Source: https://patents.google.com/patent/US9097839
Timestamp: 2018-04-26 09:50:02
Document Index: 243567618

Matched Legal Cases: ['§119', 'Application No. 200980150636', 'Application No. 200980150636', 'Application No. 2011', 'Application No. 098120172', 'Application No. 098120172']

US9097839B2 - Method for making silicone hydrogel contact lenses - Google Patents
US9097839B2
US9097839B2 US13419509 US201213419509A US9097839B2 US 9097839 B2 US9097839 B2 US 9097839B2 US 13419509 US13419509 US 13419509 US 201213419509 A US201213419509 A US 201213419509A US 9097839 B2 US9097839 B2 US 9097839B2
US13419509
US20120172478A1 (en )
This application is a divisional application of application Ser. No. 12/456,364, filed Jun. 16, 2009, now U.S. Pat. No. 8,163,206 which claims the benefit under 35 U.S.C. §119 (e) of U.S. provisional application Ser. No. 61/212,623 filed on Apr. 14, 2009, and is continuation-in-part of U.S. patent application Ser. No. 12/316,993 filed on Dec. 18, 2008, now U.S. Pat. No. 7,780,879 herein incorporated by reference in their entirety.
A “polysiloxane-containing vinylic monomer or macromer” refers to a vinylic monomer or macromer containing at least one ethylenically unsaturated group and a divalent radical of
The “ion permeability” through a lens correlates with both the Ionoflux Diffusion Coefficient and the lonoton Ion Permeability Coefficient.
In a preferred embodiment, at least one of the first and second molding surfaces is permeable to a crosslinking radiation e.g., UV radiation). More preferably, one of the first and second molding surfaces is permeable to a crosslinking radiation (e.g., UV radiation) while the other molding surface is poorly permeable to the crosslinking radiation (e.g., UV radiation). For example, one of the mold halves can be made of a UV-permeable material, while the other mold half can be made of a material containing UV absorbing materials, such as, for example carbon black, as described in U.S. Pat. Nos. 7,387,759 and 7,384,590.
Examples of siloxane-containing (meth)acrylamide monomers of formula (1) include without limitation N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)-silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]methacrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl acrylamide; N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methyl acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide; N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide. Most preferred siloxane-containing (meth)acrylamide monomers of formula (1) are N-[tris(trimethylsiloxy)silylpropyl]acrylamide and N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide.
Any polysiloxane-containing vinylic monomer or macromer” refers to a vinylic monomer or macromer containing at least one ethylenically unsaturated group and a divalent radical of
in which R1 and R2 are independently a monovalent C1-C10 alkyl, a monovalent C1-C10 aminoalkyl, a monovalent of C1-C10 hydroxyalkyl, C1-C10 ether, C1-C10 fluoroalkyl, C1-C10 fluoroether or C6-C18 aryl radical, -alk-(OCH2CH2)m—OR3, in which alk is C1-C6 alkylene divalent radical, R3 is hydrogen or C1-C6 alkyl, and m is an integer of from 1 to 10; n is an integer of 3 or higher. Examples of such vinylic monomers or macromers are monomethacrylated or monoacrylated polydimethylsiloxanes of various molecular weight (e.g., mono-3-methacryloxypropyl terminated, mono-butyl terminated polydimethylsiloxane or mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butyl terminated polydimethylsiloxane); dimethacrylated or diacrylated polydimethylsiloxanes of various molecular weight; vinyl carbonate-terminated polydimethylsiloxanes; vinyl carbamate-terminated polydimethylsiloxane; vinyl terminated polydimethylsiloxanes of various molecular weight; methacrylamide-terminated polydimethylsiloxanes; acrylamide-terminated polydimethylsiloxanes; acrylate-terminated polydimethylsiloxanes; methacrylate-terminated polydimethylsiloxanes; bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane; N,N,N′,N′-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane; polysiloxanylalkyl(meth)acrylic monomers; siloxane-containing