Photochromic ocular devices

Abstract

Described are photochromic ocular devices such as contact lenses and intraocular lenses made of an organic polymeric material and at least one photochromic material adapted upon exposure to actinic radiation to change from a less ultraviolet radiation absorbing unactivated form to a more ultraviolet radiation absorbing activated form. The photochromic ocular device is adapted upon exposure to actinic radiation to exhibit a ratio of greater than 0.5:1.0 of increased ultraviolet radiation absorbance to increased visible radiation absorbance as measured in the Ultraviolet Photochromic Performance Test described herein.

I claim:  
     
         1 . A photochromic ocular device comprising: 
 (a) an organic polymeric material; and    (b) at least one photochromic material adapted to change from a less radiation absorbing unactivated form to a more radiation absorbing activated form upon exposure to actinic radiation;    said photochromic ocular device being adapted upon exposure to actinic radiation to exhibit a ratio of increased ultraviolet radiation absorbance to increased visible radiation absorbance of greater than 0.5:1.0 as measured in the Ultraviolet Photochromic Performance Test.    
     
     
         2 . The photochromic ocular device of  claim 1  wherein the photochromic material (b) is chosen from 3H-naphtho[2,1-b]pyrans, 2H-naphtho[1,2-b]pyrans, indeno[2,′3,′3,4]naphtho[1,2-b]pyrans, or mixtures thereof.  
     
     
         3 . The photochromic ocular device of  claim 2  wherein the photochromic material (b) is an indeno[2,′3,′3,4]naphtho[1,2-b]pyrans.  
     
     
         4 . The photochromic ocular device of  claim 1  wherein photochromic material (b) is represented by a graphic formula chosen from I, II, III or mixtures thereof:  
       
         
           
           
               
               
           
         
       
       wherein, 
 (a) R 1  is the group R which is represented by one of the following formulae (IVA) to (IVF): 
 —A (formula IVA);  
 —D—A (formula TVB);  
 —D—E—U (formula IVC);  
 —D—U (formula IVD);  
 —E—U (formula IVE); or  
 —U (formula IVF);  
 wherein —A is represented by the following formula: 
 —[(OC 2 H 4 ) x (OC 3 H 6 ) y (OC 4 H 8 ) z ]—J 
 wherein —J is chosen from: hydroxy, (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl, epoxy, C 1 -C 6  alkyl, —OCH 2 COOH; —OCH(CH 3 )COOH; —OC(O) (CH 2 ) w COOH; —OC 6 H 4 SO 3 H; —OC 5 H 10 SO 3 H; —OC 4 H 8 SO 3 H; —OC 3 H 6 SO 3 H; —OC 2 H 4 SO 3 H; or —OSO 3 H; w is an integer from 1 to 18; x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 1 and 50; —D—is —C(O)— or —CH 2 —; —E— is represented by the following formula: 
 —[(OC 2 H 4 ) x (OC 3 H 6 ) y (OC 4 H 8 ) z ]— 
 wherein x, y and z are the same as defined for —A; —U is a residue of an organic polyol having at least one hydroxyl group or a derivative of said residue wherein at least one hydroxyl group has been reacted to form the group J provided that —U is not the same as —A when —J is hydroxy; or R 1  is hydrogen, C 1 -C 3  alkyl or the group, —C(O)W, W being —OR 7 , —N(R 8 )R 9 , piperidino or morpholino, wherein R 7  is allyl, C 1 -C 6  alkyl, phenyl, mono(C 1 -C 6 )alkyl substituted phenyl, mono(C 1 -C 6 )alkoxy substituted phenyl, phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkyl substituted phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkoxy substituted phenyl(C 1 -C 3 )alkyl, C 1 -C 6  alkoxy(C 2 -C 4 )alkyl or C 1 -C 6  haloalkyl; R 8  and R 9  are each independently chosen from C 1 -C 6  alkyl, C 5 -C 7  cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, said phenyl substituents being C 1 -C 6  alkyl or C 1 -C 6  alkoxy, and said halo substituent being chloro or fluoro;  
 
