INK COMPOSITION FOR COSMETIC CONTACT LENSES

Abstract

Provided are ink compositions for making cosmetic contact lenses, as well as cosmetic contact lenses and methods for their preparation and use. The ink composition comprises: (a) a colorant; and (b) a nonreactive hydrophilic polymer.

Claims

1. (canceled)

2. The cosmetic contact lens of claim 26 wherein the nonreactive hydrophilic polymer comprises a polyamide.

3. The cosmetic contact lens of claim 26 wherein the nonreactive hydrophilic polymer comprises: dextran, poly(ethylene oxide), polyvinyl alcohol (PVA), poly (N-isopropylacrylamide), poly(oligoethylene oxide), polyethylene glycol (PEG), poly (N,N-dimethylaminoethyl acrylate), poly(imine), poly(acrylic acid), or mixtures of two or more thereof.

4. The cosmetic contact lens of claim 26 wherein the binder polymer comprises a copolymer formed from a hydrophilic monomer comprising functionality selected from the group consisting of hydroxyalkyl, aminoalkyl, and mixtures thereof; a silicone-containing macromer; and optionally a silicone-containing monomer.

5. (canceled)

6. The cosmetic contact lens of claim 26 wherein the solvent comprises: ethanol, 1-propanol, 2-propanol, 1-ethoxy-2-propanol (1E2P), t-butyl alcohol, t-amyl alcohol, and 3,7-dimethyl-1,7-octanediol (D30), tripropylene glycol methyl ether (TPME), isopropyl lactate (IPL), 1-(2-hydroxy ethyl)-2-pyrrolidone (HEP), glycerol or mixtures of two or more thereof.

7. The cosmetic contact lens of claim 26 wherein the nonreactive hydrophilic polymer comprises a cyclic polyamide.

8. The cosmetic contact lens of claim 26 wherein the colorant comprises: pthalocyanine blue, pthalocyanine green, carbazole violet, vat orange #1, iron oxide black, iron oxide brown, iron oxide yellow, iron oxide red, titanium dioxide, dichlorotriazine, vinyl sulfone-based dyes, and mixtures of two or more thereof.

9. (canceled)

10. The cosmetic contact lens of claim 26 wherein the binder polymer has a weight average molecular weight in the range of about 10 to about 100 kDa.

11. The cosmetic contact lens of claim 26 wherein the nonreactive hydrophilic polymer is poly(vinylpyrrolidone).

12. The cosmetic contact lens of claim 4, wherein the hydrophilic monomer comprises 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl) (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, N,N-bis(2-hydroxypropyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N-(2-hydroxybutyl) (meth)acrylamide, N-(3-hydroxybutyl) (meth)acrylamide, N-(4-hydroxybutyl) (meth)acrylamide, or mixtures thereof.

13. cosmetic contact lens of claim 12, wherein the hydrophilic monomer is 2-hydroxyethyl (meth)acrylate.

14. The cosmetic contact lens of claims 4 to 13 wherein the silicone-containing macromer comprises a polymerizable functional group selected from the group consisting of (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamides, O-vinylethers, O-vinylcarbonates, and O-vinylcarbonates.