macromer selected from the group consisting of Macromer A, Macromer B, Macromer C, and Macromer D described in U.S. Pat. No. 5,760,100 (herein incorporated by reference in its entirety); the reaction products of glycidyl methacrylate with amino-functional polydimethylsiloxanes; hydroxyl-functionalized siloxane-containing vinylic monomers or macromers; polysiloxane-containing macromers disclosed in U.S. Pat. Nos. 4,136,250, 4,153,641, 4,182,822, 4,189,546, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203, 4,341,889, 4,486,577, 4,543,398, 4,605,712, 4,661,575, 4,684,538, 4,703,097, 4,833,218, 4,837,289, 4,954,586, 4,954,587, 5,010,141, 5,034,461, 5,070,170, 5,079,319, 5,039,761, 5,346,946, 5,358,995, 5,387,632, 5,416,132, 5,451,617, 5,486,579, 5,962,548, 5,981,675, 6,039,913, and 6,762,264 (here incorporated by reference in their entireties); polysiloxane-containing macromers disclosed in U.S. Pat. Nos. 4,259,467, 4,260,725, and 4,261,875 (herein incorporated by reference in their entireties). Di and triblock macromers consisting of polydimethylsiloxane and polyalkyleneoxides could also be of utility. For example one might use methacrylate end capped polyethyleneoxide-block-polydimethylsiloxane-block-polyethyleneoxide to enhance oxygen permeability. Suitable monofunctional hydroxyl-functionalized siloxane-containing vinylic monomers/macromers and suitable multifunctional hydroxyl-functionalized siloxane-containing vinylic monomers/macromers are commercially available from Gelest, Inc, Morrisville, Pa.
in which R′ is H or C1-C8alkyl, E is an alkyl diradical, a cycloalkyl diradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or an aryl diradical with up to 40 carbon atoms which may have ether, thio, or amine linkages in the main chain; X1 and X2 independent of each other are a linkage selected from the group consisting of a direct bond,
as defined above, D1, D2 and D3 independently of each other are a divalent radical selected from the group consisting of —(CH2CH2O)t—CH2CH2— in which t is an integer of 3 to 40, —CF2—(OCF2)a—(OCF2CF2)b—OCF2— in which a and b independent of each other is an integer of 0 to 10 provided that a+b is a number in the range of 10 to 30, and a divalent group of formula (6)
in which R3, R4, R5′, R6, R7, R8, R9 and R10, independently of one another, are C1-C8-alkyl, C1-C4 alkyl- or C1-C4-alkoxy-substituted phenyl, fluoro(C1-C18-alkyl), cyano(C1-C12-alkyl), -alk-(OCH2CH2)a—OR11 in which alk is C1-C6-alkylene divalent radical, R11 is C1-C6 alkyl and n is an integer from 1 to 10, m and p independently of each other are an integer of from 2 to 698 and (m+p) is from 5 to 700, provided that at least one of D1, D2 and D3 is represented by formula (6); and
in which Z1 and Z2 independent of each other are a linear or branched C1-C12 alkylene divalent radical, a linear or branched C1-C12 alkylene divalent radical having one or more hydroxyl groups, a radical of —(CH2CH2O)d—CH2CH2— in which d is an integer of 1 to 10, unsubstituted phenylene divalent radical, C1-C4 alkyl or C1-C4 alkoxy substituted phenylene divalent radical or C7-C12 aralkylene divalent radical; A5 is —O— or
in which X3 is —O—,
Cross-linking agents are compounds having two or more ethylenically unsaturated groups and having a molecular weight of less than 700 Daltons. Crosslinking agents may be used to improve structural integrity and mechanical strength. Examples of cross-linking agents include without limitation tetra(ethyleneglycol)diacrylate, tri(ethyleneglycol)diacrylate, ethyleneglycol diacylate, di(ethyleneglycol)diacrylate, tetraethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, ethyleneglycol dimethacylate, di(ethyleneglycol) dimethacrylate, trimethylopropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, vinyl methacrylate, ethylenediamine dimethyacrylamide, glycerol dimethacrylate, triallyl isocyanurate, triallyl cyanurate, allylmethacrylate, and combinations thereof. A preferred cross-linking agent is tetra(ethyleneglycol)diacrylate, tri(ethyleneglycol) diacrylate, ethyleneglycol diacrylate, di(ethyleneglycol)diacrylate, triallyl isocyanurate, or triallyl cyanurate.
