Claims
- 1. A radiation-curable prepolymer obtained by reacting an ethylenically unsaturated amine or an ethylenically unsaturated monohydroxy compound or a mixture thereof with an isocyanate-capped polyurethane, wherein said isocyanate-capped polyurethane is copolymerization product of:
(a) at least one polyalkylene glycol of formula HO—(R1—O)n—(R2—O)m—(R3—O)p—H (1) wherein R1, R2, and R3, independently of one other, are each linear or branched C2-C4-alkylene, and n, m and p, independently of one another, are each a number from 0 to 100, wherein the sum of (n+m+p) is 5 to 100, (b) at least one branching agent selected from the group consisting of
(i) a linear or branched aliphatic polyhydroxy compound of formula R4—(OH)x (2), wherein R4 is a linear or branched C2-C18 aliphatic multi-valent radical and x is a number≧3,
(ii) a polyether polyol, which is the polymerization product of a compound of formula (2) and a glycol, (iii) a polyester polyol, which is the polymerization product of a compound of formula (2), a dicarboxylic acid or a derivative thereof and a diol, and (iv) a cycloaliphatic polyol selected from the group consisting of a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is unsubstituted by alkyl radical, a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is substituted by one ore more C1-C4 alkyl radicals, and an unsubstituted mono- and disaccharide, and (v) an aralkyl polyol having at least three hydroxy C1-C4 alkyl radicals, and (c) at least one di- or polyisocyanate of formula R5—(NCO)y (3) wherein R5 is the radical of an aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic or araliphatic di- or polyisocyanate and y is a number from 2 to 6, wherein said ethylenically unsaturated monohydroxy compound is a hydroxy-substituted lower alkylacrylate, a hydroxy-substituted lower alkylmethacrylate, a hydroxy-substituted lower alkyl-acrylamides, a hydroxy-substituted lower alkyl-methacrylamide, or a hydroxy-substituted lower alkylvinylether, wherein said ethylenically unsaturated amine has formula (4), (4′) or (4″) 3In which, l, j and k, independent of one another, are o or 1; R6 is hydrogen, a linear or branched C1-C24 alkyl, a C2-C24 alkoxyalkyl, a C2-C24 alkylcarbonyl, a C2-C24 alkoxycarbonyl, an unsubstituted or C1-C4 alkyl- or C1-C4 alkoxy-substituted C6-C10 aryl, a C7-C18 aralkyl, a C13-C22 arylalkylaryl, a C3-C8 cycloalkyl, a C4-C14cycloalkylalkyl, a C7-C18 cycloalkylalkylcycloalkyl, a C5-C20 alkylcycloalkylalkyl, or an aliphatic-heterocyclic radical; Z is a C1-C12 alkylene radical, phenylene radical or C7-C12 aralkylene radical; R7 and R7′, independently of each other, are hydrogen, C1-C4 alkyl or halogen; and Q is a radical of formula (5) 4wherein q is the number 0 or 1, each of R8 and R9 independently of the other is hydrogen, C1-C4 alkyl, phenyl, carboxy or halogen, R10 is hydrogen, C1-C4 alkyl or halogen, and Z′ is a linear or branched C1-C12 alkylene, an unsubstituted phenylene, an C1-C4 alkyl- or C1-C4 alkoxy-substituted phenylene, or a C7-C12 aralkylene.
- 2. A radiation-curable prepolymer of claim 1, wherein component (a) consists of one or more polyalkylene glycols of formula (1a)
- 3. A radiation-curable prepolymer of claim 2, wherein said ethylenically unsaturated amine is 2-terbutylaminoethylmethacrylate or 2-terbutylaminoethylacrylate, wherein said ethylenically unsaturated hydroxy compound is 2-hydroxyethylmethacrylate or 2-hydroxyehtylcrylate, wherein component (c) consists of a diisocyanate selected from the group consisting isophorone diisocyanate (IPDI), toluylene-2,4-diisocyanate (TDI), methylenebis(cyclohexyl-isocyanate), 1,6-diisocyanato-2,2,4-trimethyl-n-hexane (TMDI), methylenebis(phenyl-isocyanate) and hexamethylene-diisocyanate (HMDI).