15. The cosmetic contact lens of claim 4, wherein the silicone-containing macromer comprises a chemical structure shown in Formula I: ##STR00009## wherein Z is selected from O, N, S or NCH.sub.2CH.sub.2O; when Z=O or S, R.sub.2 is not required; wherein R.sub.1 is a hydrogen atom or methyl; wherein n is a whole number between 1 and 200; wherein R.sub.3 is an alkylene segment (CH.sub.2).sub.y in which y is a whole number from 1 to 6, and each methylene group may be optionally further and independently substituted with a group selected from the group consisting of ethers, amines, esters, ketones, carbonyls, carboxylates, and carbamates, or when y is 2 or more a non-terminal methylene group is optionally replaced with a carbamate group; or wherein R.sub.3 is an oxyalkylene segment O(CH.sub.2).sub.z in which z is a whole number from 1 to 3, or wherein R.sub.3 is a mixture of alkylene and oxyalkylene segments and the sum of y and z is between 1 and 9; wherein R.sub.2 and R.sub.4 are independently a hydrogen atom, a linear, branched, or cyclic alkyl group containing between one and six carbon atoms, a linear, branched, or cyclic alkoxy group containing between one and six carbon atoms, a linear or branched polyethyelenoxyalkyl group, an alkyl-siloxanyl-alkyl group, a phenyl group, a benzyl group, a substituted or un-substituted aryl group, a fluoroalkyl group, a partially fluorinated alkyl group, a perfluoroalkyl group, a fluorine atom, a mono-, di, or tri-hydroxyalkyl group containing between one and six carbon atoms, or combinations thereof; and wherein R.sub.5 is a substituted or un-substituted linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms or an aryl group, any of which may be further substituted with one or more fluorine atoms or trimethylsiloxy groups.

16. The cosmetic contact lens of claim 4, wherein the silicone-containing macromer is selected from the group consisting of monoalkyl terminated, mono(meth)acrylate terminated poly(dialkylsiloxanes), monoalkyl terminated, monoalkyl terminated, mono(meth)acrylate terminated poly(diarylsiloxanes), monoalkyl terminated, mono(meth)acrylate terminated poly(alkylarylsiloxanes), and mixtures thereof.

17. The cosmetic contact lens of claim 16, wherein the silicone-containing macromer is mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane.

18. The cosmetic contact lens of 4, wherein the silicone-containing macromer comprises a chemical structure shown in Formula VIII: ##STR00010## wherein Z is selected from O, N, S or NCH.sub.2CH.sub.2O; wherein R.sub.1 is independently hydrogen atom or methyl group; wherein R.sub.2, R.sub.3, and R.sub.4 are independently a hydrogen atom or a linear, branched, or cyclic alkyl group containing one to eight carbon atoms, any of which may be further substituted with at least one hydroxy group, and which may be optionally substituted with amido, ether, amino, carboxyl, carbonyl groups and combinations thereof; for Z=O and S, R.sub.2 is not required; wherein n is the number of siloxane repeating units and is from 4 to 200; and wherein R.sub.5 is selected from straight or branched C.sub.1 to C.sub.8 alkyl groups.

19. The cosmetic contact lens of 4, wherein the silicone-containing macromer is mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated polydimethylsiloxane.

20. The cosmetic contact lens of 4, wherein the silicone-containing macromer is selected from the group consisting of mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane, mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated polydimethylsiloxane, and mixtures thereof.

21. The cosmetic contact lens of 4, wherein the silicone-containing macromer has a number average molecular weight greater than 500 Daltons.

22. The ink cosmetic contact lens of 4, wherein the silicone-containing macromer has a number average molecular weight between about 500 Daltons and about 20,000 Daltons.

23. The cosmetic contact lens of 4, wherein the repeating units of the silicone-containing macromer are present in the range of about 30 and about 80 weight percent of the total weight of the binder polymer.

24. The cosmetic contact lens of 4, wherein the silicone-containing monomer is selected from the group consisting of: 3-methacryloxypropyl tris(trimethylsiloxy)silane, 3-acryloxypropyl tris(trimethylsiloxy)silane, 3-methacrylamidopropyl tris(trimethylsiloxy)silane, 3-acrylamidopropyl tris(trimethylsiloxy)silane, tris(trimethylsiloxy)silylstyrene, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester, N-(2,3-dihydroxylpropyl) N-(3-tetra(dimethylsiloxy)dimethylbutylsilane)propyl) acrylamide and mixtures thereof.

25. A method for making the cosmetic contact lens of claim 26, the method comprising: (i) applying a clear coat to a lens forming surface of a first lens forming mold; (ii) applying to the clear coat the ink composition; (iii) optionally repeating step (i), step (ii), or both step (i) and step (ii); (iv) dispensing a lens material to the first lens forming mold; (v) applying a second lens forming mold; and (vi) curing the lens material to form the cosmetic contact lens.

