t h a c r y l a t e ; d i e t h y l e n e g l y c o l d i m e t h a c r y l a t e ; a l l y l m e t ha c r y l a t e ; 1 , 3 - p r o p a n e d i o l d i m e t h a c r y l a t e ; 2 , 3 - p r o p a n e d i o ld i m e t h a c r y l a t e ; 1 , 6 - h e x a n e d i o l d i m e t h a c r y l a t e ; 1 , 4 - b u t a n ed i o l d i m e t h a c r y l a t e ; C H 2 : C ( C H 3 ) C ( : O ) O i( C H 2 C H 2 O ) P 4C(:O)C(CH3):CH2 W h e r e p : 1 - 5 0 ; a n dC H 2 : C ( C H 3 ) C ( : O ) O ( C H 2 ) t O i C ( : O ) C ( C H 3 ) : C H 2W h e r e t : 3 - 2 0 ; a n d t h e i r c o r r e s p o n d i n g a c r y l a t e s . A r e f e r r e dc r o s s - l i n k i n g monomer i s C H 2 : C ( C H 3 ) C ( : O ) O( C H 2 C H 2 O ) P i C ( : O ) C ( C H 3 ) : C H 2 W h e r e p i s s u c h t h a tt h e n u m b e r - a v e r a g e m o l e c u l a r W e i g h t i s a b o u t 4 0 0 , a b o u t6 0 0 , o r a b o u t 1 0 0 0 .

G e n e r a l l y , t h e t o t a l a m o u n t o f h e c r o s s - l i n k i n g c o m p o n e n ti s a t l e a s t 0.1 b y W e i g h t a n d , d e p e n d i n g o n t h e i d e n t i t y a n dc o n c e n t r a t i o n o f t h e r e m a i n i n g c o m p o n e n t s a n d t h e d e s i r e dp h y s i c a l p r o p e r t i e s , c a n r a n g e t o a b o u t 20 by W e i g h t . Thep r e f e r r e d c o n c e n t r a t i o n r a n g e f o r t h e c r o s s - l i n k i n g compon e n t i s 1-5 f o r s m a l l , h y d r o p h o b i c compounds W i t hm o l e c u l a r W e i g h t s t y p i c a l l y l e s s t h a n 5 0 0 D a l t o n s , a n d 5-17( W / W ) f o r l a r g e r , h y d r o p h i l i c c o m p o u n d s W i t h m o l e c u l a rW e i g h t s t y p i c a l l y b e t W e e n 5 0 0- 5 0 0 0 D a l t o n s .

S u i t a b l e p o l y m e r i z a t i o n i n i t i a t o r s f o r d e v i c e m a t e r i a l s cont a i n i n g a UV/Vls s a b s o r b e r o f t h e pr e s e n t i n v e n t i o n i n c l u d et h e r m a l i n i t i a t o r s a n d p h o t o i n i t i a t o r s . P r e f e r r e d t h e r m a l i n it i a t o r s i n c l u d e p e r o x y f r e e - r a d i c a l i n i t i a t o r s , s u c h a s t - b u t y l( p e r o x y - 2 - e t h y l ) h e x a n o a t e a n d d i - ( t e r t - b u t y l c y c l o h e x y l ) p e ro x y d i c a r b o n a t e ( c o m m e r c i a l l y a v a i l a b l e a s Perkadox 1 6f r o m AkZo C h e m i c a l s I n c . , C h i c a g o , I l l . ) . I n i t i a t o r s a r e t y p ic a l l y p r e s e n t i n a n amount f a b o u t 5% W / W ) o r l e s s . Becausef r e e - r a d i c a l i n i t i a t o r s do n o t become c h e m i c a l l y a p a r t o f t h ep o l y m e r s f o r m e d , t h e t o t a l a m o u n t o f i n i t i a t o r i s c u s t o m a r i l yn o t i n c l u d e d When d e t e r m i n i n g t h e a m o u n t s o f o t h e r i n g r ed i e n t s .

