SILICONE HYDROGEL INK BINDER FOR CONTACT LENSES

Abstract

A silicone hydrogel ink binder includes (a) one or more colorants, (b) a solvent, and (c) a silicone copolymer including a reaction product of (i) a copolymerization product of a polymerization composition comprising (1) an alkylacrylamide monomer, (2) a hydroxyethyl acrylate monomer, (3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (ii) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

Claims

1. A silicone hydrogel ink binder, comprising (a) one or more colorants, (b) a solvent, and (c) a silicone copolymer comprising a reaction product of (i) a copolymerization product of a polymerization composition comprising (1) an alkylacrylamide monomer, (2) a hydroxyethyl acrylate monomer, (3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (ii) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

2. The silicone hydrogel ink binder according to claim 1, wherein the one or more colorants comprises a pigment.

3. The silicone hydrogel ink binder according to claim 2, wherein the pigment is an iron oxide black.

4. The silicone hydrogel ink binder according to claim 1, wherein the alkylacrylamide monomer is N,N-dimethylacrylamide.

5. The silicone hydrogel ink binder according to claim 1, wherein the non-bulky organosilicon-containing monomer is represented by the following structure: ##STR00064## wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R.sup.10 and R.sup.11 are independently hydrogen or alkyl wherein at least one of R.sup.10 and R.sup.11 is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon-containing monomer is represented by the following structure: ##STR00065## wherein R.sup.12 is H or methyl; X is O or NR.sup.16; wherein R.sup.16 is hydrogen or C.sub.1 to C.sub.4 alkyl, which may be further substituted with one or more hydroxyl groups; R.sup.13 is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R.sup.14 is independently a phenyl or C.sub.1 to C.sub.4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R.sup.15 is a C.sub.1 to C.sub.4 alkyl; and a is 2 to 50.

6. The silicone hydrogel ink binder according to claim 1, wherein the bulky siloxane monomer is represented by the following structure: ##STR00066## wherein X denotes O or NR.sup.19 where each R.sup.19 is hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 independently denotes hydrogen or methyl; each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure: ##STR00067## wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure: ##STR00068## wherein X denotes NR.sup.19; wherein R.sup.19 denotes hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 denotes hydrogen or methyl; each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure: ##STR00069## wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10.

7. The silicone hydrogel ink binder according to claim 1, wherein the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, 1, 1-dimethyl-2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

8. The silicone hydrogel ink binder according to claim 1, wherein the silicone copolymer comprises: from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer; from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer; from about 5 to about 20 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group; from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group; and from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

9. The silicone hydrogel ink binder according to claim 1, wherein the silicone copolymer has a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons.

10. A colored silicone hydrogel contact lens having a colored film on a surface thereof, the colored film comprising a polymerization product of a silicone hydrogel ink binder comprising (a) one or more colorants, (b) a solvent, and (c) a silicone copolymer comprising a reaction product of (i) a copolymerization product of a polymerization composition comprising (1) an alkylacrylamide monomer, (2) a hydroxyethyl acrylate monomer, (3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (ii) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

11. The colored silicone hydrogel contact lens according to claim 10, wherein the one or more colorants comprises a pigment.

12. The colored silicone hydrogel contact lens according to claim 10, wherein the alkylacrylamide monomer is N,N-dimethylacrylamide.

13. The colored silicone hydrogel contact lens according to claim 10, wherein the non-bulky organosilicon-containing monomer is represented by the following structure: ##STR00070## wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R.sup.10 and R.sup.11 are independently hydrogen or alkyl wherein at least one of R.sup.10 and R.sup.11 is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon-containing monomer is represented by the following structure: ##STR00071## wherein R.sup.12 is H or methyl; X is O or NR.sup.16; wherein R.sup.16 is hydrogen or C.sub.1 to C.sub.4 alkyl, which may be further substituted with one or more hydroxyl groups; R.sup.13 is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R.sup.14 is independently a phenyl or C.sub.1 to C.sub.4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R.sup.15 is a C.sub.1 to C.sub.4 alkyl; and a is 2 to 50.

14. The colored silicone hydrogel contact lens according to claim 10, wherein the bulky siloxane monomer is represented by the following structure: ##STR00072## wherein X denotes O or NR.sup.19 where each R.sup.19 is hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 independently denotes hydrogen or methyl; each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure: ##STR00073## wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure: ##STR00074## wherein X denotes NR.sup.19; wherein R.sup.19 denotes hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 denotes hydrogen or methyl; each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure: ##STR00075## wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10.

15. The colored silicone hydrogel contact lens according to claim 10, wherein the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, 1, 1-dimethyl-2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

16. The colored silicone hydrogel contact lens according to claim 10, wherein the silicone copolymer comprises: from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer; from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer; from about 5 to about 20 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group; from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group; and from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

17. The colored silicone hydrogel contact lens according to claim 10, wherein the silicone copolymer has a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons.

18. The colored silicone hydrogel contact lens according to claim 10, which is optically clear.

19. A method, comprising: (a) applying, to at least a portion of a molding surface of a contact lens mold, a silicone hydrogel ink binder comprising (i) one or more colorants, (ii) a solvent, and (iii) a silicone copolymer comprising a reaction product of (1) a copolymerization product of a polymerization composition comprising (i1) an alkylacrylamide monomer, (i2) a hydroxyethyl acrylate monomer, (i3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (i4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (2) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group; and (b) curing the silicone hydrogel ink binder to form a colored film which comprises a colorant-entrapping polymer network and the colorant entrapped therein, wherein the colored film contains a first surface in contact with the molding surface and an exposed second surface.

20. The method according to claim 19, further comprising: dispensing a silicone hydrogel contact lens-forming mixture comprising a silicone hydrogel contact lens-forming material into the contact lens mold having the colored film; curing the silicone hydrogel contact lens-forming mixture comprising the silicone hydrogel contact lens-forming material to form a colored silicone contact lens, whereby the colored film detaches from the molding surface and becomes integral with the body of the silicone contact lens; and hydrating the colored silicone contact lens to form a colored silicone hydrogel contact lens.

Description

DETAILED DESCRIPTION

[0014] Various illustrative embodiments described herein include a silicone hydrogel ink binder and colored silicone hydrogel contact lenses made therefrom.

Definitions

[0015] To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.

[0016] A prepolymer refers to a starting polymer which can be cured (e.g., crosslinked and/or polymerized) actinically or thermally or chemically to obtain a crosslinked and/or polymerized polymer having a molecular weight higher than the molecular weight of the starting polymer.

[0017] A crosslinkable prepolymer refers to a starting polymer which can be crosslinked to obtain a crosslinked polymer having a molecular weight higher than the molecular weight of the starting polymer.

[0018] A colorant refers to either a dye or a pigment or a mixture thereof that is used to print a color image on an article.

[0019] A dye refers to a substance that is soluble in a solvent and that is used to impart color. A dye is typically translucent and absorb but do not scatter light. A dye can cover both optical regions of contact lenses and non-optical regions of contact lenses. Nearly any dye can be used in the present disclosure, so long as it can be used in an apparatus as described below. These dyes include fluorescent dyes, phosphorescent dyes, and conventional dyes.

[0020] A pigment refers to a powdered substance that is suspended in a liquid in which it is insoluble. A pigment can be used to impart color. Pigments, in general, are more opaque than dyes.

[0021] The term hydrogel or hydrogel material as used herein refers to a crosslinked polymeric material that has a three-dimensional polymer network (i.e., polymer matrix), is insoluble in water, but can hold at least about 10 percent by weight of water in its polymer matrix when it is fully hydrated.

[0022] The term silicone hydrogel or SiHy as used herein interchangeably refers to a hydrogel containing silicone. A silicone hydrogel (SiHy) typically is obtained by copolymerization of a polymerizable composition comprising at least one silicone hydrogel contact lens-forming material.

[0023] The term (meth) as used herein denotes an optional methyl substituent. Thus, terms such as (meth)acrylate denotes either methacrylate or acrylate, and (meth)acrylamide denotes either methacrylamide or acrylamide.

[0024] A contact lens refers to contact lenses that reside in or on the eye. These lenses can provide optical correction, wound care, drug delivery, diagnostic functionality or cosmetic enhancement or effect or a combination of these properties. Suitable contact lenses include, for example, contact lenses such as soft contact lenses, e.g., a soft, hydrogel lens; soft, non-hydrogel lens and the like, hard contact lenses, e.g., a hard, gas permeable lens material, a hybrid lens and the like. A contact lens can be in a dry state or a wet state. A dry state refers to a soft contact lens in a state prior to hydration or the state of a hard lens under storage or use conditions. A wet state refers to a soft contact lens in a hydrated state. As is understood by one skilled in the art, a contact lens is considered to be soft if it can be folded back upon itself without breaking. A contact lens can be tinted before printing any color patterns.

[0025] While compositions and processes are described in terms of comprising various components or steps, the compositions and processes can also consist essentially of or consist of the various components or steps, unless stated otherwise.

[0026] The terms a, an, and the are intended to include plural alternatives, e.g., at least one. The terms including, with, and having, as used herein, are defined as comprising (i.e., open language), unless specified otherwise.

[0027] Various numerical ranges are disclosed herein. When Applicant discloses or claims a range of any type, Applicant's intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. For example, all numerical end points of ranges disclosed herein are approximate, unless excluded by proviso.

[0028] Values or ranges may be expressed herein as about, from about one particular value, and/or to about another particular value. When such values or ranges are expressed, other embodiments disclosed include the specific value recited, from the one particular value, and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent about, it will be understood that the particular value forms another embodiment. It will be further understood that there are a number of values disclosed therein, and that each value is also herein disclosed as about that particular value in addition to the value itself. In another aspect, use of the term about means20% of the stated value, 15% of the stated value, 10% of the stated value, 5% of the stated value, 3% of the stated value, or 1% of the stated value.

[0029] The terms wt. %, vol. % or mol. % refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material are 10 mol. % of component.

[0030] Applicant reserves the right to proviso out or exclude any individual members of any such group of values or ranges, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed according to a range or in any similar manner, if for any reason Applicant chooses to claim less than the full measure of the disclosure, for example, to account for a reference that Applicant may be unaware of at the time of the filing of the application. Further, Applicant reserves the right to proviso out or exclude any members of a claimed group.

[0031] Silicone hydrogels (SiHy) such as contact lenses, which are made of a hydrated, crosslinked polymeric material that contains silicone and a certain amount of water within the lens polymer matrix at equilibrium, are increasingly becoming popular as compared to the conventional hydrogels. In the field of contact lenses, various physical and chemical properties such as, for example, oxygen permeability, wettability, material strength and stability, are but a few of the factors that must be carefully balanced in order to provide a useable contact lens. For example, oxygen permeability is a desirable property for contact lens materials since the human cornea will be damaged if it is deprived of oxygen for an extended period. Oxygen permeability is conventionally expressed in units of Barrer, and also called Dk. Oxygen transmissibility is a property of contact lens materials related to oxygen permeability where oxygen permeability is divided by lens thickness, or Dk/t. Wettability also is important in that, if the lens is not sufficiently wettable, it does not remain lubricated and therefore cannot be worn comfortably in the eye. A challenge in developing improved silicone contact lenses is that attempting to increase oxygen permeability can compromise other desired properties of the material, such as machinability or optical clarity.

[0032] One challenge in preparing colored silicone hydrogel contact lenses without a silicone hydrogel ink binder is that the colored silicone hydrogel contact lenses may have mechanical and rheological defects. The challenge in preparing colored silicone hydrogel contact lenses by incorporating a colored film from the silicone hydrogel ink binder into a silicone hydrogel contact lenses is that when hydrating the colored silicone contact lens, the expansion of the colored film does not match the expansion of the silicone hydrogel contact lens thereby resulting in an uneven ink domain expansion of the ink pattern on the colored silicone hydrogel contact lenses. If the print pattern undergoes significant non-reversible expansion during hydration of the colored silicone contact lens, the final print quality will be compromised.

[0033] The non-limiting illustrative embodiments disclosed herein overcome the foregoing drawbacks by providing a silicone hydrogel ink binder that can form a colored film on a silicone hydrogel contact lenses without any ink domain expansion after being hydrated. The present disclosure is partly based on the discovery that when the silicone copolymer disclosed herein is used in an ink binder for making colored silicone hydrogel contact lenses by using a print-on-mold process, the expansion of the colored film will be comparable to the expansion of the silicone hydrogel contact lens during hydration. As a result, colored silicone hydrogel contact lenses with higher print quality without any ink domain expansion can be produced that are optically clear, and have a matching Dk by using a silicone copolymer of the present disclosure as a binder polymer in an ink binder for making colored silicone hydrogel contact lenses.