26. A cosmetic contact lens comprising: a contact lens having applied thereon an ink composition, the ink composition comprising: (a) from 0.1 to about 25 weight percent of a colorant from about 1 to about 50 weight percent of a nonreactive hydrophilic polymer; from about 1 to 60 weight percent of a binder polymer; and from about 50 to about 95 weight percent of a solvent, each based on the total weight of the ink composition.

27. The cosmetic contact lens of claim 26 that is a cosmetic silicone hydrogel contact lens.

28. The cosmetic contact lens of claim 27 further comprising an internal wetting agent.

29. The cosmetic contact lens of of claim 26 wherein the lens comprises multiple layers of ink composition wherein the multiple layers of ink composition may be the same or different.

30. The cosmetic contact lens of of claim 26 further comprising an ink layer that is free of nonreactive hydrophilic polymer.

Description

EXAMPLES

[0067] Imaging was used to qualitatively assess the overall quality of a printed pattern in comparison to the desired design (smear in the tables); the level of smear was categorized based on severity (minor, moderate, severe, or none in the tables). Imaging was also used to assess the degree of roundness and level of distortion of the lenses (round or out of round (OOR) in the tables). Unacceptable levels of haze or translucency were also noted by imaging (hazy or none). Images of the silicone hydrogel printed contact lenses were captured using a Nikon SMZ18 stereo microscope with a P2-DBF Fiber diascopic illumination base (1? objective with 0.75-1? magnification). The printed silicone hydrogel contact lenses were placed concave side up into a crystal cell completely filled with borate buffered packing solution. Samples were placed in the viewing window, and the microscope adjusted to focus the image.

[0068] The durability of the printed pattern was assessed by rubbing the printed surface with a cotton swab. The test consists of 50 swipes of the lens. Each swipe started at the lens center on the printed surface and then proceeded in a single direction. Each lens was systematically evaluated, swiping in four orthogonal directions. If the pattern stayed intact for 50 such swipes, then it is deemed permanent (no rub off in the tables). Otherwise, if any portion of the printed pattern is dislodged, disturbed, or removed during the 50 swipes, then the pattern was deemed to rub off (rubs off in the tables).

[0069] Wettability of lenses was determined using a sessile drop technique using KRUSS DSA-100 TM instrument at room temperature and using deionized water as probe solution (Sessile Drop in the tables). The lenses to be tested were rinsed in deionized water to remove carry over from packing solution. Each test lens was placed on blotting lint free wipes which were dampened with packing solution. Both sides of the lens were contacted with the wipe to remove surface water without drying the lens. To ensure proper flattening, lenses were placed bowl side down on the convex surface of contact lens plastic molds. The plastic mold and the lens were placed in the sessile drop instrument holder, ensuring proper central syringe alignment. A 3 to 4 microliter drop of deionized water was formed on the syringe tip using DSA 100-Drop Shape Analysis software ensuring the liquid drop was hanging away from the lens. The drop was released smoothly on the lens surface by moving the needle down. The needle was withdrawn away immediately after dispensing the drop. The liquid drop was allowed to equilibrate on the lens for 5 to 10 seconds, and the contact angle was measured between the drop image and the lens surface. Typically, three to five lenses were evaluated, and the average contact angle reported. The standard deviations were determined and reported in the tables in parentheses O.

[0070] The following abbreviations will be used throughout the Examples and have the following meanings: [0071] L: liter(s) [0072] mL: milliliter(s) [0073] equiv. or eq.: equivalent(s) [0074] kg: kilogram(s) [0075] g: gram(s) [0076] mg: milligram(s) [0077] mol: mole [0078] mmol: millimole [0079] min: minute(s) [0080] cm: centimeter(s) [0081] nm: nanometer(s) [0082] rpm: revolutions per minute [0083] Da: dalton or grams/mole [0084] kDa: kilodalton or an atomic mass unit equal to 1,000 daltons [0085] wt. %: weight percent [0086] TL03 lights: Phillips TLK 40W/03 bulbs [0087] BC: base curve plastic mold [0088] FC: front curve plastic mold [0089] PP: polypropylene which is the homopolymer of propylene and is used as a plastic mold resin or component [0090] TT: Tuftec which is a hydrogenated styrene butadiene block copolymer (Asahi Kasei Chemicals) and is used as a plastic mold resin or component