- 4. A radiation-curable prepolymer of claim 1, wherein component (a) consists of one or more polyalkylene glycols of formula (1a)
- 5. A radiation-curable prepolymer of claim 4, wherein said ethylenically unsaturated amine is 2-terbutylaminoethylmethacrylate or 2-terbutylaminoethylacrylate, wherein said ethylenically unsaturated hydroxy compound is 2-hydroxyethylmethacrylate or 2-hydroxyehtylcrylate, wherein component (c) consists of a diisocyanate selected from the group consisting isophorone diisocyanate (IPDI), toluylene-2,4-diisocyanate (TDI), methylenebis(cyclohexyl-isocyanate), 1,6-diisocyanato-2,2,4-trimethyl-n-hexane (TMDI), methylenebis(phenyl-isocyanate) and hexamethylene-diisocyanate (HMDI).
- 6. A radiation-curable prepolymer of claim 1,
wherein component (a) consists of at least one poly(ethylene glycol) and at least one hydroxy-terminated poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) or poly(propylene glycol)-poly(ethylene glycol)-poly(propylene glycol) tri-block copolymers, wherein component (b) consists of one or more linear or branched aliphatic polyhydroxy compounds of formula R4—(OH)x (2) wherein R4 is a linear or branched C3-C18 aliphatic multi-valent radical and x is a number from 3 to 8, and wherein component (c) consists of one or more diisocyanates of formula OCN—R5—NCO (3a), wherein R5 is a linear or branched C3-C18-alkylene, an unsubstituted or C1-C4-alkyl-substituted or C1-C4-alkoxy-substituted C6-C10-arylene, a C7-C18-aralkylene, a C6-C10-arylene-C1-C2-alkylene-C6-C10-arylene, a C3-C8-cyclo-alkylene, a C3-C8cycloalkylene-C1-C6-alkylene, a C3-C8-cycloalkylene-C1-C2-alkylene-C3-C8-cycloalkylene, or a C1-C6-alkylene-C3-C8-cycloalkylene-C1-C6-alkylene, wherein said ethylenically unsaturated amine is selected from the group consisting of mono-C1-C4 alkylamino-C1-C4 alkyl-acrylates, mono-C1-C4 alkylamino-C1-C4 alkyl-methacrylates, di-C1-C4alkylamino-C1-C4alkyl-acrylates and di-C1-C4alkylamino-C1-C4 alkyl-methacrylates, and wherein said ethylenically unsaturated hydroxy compound is selected from the group consisting of hydroxy-substituted C1-C6 alkylacrylates and hydroxy-substituted C1-C6 alkylmethacrylates.
- 7. A radiation-curable prepolymer of claim 6, wherein said ethylenically unsaturated amine is 2-terbutylaminoethylmethacrylate or 2-terbutylaminoethylacrylate, wherein said ethylenically unsaturated hydroxy compound is 2-hydroxyethylmethacrylate or 2-hydroxyehtylcrylate, and wherein component (c) consists of a diisocyanate selected from the group consisting isophorone diisocyanate (IPDI), toluylene-2,4-diisocyanate (TDI), methylenebis(cyclohexylisocyanate), 1,6-diisocyanato-2,2,4-trimethyl-n-hexane (TMDI), methylenebis(phenylisocyanate) and hexamethylene-diisocyanate (HMDI)
- 8. A radiation-curable prepolymer of claim 6, wherein component (b) consists of one or more polyhydroxy compounds selected from the group consisting of glycerol, diglycerol, triglycerol, 1,1,1-trishydroxymethylethane, 1,1,1-trishydroxymethylpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, erythritol, pentaerythritol, di- and tripentaerythritol, arabitol, sorbitol, disorbitol and mannitol and mixtures thereof, and wherein R5 signifies linear or branched C6-C10-alkylene, cyclohexylene-methylene or cyclohexylene-methylene-cyclohexylene either unsubstituted or substituted in the cyclohexyl moiety by 1 to 3 methyl groups, or phenylene or phenylene-methylene-phenylene either unsubstituted or substituted in the phenyl moiety by methyl.
- 9. A radiation-curable prepolymer of claim 8, wherein said ethylenically unsaturated amine is 2-terbutylaminoethylmethacrylate or 2-terbutylaminoethylacrylate, and wherein said ethylenically unsaturated hydroxy compound is 2-hydroxyethylmethacrylate or 2-hydroxyehtylcrylate, wherein component (c) consists of a diisocyanate selected from the group consisting isophorone diisocyanate (IPDI), toluylene-2,4-diisocyanate (TDI), methylenebis(cyclohexylisocyanate), 1,6-diisocyanato-2,2,4-trimethyl-n-hexane (TMDI), methylenebis(phenylisocyanate) and hexamethylene-diisocyanate (HMDI).