 (b) R 1 ′ is the group R, C 1 -C 3  alkyl or the group, —C(O)W, W being —OR 7 , —N(R 8 )R 9 , piperidino or morpholino, wherein R 7  is allyl, C 1 -C 6  alkyl, phenyl, mono(C 1 -C 6 )alkyl substituted phenyl, mono(C 1 -C 6 )alkoxy substituted phenyl, phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkyl substituted phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkoxy substituted phenyl(C 1 -C 3 )alkyl, C 1 -C 6  alkoxy(C 2 -C 4 )alkyl or C 1 -C 6  haloalkyl; R 8  and R 9  are each independently chosen from C 1 -C 6  alkyl, C 5 -C 7  cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, said phenyl substituents being C 1 -C 6  alkyl or C 1 -C 6  alkoxy, and said halo substituent being chloro or fluoro;  
 (c) R 2  is chosen from the group R, mono-R-substituted phenyl, hydrogen, C 1 -C 6  alkyl, C 3 -C 7  cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl, the group —OR 10  or —OC(O)R 10 , wherein R 10  is C 1 -C 6  alkyl, phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkyl substituted phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkoxy substituted phenyl(C 1 -C 3 )alkyl, C 1 -C 6  alkoxy(C 2 -C 4 )alkyl, C 3 -C 7  cycloalkyl or mono(C 1 -C 4 )alkyl substituted C 3 -C 7  cycloalkyl, and said phenyl substituent being C 1 -C 6  alkyl or C 1 -C 6  alkoxy;  
 (d) each R 3  and each R 4  are independently chosen from the group R, hydrogen, C 1 -C 6  alkyl, C 3 -C 7  cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl, the group —OR 10  or —OC(O)R 10 , wherein R 10  is C 1 -C 6  alkyl, phenyl(C 1 -C 3 )-alkyl, mono(C 1 -C 6 )alkyl substituted phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkoxy substituted phenyl(C 1 -C 3 )alkyl, C 1 -C 6  alkoxy(C 2 -C 4 )alkyl, C 3 -C 7  cycloalkyl or mono(C 1 -C 4 )alkyl substituted C 3 -C 7  cycloalkyl, and said phenyl substituent being C 1 -C 6  alkyl or C 1 -C 6  alkoxy; or each R 3  and each R 4  are independently a nitrogen-containing group chosen from: 
 (i) —N(R 11 )R 12  wherein R 11  and R 12  are each independently chosen from hydrogen, C 1 -C 8  alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl and fluorenyl, C 1 -C 8  alkylaryl, C 3 -C 20  cycloalkyl, C 4 -C 20  bicycloalkyl, C 5 -C 20  tricycloalkyl or C 1 -C 20  alkoxyalkyl, wherein said aryl group is phenyl or naphthyl or R 11  and R 12  come together with the nitrogen atom to form a C 3 -C 20  hetero-bicycloalkyl ring or a C 4 -C 20  hetero-tricycloalkyl ring;  
 (ii) a nitrogen containing ring represented by the following graphic formula VA:  
                     
 
  wherein each Y is independently chosen for each occurrence from —CH 2 —, —CH(R 13 )—, —C(R 13 )(R 13 )—, —CH(aryl)—, —C(aryl) 2 —, or —C(R 13 )(aryl)—, and X is chosen from —Y—, —O—, —S—, —S(O)—, —S(O 2 )—, —NH—, —N(R 13 )— or —N(aryl)—, wherein R 13  is C 1 -C 6  alkyl, said aryl is phenyl or naphthyl, m is the integer 1, 2 or 3, and p is the integer 0, 1, 2, or 3 and when p is 0, X is Y; 
 (iii) a group represented by one of the following graphic formulae VB or VC:  
                     
 
  wherein R 15 , R 16  and R 17  are each independently chosen for each occurrence in each formula from hydrogen, C 1 -C 6  alkyl, phenyl or naphthyl, or the groups R 15  and R 16  together form a ring of 5 to 8 carbon atoms and each R 14  is independently chosen for each occurrence in each formula from C 1 -C 6  alkyl, C 1 -C 6  alkoxy, fluoro or chloro and p is the same as defined hereinbefore; 
 (iv) unsubstituted, mono- or di-substituted C 4 -C 18  spirobicyclic amine; or  
 (v) unsubstituted, mono- or di-substituted C 4 -C 18  spirotricyclic amine; said substituents for (d)(iv) and (v) are independently chosen for each occurrence from aryl, C 1 -C 6  alkyl, C 1 -C 6  alkoxy or phenyl(C 1 -C 6 )alkyl and n is chosen from the integers 0, 1 or 2;  
 