[0091] Z: Zeonor which is a polycycloolefin thermoplastic polymer (Nippon Zeon Co Ltd) and is used as a plastic mold resin or component [0092] RMM: reactive monomer mixture(s) [0093] DMA: N, N-dimethylacrylamide (Jarchem) [0094] NVP: N-vinylpyrollidone [0095] HEMA: 2-hydroxyethyl methacrylate (Bimax) [0096] PVP, PVP K30, PVP K60, PVP K90: poly(N-vinylpyrrolidone) (ISP Ashland) [0097] TEGDMA: tetraethylene glycol dimethacrylate (Esstech) [0098] Omnirad 1870: blend of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphineoxide and mPDMS: mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane (M.sub.n=800-1500 daltons) (Gelest) [0099] SiMAA: 2-propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (Toray) or 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate [0100] Norbloc: 2-(2-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole (Janssen) [0101] Blue HEMA: 1-amino-4-[3-(4-(2-methacryloyloxy-ethoxy)-6-chlorotriazin-2-ylamino)-4-sulfophenylamino]anthraquinone-2-sulfonic acid, as described in US Patent No. 5,944,853 [0102] Borate Buffered Packing Solution: 18.52 grams (300 mmol) of boric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197 mmol) of sodium sulfate were dissolved in enough deionized water to fill a 2-liter volumetric flask. [0103] AIBN: azobisisobutyronitrile [0104] FTIR: Fourier Transform Infrared Spectroscopy [0105] DCA: Dynamic Contact Angle wettability [0106] DIW: deionized water [0107] IPA: isopropyl alcohol [0108] THF: tetrahydrofuran [0109] D3O: 3,7-dimethyl-3-octanol (Vigon) [0110] 1E2P: 1-ethoxy-2-propanol [0111] 3E3P: 3-ethyl 3-pentanol [0112] HEP: 1-(2-hydroxyethyl)-2-pyrrolidone [0113] IPL: isopropyl lactate [0114] Borate Buffered Packing Solution: 18.52 grams (300 mmol) of boric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197 mmol) of sodium sulfate were dissolved in enough deionized water to fill a 2-liter volumetric flask.

Preparation 1

[0115] An AIBN solution was prepared by dissolving 4 grams of AIBN in 300 grams of 1-propanol. The AIBN solution was deaerated with nitrogen gas for 15-20 minutes prior to its use. A monomer solution was prepared by dissolving 98 grams of HEMA and 98 grams of mPDMS in 91 grams of 1-propanol. The monomer solution was deaerated with nitrogen gas for 15-20 minutes prior to its use.

[0116] A two-liter jacketed reactor containing 279 grams of 1-propanol was heated to 70? C. under a nitrogen gas atmosphere using a water bath. Using a Watson-Marlow pump, the AIBN and monomer solutions were added to the reactor over four hours. The reaction mixture was stirred overnight after which the temperature was reduced to 50? C., and monomer conversion was monitored by FTIR until the carbon-carbon double bond band disappeared. Complete conversion required about 24 hours.

[0117] The reaction mixture was transferred into a clear glass jar. The copolymer was isolated by precipitation into water, suction filtration, and vacuum drying to obtain about 182 grams of product (Copolymer #1).

Example 1

[0118] Ink compositions 1A - 1D were prepared by adding 9 weight percent black iron oxide pigment (Sicovit? black 85 E 172, Rockwood Italia SpA-Divisione Silo) to the clear coat solutions listed in Table 1. The inks were mixed using a bench-scale ball mill (Ultra-Turrax? Tube Drive (UTTD) System, IKA). In addition, inks may be further manually mixed using a jar roller or use of an overhead mixer at 700-1800 rpm for 30 minutes.