- 10. A method for producing a radiation-curable prepolymer, comprising the steps of:
(I) preparing a melted reaction mixture which is at least substantially free of a solvent, the melted reaction mixture comprising the components of (a) one or more polyalkylene glycols, (b) one or more branching agents, and (c) at least one di- or polyisocyanate, wherein the stoichiometry of components (a), (b) and (c) in the melted reaction mixture is chosen so that the number of NCO equivalents of component (c) is greater than the sum of OH equivalents of components (a) and (b); (II) reacting components (a) and (b) with component (c) in the melted reaction mixture at a desired temperature to form an isocyanate-capping polyurethane; and (III) reacting the formed isocyanate-capping polyurethane, without intermediate isolation, with a radiation-curable group-capping agent, which is an ethylenically unsaturated amine (primary or secondary amine) of formula (4), (4′) or (4″) or an ethylenically unsaturated monohydroxy compound, to prepare the radiation-curable polyurethane prepolymer, wherein the one or more polyalkylene glycols of component (a) are defined by formula (1) HO—(R1—O)n—(R2—O)m—(R3—O)p—H (1) wherein R1, R2, and R3, independently of one other, are each linear or branched C2-C4-alkylene, and n, m and p, independently of one another, are each a number from 0 to 100, wherein the sum of (n+m+p) is 5 to 100, wherein the one or more branching agents are selected from the group consisting of
(i) a linear or branched aliphatic polyhydroxy compound of formula R4—(OH)x (2), wherein R4 is a linear or branched C2-C18 aliphatic multi-valent radical and x is a number≧3,
(ii) a polyether polyol, which is the polymerization product of a compound of formula (2) and a glycol, (iii) a polyester polyol, which is the polymerization product of a compound of formula (2), a dicarboxylic acid or a derivative thereof and a diol, and (iv) a cycloaliphatic polyol selected from the group consisting of a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is unsubstituted by alkyl radical, a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is substituted by one ore more C1-C4 alkyl radicals, and an unsubstituted mono- and disaccharide, and (v) an aralkyl polyol having at least three hydroxy C1-C4 alkyl radicals, wherein the at least one di- or polyisocyanate is defined by formula (3) R5—(NCO)y (3) wherein R5 is the radical of an aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic or araliphatic di- or polyisocyanate and y is a number from 2 to 6, wherein said ethylenically unsaturated monohydroxy compound is a hydroxy-substituted lower alkylacrylate, a hydroxy-substituted lower alkylmethacrylate, a hydroxy-substituted lower alkyl-acrylamides, a hydroxy-substituted lower alkylmethacrylamide, or a hydroxy-substituted lower alkylvinylether, wherein said ethylenically unsaturated amine has formula (4), (4′) or (4″) 5In which, l, j and k, independent of one another, are o or 1; R6 is hydrogen, a linear or branched C1-C24 alkyl, a C2-C24 alkoxyalkyl, a C2-C24 alkylcarbonyl, a C2-C24 alkoxycarbonyl, an unsubstituted or C1-C4 alkyl- or C1-C4 alkoxy-substituted C6-C10 aryl, a C7-C18 aralkyl, a C13-C22 arylalkylaryl, a C3-C8 cycloalkyl, a C4-C14cycloalkylalkyl, a C7-C18 cycloalkylalkylcycloalkyl, a C5-C20 alkylcycloalkylalkyl, or an aliphatic-heterocyclic radical; Z is a C1-C12 alkylene radical, phenylene radical or C7-C12 aralkylene radical; R7 and R7′, independently of each other, are hydrogen, C1-C4 alkyl or halogen; and Q is a radical of formula (5) 6wherein q is the number 0 or 1, each of R8 and R9 independently of the other is hydrogen, C1-C4 alkyl, phenyl, carboxy or halogen, R10 is hydrogen, C1-C4 alkyl or halogen, and Z′ is a linear or branched C1-C12 alkylene, an unsubstituted phenylene, an C1-C4 alkyl- or C1-C4 alkoxy-substituted phenylene, or a C7-C12 aralkylene.
- 11. A method of claim 10, wherein the melted reaction mixture further comprises a catalyst selected from the group consisting of alkali metal salts of organic carboxylic acids, tertiary amines, and tin salts of organic carboxylic acids.
- 12. A method of claim 10, wherein the melted reaction mixture further comprises a catalyst selected from the group consisting of (C1-C6-alkyl)3N (triethylamine, tri-n-butylamine), N-methylpyrrolidine, N-methylmorpholine, N,N-dimethylpiperidine, pyridine, 1,4-diaza-bicyclooctane, dibutyl tin dilaurate, and tin dioctoate.
