CA2032200C - Method of forming shaped hydrogel articles including contact lenses - Google Patents
Method of forming shaped hydrogel articles including contact lenses Download PDFInfo
- Publication number
- CA2032200C CA2032200C CA002032200A CA2032200A CA2032200C CA 2032200 C CA2032200 C CA 2032200C CA 002032200 A CA002032200 A CA 002032200A CA 2032200 A CA2032200 A CA 2032200A CA 2032200 C CA2032200 C CA 2032200C
- Authority
- CA
- Canada
- Prior art keywords
- diluent
- acrylate
- meth
- methacrylate
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims description 42
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 239000003085 diluting agent Substances 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 53
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 32
- -1 acrylate ester Chemical class 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 239000004327 boric acid Substances 0.000 claims abstract description 22
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 150000001298 alcohols Chemical class 0.000 claims abstract description 19
- 238000000465 moulding Methods 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 5
- 239000000499 gel Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 14
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical group CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims 2
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 28
- 150000002148 esters Chemical class 0.000 description 25
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 19
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 10
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 9
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229930006711 bornane-2,3-dione Natural products 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- OFLPBAZQIRUWFV-UHFFFAOYSA-N 2-[3-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 OFLPBAZQIRUWFV-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- SOQNQQKHYUJRNL-UHFFFAOYSA-N 3-[3-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCC1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 SOQNQQKHYUJRNL-UHFFFAOYSA-N 0.000 description 1
- GPHPMJLQACOKIQ-UHFFFAOYSA-N 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propyl 2-methylprop-2-enoate Chemical compound CC(C)(C)C1=CC(CCCOC(=O)C(=C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O GPHPMJLQACOKIQ-UHFFFAOYSA-N 0.000 description 1
- VDEYGKYGGKVVDS-UHFFFAOYSA-N 3-[3-tert-butyl-4-hydroxy-5-(5-methoxybenzotriazol-2-yl)phenoxy]propyl 2-methylprop-2-enoate Chemical compound N1=C2C=C(OC)C=CC2=NN1C1=CC(OCCCOC(=O)C(C)=C)=CC(C(C)(C)C)=C1O VDEYGKYGGKVVDS-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000002362 bornane-2,3-dione group Chemical group 0.000 description 1
- 239000007975 buffered saline Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical class CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00038—Production of contact lenses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2707/00—Use of elements other than metals for preformed parts, e.g. for inserts
- B29K2707/02—Boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0092—Other properties hydrophilic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/916—Hydrogel compositions
Abstract
Shaped hydrogel articles such as soft contact lenses are prepared by (1) molding or casting a polymerization mixture comprising: (a) a monomer mixture comprising a major proportion of a hydrophilic (meth)acrylate ester such as 2-hydroxyethyl methacrylate, an alkyl (meth)acrylate wherein the alkyl group contains at least four carbon atoms, and a cross-linking monomer; and (b) a water-displaceable diluent, wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (w p) and Hansen hydrogen bonding (w h) cohesion parameters falling within the area of a circle defined as having a center at w h = 20.5, w p = 13, and a radius of 8.5, to produce a shaped gel of a copolymer of said monomers and said diluent, and (2) thereafter replacing said diluent with water.
Description
METHOD OF FORMING SHAPED HYDROGEL
ARTICLE~~ INCLUDING CONTACT LENSES
The invention relater to the production of shaped hydrogel articles including soft contact lenses, and more particularly to a method for the direct molding of such articles using certain boric acid esters as water-displaceable d~~luents.
Background of the Invention Until recently, soft contact lenses of the hydrogel type have been manufactured either by lathe cutting or spin casting. In the lathe cutting method, a lens blank or button of a substantially anhydrous hydrophilic polymer (xerogel) is mechanically cut and polished to a lens shape on a fine lathe, and thereafter is contacted with water or saline to hydrate the polymer and form the desired hydrogel lens. The rnechanical steps utilized in the lathe cutting operation are similar to those used in the manufacture of hard contact lenses, except that allowance must be made for swe7_ling of the lens during hydration of the polymer.
In the spin casting rnethod, a small quantity of hydrophilic monomer rnixture is placed in a concave, optically polished mold, and the mold is rotated while the monomers are polymerized t.o form a xerogel lens. The two optical surfaces of the lens are formed simultaneously during polymerization, the outer surface being formed by the concave mold surface and the inner surface being shaped by the joint <~ctions of centrifugal force generated by the rotating mold and surface tension of the polymerization mixture. The lens produced thereby is contacted with water or saline to hydrate the polymer and form a hydrogel lens as in the case of the lathe cut lens.
More recently, an improved process for producing hydrogel contact lenses has been developed, which method is not only more economical than either the lathe cut method or the spin casting method, but it has the advantage of enabling a more precise control over the final shape of the hydrated lens. This new method comprises the direct molding of a monomer mixture wherein said mixture is dissolved in a non-aqueous, water-displaceable solvent, the mixture is placed in a mold having the shape of the final desired hydrogel (i. e., water-swollen) lens, and the monomer/solvent mixture is subjected to conditions whereby the monomers) polymerize. to thereby produce a polymer/solvent mixture in the shape of the final desired hydrogel lens. (The polymerization must be carried out in a non-aqueous medium because water inhibits the polymerization reaction.) After the polymerization is complete, the solvent is displaced with water to produce a hydrated lens whose final size and shape are quite similar to the size and shape of the original molded polymer/solvent article. Such direct molding of hydrogel contact lenses is disclosed in Larsen, U. S. Patent No.
4,495,313 and in Larsen et al., U. S. Patent No. 4,680,336.
In the Larsen patent. the water-displaceable diluents used are boric acid esters of polyhydric alcohols wherein the polyhydric alcohols have three or more hydroxyl groups.
Alternatively, the polyhydric alcohols used may be a mixture of a polyhydric alcohol having three or more hydroxyl groups and a dihydric alcohol. See, for instance, the disclosure at Col. 3, lines 60 et seq. and Col. 4, lines 18-22.
The clear teaching of the Larsen patent is that the polyhydric alcohol used to prepare the borate esters for use in the direct molding process of hydrogel contact lenses must have three or more hydro$yl groups. While it is disclosed that dihydric alcohols can be used in admixture with tri- and higher polyols, the tri- and higher polyols are essential components.
An important aspect of this invention is based on the discovery that esters of boric acid and certain dihydric alcohols (as more fully defined below) can be used as water-displaceable diluents in a direct molding process for making shaped hydrogel articles such as soft contact lenses from polymer mixtures containing as the principal monomer one or more hydrophilic (meth)acrylates such as 2-hydrozyethyl methacrylate ("HEMA"). The invention provides processing advantages in the direct molding process for producing shaped hydrogel articles, including enhanced demoldability (i. e., the ability to open the mold after the polymerization with less force), which results in economic advantages such as a saving of labor costs, and a significant increase in yield because of a reduced proportion of surface defects in the molded articles that would cause rejection. It is believed that the enhanced demoldability and significant improvement in yield is related to the fact that the boric acid esters of diols that are employed in this invention have a lower surface tension than the preferred esters of the Larsen patent, No. 4,495,313, which reduces the adhesion of the polymer/solvent mixture to the mold.
An additional significant advantage that is imparted to the direct molding process by the water-displaceable esters provided by this invention is an enhanced ability to employ hydrophobic monomers (such as W-absorbing monomers) in the polymerization mixture. When one tries to include hydrophobic monomers such as UV-absorbing monomers in a monomer/diluent mixture using as the diluent the preferred esters of the said Larsen patent, it is found that the hydrophobic monomers are often not soluble in the mixture.
Increasing medical awareness of the adverse affects of ultraviolet ("W") radiation on the eyes has led to the introduction of spectacles, goggles, contact lenses, and intraocular lenses containing a means to absorb W
radiation. With respect to both contact lenses and intraocular lenses made from polymers (usually acrylic polymers), the preferred means for imparting UV absorbing capability is to make the lens from a copolymer that contains a copolymerized W-absorbing monomer. Such monomers are disclosed, for example, in Beard et al., U.
S. Patent No. 4,528,311 and Dunks et al., U. S. Patent No.
4,716,234. It would be desirable to impart UV-absorbing properties to contact lenses made by the direct molding process by including UV-absorbing monomers in the monomer/diluent mixture. This invention makes this desired end practical.
Soft contact lenses made from hydroxyalkyl (meth)acrylate polymers such as HEMA-based polymers are finding increased acceptance. Such polymers are used in fabricating daily wear contact lenses as well as extended wear contact lenses. One factor that affects the suitability of a contact lens for wear over an extended period of time is the oxygen transmissibility of the lens, since the cornea obtains oxygen directly from the air rather than from oxygen-carrying blood. Oxygen transmission through the 20322~~
ARTICLE~~ INCLUDING CONTACT LENSES
The invention relater to the production of shaped hydrogel articles including soft contact lenses, and more particularly to a method for the direct molding of such articles using certain boric acid esters as water-displaceable d~~luents.
Background of the Invention Until recently, soft contact lenses of the hydrogel type have been manufactured either by lathe cutting or spin casting. In the lathe cutting method, a lens blank or button of a substantially anhydrous hydrophilic polymer (xerogel) is mechanically cut and polished to a lens shape on a fine lathe, and thereafter is contacted with water or saline to hydrate the polymer and form the desired hydrogel lens. The rnechanical steps utilized in the lathe cutting operation are similar to those used in the manufacture of hard contact lenses, except that allowance must be made for swe7_ling of the lens during hydration of the polymer.
In the spin casting rnethod, a small quantity of hydrophilic monomer rnixture is placed in a concave, optically polished mold, and the mold is rotated while the monomers are polymerized t.o form a xerogel lens. The two optical surfaces of the lens are formed simultaneously during polymerization, the outer surface being formed by the concave mold surface and the inner surface being shaped by the joint <~ctions of centrifugal force generated by the rotating mold and surface tension of the polymerization mixture. The lens produced thereby is contacted with water or saline to hydrate the polymer and form a hydrogel lens as in the case of the lathe cut lens.
More recently, an improved process for producing hydrogel contact lenses has been developed, which method is not only more economical than either the lathe cut method or the spin casting method, but it has the advantage of enabling a more precise control over the final shape of the hydrated lens. This new method comprises the direct molding of a monomer mixture wherein said mixture is dissolved in a non-aqueous, water-displaceable solvent, the mixture is placed in a mold having the shape of the final desired hydrogel (i. e., water-swollen) lens, and the monomer/solvent mixture is subjected to conditions whereby the monomers) polymerize. to thereby produce a polymer/solvent mixture in the shape of the final desired hydrogel lens. (The polymerization must be carried out in a non-aqueous medium because water inhibits the polymerization reaction.) After the polymerization is complete, the solvent is displaced with water to produce a hydrated lens whose final size and shape are quite similar to the size and shape of the original molded polymer/solvent article. Such direct molding of hydrogel contact lenses is disclosed in Larsen, U. S. Patent No.
4,495,313 and in Larsen et al., U. S. Patent No. 4,680,336.
In the Larsen patent. the water-displaceable diluents used are boric acid esters of polyhydric alcohols wherein the polyhydric alcohols have three or more hydroxyl groups.
Alternatively, the polyhydric alcohols used may be a mixture of a polyhydric alcohol having three or more hydroxyl groups and a dihydric alcohol. See, for instance, the disclosure at Col. 3, lines 60 et seq. and Col. 4, lines 18-22.
The clear teaching of the Larsen patent is that the polyhydric alcohol used to prepare the borate esters for use in the direct molding process of hydrogel contact lenses must have three or more hydro$yl groups. While it is disclosed that dihydric alcohols can be used in admixture with tri- and higher polyols, the tri- and higher polyols are essential components.
An important aspect of this invention is based on the discovery that esters of boric acid and certain dihydric alcohols (as more fully defined below) can be used as water-displaceable diluents in a direct molding process for making shaped hydrogel articles such as soft contact lenses from polymer mixtures containing as the principal monomer one or more hydrophilic (meth)acrylates such as 2-hydrozyethyl methacrylate ("HEMA"). The invention provides processing advantages in the direct molding process for producing shaped hydrogel articles, including enhanced demoldability (i. e., the ability to open the mold after the polymerization with less force), which results in economic advantages such as a saving of labor costs, and a significant increase in yield because of a reduced proportion of surface defects in the molded articles that would cause rejection. It is believed that the enhanced demoldability and significant improvement in yield is related to the fact that the boric acid esters of diols that are employed in this invention have a lower surface tension than the preferred esters of the Larsen patent, No. 4,495,313, which reduces the adhesion of the polymer/solvent mixture to the mold.
An additional significant advantage that is imparted to the direct molding process by the water-displaceable esters provided by this invention is an enhanced ability to employ hydrophobic monomers (such as W-absorbing monomers) in the polymerization mixture. When one tries to include hydrophobic monomers such as UV-absorbing monomers in a monomer/diluent mixture using as the diluent the preferred esters of the said Larsen patent, it is found that the hydrophobic monomers are often not soluble in the mixture.
Increasing medical awareness of the adverse affects of ultraviolet ("W") radiation on the eyes has led to the introduction of spectacles, goggles, contact lenses, and intraocular lenses containing a means to absorb W
radiation. With respect to both contact lenses and intraocular lenses made from polymers (usually acrylic polymers), the preferred means for imparting UV absorbing capability is to make the lens from a copolymer that contains a copolymerized W-absorbing monomer. Such monomers are disclosed, for example, in Beard et al., U.
S. Patent No. 4,528,311 and Dunks et al., U. S. Patent No.
4,716,234. It would be desirable to impart UV-absorbing properties to contact lenses made by the direct molding process by including UV-absorbing monomers in the monomer/diluent mixture. This invention makes this desired end practical.
Soft contact lenses made from hydroxyalkyl (meth)acrylate polymers such as HEMA-based polymers are finding increased acceptance. Such polymers are used in fabricating daily wear contact lenses as well as extended wear contact lenses. One factor that affects the suitability of a contact lens for wear over an extended period of time is the oxygen transmissibility of the lens, since the cornea obtains oxygen directly from the air rather than from oxygen-carrying blood. Oxygen transmission through the 20322~~
lens is essential for an extended wear lens, and is desirable for a daily wear lens. As a general rule, the more oxygen that is transmitted through the lens the better. One of the factors that affects the oxygen transmissibility of a contact lens is the thickness of the lens. The oxygen transmissibility of a contact lens is inversely proportional to the thickness of the lens. The comfort to the wearer of a contact lens is also inversely proportional to the lens's thickness. For these two reasons, i. e., to maximize oxygen transmission and to optimize comfort, if optical considerations permit, it is desirable to make HEMA-based contact lenses as thin as possible.
The HEMA-based contact lenses that are available today usually vary in thickness from about 0.03 to about 0.6 millimeter in the hydrogel (water-swollen) state. The degree to which such lenses can ~be made thin is limited by the strength of the lens. Attempts to make them stronger (which would enable them to be made thinner) by increasing the proportion of polyfunctional cross-linker in the polymer are generally unsuccessful because the polymers also become more brittle when the cross-linking monomer proportion is increased beyond a certain point.
The major novelty of this invention resides in the incorporation in a copolymer of a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl methacrylate of one or more C6 or higher alkyl (meth)acrylate comonomers.
It has been found that such copolymers exhibit increased strength under conditions of low stress (that is, under the conditions of normal use) without a concurrent increase in brittleness, so that articles such as hydrogel contact lenses made from such copolymers can be made thinner.
The HEMA-based contact lenses that are available today usually vary in thickness from about 0.03 to about 0.6 millimeter in the hydrogel (water-swollen) state. The degree to which such lenses can ~be made thin is limited by the strength of the lens. Attempts to make them stronger (which would enable them to be made thinner) by increasing the proportion of polyfunctional cross-linker in the polymer are generally unsuccessful because the polymers also become more brittle when the cross-linking monomer proportion is increased beyond a certain point.
The major novelty of this invention resides in the incorporation in a copolymer of a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl methacrylate of one or more C6 or higher alkyl (meth)acrylate comonomers.
It has been found that such copolymers exhibit increased strength under conditions of low stress (that is, under the conditions of normal use) without a concurrent increase in brittleness, so that articles such as hydrogel contact lenses made from such copolymers can be made thinner.
The prior art has incorporated hydrophobic monomers in hydrophilic polymers intended for use in soft contact lenses. For instance, such polymers are disclosed in Singer et al., U.S. Patent No. 4,620,954 and in Izumitani et al., U.S. Patent No. 4,625.009. In these patents the hydrophilic monomer is N-vinyl pyrrolidone or N,N-dimethyl acrylamide. Holcombe, in U. S. Patent Nos. 3,926,892 and 3.965,063, has disclosed that lauryl acrylate or methacrylate can be a comonomer in a HEMA copolymer that also contains isobutyl methacrylate and either cyclohexyl methacrylate or N-(1,1-dimethyl-3-oxobutyl) acrylamide.
