초록 ▼

Described are photochromic ocular devices such as contact lenses and intraocular lenses made of an organic polymeric material and at least one photochromic material capable upon exposure to actinic radiation to change from a less ultraviolet radiation absorbing unactivated form to a more ultraviolet

Described are photochromic ocular devices such as contact lenses and intraocular lenses made of an organic polymeric material and at least one photochromic material capable 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 capable 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.

대표청구항 ▼

I claim: 1. A photochromic ocular device selected from a contact lens and an intraocular device, comprising: (A) an organic polymeric material; and (B) at least one organic photochromic material able to change from a less radiation absorbing unactivated form to a more radiation absorbing activated

I claim: 1. A photochromic ocular device selected from a contact lens and an intraocular device, comprising: (A) an organic polymeric material; and (B) at least one organic photochromic material able to change from a less radiation absorbing unactivated form to a more radiation absorbing activated form upon exposure to actinic radiation; wherein said photochromic ocular device upon exposure to actinic radiation exhibits 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, and wherein the photochromic material of (B) is represented by Structure II: wherein, (a) R is a group which is represented by one of the following formulae: --A (formula IVA); --D--A (formula IVB); --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: --[(OC2H4)x(OC3H6 )y(OC4H8)z]--J wherein--J is selected from: hydroxy; (meth)acryloxy; 2-(methacryloxy)ethylcarbamyl; epoxy;--OCH2COOH;--OCH(CH3)COOH;--OC(O)(CH2)wCOOH;--OC6H4SO3H;--OC5H10SO3H;--OC4H8SO3H;--OC3H6SO3H;--OC2H4SO3H; and--OSO3H; 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--CH2--;--E--is represented by the following formula: --[(OC2H4)x(OC3H6 )y(OC4H8)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; (b) at least one R3 group in Structure II is attached at each of positions 6 and 11, each R3 is independently selected from the group R wherein R is--A,--EU, or--U, phenyl, mono-substituted phenyl, di-substituted phenyl, and the group--OR10, wherein R10 is C1-C6 alkyl, phenyl(C1-C3)-alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl or mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, the phenyl substituent being C1-C6 alkyl or C1-C6 alkoxy; or each R3 is independently a nitrogen-containing group selected from: (i)--N(R11)R12 wherein R11 and R12 are each independently selected from hydrogen, C1-C8 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, C1-C8 alkylaryl, C3-C20 cycloalkyl, C4-C20 bicycloalkyl, C5-C20 tricycloalkyl and C1-C20 alkoxyalkyl, wherein the aryl group is phenyl or naphthyl or R11 and R12 come together with the nitrogen atom to form a C3-C20 hetero-bicycloalkyl ring or a C4-C20 hetero-tricycloalkyl ring; (ii) a nitrogen containing ring represented by the following graphic formula VA: wherein each Y is independently selected for each occurrence from--CH2--,--CH(R13)--,--C(R13)(R13)--,--CH(aryl)-,--C(aryl)2-, and--C(R13)(aryl)-, and X is selected from--Y--,--O--,--S--,--S(O)--,--S(O2)--,--NH--,--N(R13)--and--N(aryl)-, wherein R13 is C1-C6 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 O, X is Y; (iii) a group represented by one of the following graphic formulae VB and VC: wherein R15, R16 and R17 are each independently selected for each occurrence in each formula from hydrogen, C1-C6 alkyl, phenyl and naphthyl, or the groups R15 and R16 together form a ring of 5 to 8 carbon atoms and each R14 is independently selected for each occurrence in each formula from C1-C6 alkyl, C1-C6 alkoxy, fluoro and chloro and p is the same as defined above; (iv) unsubstituted, mono-or di-substituted C4-C18 spirobicyclic amine; and (v) unsubstituted, mono-or