The d e v i c e m a t e r i a l s c o n t a i n i n g a UV/Vis a b s o r b e r o f t h ep r e s e n t i n v e n t i o n o pt i o n a l l y a l s o c o n t a i n a r e a c t i v e c o l o r a n t .S u i t a b l e r e a c t i v e b l u e - l i g h t a b s o r b i n g c o m p o u n d s i n c l u d e


7/9

US 8 , 2 6 2 , 9 4 7 B27

t h o s e d e s c r i b e d i n U S . a t . N o . 5 , 4 7 0 , 9 3 2 . B l u e - l i g h t a b s o r be r s a r e t y p i c a l l y p r e s e n t i n an amount f rom about 0 . 0 1 -0.5( W e i g h t ) .

I n a d d i t i o n t o t h e UV/V s i s a b s o r b e r of Formula I , ad e v i c e - f o r m i n g m o n o m e r , a c r o s s - l i n k i n g a g e n t , a n d o p t i o na l l y a UV b s o r b e r o r o t h e r v i s i b l e l i g h t a b s o r b e r , t h e mater i a l s o f t h e p r e s e n t i n v e n t i o n may l s o c o n t a i n o t h e r i n g r e d ie n t s , i n c l u d i n g b u t n o t l i m i t e d t o a g e n t s t o r e d u c e t a c k o rg l i s t e n i n g s . Examples o f a g e n t s t o r e d u c e t a c k a r e t h o s e d i sc l o s e d i n U S . P u b l i c a t i o n N o s . 2009/0132039 A1 and 2 0 0 9 /0137745 A 1 . Examples o f a g e n t s t o r e d u c e g l i s t e n i n g s a r et h o s e d i s c l o s e d i n U S . P u b l i c a t i o n N o s . 2009/0093604 A1and 2009/0088544 A1.

IOLs c o n s t r u c t e d o f t h e m a t e r i a l s o f t h e p r e s e n t i n v e n t i o nc a n be o f any d e s ig n c a p a b l e o f b e i n g r o l l e d o r f o l d e d i n t o as m a l l c r o s s s e c t i o n t h a t can ? t through a r e l a t i v e l y s m a l l e ri n c i s i o n . For example, t h e IOLs can be of What s knoWn s ao n e p i e c e o r m u l t i p i e c e d e s i g n , a n d c o m p r i s e o p t i c a n d h a p t i cc o m p o n e n t s . The o p t i c i s t h a t p o r t i o n Which s e r v e s a s t h el e n s . The a p t i c s a r e a t t a c h e d t o t h e o p t i c a n d h o l d t h e o p t i c i ni t s p r o p e r p l a c e i n t h e e y e . The o p t i c a n d h a p t i c ( s ) c a n b e o ft h e same o r d i f f e r e n t m a t e r i a l . A u l t i p i e c e l e n s i s s o c a l l e db e c a u s e t h e o p t i c a n d t h e h a p t i c ( s ) a r e made s e p a r a t e l y a n dt h e n t h e h a p t i c s a r e a t t a c h e d t o t h e o p t i c . I n a s i n g l e p i e c el e n s , t h e o p t i c a n d t h e h a p t i c s a r e formed o u t o f o n e p i e c e o fm a t e r i a l . Depending o n h e m a t e r i a l , t h e h a p t i c s a r e t h e n c u t ,o r l a t h e d , o u t o f t h e m a t e r i a l t o produce t h e I O L .

I n a d di t i o n t o I O L s , t h e m a t e r i a l s o f t h e p r e s e n t i n v e n t i o na r e a l s o s u i t a b l e f o r u s e i n o t h e r ophthalmic d e v i c e s , such a sc o n t a c t l e n s e s , k e r a t o p r o s t h e s e s , a n d c o r n e a l i n l a y s o r r i n g s .The i n v e n t i o n W i l l b e f u r t h e r i l l u s t r a t e d b y t h e f o l l o W i n ge x a m p l e s , Which a r e i n t e n d e d t o b e i l l u s t r a t i v e , b u t n o t l i mi t i n g .