A monomer mixture of the invention can be prepared by dissolving all of the desirable components in any suitable solvent known to a person skilled in the art. Example of suitable solvents includes without limitation, water, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether dipropylene glycol dimethyl ether, polyethylene glycols, polypropylene glycols, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol, tert-amyl, alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol-2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, isopropanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethyl formamide, dimethyl acetamide, dimethylpropionamide, N-methylpyrrolidinone, and mixtures thereof.
After the monomer mixture is dispensed into the mold, it is polymerized to produce a contact lens. Crosslinking may be initiated by exposing the monomer mixture in the mold to a spatial limitation of actinic radiation to crosslink the polymerizable components in the monomer mixture. The crosslinking according to the invention may be effected in a very short time, e.g. in ≦ about 120 seconds, preferably in ≦ about 80 seconds, more preferably in ≦ 50 about seconds, even more preferably in ≦ about 30 seconds, and most preferably in 5 to 30 seconds.
UV-Intensity Modulus G′
Formulation No. (mW/cm2) Irradiation Time (s) (KPa)*
Lenses are prepared by cast-molding from formulation III prepared in Example 4 in a reusable mold, similar to the mold shown in FIGS. 1-6 in U.S. Pat. Nos. 7,384,590 and 7,387,759 (FIGS. 1-6). The mold comprises a female mold half made of CaF2 and a male mold half made of PMMA. The UV irradiation source is a Hamamatsu lamp with the WG335+TM297 cut off filter at an intensity of about 4 mW/cm2. The lens formulation in the mold is irradiated with UV irradition for about 25 seconds. Resultant lenses are extracted with isopropanol, rinsed in water, dipped in a propanol solution of polyacrylic acid, and hydrated in water. The obtained lenses are determined to have the following properties: ion permeability of about 8.0 to about 9.0 relative to Alsacon lens material; apparent Dk (single point) of about 90 to 100; a water content of about 30% to about 33%; and an elastic modulus of about 0.60 MPa to about 0.65 MPa.
202 g of the α,ω-hydroxypropyl-terminated polydimethylsiloxane KF-6001 from Shin-Etsu having a mean molecular weight of 2000 g/mol (1.00 meq/g of hydroxyl groups according to titration) are introduced into a flask. The flask contents are evacuated to approx. 0.1 mbar and decompressed with argon. This operation is repeated twice. The degased siloxane is dissolved in 202 ml of freshly distilled toluene kept under argon, and 100 mg of dibutyltin dilaurate (DBTDL) are added. After complete homogenization of the solution, all the perfluoropolyether reacted with isophorone diisocyanate (IPDI) is added under argon. After stirring overnight at room temperature, the reaction is complete. The solvent is stripped off under a high vacuum at room temperature. Microtitration shows 0.36 meq/g of hydroxyl groups (theory 0.37 meq/g).
H2O Elongation Elastic
Formulation No. (by weight) Dk IP at break Modulus (MPa)
Formulation Norbloc Initiator Methacrylamide DMA 1-hexanol PDMS
74-7 1.28% 0.99% Irgacure OXE01 16.8% 23.7% 24.7% 32.6%
Lenses from formulation 86-1 are prepared by cast-molding in a reusable mold. The mold comprises a female mold half made of glass and a male mold half made of quartz. The UV irradiation source is a Hamamatsu lamp with the WG335+TM297+TM330+TM395 nm cut off filters at an intensity of about 4.2 mW/cm2 as measured by the IL1700 detector. The lens formulation in the mold is irradiated for about 150 seconds. Resultant lenses are extracted with isopropanol, rinsed in water, dipped in a propanol solution of polyacrylic acid, and hydrated in water. The UV/Vis spectrum of a lens is measured in phosphate-buffered saline (PBS). This lens has an average % T in the UVA and UVB range of 3.2 and 0.11, respectively. These values are well within the requirement of <10% Transmittance in the UVA range and <1% Transmittance in the UVB range.