TABLE-US-00001 TABLE 1 Clear Clear Clear Clear Coat 1A Coat 1B Coat 1C Coat 1D Component (weight %) (weight %) (weight %) (weight %) Copolymer 8.4 7.3 3 3 #1 PVP K60 0 0 5.7 6.75 PVP K30 19.6 14.7 23.3 20.25 HEP 0 0 6.8 0 IPL 36 0 0 0 D3O 0 7.7 0 23.1 1E2P 36 70.3 61.2 46.9 Total 100 100 100 100

Example 2

[0119] Front curve molds were printed using a laboratory scale pad printer first with a clear coating (Clear Coats 1A-1D) and then with a Vivid? clich? pattern using Inks 1A-1D. These printed front curve molds were degassed for at least 12 hours under nitrogen. Printed contact lenses were fabricated in a glove box wherein the oxygen gas level was maintained between 0.5 and 5%. About 100 microliters of RMM#1 listed in Table 2 were dosed into the printed front curve molds at ambient temperature. The time between dosing RMM#1 and placing the BC is termed Dwell 1. The nominal Dwell 1 time was not more than 5 seconds unless noted otherwise. The base curve molds were then placed over the RMM#1. Next, a clear quartz plate was placed on top of the mold assemblies. The pallets containing the mold assemblies were then moved into the curing chamber at 60-70? C. The time between placing the weight and starting cure is termed Dwell 2. The nominal Dwell 2 was not less than 5 minutes unless noted otherwise. Cure is started via irradiation of the pallets containing the mold assemblies with TL 20W/03 T fluorescent bulbs (Philips) and positioned to achieve an intensity of 4.0 mW/cm.sup.2 for 8 minutes.

TABLE-US-00002 TABLE 2 Component Weight Percent mPDMS 28 SIMAA 31 DMA 22.6 HEMA 6 PVP K90 9 TEGDMA 1.25 Norbloc 1.8 Blue HEMA 0.02 OmniRad 1870 0.33 ? Reactive Components 100 The final reactive monomer mixture RMM#1 was prepared by combining the component mixture listed above with D3O diluent to make a solution comprised of 77 weight percent reactive components and 23 weight percent D3O diluent.

[0120] The printed lenses were manually de-molded with most lenses adhering to the FC and released by submerging the lenses in 70 percent IPA for about one or two hours, followed by washing two times with 70 percent IPA, optionally two times with 25 percent IPA, two times with DI, and finally two times with borate buffered packaging solution. Each washing step lasted about 30 minutes. A person of ordinary skill recognizes that the exact lens release process can be varied depending on the lens formulation and mold materials, regarding the concentrations of the aqueous isopropanol solutions, the number of washings with each solvent, and the duration of each step. The purpose of the lens release process is to release all lenses without defects and transition from diluent swollen networks to the packaging solution swollen hydrogels. The lenses were transferred into vials and subsequently sterilized by autoclaving at 122? C. for 30 minutes. The sterile printed lenses (2A-2D, made from ink compositions 1A-1D respectively) were evaluated for haze, smear, durability, and shape, and the results listed in Table 3 [Dwell 1=5 seconds; Dwell 2=300 seconds].

TABLE-US-00003 TABLE 3 Printed Printed Printed Printed Lens 2A Lens 2B Lens 2C Lens 2D Test (weight %) (weight %) (weight %) (weight %) Haze None None None None Smear None None Moderate Minor Durability Rubs Off No Rub Off No Rub Off No Rub Off Shape Round Round Round Round Sessile Drop 78 (11.0) 78 (3.0)

[0121] As shown in Table 3, printed lenses 2B and 2D were transparent and round and exhibited no print rub off with only minor or no smear. Printed lens 2D was also wettable.