 (e) R 5  and R 6  together form an oxo group, a spiro-carbocyclic ring containing 3 to 6 carbon atoms or a spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-carbocyclic and spiro-heterocyclic groups being annellated with 0, 1 or 2 benzene rings; or R 5  and R 6  are each independently the group R, hydrogen, hydroxy, C 1 -C 6  alkyl, C 3 -C 7  cycloalkyl, allyl, phenyl, mono-substituted phenyl, benzyl, mono-substituted benzyl, chloro, fluoro, the group, —C(O)X′, wherein X′is hydroxy, C 1 -C 6  alkyl, C 1 -C 6  alkoxy, phenyl, mono-substituted phenyl, amino, mono(C 1 -C 6 )alkylamino, or di(C 1 -C 6 )alkylamino; or R 5  and R 6  are each independently the group, —OR 18 , wherein R 18  is C 1 -C 6  alkyl, phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkyl substituted phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 6 )alkoxy substituted phenyl(C 1 -C 3 )alkyl, C 1 -C 6  alkoxy(C 2 -C 4 )alkyl, C 3 -C 7  cycloalkyl, mono(C 1 -C 4 )alkyl substituted C 3 -C 7  cycloalkyl, C 1 -C 6  chloroalkyl, C 1 -C 6  fluoroalkyl, allyl, the group, —CH(R 1 g)Y′, wherein R 19  is hydrogen or C 1 -C 3  alkyl and Y′ is CN, CF 3 , or COOR 20  and R 20  is hydrogen or C 1 -C 3  alkyl; or R 18  is the group, —C(O)Z, wherein Z is hydrogen, C 1 -C 6  alkyl, C 1 -C 6  alkoxy, the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, phenoxy, mono- or di-(C 1 -C 6 )alkyl substituted phenoxy, mono- or di-(C 1 -C 6 )alkoxy substituted phenoxy, amino, mono(C 1 -C 6 )alkylamino, di(C 1 -C 6 )alkylamino, phenylamino, mono- or di-(C 1 -C 6 )alkyl substituted phenylamino, or mono- or di-(C 1 -C 6 )alkoxy substituted phenylamino, each of said phenyl, benzyl and aryl group substituents being C 1 -C 6  alkyl or C 1 -C 6  alkoxy;  
 (f) B and B′ are each independently chosen from: 
 (i) the unsubstituted, mono-, di-or tri- substituted aryl groups, phenyl or naphthyl;  
 (ii) 9-julolidinyl or the unsubstituted, mono- or di-substituted heteroaromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl or fluorenyl, each of said aryl and heteroaromatic substituents in (f)(i) and (ii) being chosen from the group R, hydroxy, aryl, mono(C 1 -C 6 )alkoxyaryl, di(C 1 -C 6 )alkoxyaryl, mono(C 1 -C 6 )alkylaryl, di(C 1 -C 6 )alkylaryl, chloroaryl, fluoroaryl, C 3 -C 7  cycloalkylaryl, C 3 -C 7  cycloalkyl, C 3 -C 7  cycloalkyloxy, C 3 -C 7  cycloalkyloxy(C 1 -C 6 )alkyl, C 3 -C 7  cycloalkyloxy(C 1 -C 6 )alkoxy, aryl(C 1 -C 6 )alkyl, aryl(C 1 -C 6 )alkoxy, aryloxy, aryloxy(C 1 -C 6 )alkyl, aryloxy(C 1 -C 6 )alkoxy, mono- or di-(C 1 -C 6 )alkylaryl(C 1 -C 6 )alkyl, mono- or di-(C 1 -C 6 )alkoxyaryl(C 1 -C 6 )alkyl, mono- or di-(C 1 -C 6 )alkylaryl(C 1 -C 6 )alkoxy, mono- or di-(C 1 -C 6 )alkoxyaryl(C 1 -C 6 )alkoxy, amino, mono(C 1 -C 6 )alkylamino, di(C 1 -C 6 )alkylamino, diarylamino, N-(C 1 -C 6 )alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, C 1 -C 6  alkyl, C 1 -C 6  chloroalkyl, C 1 -C 6  fluoroalkyl, C 1 -C 6  alkoxy, mono(C 1 -C 6 )alkoxy(C 1 -C 4 )alkyl, acryloxy, methacryloxy, bromo, chloro or fluoro, said aryl being phenyl or naphthyl;  
 (iii) the unsubstituted or mono-substituted groups, pyrazolyl, imidazolyl, pyridyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl or acridinyl, each of said substituents being chosen from C 1 -C 6  alkyl, C 1 -C 4  alkoxy, phenyl, fluoro, chloro or bromo;  
 (iv) monosubstituted phenyl, having at the para position a substituent that is —(CH 2 ) t — or —O—(CH 2 ) t —, wherein t is the integer 1, 2, 3, 4, 5 or 6, said substituent being connected to an aryl group on another photochromic material;  
 (v) the group represented by one of the following graphic formulae VIA or VIB:  
                     