LPEG CE
Formulation Norbloc 2000 Initiator solvent TRIS-AM DMA PDMS CuP
56-2 0.79% 0.5% 0.99% Irgacure 369 23.3% 1-nonanol 20.3% 22.8% 31.3% —
85-1 1.28% 0.49% 0.99% TPO 23.1% 1-propanol 20.2% 22.7% 31.1% 0.1%
08-1 0.99% 0.5% 0.99% TPO 23.3% 1-propanol 20.3% 22.8% 31.2% 0.1%
1. A lens-forming composition suitable for making silicone hydrogel contact lenses according to a curing method based on a spatial limitation of actinic radiation, comprising:
(1) from about 10% to about 50% by weight of at least one hydrophilic amide-type vinylic monomer;
(2) from about 10% to about 40% by weight of at least one siloxane-containing (meth)acrylamide of formula (1)
in which R is H or CH3 R3 and R4 indeendentl of each other are H C1-C6 alkyl, or a monovalent radical of formula (2)
in which Y is a C1-C6 alkylene divalent radical or a C1-C6 alkylene divalent radical containing one or more hydroxyl groups, m is an integer of 0 to 5, p is an integer of 1 to 6, and A1, A2 and A3 independent of each other are C1-C6alkyl, phenyl, benzyl, or a radical of formula (3)
in which B1, B2 and B3 independent of each other are C1-C6 alkyl, phenyl, or benzyl, provided that at least one of R3 and R4 is a radical of formula (2), and provided that at least two of A1 A2 and A3 are radicals of formula (3);
(3) from about 10% to about 40% by weight of a polysiloxane-containing vinylic macromere of formula (4);
r is an integer of 1,
which R′ is H or C1-C8 alkyl, E is an alkyl diradical, a cycloalkyl diradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or an aryl diradical with up to 40 carbon atoms which may have ether, thio, or amine linkages in the main chain,
in which R′ is H or C1-C8 alkyl,
U1-D2
U2-D3
ω (5)
in which ν is 0 or 1, ω is an integer of from 0 to 5, U1 and U2 independent of each other represent a divalent radical of —R′1—X4-E-X5—R′2 as defined above or a divalent radical of
in which R3, R4, R5′, R6, R7, R8, R9 and R10, independently of one another, are C1-C8-alkyl, C1-C4 alkyl- or C1-C4- alkoxy-substituted phenyl, fluoro(C1-C18-alkyl), cyano(C1-C12-alkyl), -alk-(OCH2CH2)n—OR11 in which alk is C1-C6-alkylene divalent radical, R11 is C1-C6 alkyl and n is an integer from 1 to 10, m and p independently of each other are an integer of from 2 to 698 and (m+p) is from 5 to 700, provided that at least one of D1, D2 and D3 is represented by formula (6), and
in which Z1 and Z2 independent of each other are a linear or branched C1-C12 alkylene divalent radical, a linear or branched C1-C12 alkylene divalent radical having one or more hydroxyl groups, a radical of —(CH2CH2O)d—CH2CH2 in which d is an integer of 1 to 10, unsubstituted phenylene divalent radical, C1-C4 alkyl or C1-C4 alkoxy substituted phenylene divalent radical or C7-C12 aralkylene divalent radical; A5 is —O— or
as defined above or —S— and R17 is a C1-C12 alkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl or dialkylaminoalkyl radical;
(4) from about 0.1% to about 1.3% by weight of a photoinitiator, and
(5) from 0 to about 5% by weight of a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent; provided that components (1) to (5) and any additional components add up to 100% by weight,
wherein if one or more methacrylate monomers are present in the lens-forming composition, the total amount of the methacrylate monomers is less than about 5% by weight, and wherein the lens forming composition is characterized by having a curing time of less than 30 seconds by a UV light having an UV-intensity of about 4.1 mW/cm2.
2. The lens-forming composition of claim 1, wherein the siloxane-containing (meth)acrylamide monomeris selected from the group consisting of N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)-silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]methacrylamide, N-[tris (dimethyl-phenylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]methacrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2- methyl acrylamide; N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl) acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methyl acrylamide; N,-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide; N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide.
3. The lens-forming composition of claim 1, wherein the monomer mixture comprises a polysiloxane-containing vinylic macromer of formula (4) in which D1, D2 and D3 independently of each other are a divalent radical of formula (6).