The polymerization technique disclosed by Holcombe is bulk polymerization. No actual operative example of the use of lauryl methacrylate in the copolymer system contemplated by Holcombe is disclosed by Holcombe.
In addition to the Holcombe patents, the Singer et al.
patent. and the Izumitani et al. patent, all of which were cited above, Japanese Patent Nos. 61166516 and 61205901 (assigned to Hoya Corporation, the assignee of the Izumitani et al. patent) disclose contact lenses made from copolymers of N,N-dimethyl acrylamide or N-vinyl pyrrolidone and hydrophobic monomers.
Dunks et al., in U.S. Patent No. 4,716,234, disclose the incorporation of certain benzotriazole (meth)acrylate esters in various polymers as UV absorbers. Among the many polymers mentioned are HEMA polymers. Benzotriazole (meth)acrylate esters are hydrophobic in nature.
Seiderman, in U.S. Patent No. 3,503,942, discloses hydrophilic plastic contact lenses made from a bulk polymerized copolymer of hydroxyalkyl acrylate or methacrylate and up to about 35 wt% of an alkyl acrylate or methacrylate, some of which can be a C5-20a1ky1 2~~~2~~
_~_ acrylate or methacrylate.
Brief Summary of the Invention Shaped hydrogel articles such as soft contact lenses are prepared by the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of one or more hydrophilic (meth)acrylate monomers such as 2-hydroayethyl methacrylate, an alkyl (meth)acrylate wherein the alkyl group contains at least four carbon atoms. and one or more cross-linking monomers and (b) a water-displaceable diluent. wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (wp) and Hansen hydrogen bonding (wh) cohesion parameters falling within the area of a circle defined as having a center at wh = 20.5. wp = 13. and a radius of 8.5.
to produce a shaped gel of a copolymer of said monomers and said diluent, and (2) thereafter replacing said diluent with water.
In an important aspect of the invention, soft contact lenses are prepared by the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a hydrophilic (meth)acrylate monomer such as 2-hydroayethyl methacrylate, _ ' 2U~22~~
one or more cross-linking monomers, and an alkyl (meth)acrylate monomer wherein the alkyl group contains at least four carbon atoms; and (b) a water-displaceable diluent, Wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (wp) and Hansen hydrogen bonding (wh) cohesion parameters falling within the area of a circle defined as having a center at wh =
20.5, wp = 13, and a radius of 8.5, to produce a shaped gel of a copolymer of said monomers and said diluent. and (2) thereafter replacing said diluent with water.
The Prior Art The Larsen patent (No. 4,495,313) cited above is the most relevant prior art known to Applicants with respect to the use of borate esters as water displaceable diluents in the preparation of molded or cast hydrogel articles. The Seiderman patent (No. 3.503,942) cited above is the most relevant prior art known to Applicants with respect to the use of copolymers of hydroxyalkyl (meth)acrylate and alkyl (meth)acrylate in the preparation of contact lenses.
The Larsen et al. patent. No. 4,680,336. discloses the use in a direct molding process for making hydrogel articles of certain diluents that are selected on the basis of their viscosity and their Hansen polar and hydrogen bonding cohesion parameters.
~_ ~03~~0~
Other U. S. patents relating to the direct molding of hydrogel articles such as soft contact lenses include Larsen, U. S. Patent Nos. 4,565,348 and 4,640,489, Ohkada et al., No. 4,347,198, Shepard, No. 4,208,364, and Wichterle et al., Re. 27,401 (No. 3,220,960).
Other-patents that disclose the preparation of contact lenses from hydroxyalkyl (meth)acrylates and alkyl (meth)acrylates are Masuhara et al., U.S. Patent No.
3,988,274, Tarumi et al., U.S. Patent No. 4,143,017, and Kato et al., U.S. Patent No. 4,529,747.
Brief Description of the Drawinqs_ Fig. 1 is a plot of the Hansen cohesion parameters, wh and wp, for several dihydric alcohols;
Fig. 2 is a calibration graph used in the determination of the Young's modulus of soft contact lenses; -and:' Fig. 3 is a side view, partially schematic, of the test fixture and assembly used to determine the force required to open the molds in which contact lenses comprising polymer/diluent mixtures were produced; and Fig. 4 is a front view of the same fixture and assembly shown in Fig. 3.
Detailed Description of the Invention A major novelty of the invention resides in the addition of C4 and higher alkyl (meth)acrylates to hydroxyalkyl (meth)acrylate copolymers intended for use in soft contact lenses. [As used herein, the expression "(meth)acrylate"
is intended to represent "methacrylate and/or acrylate".]
Such C4 and higher (meth)acrylate esters include, for example:
VTN-26 n-butyl acrylate and methacrylate, n-hexyl acrylate and methacrylate, 2-ethylhexyl methacrylate and other octyl acrylates and methacrylates, n-decyl acrylate and methacrylate, isodecyl acrylate and methacrylate, dodecyl acrylate and mechacrylate, stearyl methacrylate, and other alkyl acrylates and methacrylates that have alkyl groups containing four or more carbon atoms.
Preferably, the alkyl group in the alkyl (meth)acrylate contains a linear chain that is at least six carbon atoms long and up to, e.g., twenty carbon atoms long.
The monomer mixture used in the invention contains a hydroxyalkyl (meth)acrylate such as HEMA, 2-hydroxyethyl acrylate, glycerol mono-acrylate, glycerol mono-methacrylate. or the like, as the major component, one or more polyfunctional cross-linking monomers, and optionally small amounts of other monomers such as methacrylic acid, as well as the C6 or higher alkyl (meth)acrylate. Other hydrophilic monomers that can be employed in the monomer mixture include 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, N-vinyl pyrrolidone, and the like. The polyfunctional cross-linking monomers that can be employed, either singly or in combination, include ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate (wherein the polyethylene glycol has a molecular weight up to, e. g., about 400), and other polyacrylate and polymethacrylate esters that contain two or more (meth)acrylate groups. The polyfunctional cross-linking monomer is used in the usual amounts, e. g., from about 0.1 to about 1.25 parts by weight per 100 parts by weight of hydroxyalkyl (meth)acrylate. Other monomers that can be used include methacrylic acid, which is used to influence the amount of water that the hydrogel will absorb at equilibrium. Meth.acrylic acid is usually employed in amounts of from about 0.25 to about 7 parts, by weight, per 100 parts of hydroxyalkyl (meth)acrylate, depending, in part, upon factors such as the proportion of C6 or higher alkyl (meth)acrylate i.n the copolymer. As a general rule, more methacrylic acid. will be used as the proportion of the alkyl (meth)acrylate monomer is increased. The C6 or higher alkyl (meth)acrylate is used in an amount sufficient to enhance the elastic strength of the hydrogel comprising the water-swollen copolymer. Such amount is usually from about 10 to about 50 parts, and preferably from about 10 to 30 parts, by weight, per 100 parts by weight of hydroxyalkyl (meth)acrylate such as HEMA.
The monomer mixture can also contain one or more ultraviolet absorbing monomers. Illustrative of such UV-absorbing monomers are the benzotriazole (meth)acrylate esters, for instance, the 2-[2'-hydroxy-5'-acryloyloxy-alkylphenyl]-2H-benzotriazoles disclosed by Beard et al.
in U.S. Patent No. 4,528,311, the 2-[2'-hydroxy-5'-acryloyloxy-alkoxyphenyl]-2H-benzotriazoles disclosed by Dunks et al. in U.S. Patent No. 4,716,234, and the 2-(2'-hydroxyphenyl)-5(6)-(acryloylalkoxy)benzotriazoles.
Specific illustrative benzotriazole UV-absorbing (meth)acrylate ester., that can be used in the invention include the followings compounds:
2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxyethylphenyl)-5-chloro-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxypropylphenyl)-5-chloro-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butylphenyl)-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloaypropyl-3'-tert-butylphenyl)-5-chloro-2H-benzotriazole;
2-[2'-hydroxy-5'-(2-methacryloyloayethoay)-3' tert-butylphenyl]-5-methoxy-2H-benzotriazole;
2-[2'-hydroxy-5'-(gamma-methacryloyloxypropoxy)-3'-tert-butylphenyl]-5-methoxy-2H-benzotriazole; and 2-(3'-~-butyl-2'-hydroxy-5'-methoxyphenyl)-5-(3'-methacryloyloxypropoxy)benzotriazole.
Other UV-absorbing monomers that can be included in the polymerization reaction mixture include benzophenone derivatives, and the like.
The benzotriazole UV-absorbing (meth)acrylate esters are used in the monomer mixture in an amount effective to absorb W radiation in the finished lens product.
Usually, the proportion of the UV-absorbing monomer will be within the range of from about 1 to about 10 parts by weight per 100 parts by weight of the major hydrophilic monomers) such as HEMA.
A polymerization catalyst is included in the monomer mixture. The polymerization catalyst can be a free radical generating compound such as lauroyl peroxide, benzoyl peroxide, isopropyl percarbonate, azobisisobutyronitrile, or the like, that generates free radicals at moderately elevated temperatures, or the polymerization catalyst can be a photoinitiator system such as a tertiary amine plus a diketone. One illustrative ezample of such a photoinitiator system is camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate.
Another illustrative photoinitiator is 4-(2-hydroxyethozy)phenyl 2-hydroay-2-propyl ketone. The catalyst is used in the polymerization reaction mixture in catalytically effective amounts, e. g., from about 0.25 to about 1.5 parts by weight per 100 parts of hydroxyalkyl (meth)acrylate.
The boric acid esters are esters that are used in the invention as water-displaceable diluents in the direct molding of hydrogel articles comprise borate esters of certain dihydric alcohols, said dihydric alcohols having Hansen polar (wp) and Hansen hydrogen bonding (wh) cohesion parameters falling within the area of a circle defined as having a center at wh = 20.5, wp = 13, and a radius of 8.5. It is also required that the ester of boric acid and the dihydrozy compound have a viscosity of at least 100 MPa Sec at 30°C, and preferably at least about 500 MPa sec at 30°C.
The boric acid esters are prepared by procedures analogous to those that are known in the art. as by reacting boric acid with the dihydric alcohol (for brevity. dihydric alcohols will occasionally be referred to herein as "diols" ) and removing the water formed by the reaction by normal procedures such as by vacuum distillation. The reaction of boric acid with the dihydric alcohol is carried out at a temperature and for a period of time sufficient to form the ester. Typical reaction ~Q~2~0~
temperatures are usually found within the range of from about 50° to about 120°C. At these temperatures, reaction times of from about two to about twelve hours are typical. In any event, the reaction is continued until the water content of the ester is less than about 2%, by weight. The proportion of boric acid to dihydric alcohol is selected so that the viscosity of the ester is at least 100 MPa Sec at 30°C. The examples, below, give representative proportions of boric acid to dihydric alcohol that have been found to give the desired viscosity in the ester product. In certain cases. it may be desirable to include a small proportion of a monohydric alcohol in the esterification reaction mixture to control the molecular weight of the ester product.
The dihydric alcohols used in preparing the water-displaceable borate ester diluents used in the invention are those having Hansen polar (wp) and Hansen hydrogen bonding (wh) cohesion parameters falling within the area of a circle defined as having a center at wh = 20.5, wp = 13. and a radius of 8.5. The Hansen cohesion parameter w is usually expressed in terms of three components (wh, wp, wd) where wh is the hydrogen bonding cohesion parameter, wp is the polar cohesion parameter, and wd is the dispersion cohesion parameter. It has been found that for the purposes of this invention the dispersion cohesion parameters of the dihydric alcohols are substantially the same (the values that have been determined vary between about 15.7 and 17.0), and therefore have little effect in determining the suitability of any particular dihydric alcohol for use in the invention. The consideration of the Hansen cohesion parameters for the dihydric alcohol used in making the borate ester diluent is accordingly reduced to a 2o3z2oo two-dimensional function on the basis of polar and hydrogen bonding cohesion parameters.
Hansen cohesion parameters are known in the art.
Reference is made to "CRC Handbook of Solubility Parameters and Other Cohesion Parameters", by Allan F. M.
Barton, CRC Press. Inc., Boca Raton, Florida (1983), especially pages 85-87, 141, and 153-164, Hansen, "THE
UNIVERSALITY OF THE SOLUBILITY PARAMETER", I&EC Product Research and Development, Vol. 8, No. 1, March 1969, pages 2-11, Wernick, "Stereographic Display of Three-Dimensional Solubility Parameter Correlations", Ind. Eng. Chem. Prod.
Res. Dev., Vol. 23, No. 2, 1984, pages 240-245, and Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., Suppl. Vol., Interscience, NY 1971, pages 891 and 892, for illustrative discussions of the Hansen cohesion parameters and how to determine them.
The Hansen cohesion parameters, wh and wp, for selected polyhydric alcohols are displayed in Table I, below. The Hansen and Beerbower data as reported in the CRC Handbook were used when available. For diols that were not listed, the values were calculated from group contributions using the Hansen and Beerbower data as shown in the CRC Handbook, pp. 85-87 and Kirk-Othmer, pp.
891-892. The values for wp were calculated by the simple additive method as suggested in Kirk-Othmer.
Table I
DIOL ABBREVIATION w wh p ETHYLENE GLYCOL EG 11.0 26.0 1,2-PROPANEDIOL 1,2-PD 9.4 23.3 1,3-PROPANEDIOL 1,3-PD 14.0 23.2 1,2-BUTANEDIOL 1,2-BD 7.7 20.8 1,3-BUTANEDIOL 1,3-BD 10.0 21.5 1,4-BUTANEDIOL 1,4-BD 10.0 21.5 2,3-BUTANEDIOL 2,3-BD 7.7 20.8 1,6-HEXANEDIOL 1,6-HD $.4 17.8 2,5-HEXANEDIOL 2,5-HD 8.4 17.8 1,8-OCTANEDIOL 1,8-OD 6.3 15.5 1,10-DECANEDIOL 1,10-DD 5.0 13.8 DIETHYLENE GLYCOL DEG 14.7 20.5 POLYETHYLENE GLYCOL (400 mw) PEG 400 11.6 14.5 POLYETHYLENE GLYCOL (1000 mw) PEG 1000 10.9 12.6 DIPROPYLENE GLYCOL DPG 20.3 18.4 TRIPROPYLENE GLYCOL TPG 9.8 16.1 POLYPROPYLENE GLYCOL (400 mw) PPG 400 8.3 12.9 The data presented in Table I is displayed as a plot of wh versus wp in Fig. 1.
The examples set forth below illustrate the practice of the invention. In the examples, all parts are by weight, unless otherwise indicated.
~0~2~00 I» ustrative molding procedure Contact lenses are molded from the following polymerization reaction mixture:
Component ,arts, by Weight HEMA 100.0 Methacrylic acid 2.00 Ethylene glycol dimethacrylate 0.4 Darocure 1173(1) 0.35 1,4-butanediol Boric Acid Ester(2) 102.75 (1) 4-(2-hydroxyethoxy)phenyl 2-hydroxy-2-propyl ketone (2) Produced by reacting 797 parts. by weight, of 1,4-butanediol with 203 parts, by weight, of boric acid at a temperature of 90°C for 4 hours under 750 mm Hg vacuum.
The polymerization reaction mixture is placed in transparent polystyrene molds of the type described in Larsen, U. S. Patent No. 4,640,489 (see, especially, Fig.
2 of the Larsen patent), and is exposed on one side of the polystyrene mold to 1.7 Joules/cm2 of ultraviolet radiation for 6 to 12 minutes (the exact exposure time is not narrowly critical).
Illustrative monomer/diluent recipe for W-absorbing lens.
Using conditions analogous to those described above in Example 1, contact lenses are molded from the following polymerization reaction mixture:
~~3~~~~
component Parts, by Weight HEMA 100.00 Methacrylic acid 2.04 Ethylene glycol dimethacrylate 0.4 2-(2'hydroxy-5'-methacryloxypropyl-3'-~-butylphenyl)-5-chloro-2H-benzotriazole 3.00 Camphorquinone 0.40 Ethyl 4-(N,N-dimethylamino)benzoate 0.60 1,4-butanediol Boric Acid Ester(1) 77.45 (1) Produced by reacting 797 parts, by weight. of 1,4-butanediol with 203 parts, by weight, of boric acid at a temperature of 90°C for 4 hours under a vacuum of 750 mm Hg.