 
  wherein L is carbon or oxygen and M is oxygen or substituted nitrogen, provided that when M is substituted nitrogen, L is carbon, said nitrogen substituents being chosen from hydrogen, C 1 -C 6  alkyl and C 2 -C 6  acyl; each R 21  is C 1 -C 6  alkyl, C 1 -C 6  alkoxy, hydroxy, chloro or fluoro; R 22  and R 23  are each hydrogen or C 1 -C 6  alkyl; and q is the integer 0, 1 or 2; 
 (vi) C 1 -C 6  alkyl, C 1 -C 6  chloroalkyl, -C 1 -C 6  fluoroalkyl, C 1 -C 6  alkoxy(C 1 -C 4 )alkyl, C 3 -C 6  cycloalkyl, mono(C 1 -C 6 )alkoxy(C 3 -C 6 )cycloalkyl, mono(C 1 -C 6 )alkyl(C 3 -C 6 )-cycloalkyl, chloro(C 3 -C 6 )cycloalkyl, fluoro(C 3 -C 6 )cycloalkyl or C 4 -C 12  bicycloalkyl; and  
 (vii) the group represented by the following graphic formula VIC:  
                     
 wherein P is hydrogen or C 1 -C 4  alkyl and Q is chosen from an unsubstituted, mono- or di-substituted group, said group being chosen from naphthyl, phenyl, furanyl or thienyl, each of said group substituents being C 1 -C 4  alkyl, C 1 -C 4  alkoxy, fluoro or chloro; or  
 
 (g) B and B′ taken together form fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene or a member chosen from saturated C 3 -C 12  spiro-monocyclic hydrocarbon rings, saturated C 7 -C 12  spiro-bicyclic hydrocarbon rings, or saturated C 7 -C 12  spiro-tricyclic hydrocarbon rings, each of said fluoren-9-ylidene substituents being chosen from C 1 -C 4  alkyl, C 1 -C 4  alkoxy, fluoro or chloro.  
 
     
     