- 13. A method of claim 10, wherein said ethylenically unsaturated amine is selected from the group consisting of mono-C1-C4 alkylamino-C1-C4 alkyl-acrylates, mono-C1-C4 alkylamino-C1-C4 alkyl-methacrylates, di-C1-C4 alkylamino-C1-C4 alkyl-acrylates and di-C1-C4 alkylamino-C1-C4 alkyl-methacrylates, and wherein said ethylenically unsaturated hydroxy compound is selected from the group consisting of hydroxy-substituted C1-C6 alkylacrylates and hydroxy-substituted C1-C6 alkylmethacrylates.
- 14. A method of claim 13, wherein component (a) consists of one or more polyalkylene glycols of formula (1a)
- 15. A method of claim 13, wherein component (a) consists of one or more polyalkylene glycols of formula (1a)
- 16. A method of claim 13, wherein component (a) consists of one or more polyalkylene glycols of formula (1a)
- 17. A method of claim 13, wherein component (a) consists of at least one poly(ethylene glycol) and at least one hydroxy-terminated poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) or poly(propylene glycol)-poly(ethylene glycol)-poly(propylene glycol) tri-block copolymers, wherein component (b) consists of one or more linear or branched aliphatic polyhydroxy compounds of formula (2)
- 18. A method of claim 17, wherein component (b) consists of one or more polyhydroxy compounds selected from the group consisting of glycerol, diglycerol, triglycerol, 1,1,1-trishydroxymethylethane, 1,1,1-trishydroxymethylpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, erythritol, pentaerythritol, di- and tripentaerythritol, arabitol, sorbitol, disorbitol and mannitol and mixtures thereof, and wherein R5 signifies linear or branched C6-C10-alkylene, cyclohexylene-methylene or cyclohexylene-methylene-cyclohexylene either unsubstituted or substituted in the cyclohexyl moiety by 1 to 3 methyl groups, or phenylene or phenylene-methylene-phenylene either unsubstituted or substituted in the phenyl moiety by methyl.
- 19. A polymer obtained by crosslinking with an actinic radiation mean a radiation-curable prepolymer in the presence of or in the absence of one or more additional vinylic comonomers, wherein said radiation-curable prepolymer is a reaction product of an ethylenically unsaturated amine or an ethylenically unsaturated monohydroxy compound or a mixture thereof with an isocyanate-capped polyurethane, wherein said isocyanate-capped polyurethane is a copolymerization product of the components of:
(a) at least one polyalkylene glycol of formula HO—(R1—O)n—(R2—O)m—(R3—O)p—H (1) wherein R1, R2, and R3, independently of one other, are each linear or branched C2-C4-alkylene, and n, m and p, independently of one another, are each a number from 0 to 100, wherein the sum of (n+m+p) is 5 to 100, (b) at least one branching agent selected from the group consisting of
(ii) a linear or branched aliphatic polyhydroxy compound of formula R4—(OH)x (2), wherein R4 is a linear or branched C2-C18 aliphatic multi-valent radical and x is a number≧3,
(ii) a polyether polyol, which is the polymerization product of a compound of formula (2) and a glycol, (iii) a polyester polyol, which is the polymerization product of a compound of formula (2), a dicarboxylic acid or a derivative thereof and a diol, and (iv) a cycloaliphatic polyol selected from the group consisting of a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is unsubstituted by alkyl radical, a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is substituted by one ore more C1-C4 alkyl radicals, and an unsubstituted mono- and disaccharide, and (v) an aralkyl polyol having at least three hydroxy C1-C4 alkyl radicals, and (c) at least one di- or polyisocyanate of formula R5—(NCO)y (3) wherein R5 is the radical of an aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic or araliphatic di- or polyisocyanate and y is a number from 2 to 6, wherein said ethylenically unsaturated monohydroxy compound is a hydroxy-substituted lower alkylacrylate, a hydroxy-substituted lower alkylmethacrylate, a hydroxy-substituted lower alkyl-acrylamides, a hydroxy-substituted lower alkyl-methacrylamide, or a hydroxy-substituted lower alkylvinylether, wherein said ethylenically unsaturated amine has formula (4), (4′) or (4″) 7In which, l, j and k, independent of one another, are o or 1; R6 is hydrogen, a linear or branched C1-C24 alkyl, a C2-C24 alkoxyalkyl, a C2-C24 alkylcarbonyl, a C2-C24 alkoxycarbonyl, an unsubstituted or C1-C4 alkyl- or C1-C4 alkoxy-substituted C6-C10 aryl, a C7-C18 aralkyl, a C13-C22 arylalkylaryl, a C3-C8 cycloalkyl, a C4-C14 cycloalkylalkyl, a C7-C18 cycloalkylalkylcycloalkyl, a C5-C20 alkylcycloalkylalkyl, or an aliphatic-heterocyclic radical; Z is a C1-C12 alkylene radical, phenylene radical or C7-C12 aralkylene radical; R7 and R7′, independently of each other, are hydrogen, C1-C4 alkyl or halogen; and Q is a radical of formula (5) 8wherein q is the number 0 or 1, each of R8 and R9 independently of the other is hydrogen, C1-C4 alkyl, phenyl, carboxy or halogen, R10 is hydrogen, C1-C4 alkyl or halogen, and Z′ is a linear or branched C1-C12 alkylene, an unsubstituted phenylene, an C1-C4 alkyl- or C1-C4 alkoxy-substituted phenylene, or a C7-C12 aralkylene.