[0034] In non-limiting illustrative embodiments, a silicone hydrogel ink binder of the present disclosure includes at least (a) one or more colorants, (b) a solvent, and (c) a silicone copolymer comprising a reaction product of (i) a copolymerization product of a polymerization composition comprising (1) an alkylacrylamide monomer, (2) a hydroxyethyl acrylate monomer, (3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (ii) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0035] In some embodiments, a colorant can be a dye, or a pigment. In one embodiment, a colorant in silicone hydrogel ink binder of the present disclosure comprises at least one pigment. A colorant also may be a mixture of two or more pigments, which in combination provides a desired color, since any color can be obtained by merely mixing two or more primary colors together. The term primary colors refers to cyan, yellow, magenta, white, and black. A colorant may also be a mixture of at least one pigment and at least one dye. A person skill in the art will know how to select colorants.

[0036] In some embodiments, a pigment is a non-pearlescent pigment about 5 microns or smaller in size. Larger particles of a pigment can be ground into smaller particles. As one skilled in the art will appreciate, any number of methods known in the art can be used to grind pigment. For example, methods of reducing a pigment's particle size include high speed mixers, Kady Mills (rotor stator dispersion device), colloid mills, homogenizers, microfluidizers, sonalators, ultrasonic mills, roll mills, ball mills, roller mills, vibrating ball mills, attritors, sand mills, varikinetic dispensers, three-roll mills, Banbury mixers, or other methods well known to those of skill in the art. In the case of pearlescent pigments, platelet breakage should be minimized during processing to maintain a sufficient level of dispersion. Pearlescent pigments require gentle handling during mixing and they should not be ground, or subjected to prolonged mixing, milling or high shear since such operations can damage the pigments.

[0037] In some embodiments, a solvent can be water, an organic or inorganic solvent, a mixture of several organic solvents, or a mixture of water and one or more water soluble or water miscible organic solvents. Any known solvents can be used, so long as they can dissolve the silicone copolymer in the silicone hydrogel ink binder of the present disclosure and aid in the stability of the colorant. Suitable solvents include, for example, water, acetone, alcohols (e.g., methanol, ethanol, propanol, isopropanol, 2-ethyoxyethanol, etc.), glycols, ketones, esters, cyclopentanone, cyclohexanone, tetrahydrofuran, acetone, methyl-2-pyrrolidone, dimethyl formamide, acetophenone, methylene dichloride, dimethyl sulfoxide, gamma-butyrolactone, ethylene dichloride, isophorone, o-dichlorobenzene, tetrahydrofuran, diacetone alcohol, methyl ethyl ketone, acetone, 2-nitropropane, ethylene glycol monoethyl ether, propylene carbonate, cyclohexanol, chloroform, trichloroethylene, 1,4-dioxane, ethyl acetate, ethyl lactate, ethylene glycol monobutyl ether, chlorobenzene, nitroethane, ethylene glycol monomethyl ether, butyl acetate, 1-butanol, methyl isobutyl ketone, nitromethane, toluene, ethanol, diethylene glycol, benzene, diethyl ether, ethanolamine, carbon tetrachloride, propylene glycol, hexane, ethylene glycol, and formamide.

[0038] In non-limiting illustrative embodiments, a silicone copolymer comprises a reaction product of (a) a copolymerization product of a polymerization composition comprising (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0039] In some embodiments, an alkylacrylamide monomer for use in the polymerization composition includes, for example, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, and the like.

[0040] In some embodiments, the polymerization composition can contain from about 20 wt. % to about 60 wt. %, based on the total weight of the polymerization composition, of the alkylacrylamide monomer. In some embodiments, the polymerization composition can contain from about 40 wt. % to about 45 wt. %, based on the total weight of the polymerization composition, of the alkylacrylamide monomer.

[0041] In some embodiments, a hydroxyethyl acrylate monomer for use in the polymerization composition is represented by the following structure:

##STR00001##

[0042] In some embodiments, the polymerization composition can contain from about 0.01 wt. % to about 40 wt. %, based on the total weight of the polymerization composition, of the hydroxyethyl acrylate monomer. In some embodiments, the polymerization composition can contain from about 20 wt. % to about 30 wt. %, based on the total weight of the polymerization composition, of the hydroxyethyl acrylate monomer.

[0043] The polymerization composition further includes a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group. An organosilicon-containing monomer as used herein contains at least one [siloxanyl] or at least one [silyl-alkyl-siloxanyl]repeating unit, in a monomer, macromer or prepolymer. In an illustrative embodiment, an example of a non-bulky organosilicon-containing monomers is represented by a structure of Formula Ia:

##STR00002## [0044] wherein V is ethylenically unsaturated polymerizable group, L is a linking group or a bond; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are independently hydrogen, an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aryl group; R.sup.10 and R.sup.11 are independently hydrogen or an alkyl group wherein at least one of R.sup.10 and R.sup.11 is hydrogen; y is 2 to 7 and n is 1 to 100 or from 1 to 20.

[0045] Ethylenically unsaturated polymerizable groups are well known to those skilled in the art. Suitable ethylenically unsaturated polymerizable groups include, for example, (meth)acrylates, vinyl carbonates, O-vinyl carbamates, N-vinyl carbamates, and (meth)acrylamides.

[0046] Linking groups can be any divalent radical or moiety and include, for example, a substituted or unsubstituted C.sub.1 to C.sub.12 alkyl group, an alkyl ether group, an alkenyl group, an alkenyl ether group, a halo alkyl group, a substituted or unsubstituted siloxane group, and monomers capable of propagating ring opening.

[0047] In one embodiment, V is a (meth)acrylate, L is a C.sub.1 to C.sub.12 alkylene group, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.1, and R.sup.9 are independently a C.sub.1 to C.sub.12 alkyl group, R.sup.10 and R.sup.11 are independently H or a C.sub.1 to C.sub.12 alkyl group, y is 2 to 7 and n is 3 to 8.

[0048] In one embodiment, V is a (meth)acrylate, L is a C.sub.1 to C.sub.6 alkyl group, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are independently a C.sub.1 to C.sub.6 alkyl group, R.sup.10 and R.sup.11 are independently H or a C.sub.1 to C.sub.6 alkyl group, y is 2 to 7 and n is 1 to 20.

[0049] Non-bulky organosilicon-containing monomers represented by a structure of Formula Ia are known in the art, see, e.g., U.S. Pat. Nos. 7,915,323, 7,994,356, 8,420,711, 8,827,447 and 9,039,174, the contents of which are incorporated by reference herein.

[0050] In an illustrative embodiment, as may be combined with one or more of the preceding paragraphs, an example of a non-bulky organosilicon-containing monomer is represented by a structure of Formula Ib:

##STR00003## [0051] wherein R.sup.12 is H or methyl; X is O or NR.sup.16; wherein R.sup.16 is selected from H, or C.sub.1 to C.sub.4 alkyl, which may be further substituted with one or more hydroxyl groups, and in some embodiments is H or methyl; R.sup.13 is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of ether groups, hydroxyl groups, carbamate groups and combinations thereof, and in another embodiment a C.sub.1 to C.sub.6 alkylene group which may be substituted with ether, hydroxyl and combinations thereof, and in yet another embodiment a C.sub.1 or C.sub.3 to C.sub.4 alkylene group which may be substituted with ether, hydroxyl and combinations thereof; each R.sup.14 is independently a phenyl or a C.sub.1 to C.sub.4 alkyl group which may be substituted with fluorine, hydroxyl or ether, and in another embodiment each R.sup.14 is independently selected from ethyl and methyl groups, and in yet another embodiment, each R.sup.14 is methyl; R.sup.15 is a C.sub.1 to C.sub.4 alkyl group; a is 2 to 50, and in some embodiments 5 to 15.

[0052] Non-bulky organosilicon-containing monomers represented by a structure of Formula Ib are known in the art, see, e.g., U.S. Pat. Nos. 8,703,891, 8,937,110, 8,937,111, 9,156,934 and 9,244,197, the contents of which are incorporated by reference herein.

[0053] Representative examples of non-bulky organosilicon-containing monomers for use herein include:

[0054] M1EDS6: a compound having the structure and available from Gelest:

##STR00004##

[0055] MCR-M11: a compound having the structure:

##STR00005##

[0056] M1-MCR-C12: a compound having the structure:

##STR00006##

wherein n is an average of 12.

[0057] In some embodiments, the polymerization composition can contain from about 0.10 wt. % to about 30 wt. %, based on the total weight of the polymerization composition, of a non-bulky organosilicon-containing monomer. In some embodiments, the polymerization composition can contain from about 5 wt. % to about 15 wt. %, based on the total weight of the polymerization composition, of a non-bulky organosilicon-containing monomer.

[0058] The polymerization composition further includes a bulky siloxane monomer having an ethylenically unsaturated reactive end group. The term bulky refers to groups on the siloxane monomer that are sterically and/or electronically encumbering, i.e., sterically hindering. In a non-limiting illustrative embodiment, suitable bulky siloxane monomers include, for example, a bulky polysiloxanylalkyl (meth)acrylic monomer, a bulky polysiloxanylalkyl carbamate monomer and mixtures thereof. In one embodiment, a representative example of a bulky siloxane monomer is represented by a structure of Formula II:

##STR00007## [0059] wherein X denotes O or NR.sup.19, where each R.sup.19 is hydrogen or a C.sub.1-C.sub.4 alkyl group; R.sup.17 independently denotes hydrogen or methyl; each R.sup.18 independently denotes a lower alkyl radical such as a C.sub.1-C.sub.6 group, a phenyl radical or a group represented by the following structure:

##STR00008## [0060] wherein each R.sup.18 independently denotes a lower alkyl radical such as a C.sub.1-C.sub.6 group or a phenyl radical; and h is 1 to 10; or is represented by a structure of Formula III:

##STR00009## [0061] wherein X denotes NR.sup.19 wherein R.sup.19 denotes hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 denotes hydrogen or methyl; each R.sup.18 independently denotes a lower alkyl radical such as a C.sub.1-C.sub.6 group, a phenyl radical or a group represented by the following structure:

##STR00010## [0062] wherein each R.sup.18 independently denotes a lower alkyl radical such as a C.sub.1-C.sub.6 group or a phenyl radical; and h is 1 to 10.

[0063] Representative examples of bulky siloxane monomers include 3-methacryloyloxypropyltris(trimethylsiloxy)silane ortris(trimethylsiloxy)silylpropyl methacrylate, sometimes referred to as TRIS and tris(trimethylsiloxy)silylpropyl vinyl carbamate, sometimes referred to as TRIS-VC, pentamethyldisiloxanyl methylmethacrylate, phenyltetramethyl-disiloxanylethyl acetate, and methyldi(trimethylsiloxy)methacryloxymethyl silane, (3-methacryloxy-2-hydroxy propoxy)propyl bis(trimethyl siloxy)methyl silane, sometimes referred to as Sigma and the like and mixtures thereof. In one embodiment, the bulky siloxane monomer is a tris(trialkylsiloxy)silylalkyl methacrylate-containing monomer such as a tris(trimethylsiloxy)silylpropyl methacrylate-containing monomer.

[0064] Such bulky monomers may be copolymerized with a silicone macromonomer, which is a poly(organosiloxane) capped with an unsaturated group at two or more ends of the molecule. U.S. Pat. No. 4,153,641 discloses, for example, various unsaturated groups such as acryloxy or methacryloxy groups.

[0065] In some embodiments, the polymerization composition can contain from about 5 wt. % to about 30 wt. %, based on the total weight of the polymerization composition, of a bulky organosilicon-containing monomer. In some embodiments, the polymerization composition can contain from about 15 wt. % to about 25 wt. %, based on the total weight of the polymerization composition, of a bulky organosilicon-containing monomer.

[0066] In an illustrative embodiment, as may be combined with one or more of the preceding paragraphs, a copolymerization product of a polymerization composition comprising (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group can be prepared using free radical polymerization techniques with the structure of the polymer being completely random or controlled by the reactivity ratios of the respective monomers.