         5 . The photochromic ocular device of  claim 4  wherein photochromic material (b) is represented by graphic formula I, III or mixtures thereof, wherein: 
 (a) R 1 ′ is the group R represented by formulae: (IVA); (IVB); (IVE); or (IVF); or R 1 ′ is the group, —C(O)W, W being —OR 7  or —N(R 8 )R 9 , wherein R 7  is C 1 -C 4  alkyl, phenyl, mono(C 2 -C 4 )alkyl substituted phenyl, mono(C 1 -C 4 )alkoxy substituted phenyl, phenyl(C 1 -C 2 )alkyl, mono(C 1 -C 4 )alkyl substituted phenyl(C 1 -C 2 )alkyl, mono(C 1 -C 4 )alkoxy substituted phenyl(C 1 -C 2 )alkyl, mono(C 1 -C 4 )alkoxy(C 2 -C 3 )alkyl or C 1 -C 4  haloalkyl; R 8  and R 9  are each chosen independently from C 1 -C 4  alkyl, C 5 -C 7  cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, said phenyl substituents being C 1 -C 4  alkyl or C 1 -C 4  alkoxy, said halo substituents being chloro or fluoro;  
 (b) R 2  is chosen from the group R, mono-R-substituted phenyl, hydrogen, C 1 -C 3  alkyl, C 3 -C 5  cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl or the group —OR 10 , wherein R 10  is C 1 -C 4  alkyl, phenyl(C 1 -C 2 )alkyl, mono(C 1 -C 4 )alkyl substituted phenyl(C 1 -C 2 )alkyl, mono(C 1 -C 4 )alkoxy substituted phenyl(C 1 -C 2 )alkyl, C 1 -C 4  alkoxy(C 2 -C 4 )alkyl, C 5 -C 7  cycloalkyl or mono(C 1 -C 3 )alkyl substituted C 5 -C 7  cycloalkyl; said phenyl substituents being C 1 -C 3  alkyl or C 1 -C 3  alkoxy;  
 (c) each R 3  is independently chosen from the group R or the group —OR 10 , wherein R 10  is C 1 -C 4  alkyl, phenyl(C 1 -C 2 )alkyl, mono(C 1 -C 4 )alkyl substituted phenyl(C 1 -C 2 )alkyl, mono(C 1 -C 4 )alkoxy substituted phenyl(C 1 -C 2 )alkyl, C 1 -C 4  alkoxy(C 2 -C 4 )alkyl, C 5 -C 7  cycloalkyl or mono(C 1 -C 3 )alkyl substituted C 5 -C 7  cycloalkyl and said phenyl substituents being C 1 -C 3  alkyl or C 1 -C 3  alkoxy; or each R 3  is independently a nitrogen-containing group chosen from: 
 (i) —N(R 11 )R 12 , R 11 and R 12  each being independently chosen from C 1 -C 6  alkyl or phenyl;  
 (ii) a nitrogen containing ring represented by the graphic formula VA wherein each Y being —CH 2 — and X being independently chosen from —Y—, —O—, —S—, —N(R 13 )— and —N(phenyl)—, R 13  being C 1 -C 6  alkyl, m being chosen from the integer 1, 2 or 3, and p being chosen from the integer 0, 1, 2 or 3;  
 (iii) a group represented by one of graphic formulae VB or VC wherein R 15 , R 16  and R 17  each being independently chosen from hydrogen or C 1 -C 5  alkyl, R 14  being independently chosen from hydrogen, C 1 -C 4  alkyl, C 1 - 4  alkoxy, fluoro or chloro;  
 (iv) unsubstituted or mono-substituted C 5 -C 18  spirobicyclic amine; or  
 (v) unsubstituted or mono-substituted C 5 -C 18  spirotricyclic amine; said substituents for (c)(iv) and (v) are independently chosen for each occurrence from phenyl, C 1 -C 6  alkyl or C 1 -C 6  alkoxy and n being chosen from the integer 1 or 2;  
 