- 20. A medical device, wherein the medical device is obtained by curing, in a mold with an actinic radiation mean, (I) an essentially solvent-free liquid or melt of a radiation-curable prepolymer in the presence of or in the absence of one or more additional vinylic comonomers, or (II) an aqueous solution of said radiation-curable prepolymer in the presence of or in the absence of one or more additional vinylic comonomers, wherein said radiation-curable prepolymer is a reaction product of an ethylenically unsaturated amine or an ethylenically unsaturated monohydroxy compound or a mixture thereof with an isocyanate-capped polyurethane, wherein said isocyanate-capped polyurethane is a copolymerization product of the components of:
(a) at least one polyalkylene glycol of formula HO—(R1—O)n—(R2—O)m—(R3—O)p—H (1) wherein R1, R2, and R3, independently of one other, are each linear or branched C2-C4-alkylene, and n, m and p, independently of one another, are each a number from 0 to 100, wherein the sum of (n+m+p) is 5 to 100, (b) at least one branching agent selected from the group consisting of
(iii) a linear or branched aliphatic polyhydroxy compound of formula R4—(OH)x (2), wherein R4 is a linear or branched C2-C18 aliphatic multi-valent radical and x is a number≧3,
(ii) a polyether polyol, which is the polymerization product of a compound of formula (2) and a glycol, (iii) a polyester polyol, which is the polymerization product of a compound of formula (2), a dicarboxylic acid or a derivative thereof and a diol, and (iv) a cycloaliphatic polyol selected from the group consisting of a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is unsubstituted by alkyl radical, a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is substituted by one ore more C1-C4 alkyl radicals, and an unsubstituted mono- and disaccharide, and (v) an aralkyl polyol having at least three hydroxy C1-C4 alkyl radicals, and (c) at least one di- or polyisocyanate of formula R5—(NCO)y (3) wherein R5 is the radical of an aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic or araliphatic di- or polyisocyanate and y is a number from 2 to 6, wherein said ethylenically unsaturated monohydroxy compound is a hydroxy-substituted lower alkylacrylate, a hydroxy-substituted lower alkylmethacrylate, a hydroxy-substituted lower alkyl-acrylamides, a hydroxy-substituted lower alkyl-methacrylamide, or a hydroxy-substituted lower alkylvinylether, wherein said ethylenically unsaturated amine has formula (4), (4′) or (4″) 9In which, l, j and k, independent of one another, are o or 1; R6 is hydrogen, a linear or branched C1-C24 alkyl, a C2-C24 alkoxyalkyl, a C2-C24 alkylcarbonyl, a C2-C24 alkoxycarbonyl, an unsubstituted or C1-C4 alkyl- or C1-C4 alkoxy-substituted C6-C10 aryl, a C7-C18 aralkyl, a C13-C22 arylalkylaryl, a C3-C8 cycloalkyl, a C4-C14 cycloalkylalkyl, a C7-C18 cycloalkylalkylcycloalkyl, a C5-C20 alkylcycloalkylalkyl, or an aliphatic-heterocyclic radical; Z is a C1-C12 alkylene radical, phenylene radical or C7-C12 aralkylene radical; R7 and R7′, independently of each other, are hydrogen, C1-C4 alkyl or halogen; and Q is a radical of formula (5) 10wherein q is the number 0 or 1, each of R8 and R9 independently of the other is hydrogen, C1-C4 alkyl, phenyl, carboxy or halogen, R10 is hydrogen, C1-C4 alkyl or halogen, and Z′ is a linear or branched C1-C12 alkylene, an unsubstituted phenylene, an C1-C4 alkyl- or C1-C4 alkoxy-substituted phenylene, or a C7-C12 aralkylene.
- 21. A medical device of claim 20, wherein said medical device is an ophthalmic device.