EXAMPLES y n t h e s i s o f 4 - a l l y l - 2 - ( h y d r o x y m e t h y l ) - 6 - m e t h o x y p h e

n o l . I n a 2 l i t e r r o u n d bottom ? a s k e q u i p p e d W i t h n i t r o g e ni n l e t a n d m a g n e t i c s t i r r e r Was d i s so l v e d e u g e n o l , 99 ( A l f aA e s a r ) i n a s o l u t i o n c o m p r i s e d o f 286 g NaOH n 1 . 2 L W a t e ra t 0 C . A o l u t i o n o f f o r m a l d e h y d e ( 8 2 8 g , 1 0 . 2 m o l ) , 3 7 W t .% o l u t i o n i n W a t e r , A . C . S . r e a g e n t ( S i g m a - A l d r i c h ) Wasadded d r o p W i s e t o t h e s t i r r i n g s o l u t i o n . The m i x t u r e Wass t i r r e d u n d e r n i t r o g e n a t a m b i e n t t e m p e r a t u r e f o r 4 h o u r s andt h e n 5 5 C . f o r 20 . The r e a c t i o n m i x t u r e Was poured i n t o 1L t h y l a c e t a t e and Washed i t h 1 N C l and d e i o n i Z e d W a t e r .The c r u d e p r o d u c t c o n t a i n i n g ~30 mol % n r e a c t e d e u g e n o lWas u s e d i n t h e n e x t s t e p W i t h o u t f u r t h e r p u r i ? c a t i o n .

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EXAMPLES y n t h e s i s o f - a l l y l - 2 - ( ( 5 - c h l o r o - 2 - n i t r o p h e n y l ) d i a Z e n y l )

6 - m e t h o x y - p h e n o l . I n a 1000 ml 3 - n e c k round bottom ?aske q u i p p e d W i t h a m a g n e t i c s t i r r e r Was added 5 - c h l o r o - 2 - n it r o a n i l i n e ( A c r o s O r g a n i c s , 29 . 9 g , 1 7 3 m m o l ) , c o n c e n t r a t e da q u e o u s HCl ( 3 6 . 5 - 3 8 . 0 % , 7 5 m l ) , 1 5 0 ml d e i o n i Z e d W a t e r ,and 150 ml a b s o l u t e e t h a n o l . The s u s p e n s i o n Was c o o l e d t o10 C . and s o l u t i o n o f sodium i t r i t e ( S i g m a - A l d r i c h , 1 2 . 7g , 1 8 4 mmol) i n 5 0 ml W a t e r Was added dropWise o v e r 30minutes t 10 C . The e a c t i o n mixture Was s t i r r e d f o r 1 hourand 324 mg s u l f a m i c a c i d ( A l d r i c h ) Was a d d e d. A f t e r 1 0

20

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8m i n u t e s o f s t i r r i n g t h e s o l i d s Were ? l t e r e d o u t and t h e c o l ds o l u t i o n Was s e t a s i d e . A NaOH o l u t i o n Was p r e p a r e d byd i s s o l v i n g NaOH A l d r i c h , 3 7 . 7 g , 9 4 4 mmol) i n 1 2 0 mld e i o n i Z e d W a t e r . Approximately one f o u r t h of t h e sodiumh y d r o x i d e s o l u t i o n Was added dropWise o a s o l u t i o n of - a ll y l - 2 - ( h y d r o x y m e t h y l ) - 6 - m e t h o x y p h e n o l f r o m E x a m p l e 1 i n100 ml W a t e r and 300 ml a b s o l u t e e t h a n o l . The diaZoniumm i x t u r e and r e m a i n i n g NaOH o l u t i o n Were c o n c u r r e n t l yadded d r o p W i s e o v e r 1 h r t o t h e 4 - a l l y l - 2 - ( h y d r o x y m e t h y l )6 - m e t h o x y p h e n o l s o l u t i o n a t 1 0 C . The e s u l t i n g d a r k mixt u r e Was s t i r r e d a t 0 C . f o r 1 hour and ambient t e m p e r a t u r ef o r 2 h o u r s . The c o n t e n t s Were poured i n t o 3 l i t e r s d e i o n i Z e dW a t e r and h e pH as a d j u s t e d t o 5 u s i n g 1 N C l . The s o l i dWas ? l t e r e d and r i e d a t 5 0 C . f o r 6 4 h o u r s u s i n g P2O5 d r y i n ga g e n t t o a f f o r d 28 g (46 ) t h a t Was used i n t h e n e x t s t e pW i t h o u t f u r t h e r p u r i ? c a t i o n .