[0067] In some embodiments, a random copolymer can be obtained by (1) mixing the components to obtain a polymerization composition, (2) adding a polymerization initiator to the polymerization composition, and (3) subjecting the monomer/initiator mixture to a source of heat or radiation such as ultraviolet light, visible light, or high energy radiation to obtain a copolymerization product as discussed below. Suitable free radical thermal polymerization initiators include acetyl peroxide, lauroyl peroxide, decanoyl peroxide, coprylyl peroxide, benzoyl peroxide, tertiary butyl peroxypivalate, sodium percarbonate, tertiary butyl peroctoate, and azobisisobutyronitrile (AIBN), and the like. Representative UV initiators are those known in the art and include benzoin methyl ether, benzoin ethyl ether, Darocure 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure 651 and 184 (Ciba-Geigy), 2,2Azobis(2-methylpropionitrile) (Vazo 64) and the like. Generally, the initiator will be employed in the mixture at a concentration of about 0.01 to about 5 percent by weight of the total mixture.

[0068] Suitable polymerization conditions include, for example, a temperature of between about 60 C. to about 100 C. for a time period of about 30 minutes to about 48 hours. If desired, the reaction can be carried out in the presence of a suitable solvent. Suitable solvents are in principle all solvents which dissolve the monomers used including, for example, 1,4-dioxane, hexanol, dimethylformamide; acetone, cyclohexanone, toluene, and the like and mixtures thereof.

[0069] The copolymerization product disclosed herein can also be prepared using techniques of controlled radical polymerization, e.g., by reversible addition-fragmentation chain transfer (RAFT) polymerization or atom-transfer radical polymerization (ATRP) employing a chain transfer agent that allows construction of copolymers with a well-defined molecular weight distribution and narrow polydispersity. RAFT polymerization is particularly preferred because it is compatible with a wide variety of vinyl monomers.

[0070] In non-limiting illustrative embodiments, the RAFT agents suitable for use herein can be based upon thio carbonyl thio chemistry which is well known to those of ordinary skill in the art. The thio carbonyl thio fragment can be derived from a RAFT agent such as, for example, a xanthate-containing compound, trithiocarbonate-containing compound, dithiocarbamate-containing compound, a dithiobenzoate-containing compound or dithio ester-containing compound, wherein each compound contains a thio carbonyl thio group. One class of RAFT agents that can be used herein is of the general formula:

##STR00011##

wherein x is 1 or 2, Z is a substituted oxygen (e.g., xanthates (OR)), a substituted nitrogen (e.g., dithiocarbamates (NRR)), a substituted sulfur (e.g., trithiocarbonates (SR)), a dithiobenzoate, a substituted or unsubstituted C.sub.1-C.sub.20 alkyl or C.sub.3-C.sub.25 unsaturated, or partially or fully saturated ring (e.g., dithioesters (R)) or carboxylic acid-containing group; and R is independently a straight or branched, substituted or unsubstituted C.sub.1-C.sub.30 alkyl cyano group, a straight or branched, substituted or unsubstituted C.sub.1-C.sub.30 alkyl group, a substituted or unsubstituted C.sub.3-C.sub.30 cycloalkyl group, a substituted or unsubstituted C.sub.3-C.sub.30 cycloalkylalkyl group, a substituted or unsubstituted C.sub.3-C.sub.30 cycloalkenyl group, a substituted or unsubstituted C.sub.5-C.sub.30 aryl group, a substituted or unsubstituted C.sub.5-C.sub.30 arylalkyl group, a C.sub.1-C.sub.20 ester group; an ether or polyether-containing group; an alkyl- or arylamide group; an alkyl- or arylamine group; a substituted or unsubstituted C.sub.5-C.sub.30 heteroaryl group; a substituted or unsubstituted C.sub.3-C.sub.30 heterocyclic ring; a substituted or unsubstituted C.sub.4-C.sub.30 heterocycloalkyl group; a substituted or unsubstituted C.sub.6-C.sub.30 heteroarylalkyl group; and combinations thereof.

[0071] The substituents in the substituted oxygen, substituted nitrogen, substituted sulfur, substituted alkyl, substituted alkylene, substituted cycloalkyl, substituted cycloalkylalkyl, substituted cycloalkenyl, substituted arylalkyl, substituted aryl, substituted heterocyclic ring, substituted heteroaryl ring, substituted heteroarylalkyl, substituted heterocycloalkyl ring, substituted cyclic ring may be the same or different and include one or more substituents such as hydrogen, hydroxy, halogen, carboxyl, cyano, nitro, oxo (O), thio(S), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted amino, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted heterocycloalkyl ring, substituted or unsubstituted heteroarylalkyl, substituted or unsubstituted heterocyclic ring, and the like.

[0072] Representative examples of RAFT agents for use herein include, but are not limited to, 4-cyano-4-(dodecyl-sulfanylthiocarbonyl)sulfanylpentanoic acid, S-cyanomethyl-5-dodecyltrithiocarbonate, S-(2-cyano-2-propyl)-S-dodecyltrithiocarbonate, 3-benzylsulfanylthiocarbonylsulfanyl-propionic acid, cumyl dithiobenzoate, 2-cyanoprop-2-yl dithiobenzoate (i.e., cyanoisopropyl dithiobenzoate), 4-thiobenzoylsulfanyl-4-cyanopentanoic acid (TCA), S,S-bis(,-dimethyl-alpha-acetic acid)-trithiocarbonate (BATC), benzyl dodecyl trithiocarbonate, ethyl-2-dodecyl trithiocarbony) proprionate, S-sec propionic acid O-ethyl xanthate, -ethyl xanthylphenylacetic acid, ethyl -(o-ethyl xanthyl) proprionate, ethyl -(ethyl xanthyl) phenyl acetate, ethyl 2-(dodecyl trithiocarbonyl) phenyl acetate, ethyl 2-(dodecyl trithiocarbonyl) propionate, 2-(dodecylthiocarbonylthiol)propanoic acid, and the like and mixtures thereof.

[0073] There is no particular limitation on the organic chemistry used to form the RAFT agent and is within the purview of one skilled in the art.

[0074] The copolymerization product disclosed herein can be obtained by (1) mixing an alkylacrylamide monomer, a hydroxyethyl acrylate monomer, a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and an ultraviolet blocker having an ethylenically unsaturated reactive group with a RAFT agent and a polymerization initiator, and (2) subjecting the monomer/RAFT agent/initiator mixture to a source of heat. Suitable initiators include, for example, free-radical-generating polymerization initiators of the type illustrated by acetyl peroxide, lauroyl peroxide, decanoyl peroxide, coprylyl peroxide, benzoyl peroxide, tertiary butyl peroxypivalate, sodium percarbonate, tertiary butyl peroctoate, and azobisisobutyronitrile (AIBN).

[0075] The reaction can be carried out at a temperature of between about 50 C. to about 80 C. for a time period of about 30 minutes to about 48 hours. If desired, the reaction can be carried out in the presence of a suitable solvent. Suitable solvents are in principle all solvents which dissolve the monomer used, for example, 1,4-dioxane, hexanol, dimethylformamide; acetone, cyclohexanone, toluene, and the like and mixtures thereof.

[0076] In an illustrative embodiment, the RAFT procedure is carried using a mixture including (i) from about 2 to about 40 wt. %, based on the total weight of the mixture, of an alkylacrylamide monomer, (ii) from about 10 to about 20 wt. %, based on the total weight of the mixture, of a hydroxyethyl acrylate monomer, (iii) from about 10 to about 60 wt. %, based on the total weight of the mixture, of a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, (iv) from about 20 to about 60 wt. %, based on the total weight of the mixture, of a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and (v) from about 0.05 to about 2 wt. %, based on the total weight of the mixture, of the RAFT agent. The level of initiator employed will vary within the range of 0.01 to 2 wt. % of the mixture of monomers. In some embodiments, the mixture for the RAFT procedure further includes from about 0.1 to about 5 wt. %, based on the total weight of the mixture, of an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0077] A non-limiting schematic representation of a synthetic method for making a copolymerization product with a RAFT agent is set forth below in Scheme I below.

##STR00012##

[0078] In the case where the copolymerization product disclosed herein is obtained from ATRP polymerization, the ethylenically unsaturated groups may be introduced by appropriate selection of a suitable ATRP initiator or by displacement reactions of the terminal halogen atom. Suitable ATRP groups for use herein include any standard monofunctional or difunctional ATRP group as is well known to those of ordinary skill in the art. A comprehensive review on the use of ATRP initiators or displacement of the terminal halogen using electrophilic, nucleophilic, and radical reactions to produce telechelic polymers is disclosed in, for example, Matyjaszewski, K.; Xia, J. Chem. Rev., 101, 2921-2990 (2001).

[0079] In one embodiment, a useful ATRP group includes an ethylenically unsaturated ATRP initiator such as, for example, vinyl functionalized ATRP initiators, e.g., prop-2-enyl-2-bromoisobutyrate, vinyl chloroacetate, allyl chloroacetate, allyl bromide and the like.

[0080] In another embodiment, a useful ATRP group includes a non-ethylenically unsaturated ATRP initiator that can be converted to an ethylenically unsaturated initiator by a subsequent step. Examples of such initiators include -bromo-isobutyric acid, hydroxyethyl 2-bromopropionate, glycidol 2-bromopropionate, tert-butyl 2-bromopropionate, and 4-bromobenzyl bromide, and the like.

[0081] In an illustrative embodiment, the copolymerization product is obtained from ATRP polymerization by (1) mixing an alkylacrylamide monomer, a hydroxyethyl acrylate monomer, a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and optionally an ultraviolet blocker having an ethylenically unsaturated reactive group and/or a blue-light blocker having an ethylenically unsaturated reactive group with, for example, an ATRP initiator and suitable ATRP catalyst such as a copper(I) bromide and (2) subjecting the monomer/ATRP agent/initiator mixture to a source of heat.

[0082] The reaction can be carried out at a temperature of between about 60 C. to about 100 C. for a time period of about 30 minutes to about 48 hours. If desired, the reaction can be carried out in the presence of a suitable solvent. Suitable solvents are in principle all solvents which dissolve the monomer used, for example, 1,4-dioxane, hexanol, dimethylformamide; acetone, cyclohexanone, toluene, and the like and mixtures thereof.

[0083] In an illustrative embodiment, the ATRP procedure is carried using a mixture including (i) from about 0.1 to about 20 wt. %, based on the total weight of the mixture, of an alkylacrylamide monomer, (ii) from about 5 to about 20 wt. %, based on the total weight of the mixture, of a hydroxyethyl acrylate monomer, (iii) from about 10 to about 20 wt. %, based on the total weight of the mixture, of a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, (iv) from about 20 to about 60 wt. %, based on the total weight of the mixture, of a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and (v) from about 0.05 to about 5 wt. %, based on the total weight of the mixture, of the ATRP initiator. The level of catalyst employed will vary within the range of 0.01 to 2 wt. % of the mixture of monomers. In some embodiments, the mixture for the ATRP procedure further includes from about 20 to about 40 wt. %, based on the total weight of the mixture, of an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0084] As one skilled in the art will readily appreciate, the copolymerization product disclosed herein can contain a balance of monomeric units derived from an alkylacrylamide monomer, monomeric units derived from a hydroxyethyl acrylate monomer, monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and monomeric units derived from an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0085] In some embodiments, a copolymerization product can include from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer, from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer, from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

[0086] In one or more additional non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the copolymerization product is thereafter reacted with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group to obtain a silicone copolymer. The foregoing reaction will result in additional monomeric units derived from the hydroxyethyl acrylate monomer with the hydroxy moiety being reacted with the reactive functionality of the monomer such that the hydroxyethyl acrylate monomer contains an end functionalized group, i.e., a polymerizable ethylenically unsaturated reactive end group which can be complementary to an ethylenically unsaturated reactive group of a contact lens-forming comonomer as discussed below. Suitable polymerizable ethylenically unsaturated reactive end groups can be any of those discussed above.

[0087] In an illustrative embodiment, a polymerizable ethylenically unsaturated reactive end group can be one or more of an acrylate end group and a methacrylate end group.

[0088] Suitable monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group include, for example, 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, 1,1-dimethyl-2-isocyanatoethyl acrylate, (meth)acryloyl chloride, vinyl chloroformate and the like.

[0089] In an illustrative embodiment, the copolymerization product is present in the reaction mixture in an amount ranging from about 10 wt. % to about 90 wt. %, based on the total weight of the reaction mixture. In an illustrative embodiment, the copolymerization product is present in the reaction mixture in an amount ranging from about 50 wt. % to about 80 wt. %, based on the total weight of the reaction mixture.