di-substituted C4-C18 spirotricyclic amine; wherein substituents for (b)(iv) and (v) are independently selected for each occurrence from aryl, C1-C6 alkyl, C1-C6 alkoxy and phenyl(C1-C6)alkyl and n is selected from the integers 0, 1 and 2; (c) R5 and R6 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 R5 and R6 are each independently the group R, hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, allyl, phenyl, mono-substituted phenyl, benzyl, mono-substituted benzyl, chloro, fluoro, the group,--C(O)X', wherein X' is hydroxy, C1-C6 alkyl, C1-C6 alkoxy, phenyl, mono-substituted phenyl, amino, mono(C1-C6)alkylamino, or di(C1-C6)alkylamino; or R5 and R6 are each independently the group,--OR18, wherein R18 is C1-C6 alkyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4)alkyl, C3-C7 cycloalkyl, mono(C1-C4)alkyl substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, the group,--CH(R19)Y', wherein R19 is hydrogen or C1-C3 alkyl and Y' is CN, CF3, or COOR20 and R20 is hydrogen or C1-C3 alkyl; or R18 is the group,--C(O)Z, wherein Z is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, the unsubstituted, mono-or di-substituted aryl groups phenyl or naphthyl, phenoxy, mono-or di-(C1-C6)alkyl substituted phenoxy, mono-or di-(C1-C6)alkoxy substituted phenoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, phenylamino, mono-or di-(C1-C6)alkyl substituted phenylamino, or mono-or di-(C1-C6)alkoxy substituted phenylamino, each of said phenyl, benzyl and aryl group substituents being C1-C6 alkyl or C1-C6 alkoxy; (d) B is selected from the unsubstituted aryl groups, phenyl and naphthyl; and (e) B' is selected from: (i) the unsubstituted, mono-, di-or tri-substituted aryl groups, phenyl and 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 (e)(i) and (ii) being selected from the group R, C1-C6 alkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy, mono(C1-C6)alkoxy(C1-C4)alkyl, acryloxy, methacryloxy, bromo, chloro, fluoro, aryl, mono(C1-C6)alkoxyaryl, di(C1-C6)alkoxyaryl, mono(C1-C6)alkylaryl, di(C1-C6)alkylaryl, chloroaryl, fluoroaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkyloxy, C3-C7 cycloalkyloxy(C1-C6)alkyl, C3-C7 cycloalkyloxy(C1-C6)alkoxy, aryl(C1-C6)alkyl, aryl(C1-C6)alkoxy, aryloxy, aryloxy(C1-C6)alkyl, aryloxy(C1-C6)alkoxy, mono-or di-(C1-C6)alkylaryl(C1-C6)alkyl, mono-or di-(C1-C6)alkoxyaryl(C1-C6)alkyl, mono-or di-(C1-C6)alkylaryl(C1-C6)alkoxy, mono-or di-(C1-C6)alkoxyaryl(C1-C6)alkoxy, said aryl being phenyl or naphthyl; (iii) monosubstituted phenyl, having at the para position a substituent that is--(CH2)t--or--O--(CH2)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; (iv) the group represented by one of the following graphic formulae VIA or VIB: wherein L is carbon or oxygen and M is oxygen; each R21 is C1-C6 alkyl, C1-C6 alkoxy, hydroxy, chloro or fluoro; R22 and R23 are each hydrogen or C1-C6 alkyl; and q is the integer 0, 1 or 2; and (v) the group represented by the following graphic formula VIC: wherein P is hydrogen or C1-C4 alkyl and Q is an unsubstituted, mono-or di-substituted group, said group being selected from naphthyl, phenyl, furanyl and thienyl, each of said group substituents being C1-C4 alkyl, C1-C4 alkoxy, fluoro or chloro; provided that there is at least one R group or mono-R-substituted phenyl as a substituent on the photochromic material of (B) and if the mono-R-substituted phenyl group is B' said R group is one of formula IVA to IVF provided that--J of--A in formula IVA and IVB is not hydroxy, (meth)acryloxy or epoxy. 