A series of esters of boric acid and dihydric alcohols were made by the following general procedure:
The boric acid and dihydric alcohol were charged to a 1-liter rotating evaporator and gradually heated to 90°C
(the time to achieve 90°C was about 1 hour), while applying mild vacuum (100 torr). When 90°C was reached, a full vacuum (10 torr) was applied and the reaction was continued for 3 hours at 90°C. After cooling, water content was determined by Karl Fischer titration and the viscosity of the borate ester at 30°C was determined by a Brookfield LVF viscometer (6, 12, and 30 rpm).
The borate esters that were prepared in accordance with the foregoing general procedure are identified in Table II, below. The table identifies the diols used, using the ~4~2~~~
abbreviations mentioned in Table I, and one triol, glycerol ("gly"), that was used as a control, the mols of each component (alcohol and boric acid) and the molar ratio of the alcohol to boric acid reactants used to prepare each ester, the viscosity at 30°C (in mPa Sec), and the per cent of water in the ester. A column for comments is also included in the table.
~ABLE II
For Molar gms of ratio, React ants alc Water Visc., Acid Alc to cont., mPa sec $~r Alcohol Mols Mols acid ~ 30C Cod en nts 1 EG 3.75 12.38 3.30 0.5 Paste 2 EG 4.36 11.77 2.70 1.7 solid (1) 3 1,2-PD 3.91 9.97 2.55 0.3 85 4 1,2-PD 5.03 9.05 1.80 0.7 200 5 1,2-PD 5.68 8.52 1.50 1.4 632 (2) 6 1,3-PD 3.45 10.34 3.00 0.7 38 7 1,3-PD 5.68 8.52 1.50 1.4 40 8 1,2-BD 3.28 8.85 2.70 0.2 50 9 1,2-BD 5.08 7.61 1.5 1.1 100 (2) 10 1,3-BD 5.08 7.61 1.50 1.0 100 11 1,4-HD 3.01 9.03 3.00 1.8 1200 12 1,4-BD 3.28 8.85 2.70 1.4 14000 13 2,3-BD 3.28 8.85 2.70 0 48 14 2,3-BD 5.08 7.61 1.50 1.1 50 (2) 15 1,6-HD 2.63 7.09 2.70 0.3 27250 (3) 16 2,5-HD 2.40 7.21 3.00 0.9 15200 (3) 17 2,5-HD 2.63 7.09 2.70 0.4 100000+ (2),(3) 18 1,8-OD 2.09 5.96 2.85 0.3 solid (1),(3) 19 1,10-DD 1.88 5.07 2.70 0.3 solid (4) 20 GLY 4.06 8.13 2.00 0.6-1 18-22000 21 DEG 2.87 7.75 2.7 1.3 870 22 PEG 400 0.88 2.36 2.70 0.7 590 23 PEG 1000 0.362 0.978 2.70 0.7 Solid (1) 24 DPG 2.36 6.37 2.70 1.3 2360 25 DPG 2.75 6.19 2.25 1.5 100000+
The polymerization technique disclosed by Holcombe is bulk polymerization. No actual operative example of the use of lauryl methacrylate in the copolymer system contemplated by Holcombe is disclosed by Holcombe.
In addition to the Holcombe patents, the Singer et al.
patent. and the Izumitani et al. patent, all of which were cited above, Japanese Patent Nos. 61166516 and 61205901 (assigned to Hoya Corporation, the assignee of the Izumitani et al. patent) disclose contact lenses made from copolymers of N,N-dimethyl acrylamide or N-vinyl pyrrolidone and hydrophobic monomers.
Dunks et al., in U.S. Patent No. 4,716,234, disclose the incorporation of certain benzotriazole (meth)acrylate esters in various polymers as UV absorbers. Among the many polymers mentioned are HEMA polymers. Benzotriazole (meth)acrylate esters are hydrophobic in nature.
Seiderman, in U.S. Patent No. 3,503,942, discloses hydrophilic plastic contact lenses made from a bulk polymerized copolymer of hydroxyalkyl acrylate or methacrylate and up to about 35 wt% of an alkyl acrylate or methacrylate, some of which can be a C5-20a1ky1 2~~~2~~
_~_ acrylate or methacrylate.
Brief Summary of the Invention Shaped hydrogel articles such as soft contact lenses are prepared by the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of one or more hydrophilic (meth)acrylate monomers such as 2-hydroayethyl methacrylate, an alkyl (meth)acrylate wherein the alkyl group contains at least four carbon atoms. and one or more cross-linking monomers and (b) a water-displaceable diluent. wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (wp) and Hansen hydrogen bonding (wh) cohesion parameters falling within the area of a circle defined as having a center at wh = 20.5. wp = 13. and a radius of 8.5.
to produce a shaped gel of a copolymer of said monomers and said diluent, and (2) thereafter replacing said diluent with water.
In an important aspect of the invention, soft contact lenses are prepared by the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a hydrophilic (meth)acrylate monomer such as 2-hydroayethyl methacrylate, _ ' 2U~22~~
one or more cross-linking monomers, and an alkyl (meth)acrylate monomer wherein the alkyl group contains at least four carbon atoms; and (b) a water-displaceable diluent, Wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (wp) and Hansen hydrogen bonding (wh) cohesion parameters falling within the area of a circle defined as having a center at wh =
20.5, wp = 13, and a radius of 8.5, to produce a shaped gel of a copolymer of said monomers and said diluent. and (2) thereafter replacing said diluent with water.
The Prior Art The Larsen patent (No. 4,495,313) cited above is the most relevant prior art known to Applicants with respect to the use of borate esters as water displaceable diluents in the preparation of molded or cast hydrogel articles. The Seiderman patent (No. 3.503,942) cited above is the most relevant prior art known to Applicants with respect to the use of copolymers of hydroxyalkyl (meth)acrylate and alkyl (meth)acrylate in the preparation of contact lenses.
The Larsen et al. patent. No. 4,680,336. discloses the use in a direct molding process for making hydrogel articles of certain diluents that are selected on the basis of their viscosity and their Hansen polar and hydrogen bonding cohesion parameters.
~_ ~03~~0~
Other U. S. patents relating to the direct molding of hydrogel articles such as soft contact lenses include Larsen, U. S. Patent Nos. 4,565,348 and 4,640,489, Ohkada et al., No. 4,347,198, Shepard, No. 4,208,364, and Wichterle et al., Re. 27,401 (No. 3,220,960).
Other-patents that disclose the preparation of contact lenses from hydroxyalkyl (meth)acrylates and alkyl (meth)acrylates are Masuhara et al., U.S. Patent No.
3,988,274, Tarumi et al., U.S. Patent No. 4,143,017, and Kato et al., U.S. Patent No. 4,529,747.
Brief Description of the Drawinqs_ Fig. 1 is a plot of the Hansen cohesion parameters, wh and wp, for several dihydric alcohols;
Fig. 2 is a calibration graph used in the determination of the Young's modulus of soft contact lenses; -and:' Fig. 3 is a side view, partially schematic, of the test fixture and assembly used to determine the force required to open the molds in which contact lenses comprising polymer/diluent mixtures were produced; and Fig. 4 is a front view of the same fixture and assembly shown in Fig. 3.
Detailed Description of the Invention A major novelty of the invention resides in the addition of C4 and higher alkyl (meth)acrylates to hydroxyalkyl (meth)acrylate copolymers intended for use in soft contact lenses. [As used herein, the expression "(meth)acrylate"
is intended to represent "methacrylate and/or acrylate".]
Such C4 and higher (meth)acrylate esters include, for example:
VTN-26 n-butyl acrylate and methacrylate, n-hexyl acrylate and methacrylate, 2-ethylhexyl methacrylate and other octyl acrylates and methacrylates, n-decyl acrylate and methacrylate, isodecyl acrylate and methacrylate, dodecyl acrylate and mechacrylate, stearyl methacrylate, and other alkyl acrylates and methacrylates that have alkyl groups containing four or more carbon atoms.
Preferably, the alkyl group in the alkyl (meth)acrylate contains a linear chain that is at least six carbon atoms long and up to, e.g., twenty carbon atoms long.
The monomer mixture used in the invention contains a hydroxyalkyl (meth)acrylate such as HEMA, 2-hydroxyethyl acrylate, glycerol mono-acrylate, glycerol mono-methacrylate. or the like, as the major component, one or more polyfunctional cross-linking monomers, and optionally small amounts of other monomers such as methacrylic acid, as well as the C6 or higher alkyl (meth)acrylate. Other hydrophilic monomers that can be employed in the monomer mixture include 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, N-vinyl pyrrolidone, and the like. The polyfunctional cross-linking monomers that can be employed, either singly or in combination, include ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate (wherein the polyethylene glycol has a molecular weight up to, e. g., about 400), and other polyacrylate and polymethacrylate esters that contain two or more (meth)acrylate groups. The polyfunctional cross-linking monomer is used in the usual amounts, e. g., from about 0.1 to about 1.25 parts by weight per 100 parts by weight of hydroxyalkyl (meth)acrylate. Other monomers that can be used include methacrylic acid, which is used to influence the amount of water that the hydrogel will absorb at equilibrium. Meth.acrylic acid is usually employed in amounts of from about 0.25 to about 7 parts, by weight, per 100 parts of hydroxyalkyl (meth)acrylate, depending, in part, upon factors such as the proportion of C6 or higher alkyl (meth)acrylate i.n the copolymer. As a general rule, more methacrylic acid. will be used as the proportion of the alkyl (meth)acrylate monomer is increased. The C6 or higher alkyl (meth)acrylate is used in an amount sufficient to enhance the elastic strength of the hydrogel comprising the water-swollen copolymer. Such amount is usually from about 10 to about 50 parts, and preferably from about 10 to 30 parts, by weight, per 100 parts by weight of hydroxyalkyl (meth)acrylate such as HEMA.
The monomer mixture can also contain one or more ultraviolet absorbing monomers. Illustrative of such UV-absorbing monomers are the benzotriazole (meth)acrylate esters, for instance, the 2-[2'-hydroxy-5'-acryloyloxy-alkylphenyl]-2H-benzotriazoles disclosed by Beard et al.
in U.S. Patent No. 4,528,311, the 2-[2'-hydroxy-5'-acryloyloxy-alkoxyphenyl]-2H-benzotriazoles disclosed by Dunks et al. in U.S. Patent No. 4,716,234, and the 2-(2'-hydroxyphenyl)-5(6)-(acryloylalkoxy)benzotriazoles.
Specific illustrative benzotriazole UV-absorbing (meth)acrylate ester., that can be used in the invention include the followings compounds:
2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxyethylphenyl)-5-chloro-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxypropylphenyl)-5-chloro-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butylphenyl)-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloaypropyl-3'-tert-butylphenyl)-5-chloro-2H-benzotriazole;
2-[2'-hydroxy-5'-(2-methacryloyloayethoay)-3' tert-butylphenyl]-5-methoxy-2H-benzotriazole;
2-[2'-hydroxy-5'-(gamma-methacryloyloxypropoxy)-3'-tert-butylphenyl]-5-methoxy-2H-benzotriazole; and 2-(3'-~-butyl-2'-hydroxy-5'-methoxyphenyl)-5-(3'-methacryloyloxypropoxy)benzotriazole.
Other UV-absorbing monomers that can be included in the polymerization reaction mixture include benzophenone derivatives, and the like.
The benzotriazole UV-absorbing (meth)acrylate esters are used in the monomer mixture in an amount effective to absorb W radiation in the finished lens product.
Usually, the proportion of the UV-absorbing monomer will be within the range of from about 1 to about 10 parts by weight per 100 parts by weight of the major hydrophilic monomers) such as HEMA.
A polymerization catalyst is included in the monomer mixture. The polymerization catalyst can be a free radical generating compound such as lauroyl peroxide, benzoyl peroxide, isopropyl percarbonate, azobisisobutyronitrile, or the like, that generates free radicals at moderately elevated temperatures, or the polymerization catalyst can be a photoinitiator system such as a tertiary amine plus a diketone. One illustrative ezample of such a photoinitiator system is camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate.
Another illustrative photoinitiator is 4-(2-hydroxyethozy)phenyl 2-hydroay-2-propyl ketone. The catalyst is used in the polymerization reaction mixture in catalytically effective amounts, e. g., from about 0.25 to about 1.5 parts by weight per 100 parts of hydroxyalkyl (meth)acrylate.
The boric acid esters are esters that are used in the invention as water-displaceable diluents in the direct molding of hydrogel articles comprise borate esters of certain dihydric alcohols, said dihydric alcohols having Hansen polar (wp) and Hansen hydrogen bonding (wh) cohesion parameters falling within the area of a circle defined as having a center at wh = 20.5, wp = 13, and a radius of 8.5. It is also required that the ester of boric acid and the dihydrozy compound have a viscosity of at least 100 MPa Sec at 30°C, and preferably at least about 500 MPa sec at 30°C.
The boric acid esters are prepared by procedures analogous to those that are known in the art. as by reacting boric acid with the dihydric alcohol (for brevity. dihydric alcohols will occasionally be referred to herein as "diols" ) and removing the water formed by the reaction by normal procedures such as by vacuum distillation. The reaction of boric acid with the dihydric alcohol is carried out at a temperature and for a period of time sufficient to form the ester. Typical reaction ~Q~2~0~
temperatures are usually found within the range of from about 50° to about 120°C. At these temperatures, reaction times of from about two to about twelve hours are typical. In any event, the reaction is continued until the water content of the ester is less than about 2%, by weight. The proportion of boric acid to dihydric alcohol is selected so that the viscosity of the ester is at least 100 MPa Sec at 30°C. The examples, below, give representative proportions of boric acid to dihydric alcohol that have been found to give the desired viscosity in the ester product. In certain cases. it may be desirable to include a small proportion of a monohydric alcohol in the esterification reaction mixture to control the molecular weight of the ester product.
The dihydric alcohols used in preparing the water-displaceable borate ester diluents used in the invention are those having Hansen polar (wp) and Hansen hydrogen bonding (wh) cohesion parameters falling within the area of a circle defined as having a center at wh = 20.5, wp = 13. and a radius of 8.5. The Hansen cohesion parameter w is usually expressed in terms of three components (wh, wp, wd) where wh is the hydrogen bonding cohesion parameter, wp is the polar cohesion parameter, and wd is the dispersion cohesion parameter. It has been found that for the purposes of this invention the dispersion cohesion parameters of the dihydric alcohols are substantially the same (the values that have been determined vary between about 15.7 and 17.0), and therefore have little effect in determining the suitability of any particular dihydric alcohol for use in the invention. The consideration of the Hansen cohesion parameters for the dihydric alcohol used in making the borate ester diluent is accordingly reduced to a 2o3z2oo two-dimensional function on the basis of polar and hydrogen bonding cohesion parameters.
Hansen cohesion parameters are known in the art.
Reference is made to "CRC Handbook of Solubility Parameters and Other Cohesion Parameters", by Allan F. M.
Barton, CRC Press. Inc., Boca Raton, Florida (1983), especially pages 85-87, 141, and 153-164, Hansen, "THE
UNIVERSALITY OF THE SOLUBILITY PARAMETER", I&EC Product Research and Development, Vol. 8, No. 1, March 1969, pages 2-11, Wernick, "Stereographic Display of Three-Dimensional Solubility Parameter Correlations", Ind. Eng. Chem. Prod.
Res. Dev., Vol. 23, No. 2, 1984, pages 240-245, and Kirk-Othmer Encyclopedia of Chemical Technology, 2nd ed., Suppl. Vol., Interscience, NY 1971, pages 891 and 892, for illustrative discussions of the Hansen cohesion parameters and how to determine them.
The Hansen cohesion parameters, wh and wp, for selected polyhydric alcohols are displayed in Table I, below. The Hansen and Beerbower data as reported in the CRC Handbook were used when available. For diols that were not listed, the values were calculated from group contributions using the Hansen and Beerbower data as shown in the CRC Handbook, pp. 85-87 and Kirk-Othmer, pp.
891-892. The values for wp were calculated by the simple additive method as suggested in Kirk-Othmer.