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EXAMPLES y n t h e s i s o f 4 - a l l y l 2 - ( 5 - c h l o r o - 2 H - b e n z o [ d ] [ 1 , 2 , 3 ] t r i a

Z o l - 2 - y l ) - 6 - m e t h o x y - p h e n o l . I n a 1 L round bottom ? aske q u i p p e d W i t h a m a g n e t i c s t i r r e r , a d d i t i o n f u n n e l , p o W d e ra d d i t i o n f u n n e l , a n d n i t r o g e n i n l e t Was a d d e d 4 - a l l y l - 2 - ( ( 5c h l o r o 2 - n i t r o p h e n y l ) d i a Z e n y l ) - 6 - m e t h o x y p h e n o l ( 2 7 . 9 ,8 0 . 2 mmol) f r o m Example 2 a n d 3 0 0 ml a b s o l u t e e t h a n o l .NaOH 1 9 . 3 g , 4 8 3 mmol) Was d i s s o l v e d i n 1 4 0 ml d e i o n i z e dW a t e r and a p p r o x i m a t e l y o n e - f o u r t h by volume Was addeddropWise t o t h e r e a c t i o n m i x t u r e . The r e a c t i o n m i x t u r e Wash e a t e d t o 8 0 C . and f o r m a m i d i n e s u l ? n i c a c i d ( A l d r i c h , 2 6 . 0g , 2 4 1 mmol) Was a d d e d s l o W l y a n d c o n c u r r e n t l y W i t h t h er e m a i n i n g sodium h y d r o x i d e s o l u t i o n o v e r 3 0 m i n u t e s . Ther e a c t i o n m i x t u r e Was poured i n t o 3 L d e i o n i Z e d W a t e r anda c i d i ? e d t o p H W i t h 1 N C l . The e l l o W s o l i d Was d r i e d f o r2 0 h o u r s a t 4 2 C . a n d t h e n p u r i ? e d by d i s s o l v i n g i n h o tt o l u e n e a n d t h e n ? l t e r i n g o u t t h e d a r k i m p u r i t i e s . The l t r a t eWas c o n c e n t r a t e d doWn a n d p u r i ? e d v i a r e c r y s t a l l i Z i on s i ne t h a n o l a n d d i e t h y l e t h e r t o g i v e t h e p u r e p r o d u c t ( 5 g , 2 0 % ) .1 H NMR C D C l 3 ) d e l t a : 1 1 . 0 3 s , 1 H , p he n o l O H ) , 7 . 9 4 s ,1 H , AriH e n Z o t r i a Z o l e r i n g , 4 - p o s i t i o n ) , 7 . 8 9 (m , 1 H ,AriH e n Z o t r i a Z o l e r i n g , 7 - p o s i t i o n ) , 7 . 8 0 s , 1 H , AriHp h e n o l , 5 - p o s i t i o n ) , 7 . 4 4 ( m , 1 H , A r i H e n Z o t r i a Z o l e r i n g ,6 - p o s i t i o n ) , 6 . 8 1 s , 1 H , A r i H h e n o l , 3 - p o s i t i o n ) , 6 . 0 0 ( m ,1 H , HC:CH2), 5 . 1 6 ( m , 2 H , HC:CH2), 3 . 9 7 s , 3 H ,CH3O), 3 . 4 3 ( d , 2 H , AriC Hz) .

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t r a t i o n s Were o g e n e r a t e d by UV/V s i s s p e c t r o s c o p y . Com


8/9

US 8 , 2 6 2 , 9 4 7 B2pound 1 Was d i s s o l v e d i n chloroform and e v a l u a t e d i n aP e r k i n E l m e r Lambda 5 UV/V s i s s p e c t r o m e t e r . The e s u l t sa r e shoWn i n FIG. 1 .

EXAMPLEP o l y m e r T e s t S a m p l e s C o n t a i n i n g Compound 2

Co mpound from Example 3 Was f o r m u l a t e d a s shoWn i nT a b l e 1 . A l l comp onents Were v o r t e x mixed i n a 40 ml g l a s sv i a l , d e g a s s e d W i t h n i t r o g e n , a n d t h e n s y r i n g e ? l t e r e d u s i n g a0 . 2 m i c r o n Te?on l t e r i n t o ~ 1 mm e e p r e c t a n g u l a r p o l y p r op y l e n e m o l d s . S a m p l e s Were t h e r m a l l y c u r e d a t 9 0 C . f o r 1h o u r and 1 0 C . f o r 2 . 5 h o u r s and h e n e x t r a c t e d i n r e ? u x i n ga c e t o n e f o r 6 h o u r s W i t h f r e s h s o l v e n t r e p l a c e m e n t e v e r y 90m i n u t e s .