[0090] In an illustrative embodiment, the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group is present in the reaction mixture in an amount ranging from about 5 wt. % to about 60 wt. %, based on the total weight of the reaction mixture. In an illustrative embodiment, the monomer having a reactive functionality complementary to one of the one or more reactive functionalities of the hydrophilic monomer and a polymerizable ethylenically unsaturated reactive end group is present in the reaction mixture in an amount ranging from about 10 wt. % to about 20 wt. %, based on the total weight of the reaction mixture.

[0091] The reaction of the copolymerization product and the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group can be carried out in the presence of a catalyst. Suitable catalysts include, for example, the stannous salts of carboxylic acids, such as stannous octoate, stannous oleate, stannous acetate, and stannous laurate, dialkyltin dicarboxylates, such as dibutyltin dilaurate and dibutyltin diacetate which are known in the art as urethane catalysts, as are tertiary amines and tin mercaptides. The amount of catalyst employed is generally between about 0.01 wt. % to about 5 wt. % of the mixture catalyzed.

[0092] The reaction can be carried out at a temperature of between about 60 C. to about 100 C. for about 2 hours to about 24 hours. The reaction can be carried out in the presence of a suitable solvent as discussed above.

[0093] Accordingly, in a non-limiting illustrative embodiment, a silicone copolymer disclosed herein comprises: [0094] (i) monomeric units derived from an alkylacrylamide monomer, [0095] (ii) monomeric units derived from a hydroxyethyl acrylate monomer, [0096] (iii) monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group, [0097] (iv) monomeric units derived from a bulky siloxane monomer, and [0098] (v) monomeric units derived from a non-bulky siloxane monomer.

[0099] In some embodiments, a silicone copolymer is a silicone contact lens-forming random copolymer.

[0100] In some embodiments, a silicone copolymer disclosed herein includes: [0101] from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer, [0102] from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer, [0103] from about 5 to about 20 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group, [0104] from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and [0105] from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

[0106] In a non-liming illustrative embodiment, a silicone copolymer can be represented by the following structure:

##STR00013## [0107] where n is about 50 to about 400, m is about 5 to about 20, o is about 50 to about 200, x is about 1 to about 400, y is about 20 to about 300 and a is about 5 to about 12.

[0108] In some embodiments, a silicone copolymer disclosed herein can have a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons. The weight average molecular weight of the silicone copolymer is determined by Gel Permeation Chromatography (GPC).

[0109] In some embodiments, a silicone hydrogel ink binder of the present disclosure includes one or more colorants in an amount of from about 5 wt. % to about 35 wt. %, or from about 10 wt. % to about 15 wt. %; a solvent in an amount of from about 10 wt. % to about 60 wt. %, or from about 20 wt. % to about 25 wt. %; and a silicone copolymer in an amount of from about 5 wt. % to about 40 wt. %, or from about 10 wt. % to about 25 wt. %, based on the total weight of the silicone hydrogel ink binder. In some embodiment, the silicone hydrogel ink binder of the present disclosure further includes a polymerization initiator in an amount of from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 1 wt. %, based on the total weight of the silicone hydrogel ink binder.

[0110] The silicone hydrogel ink binders of the present disclosure can be cured in a contact lens mold to form a colored film on a molding surface of the contact lens mold. The colored film comprises a colorant-entrapping polymer network and a colorant entrapped therein, and characterized by having a printed ink pattern. The colored film can be obtained by applying, to at least a portion of a molding surface of a contact lens mold, a silicone hydrogel ink binder and curing the silicone hydrogel ink binder utilizing one or more of heat (thermal cure) and/or radiation, such as ultraviolet light, visible light, or high energy radiation. The colored film contains a first surface in contact with the molding surface and an exposed second surface, i.e., internal to a lens-forming cavity of the contact lens mold.

[0111] A silicone hydrogel ink binder can be applied to a molding surface of a mold according to any printing technologies, such as, for example, pad transfer printing (or pad printing), or inkjet printing. It is understood that other types of printing technologies could also be used to print lenses and or molds.

[0112] Once the silicone hydrogel ink binder has been applied to a molding surface of a mold, the silicone hydrogel ink binder can be cured. Generally, polymerization can be carried out for about 1 minutes to about 45 minutes, and may or may not be under an inert atmosphere of, for example, nitrogen or argon.

[0113] A polymerization initiator may be included in the mixture to facilitate the polymerization step. Representative examples of free radical thermal polymerization initiators include organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, tertiarylbutyl peroxypivalate, peroxydicarbonate, and the like. Representative examples of diazo initiators include VAZO 64, and VAZO 67. Representative UV initiators are those known in the art and include benzoin methyl ether, benzoin ethyl ether, Darocure 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure 651 and 184 (Ciba-Geigy). Representative visible light initiators include IRGACURE 819 and other phosphine oxide-type initiators, and the like. Generally, the polymerization initiator will be employed in the silicone hydrogel ink binder-forming mixture at a concentration of about 0.01 to about 5 wt. % of the total mixture.

[0114] Suitable molds for making the colored film and colored silicone hydrogel contact lenses as discussed below are well known to a person skilled in the art. For example, a mold (for cast molding) generally comprises at least two mold sections (or portions) or mold halves, i.e. first and second mold halves. The first mold half defines a first molding (or optical) surface and the second mold half defines a second molding (or optical) surface. The first and second mold halves are configured to receive each other such that a lens forming cavity is formed between the first molding surface and the second molding surface. The molding surface of a mold half is the cavity-forming surface of the mold and in direct contact with lens-forming material. Virtually all materials known in the art for making molds can be used to make molds for making the colored films and colored silicone hydrogel contact lenses of the present disclosure. In some embodiments, polymeric materials include, for example, polyethylene, polypropylene, polystyrene or the like can be used. Other materials that allow UV light transmission could be used, such as quartz glass and sapphire.

[0115] In accordance with a non-limiting illustrative embodiment, colored silicone hydrogel contact lenses can be made using the colored film of the present disclosure. The colored film has good adhesion to the silicone hydrogel contact lens by being covalently attached to the lens material of the silicone hydrogel contact lens through the polymerizable ethylenically unsaturated reactive end group moiety of the monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group. It is believed that the lens material upon curing forms an interpenetrating polymeric network with the cured or partially cured colored film. Although the silicone hydrogel ink binders of the present disclosure are designed for use with silicone hydrogel contact lenses, they could also be used with non-silicone hydrogels of appropriate composition (e.g. low water content formulations).

[0116] In some embodiments, colored silicone hydrogel contact lenses of the present disclosure can be obtained by dispensing a silicone hydrogel contact lens-forming mixture comprising a silicone hydrogel contact lens-forming material into the contact lens mold having the colored film as discussed above, curing the silicone hydrogel contact lens-forming mixture comprising the silicone hydrogel contact lens-forming material and hydrating the silicone contact lens to form the colored silicone hydrogel contact lens, whereby the colored film detaches from the molding surface and becomes integral with the body of the silicone hydrogel contact lens without any ink domain expansion.

[0117] In some embodiments, silicone hydrogel contact lenses-forming mixture can be cast directly in the molds containing the colored film, e.g., polypropylene molds, from the silicone hydrogel contact lenses-forming mixtures, e.g., by spincasting and static casting methods. Spincasting methods are disclosed in U.S. Pat. Nos. 3,408,429 and 3,660,545, and static casting methods are disclosed in U.S. Pat. Nos. 4,113,224, 4,197,266, and 5,271,875. Spincasting methods involve charging the silicone hydrogel contact lenses-forming mixtures to be polymerized to a mold, and spinning the mold in a controlled manner while exposing the mixture to a radiation source such as UV light. Static casting methods involve charging the silicone hydrogel contact lens-forming mixture between two mold sections, one mold section shaped to form the anterior lens surface and the other mold section shaped to form the posterior lens surface, and curing the silicone hydrogel contact lenses-forming mixture while retained in the mold assembly to form a silicone hydrogel contact lens, for example, by free radical polymerization of the silicone hydrogel contact lenses-forming mixture. Examples of free radical reaction techniques to cure the lens material include thermal radiation, infrared radiation, electron beam radiation, gamma radiation, ultraviolet (UV) radiation, and the like; or combinations of such techniques may be used. U.S. Pat. No. 5,271,875 describes a static cast molding method that permits molding of a finished lens in a mold cavity defined by a posterior mold and an anterior mold. As an additional method, U.S. Pat. No. 4,555,732 discloses a process where an excess of a silicone hydrogel contact lens-forming mixture is cured by spincasting in a mold to form a shaped article having an anterior lens surface and a relatively large thickness, and the posterior surface of the cured spincast article is subsequently lathed to provide a contact lens having the desired thickness and posterior lens surface.

[0118] Polymerization may be facilitated by exposing the silicone hydrogel contact lens-forming mixture to heat (thermal cure) and/or radiation, such as ultraviolet light, visible light, or high energy radiation. A polymerization initiator may be included in the silicone hydrogel contact lens-forming mixture to facilitate the polymerization step. Representative examples of free radical thermal polymerization initiators include organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, tertiarylbutyl peroxypivalate, peroxydicarbonate, and the like. Representative examples of diazo initiators include VAZO 64, and VAZO 67. Representative UV initiators are those known in the art and include benzoin methyl ether, benzoin ethyl ether, Darocure 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure 651 and 184 (Ciba-Geigy). Representative visible light initiators include IRGACURE 819 and other phosphine oxide-type initiators, and the like. Generally, the initiator will be employed in the silicone hydrogel contact lens-forming mixture at a concentration of about 0.01 to about 5 wt. % of the total mixture.

[0119] Polymerization is generally performed in a reaction medium, such as, for example, a solution or dispersion using a solvent, e.g., water or an alkanol containing from 1 to 4 carbon atoms such as methanol, ethanol or propan-2-ol. Alternatively, a mixture of any of the above solvents may be used.

[0120] Generally, polymerization can be carried out for about 15 minutes to about 72 hours, and under an inert atmosphere of, for example, nitrogen or argon. If desired, the resulting polymerization product can be dried under vacuum, e.g., for about 5 to about 72 hours, or left in an aqueous solution prior to use.

[0121] Polymerization of the silicone hydrogel contact lens-forming mixtures will yield a colored polymer, that when hydrated, forms a colored silicon hydrogel contact lens with little to no ink domain expansion, i.e., the ink pattern of colored film remains the same. In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone hydrogels disclosed herein can be high water content silicone hydrogels having an equilibrium water content of at least about 50 wt. %. In another illustrative embodiment, the silicone hydrogels disclosed herein can be high water content silicone hydrogels having an equilibrium water content of at least about 60 wt. %. In another illustrative embodiment, the silicone hydrogels disclosed herein can be high water content silicone hydrogels having an equilibrium water content of at least about 70 wt. %. In another illustrative embodiment, the silicone hydrogels disclosed herein can be high water content silicone hydrogels having an equilibrium water content of from about 50 wt. % to about 80 wt. %.

[0122] In a non-limiting illustrative embodiment, a colored silicone hydrogel contact lens disclosed herein can have an oxygen permeability of at least about 80 Barrers. In some embodiments, a silicone hydrogel contact lens disclosed herein can have an oxygen permeability of from about 90 Barrers to about 130 Barrers.

[0123] In a non-limiting illustrative embodiment, a silicone hydrogel contact lens disclosed herein can have an equilibrium water content of at least about 20 wt. %. In another illustrative embodiment, a silicone hydrogel contact lens can have an equilibrium water content of from about 20 wt. % to about 60 wt. %.

[0124] The silicone hydrogel contact lenses obtained herein may be subjected to optional machining operations. For example, the optional machining steps may include buffing or polishing a lens edge and/or surface. Generally, such machining processes may be performed before or after the product is released from a mold part, e.g., the lens is dry released from the mold by employing vacuum tweezers to lift the lens from the mold, after which the lens is transferred by means of mechanical tweezers to a second set of vacuum tweezers and placed against a rotating surface to smooth the surface or edges. The lens may then be turned over in order to machine the other side of the lens.

[0125] The lens may then be transferred to individual lens packages containing a buffered saline solution. The saline solution may be added to the package either before or after transfer of the lens. Appropriate packaging designs and materials are known in the art. A plastic package is releasably sealed with a film. Suitable sealing films are known in the art and include foils, polymer films and mixtures thereof. The sealed packages containing the lenses are then sterilized to ensure a sterile product. Suitable sterilization means and conditions are known in the art and include, for example, autoclaving.

[0126] Suitable silicone hydrogel contact lens-forming material includes, for example, a monofunctional silicone monomer represented by a structure of Formula IV:

##STR00014##

wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently hydrogen, an alkyl group, a halo alkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a haloalkenyl group, an aryl group and a heteroaryl group; R.sup.5, R.sup.6 and R.sup.7 are independently a straight or branched alkyl group; x is from 1 to 6; and y is from 3 to 15.