 (d) R 5  and R 6  are each independently chosen from the group R, hydrogen, hydroxy, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, chloro, fluoro and the group, —OR 18 , wherein R 18  is C 1 -C 3  alkyl, phenyl(C 1 -C 2 )alkyl, mono(C 1 -C 3 )alkyl substituted phenyl(C 1 -C 3 )alkyl, mono(C 1 -C 3 )alkoxy substituted phenyl(C 1 -C 3 )alkyl, C 1 -C 3  alkoxy(C 2 -C 4 )alkyl, C 1 -C 3  chloroalkyl, C 1 -C 3  fluoroalkyl, the group, —CH(R 19 )Y′, wherein R 19  is hydrogen or C 1 -C 2  alkyl and Y′ is CN or COOR 20 , and R 20  is hydrogen or C 1 -C 2  alkyl, or R 18  is the group, —C(O)Z, wherein Z is hydrogen, C 1 -C 3  alkyl, C 1 -C 3  alkoxy, phenyl, naphthyl, mono-substituted aryl groups, phenyl or naphthyl, phenoxy, mono- or di-(C 1 -C 3 )alkyl substituted phenoxy, mono- or di-(C 1 -C 3 )alkoxy substituted phenoxy, mono(C 1 -C 3 )alkylamino, phenylamino, mono- or di-(C 1 -C 3 )alkyl substituted phenylamino, or mono- or di-(C 1 -C 3 )alkoxy substituted phenylamino, and said aryl substituents being C 1 -C 3  alkyl or C 1 -C 3  alkoxy;  
 (e) B and B′ are each independently chosen from: 
 (i) phenyl, mono-substituted or di-substituted phenyl, each of said phenyl substituents being independently chosen from the group R, hydroxy, aryl, arlyoxy, aryl(C 1 -C 3 )alkyl, amino, mono(C 1 -C 3 )alkylamino, di(C 1 -C 3 )alkylamino, N-(C 1 -C 3 )alkylpiperazino, indolino, piperidino, morpholino, pyrryl, C 1 -C 3  alkyl, C 1 -C 3  chloroalkyl, C 1 -C 3  fluoroalkyl, C 1 -C 3  alkoxy, mono(C 1 -C 3 )alkoxy(C 1 -C 3 )alkyl, chloro or fluoro;  
 (ii) the groups represented by one of graphic formulae VIA or VIB: wherein L is carbon and M is oxygen, R 21  is C 1 -C 3  alkyl or C 1 -C 3  alkoxy; R 22  and R 23  are each hydrogen or C 1 -C 4  alkyl; and q is 0 or 1;  
 (iii) C 1 -C 4  alkyl; or  
 (iv) the group represented by graphic formula VIC wherein P is hydrogen or methyl and Q is phenyl or mono- substituted phenyl, said phenyl substituents being C 1 -C 3  alkyl, C 1 -C 3  alkoxy or fluoro; or  
 
 (f) B and B′ taken together form fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or a member chosen from saturated C 3 -C 8  spiro-monocyclic hydrocarbon rings, saturated C 7 -C 10  spiro-bicyclic hydrocarbon rings, or saturated C 7 -C 10  spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituent being chosen from C 1 -C 3  alkyl, C 1 -C 3  alkoxy, fluoro or chloro.  
 
     
     
         6 . The photochromic ocular device of  claim 5  wherein photochromic material (b) is represented by graphic formula III wherein: 
 (a) each R 3  is the group R represented by formula (IVE) or (IVF), or the group, OR 10 , wherein R 10  is C 1 -C 3  alkyl; or each R 3  is chosen from: 
 (i) —N(R 11 )R 12 , R 11  and R 12  each being C 1 -C 3  alkyl;  
 (ii) a nitrogen containing ring represented by graphic formula VA wherein each Y for each occurrence being —CH 2 — and X being independently chosen from —Y—, —O—, and —N(R 13 )—, R 13  being C 1 -C 4  alkyl, m being chosen from the integer 1 or 2, and p being chosen from the integer 0, 1 or 2; or  
 (iii) a group represented by graphic formulae VC or VB wherein R 15 , R 16 , and R 17  each being hydrogen and n is 1 or 2;  
 
 (b) R 5  and R 6  are each the group R, hydrogen, hydroxy, C 1 -C 4  alkyl, or the group, —OR 18 , wherein R 18  is C 1 -C 3  alkyl;  
 (c) B and B′ are each independently chosen from: 
 (i) phenyl, mono- or di-substituted phenyl, each of said phenyl substituents being chosen from the group R, hydroxy, C 1 -C 3  alkyl, C 1 -C 3  alkoxy, phenyl, piperidino, morpholino, fluoro or chloro; or  
 
 (d) B and B′ taken together form fluoren-9-ylidene, adamantylidene, bornylidene, norbornylidene, or bicyclo[3.3.1]nonan-9-ylidene.  
 