- 22. An ophthalmic device of claim 21, wherein the curing is effected by UV irradiation in the presence of or in the absence of a photoinitiator.
- 23. An ophthalmic device of claim 21, wherein component (a) consists of one or more polyalkylene glycols of formula (1a)
- 24. An opthalmic device of claim 23, wherein said ethylenically unsaturated amine is 2-terbutylaminoethylmethacrylate or 2-terbutylaminoethylacrylate, wherein said ethylenically unsaturated hydroxy compound is 2-hydroxyethylmethacrylate or 2-hydroxyehtylcrylate, and wherein component (c) consists of a diisocyanate selected from the group consisting isophorone diisocyanate (IPDI), toluylene-2,4-diisocyanate (TDI), methylenebis(cyclohexyl-isocyanate), 1,6-diisocyanato-2,2,4-trimethyl-n-hexane (TMDI), methylenebis(phenyl-isocyanate) and hexamethylene-diisocyanate (HMDI).
- 25. An ophthalmic device of claim 21, wherein component (a) consists of one or more polyalkylene glycols of formula (1a)
- 26. An ophthalmic device of claim 21, wherein component (c) consists of a diisocyanate selected from the group consisting isophorone diisocyanate (IPDI), toluylene-2,4-diisocyanate (TDI), methylenebis(cyclohexyl-isocyanate), 1,6-diisocyanato-2,2,4trimethyl-n-hexane (TMDI), methylenebis(phenyl-isocyanate) and hexamethylene-diisocyanate (HMDI), wherein said ethylenically unsaturated amine is 2-terbutylaminoethylmethacrylate or 2-terbutylaminoethylacrylate, and wherein said ethylenically unsaturated hydroxy compound is 2-hydroxyethylmethacrylate or 2-hydroxyehtylcrylate.
- 27. An ophthalmic device of claim 21, wherein component (a) consists of at least one poly(ethylene glycol) and at least one hydroxy-terminated poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) or poly(propylene glycol)-poly(ethylene glycol)-poly(propylene glycol) tri-block copolymers,
wherein component (b) consists of one or more linear or branched aliphatic polyhydroxy compounds of formula (2) R4—(OH)x (2) wherein R4 is a linear or branched C3-C18 aliphatic multi-valent radical and x is a number from 3 to 8, and wherein component (c) consists of one or more diisocyanates of formula OCN—R5—NCO (3a), wherein R5 is a linear or branched C3-C18-alkylene, an unsubstituted or C1-C4-alkyl-substituted or C1-C4-alkoxy-substituted C6-C10-arylene, a C7-C18-aralkylene, a C6-C10-arylene-C1-C2-alkylene-C6-C10-arylene, a C3-C8-cyclo-alkylene, a C3-C8cycloalkylene-C1-C6-alkylene, a C3-C8-cycloalkylene-C1-C2-alkylene-C3-C8-cycloalkylene, or a C1-C6-alkylene-C3-C8-cycloalkylene-C1-C6-alkylene, wherein said ethylenically unsaturated amine is selected from the group consisting of mono-C1-C4alkylamino-C1-C4 alkyl-acrylates, mono-C1-C4alkylamino-C1-C4 alkyl-methacrylates, di-C1-C4 alkylamino-C1-C4 alkyl-acrylates and di-C1-C4 alkylamino-C1-C4 alkyl-methacrylates, and wherein said ethylenically unsaturated hydroxy compound is selected from the group consisting of hydroxy-substituted C1-C6 alkylacrylates and hydroxy-substituted C1-C6 alkylmethacrylates.
- 28. An ophthalmic device of claim 27, wherein R5 signifies linear or branched C6-C1--alkylene, cyclohexylene-methylene or cyclohexylene-methylene-cyclohexylene either unsubstituted or substituted in the cyclohexyl moiety by 1 to 3 methyl groups, or phenylene or phenylene-methylene-phenylene either unsubstituted or substituted in the phenyl moiety by methyl.
- 29. An ophthalmic device of claim 28, wherein said ethylenically unsaturated amine is 2-terbutylaminoethylmethacrylate or 2-terbutylaminoethylacrylate, wherein said ethylenically unsaturated hydroxy compound is 2-hydroxyethylmethacrylate or 2-hydroxyehtylcrylate, and wherein component (c) consists of a diisocyanate selected from the group consisting isophorone diisocyanate (IPDI), toluylene-2,4-diisocyanate (TDI), methylenebis(cyclohexylisocyanate), 1,6-diisocyanato-2,2,4-trimethyl-n-hexane (TMDI), methylenebis(phenylisocyanate) and hexamethylene-diisocyanate (HMDI).