Table I
DIOL ABBREVIATION w wh p ETHYLENE GLYCOL EG 11.0 26.0 1,2-PROPANEDIOL 1,2-PD 9.4 23.3 1,3-PROPANEDIOL 1,3-PD 14.0 23.2 1,2-BUTANEDIOL 1,2-BD 7.7 20.8 1,3-BUTANEDIOL 1,3-BD 10.0 21.5 1,4-BUTANEDIOL 1,4-BD 10.0 21.5 2,3-BUTANEDIOL 2,3-BD 7.7 20.8 1,6-HEXANEDIOL 1,6-HD $.4 17.8 2,5-HEXANEDIOL 2,5-HD 8.4 17.8 1,8-OCTANEDIOL 1,8-OD 6.3 15.5 1,10-DECANEDIOL 1,10-DD 5.0 13.8 DIETHYLENE GLYCOL DEG 14.7 20.5 POLYETHYLENE GLYCOL (400 mw) PEG 400 11.6 14.5 POLYETHYLENE GLYCOL (1000 mw) PEG 1000 10.9 12.6 DIPROPYLENE GLYCOL DPG 20.3 18.4 TRIPROPYLENE GLYCOL TPG 9.8 16.1 POLYPROPYLENE GLYCOL (400 mw) PPG 400 8.3 12.9 The data presented in Table I is displayed as a plot of wh versus wp in Fig. 1.
The examples set forth below illustrate the practice of the invention. In the examples, all parts are by weight, unless otherwise indicated.
~0~2~00 I» ustrative molding procedure Contact lenses are molded from the following polymerization reaction mixture:
Component ,arts, by Weight HEMA 100.0 Methacrylic acid 2.00 Ethylene glycol dimethacrylate 0.4 Darocure 1173(1) 0.35 1,4-butanediol Boric Acid Ester(2) 102.75 (1) 4-(2-hydroxyethoxy)phenyl 2-hydroxy-2-propyl ketone (2) Produced by reacting 797 parts. by weight, of 1,4-butanediol with 203 parts, by weight, of boric acid at a temperature of 90°C for 4 hours under 750 mm Hg vacuum.
The polymerization reaction mixture is placed in transparent polystyrene molds of the type described in Larsen, U. S. Patent No. 4,640,489 (see, especially, Fig.
2 of the Larsen patent), and is exposed on one side of the polystyrene mold to 1.7 Joules/cm2 of ultraviolet radiation for 6 to 12 minutes (the exact exposure time is not narrowly critical).
Illustrative monomer/diluent recipe for W-absorbing lens.
Using conditions analogous to those described above in Example 1, contact lenses are molded from the following polymerization reaction mixture:
~~3~~~~
component Parts, by Weight HEMA 100.00 Methacrylic acid 2.04 Ethylene glycol dimethacrylate 0.4 2-(2'hydroxy-5'-methacryloxypropyl-3'-~-butylphenyl)-5-chloro-2H-benzotriazole 3.00 Camphorquinone 0.40 Ethyl 4-(N,N-dimethylamino)benzoate 0.60 1,4-butanediol Boric Acid Ester(1) 77.45 (1) Produced by reacting 797 parts, by weight. of 1,4-butanediol with 203 parts, by weight, of boric acid at a temperature of 90°C for 4 hours under a vacuum of 750 mm Hg.
A series of esters of boric acid and dihydric alcohols were made by the following general procedure:
The boric acid and dihydric alcohol were charged to a 1-liter rotating evaporator and gradually heated to 90°C
(the time to achieve 90°C was about 1 hour), while applying mild vacuum (100 torr). When 90°C was reached, a full vacuum (10 torr) was applied and the reaction was continued for 3 hours at 90°C. After cooling, water content was determined by Karl Fischer titration and the viscosity of the borate ester at 30°C was determined by a Brookfield LVF viscometer (6, 12, and 30 rpm).
The borate esters that were prepared in accordance with the foregoing general procedure are identified in Table II, below. The table identifies the diols used, using the ~4~2~~~
abbreviations mentioned in Table I, and one triol, glycerol ("gly"), that was used as a control, the mols of each component (alcohol and boric acid) and the molar ratio of the alcohol to boric acid reactants used to prepare each ester, the viscosity at 30°C (in mPa Sec), and the per cent of water in the ester. A column for comments is also included in the table.
~ABLE II
For Molar gms of ratio, React ants alc Water Visc., Acid Alc to cont., mPa sec $~r Alcohol Mols Mols acid ~ 30C Cod en nts 1 EG 3.75 12.38 3.30 0.5 Paste 2 EG 4.36 11.77 2.70 1.7 solid (1) 3 1,2-PD 3.91 9.97 2.55 0.3 85 4 1,2-PD 5.03 9.05 1.80 0.7 200 5 1,2-PD 5.68 8.52 1.50 1.4 632 (2) 6 1,3-PD 3.45 10.34 3.00 0.7 38 7 1,3-PD 5.68 8.52 1.50 1.4 40 8 1,2-BD 3.28 8.85 2.70 0.2 50 9 1,2-BD 5.08 7.61 1.5 1.1 100 (2) 10 1,3-BD 5.08 7.61 1.50 1.0 100 11 1,4-HD 3.01 9.03 3.00 1.8 1200 12 1,4-BD 3.28 8.85 2.70 1.4 14000 13 2,3-BD 3.28 8.85 2.70 0 48 14 2,3-BD 5.08 7.61 1.50 1.1 50 (2) 15 1,6-HD 2.63 7.09 2.70 0.3 27250 (3) 16 2,5-HD 2.40 7.21 3.00 0.9 15200 (3) 17 2,5-HD 2.63 7.09 2.70 0.4 100000+ (2),(3) 18 1,8-OD 2.09 5.96 2.85 0.3 solid (1),(3) 19 1,10-DD 1.88 5.07 2.70 0.3 solid (4) 20 GLY 4.06 8.13 2.00 0.6-1 18-22000 21 DEG 2.87 7.75 2.7 1.3 870 22 PEG 400 0.88 2.36 2.70 0.7 590 23 PEG 1000 0.362 0.978 2.70 0.7 Solid (1) 24 DPG 2.36 6.37 2.70 1.3 2360 25 DPG 2.75 6.19 2.25 1.5 100000+
26 TPG 1.72 4.65 2.70 0.9 1000 27 PPG 400 1.04 2.34 2.25 0.9 900 (4) 203~~4 (1) Diluent solid, but useable when mixed with monomers.
(2) Boric acid crystals formed when mixed with water.
(3) Not completely compatible with water (in a mixture of 1 part ester to 10 parts water, by weight), but can be used because it is displaceable after a wash with ethanol or a mixture of ethanol and water.
(4) Not compatible with either water or monomer mixture (1:1 monomer:diluent, by weight); cannot be used.
Many of the borate esters identified above in Table II
were evaluated as water-displaceable diluents with the following monomer formulation:
Component parts, tzy Weight HEMA 100.0 Methacrylic acid 2.0 Ethylene glycol dimethacrylate 0.4 Darocure 1173 0.35 Diluent 102.75 This monomer formulation, which contains 0.4 part of cross-linking monomer, was selected for evaluation because the Young's modulus values of the hydrogels prepared from this formulation can be correlated well with expected performance in the contact lens application. It has been found that if the Young's modulus of a hydrogel prepared using this formulation (which includes 0.4 part of a polyfunctional cross-linking monomer) is at least about 0.10-0.12 MPa, then a hydrogel prepared from a similar formulation, which may contain a slightly higher proportion of cross-linking monomer, can be eapected to be strong enough for use as a soft contact lens. In conventional commercial practice, the amount of 20~2~0 polyfunctional cross-linking monomers) such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate is normally from about 0.2-1.0 part in a formulation similar to that used in this Example.
Soft contact lenses were prepared from the monomer/diluent mixtures set forth above in transparent polystyrene molds as described above in Example 1. The monomer/diluent mixture in each mold was eaposed on one side to about 1.7 Joules/cm2 of ultraviolet radiation for 10 minutes at 55°C (TL09 lamps, with peak radiation at 350 nm).
The lenses prepared from the diluent/monomer mixtures were evaluated for:
(1) Appearance of lens, both in the mold and after demolding; and (2) Young's modulus of the hydrated lens; and (3) Force required to demold the molded lenses.
The results of these evaluations are displayed in Tables III and IV, below. Table III displays the Run No., the dihydric alcohol used to make the borate ester diluent, lens appearance (C=clear, W=white, OS=opaque surface, SO=slightly opaque), and the Young's modulus "E", in MPa.
Table IV displays the force required to demold the molded lenses at three different temperatures.
TABLE III
EVALUATION OF MOLDED LENSES
Ester Appea rance ~ 8lcohol Mold 'Final ~ Comments 1 EG C C .20 2 EG C C .23 3 1,2-PD C C .11 4 1,2-PD C C .18 5 1,2-PD C C/OS .17 (1) 7 1,3-PD - C/OS - (2) 8 1,2-BD C C .25 9 1,2-BD OS - - (2) 10 1,3-BD OS - - (2) 11 1,4-BD C C .24 13 2,3-BD C C .08 14 2,3-BD OS - - (2) 15 1,6-HD C C .19 16 2,5-HD C C .19 18 1,8-OD C SO .21 20 GLY C C .25 (control) 21 DEG C C .29 22 PEG 400 C C .34 23 PEG 1000 C C .30 24 DPG C C .28 25 DPG C C .27 26 TPG C C .27 (1) Dissolved the polystyrene mold slightly which caused a slightly opaque surface.
(2) Dissolved the polystyrene mold; could not be demolded.
2~322~~
The Young's modulus values of the lenses displayed in Table III were determined by the following procedure:
This test is useful for comparative non-destructive modulus testing of lenses of almost identical physical dimensions. The test has been calibrated against similar lenses tested in an accurate test as described in Larsen et al., U. S. Patent No. 4,680.336 (column 9-10).
The lenses useful in this test are a -1.0 diopter, 8.9 +/-0.3 mm BC (base curve), 0.15 +/- 0.01 mm center thickness, 14.0 +/- 0.5 mm diameter.
Test The lens dimensions are measured and, if within the specification, the lens is placed on top of a transparent acrylic cylinder (13 mm outer diameter, 9.8 mm inner diameter, 7.2 mm height) so that the lens front curve rests against the inner (9.8 mm diameter) top surface of the acrylic cylinder. The set-up is immersed in 0.9%
saline in the center thickness-measuring chamber of an Optimec JCF/R/SI Contact Lens Analyzer. The cylinder and lens are centered so that the lens is in a horizontal position, and the center thickness scale is adjusted so that it can measure deflection on the center of the front curve surface.
A 3 mm stainless steel ball (weight 0.2584 gram) is 203~~00 carefully placed on the concave side of the lens. The central part of the lens will deflect depending on the modulus of the lens. The deflection is read in mm on the center thickness scale, and the modulus can be determined from the calibration graph, Fig. 2.
A minimum of 3 lenses from the same batch are being tested, and the deflection of each lens is measured 3 times. The modulus is the average of at least 9 measurements.
m Ester Demol d Force~~.bs) No. Diol 30C 55 C 80 C
1 EG 6.49 (1.11) 5.15 4.76 (1.08) 2 EG (1) N/A (2) 6.15 (0.54) 3 1,2-PD 3.94 (0.43) 2.87 (0.52) 2.73 (0.52) 4 1,2-PD 4.53 (0.32) 3.20 (0.42) 3.26 (0.75) 5 1,2-PD 1.46 (0.77) 1.99 (0.87) 2.39 (1.03) 6 1,3-PD 3.95 (0.38) 3.11 (0.63) 2.68 (0.25) 7 1,3-PD (3) (3 ) (3) 10 1,3-BD (3) (3 ) (3) 11 1,4-BD 4.99 (0.63) 4.51 (0.47) 3.44 (0.53) 12 1,4-BD 5.70 (0.33) 3.91 (0.91) 3.50 (0.31) 20 GLY (1) (1 ) (1) 21 DEG 2.81 (0.66) 2.42 (0.71) 1.56 (0.64) 22 PEG 400 3.39 (0.36) 2.76 (0.51) 1.36 (0.43) 23 PEG 1000 3.47 (1.01) 3.53 (0.57) 3.03 (0.71) 24 DPG 0.86 (0.49) 1.08 (0.41) 1.18 (0.18) 25 DPG 0.92 (0.21) 0.76 (0.32) 1.11 (0.52) 26 TPG 1.75 0.57) 1.76 (0.61) 2.18 (0.35) 27 TPG (4) (4 ) (4) ~03~~00 The numbers in parentheses are standard deviations.
(1) The flange on the top half of the mold broke during force measurement.
(2) Data not available (3) Not possible to demold. The polymer/diluent mixture dissolvedlt~tle mold and bonded the two halves of the mold together.
(4) Demold force too low to measure.
Demo 1 d fi"'P~,s t .
The test employed to evaluate the force required to open the mold in which the polymer/diluent mixtures were produced, the results of which are displayed in Table IV, is as follows:
This test is useful for quantifying the minimum force required to separate the front and back halves of the mold (as described in Larsen, U. S. Patent No. 4,640,489) which are bound together by a polymer matrix containing some known level of diluent. The mold dimensions should remain constant for all samples analyzed.
Instrumentation The test fixture and assembly used to measure the forces to open the molds is shown in Fig. 3 and Fig. 4. In Fig.
3 as shown the instrument used for measuring the force is a laboratory tensile testing apparatus 10, such as an Instron model #1122. A 50 lb load cell (not shown) is used with the chart recorder 12 being set at 20 lbs full scale.
The temperature is controlled by a heat gun (not shown), such as a Variternp heat gun (Model VT-750A) connected to a Staco type 3PN2210 rheostat. A T-type thermocouple (not shown) inserted in the polymer/diluent'~mixture is used to measure the temperature of the polymer/diluent mixture.
Referring~t~o Fig. 4, a fixture 14 holds the specimen 16 in place during the test and a lever 18 is used to pull the top half 20 of the mold away from the bottom half 22.
The specimen is comprised of the top 20 and bottom 22 halves of the mold 16, which are bound together by the polymer/diluent matrix 24. The specimens for testing are freshly produced filled molds of constant dimensions. The molds are placed in a dessicator immediately after polymerization so as to prevent moisture from being absorbed by the polymer or the diluent.
The specimen to be tested is placed in the sample holder as shown in Fig. 3. The sample fixture is held by the lower grip of the Instron with a pressure of 36 PSI. The entire specimen is situated at a 20° angle to the horizontal plane when placed in the fixture. The bottom half 22 of the mold is kept in place during the test by inserting four pins (only two are shown, in cross-section) 26, 28 around the circumference of the bottom half 22 of the mold at 90° intervals.
The lever 18 used to pull the top half 20 away from the bottom half 22 is positioned between the two halves and is held in place by the upper grip 30 of the Instron. The rate at which the lever pulls the top half is controlled by the cross-head speed of the Instron.
20322~~~
(2) Boric acid crystals formed when mixed with water.
(3) Not completely compatible with water (in a mixture of 1 part ester to 10 parts water, by weight), but can be used because it is displaceable after a wash with ethanol or a mixture of ethanol and water.
(4) Not compatible with either water or monomer mixture (1:1 monomer:diluent, by weight); cannot be used.
Many of the borate esters identified above in Table II
were evaluated as water-displaceable diluents with the following monomer formulation:
Component parts, tzy Weight HEMA 100.0 Methacrylic acid 2.0 Ethylene glycol dimethacrylate 0.4 Darocure 1173 0.35 Diluent 102.75 This monomer formulation, which contains 0.4 part of cross-linking monomer, was selected for evaluation because the Young's modulus values of the hydrogels prepared from this formulation can be correlated well with expected performance in the contact lens application. It has been found that if the Young's modulus of a hydrogel prepared using this formulation (which includes 0.4 part of a polyfunctional cross-linking monomer) is at least about 0.10-0.12 MPa, then a hydrogel prepared from a similar formulation, which may contain a slightly higher proportion of cross-linking monomer, can be eapected to be strong enough for use as a soft contact lens. In conventional commercial practice, the amount of 20~2~0 polyfunctional cross-linking monomers) such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate is normally from about 0.2-1.0 part in a formulation similar to that used in this Example.
Soft contact lenses were prepared from the monomer/diluent mixtures set forth above in transparent polystyrene molds as described above in Example 1. The monomer/diluent mixture in each mold was eaposed on one side to about 1.7 Joules/cm2 of ultraviolet radiation for 10 minutes at 55°C (TL09 lamps, with peak radiation at 350 nm).
The lenses prepared from the diluent/monomer mixtures were evaluated for:
(1) Appearance of lens, both in the mold and after demolding; and (2) Young's modulus of the hydrated lens; and (3) Force required to demold the molded lenses.
The results of these evaluations are displayed in Tables III and IV, below. Table III displays the Run No., the dihydric alcohol used to make the borate ester diluent, lens appearance (C=clear, W=white, OS=opaque surface, SO=slightly opaque), and the Young's modulus "E", in MPa.
Table IV displays the force required to demold the molded lenses at three different temperatures.