[0127] In some embodiments, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 of the monofunctional silicone monomer represented by a structure of Formula IV are independently hydrogen, a C.sub.1 to C.sub.12 alkyl group, a C.sub.1 to C.sub.12 halo alkyl group, a C.sub.3 to C.sub.12 cycloalkyl group, a C.sub.3 to C.sub.12 heterocycloalkyl group, a C.sub.2 to C.sub.12 alkenyl group, a C.sub.2 to C.sub.12 haloalkenyl group, a C.sub.6 to C.sub.12 aromatic group and a C.sub.6 to C.sub.12 heteroaromatic group; R.sup.5, R.sup.6 and R.sup.7 are independently a straight or branched C.sub.1 to C.sub.12 alkyl group; x is from 1 to 6; and y is from 3 to 8.

[0128] In some embodiments, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 of the monofunctional silicone monomer represented by a structure of Formula IV are independently hydrogen, a C.sub.1 to C.sub.6 alkyl group; R.sup.5, R.sup.6 and R.sup.7 are independently a straight or branched C.sub.1 to C.sub.6 alkyl group; x is from 1 to 6; and y is from 3 to 8.

[0129] In some embodiments, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently a C.sub.1 to C.sub.3 alkyl group; R.sup.5 and R.sup.6 are independently a C.sub.1 to C.sub.3 alkyl group; R.sup.7 is a straight or branched C.sub.3 to C.sub.6 alkyl group; x is from 2 to 4; and y is from 3 to 15.

[0130] Representative examples of alkyl groups for use herein include, by way of example, a straight or branched alkyl chain radical containing carbon and hydrogen atoms of from 1 to about 30 carbon atoms or from 1 to about 12 carbon atoms or from 1 to about 6 carbon atoms with or without unsaturation, to the rest of the molecule, e.g., methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, methylene, ethylene, etc., and the like, optionally containing one or more heteroatoms, e.g., O and N, and the like, or one or more halogen atoms, e.g., fluorine, chlorine, bromine, and iodine, to form a halo alkyl group.

[0131] Representative examples of cycloalkyl groups for use herein include, by way of example, a substituted or unsubstituted, non-aromatic mono or multicyclic ring system of about 3 to about 30 carbon atoms or from 3 to about 12 carbon atoms or from 3 to about 6 carbon atoms such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, perhydronapththyl, adamantyl and norbornyl groups, bridged cyclic groups or sprirobicyclic groups, e.g., spiro-(4, 4)-non-2-yl and the like, optionally containing one or more heteroatoms, e.g., O and N, and the like to form a heterocycloalkyl group.

[0132] Representative examples of cycloalkylalkyl groups for use herein include, by way of example, a substituted or unsubstituted, cyclic ring-containing radical containing from about 4 to about 30 carbon atoms or from 3 to about 6 carbon atoms directly attached to the alkyl group which is then attached to the main structure of the monomer at any carbon from the alkyl group that results in the creation of a stable structure such as, for example, cyclopropylmethyl, cyclobutylethyl, cyclopentylethyl and the like, wherein the cyclic ring can optionally contain one or more heteroatoms, e.g., O and N, and the like to form a heterocycloalkylalkyl group.

[0133] Representative examples of cycloalkenyl groups for use herein include, by way of example, a substituted or unsubstituted cyclic ring-containing radical containing from about 3 to about 30 carbon atoms or from 3 to about 6 carbon atoms with at least one carbon-carbon double bond such as, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl and the like, wherein the cyclic ring can optionally contain one or more heteroatoms, e.g., O and N, and the like to form a heterocycloalkenyl group.

[0134] Representative examples of aryl groups for use herein include, by way of example, a substituted or unsubstituted, monoaromatic or polyaromatic radical containing from about 6 to about 30 carbon atoms or from about 6 to about 12 carbon atoms such as, for example, phenyl, naphthyl, tetrahydronapthyl, indenyl, biphenyl and the like, optionally containing one or more heteroatoms, e.g., O and N, and the like to form a heteroaryl group.

[0135] In an illustrative embodiment, the monofunctional silicone monomer represented by the structure of Formula IV is either commercially available from such sources as ShinEtsu or can be made by methods within the purview of one skilled in the art. For example, in an illustrative embodiment, the monofunctional silicone monomer represented by the structure of Formula IV can be prepared according to the following reaction Scheme I.

##STR00015##

[0136] In some embodiments, the one or more monofunctional silicone monomers represented by a structure of Formula IV as disclosed herein can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 5 wt. % to about 40 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture. In some embodiments, the one or more silicone monomers represented by a structure of Formula I as disclosed herein can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 7 wt. % to about 15 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture.

[0137] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more non-bulky organosilicon-containing monomers as discussed above.

[0138] Representative examples of the non-bulky organosilicon-containing monomers include:

[0139] M1EDS6: a compound having the structure and available from Gelest:

##STR00016##

[0140] MCR-M11: a compound having the structure:

##STR00017##

[0141] M1-MCR-C12: a compound having the structure:

##STR00018##

wherein n is an average of 12.

[0142] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more polysiloxane prepolymers represented by a structure of Formula V:

##STR00019##

wherein each V is an independently reactive functional end group and includes, by way of example, a hydroxyl-containing reactive functional end group, and an amine-containing reactive functional end group, R.sup.17 to R.sup.22 are independently straight or branched, substituted or unsubstituted C.sub.1-C.sub.30 alkyl group, a substituted or unsubstituted C.sub.3-C.sub.30 cycloalkyl group, a substituted or unsubstituted C.sub.4-C.sub.30 cycloalkylalkyl group, a substituted or unsubstituted C.sub.3-C.sub.30 cycloalkenyl group, a substituted or unsubstituted C.sub.6-C.sub.30 aryl group, and a substituted or unsubstituted C.sub.7-C.sub.30 arylalkyl group, and L is independently a linking group.

[0143] A hydroxyl-containing reactive functional end group for use herein is a group of the general Formula OH. Representative examples of amine-containing reactive functional end groups for use herein include, by way of example, a (meth)acrylamide-containing reactive functional end group.

[0144] Linking group L is independently a straight or branched alkyl group, cycloalkyl group, an aryl group, an ether or polyether group, and an ester group as defined herein.

[0145] A representative example of a polysiloxane prepolymer is as follows:

##STR00020##

[0146] Methods for making the polysiloxane prepolymers described herein are well known and within the purview of one skilled in the art. In addition, the polysiloxane prepolymers are also commercially available from such sources as, for example, Gelest, Silar, Shin-Etsu, Momentive and Siltech.

[0147] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more bulky siloxane monomers as discussed above.

[0148] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more silicone-containing vinyl carbonate or vinyl carbamate monomers. Suitable one or more silicone-containing vinyl carbonate or vinyl carbamate monomers include, for example, 1,3-bis[4-vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane; 3-(trimethylsilyl)propyl vinyl carbonate; 3-(vinyloxycarbonylthio)propyl-[tris(trimethylsiloxy)silane]; 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate; 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate; 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate; t-butyldimethylsiloxyethyl vinyl carbonate; trimethylsilylethyl vinyl carbonate; trimethylsilylmethyl vinyl carbonate and the like and mixtures thereof.

[0149] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more polyurethane-polysiloxane macromonomers (also sometimes referred to as prepolymers), which may have hard-soft-hard blocks like traditional urethane elastomers. They may be end-capped with a hydrophilic monomer such as HEMA. Examples of such silicone urethanes are disclosed in a variety or publications, including Lai, Yu-Chin, The Role of Bulky Polysiloxanylalkyl Methacrylates in Polyurethane-Polysiloxane Hydrogels, Journal of Applied Polymer Science, Vol. 60, 1193-1199 (1996). PCT Published Application No. WO 96/31792 discloses examples of such monomers, which disclosure is hereby incorporated by reference in its entirety. Further examples of silicone urethane monomers are represented by Formulae VI and VII:

##STR00021##

wherein: [0150] D independently denotes an alkyl diradical, an alkyl cycloalkyl diradical, a cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 6 to about 30 carbon atoms; [0151] G independently denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 1 to about 40 carbon atoms and which may contain ether, thio or amine linkages in the main chain; [0152] * denotes a urethane or ureido linkage; [0153] a is at least 1; [0154] A independently denotes a divalent polymeric radical of Formula VIII:

##STR00022##

wherein each R.sup.s independently denotes an alkyl or fluoro-substituted alkyl group having 1 to about 10 carbon atoms which may contain ether linkages between the carbon atoms; m is at least 1; and p is a number that provides a moiety weight of about 400 to about 10,000; [0155] each of E and E independently denotes a polymerizable unsaturated organic radical represented by Formula IX:

##STR00023## [0156] wherein: R.sup.3 is hydrogen or methyl; [0157] R.sup.4 is hydrogen, an alkyl radical having 1 to 6 carbon atoms, or a COYR.sup.6 radical wherein Y is O, S or NH; [0158] R.sup.5 is a divalent alkylene radical having 1 to about 10 carbon atoms; [0159] R.sup.6 is a alkyl radical having 1 to about 12 carbon atoms;

##STR00024## [0160] Ar denotes an aromatic radical having about 6 to about 30 carbon atoms; [0161] w is 0 to 6; x is 0 or 1; y is 0 or 1; and z is 0 or 1.

[0162] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more silicone-containing urethane monomers represented by Formula X:

##STR00025##

wherein m is at least 1 and is preferably 3 or 4, a is at least 1 and preferably is 1, p is a number which provides a moiety weight of about 400 to about 10,000 and is preferably at least about 30, R.sup.7 is a diradical of a diisocyanate after removal of the isocyanate group, such as the diradical of isophorone diisocyanate, and each E is a group represented by:

##STR00026##

[0163] In another embodiment, a silicone hydrogel material comprises (in bulk, that is, in the silicone hydrogel contact lens-forming mixture that is copolymerized) about 5 to about 50 percent, or from about 10 to about 25, by weight of one or more silicone macromonomers, about 5 to about 75 percent, or about 30 to about 60 percent, by weight of one or more polysiloxanylalkyl (meth)acrylic monomers, and about 10 to about 50 percent, or about 20 to about 40 percent, by weight of a hydrophilic monomer. In general, the silicone macromonomer is a poly(organosiloxane) capped with an unsaturated group at two or more ends of the molecule. In addition to the end groups in the above structural Formulas, U.S. Pat. No. 4,153,641 discloses additional unsaturated groups, including acryloxy or methacryloxy. Fumarate-containing materials such as those disclosed in U.S. Pat. Nos. 5,310,779; 5,449,729 and 5,512,205 are also useful substrates in accordance with the non-limiting embodiments described herein. The silane macromonomer may be a silicone-containing vinyl carbonate or vinyl carbamate or a polyurethane-polysiloxane having one or more hard-soft-hard blocks and end-capped with a hydrophilic monomer.

[0164] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more monomers of Formula XI:

##STR00027##

wherein X is the residue of a ring opening agent; L is the same or different and is a linking group or a bond; V is an ethylenically unsaturated polymerizable group; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 are independently hydrogen, an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R.sub.7 and R.sub.8 are independently hydrogen or an alkyl group wherein at least one of R.sub.7 or R.sub.8 is hydrogen; y is 2-7 and n is 1-100.

[0165] Ring opening agents are well known in the literature. Non-limiting examples of anionic ring opening agents include alkyl lithium, an alkoxide, trialkylsiloxylithium wherein the alkyl group may or may not contain halo atoms.

[0166] Linking groups can be any divalent radical or moiety and include substituted or unsubstituted alkyl, alkyl ether, alkenyls, alkenyl ethers, halo alkyls, substituted or unsubstituted siloxanes, and monomers capable of propagating ring opening.

[0167] Ethylenically unsaturated polymerizable groups are well known to those skilled in the art. Non-limiting examples of ethylenically unsaturated polymerizable groups would include acrylates, methacrylates, vinyl carbonates, O-vinyl carbamates, N-vinyl carbamates, acrylamides and methacrylamides.

[0168] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more monomers of Formula XII:

##STR00028##

wherein L is the same or different and is a linking group or a bond; V is the same or different and is an ethylenically unsaturated polymerizable group; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.9 are independently hydrogen, an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R.sub.7 and R.sub.8 are independently hydrogen or an alkyl group wherein at least one of R.sub.7 or R.sub.8 is hydrogen; y is 2-7 and n is 1-100.