TABLEE x a m p l e( % W / W )Component 5

Compound 2 2 . 5BZA 8 2 . 7BZMA 9 . 9polyPEG 3 . 2BDDA 1 . 7AIBN 1 . 0

BZA b e n z y l a c r y l a t eBZMA b e n z y l m e t h a c r y l a t epolyPEG = 4 0 0 0 m o l e c u l a r W e i g h t p o l y m e r o f p o l y e t h y l e n e g l y c o l ( 5 5 0) - m e t h a c r yl a t e( p o l y P E G m a c r o m o n o m e r )BDDA 1 , 4 - b u t a n e d i o l d i a c r y l a t eALBN 2 , 2 ' - A z o b i s ( 2 - m e t h y l p r o p i o n i t r i l e )

The p o l y m e r t e s t s a m p l e s Were t e s t e d f o r % x t r a c t a b l e s ,r e f r a c t i v e i n d e x , a n d e q u i l i b r i u m W a t e r c o n t e n t ( 3 5 C . ) a sshoWn i n T a b l e 2 . The e s t s a m p l e s Were a l s o examined f o rg l i s t e n i n g s a f t e r e q u i l i b r a t i n g t e s t s a m p l e s a t 4 5 C . f o r 2 0h o u r s f o l l o W e d by c o o l i n g t o 2 2 C . T e n s i l e p r o p e r t i e s Weremeasured and v a l u e s a r e r e p o r t e d i n T a b l e 3 .

TABLEG l i s t e n i n g s

% EWC 3 5 C . ) P e r T e s tE x a m p l e E x t r a c t a b l e s ( % ) R . I . ( 3 5 C . ) S a m p l e5 4 . 8 10.2 1 . 1 1 . 5 6 0 5 1 0 t o v e r y feW

l S a m p l e Was q u i l i b r a t e d in d e i o n i z e d W a t e r f o r 2 0 h o u r s a t 4 5 C . , t h e n c o o l e d to a m b i e n tt e m p e r a t u r e a n d i n s p e c t e d by n o p t i c a l m i c r o s c o p e 1 - 2 h o u r s l a t e r

TABLE25% 100

S t r e s s At Y o u n g s S e c a n t S e c a n tBreak S t r a i n At Modulus Modulus ModulusE x a m p l e ( M P a ) B r e a k ( % ) ( M P a ) ( M P a ) ( M P a )

5 6 . 1 r 0 . 7 140 z 13 105 z 12 15.2 r 1 . 5 4.6 r 0 . 3

UV/Vis i s s p e c t r a from ~1 mm h i c k sample s e c t i o n s Werec o l l e c t e d u s i n g a P e r k i n E l m e r Lambda 3 5 UV/Vis i s s p e ct r o m e t e r . As shoWn i n F I G . 2 , t h e UV/Vis i s s p e c t r u m o fe x t r a c t e d a n d u n e x t r a c t e d t e s t s a m p l e s f o r t h e p o l y m e r i cm a t e r i a l o f Example 5 con?rms t h a t n o t a l l o f t h e UVa b s o r b e r i s c o v a l e n t l y i n c o r p o r a t e d i n t h e p o l y m e r n e t W o r k .The r e l a t i v e l y h i g h % x t r a c t a b l e s i n T a b l e 2 c o r r o b o r a t e st h e s e r e s u l t s . T h i s i s a t t r i b u t e d t o t h e r e l a t i v e l y s l o W r e a c t i o nk i n e t i c s o f t h e p r o p e n y l d o u b l e bond o f Compound u n d e rt h e g i v e n r e a c t i o n c o n d i t i o n s . R e l a t i v e l y l o W i n c o r p o r a t i o n o f

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1 0t h e UV/Vis s a b s o r b e r s can be e a s i l y c i r c u m v e n t e d by conv e r t i n g t h e p r o p e n y l d o u b l e bond o a ( m e t h ) a c r y l a t e g r o u p a sd e s c r i b e d a b o v e ( e . g . , Compounds 2 a n d 3 ) .