TABLE III
EVALUATION OF MOLDED LENSES
Ester Appea rance ~ 8lcohol Mold 'Final ~ Comments 1 EG C C .20 2 EG C C .23 3 1,2-PD C C .11 4 1,2-PD C C .18 5 1,2-PD C C/OS .17 (1) 7 1,3-PD - C/OS - (2) 8 1,2-BD C C .25 9 1,2-BD OS - - (2) 10 1,3-BD OS - - (2) 11 1,4-BD C C .24 13 2,3-BD C C .08 14 2,3-BD OS - - (2) 15 1,6-HD C C .19 16 2,5-HD C C .19 18 1,8-OD C SO .21 20 GLY C C .25 (control) 21 DEG C C .29 22 PEG 400 C C .34 23 PEG 1000 C C .30 24 DPG C C .28 25 DPG C C .27 26 TPG C C .27 (1) Dissolved the polystyrene mold slightly which caused a slightly opaque surface.
(2) Dissolved the polystyrene mold; could not be demolded.
2~322~~
The Young's modulus values of the lenses displayed in Table III were determined by the following procedure:
This test is useful for comparative non-destructive modulus testing of lenses of almost identical physical dimensions. The test has been calibrated against similar lenses tested in an accurate test as described in Larsen et al., U. S. Patent No. 4,680.336 (column 9-10).
The lenses useful in this test are a -1.0 diopter, 8.9 +/-0.3 mm BC (base curve), 0.15 +/- 0.01 mm center thickness, 14.0 +/- 0.5 mm diameter.
Test The lens dimensions are measured and, if within the specification, the lens is placed on top of a transparent acrylic cylinder (13 mm outer diameter, 9.8 mm inner diameter, 7.2 mm height) so that the lens front curve rests against the inner (9.8 mm diameter) top surface of the acrylic cylinder. The set-up is immersed in 0.9%
saline in the center thickness-measuring chamber of an Optimec JCF/R/SI Contact Lens Analyzer. The cylinder and lens are centered so that the lens is in a horizontal position, and the center thickness scale is adjusted so that it can measure deflection on the center of the front curve surface.
A 3 mm stainless steel ball (weight 0.2584 gram) is 203~~00 carefully placed on the concave side of the lens. The central part of the lens will deflect depending on the modulus of the lens. The deflection is read in mm on the center thickness scale, and the modulus can be determined from the calibration graph, Fig. 2.
A minimum of 3 lenses from the same batch are being tested, and the deflection of each lens is measured 3 times. The modulus is the average of at least 9 measurements.
m Ester Demol d Force~~.bs) No. Diol 30C 55 C 80 C
1 EG 6.49 (1.11) 5.15 4.76 (1.08) 2 EG (1) N/A (2) 6.15 (0.54) 3 1,2-PD 3.94 (0.43) 2.87 (0.52) 2.73 (0.52) 4 1,2-PD 4.53 (0.32) 3.20 (0.42) 3.26 (0.75) 5 1,2-PD 1.46 (0.77) 1.99 (0.87) 2.39 (1.03) 6 1,3-PD 3.95 (0.38) 3.11 (0.63) 2.68 (0.25) 7 1,3-PD (3) (3 ) (3) 10 1,3-BD (3) (3 ) (3) 11 1,4-BD 4.99 (0.63) 4.51 (0.47) 3.44 (0.53) 12 1,4-BD 5.70 (0.33) 3.91 (0.91) 3.50 (0.31) 20 GLY (1) (1 ) (1) 21 DEG 2.81 (0.66) 2.42 (0.71) 1.56 (0.64) 22 PEG 400 3.39 (0.36) 2.76 (0.51) 1.36 (0.43) 23 PEG 1000 3.47 (1.01) 3.53 (0.57) 3.03 (0.71) 24 DPG 0.86 (0.49) 1.08 (0.41) 1.18 (0.18) 25 DPG 0.92 (0.21) 0.76 (0.32) 1.11 (0.52) 26 TPG 1.75 0.57) 1.76 (0.61) 2.18 (0.35) 27 TPG (4) (4 ) (4) ~03~~00 The numbers in parentheses are standard deviations.
(1) The flange on the top half of the mold broke during force measurement.
(2) Data not available (3) Not possible to demold. The polymer/diluent mixture dissolvedlt~tle mold and bonded the two halves of the mold together.
(4) Demold force too low to measure.
Demo 1 d fi"'P~,s t .
The test employed to evaluate the force required to open the mold in which the polymer/diluent mixtures were produced, the results of which are displayed in Table IV, is as follows:
This test is useful for quantifying the minimum force required to separate the front and back halves of the mold (as described in Larsen, U. S. Patent No. 4,640,489) which are bound together by a polymer matrix containing some known level of diluent. The mold dimensions should remain constant for all samples analyzed.
Instrumentation The test fixture and assembly used to measure the forces to open the molds is shown in Fig. 3 and Fig. 4. In Fig.
3 as shown the instrument used for measuring the force is a laboratory tensile testing apparatus 10, such as an Instron model #1122. A 50 lb load cell (not shown) is used with the chart recorder 12 being set at 20 lbs full scale.
The temperature is controlled by a heat gun (not shown), such as a Variternp heat gun (Model VT-750A) connected to a Staco type 3PN2210 rheostat. A T-type thermocouple (not shown) inserted in the polymer/diluent'~mixture is used to measure the temperature of the polymer/diluent mixture.
Referring~t~o Fig. 4, a fixture 14 holds the specimen 16 in place during the test and a lever 18 is used to pull the top half 20 of the mold away from the bottom half 22.
The specimen is comprised of the top 20 and bottom 22 halves of the mold 16, which are bound together by the polymer/diluent matrix 24. The specimens for testing are freshly produced filled molds of constant dimensions. The molds are placed in a dessicator immediately after polymerization so as to prevent moisture from being absorbed by the polymer or the diluent.
The specimen to be tested is placed in the sample holder as shown in Fig. 3. The sample fixture is held by the lower grip of the Instron with a pressure of 36 PSI. The entire specimen is situated at a 20° angle to the horizontal plane when placed in the fixture. The bottom half 22 of the mold is kept in place during the test by inserting four pins (only two are shown, in cross-section) 26, 28 around the circumference of the bottom half 22 of the mold at 90° intervals.
The lever 18 used to pull the top half 20 away from the bottom half 22 is positioned between the two halves and is held in place by the upper grip 30 of the Instron. The rate at which the lever pulls the top half is controlled by the cross-head speed of the Instron.
20322~~~
The air flow of the heat gun is directed directly at the top half of the mold to maintain consistent heating. The temperature of the air flow can be controlled with the rheostat.
The sample temperature is monitored by inserting a thermocouple in such a way as to measure the change in temperature of the polymer/diluent matrix 24. When the thermocouple measures the desired temperature, the cross-head of the Instron is raised at a speed of 1 inch/min. The force to demold was measured at 30°, 55°, and 80°C.
The force required to break the adhesion of the polymer/diluent to the top half 20 as a function of time if recorded by the chart recorder of the Instron. From this recording, the minimum demold force is determined.
From the data presented above, it can be seen that only those esters made from diols falling within the defined Hansen parameter area give transparent lenses (which is essential for the contact lens application), and only those having viscosities greater than 100 MPa sec have modulus values high enough to be strong enough to be used in the contact lens application.
The demold data clearly demonstrate that the diol esters of this invention give much easier demoldability (less force needed to demold) than do the preferred esters of the Larsen patent, No. 4,495,313.
As an illustration of the yield improvement that can be obtained by employing the diol-borate esters of this invention in place of a glycerol-borate ester, the number of surface flaws was determined on three batches of 80 ~032~00 lenses from each of monomer/ester mixtures, using a formulation analogous to that set forth above in Example 1. When the diluent used was a diethylene glycol/boric acid ester (ester No. 21 in Table II), the percentage of surface defects was found to be 10.4%, when the diluent was a 1,4-butanediol/boric acid ester (ester No. 12 in Table II), the percentage of surface defects was found to be 13.0%, and when the diluent was a glycerol/boric acid ester (ester No. 20 in Table II), the percentage of surface defects was found to be 30.4%. This is a valuable improvement over the process taught in the Larsen patent, No. 4,495,313.
Example 4 Preparation of Alkyl (Meth)acrylate Modified HEMA Using Borate Ester Water-Displaceable Diluent.
To the following:
102.118 hydroxyethyl methacrylate (HEMA) 3.828 methacrylic acid (MAA) 0.858 ethylene glycol dimethacrylate (EGDMA) O.lOg trimethylolpropane trimethacrylate (TMPTA) 0.368 DAROCURE(1) 136.758 water-displaceable diluent(2);
(1) 4-(2-hydroxyethoxy)phenyl 2-hydroxy-2-propyl ketone.
(2) Produced by reacting 1094.84 parts, by weight, 1,4-butanediol with 278.64 parts, by weight, boric acid at a temperature of 90°C for 2 hours under a pressure of 10 torr in a rotating evaporator.
was added 20.08 of an alkyl (meth)acrylate or other hydrophobic ester of methacrylic acid. The monomer _ ~0~22~~
The sample temperature is monitored by inserting a thermocouple in such a way as to measure the change in temperature of the polymer/diluent matrix 24. When the thermocouple measures the desired temperature, the cross-head of the Instron is raised at a speed of 1 inch/min. The force to demold was measured at 30°, 55°, and 80°C.
The force required to break the adhesion of the polymer/diluent to the top half 20 as a function of time if recorded by the chart recorder of the Instron. From this recording, the minimum demold force is determined.
From the data presented above, it can be seen that only those esters made from diols falling within the defined Hansen parameter area give transparent lenses (which is essential for the contact lens application), and only those having viscosities greater than 100 MPa sec have modulus values high enough to be strong enough to be used in the contact lens application.
The demold data clearly demonstrate that the diol esters of this invention give much easier demoldability (less force needed to demold) than do the preferred esters of the Larsen patent, No. 4,495,313.
As an illustration of the yield improvement that can be obtained by employing the diol-borate esters of this invention in place of a glycerol-borate ester, the number of surface flaws was determined on three batches of 80 ~032~00 lenses from each of monomer/ester mixtures, using a formulation analogous to that set forth above in Example 1. When the diluent used was a diethylene glycol/boric acid ester (ester No. 21 in Table II), the percentage of surface defects was found to be 10.4%, when the diluent was a 1,4-butanediol/boric acid ester (ester No. 12 in Table II), the percentage of surface defects was found to be 13.0%, and when the diluent was a glycerol/boric acid ester (ester No. 20 in Table II), the percentage of surface defects was found to be 30.4%. This is a valuable improvement over the process taught in the Larsen patent, No. 4,495,313.
Example 4 Preparation of Alkyl (Meth)acrylate Modified HEMA Using Borate Ester Water-Displaceable Diluent.
To the following:
102.118 hydroxyethyl methacrylate (HEMA) 3.828 methacrylic acid (MAA) 0.858 ethylene glycol dimethacrylate (EGDMA) O.lOg trimethylolpropane trimethacrylate (TMPTA) 0.368 DAROCURE(1) 136.758 water-displaceable diluent(2);
(1) 4-(2-hydroxyethoxy)phenyl 2-hydroxy-2-propyl ketone.
(2) Produced by reacting 1094.84 parts, by weight, 1,4-butanediol with 278.64 parts, by weight, boric acid at a temperature of 90°C for 2 hours under a pressure of 10 torr in a rotating evaporator.
was added 20.08 of an alkyl (meth)acrylate or other hydrophobic ester of methacrylic acid. The monomer _ ~0~22~~
mixture was placed in a vacuum oven at 40 mm Hg for 3 hours to remove the oxygen. The vacuum oven was then filled with nitrogen gas. Clear polystyrene contact lens molds of the type shown in Fig. 2 of Larsen, U. S. Patent No. 4,640,489, were filled with the selected mixture in a nitrogen filled glove boa. The filled frames were polymerized by exposure on one side to about 1.7 Joules/cm2 of W light from Philips TL40W/09n fluorescent bulbs with a maximum output at 365 nm. The exposure to W light was carried out for about 10 minutes (the exact time is not narrowly critical). After polymerization, the polymer/diluent mixture was washed with a 50:50 ethanol: water (by volume) mixture, followed by a wash with pure water to displace the diluent with water. The lens was then packed in standard soft contact lens packing solution (buffered saline) for storage.
Table V, below, displays the hydrophobic group of the methacrylic ester, the appearance of the hydrogel (i, e., the polymer swollen with water), the percent of water in the hydrogel, the compression modulus (referred to as "stiffness") of the hydrogel, and the oxygen transmissibility of the hydrogel.
The stiffness of the hydrogel was measured by the following procedure:
Compression modulus values were obtained using a constant-rate-of-crosshead movement testing machine in compression mode. The contact lens specimen to be tested is first sliced through in two cuts at right angles to each other, each cut going through the center of the lens (looking at the face of the lens), to form four pie-shaped pieces. This is done in order to insure that the specimen will lie flat during the testing. The test piece is compressed between two flat disks at a rate of 0.002 inch/minute. Compression stress and strain were monitored using a strip chart recorder at a chart speed of 2 inches/minute. The full scale deflection of the load cell is 0.110 pound. Zero compression Was assumed when a load value of 0.005 pound Was reached. The units of the compression modulus in the table are pounds per square inch.
The oxygen permeability Was measured by the method of Fatt et al., "Measurement of Oxygen Transmissibility and Permeability of Hydrogel Lenses and Materials", International Contact Lens Clinic, Vol. 9/No.2, March/April 1982, pages 76-88. The oxygen permeability is expressed as "Dk", where D represents the diffusion coefficient for oaygen in the material being tested, and k represents the solubiliby of ozygen in the material. The units are (cm2/sec)(ml 02/ml x mmHg). (The numerical values given in the table should be multiplied by 10-11 to give the actual values.) Table V
livdrophobic Gro up Appearance % water Stiffness Dk None (control) (1) clear 60.4 20.2 30 benzyl clear 58.3 32.1 23 2-butyl clear 64.9 26.8 26 n-butyl clear 65.0 41.2 42 t-butyl clear 63.0 27.0 31 n-hexyl clear 61.3 43.2 30 2-ethylhexyl clear 59.0 38.1 30 n-octyl clear 64.4 25.7 (2) 40 n-dodecyl clear 66.5 43.6 39 _~032~00 (1) The formulation for the control was the following:
HEMA 4 88.2 parts Methacrylic acid 8.2 parts Ethylene glycol dimethacrylate 3.1 parts Trimethylolpropane trimethacrylate 0.49 part DAROCURE 1173 1.79 parts 48 parts of this monomer mixture were mixedwith 52 parts of the previously described diluent.
(2) The low stiffness value found for this hydrogel is bel ieved to be anomolous.
To illustrate that oxygen transmissibility is greater for thinner hydrogel contact lenses, the oxygen transmissibility Dk/1 was measured for contact lenses made of the same material but having different thicknesses.
The lens material was made as described above, using as the hydrophobic groups 2-ethylhexyl and n-dodecyl. The thicknesses and oxygen transmissibilities were as follows:
Hydrophobic Thickness Group at Center Dk/1 120% in polymer) Microns 2-ethylhexyl 110 18.9 x 10 9 " 60 29.3 x 10 9 37.8 x 10 9 n-dodecyl 110 20.2 x 10 9 30 " 60 29.9 x 10 9 30 43.0 x 10 9 ~032~~~
Table V, below, displays the hydrophobic group of the methacrylic ester, the appearance of the hydrogel (i, e., the polymer swollen with water), the percent of water in the hydrogel, the compression modulus (referred to as "stiffness") of the hydrogel, and the oxygen transmissibility of the hydrogel.
The stiffness of the hydrogel was measured by the following procedure:
Compression modulus values were obtained using a constant-rate-of-crosshead movement testing machine in compression mode. The contact lens specimen to be tested is first sliced through in two cuts at right angles to each other, each cut going through the center of the lens (looking at the face of the lens), to form four pie-shaped pieces. This is done in order to insure that the specimen will lie flat during the testing. The test piece is compressed between two flat disks at a rate of 0.002 inch/minute. Compression stress and strain were monitored using a strip chart recorder at a chart speed of 2 inches/minute. The full scale deflection of the load cell is 0.110 pound. Zero compression Was assumed when a load value of 0.005 pound Was reached. The units of the compression modulus in the table are pounds per square inch.