Example 3

[0122] Ink compositions 3A-3C were prepared by adding 9 weight percent black iron oxide pigment (Sicovit? black 85 E 172, Rockwood Italia SpA-Divisione Silo) to the clear coat solutions listed in Table 4. The inks were mixed using a bench-scale ball mill (Ultra-Turrax? Tube Drive (UTTD) System, IKA). In addition, inks may be further manually mixed using a jar roller or use of an overhead mixer at 700-1800 rpm for 30 minutes.

TABLE-US-00004 TABLE 4 Clear Clear Clear Coat 3A Coat 3B Coat 3C Component (weight %) (weight %) (weight %) Copolymer 3 3 6.0 #1 PVP K60 5.7 6.75 7.75 PVP K30 23.3 20.25 13.25 HEP 6.8 0 14.0 IPL 0 0 38 D3O 0 23.1 0 1E2P 61.2 46.9 16.0 1-Propanol 0 0 5 Total 100 100 100

Example 4

[0123] Front curve molds were printed using a laboratory scale pad printer first with a clear coating (Clear Coats 3A-3C) and then with a Vivid? clich? pattern using Inks 3A-3C. These printed front curve molds were degassed for at least 12 hours under nitrogen. Printed contact lenses were fabricated in a glove box wherein the oxygen gas level was maintained between 0.5 and 5%. About 100 microliters of RMM#1 listed in Table 2 were dosed into the printed front curve molds at ambient temperature. The time between dosing RMM#1 and placing the BC is termed Dwell 1. The nominal Dwell 1 time was not more than 5 seconds unless noted otherwise. The base curve molds were then placed over the RMM#1. Next, a clear quartz plate was placed on top of the mold assemblies. The pallets containing the mold assemblies were then moved into the curing chamber at 60-70? C. The time between placing the weight and starting cure is termed Dwell 2. The nominal Dwell 2 was not less than 5 minutes unless noted otherwise. Cure is started via irradiation of the pallets containing the mold assemblies with TL 20W/03 T fluorescent bulbs (Philips) and positioned to achieve an intensity of 4.0 mW/cm.sup.2 for 8 minutes.

[0124] The printed lenses were manually de-molded with most lenses adhering to the FC and released by submerging the lenses in 70 percent IPA for about one or two hours, followed by washing two times with 70 percent IPA, optionally two times with 25 percent IPA, two times with DI, and finally two times with borate buffered packaging solution. Each washing step lasted about 30 minutes. A person of ordinary skill recognizes that the exact lens release process can be varied depending on the lens formulation and mold materials, regarding the concentrations of the aqueous isopropanol solutions, the number of washings with each solvent, and the duration of each step. The purpose of the lens release process is to release all lenses without defects and transition from diluent swollen networks to the packaging solution swollen hydrogels. The lenses were transferred into vials and subsequently sterilized by autoclaving at 122? C. for 30 minutes. The sterile printed lenses (4A-4C, made from ink compositions 3A-3C respectively) were evaluated for haze, smear, durability, and shape, and the results listed in Table 5 [Dwell 1=5 seconds; Dwell 2=300 seconds].

TABLE-US-00005 TABLE 5 Printed Printed Printed Lens 4A Lens 4B Lens 4C Test (weight %) (weight %) (weight %) Haze None None None Smear Moderate Minor None Durability No Rub Off No Rub Off No Rub Off Shape Round Round Round Sessile Drop 78 (11.1) 77.7 (2.9) 93 (10)

[0125] As shown in Table 5, printed lenses 4B and 4C were transparent and round and exhibited no print rub off with only minor or no smear. Printed lens 4B was also wettable.

[0126] Example 5

[0127] Ink compositions 5A -5D were prepared by adding 9 weight percent black iron oxide pigment (Sicovit? black 85 E 172, Rockwood Italia SpA-Divisione Silo) to the clear coat solutions listed in Table 6. The inks were mixed using a bench-scale ball mill (Ultra-Turrax? Tube Drive (UTTD) System, IKA). In addition, inks may be further manually mixed using a jar roller or use of an overhead mixer at 700-1800 rpm for 30 minutes.