     
     
         7 . The photochromic ocular device of  claim 5  wherein photochromic material (b) is chosen from: 
 (a) 3-(4-methoxyphenyl)-3-phenyl-6,11-dimethoxy-13-methyl-13-(2-{2-[N-(2-methacryloxyethyl)carbamoyloxy]ethoxy) ethoxy)-3H,13H-indeno[2,′3,′3,4]naphtho[1,2-b]pyran;  
 (b) 3-(4-methoxyphenyl)-3-phenyl-6,11-dimethoxy-13-methyl-13-(2-(2-(2-methacryloxyethyl)ethoxy)ethoxy)-3H,13H-indeno[2,′3,′3,4]naphtho[1,2-b]pyran;  
 (c) 3,3-diphenyl-6,7-dimethoxy-13-methyl-13-(2-(2-(2-methacryloxyethyl)ethoxy)ethoxy)-3H,13H-indeno[2,′3,′3,4]naphtho [1,2-b]pyran;  
 (d) 3-(4-methoxyphenyl)-3-(2,4-dimethoxyphenyl-6,11-dimethoxy-13-methyl-13-(2-(2-(2-methacryloxyethyl)ethoxy)ethoxy)-3H,13H-indeno[2,′3,′3,4]naphtho[1,2-b]pyran;  
 (e) 3-(4-methoxyphenyl)-3-phenyl-6-methoxy-7-morpholino-13-methyl-13-(2-(2-(2-methacryloxyethyl)ethoxy)ethoxy)-3H,13H-indeno[2,′3,′3,4]naphtho[1,2-b]pyran;  
 (f) 3,3-diphenyl-6,7,10,11-tetramethoxy-13-ethyl-13-(2-{2-[N-(2-methacryloxyethyl)carbamoyloxy]ethoxylethoxy)-3H,13H-indeno[2,′3,′3,4]naphtho[1,2-b]pyran;  
 (g) 2,2-diphenyl-5-(2-(2-(2-methacryloxyethyl)ethoxy) ethoxy)carbonyl-9-methoxy-2H-naphtho[1,2-b]pyran;  
 (h) 2,2-di(4-fluorophenyl)-5-(2-(2-(2-methacryloxy-ethyl)ethoxy)ethoxy)carbonyl-6-phenyl-9-methoxy-2H-naphtho[1,2-b]pyran;  
 (i) 2,2-diphenyl-5-(2-(2-(2-methacryloxyethyl)ethoxy) ethoxy)carbonyl-8,9-dimethoxy-2H-naphtho[1,2-b]pyran; or  
 (j) mixtures thereof.  
 
     
     
         8 . The photochromic ocular device of  claim 1  wherein photochromic material (b) is chosen from: 
 (a) a single photochromic compound;  
 (b) a mixture of photochromic compounds;  
 (c) a material comprising at least one photochromic compound;  
 (d) a material to which at least one photochromic compound is chemically bonded;  
 (e) material (c) or (d) comprising a coating to substantially prevent contact of the at least one photochromic compound with external materials;  
 (f) a photochromic polymer; or  
 (g) mixtures thereof.  
 
     
     
         9 . The photochromic ocular device of  claim 1  further comprising at least one other photochromic material (c) that is different from photochromic material (b).  
     
     
         10 . The photochromic ocular device of  claim 9  wherein photochromic compound (c) is an organic photochromic compound.  
     
     
         11 . The photochromic ocular device of  claim 10  wherein photochromic compound (c) is an organic photochromic compound and is chosen from chromenes; spiropyrans; oxazines; mercury dithizonates, fulgides, fulgimides or mixtures thereof.  
     
     
         12 . The photochromic ocular device of  claim 11  wherein photochromic compound (c) is an organic photochromic compound and is chosen from chromenes comprising naphthopyrans, benzopyrans, indenonaphthopyrans, phenanthropyrans or mixtures thereof.  
     
     
         13 . The photochromic ocular device of  claim 12  wherein photochromic compound (c) is an organic photochromic compound and is chosen from naphthopyrans, indenonaphthopyrans, or a mixture thereof.  
     
     
         14 . The photochromic ocular device of  claim 9  wherein photochromic material (c) is chosen from: 
 (a) a single photochromic compound;  
 (b) a mixture of photochromic compounds;  
 (c) a material comprising at least one photochromic compound;  
 (d) a material to which at least one photochromic compound is chemically bonded;  
 (e) material (c) or (d) comprising a coating to substantially prevent contact of the at least one photochromic compound with external materials;  
 (f) a photochromic polymer; or  
 (g) mixtures thereof.  
 