The oxygen permeability Was measured by the method of Fatt et al., "Measurement of Oxygen Transmissibility and Permeability of Hydrogel Lenses and Materials", International Contact Lens Clinic, Vol. 9/No.2, March/April 1982, pages 76-88. The oxygen permeability is expressed as "Dk", where D represents the diffusion coefficient for oaygen in the material being tested, and k represents the solubiliby of ozygen in the material. The units are (cm2/sec)(ml 02/ml x mmHg). (The numerical values given in the table should be multiplied by 10-11 to give the actual values.) Table V
livdrophobic Gro up Appearance % water Stiffness Dk None (control) (1) clear 60.4 20.2 30 benzyl clear 58.3 32.1 23 2-butyl clear 64.9 26.8 26 n-butyl clear 65.0 41.2 42 t-butyl clear 63.0 27.0 31 n-hexyl clear 61.3 43.2 30 2-ethylhexyl clear 59.0 38.1 30 n-octyl clear 64.4 25.7 (2) 40 n-dodecyl clear 66.5 43.6 39 _~032~00 (1) The formulation for the control was the following:
HEMA 4 88.2 parts Methacrylic acid 8.2 parts Ethylene glycol dimethacrylate 3.1 parts Trimethylolpropane trimethacrylate 0.49 part DAROCURE 1173 1.79 parts 48 parts of this monomer mixture were mixedwith 52 parts of the previously described diluent.
(2) The low stiffness value found for this hydrogel is bel ieved to be anomolous.
To illustrate that oxygen transmissibility is greater for thinner hydrogel contact lenses, the oxygen transmissibility Dk/1 was measured for contact lenses made of the same material but having different thicknesses.
The lens material was made as described above, using as the hydrophobic groups 2-ethylhexyl and n-dodecyl. The thicknesses and oxygen transmissibilities were as follows:
Hydrophobic Thickness Group at Center Dk/1 120% in polymer) Microns 2-ethylhexyl 110 18.9 x 10 9 " 60 29.3 x 10 9 37.8 x 10 9 n-dodecyl 110 20.2 x 10 9 30 " 60 29.9 x 10 9 30 43.0 x 10 9 ~032~~~
Control Preparation of hydrophobically modified HEMA by bulk polymerization with no diluent.
To the following:
0.8g HEMA (including 0.0016g EGDMA and 0.032g MAA) 0.00288 DAROCURE
was added 0.28 of a hydrophobic ester of methacrylic acid.
The mixture was prepared in a 20 ml pyrex scintillation vial. The mixture was deoxygenated with blowing nitrogen for 1 minute and sealed with a polyseal cap. The vials were laid on their side under two Philips TL20W/09N bulbs such that the liquid level was between 5 and 6 cm from the lights. The material was photopolymerized for 10 minutes.
The results are summarized in Table VI:
TABLE VI
HYDROPHOBIC GRO UP APPEARANCE
before p~.ymerization after n-butyl clear clear 2-butyl clear clear t-butyl clear clear cyclohexyl clear clear n-hexyl clear translucent benzyl clear clear n-octyl clear opaque n-dodecyl clear opaque n-stearyl clear opaque 2-ethylhexyl clear sl. cloudy It is believed that the translucency, opacity, or slight cloudiness that was observed in those lenses made by bulk polymerization wherein the alkyl group in the alkyl methacrylate had 6 or more carbon atoms was caused by incompatibility that developed during the polymerization.
To the following:
0.8g HEMA (including 0.0016g EGDMA and 0.032g MAA) 0.00288 DAROCURE
was added 0.28 of a hydrophobic ester of methacrylic acid.
The mixture was prepared in a 20 ml pyrex scintillation vial. The mixture was deoxygenated with blowing nitrogen for 1 minute and sealed with a polyseal cap. The vials were laid on their side under two Philips TL20W/09N bulbs such that the liquid level was between 5 and 6 cm from the lights. The material was photopolymerized for 10 minutes.
The results are summarized in Table VI:
TABLE VI
HYDROPHOBIC GRO UP APPEARANCE
before p~.ymerization after n-butyl clear clear 2-butyl clear clear t-butyl clear clear cyclohexyl clear clear n-hexyl clear translucent benzyl clear clear n-octyl clear opaque n-dodecyl clear opaque n-stearyl clear opaque 2-ethylhexyl clear sl. cloudy It is believed that the translucency, opacity, or slight cloudiness that was observed in those lenses made by bulk polymerization wherein the alkyl group in the alkyl methacrylate had 6 or more carbon atoms was caused by incompatibility that developed during the polymerization.
Claims (16)
1. Process for producing shaped hydrogel articles which comprises the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a hydrophilic (meth)acrylate ester monomer, an alkyl (meth)acrylate wherein the alkyl group contains at least four carbon atoms, and a cross-linking monomer; and (b) a water-displaceable diluent, wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (w p) and Hansen hydrogen bonding (w h) cohesion parameters falling within the area of a circle defined as having a center at w h = 20.5, w p = 13, and a radius of 8.5, to produce a shaped gel of a copolymer of said monomers and said diluent, and (2) thereafter replacing said diluent with water.
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a hydrophilic (meth)acrylate ester monomer, an alkyl (meth)acrylate wherein the alkyl group contains at least four carbon atoms, and a cross-linking monomer; and (b) a water-displaceable diluent, wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (w p) and Hansen hydrogen bonding (w h) cohesion parameters falling within the area of a circle defined as having a center at w h = 20.5, w p = 13, and a radius of 8.5, to produce a shaped gel of a copolymer of said monomers and said diluent, and (2) thereafter replacing said diluent with water.
2. The process of Claim 1 wherein the said hydrophilic monomer is a hydroxyalkyl (meth)acrylate.
3. The process of Claim 2 wherein the hydroxyalkyl (meth)acrylate is 2-hydroxyethyl methacrylate.
4. The process of Claim 1 wherein said alkyl (meth)acrylate is n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, or n-dodecyl methacrylate.
5. The process of Claim 1 wherein said dihydric alcohol is 1,4-butanediol.
6. The process of Claim 1 wherein said dihydric alcohol is diethylene glycol.
7. The process of Claim 1 wherein the monomer mixture contains methacrylic acid.
8. The process of Claim 1 wherein the shaped hydrogel article is a contact lens.
9. Process for producing contact lenses which comprises the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a hydrophilic (meth)acrylate ester, a cross-linking monomer, and an alkyl (meth)acrylate wherein the alkyl group contains at least four carbon atoms; and (b) a water-displaceable diluent. wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (w p) and Hansen hydrogen bonding (w h) cohesion parameters falling within the area of a circle defined as having a center at w h = 20.5, w p = 13, and a radius of 8.5, to produce a shaped gel of a copolymer of said monomers and said diluent, and (2) thereafter replacing said diluent with water.
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a hydrophilic (meth)acrylate ester, a cross-linking monomer, and an alkyl (meth)acrylate wherein the alkyl group contains at least four carbon atoms; and (b) a water-displaceable diluent. wherein said diluent has a viscosity of at least 100 MPa Sec at 30°C, and wherein said diluent consists essentially of a boric acid ester of certain dihydric alcohols, said dihydric alcohols having Hansen polar (w p) and Hansen hydrogen bonding (w h) cohesion parameters falling within the area of a circle defined as having a center at w h = 20.5, w p = 13, and a radius of 8.5, to produce a shaped gel of a copolymer of said monomers and said diluent, and (2) thereafter replacing said diluent with water.
10. The process of Claim 9 wherein the said hydrophilic monomer is a hydroxyalkyl (meth)acrylate.
11. The process of Claim 10 wherein the hydroxyalkyl (meth)acrylate is 2-hydroxyethyl methacrylate.
12. The process of Claim 9 wherein said diluent has a viscosity of at least 500 MPa Sec at 30°C.
13. The process of Claim 9 wherein said alkyl (meth)acrylate is n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, or n-dodecyl methacrylate.
14. The process of Claim 9 wherein said dihydric alcohol is 1,4-butanediol.
15. The process of Claim 9 wherein said dihydric alcohol is diethylene glycol.
16. The process of Claim 9 wherein the monomer mixture contains methacrylic acid.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/451,077 US5039459A (en) | 1988-11-25 | 1989-12-15 | Method of forming shaped hydrogel articles including contact lenses |
US451,077 | 1989-12-15 |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2032200A1 CA2032200A1 (en) | 1991-06-16 |
CA2032200C true CA2032200C (en) | 2001-10-09 |
Family
ID=23790716
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002032200A Expired - Lifetime CA2032200C (en) | 1989-12-15 | 1990-12-13 | Method of forming shaped hydrogel articles including contact lenses |
Country Status (27)
Country | Link |
---|---|
US (1) | US5039459A (en) |
EP (1) | EP0433085B1 (en) |
JP (1) | JP2941959B2 (en) |
KR (1) | KR100232615B1 (en) |
CN (1) | CN1027521C (en) |
AT (1) | ATE154446T1 (en) |
AU (1) | AU626744B2 (en) |
BR (1) | BR9006395A (en) |
CA (1) | CA2032200C (en) |
CZ (1) | CZ279965B6 (en) |
DE (1) | DE69030915T2 (en) |
DK (1) | DK0433085T3 (en) |
ES (1) | ES2104591T3 (en) |
FI (1) | FI906179A (en) |
GR (1) | GR1000727B (en) |
HK (1) | HK1000673A1 (en) |
HU (1) | HU207964B (en) |
IE (1) | IE79671B1 (en) |
IL (1) | IL96651A (en) |
MX (1) | MX174569B (en) |
NO (1) | NO178466C (en) |
NZ (1) | NZ236398A (en) |
PT (1) | PT96209B (en) |
RO (1) | RO108099B1 (en) |
RU (1) | RU2091409C1 (en) |
YU (1) | YU47088B (en) |
ZA (1) | ZA9010079B (en) |
Families Citing this family (214)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2009668A1 (en) | 1989-02-16 | 1990-08-16 | Ashok R. Thakrar | Colored contact lenses and method of making same |
US5326505A (en) * | 1992-12-21 | 1994-07-05 | Johnson & Johnson Vision Products, Inc. | Method for treating an ophthalmic lens mold |
ATE160343T1 (en) * | 1993-04-22 | 1997-12-15 | Jessen Wesley Corp | UV-ABSORBING BENZOTRIAZOLES CONTAINING A STYRENE GROUP |
US5457140A (en) * | 1993-07-22 | 1995-10-10 | Johnson & Johnson Vision Products, Inc. | Method of forming shaped hydrogel articles including contact lenses using inert, displaceable diluents |
US5697495A (en) * | 1993-11-02 | 1997-12-16 | Johnson & Johnson Vision Products, Inc. | Packaging arrangement for contact lenses |
USRE37558E1 (en) * | 1993-11-02 | 2002-02-26 | Johnson & Johnson Vision Care, Inc. | Packaging arrangement for contact lenses |
US5823327A (en) * | 1993-11-02 | 1998-10-20 | Johnson & Johnson Vision Products, Inc. | Packaging arrangement for contact lenses |
US5804107A (en) * | 1994-06-10 | 1998-09-08 | Johnson & Johnson Vision Products, Inc. | Consolidated contact lens molding |
IL113693A0 (en) * | 1994-06-10 | 1995-08-31 | Johnson & Johnson Vision Prod | Contact lens production line pallet system |
US5578331A (en) * | 1994-06-10 | 1996-11-26 | Vision Products, Inc. | Automated apparatus for preparing contact lenses for inspection and packaging |
US5540410A (en) | 1994-06-10 | 1996-07-30 | Johnson & Johnson Vision Prod | Mold halves and molding assembly for making contact lenses |
US5545366A (en) * | 1994-06-10 | 1996-08-13 | Lust; Victor | Molding arrangement to achieve short mold cycle time and method of molding |
IL113826A0 (en) * | 1994-06-10 | 1995-08-31 | Johnson & Johnson Vision Prod | Method and apparatus for demolding ophthalmic contact lenses |
US5658602A (en) * | 1994-06-10 | 1997-08-19 | Johnson & Johnson Vision Products, Inc. | Method and apparatus for contact lens mold filling and assembly |
US5814134A (en) * | 1994-06-10 | 1998-09-29 | Johnson & Johnson Vision Products, Inc. | Apparatus and method for degassing deionized water for inspection and packaging |
US5837314A (en) * | 1994-06-10 | 1998-11-17 | Johnson & Johnson Vision Products, Inc. | Method and apparatus for applying a surfactant to mold surfaces |
US5850107A (en) * | 1994-06-10 | 1998-12-15 | Johnson & Johnson Vision Products, Inc. | Mold separation method and apparatus |
US5696686A (en) * | 1994-06-10 | 1997-12-09 | Johnson & Johnson Vision Products, Inc. | Computer system for quality control correlations |
US5461570A (en) * | 1994-06-10 | 1995-10-24 | Johnson & Johnson Vision Products, Inc. | Computer system for quality control correlations |
US5607642A (en) * | 1994-06-10 | 1997-03-04 | Johnson & Johnson Vision Products, Inc. | Interactive control system for packaging control of contact lenses |
US5542978A (en) * | 1994-06-10 | 1996-08-06 | Johnson & Johnson Vision Products, Inc. | Apparatus for applying a surfactant to mold surfaces |
IL113694A0 (en) * | 1994-06-10 | 1995-08-31 | Johnson & Johnson Vision Prod | Apparatus for removing and transporting articles from molds |
US5597519A (en) * | 1994-06-10 | 1997-01-28 | Johnson & Johnson Vision Products, Inc. | Ultraviolet cycling oven for polymerization of contact lenses |
US5656208A (en) * | 1994-06-10 | 1997-08-12 | Johnson & Johnson Vision Products, Inc. | Method and apparatus for contact lens mold filling and assembly |
US6752581B1 (en) * | 1994-06-10 | 2004-06-22 | Johnson & Johnson Vision Care, Inc. | Apparatus for removing and transporting articles from molds |
IL113691A0 (en) * | 1994-06-10 | 1995-08-31 | Johnson & Johnson Vision Prod | Low oxygen molding of soft contact lenses |
US5895192C1 (en) | 1994-06-10 | 2001-11-06 | Johnson & Johnson Vision Prod | Apparatus and method for removing and transporting articles from molds |
IL113904A0 (en) * | 1994-06-10 | 1995-08-31 | Johnson & Johnson Vision Prod | Mold clamping and precure of a polymerizable hydrogel |
US5528878A (en) * | 1994-06-10 | 1996-06-25 | Johnson & Johnson Vision Products, Inc. | Automated apparatus and method for consolidating products for packaging |
US5760100B1 (en) | 1994-09-06 | 2000-11-14 | Ciba Vision Corp | Extended wear ophthalmic lens |
US7468398B2 (en) | 1994-09-06 | 2008-12-23 | Ciba Vision Corporation | Extended wear ophthalmic lens |
US5910519A (en) * | 1995-03-24 | 1999-06-08 | Johnson & Johnson Vision Products, Inc. | Method of forming shaped hydrogel articles including contact lenses using inert, displaceable diluents |
US5685420A (en) * | 1995-03-31 | 1997-11-11 | Johnson & Johnson Vision Products, Inc. | Composite packaging arrangement for contact lenses |
DE69617637T2 (en) * | 1995-09-06 | 2002-07-18 | Menicon Co Ltd | METHOD FOR THE PRODUCTION OF CONTACT LENSES AND THE CONTACT LENSES PRODUCED IN THIS PROCESS |
AU712870B2 (en) | 1995-09-29 | 1999-11-18 | Johnson & Johnson Vision Products, Inc. | Automated apparatus and method for consolidating products for packaging |
JP2959997B2 (en) * | 1995-10-30 | 1999-10-06 | ホーヤ株式会社 | Method for producing 2-hydroxyethyl methacrylate polymer, hydrogel and hydrated soft contact lens |