2. The photochromic ocular device of claim 1 wherein the photochromic materials of (B) are represented by Structure II wherein: (a) each R3 independently comprises the group R represented by formula: (IVA); (IVE); or (IVF) or the group--OR10, wherein R10 is C1-C4 alkyl, phenyl(C1-C2)alkyl, mono(C1-C4)alkyl substituted phenyl(C1-C2)alkyl, mono(C1-C4)alkoxy substituted phenyl(C1-C2)alkyl, C1-C4 alkoxy(C2-C4)alkyl, C5-C7 cycloalkyl or mono(C1-C3)alkyl substituted C5-C7 cycloalkyl and said phenyl substituents being C1-C3 alkyl or C1-C3 alkoxy; or each R3 is independently a nitrogen-containing group selected from: (i)--N(R11)R12, R11 and R12 each being independently selected from C1-C6 alkyl and phenyl; (ii) a nitrogen-containing ring represented by the graphic formula VA wherein each Y is--CH2--and X is independently selected from--Y--,--O--,--S--,--N(R13)--and--N(phenyl)-, R13 being C1-C6 alkyl, m being selected from the integers 1, 2 and 3, and p selected from the integers 0, 1, 2 and 3; (iii) a group represented by one of graphic formulae VB and VC wherein R15, R16 and R17 each are independently selected from hydrogen and C1-C5 alkyl, R14 is independently selected from hydrogen, C1-C4 alkyl, C1-4 alkoxy, fluoro and chloro; (iv) unsubstituted or mono-substituted C5-C18 spirobicyclic amine; and (v) unsubstituted or mono-substituted C5-C18 spirotricyclic amine; the substituents for (a)(iv) and (v) independently selected for each occurrence from phenyl, C1-C6 alkyl and C1-C6 alkoxy and n selected from the integers 1 and 2; (b) R5 and R6 are each independently selected from the group R, hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, chloro, fluoro and the group,--OR18, wherein R18 is C1-C3 alkyl, phenyl(C1-C2)alkyl, mono(C1-C3)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C3)alkoxy substituted phenyl(C1-C3)alkyl, C1-C3 alkoxy(C2-C4)alkyl, C1-C3 chloroalkyl, C1-C3 fluoroalkyl, the group,--CH(R19)Y', wherein R19 is hydrogen or C1-C2 alkyl and Y' is CN or COOR20, and R20 is hydrogen or C1-C2 alkyl, or R18 is the group,--C(O)Z, wherein Z is hydrogen, C1-C3 alkyl, C1-C3 alkoxy, phenyl, naphthyl, mono-substituted aryl groups, phenyl or naphthyl, phenoxy, mono-or di-(C1-C3)alkyl substituted phenoxy, mono-or di-(C1-C3)alkoxy substituted phenoxy, mono(C1-C3)alkylamino, phenylamino, mono-or di-(C1-C3)alkyl substituted phenylamino, or mono-or di-(C1-C3)alkoxy substituted phenylamino, and said aryl substituents being C1-C3 alkyl or C1-C3 alkoxy; (c) B is phenyl; and (d) B' is selected from: (i) phenyl, mono-substituted or di-substituted phenyl, each of said phenyl substituents being independently selected from the group R, awl, aryloxy, aryl(C1-C3)alkyl, C1-C3 alkyl, C1-C3 chloroalkyl, C1-C3 fluoroalkyl, C1-C3 alkoxy, mono(C1-C3)alkoxy(C1-C3)alkyl, chloro and fluoro; (ii) the groups represented by one of graphic formulae VIA and VIB: wherein L is carbon and M is oxygen, R21 is C1-C3 alkyl or C1-C3 alkoxy; R22 and R23 are each hydrogen or C1-C4 alkyl; and q is 0 or 1; and (iii) 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 C1-C3 alkyl, C1-C3 alkoxy or fluoro. 3. The photochromic ocular device of claim 2 wherein the photochromic material of (B) is represented by Structure II wherein: (a) each R3 is the group R represented by formula (IVE) or (IVF), or the group, OR10, wherein R10 is C1-C3 alkyl; or each R3 is selected from: (i)--N(R11)R12, R11 and R12 each independently being C1-C3 alkyl; (ii) a nitrogen-containing ring represented by graphic formula VA wherein each Y for each occurrence is--CH2--and X is independently selected from--Y--,--O--, and--N(R13)--, R13 being C1-C4 alkyl, m being selected from the integers 1 and 2, and p being selected from the integers 0, 1 and 2; and (iii) a group represented by graphic formula VC or VB wherein R15, R16, and R17 each independently comprise hydrogen and n is 1 or 2; (b) R5 and R6 are each independently the group R, hydrogen, C1-C4 alkyl, or the group,--OR18, wherein R18 is C1-C3 alkyl; (c) B is phenyl; and (d) B' is selected from phenyl, mono-and di-substituted phenyl, each of the phenyl substituents being selected from the group R, C1-C3 alkyl, C1-C3 alkoxy, phenyl, fluoro and chloro. 