TABLE-US-00006 TABLE 6 Clear Clear Clear Clear Coat 5A Coat 5B Coat 5C Coat 5D Component (weight %) (weight %) (weight %) (weight %) PVP K60 10 8 8 8.75 PVP K30 19 24 24 26.25 HEP 0 0 0 6.5 IPL 0 51 17 0 D30 7 0 0 0 1E2P 64 17 51 58.5 Total 100 100 100 100

Example 6

[0128] Front curve molds were printed using a laboratory scale pad printer first with a clear coating (Clear Coats 5A-5D) and then with a Vivid? clich? pattern using Inks 5A-5D. These printed front curve molds were degassed for at least 12 hours under nitrogen. Printed contact lenses were fabricated in a glove box wherein the oxygen gas level was maintained between 0.5 and 5%. About 100 microliters of RMM#1 listed in Table 2 were dosed into the printed front curve molds at ambient temperature. The time between dosing RMM#1 and placing the BC is termed Dwell 1. The nominal Dwell 1 time was not more than 5 seconds unless noted otherwise. The base curve molds were then placed over the RMM#1. Next, a clear quartz plate was placed on top of the mold assemblies. The pallets containing the mold assemblies were then moved into the curing chamber at 60-70? C. The time between placing the weight and starting cure is termed Dwell 2. The nominal Dwell 2 was not less than 5 minutes unless noted otherwise. Cure is started via irradiation of the pallets containing the mold assemblies with TL 20W/03 T fluorescent bulbs (Philips) and positioned to achieve an intensity of 4.0 mW/cm.sup.2 for 8 minutes.

[0129] The printed lenses were manually de-molded with most lenses adhering to the FC and released by submerging the lenses in 70 percent IPA for about one or two hours, followed by washing two times with 70 percent IPA, optionally two times with 25 percent IPA, two times with DI, and finally two times with borate buffered packaging solution. Each washing step lasted about 30 minutes. A person of ordinary skill recognizes that the exact lens release process can be varied depending on the lens formulation and mold materials, regarding the concentrations of the aqueous isopropanol solutions, the number of washings with each solvent, and the duration of each step. The purpose of the lens release process is to release all lenses without defects and transition from diluent swollen networks to the packaging solution swollen hydrogels. The lenses were transferred into vials and subsequently sterilized by autoclaving at 122? C. for 30 minutes.

[0130] The sterile printed lenses (6A-6D, made from ink compositions 5A-5D respectively) were evaluated for haze, smear, durability, and shape, and the results listed in Table 7 [Dwell 1=5 seconds; Dwell 2=300 seconds].

TABLE-US-00007 TABLE 7 Printed Printed Printed Printed Lens 6A Lens 6B Lens 6C Lens 6D Test (weight %) (weight %) (weight %) (weight %) Haze None None None None Smear Severe Moderate Minor Minor Durability No Rub Off No Rub Off No Rub Off No Rub Off Shape Round Round Round Round Sessile Drop 89 (7.1) 69 (15.2) 70 (38.8) 61.5 (3.2)

[0131] As shown in Table 7, printed lenses 6C and 6D were transparent and round and exhibited no print rub off with only minor smear. Printed lenses 6C and 6D were also wettable.

Example 7

[0132] Ink composition 7A was prepared by adding 9 weight percent black iron oxide pigment (Sicovit? black 85 E 172, Rockwood Italia SpA-Divisione Silo) to the clear coat solutions listed in Table 8. Ink set compositions 7B were prepared by adding a combination of black, blue, and white pigments at various concentrations between 3.8-9.0 weight percent, to the clear coat solutions listed in Table 8 to create a set of 3 colored inks. The Set of 3 inks were used to create one cosmetic ink design for printed lens 7B. The inks were mixed using a bench-scale ball mill (Ultra-Turrax? Tube Drive (UTTD) System, IKA). In addition, inks may be further manually mixed using a jar roller or use of an overhead mixer at 700-1800 rpm for 30 minutes.