EXAMPLEA c r y l i c IOL F o r m u l a t i o n s

Compounds Was f o r m u l a t e d i n IOL a t e r i a l s a s shoWn nT a b l e 4 . A l l comp onents Were v o r t e x mixed i n a 30 ml g l a s sv i a l , d e g a s s e d W i t h n i t r o g e n , a n d t h e n s y r i n g e ? l t e r e d u s i n g a0 . 2 m i c r o n Te?on l t e r i n t o ~ 1 mm e e p r e c t a n g u l a r p o l y p r op y l e n e m o l d s . S a m p l e s Were t h e r m a l l y c u r e d a t 7 0 C . f o r 1hour and 1 0 C . f o r 2 h o u r s and h e n e x t r a c t e d i n a c e t o n e a t5 0 C . f o r 6 h o u r s W i t h f r e s h s o l v e n t r e p l a c e m e n t e v e r y 9 0m i n u t e s .

TABLEEXAMPLE% /W

Component 6A 6B 6C 6DCompound 2 2 . 4 9 2 . 5 0 2 . 4 8 2 . 4 8PEA 0 0 7 3 . 1 7 3 . 0PEMA 0 0 1 9 . 9 2 0 . 0BZA 8 2 . 7 9 2 . 9 0 0BZMA 9 . 9 2 0 0 0S e c o n d a r y a l c o h o l 0 3 . 1 0 0 3 . 0 1e t h o x y l a t e , m e t h a c r y l i ca c i d e s t e rPolyPEGMA 3 . 2 0 0 0 3 . 0 0 0BDDA 1 . 7 0 1 . 5 0 1 . 5 3 1 . 5 2AIBN 1 . 0 1 0 . 5 3 0 . 6 0 0 . 5 0

PEA 2 - p h e n y l e t h y l a c r y l a t ePEMA 2 - p h e n y l e t h y l m e t h a c r y l a t eBZA b e n z y l a c r y l a t eBZMA b e n z y l m e t h a c r y l a t eBDDA 1 , 4 - b u t a n e d i o l d i a c r y l a t e S e c o n d a r y a l c o h o l e t h o x y l a t e ,r i e t l g a i z r y l i c a c i d e s t e r = m e t h a c r y l i c a c i d e s t e r o f T e r g i t o l T M NP-70 s u r f a c t a n t (Dow/Union

ar 1 eP o l y P E ( ) } M A = M a c r o m o n o m e r o f p o l y ( e t h y l e n e g l y c o l ) m o n o m e t h y l e t h e r m e t h a c r y l a t e(MW 5 5 0 ) ,Mn S E C ) : 4 1 0 0 D a l t o n s ,Mn N M R ) : 3 2 0 0 D a l t o n s ,PDI = 1.5AlIBN = 2,2'-Azobis(2-methylpropionitrile)

TABLEEXAMPLE% /W

Component 6A 6B 6C 6DCompound 4 1 . 4 9 2 . 0 0 2 . 4 8 3 . 0 0PEA 0 0 7 3 . 1 7 3 . 0PEMA 0 0 1 9 . 9 1 9 . 5BZA 8 3 . 7 9 3 . 4 0 0BZMA 9 . 9 2 0 0 0S e c o n d a r y a l c o h o l 0 3 . 1 0 0 3 . 0 1e t h o x y l a t e , m e t h a c r y l i ca c i d e s t e rPolyPEGMA 3 . 2 0 0 0 3 . 0 0 0BDDA 1 . 7 0 1 . 5 0 1 . 5 3 1 . 5 2AIBN 1 . 0 1 0 . 5 3 0 . 6 0 0 . 5 0

T h i s i n v e n t i o n h a s been d e s c r i b e d by r e f e r e n c e t o c e r t a i np r e f e r r e d e m b o d i m e n t s ; h o W e v e r , i t s h o u l d b e u n d e r s t o o dt h a t i t may be embodied i n o t h e r s p e c i ? c f o r m s o r v a r i a t i o n st h e r e o f W i t h o u t d e p a r t i n g f r o m i t s s p e c i a l o r e s s e n t i a l c h a ra c t e r i s t i c s . The embodiments d e s c r i b e d above a r e t h e r e f o r ec o n s i d e r e d t o be l l u s t r a t i v e i n a l l r e s p e c t s and o t r e s t r i c t i v e ,t h e s c o p e o f t h e i n v e n t i o n b e i n g i n d i c a t e d b y t h e a p p e n d e dc l a i m s r a t h e r t h a n b y t h e f o r e g o i n g d e s c r i p t i o n .