[0169] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more monomers of Formulae XIII and XIV:

##STR00029##

wherein R.sub.9, R.sub.10 and R.sub.11 are independently hydrogen, an alkyl group, a haloalkyl group or other substituted alkyl groups; n is as defined above and n.sup.1 is 0-10; and,

##STR00030##

wherein n is 1 to 100, or n is 2 to 80, or n is 3 to 20, or n is 5 to 15.

[0170] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more monomers of Formulas XV-XIX:

##STR00031##

[0171] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more monomers of Formulas XX-XXII:

##STR00032## [0172] wherein R.sub.9, R.sub.10 and R.sub.11 are independently hydrogen, an alkyl group, a haloalkyl group or other substituted alkyl groups and n and n.sup.1 are as defined above.

[0173] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more monomers of Formulas XXIII-XXV:

##STR00033## [0174] wherein n is as defined above and X.sup. is a counterion to provide an overall neutral charge.

[0175] Counterions capable of providing an overall neutral charge are well known to those of ordinary skill in the art and would include, for example, halide ions.

[0176] Suitable silicone hydrogel contact lens-forming material further includes, for example, as a class of representative silicone hydrogel contact lens-forming material, one or more monomers of Formula XXVI:

##STR00034##

[0177] In accordance with one or more additional non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more silicone hydrogel contact lens-forming material can be present in the silicone hydrogel contact lens-forming mixture in a major amount. In accordance with one or more additional non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more silicone hydrogel contact lens-forming material can be present in the silicone hydrogel contact lens-forming mixture in an amount greater than about 50 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture. In some embodiments, the one or more silicone hydrogel contact lens-forming material can be present in the silicone hydrogel contact lens-forming mixture in an amount greater than about 50 wt. % and up to 95 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture.

[0178] The above silicone materials are merely exemplary, and other materials for use as substrates that have been disclosed in various publications and are being continuously developed for use in contact lenses and other silicone hydrogels can also be used. For example, a silicone hydrogel can be formed from at least a cationic monomer such as cationic silicone-containing monomers or cationic fluorinated silicone-containing monomers.

[0179] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone hydrogel contact lens-forming mixture can further contain one or more hydrophilic comonomers. Suitable hydrophilic comonomers include, for example, unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl-containing-(meth)acrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamates, hydrophilic oxazolones, and poly(alkene glycols) functionalized with polymerizable groups and the like and mixtures thereof. Representative examples of unsaturated carboxylic acids include, but are not limited to, methacrylic acid, acrylic acid and the like and mixtures thereof. Representative examples of acrylamides include, but are not limited to, alkylamides such as N,N-dimethylacrylamide, N,N-dimethylmethacrylamide and the like and mixtures thereof. Representative examples of cyclic lactams include, but are not limited to, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, N-vinyl-2-piperidone and the like and mixtures thereof. Representative examples of hydroxyl-containing (meth)acrylates include, but are not limited to, 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate and the like and mixtures thereof.

[0180] Additional hydrophilic comonomers include, for example, the hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Pat. No. 5,070,215, and the hydrophilic oxazolone monomers disclosed in U.S. Pat. No. 4,910,277. Other suitable silicone hydrogel-forming hydrophilic comonomers will be apparent to one skilled in the art. Mixtures of the foregoing hydrophilic comonomers can also be used in the silicone hydrogel contact lens-forming mixtures herein.

[0181] In accordance with one or more additional non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more hydrophilic comonomers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 20 wt. % to about 60 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture. In another illustrative embodiment, the one or more hydrophilic comonomers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 25 wt. % to about 45 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture.

[0182] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone hydrogel contact lens-forming mixture can further contain one or more crosslinking agents. Suitable crosslinking agents for use herein are known in the art. For example, in non-limiting illustrative embodiments, suitable one or more cross-linking agents include one or more crosslinking agents containing at least two ethylenically unsaturated reactive end groups. In one embodiment, the ethylenically unsaturated reactive end groups are (meth)acrylate-containing reactive end groups. In another embodiment, the ethylenically unsaturated reactive end groups are non-(meth)acrylate reactive end groups. In one embodiment, the ethylenically unsaturated reactive end groups are a combination of one or more (meth)acrylate-containing reactive end groups and one or more non-(meth)acrylate reactive end groups.

[0183] In an illustrative embodiment, useful one or more crosslinking agents containing at least two ethylenically unsaturated reactive end groups include, for example, one or more di-, tri- or tetra(meth)acrylate-containing crosslinking agents. In an illustrative embodiment, useful one or more di-, tri- or tetra(meth)acrylate-containing crosslinking agents include, for example, alkanepolyol di-, tri- or tetra(meth)acrylate-containing crosslinking agents such as, for example, one or more alkylene glycol di(meth)acrylate crosslinking agents, one or more alkylene glycol tri(meth)acrylate crosslinking agents, one or more alkylene glycol tetra(meth)acrylate crosslinking agents, one or more alkanediol di(meth)acrylate crosslinking agents, alkanediol tri(meth)acrylate crosslinking agents, alkanediol tetra(meth)acrylate crosslinking agents, agents, one or more alkanetriol di(meth)acrylate crosslinking agents, alkanetriol tri(meth)acrylate crosslinking agents, alkanetriol tetra(meth)acrylate crosslinking agents, agents, one or more alkanetetraol di(meth)acrylate crosslinking agents, alkanetetraol tri(meth)acrylate crosslinking agents, alkanetetraol tetra(meth)acrylate crosslinking agents and the like and mixtures thereof.

[0184] In an illustrative embodiment, one or more alkylene glycol di(meth)acrylate crosslinking agents include tetraethylene glycol dimethacrylate, ethylene glycol di(meth)acrylates having up to about 10 ethylene glycol repeating units, butyleneglycol di(meth)acrylate and the like. In one embodiment, one or more alkanediol di(meth)acrylate crosslinking agents include butanediol di(meth)acrylate crosslinking agents, hexanediol di(meth)acrylate and the like. In one embodiment, one or more alkanetriol tri(meth)acrylate crosslinking agents are trimethylol propane trimethacrylate crosslinking agents. In one embodiment, one or more alkanetetraol tetra(meth)acrylate crosslinking agents are pentaerythritol tetramethacrylate crosslinking agents.

[0185] In a non-limiting illustrative embodiment, suitable crosslinking agents include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, allyl acrylate, 1,3-propanediol diacrylate, 2,3-propanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, triethylene glycol diacrylate, cyclohexane-1,1-diyldimethanol diacrylate, 1,4-cyclohexanediol diacrylate, 1,3-adamantanediol diacrylate, 1,3-adamantanedimethyl diacrylate, 2,2-diethyl-1,3-propanediol diacrylate, 2,2-diisobutyl-1,3-propanediol diacrylate, 1,3-cyclohexanedimethyl diacrylate, 1,4-cyclohexanedimethyl diacrylate; neopentyl glycol diacrylate, tetraethyleneglycol diacrylate, polyethyleneglycol diacrylate; and their corresponding methacrylates.

[0186] In a non-limiting illustrative embodiment, suitable crosslinking agents include, for example, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, poly(ethylene glycol) diacrylate (Mn=700 Daltons), poly(ethylene glycol) dimethacrylate (Mn=700 Daltons), and poly(ethylene glycol) dimethacrylate (Mn=1000 Daltons).

[0187] In one embodiment, the one or more crosslinking agents containing at least two ethylenically unsaturated reactive end groups include at least one allyl-containing reactive end group and at least one (meth)acrylate-containing reactive end group. In an illustrative embodiment, the one or more crosslinking agents can be allyl methacrylate.

[0188] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more crosslinking agents can be present in the silicone hydrogel contact lens-forming mixture in a silicone hydrogel-forming amount. In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more crosslinking agents are present in the silicone hydrogel contact lens-forming mixture in an amount of about 0.1 to about 3.0 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture. In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more crosslinking agents are present in the silicone hydrogel contact lens-forming mixture in an amount of about 0.2 to about 1.0 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture.

[0189] In accordance with one or more additional non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone hydrogel contact lens-forming mixture can further contain one or more additional comonomers. In an illustrative embodiment, the one or more additional comonomers can include, for example, both an ethylenically unsaturated group (that permits the monomer to copolymerize with the hydrophilic comonomer) and an epoxide group (that does not react with the hydrophilic comonomer but remains to react with the copolymer). Suitable additional comonomers include, for example, glycidyl methacrylate, glycidyl acrylate, glycidyl vinylcarbonate, glycidyl vinylcarbamate, 4-vinyl-1-cyclohexene-1,2-epoxide and the like.

[0190] In non-limiting illustrative embodiments, the one or more additional comonomers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 1 wt. % to about 20 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture. In another illustrative embodiment, the one or more additional comonomers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 3 wt. % to about 10 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture.

[0191] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone hydrogel contact lens-forming mixture can further contain a reactive (polymerizable) ultraviolet (UV) light absorber and/or a reactive blue-light absorber. Suitable reactive UV light absorbers can be any known reactive UV light absorber. In non-limiting illustrative embodiments, suitable reactive UV light absorbers include, for example, 2-(2-hydroxy-3-methallyl-5-methylphenyl)benzotriazole, commercially available as o-Methallyl Tinuvin P (oMTP) from Polysciences, Inc., Warrington, Pa., 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenylethyl methacrylate, and 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethyl methacrylate.

[0192] In one illustrative embodiment, suitable UV light absorbers include, for example, one or more compounds of the following formulas:

##STR00035## [0193] (2-Propenoic acid, 2-methyl,2-(4-benzoyl-3-hydroxyphenoxy)-1-[(4-benzoyl3-hydroxyphenoxy)methyl ester),

##STR00036##

These compounds are merely illustrative and not intended to be limiting. Any known UV blocker or later developed UV blocker is contemplated for use herein.

[0194] In illustrative embodiments, the UV light absorbers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 0.1 to about 5 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture. In another illustrative embodiment, the UV light absorbers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 1.5 to about 2.5 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture. In yet another non-limiting illustrative embodiment, the UV light absorbers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 1.5 to about 2 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture.

[0195] Many reactive blue-light absorbing compounds are known. Preferred reactive blue-light absorbing compounds are those described in U.S. Pat. Nos. 5,470,932; 8,207,244; and 8,329,775, the contents of which are hereby incorporated by reference. In one embodiment, a blue-light absorbing dye is N-2-[3-(2-methylphenylazo)-4-hydroxyphenyl]ethyl methacrylamide. In illustrative embodiments, the blue-light absorbers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 0.005 to about 1 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture. In another illustrative embodiment, the blue-light absorbers can be present in the silicone hydrogel contact lens-forming mixture in an amount ranging from about 0.01 to about 1 wt. %, based on the total weight of the silicone hydrogel contact lens-forming mixture.

[0196] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone hydrogel contact lens-forming mixture can further contain a diluent. Suitable diluents include, for example, at least one or more boric acid esters of a C.sub.1 to C.sub.8 monohydric alcohol, water-soluble or partly water-soluble monohydric alcohols and mixtures thereof. In one embodiment, a diluent includes, for example, at least one or more boric acid esters of a C.sub.1 to C.sub.5 monohydric alcohol. Suitable boric acid esters of a C.sub.1 to C.sub.8 monohydric alcohol include, for example, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, and tri-tert-butyl borate. Suitable water-soluble or partly water-soluble monohydric alcohols include, for example, monohydric alcohols having from 1 to 5 carbon atoms such as methanol, ethanol, isopropyl alcohol, 1-propanol, t-butyl alcohol, 2-butyl alcohol, 2-methyl-1-propanol, t-amyl alcohol and other C.sub.5 isomers.

[0197] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone hydrogel contact lens-forming mixture contains about 5 wt. % to about 50 wt. % of the diluent, based on the total weight of the silicone hydrogel contact lens-forming mixture. In one embodiment, the silicone hydrogel contact lens-forming mixture contains about 15 wt. % to about 30 wt. % of the diluent, based on the total weight of the silicone hydrogel contact lens-forming mixture.

[0198] The silicone hydrogel contact lens-forming mixture may further contain, as necessary and within limits not to impair the purpose and effect of the illustrative embodiments, various additives such as an antioxidant, coloring agent, lubricant, internal wetting agent, toughening agent and the like and other constituents as are well known in the art.

[0199] As one skilled in the art will readily appreciate other steps may be included in the molding and packaging process described above. Such other steps can include, for example, coating the formed lens, surface treating the lens during formation (e.g., via mold transfer), inspecting the lens, discarding defective lenses, cleaning the mold halves, reusing the mold halves, and the like and combinations thereof.