US5922249A (en) * | 1995-12-08 | 1999-07-13 | Novartis Ag | Ophthalmic lens production process |
US5916494A (en) | 1995-12-29 | 1999-06-29 | Johnson & Johnson Vision Products, Inc. | Rotational indexing base curve deposition array |
SG54538A1 (en) * | 1996-08-05 | 1998-11-16 | Hoya Corp | Soft contact lens with high moisture content and method for producing the same |
US5938988A (en) * | 1996-08-19 | 1999-08-17 | Johnson & Johnson Vision Products, Inc. | Multiple optical curve molds formed in a solid piece of polymer |
US6326448B1 (en) | 1997-08-20 | 2001-12-04 | Menicon Co., Ltd. | Soft intraocular lens material |
JP3641110B2 (en) * | 1997-08-20 | 2005-04-20 | 株式会社メニコン | Materials for soft intraocular lenses |
US6047082A (en) * | 1997-11-14 | 2000-04-04 | Wesley Jessen Corporation | Automatic lens inspection system |
US6943203B2 (en) * | 1998-03-02 | 2005-09-13 | Johnson & Johnson Vision Care, Inc. | Soft contact lenses |
US6367929B1 (en) | 1998-03-02 | 2002-04-09 | Johnson & Johnson Vision Care, Inc. | Hydrogel with internal wetting agent |
US6849671B2 (en) | 1998-03-02 | 2005-02-01 | Johnson & Johnson Vision Care, Inc. | Contact lenses |
US6822016B2 (en) * | 2001-09-10 | 2004-11-23 | Johnson & Johnson Vision Care, Inc. | Biomedical devices containing internal wetting agents |
US5962548A (en) * | 1998-03-02 | 1999-10-05 | Johnson & Johnson Vision Products, Inc. | Silicone hydrogel polymers |
US20070043140A1 (en) * | 1998-03-02 | 2007-02-22 | Lorenz Kathrine O | Method for the mitigation of symptoms of contact lens related dry eye |
US7461937B2 (en) * | 2001-09-10 | 2008-12-09 | Johnson & Johnson Vision Care, Inc. | Soft contact lenses displaying superior on-eye comfort |
US7052131B2 (en) * | 2001-09-10 | 2006-05-30 | J&J Vision Care, Inc. | Biomedical devices containing internal wetting agents |
US5998498A (en) * | 1998-03-02 | 1999-12-07 | Johnson & Johnson Vision Products, Inc. | Soft contact lenses |
US6242042B1 (en) | 1998-09-14 | 2001-06-05 | Lrc Products Ltd. | Aqueous coating composition and method |
SG87848A1 (en) | 1998-11-05 | 2002-04-16 | Johnson & Johnson Vision Prod | Missing lens detection system and method |
US6246062B1 (en) | 1998-11-05 | 2001-06-12 | Johnson & Johnson Vision Care, Inc. | Missing lens detection system and method |
US20040112008A1 (en) | 1998-12-21 | 2004-06-17 | Voss Leslie A. | Heat seal apparatus for lens packages |
US20040074525A1 (en) * | 2001-03-27 | 2004-04-22 | Widman Michael F. | Transfer apparatus and method and a transfer apparatus cleaner and method |
US20070157553A1 (en) * | 1998-12-21 | 2007-07-12 | Voss Leslie A | Heat seal apparatus for lens packages |
US6610220B1 (en) | 1998-12-28 | 2003-08-26 | Johnson & Johnson Vision Care, Inc. | Process of manufacturing contact lenses with measured exposure to oxygen |
US6494021B1 (en) | 1999-02-18 | 2002-12-17 | Johnson & Johnson Vision Care, Inc. | Contact lens transfer and material removal system |
US6207086B1 (en) | 1999-02-18 | 2001-03-27 | Johnson & Johnson Vision Care, Inc. | Method and apparatus for washing or hydration of ophthalmic devices |
US6592816B1 (en) | 1999-03-01 | 2003-07-15 | Johnson & Johnson Vision Care, Inc. | Sterilization system |
US7879288B2 (en) * | 1999-03-01 | 2011-02-01 | Johnson & Johnson Vision Care, Inc. | Method and apparatus of sterilization using monochromatic UV radiation source |
US6827885B2 (en) | 2000-03-31 | 2004-12-07 | Bausch & Lomb Incorporated | Methods and devices to control polymerization |
KR20040005856A (en) * | 2000-11-03 | 2004-01-16 | 존슨 앤드 존슨 비젼 케어, 인코포레이티드 | Solvents useful in the preparation of polymers containing hydrophilic and hydrophobic monomers |
US6861123B2 (en) * | 2000-12-01 | 2005-03-01 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogel contact lens |
US20040151755A1 (en) * | 2000-12-21 | 2004-08-05 | Osman Rathore | Antimicrobial lenses displaying extended efficacy, processes to prepare them and methods of their use |
US6577387B2 (en) | 2000-12-29 | 2003-06-10 | Johnson & Johnson Vision Care, Inc. | Inspection of ophthalmic lenses using absorption |
ATE317758T1 (en) * | 2001-01-24 | 2006-03-15 | Novartis Pharma Gmbh | METHOD FOR PRODUCING LENSES |
CA2440900A1 (en) | 2001-03-16 | 2002-09-26 | Novartis Ag | Colored printing ink for contact lenses |
US6663801B2 (en) * | 2001-04-06 | 2003-12-16 | Johnson & Johnson Vision Care, Inc. | Silicon carbide IR-emitter heating device and method for demolding lenses |
US7008570B2 (en) * | 2001-08-09 | 2006-03-07 | Stephen Pegram | Method and apparatus for contact lens mold assembly |
US6836692B2 (en) * | 2001-08-09 | 2004-12-28 | Johnson & Johnson Vision Care, Inc. | System and method for intelligent lens transfer |
EP1474719A4 (en) * | 2002-02-15 | 2005-12-14 | Zms Llc | Polymerization process and materials for biomedical applications |
US7001138B2 (en) * | 2002-03-01 | 2006-02-21 | Johnson & Johnson Vision Care, Inc. | Split collar for mechanical arm connection |
US6846892B2 (en) * | 2002-03-11 | 2005-01-25 | Johnson & Johnson Vision Care, Inc. | Low polydispersity poly-HEMA compositions |
US20060100408A1 (en) * | 2002-03-11 | 2006-05-11 | Powell P M | Method for forming contact lenses comprising therapeutic agents |
US20030223954A1 (en) * | 2002-05-31 | 2003-12-04 | Ruscio Dominic V. | Polymeric materials for use as photoablatable inlays |
US8158695B2 (en) * | 2002-09-06 | 2012-04-17 | Johnson & Johnson Vision Care, Inc. | Forming clear, wettable silicone hydrogel articles without surface treatments |
US20040150788A1 (en) | 2002-11-22 | 2004-08-05 | Ann-Margret Andersson | Antimicrobial lenses, processes to prepare them and methods of their use |
US20080299179A1 (en) * | 2002-09-06 | 2008-12-04 | Osman Rathore | Solutions for ophthalmic lenses containing at least one silicone containing component |
US20070138692A1 (en) * | 2002-09-06 | 2007-06-21 | Ford James D | Process for forming clear, wettable silicone hydrogel articles |
US7368127B2 (en) * | 2002-12-19 | 2008-05-06 | Johnson & Johnson Vision Care, Inc. | Biomedical devices with peptide containing coatings |
US20040120982A1 (en) * | 2002-12-19 | 2004-06-24 | Zanini Diana | Biomedical devices with coatings attached via latent reactive components |
EP1623269B2 (en) * | 2003-04-24 | 2022-08-31 | CooperVision International Limited | Hydrogel contact lenses and package systems and production methods for same |
US8097565B2 (en) * | 2003-06-30 | 2012-01-17 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes |
GB0322640D0 (en) * | 2003-09-26 | 2003-10-29 | 1800 Contacts | Process |
US7214809B2 (en) | 2004-02-11 | 2007-05-08 | Johnson & Johnson Vision Care, Inc. | (Meth)acrylamide monomers containing hydroxy and silicone functionalities |
US7786185B2 (en) | 2004-03-05 | 2010-08-31 | Johnson & Johnson Vision Care, Inc. | Wettable hydrogels comprising acyclic polyamides |
US20060043623A1 (en) | 2004-08-27 | 2006-03-02 | Powell P M | Masked precure of ophthalmic lenses: systems and methods thereof |
US7249848B2 (en) * | 2004-09-30 | 2007-07-31 | Johnson & Johnson Vision Care, Inc. | Wettable hydrogels comprising reactive, hydrophilic, polymeric internal wetting agents |
US7473738B2 (en) * | 2004-09-30 | 2009-01-06 | Johnson & Johnson Vision Care, Inc. | Lactam polymer derivatives |
US7247692B2 (en) * | 2004-09-30 | 2007-07-24 | Johnson & Johnson Vision Care, Inc. | Biomedical devices containing amphiphilic block copolymers |
SG177132A1 (en) | 2005-02-14 | 2012-01-30 | Johnson & Johnson Vision Care | A comfortable ophthalmic device and methods of its production |
US20060232766A1 (en) * | 2005-03-31 | 2006-10-19 | Watterson Robert J Jr | Methods of inspecting ophthalmic lenses |
US8158037B2 (en) | 2005-04-08 | 2012-04-17 | Johnson & Johnson Vision Care, Inc. | Photochromic materials having extended pi-conjugated systems and compositions and articles including the same |
US20060226402A1 (en) * | 2005-04-08 | 2006-10-12 | Beon-Kyu Kim | Ophthalmic devices comprising photochromic materials having extended PI-conjugated systems |
US20060227287A1 (en) * | 2005-04-08 | 2006-10-12 | Frank Molock | Photochromic ophthalmic devices made with dual initiator system |
US9052438B2 (en) * | 2005-04-08 | 2015-06-09 | Johnson & Johnson Vision Care, Inc. | Ophthalmic devices comprising photochromic materials with reactive substituents |
MY161660A (en) * | 2005-05-04 | 2017-04-28 | Novartis Ag | Automated inspection of colored contact lenses |
US9102110B2 (en) * | 2005-08-09 | 2015-08-11 | Coopervision International Holding Company, Lp | Systems and methods for removing lenses from lens molds |
US20070155851A1 (en) * | 2005-12-30 | 2007-07-05 | Azaam Alli | Silicone containing polymers formed from non-reactive silicone containing prepolymers |
US9052529B2 (en) | 2006-02-10 | 2015-06-09 | Johnson & Johnson Vision Care, Inc. | Comfortable ophthalmic device and methods of its production |
US8414804B2 (en) * | 2006-03-23 | 2013-04-09 | Johnson & Johnson Vision Care, Inc. | Process for making ophthalmic lenses |
US8231218B2 (en) | 2006-06-15 | 2012-07-31 | Coopervision International Holding Company, Lp | Wettable silicone hydrogel contact lenses and related compositions and methods |
US7960465B2 (en) | 2006-06-30 | 2011-06-14 | Johnson & Johnson Vision Care, Inc. | Antimicrobial lenses, processes to prepare them and methods of their use |
WO2008073593A2 (en) * | 2006-10-31 | 2008-06-19 | Johnson & Johnson Vision Care, Inc. | Processes to prepare antimicrobial contact lenses |
US20080102095A1 (en) * | 2006-10-31 | 2008-05-01 | Kent Young | Acidic processes to prepare antimicrobial contact lenses |
US20080100797A1 (en) * | 2006-10-31 | 2008-05-01 | Nayiby Alvarez-Carrigan | Antimicrobial contact lenses with reduced haze and preparation thereof |
CA2705785A1 (en) | 2006-11-14 | 2008-05-22 | Saul Yedgar | Use of lipid conjugates in the treatment of diseases or disorders of the eye |
US8214746B2 (en) * | 2007-03-15 | 2012-07-03 | Accenture Global Services Limited | Establishment of message context in a collaboration system |
EP2142219A2 (en) * | 2007-03-30 | 2010-01-13 | Johnson & Johnson Vision Care, Inc. | Preparation of antimicrobial contact lenses with reduced haze using swelling agents |
US20080241225A1 (en) * | 2007-03-31 | 2008-10-02 | Hill Gregory A | Basic processes to prepare antimicrobial contact lenses |
CA2693808C (en) * | 2007-07-19 | 2015-10-20 | Alcon, Inc. | High ion and metabolite flux lenses and materials |
US8119753B2 (en) * | 2007-10-23 | 2012-02-21 | Bausch & Lomb Incorporated | Silicone hydrogels with amino surface groups |
US8272735B2 (en) * | 2008-09-30 | 2012-09-25 | Johnson & Johnson Vision Care, Inc. | Lens design simplification process |
US20100109176A1 (en) | 2008-11-03 | 2010-05-06 | Chris Davison | Machined lens molds and methods for making and using same |
KR101506430B1 (en) * | 2008-12-18 | 2015-03-26 | 노파르티스 아게 | Method for making silicone hydrogel contact lenses |
US8960901B2 (en) | 2009-02-02 | 2015-02-24 | Johnson & Johnson Vision Care, Inc. | Myopia control ophthalmic lenses |
JP2012520353A (en) | 2009-03-13 | 2012-09-06 | コグニス・アイピー・マネージメント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Monomers and macromers for forming hydrogels |
US20100249273A1 (en) | 2009-03-31 | 2010-09-30 | Scales Charles W | Polymeric articles comprising oxygen permeability enhancing particles |
EP2446319B1 (en) | 2009-06-25 | 2016-03-30 | Johnson & Johnson Vision Care Inc. | Design of myopia control ophthalmic lenses |
US8313675B2 (en) * | 2009-08-31 | 2012-11-20 | Coopervision International Holding Company, Lp | Demolding of ophthalmic lenses during the manufacture thereof |
EP2533680B1 (en) | 2010-02-12 | 2018-05-30 | Johnson & Johnson Vision Care Inc. | Apparatus to obtain clinical ophthalmic high order optical aberrations |
US9690115B2 (en) | 2010-04-13 | 2017-06-27 | Johnson & Johnson Vision Care, Inc. | Contact lenses displaying reduced indoor glare |
US8697770B2 (en) | 2010-04-13 | 2014-04-15 | Johnson & Johnson Vision Care, Inc. | Pupil-only photochromic contact lenses displaying desirable optics and comfort |
US8877103B2 (en) | 2010-04-13 | 2014-11-04 | Johnson & Johnson Vision Care, Inc. | Process for manufacture of a thermochromic contact lens material |
US9522980B2 (en) | 2010-05-06 | 2016-12-20 | Johnson & Johnson Vision Care, Inc. | Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same |
KR102139022B1 (en) | 2010-07-30 | 2020-07-29 | 알콘 인코포레이티드 | A silicone hydrogel lens with a crosslinked hydrophilic coating |
US9612363B2 (en) | 2010-11-04 | 2017-04-04 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogel reactive mixtures comprising borates |
WO2012064787A2 (en) | 2010-11-08 | 2012-05-18 | W&L Polymers, Ltd. | Gels and hydrogels |
US9623614B2 (en) | 2010-11-10 | 2017-04-18 | Novartis Ag | Method for making contact lenses |
WO2012095293A2 (en) | 2011-01-14 | 2012-07-19 | Cognis Ip Management Gmbh | Process for the synthesis of compounds from cyclic carbonates |
US8801176B2 (en) | 2011-03-24 | 2014-08-12 | Johnson & Johnson Vision Care, Inc. | Contact lenses with improved movement |
US8672476B2 (en) | 2011-03-24 | 2014-03-18 | Johnson & Johnson Vision Care, Inc. | Contact lenses with improved movement |
US9170349B2 (en) | 2011-05-04 | 2015-10-27 | Johnson & Johnson Vision Care, Inc. | Medical devices having homogeneous charge density and methods for making same |
US20130203813A1 (en) | 2011-05-04 | 2013-08-08 | Johnson & Johnson Vision Care, Inc. | Medical devices having homogeneous charge density and methods for making same |
US10383839B2 (en) | 2011-06-30 | 2019-08-20 | Johnson & Johnson Vision Care, Inc. | Esters for treatment of ocular inflammatory conditions |
US9188702B2 (en) | 2011-09-30 | 2015-11-17 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogels having improved curing speed and other properties |
HUE029018T2 (en) | 2011-10-12 | 2017-02-28 | Novartis Ag | Method for making uv-absorbing ophthalmic lenses by coating |
US10209534B2 (en) | 2012-03-27 | 2019-02-19 | Johnson & Johnson Vision Care, Inc. | Increased stiffness center optic in soft contact lenses for astigmatism correction |
US9297929B2 (en) | 2012-05-25 | 2016-03-29 | Johnson & Johnson Vision Care, Inc. | Contact lenses comprising water soluble N-(2 hydroxyalkyl) (meth)acrylamide polymers or copolymers |
US9244196B2 (en) | 2012-05-25 | 2016-01-26 | Johnson & Johnson Vision Care, Inc. | Polymers and nanogel materials and methods for making and using the same |
US10073192B2 (en) | 2012-05-25 | 2018-09-11 | Johnson & Johnson Vision Care, Inc. | Polymers and nanogel materials and methods for making and using the same |
WO2013177523A2 (en) | 2012-05-25 | 2013-11-28 | Johnson & Johnson Vision Care, Inc. | Polymers and nanogel materials and methods for making and using the same |