     
     
         15 . The photochromic ocular device of  claim 1  wherein the organic polymeric material is polymerized from monomers chosen from hydroxyethyl methacrylate, N-vinyl pyrrolidone, methacrylic acid, methyl methacrylate, styrene, alpha-methylstyrene, vinyltoluene, p-chlorostyrene, o-chlorostyrene, p-bromostyrene, o-bromostyrene, divinylbenzene, divinylbiphenyl, vinyl acetate, vinyl propionate, vinyl benzoate, ethyl(meth)acrylate, isopropyl(meth)acrylate, allyl(meth)acrylate, phenyl(meth)acrylate, benzyl (meth)acrylate, p-chlorophenyl(meth)acrylate, p-chlorobenzyl (meth)acrylate, p-bromophenyl(meth)acrylate, p-bromobenzyl (meth)acrylate, naphthyl(meth)acrylate, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, 2-hydroxy-3-phenoxypropyl(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerol di(meth)acrylate, 3-acryloyloxyglycerol monomethacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 2,2-bis(4-(meth) acryloyloxy(2′-hydroxypropyloxy)phenyl)propane, diisopropyl fumarate, diisopropyl maleate, dibenzyl fumarate, dibenzyl maleate, dibenzyl mesaconate, maleic anhydride, itaconic anhydride or mixtures thereof.  
     
     
         16 . The photochromic ocular device of  claim 1  wherein the ratio of increased ultraviolet radiation absorbance to increased visible radiation absorbance as measured in the Ultraviolet Photochromic Performance Test is at least 1.0:1.0.  
     
     
         17 . The photochromic ocular device of  claim 1  wherein the organic polymeric material is a hydrogel polymer comprising a polymerizate of at least one hydrophilic monomer and at least one crosslinking agent.  
     
     
         18 . The photochromic ocular device of  claim 17  wherein the at least one hydrophilic monomer is chosen from: unsaturated carboxylic acids; (meth)acrylic substituted alcohols; vinyl lactams; (meth)acrylamides; or mixtures thereof.  
     
     
         19 . The photochromic ocular device of  claim 17  wherein the at least one crosslinking agent is chosen from divinylbenzene; di-or tri(meth)acrylates of diethyleneglycol, triethyleneglycol, butyleneglycol or hexane-1,6-diol; or mixtures thereof.  
     
     
         20 . The photochromic ocular device of  claim 17  wherein the organic polymeric material is a hydrogel polymer further comprising at least one silicone-containing monomer comprising at least one unsaturated group.  
     
     
         21 . The photochromic ocular device of  claim 20  wherein the at least one silicone-containing monomer comprising at least one unsaturated group is chosen from methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanyl methylmethacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, methyldi(trimethylsiloxy)methacryloxymethyl silane, 3-[tris(trimethylsiloxy)silyl]propylvinylcarbamate, or 3-[tris(trimethylsiloxy)silyl]propylvinylcarbonate.  
     
     
         22 . The photochromic ocular device of  claim 1  further comprising at least one ultraviolet absorbing material.  
     
     
         23 . The photochromic ocular device of  claim 22  wherein the at least one ultraviolet absorbing material is a monomer chosen from: 2-(21-hydroxy-5′-methacryloxyethyl-phenyl)-2H-benzotriazole; 2-(2′-hydroxy-5′-methacryloxyethyl-phenyl)-5-chloro-2H-benzotriazole; 2-(2′-hydroxy-5′-methacryloxy-propylphenyl)-5-chloro-2H-benzotriazole; 2-(2′-hydroxy-5′-methacryloxypropyl-3′-tert-butylphenyl)-2H-benzotriazole; 2-(2′-hydroxy-5′-methacryloxypropyl-3′-tert-butylphenyl)-5-chloro-2H-benzotriazole; 2-[2′-hydroxy-5′-(2-methacryloyloxyethoxy)-3′-tert-butylphenyl]-5-methoxy-2H-benzotriazole; 2-[2′-hydroxy-5′-(gamma-methacryloyloxypropoxy)-3′-tert-butylphenyl]-5-methoxy-2H-benzotriazole; 2-(3′-t-butyl-2′-hydroxy-5′-methoxyphenyl)-5-(31-methacryloyloxypropoxy)benzotriazole or mixtures thereof.