[0200] The following examples are provided to enable one skilled in the art to practice the invention and are merely illustrative of the invention. The examples should not be read as limiting the scope of the invention as defined in the claims.

[0201] In the examples, the following abbreviations are used. [0202] DMA: N,N-dimethylacrylamide. [0203] NVP: N-vinyl-2-pyrrolidone. [0204] HEMA: 2-hydroxyethyl methacrylate. [0205] MEMA: 2-Methoxyethyl methacrylate or Ethylene glycol methyl ether methacrylate. [0206] EGDMA: Ethylene glycol dimethacrylate. [0207] MAA: Methacrylic acid. [0208] IMVT: 1,4-bis(4-(2-methacryloxyethyl)phenylamino)anthraquinone. [0209] UV416: 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate. [0210] TrisMA: tris(trimethylsiloxy)silylpropyl methacrylate. [0211] Irgacure 819 (photoinitiator): a compound having the structure:

##STR00037##

[0212] M1EDS6: A compound having the following structure and available from Gelest:

##STR00038##

[0213] Ma2D37: A compound having the structure:

##STR00039##

[0214] X-22-1666C: A compound available from ShinEtsu and having the following structure:

##STR00040##

[0215] SA monomer: A compound having the structure:

##STR00041##

[0216] SiCO is TRIS-MCRM11-DMA-HEA-SA which is a copolymer represented by the following structure:

##STR00042##

where n is 126, m is 8, o is 73, x is 57, y is 33 and z is 3. [0217] Vazo 64: azo bis-isobutylnitrile (AIBN). [0218] HEA: Hydroxyethyl acrylate. [0219] DEGDA: Diethylene glycol diacrylate. [0220] TPO: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

Example 1

[0221] A silicone hydrogel ink binder was prepared using the reaction components listed in Table 1 below, as amounts per weight percent.

TABLE-US-00001 TABLE 1 Component (Wt. %) SiCO 35 Ethyl-1-lactate 27 Cyclopentanone 10 Iron oxide black 26 Irgacure 819 2 ZrO.sub.2 and SiO.sub.2 grinding media 33*

Silicone Hydrogel Ink Binder Preparation

[0222] The silicone hydrogel ink binder was prepared by combining 14 g of SiCO with 10.8 g of ethyl-1-lactate, 4 g of cyclopentanone, and 14 g of milling beads. The mixture was then processed in a speed mixer for 10 minutes at 2500 rpm. After this initial mixing, the copolymer's dissolution was checked. If it was not fully dissolved, the mixture was blended for an additional 5 minutes at the same speed. Once the copolymer was completely dissolved, 10.4 g of iron oxide black (ink pigment) and 2 g of Irgacure 819 were added. This mixture was then subjected to another round of speed mixing: first for 10 minutes at 1000 rpm, followed by 10 minutes at 800 rpm. The resulting ink had a viscosity of 1600 cp as measured by BYK CAP 2000+ Viscometer.

Colored Film

[0223] The silicone hydrogel ink binder was poured into the loading cup of a Teca Printer and then printed onto polypropylene molds. After printing, the printed molds were cured under 3 mW/cm.sup.2 intensity UV or 420 nm LED light for 10 minutes.

Example 2

[0224] A colored silicone hydrogel contact lens was obtained from a silicone hydrogel contact lens-forming mixture made by mixing the following components, listed in Table 2 at amounts per weight.

TABLE-US-00002 TABLE 2 Formulation SiCO 69.3 HEMA 15 DMA 15 Irgacure 819 0.7

[0225] The silicone hydrogel contact lens-forming mixture was cast into a colored silicone hydrogel contact lens by introducing the silicone hydrogel contact lens-forming mixture to the mold assembly containing the colored film of Example 1. After waiting for 1 minute, the silicone hydrogel contact lens-forming mixture was cured at 4 mW/Cm.sup.2 UV/420 nm for 15 minutes.

[0226] The colored silicone hydrogel lens was dry released from the mold and placed in a phosphate buffer solution for 4 hours for complete hydration.

[0227] Following hydrating the ink pattern of the colored film of the colored silicone hydrogel contact lens did not expand or rubbed away from the lens after hydration and the lens had good resolution.

Example 3

[0228] A colored silicone hydrogel contact lens was obtained from a silicone hydrogel contact lens-forming mixture made by mixing the following components, listed in Table 3 at amounts per weight.

TABLE-US-00003 TABLE 3 Formulation Ma2D37 6.00 M1EDS6 15.00 TRIS-MA 28.00 DMA 7.00 HEMA 1.00 NVP 34.00 UV-416 1.00 EGDMA 0.1 IMVT 0.02 Irgacure 819 0.50 Hexanol 7.38

[0229] The silicone hydrogel contact lens-forming mixture was cast into a colored silicone hydrogel contact lens by introducing the silicone hydrogel contact lens-forming mixture to the mold assembly containing the colored film of Example 1. Prior to introducing the silicone hydrogel contact lens-forming mixture to the mold assembly, the molds were put in a N.sub.2 chamber and waited for 30 minutes so that all surface adsorbed O.sub.2 gets removed from the molds. Next, the silicone hydrogel contact lens-forming mixture were introduced to the mold assembly. After waiting for 1 minute, lenses were cured at 4.5 mW/Cm.sup.2 UV/420 nm for 28 minutes.

[0230] The colored silicone hydrogel lens was dry released from the mold and placed in a phosphate buffer solution for 4 hours for a complete hydration.

[0231] Following hydrating, the ink pattern of the colored film of the colored silicone hydrogel contact lens did not expand or rubbed away from the lens and the lens had good resolution.

Example 4

[0232] A colored silicone hydrogel contact lens was obtained from a silicone hydrogel contact lens-forming mixture made by mixing the following components, listed in Table 4 at amounts per weight.

TABLE-US-00004 TABLE 4 Formulation X22-1666C 39.40 MAA 5.00 MEMA 5.40 NVP 46.18 UV-416 1.00 EGDMA 0.75 IMVT 0.02 Vazo64 1.00 SA Monomer 1.25

[0233] The silicone hydrogel contact lens-forming mixture was cast into a colored silicone hydrogel contact lens by introducing the silicone hydrogel contact lens-forming mixture to the polypropylene mold assembly containing the colored film of Example 1. After waiting for 1 minute, the silicone hydrogel contact lens-forming mixture was cured thermally in a Blue M oven (30 minutes N.sub.2 purge at RT, ramp at 10 C/min to 110 C., then wait for 45 minutes at 110 C., and then cooled down at a rate of 20 C./min to 30 C.

[0234] The colored silicone hydrogel lens was dry released from the mold and placed in a phosphate buffer solution for 4 hours for a complete hydration.

[0235] Following hydrating, the ink pattern of the colored film of the colored silicone hydrogel contact lens did not expand or come off from the lens after hydration and the lens had moderate resolution.

Comparative Example A

[0236] An activated poly HEMA-co-NVP ink binder was prepared using the reaction components listed in Table 5 below, at amounts per weight percent. The activation solution used in making the activated poly HEMA-co-NVP ink binder was prepared using the components listed in Table 6 below, at amounts per weight percent. The chemical structure of poly HEMA-co-NVP binder is below.

##STR00043##

TABLE-US-00005 TABLE 5 Formulation Poly HEMA- co- 36.00 NVP binder Black iron oxide 15.00 Ethyl 1-lactate 27.00 IPA 12.00 activation solution 10.00 vicosity after 1600 cp pigment milling

TABLE-US-00006 TABLE 6 Activation Solution HEA 50.00 DEGDA 30.00 TPO 20.00

Activated Poly HEMA-Co-NVP Ink Binder Preparation

[0237] The activated poly HEMA-co-NVP ink binder was prepared by combining 10.90 g of poly HEMA-co-NVP polymer having a weight average molecular weight of 13 kDa with 8.20 g of ethyl-1-lactate, 3.62 g of iso-propanol, and 3.05 g of activation solution from a master batch prepared separately. The activation solution master batch was prepared by thoroughly mixing 5.06 g of HEA, 3.10 g of DEGDA and 2.02 g of TPO. The poly HEMA-co-NVP containing reaction mixture was then processed in a speed mixer for 10 minutes at 2500 rpm. After this initial mixing, 4.50 g black iron oxide was added. The mixture was blended for an additional 5 minutes at the same speed. This mixture was then subjected to another round of speed mixing: first for 10 minutes at 1000 rpm, followed by 10 minutes at 800 rpm. The resulting activated poly HEMA-co-NVP ink binder had a viscosity of 1600 cp as measured by a BYK CAP 2000+ Viscometer.

Colored Film

[0238] The activated poly HEMA-co-NVP ink binder preparation was poured into a loading cup of a Teca Printer and then printed onto polypropylene molds. After printing, the printed molds were cured under 3 mW/cm.sup.2 intensity UV or 420 nm LED light for 10 minutes.

Comparative Example B

[0239] A colored silicone hydrogel contact lens was obtained from a silicone hydrogel contact lens-forming mixture made by mixing the following components, listed in Table 7 at amounts per weight.

TABLE-US-00007 TABLE 7 Formulation Ma2D37 7.01 M1EDS6 15.00 TRIS-MA 28.00 DMA 7.00 HEMA 1.00 NVP 34.00 IMVT 0.02 Irgacure 819 0.50 Hexanol 7.38

[0240] The silicone hydrogel contact lens-forming mixture of Table 7 was cast into a colored silicone hydrogel contact lens by introducing the silicone hydrogel contact lens-forming mixture to the mold assembly containing the colored film of Comparative Example 5. Prior to introducing the silicone hydrogel contact lens-forming mixture to the mold assembly, the molds were put in a N.sub.2 chamber and waited for 30 minutes so that all surface adsorbed 02 gets removed from the molds. Next, the silicone hydrogel contact lens-forming mixture were introduced to the mold assembly. After waiting for 1 minute, lenses were cured at 4.5 mW/Cm.sup.2 UV/420 nm for 28 minutes.

[0241] The colored silicone hydrogel contact lens was dry released from the mold assembly and placed in a phosphate buffer solution for 4 hours for a complete hydration.

[0242] Following hydrating, the ink pattern of the colored film of the colored silicone hydrogel contact lens was distorted and ink bleeding was observed, with the lens having no resolution.

Comparative Example C

[0243] An activated poly DMA-co-MPEG ink binder was prepared using the reaction components listed in Table 8 below, at amounts per weight percent. The activation solution used in making the activated poly DMA-co-MPEG ink binder was prepared using the components listed in Table 9 below, at amounts per weight percent. The chemical structure of poly-DMA-co-MPEG is below:

##STR00044##

TABLE-US-00008 TABLE 8 Formulation Poly DMA- co- 36.00 MPEG binder Black iron oxide 15.00 Ethyl 1-lactate 27.00 IPA 12.00 Activation 10.00 solution vicosity after 800 cp pigment milling

TABLE-US-00009 TABLE 9 Activation Solution HEA 50.00 DEGDA 30.00 TPO 20.00

Activated Poly DMA-Co-MPEG Ink Binder Preparation

[0244] The activated poly DMA-co-MPEG ink binder was prepared by combining 10.90 g of poly DMA-co-MPEG polymer having a weight average molecular weight of 30 kDa with 8.20 g of ethyl-1-lactate, 3.62 g of iso-propanol, and 3.05 g of activation solution from a master batch prepared separately. The activation solution master batch was prepared by thoroughly mixing 5.06 g of HEA, 3.10 g of DEGDA and 2.02 g of TPO. The poly DMA-co-MPEG containing reaction mixture was then processed in a speed mixer for 10 minutes at 2500 rpm. After this initial mixing, the 4.50 g black iron oxide was added. The mixture was blended for an additional 5 minutes at the same speed. This mixture was then subjected to another round of speed mixing: first for 10 minutes at 1000 rpm, followed by 10 minutes at 800 rpm. The resulting activated poly DMA-co-MPEG ink binder had a viscosity of 800 cp as measured by a BYK CAP 2000+ Viscometer

Colored Film

[0245] The activated poly DMA-co-MPEG ink binder preparation was poured into a loading cup of a Teca Printer and then printed onto polypropylene molds. After printing, the printed molds were cured under 3 mW/cm.sup.2 intensity UV or 420 nm LED light for 10 minutes.

Comparative Example D

[0246] A colored silicone hydrogel contact lens was obtained from a silicone hydrogel contact lens-forming mixture made by mixing the following components, listed in Table 10, at amounts per weight.