WO2014095690A1 (en) | 2012-12-17 | 2014-06-26 | Novartis Ag | Method for making improved uv-absorbing ophthalmic lenses |
US8967799B2 (en) | 2012-12-20 | 2015-03-03 | Bausch & Lomb Incorporated | Method of preparing water extractable silicon-containing biomedical devices |
US20140291875A1 (en) | 2013-02-12 | 2014-10-02 | Coopervision International Holding Company, Lp | Methods and Apparatus Useful in the Manufacture of Contact Lenses |
US9708087B2 (en) | 2013-12-17 | 2017-07-18 | Novartis Ag | Silicone hydrogel lens with a crosslinked hydrophilic coating |
CN106715101B (en) | 2014-08-26 | 2019-11-05 | 诺华股份有限公司 | Method for applying stable coating in silicone hydrogel contact lens on piece |
EP3391101B1 (en) | 2015-12-15 | 2020-07-08 | Alcon Inc. | Method for applying stable coating on silicone hydrogel contact lenses |
US11125916B2 (en) | 2016-07-06 | 2021-09-21 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogels comprising N-alkyl methacrylamides and contact lenses made thereof |
US10371865B2 (en) | 2016-07-06 | 2019-08-06 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogels comprising polyamides |
US10370476B2 (en) | 2016-07-06 | 2019-08-06 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogels comprising high levels of polyamides |
WO2018009309A1 (en) | 2016-07-06 | 2018-01-11 | Johnson & Johnson Vision Care, Inc. | Increased stiffness center optic in soft contact lenses for astigmatism correction |
US11021558B2 (en) | 2016-08-05 | 2021-06-01 | Johnson & Johnson Vision Care, Inc. | Polymer compositions containing grafted polymeric networks and processes for their preparation and use |
US10676575B2 (en) | 2016-10-06 | 2020-06-09 | Johnson & Johnson Vision Care, Inc. | Tri-block prepolymers and their use in silicone hydrogels |
US10894111B2 (en) * | 2016-12-16 | 2021-01-19 | Benz Research And Development Corp. | High refractive index hydrophilic materials |
US10752720B2 (en) | 2017-06-26 | 2020-08-25 | Johnson & Johnson Vision Care, Inc. | Polymerizable blockers of high energy light |
US10526296B2 (en) | 2017-06-30 | 2020-01-07 | Johnson & Johnson Vision Care, Inc. | Hydroxyphenyl naphthotriazoles as polymerizable blockers of high energy light |
US10723732B2 (en) | 2017-06-30 | 2020-07-28 | Johnson & Johnson Vision Care, Inc. | Hydroxyphenyl phenanthrolines as polymerizable blockers of high energy light |
CN111386478B (en) | 2017-12-13 | 2023-11-14 | 爱尔康公司 | Zhou Pao and month polishing gradient contact lens |
US11034789B2 (en) | 2018-01-30 | 2021-06-15 | Johnson & Johnson Vision Care, Inc. | Ophthalmic devices containing localized grafted networks and processes for their preparation and use |
US10961341B2 (en) | 2018-01-30 | 2021-03-30 | Johnson & Johnson Vision Care, Inc. | Ophthalmic devices derived from grafted polymeric networks and processes for their preparation and use |
US20210061934A1 (en) | 2019-08-30 | 2021-03-04 | Johnson & Johnson Vision Care, Inc. | Contact lens displaying improved vision attributes |
US10935695B2 (en) | 2018-03-02 | 2021-03-02 | Johnson & Johnson Vision Care, Inc. | Polymerizable absorbers of UV and high energy visible light |
US10996491B2 (en) | 2018-03-23 | 2021-05-04 | Johnson & Johnson Vision Care, Inc. | Ink composition for cosmetic contact lenses |
US11046636B2 (en) | 2018-06-29 | 2021-06-29 | Johnson & Johnson Vision Care, Inc. | Polymerizable absorbers of UV and high energy visible light |
US10932902B2 (en) | 2018-08-03 | 2021-03-02 | Johnson & Johnson Vision Care, Inc. | Dynamically tunable apodized multiple-focus opthalmic devices and methods |
US20200073145A1 (en) | 2018-09-05 | 2020-03-05 | Johnson & Johnson Vision Care, Inc. | Vision care kit |
US11493668B2 (en) | 2018-09-26 | 2022-11-08 | Johnson & Johnson Vision Care, Inc. | Polymerizable absorbers of UV and high energy visible light |
US11724471B2 (en) | 2019-03-28 | 2023-08-15 | Johnson & Johnson Vision Care, Inc. | Methods for the manufacture of photoabsorbing contact lenses and photoabsorbing contact lenses produced thereby |
US11578176B2 (en) | 2019-06-24 | 2023-02-14 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogel contact lenses having non-uniform morphology |
US20200407324A1 (en) | 2019-06-28 | 2020-12-31 | Johnson & Johnson Vision Care, Inc. | Polymerizable fused tricyclic compounds as absorbers of uv and visible light |
US11958824B2 (en) | 2019-06-28 | 2024-04-16 | Johnson & Johnson Vision Care, Inc. | Photostable mimics of macular pigment |
US20210003754A1 (en) | 2019-07-02 | 2021-01-07 | Johnson & Johnson Vision Care, Inc. | Core-shell particles and methods of making and using thereof |
US11543683B2 (en) | 2019-08-30 | 2023-01-03 | Johnson & Johnson Vision Care, Inc. | Multifocal contact lens displaying improved vision attributes |
US11891526B2 (en) | 2019-09-12 | 2024-02-06 | Johnson & Johnson Vision Care, Inc. | Ink composition for cosmetic contact lenses |
US11360240B2 (en) | 2019-12-19 | 2022-06-14 | Johnson & Johnson Vision Care, Inc. | Contact lens containing photosensitive chromophore and package therefor |
US20210301088A1 (en) | 2020-03-18 | 2021-09-30 | Johnson & Johnson Vision Care, Inc. | Ophthalmic devices containing transition metal complexes as high energy visible light filters |
US11853013B2 (en) | 2020-06-15 | 2023-12-26 | Johnson & Johnson Vision Care, Inc. | Systems and methods for indicating the time elapsed since the occurrence of a triggering event |
US20210388142A1 (en) | 2020-06-16 | 2021-12-16 | Johnson & Johnson Vision Care, Inc. | Amino acid-based polymerizable compounds and ophthalmic devices prepared therefrom |
US20210388141A1 (en) | 2020-06-16 | 2021-12-16 | Johnson & Johnson Vision Care, Inc. | Imidazolium zwitterion polymerizable compounds and ophthalmic devices incorporating them |
CN111808533A (en) * | 2020-07-19 | 2020-10-23 | 湖州飞鹿新能源科技有限公司 | Crystalline silicon polishing gel special for Topcon battery and use method thereof |
TW202225787A (en) | 2020-09-14 | 2022-07-01 | 美商壯生和壯生視覺關懷公司 | Single touch contact lens package |
TW202231215A (en) | 2020-09-14 | 2022-08-16 | 美商壯生和壯生視覺關懷公司 | Single touch contact lens case |
US20220113558A1 (en) | 2020-10-13 | 2022-04-14 | Johnson & Johnson Vision Care, Inc. | Contact lens position and rotation control using the pressure of the eyelid margin |
AU2021396636A1 (en) | 2020-12-13 | 2023-01-19 | Johnson & Johnson Vision Care, Inc. | Contact lens packages and methods of opening |
WO2022130089A1 (en) | 2020-12-18 | 2022-06-23 | Johnson & Johnson Vision Care, Inc. | Photostable mimics of macular pigment |
US20220220417A1 (en) | 2021-01-12 | 2022-07-14 | Johnson & Johnson Vision Care, Inc. | Compositions for Ophthalmologic Devices |
US20230023885A1 (en) | 2021-06-30 | 2023-01-26 | Johnson & Johnson Vision Care, Inc. | Ophthalmic devices derived from grafted polymeric networks and processes for their preparation and use |
US20230037781A1 (en) | 2021-06-30 | 2023-02-09 | Johnson & Johnson Vision Care, Inc. | Transition metal complexes as visible light absorbers |
CA3173598A1 (en) | 2021-09-13 | 2023-03-13 | Johnson & Johnson Vision Care, Inc. | Contact lens packages and methods of handling and manufacture |
US11912800B2 (en) | 2021-09-29 | 2024-02-27 | Johnson & Johnson Vision Care, Inc. | Amide-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses |
US11708209B2 (en) | 2021-11-05 | 2023-07-25 | Johnson & Johnson Vision Care, Inc. | Touchless contact lens packages and methods of handling |
WO2023105470A1 (en) | 2021-12-08 | 2023-06-15 | Johnson & Johnson Vision Care, Inc. | Slotted contact lens packages and methods of handling |
TW202335928A (en) | 2021-12-08 | 2023-09-16 | 美商壯生和壯生視覺關懷公司 | Contact lens packages having lens lifting arms and methods of handling |
TW202340053A (en) | 2021-12-13 | 2023-10-16 | 美商壯生和壯生視覺關懷公司 | Contact lens packages with sliding or tilting lens transfer and methods of handling |
WO2023111853A1 (en) | 2021-12-14 | 2023-06-22 | Johnson & Johnson Vision Care, Inc. | Contact lens packages having twisting or thimble levers and methods of handling |
WO2023111851A1 (en) | 2021-12-15 | 2023-06-22 | Johnson & Johnson Vision Care, Inc. | Solutionless contact lens packages and methods of manufacture |
WO2023111852A1 (en) | 2021-12-15 | 2023-06-22 | Johnson & Johnson Vision Care, Inc. | No-touch contact lens packages and methods of handling |
WO2023111941A1 (en) | 2021-12-16 | 2023-06-22 | Johnson & Johnson Vision Care, Inc. | No-touch contact lens packages and methods of handling |
WO2023111939A1 (en) | 2021-12-16 | 2023-06-22 | Johnson & Johnson Vision Care, Inc. | Pressurized or vacuum-sealed contact lens packages |
WO2023111947A1 (en) | 2021-12-17 | 2023-06-22 | Johnson & Johnson Vision Care, Inc. | Contact lens dispenser |
WO2023111943A1 (en) | 2021-12-17 | 2023-06-22 | Johnson & Johnson Vision Care, Inc. | Contact lens packages having a pivot mechanism and methods of handling |
US20230296807A1 (en) | 2021-12-20 | 2023-09-21 | Johnson & Johnson Vision Care, Inc. | Contact lenses containing light absorbing regions and methods for their preparation |
US20230350230A1 (en) | 2022-04-28 | 2023-11-02 | Johnson & Johnson Vision Care, Inc. | Using particles for light filtering |
WO2023209446A1 (en) | 2022-04-28 | 2023-11-02 | Johnson & Johnson Vision Care, Inc. | Shape engineering of particles to create a narrow spectral filter against a specific portion of the light spectrum |
US20230348718A1 (en) | 2022-04-28 | 2023-11-02 | Johnson & Johnson Vision Care, Inc. | Light-filtering materials for biomaterial integration and methods thereof |
US11733440B1 (en) | 2022-04-28 | 2023-08-22 | Johnson & Johnson Vision Care, Inc. | Thermally stable nanoparticles and methods thereof |
US20230348717A1 (en) | 2022-04-28 | 2023-11-02 | Johnson & Johnson Vision Care, Inc. | Particle surface modification to increase compatibility and stability in hydrogels |
WO2023242688A1 (en) | 2022-06-16 | 2023-12-21 | Johnson & Johnson Vision Care, Inc. | Ophthalmic devices containing photostable mimics of macular pigment and other visible light filters |
US20240099434A1 (en) | 2022-09-27 | 2024-03-28 | Johnson & Johnson Vision Care, Inc. | Contact lens package with draining port |
US20240099435A1 (en) | 2022-09-27 | 2024-03-28 | Johnson & Johnson Vision Care, Inc. | Flat contact lens packages and methods of handling |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH461106A (en) * | 1965-05-24 | 1968-08-15 | Ceskoslovenska Akademie Ved | Process for the manufacture of articles from hydrogels by polymerization casting |
US3503942A (en) * | 1965-10-23 | 1970-03-31 | Maurice Seiderman | Hydrophilic plastic contact lens |
US3926892A (en) * | 1974-06-06 | 1975-12-16 | Burton Parsons & Company Inc | Hydrophilic contact lenses and lens polymer |
US3965063A (en) * | 1974-06-06 | 1976-06-22 | Burton, Parsons And Company, Inc. | Hydrophilic contact lenses and lens polymer |
FR2402525A1 (en) * | 1977-09-12 | 1979-04-06 | Toray Industries | PROCESS FOR MANUFACTURING COMPOSITIONS OF SOFT CONTACT LENSES AND NEW PRODUCTS THUS OBTAINED |
US4452776A (en) * | 1979-08-20 | 1984-06-05 | Eye Research Institute Of Retina Foundation | Hydrogel implant article and method |
US4495313A (en) * | 1981-04-30 | 1985-01-22 | Mia Lens Production A/S | Preparation of hydrogel for soft contact lens with water displaceable boric acid ester |
NZ200362A (en) * | 1981-04-30 | 1985-10-11 | Mia Lens Prod | A method of forming a hydrophilic polymer suitable for use in the manufacture of soft contact lenses and a mould for use in the polymerization |
US4528311A (en) * | 1983-07-11 | 1985-07-09 | Iolab Corporation | Ultraviolet absorbing polymers comprising 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazoles |
US4680336A (en) * | 1984-11-21 | 1987-07-14 | Vistakon, Inc. | Method of forming shaped hydrogel articles |
JP2543335B2 (en) * | 1985-03-30 | 1996-10-16 | ホ−ヤ株式会社 | High water content contact lens |
US4889664A (en) * | 1988-11-25 | 1989-12-26 | Vistakon, Inc. | Method of forming shaped hydrogel articles including contact lenses |
-
1989
- 1989-12-15 US US07/451,077 patent/US5039459A/en not_active Expired - Lifetime
-
1990
- 1990-12-07 NZ NZ236398A patent/NZ236398A/en unknown
- 1990-12-11 GR GR900100854A patent/GR1000727B/en unknown
- 1990-12-13 MX MX023708A patent/MX174569B/en unknown
- 1990-12-13 IL IL9665190A patent/IL96651A/en not_active IP Right Cessation
- 1990-12-13 CA CA002032200A patent/CA2032200C/en not_active Expired - Lifetime
- 1990-12-14 CZ CS906274A patent/CZ279965B6/en unknown
- 1990-12-14 HU HU908277A patent/HU207964B/en not_active IP Right Cessation
- 1990-12-14 ZA ZA9010079A patent/ZA9010079B/en unknown
- 1990-12-14 AT AT90313675T patent/ATE154446T1/en not_active IP Right Cessation
- 1990-12-14 JP JP2410528A patent/JP2941959B2/en not_active Expired - Lifetime
- 1990-12-14 NO NO905409A patent/NO178466C/en unknown
- 1990-12-14 DE DE69030915T patent/DE69030915T2/en not_active Expired - Lifetime
- 1990-12-14 EP EP90313675A patent/EP0433085B1/en not_active Expired - Lifetime
- 1990-12-14 FI FI906179A patent/FI906179A/en not_active IP Right Cessation
- 1990-12-14 YU YU235390A patent/YU47088B/en unknown
- 1990-12-14 PT PT96209A patent/PT96209B/en not_active IP Right Cessation
- 1990-12-14 KR KR1019900020577A patent/KR100232615B1/en not_active IP Right Cessation
- 1990-12-14 IE IE452690A patent/IE79671B1/en not_active IP Right Cessation
- 1990-12-14 DK DK90313675.2T patent/DK0433085T3/en active
- 1990-12-14 RU SU904894080A patent/RU2091409C1/en active
- 1990-12-14 AU AU68088/90A patent/AU626744B2/en not_active Expired
- 1990-12-14 RO RO146544A patent/RO108099B1/en unknown
- 1990-12-14 BR BR909006395A patent/BR9006395A/en not_active IP Right Cessation
- 1990-12-14 ES ES90313675T patent/ES2104591T3/en not_active Expired - Lifetime
- 1990-12-15 CN CN90110408A patent/CN1027521C/en not_active Expired - Lifetime
-
1997
- 1997-11-26 HK HK97102245A patent/HK1000673A1/en not_active IP Right Cessation
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2032200C (en) | Method of forming shaped hydrogel articles including contact lenses | |
CA2003806C (en) | Method of forming shaped hydrogel articles including contact lenses | |
US6011081A (en) | Contact lens having improved dimensional stability | |
EP0182659A2 (en) | Shaped hydrogel articles | |
US5532289A (en) | Contact lens having improved dimensional stability | |
JP2010061148A (en) | Ionic contact lens | |
US4450262A (en) | Hydrophilic copolymer compositions useful as contact lenses | |
RU2080637C1 (en) | Process of manufacture of shaped articles from hydrogel | |
JPH0688949A (en) | Transparent water-containing gel material | |
JPS6337312A (en) | Material for soft contact lens |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKEX | Expiry |