9/9

US 8 , 2 6 2 , 9 4 7 B21 1

I c l a i m :1 . A e n Z o t r i a Z o l e compound o f t h e f o r m u l a

HO 0R2NN

R 3 NX

w h e r e i nX:C3-C4 l k e n y l , C 3 - C 4 l k y l , CH2CH2CH2SCH2CH2 rC H 2 C H 2 C H 2 S C H 2 C H 2 C H 2 ;Y I n o t h i n g i f X:C3-C4 l k e n y l , o t h e r w i s e

Rl:H, C H 3 , C H 2 C H 3 , o r CHZOH;R 2 : C 1 - C 4 a l k y l ; a n dR3:H, C H 3 , C H 3 O , F , C l , B r , I , o r C F 3 .2 . The b e n Z o t r i a Z o l e compound o f c l a i m 1 , w h e r e i n

Y I n o t h i n g i f X:C3-C4 a l k e n y l , o t h e r w i s e Y:iO4C( : O ) * C ( R l ) : C H 2 ;R 2 : C l - C 2 a l k y l ; a n dR3:CH3, C H 3 O , F , C 1 , o r C F 3 .3 . An n t r a o c u l a r l e n s c o m p r i s i n g a b e n Z o t r i a Z o l e c o m

pound o f c l a i m 2 .4 . The b e n Z o t r i a Z o l e compound o f c l a i m 2 , w h e r e i n t h e

compound s s e l e c t e d f r o m t h e g r o u p c o n s i s t i n g o f :2 - ( 3 - ( 3 - ( 5 - c h l o r o - 2 H - b e n Z o [ d ] [ l , 2 , 3 ] t r i a Z o l - 2 - y l ) - 4 - h yd r o x y - 5 - m e t h o x y - p h e n y l ) p r o p y l t h i o ) e t h y l m e t h a c r yl a t e ;4 - a l l y l - 2 - ( 5 - c h l o r o - 2 H - b e n Z o [ d ] [ l , 2 , 3 ] t r i a Z o l - 2 - y l ) - 6m e t h o x y p h e n o ld r o x y - 5 - m e t h o x y p h e n y l ) - p r o p y l m e t h a c r y l a t e ;4 - a l l y l - 2 - m e t h o X y - 6 - ( 5 - ( t r i ? u o r o m e t h y l ) - 2 H - b e n Z o [ d ] 1 ,2 , 3 ] - t r i a Z o l - 2 - y l ) p h e n o l ; a n d3 - ( 4 - h y d r o X y - 3 - m e t h o x y - 5 - ( 5 - ( t r i ? u o r o m e t h y l ) - 2 Hb e n Z o [ d ] [ l , 2 , 3 ] t r i a Z o l - 2 - y l ) p h e n y l ) p r o p y l m e t h a c r yl a t e .5 . The b e n Z o t r i a Z o l e compound o f c l a i m 4 , w h e r e i n t h e

c o m p o u n d s 2 - ( 3 - ( 3 - ( 5 - c h l o r o - 2 H - b e n Z o [ d ] [ l , 2 , 3 ] t r i a Z o l - 2y l ) - 4 - h y d r o x y - 5 - m e t h o X y - p h e n y l ) p r o p y l t h i o ) e t h y l m e t ha c r y l a t e .6 . The b e n Z o t r i a Z o l e compound o f c l a i m 4 , w h e r e i n t h ec o m p o u n d i s 3 - ( 4 - h y d r o x y - 3 - m e t h o X y - 5 - ( 5 - ( t r i ? u o r o me t h y l ) - 2 H - b e n Z o [ d ] [ l , 2 , 3 ] t r i a Z o l - 2 - y l ) p h e n y l ) p r o p y l m e t ha c r y l a t e .

7 . An n t r a o c u l a r l e n s comprising a b e n Z o t r i a Z o l e compound o f c l a i m 4 .8 . A o p o l y m e r i c o p h t h a l m i c d e v i c e m a t e r i a l f o r m e d b yc o p o l y m e r i Z i n g a c o m p o s i t i o n c o m p r i s i n g a b e n Z o t r i a Z o l ecompound o f c l a i m 1 and a d e v i c e - f o r m i n g monomers e l e c t e d from h e g r o u p c o n s i s t i n g o f a c r y l i c monomers ands i l i c o n e - c o n t a i n i n g monomers.