[0247] The colored silicone hydrogel contact lens was dry released from the mold assembly and placed in a phosphate buffer solution for 4 hours for a complete hydration.

[0248] Following hydrating, the ink pattern of the colored film of the colored silicone hydrogel contact lens was distorted and ink bleeding was observed, with the lens having no resolution.

TABLE-US-00010 TABLE 10 Formulation Ma2D37 7.01 M1EDS6 15.00 TRIS-MA 28.00 DMA 7.00 HEMA 1.00 NVP 34.00 IMVT 0.02 Irgacure 819 0.50 Hexanol 7.38

[0249] The silicone hydrogel contact lens-forming mixture of Table 10 was cast into a colored silicone hydrogel contact lens by introducing the silicone hydrogel contact lens-forming mixture to the mold assembly containing the colored film of Comparative Example C. Prior to introducing the silicone hydrogel contact lens-forming mixture to the mold assembly, the molds were put in a N.sub.2 chamber and waited for 30 minutes so that all surface adsorbed 02 gets removed from the molds. Next, the silicone hydrogel contact lens-forming mixture were introduced to the mold assembly. There was a poor transfer of ink from pad to mold. After waiting for 1 minute, the lenses were cured at 4.5 mW/Cm.sup.2 UV/420 nm for 28 minutes.

[0250] The colored silicone hydrogel contact lens was dry released from the mold assembly and placed in a phosphate buffer solution for 4 hours for a complete hydration.

[0251] Following hydrating, the ink pattern of the colored film of the colored silicone hydrogel contact lens was distorted and ink bleeding was observed, with the lens having no resolution.

Comparative Example E

A Silicone Hydrogel Ink Binder Preparation

[0252] An activation solution was first prepared by mixing 85 g of HEMA, 5 g of Irgacure 819 in 10 g of hexanol. Next, 0.45 g of the activation solution from this master batch was added to a mixture of 2.24 g of black iron oxide and 6.8 g of PDMS-IEM methacrylate having a weight average molecular weight of 9 kDa. This mixture was then subjected to speed mixing: first for 10 minutes at 1000 rpm, followed by 10 minutes at 800 rpm. The resulting activated silicone hydrogel ink binder had a viscosity of 2800 cp as measured by BYK CAP 2000+ Viscometer.

[0253] The chemical structure of the PDMS-IEM methacrylate is below:

##STR00045##

Colored Film

[0254] The silicone hydrogel ink binder preparation was poured into a loading cup of a Teca Printer and then printed onto polypropylene molds. After printing, the printed molds were cured under 3 mW/cm.sup.2 intensity UV or 420 nm LED light for 10 minutes.

Comparative Example F

[0255] A colored silicone hydrogel contact lens was obtained from a silicone hydrogel contact lens-forming mixture made by mixing the following components, listed in Table 11, at amounts per weight.

TABLE-US-00011 TABLE 11 Formulation Ma2D37 7.01 M1EDS6 15.00 TRIS-MA 28.00 DMA 7.00 HEMA 1.00 NVP 34.00 IMVT 0.02 Irgacure 819 0.50 Hexanol 7.38

[0256] The silicone hydrogel contact lens-forming mixture of Table 11 was cast into a colored silicone hydrogel contact lens by introducing the silicone hydrogel contact lens-forming mixture to the mold assembly containing the colored film of Comparative Example C. Prior to introducing the silicone hydrogel contact lens-forming mixture to the mold assembly, the molds were put in a N.sub.2 chamber and waited for 30 minutes so that all surface adsorbed 02 gets removed from the molds. Next, the silicone hydrogel contact lens-forming mixture were introduced to the mold assembly. There was a poor transfer of ink from pad to mold. After waiting for 1 minute, the lenses were cured at 4.5 mW/Cm.sup.2 UV/420 nm for 28 minutes.

[0257] The colored silicone hydrogel contact lens was dry released from the mold assembly and placed in a phosphate buffer solution for 4 hours for a complete hydration.

[0258] Following hydrating, the ink pattern of the colored film of the colored silicone hydrogel contact lens was free of any distortion, but ink bleeding was observed with the lens having no resolution.

[0259] According to an aspect of the present disclosure, a silicone hydrogel ink binder comprises (a) one or more colorants, (b) a solvent, and (c) a silicone copolymer comprising a reaction product of (i) a copolymerization product of a polymerization composition comprising (1) an alkylacrylamide monomer, (2) a hydroxyethyl acrylate monomer, (3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (ii) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0260] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more colorants comprises a pigment.

[0261] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the pigment is an iron oxide black.

[0262] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the alkylacrylamide monomer is N,N-dimethylacrylamide.

[0263] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the non-bulky organosilicon-containing monomer is represented by the following structure:

##STR00046## [0264] wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.1, and R.sup.9 are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R.sup.10 and R.sup.11 are independently hydrogen or alkyl wherein at least one of R.sup.10 and R.sup.11 is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon-containing monomer is represented by the following structure:

##STR00047## [0265] wherein R.sup.12 is H or methyl; X is O or NR.sup.16; wherein R.sup.16 is hydrogen or C.sub.1 to C.sub.4 alkyl, which may be further substituted with one or more hydroxyl groups; R.sup.13 is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R.sup.14 is independently a phenyl or C.sub.1 to C.sub.4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R.sup.15 is a C.sub.1 to C.sub.4 alkyl; and a is 2 to 50.

[0266] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is selected from the group consisting of a bulky polysiloxanylalkyl (meth)acrylic monomer, a bulky polysiloxanylalkyl carbamate monomer and mixtures thereof.

[0267] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is represented by the following structure:

##STR00048## [0268] wherein X denotes O or NR.sup.19 where each R.sup.19 is hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 independently denotes hydrogen or methyl; each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure:

##STR00049## [0269] wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure:

##STR00050## [0270] wherein X denotes NR.sup.19; wherein R.sup.19 denotes hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 denotes hydrogen or methyl; each R.sup.8 independently denotes a a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure:

##STR00051## [0271] wherein each R.sup.18 independently denotes a a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10.

[0272] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, 1, 1-dimethyl-2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

[0273] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone copolymer comprises: [0274] from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer, [0275] from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer, [0276] from about 5 to about 20 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group, [0277] from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and [0278] from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

[0279] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone copolymer has a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons.

[0280] According to another aspect of the present disclosure, a colored silicone hydrogel contact lens having a colored film on a surface thereof, the colored film comprising a polymerization product of a silicone hydrogel ink binder comprising (a) one or more colorants, (b) a solvent, and (c) a silicone copolymer comprising a reaction product of (i) a copolymerization product of a polymerization composition comprising (1) an alkylacrylamide monomer, (2) a hydroxyethyl acrylate monomer, (3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (ii) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0281] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more colorants comprises a pigment.

[0282] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the pigment is an iron oxide black.

[0283] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the alkylacrylamide monomer is N,N-dimethylacrylamide.

[0284] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the non-bulky organosilicon-containing monomer is represented by the following structure:

##STR00052## [0285] wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.1, and R.sup.9 are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R.sup.10 and R.sup.11 are independently hydrogen or alkyl wherein at least one of R.sup.10 and R.sup.11 is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon-containing monomer is represented by the following structure:

##STR00053## [0286] wherein R.sup.12 is H or methyl; X is O or NR.sup.16; wherein R.sup.16 is hydrogen or C.sub.1 to C.sub.4 alkyl, which may be further substituted with one or more hydroxyl groups; R.sup.13 is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R.sup.14 is independently a phenyl or C.sub.1 to C.sub.4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R.sup.15 is a C.sub.1 to C.sub.4 alkyl; and a is 2 to 50.

[0287] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is selected from the group consisting of a bulky polysiloxanylalkyl (meth)acrylic monomer, a bulky polysiloxanylalkyl carbamate monomer and mixtures thereof.

[0288] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is represented by the following structure:

##STR00054## [0289] wherein X denotes O or NR.sup.19 where each R.sup.19 is hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 independently denotes hydrogen or methyl; each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure:

##STR00055## [0290] wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure:

##STR00056## [0291] wherein X denotes NR.sup.19; wherein R.sup.19 denotes hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 denotes hydrogen or methyl; each R.sup.8 independently denotes a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure:

##STR00057## [0292] wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10.

[0293] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, 1, 1-dimethyl-2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

[0294] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone copolymer comprises: [0295] from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer, [0296] from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer, [0297] from about 5 to about 20 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group, [0298] from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and [0299] from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

[0300] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone copolymer has a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons.

[0301] According to yet another aspect of the present disclosure, a method comprises: [0302] (a) applying, to at least a portion of a molding surface of a contact lens mold, a silicone hydrogel ink binder comprising (i) one or more colorants, (ii) a solvent, and (iii) a silicone copolymer comprising a reaction product of (1) a copolymerization product of a polymerization composition comprising (i1) an alkylacrylamide monomer, (i2) a hydroxyethyl acrylate monomer, (i3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (i4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (2) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group, and [0303] (b) curing the silicone hydrogel ink binder to form a colored film which comprises a colorant-entrapping polymer network and the colorant entrapped therein, wherein the colored film contains a first surface in contact with the molding surface and an exposed second surface.

[0304] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more colorants comprises a pigment.

[0305] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the pigment is an iron oxide black.

[0306] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the alkylacrylamide monomer is N,N-dimethylacrylamide.

[0307] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the non-bulky organosilicon-containing monomer is represented by the following structure:

##STR00058## [0308] wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R.sup.10 and R.sup.11 are independently hydrogen or alkyl wherein at least one of R.sup.10 and R.sup.11 is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon-containing monomer is represented by the following structure:

##STR00059## [0309] wherein R.sup.12 is H or methyl; X is O or NR.sup.16; wherein R.sup.16 is hydrogen or C.sub.1 to C.sub.4 alkyl, which may be further substituted with one or more hydroxyl groups; R.sup.13 is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R.sup.14 is independently a phenyl or C.sub.1 to C.sub.4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R.sup.15 is a C.sub.1 to C.sub.4 alkyl; and a is 2 to 50.

[0310] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is selected from the group consisting of a bulky polysiloxanylalkyl (meth)acrylic monomer, a bulky polysiloxanylalkyl carbamate monomer and mixtures thereof.

[0311] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is represented by the following structure:

##STR00060## [0312] wherein X denotes O or NR.sup.19 where each R.sup.19 is hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 independently denotes hydrogen or methyl; each R.sup.18 independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:

##STR00061## [0313] wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure:

##STR00062## [0314] wherein X denotes NR.sup.19; wherein R.sup.19 denotes hydrogen or a C.sub.1-C.sub.4 alkyl; R.sup.17 denotes hydrogen or methyl; each R.sup.8 independently denotes a C.sub.1-C.sub.6 alkyl radical, a phenyl radical or a group represented by the following structure:

##STR00063## [0315] wherein each R.sup.18 independently denotes a C.sub.1-C.sub.6 alkyl radical or a phenyl radical; and h is 1 to 10.

[0316] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, 1, 1-dimethyl-2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

[0317] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone copolymer comprises: [0318] from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer, [0319] from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer, [0320] from about 5 to about 20 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group, [0321] from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and [0322] from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

[0323] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone copolymer has a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons.

[0324] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the method further comprises: [0325] dispensing a silicone hydrogel contact lens-forming mixture comprising a silicone hydrogel contact lens-forming material into the contact lens mold having the colored film, [0326] curing the silicone hydrogel contact lens-forming mixture comprising the silicone hydrogel contact lens-forming material to form a colored silicone contact lens, whereby the colored film detaches from the molding surface and becomes integral with the body of the silicone contact lens, and [0327] hydrating the colored silicone contact lens to form a colored silicone hydrogel contact lens.

[0328] Various features disclosed herein are, for brevity, described in the context of a single embodiment, but may also be provided separately or in any suitable sub-combination. All combinations of the embodiments are specifically embraced by the illustrative embodiments disclosed herein just as if each and every combination was individually and explicitly disclosed. In addition, all sub-combinations listed in the embodiments describing such variables are also specifically embraced by the present compositions and are disclosed herein just as if each and every such sub-combination was individually and explicitly disclosed herein.

[0329] It will be understood that various modifications may be made to the embodiments disclosed herein. Therefore, the above description should not be construed as limiting, but merely as exemplifications of preferred embodiments. For example, the functions described above and implemented as the best mode for operating the present invention are for illustration purposes only. Other arrangements and methods may be implemented by those skilled in the art without departing from the scope and spirit of this invention. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the features and advantages appended hereto.