4. The lens-forming composition of claim 1, wherein the monomer mixture comprises a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent in an amount from about 0.2% to about 5.0% by weight.
5. The lens-forming composition of claim 4, wherein the monomer mixture comprises a polymerizable UV-absorbing agent which comprises a benzotriazole- and/or benzophenone-moiety.
6. The lens-forming composition of claim 5, wherein the photoinitiator is a benzoylphosphine oxide photoinitiator.
7. The lens-forming composition of claim 4, wherein the monomer mixture comprises a polymerizable latent UV-absorbing agent.
8. The lens-forming composition of claim 1, wherein the hydrophilic amide-type vinylic monomer is selected from the group consisting of 2-acrylamidoglycolic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid or salt thereof, (3-acrylamidopropyl)-trimethylammonium chloride, 3-acryloylamino-1-propanol, N-(butoxymethyl)acrylamide, N-tert-butylacrylamide, diacetone acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-hydroxyethyl acrylamide, N-(hydroxymethyl)acrylamide, N-(isobutoxymethyl)acrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, methacrylamide, N-phenylacrylamide, N-[Tris(hydroxymethyl)methyl]acrylamide,N-methyl-3-methylene-2-pyrrolidone, and a mixture thereof.
9. The lens-forming composition of claim 8, wherein the siloxane-containing (meth)acrylamide monomeris selected from the group consisting of N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)-silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethyl-phenylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]methacrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl acrylamide; N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl) acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methyl acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide; N[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N[2-hydroxy-3-(3-(t-butyldimethylsilyppropyloxy)propyl]acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide; N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide.
10. The lens-forming composition of claim 9, wherein the monomer mixture comprises a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent in an amount from about 0.2% to about 5.0% by weight.
11. The lens-forming composition of claim 10, wherein the monomer mixture comprises a polymerizable UV-absorbing agent which comprises a benzotriazole- and/or benzophenone-moiety.
12. The lens-forming composition of claim 10, wherein the photoinitiator is a benzoylphosphine oxide photoinitiator.
13. The lens-forming composition of claim 10, wherein the monomer mixture comprises a polymerizable latent UV-absorbing agent.
US13419509 2007-12-20 2012-03-14 Method for making silicone hydrogel contact lenses Active 2030-05-20 US9097839B2 (en)
US12456364 Division US8163206B2 (en) 2007-12-20 2009-06-16 Method for making silicone hydrogel contact lenses
US20120172478A1 true US20120172478A1 (en) 2012-07-05
US9097839B2 true US9097839B2 (en) 2015-08-04
US20060142410A1 (en) 2003-01-10 2006-06-29 Masaki Baba Silicone-containing ocular lens material with high safety and preparing method thereof
US20120213922A1 (en) 2004-04-01 2012-08-23 Michael Hugh Quinn Colored ink for pad transfer printing of silicone hydrogel lenses
English Translation of China Office Action dated Mar. 28, 2013, Chinese Patent Application No. 200980150636.1.
English Translation of Chinese Office Action dated Mar. 28, 2013, Chinese Patent Application No. 200980150636.1.
English Translation of Japan Office Action Notification of Reasons for Rejection, Dispatch No. 678564, Dispatch Date: Oct. 17, 2013, Japanese Patent Application No. 2011-542147.
English Translation of Taiwan Search Report, dated Apr. 18, 2014, Taiwan Patent Application No. 098120172.
English Translation of Taiwan Search Report, dated Jan. 9, 2015, Taiwan Patent Application No. 098120172.
PCT International Search Report for PCT/US2009/047428 dated Jan. 28, 2010.
PCT Written Opinion of the International Searching Authority dated Jan. 28, 2010 for International Application No. PCT/US2009/047428, international filing date Jun. 16, 2009.
PCT Written Opinion of the International Searching Authority for PCT/US2009/047428 dated Jun. 18, 2011.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHANG, FRANK;VOGT, JURGEN;PRUITT, JOHN DALLAS;AND OTHERS;SIGNING DATES FROM 20090429 TO 20090719;REEL/FRAME:028672/0654