- 30. An ophthalmic device of claim 21, wherein said ophthalmic device is a contact lens characterized by having a water content of from about 30% to about 80%, an eleongation at break of at least 200%, and a modulus of from about 0.01 to about 1.8 N/mm2.
- 31. A method for making a contact lens, comprising the steps of:
(I) introducing a radiation-curable prepolymer, which is liquid or readily meltable, and which is essentially free from solvents, into a mold, in the presence or in the absence of one or more additional vinylic comonomers, and optionally in the presence of a photo-initiator; (II) initiating by UV irradiation photo-crosslinking of the radiation-curable prepolymer; and (III) opening the mold so that the contact lens can be removed from the mold, wherein said radiation-curable prepolymer is obtained by reacting an ethylenically unsaturated amine or an ethylenically unsaturated monohydroxy compound or a mixture thereof with an isocyanate-capped polyurethane, wherein said isocyanate-capped polyurethane is copolymerization product of:
(a) at least one polyalkylene glycol of formula HO—(R1—O)n—(R2—O)m—(R3—O)p—H (1) wherein R1, R2, and R3, independently of one other, are each linear or branched C2-C4-alkylene, and n, m and p, independently of one another, are each a number from 0 to 100, wherein the sum of (n+m+p) is 5 to 100,
(b) at least one branching agent selected from the group consisting of
(i) a linear or branched aliphatic polyhydroxy compound of formula R4—(OH)x (2), wherein R4 is a linear or branched C2-C18 aliphatic multi-valent radical and x is a number≧3, (ii) a polyether polyol, which is the polymerization product of a compound of formula (2) and a glycol, (iii) a polyester polyol, which is the polymerization product of a compound of formula (2), a dicarboxylic acid or a derivative thereof and a diol, and (iv) a cycloaliphatic polyol selected from the group consisting of a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is unsubstituted by alkyl radical, a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is substituted by one ore more C1-C4 alkyl radicals, and an unsubstituted mono- and disaccharide, and (v) an aralkyl polyol having at least three hydroxy C1-C4 alkyl radicals, and (c) at least one di- or polyisocyanate of formula R5—(NCO)y (3) wherein R5 is the radical of an aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic or araliphatic di- or polyisocyanate and y is a number from 2 to 6, wherein said ethylenically unsaturated monohydroxy compound is a hydroxy-substituted lower alkylacrylate, a hydroxy-substituted lower alkylmethacrylate, a hydroxy-substituted lower alkyl-acrylamides, a hydroxy-substituted lower alkyl-methacrylamide, or a hydroxy-substituted lower alkylvinylether, wherein said ethylenically unsaturated amine has formula (4), (4′) or (4″) 11In which, l, j and k, independent of one another, are o or 1; R6 is hydrogen, a linear or branched C1-C24 alkyl, a C2-C24 alkoxyalkyl, a C2-C24 alkylcarbonyl, a C2-C24 alkoxycarbonyl, an unsubstituted or C1-C4 alkyl- or C1-C4 alkoxy-substituted C6-C10 aryl, a C7-C18 aralkyl, a C13-C22 arylalkylaryl, a C3-C8 cycloalkyl, a C4-C14 cycloalkylalkyl, a C7-C18 cycloalkylalkylcycloalkyl, a C5-C20 alkylcycloalkylalkyl, or an aliphatic-heterocyclic radical; Z is a C1-C12 alkylene radical, phenylene radical or C7-C12 aralkylene radical; R7 and R7′, independently of each other, are hydrogen, C1-C4 alkyl or halogen; and Q is a radical of formula (5) 12wherein q is the number 0 or 1, each of R8 and R9 independently of the other is hydrogen, C1-C4 alkyl, phenyl, carboxy or halogen, R10 is hydrogen, C1-C4 alkyl or halogen, and Z1 is a linear or branched C1-C12 alkylene, an unsubstituted phenylene, an C1-C4 alkyl- or C1-C4 alkoxy-substituted phenylene, or a C7-C12 aralkylene.
- 32. A method of claim 31, wherein said radiation-curable prepolymer is substantially purified before introducing step.
- 33. A method of claim 32, further comprising the step of (IV) hydrating said contact lens in water, in an aqueous salt solution having an osmolarity of about 200 to 450 mOsm/ml, or in a mixture of water or an aqueous salt solution with a physiologically compatible polar organic solvent.