4. The photochromic ocular device of claim 2 wherein the photochromic material of (B) is selected 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-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; (e) 3,3-diphenyl-6,7,10,11-tetramethoxy-13-ethyl-13-(2-{2-[N-(2-methacryloxyethyl)carbamoyloxy]ethoxy}ethoxy)-3H,13H-indeno[2,'3,'3,4] naphtho[1,2-b]pyran; (f) 3-(4-methoxyphenyl)-3-phenyl-6,11-dimethoxy-13-methyl-13-(2-(2-hydroxyethyl)ethoxy)-3H,13H-indeno[2,'3,'3,4]-naphtho-[1,2-b]pyran; and (i) mixtures thereof. 5. The photochromic ocular device of claim 1 wherein the photochromic material of (B) is selected 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 photochromic compound with external materials; (f) a photochromic polymer; and (g) mixtures thereof. 6. The photochromic ocular device of claim 1 further comprising at least one other photochromic material (c) that is different from the photochromic material of (B). 7. The photochromic ocular device of claim 6 wherein photochromic compound (c) is an organic photochromic compound. 8. The photochromic ocular device of claim 7 wherein photochromic compound (c) is an organic photochromic compound and is selected from chromenes; spiropyrans; oxazines; mercury dithizonates, fulgides, fulgimides or mixtures thereof. 9. The photochromic ocular device of claim 8 wherein the chromene photochromic compound (c) is selected from naphthopyrans, benzopyrans, indenonaphthopyrans, phenanthropyrans and mixtures thereof. 10. The photochromic ocular device of claim 9 wherein the chromene photochromic compound (c) is selected from naphthopyrans, indenonaphthopyrans, and mixtures thereof. 11. The photochromic ocular device of claim 6 wherein photochromic material (c) is selected 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; and (g) mixtures thereof. 12. The photochromic ocular device of claim 1 wherein the organic polymeric material is a polymer prepared from a monomer selected 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 and mixtures thereof. 13. 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. 14. 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. 15. The photochromic ocular device of claim 14 wherein the at least one hydrophilic monomer is selected from: unsaturated carboxylic acids; (meth)acrylic substituted alcohols; vinyl lactams; (meth)acrylamides; and mixtures thereof. 16. The photochromic ocular device of claim 14 wherein the at least one crosslinking agent is selected from divinylbenzene; di-or tri(meth)acrylates of diethyleneglycol, triethyleneglycol, butyleneglycol or hexane-1,6-diol; and mixtures thereof. 17. The photochromic ocular device of claim 14 wherein the hydrogel polymer further comprises at least one silicone-containing monomer comprising at least one unsaturated group. 18. The photochromic ocular device of claim 17 wherein the at least one silicone-containing monomer is selected from methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanyl methyl methacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, methyldi(trimethylsiloxy)methacryloxymethyl silane, 3-[tris(trimethylsiloxy)silyl]propylvinylcarbamate, and 3-[tris(trimethylsiloxy)silyl]propylvinylcarbonate. 19. The photochromic ocular device of claim 1 further comprising at least one non-photochromic ultraviolet absorbing material. 20. The photochromic ocular device of claim 19 wherein the at least one ultraviolet absorbing material is a monomer selected from: 2-(2'-hydroxy-5'-methacryloxyethyl-phenyl)-2H-benzotriazole; 2-(2'-hydroxy-5'-methacryloxyethyl-phenyl)-6-chloro-2H-benzotriazole; 2-(2'-hydroxy-5'-methacryloxy-propyl phenyl)-5-chloro-2H-benzotriazole; 2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butylphenyl)-2H-benzotriazole; 2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butyl phenyl)-5-chloro-2H-benzotriazole; 2-[2'-hydroxy-5'-(2-methacryloyloxyethoxy)-3'-tert-butyl phenyl]-5-methoxy-2H-benzotriazole; 2-[2'-hydroxy-5'-(gamma-methacryloyloxypropoxy)-3'-tert-butyl phenyl]-5-methoxy-2H-benzotriazole; 2-(3'-t-butyl-2'-hydroxy-5'-methoxyphenyl)-5-(3'-methacryloyloxypropoxy) benzotriazole and mixtures thereof.