1 0

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1 29 . The o p h t h a l m i c d e v i c e m a t e r i a l o f c l a i m 8 , w h e r e i n t h e

c o m p o s i t i o n c o m p r i s e s from . 1 t o 5% /w o f t h e b e n Z o t r i aZ o l e c o m p o u n d .1 0 . The p h t h a l m i c d e v i c e m a t e r i a l o f c l a i m 9 , w h e r e i n t h e

c o m p o s i t i o n c o m p r i s e s from 0 . 5 t o 4% /w o f t h e b e n Z o t r i aZ o l e c o m p o u n d .1 1 . The o p h t h a l m i c d e v i c e m a t e r i a l o f c l a i m 1 0 , w h e r e i n

t h e c o m p o s i t i o n c o m p r i s e s from t o 3% /w o f t h e b e n Z o tr i a Z o l e c o m p o u n d .1 2 . The p h t h a l m i c d e v i c e m a t e r i a l o f c l a i m 8 , w h e r e i n t h e

c o m p o s i t i o n c o m p r i s e s a d e v i c e - f o r m i n g monomer o f f o rm u l a [ I V ] :

[ W ]

w h e r e i n f o r m u l a [ I V ] :A s H , C H 3 , CH2CH3, o r CHZOH;C s ( C H 2 ) W ;m s 2 - 6 ;Z i s l - l O ;Y s a d i r e c t b o n d , 0 , S , o r N R ' , p r o v i d e d t h a t i f Y i s O , S ,

o r N R ' , t h e n B s ( C H 2 ) m ;

w s 0 - 6 , p r o v i d e d t h a t m+w8; a n dD s H , C l - C 4 a l k y l , C l - C 4 a l k o x y , C 6 H 5 , CH2C6H5 o rh a l o g e n .1 3 . The o p h t h a l m i c d e v i c e m a t e r i a l o f c l a i m 1 2 , w h e r e i n i n

f o r m u l a [ I V ] :A s H r CH3;B s ( C H 2 ) m ;m s 2 - 5 ;Y s a d i r e c t bond o r O;w s O - l ; andD s H .1 4 . The o p h t h a l m i c d e v i c e m a t e r i a l o f c l a i m 1 3 , w h e r e i n

t h e c o m p o s i t i o n c o m p r i s e s a monomer s e l e c t e d from t h eg r o u p c o n s i s t i n g o f : 2 - p h e n y l e t h y l m e t h a c r y l a t e ; 4 - p h e n y lb u t y l m e t h a c r y l a t e ; 5 - p h e n y l p e n t y l m e t h a c r y l a t e ; 2 - b e n Z yl o x y e t h y l m e t h a c r y l a t e ; a n d 3 - b e n Z y l o X y p r o p y l m e t h a c r yl a t e ; a n d t h e i r c o r r e s p o n d i n g a c r y l a t e s .

1 5 . The p h t h a l m i c d e v i c e m a t e r i a l o f c l a i m 8 , w h e r e i n t h ec o m p o s i t i o n c o m p r i s e s a c r o s s - l i n k i n g a g e n t .

1 6 . The p h t h a l m i c d e v i c e m a t e r i a l o f c l a i m 8 , w h e r e i n t h ec o m p o s i t i o n c o m p r i s e s a r e a c t i v e b l u e - l i g h t a b s o r b i n g comp o u n d .

1 7 . An o p h t h a l m i c d e v i c e c o m p r i s i n g t h e o p h t h a l m i cd e v i c e m a t e r i a l o f c l a i m 8 .1 8 . The o p h t h a l m i c d e v i c e o f c l a i m 1 7 , w h e r e i n t h e o p ht h a l m i c d e v i c e i s s e l e c t e d from t h e g r o u p c o n s i s t i n g o f ani n t r a o c u l a r l e n s ; a c o n t a c t l e n s ; a k e r a t o p r o s t h e s i s ; a c o r n e a li n l a y ; a n d a c o r n e a l r i n g .

1 9 . An n t r a o c u l a r l e n s comprising a b e n Z o t r i a Z o l e compound o f c l a i m 1 .

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