- 34. A method for making a contact lens, comprising the steps of:
(I) introducing an aqueous solution of a radiation-curable prepolymer having a concentration of from 30% to 90% by weight, into a mold, wherein the aqueous solution optionally contains one or more compounds selected from the group consisting of physiologically compatible salts, isotonizing agents conventionally used in the field of contact lens care, vinylic comonomers and photo-initiators; (II) initiating by UV irradiation photo-crosslinking of the radiation-curable prepolymer; and (III)opening the mold so that the contact lens is removed from the mold, wherein said radiation-curable prepolymer is obtained by reacting an ethylenically unsaturated amine or an ethylenically unsaturated monohydroxy compound or a mixture thereof with an isocyanate-capped polyurethane, wherein said isocyanate-capped polyurethane is copolymerization product of:
(a) at least one polyalkylene glycol of formula HO—(R1—O)n‘3(R2—O)m—(R3—O)p—H (1) wherein R1, R2, and R3, independently of one other, are each linear or branched C2-C4-alkylene, and n, m and p, independently of one another, are each a number from 0 to 100, wherein the sum of (n+m+p) is 5 to 100,
(b) at least one branching agent selected from the group consisting of
(i) a linear or branched aliphatic polyhydroxy compound of formula R4—(OH)x (2), wherein R4 is a linear or branched C2-C18 aliphatic multi-valent radical and x is a number≧3, (ii) a polyether polyol, which is the polymerization product of a compound of formula (2) and a glycol, (iii) a polyester polyol, which is the polymerization product of a compound of formula (2), a dicarboxylic acid or a derivative thereof and a diol, and (iv) a cycloaliphatic polyol selected from the group consisting of a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is unsubstituted by alkyl radical, a C5-C8-cycloalkane which is substituted by ≧3 hydroxy groups and which is substituted by one ore more C1-C4 alkyl radicals, and an unsubstituted mono- and disaccharide, and (v) an aralkyl polyol having at least three hydroxy C1-C4 alkyl radicals, and (c) at least one di- or polyisocyanate of formula R5—(NCO)y (3) wherein R5 is the radical of an aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic or araliphatic di- or polyisocyanate and y is a number from 2 to 6, wherein said ethylenically unsaturated monohydroxy compound is a hydroxy-substituted lower alkylacrylate, a hydroxy-substituted lower alkylmethacrylate, a hydroxy-substituted lower alkyl-acrylamides, a hydroxy-substituted lower alkyl-methacrylamide, or a hydroxy-substituted lower alkylvinylether, wherein said ethylenically unsaturated amine has formula (4), (4′) or (4″) 13In which, l, j and k, independent of one another, are o or 1; R6 is hydrogen, a linear or branched C1-C24 alkyl, a C2-C24 alkoxyalkyl, a C2-C24 alkylcarbonyl, a C2-C24 alkoxycarbonyl, an unsubstituted or C1-C4 alkyl- or C1-C4 alkoxy-substituted C6-C10 aryl, a C7-C18 aralkyl, a C13-C22 arylalkylaryl, a C3-C8 cycloalkyl, a C4-C14 cycloalkylalkyl, a C7-C18 cycloalkylalkylcycloalkyl, a C5-C20 alkylcycloalkylalkyl, or an aliphatic-heterocyclic radical; Z is a C1-C12 alkylene radical, phenylene radical or C7-C12 aralkylene radical; R7 and R7′, independently of each other, are hydrogen, C1-C4 alkyl or halogen; and Q is a radical of formula (5) 14wherein q is the number 0 or 1, each of R8 and R9 independently of the other is hydrogen, C1-C4 alkyl, phenyl, carboxy or halogen, R10 is hydrogen, C1-C4 alkyl or halogen, and Z′ is a linear or branched C1-C12 alkylene, an unsubstituted phenylene, an C1-C4 alkyl- or C1-C4 alkoxy-substituted phenylene, or a C7-C12 aralkylene.
- 35. A method of claim 34, wherein said radiation-curable prepolymer is substantially purified before introducing step.
- 36. A method of claim 35, wherein said aqueous solution contains a photoinitiator in an amount of up to 5% by weight of the radiation-curable prepolymer.
- 37. A method of claim 35, wherein said aqueous solution contains buffer salts conventionally used in the field of contact lens care and/or isotonizing agents conventionally used in the field of contact lens care.
Parent Case Info
[0001] This application claims benefit under 35 U.S.C. § 119 (e) of U.S. provisional application serial No. 60/403,333 filed Aug. 14, 2002, incorporated by reference in its entirety.
Provisional Applications (1)
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Number |
Date |
Country |
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60403333 |
Aug 2002 |
US |