TABLE-US-00008 TABLE 8 Clear Clear Coat 7A Coat 7B Component (weight %) (weight %) PVP K60 8.0 15.0 PVP K30 14.0 0 Binding Polymer 6.0 5.0 Glycerol 0 1.0 HEP 10.0 6.0 IPL 25.0 13.0 IE2P 37.0 60.0 Total 100 100

[0133] Front curve molds were printed using a pad printer first with a clear coating (Clear Coats 7A and 7B) and then with clich? patterns using Inks 7A or 7B. Printed contact lenses were fabricated in a pilot facility production line wherein the oxygen gas level was maintained between 0.5 and 5%. About 100 microliters of RMM#2 listed in Table 9 were dosed into the printed front curve molds at ambient temperature. The time between dosing RMM#2 and placing the BC is termed Dwell 1. The nominal Dwell 1 time was not more than 5 seconds unless noted otherwise. The base curve molds were then placed over the RMM#2. Next, precure weights were placed on top of the mold assemblies. The pallets containing the mold assemblies were then moved into the heated precure tunnel at 30? C. The time between placing the weight and starting cure is termed Dwell 2. The nominal Dwell 2 was not less than 5 minutes unless noted otherwise. Cure is started via irradiation of the pallets containing the mold assemblies with TL 20W/03 T fluorescent bulbs (Philips) and positioned to achieve an intensity of 4.0 mW/cm.sup.2 for 8 minutes.

TABLE-US-00009 TABLE 9 RMM#2 Weight Component Percent mPDMS 31.0 SIMAA 28.0 DMA 24.0 HEMA 5.85 PVP K90 7 TEGDMA 1.66 Norbloc 2.0 Blue HEMA 0.02 OmniRad 184 0.14 OmniRad 1870 0.34 ? Reactive Components 100 The final reactive monomer mixture RMM#2 was prepared by combining the component mixture listed above with D3O diluent to make a solution comprised of 77 weight percent reactive components and 23 weight percent D3O diluent.

[0134] The printed lenses were de-molded with most lenses adhering to the FC and released by submerging the lenses in 70 percent IPA for about one or two hours, followed by washing two times with 70 percent IPA, optionally two times with 25 percent IPA, two times with DI, and finally once with borate buffered packaging solution. Each washing step lasted about 30 minutes. A person of ordinary skill recognizes that the exact lens release process can be varied depending on the lens formulation and mold materials, regarding the concentrations of the aqueous isopropanol solutions, the number of washings with each solvent, and the duration of each step. The purpose of the lens release process is to release all lenses without defects and transition from diluent swollen networks to the packaging solution swollen hydrogels. The lenses were inspected and packaged in heat sealed blisters and subsequently sterilized by autoclaving at 121? C. for 18 minutes. The sterile printed lenses (7A-7B, made from ink compositions 7A-7B respectively) were evaluated for haze, smear, durability, shape, and wettability and the results listed in Table 3 (Dwell 1=5 seconds; Dwell 2=300 seconds).

TABLE-US-00010 TABLE 10 Printed Printed Test Lens 7A Lens 7B Colored layers 1 3 Haze None None Smear None None Durability No Rub Off No Rub Off Shape Round Round DCA 60(10) 64(17) Sessile Drop 77.1 (7) 97.9 (8)

[0135] As shown in Table 10, printed lenses 7A and 7B were transparent, round, exhibited no print rub off or smear, and were wettable.

Example 8

[0136] Ink set compositions 8A were prepared by adding a combination of black, blue, and white pigments at various concentrations between 3.8-9.0 weight percent, to the Ink Base solutions listed in Table 8 to create a set of 3 colored inks. The Set of 3 inks were used to create one cosmetic ink design for printed lens 8A. The inks were mixed using a bench-scale ball mill (Ultra-Turrax? Tube Drive (UTTD) System, IKA). In addition, inks may be further manually mixed using a jar roller or use of an overhead mixer at 700-1800 rpm for 30 minutes.

TABLE-US-00011 TABLE 11 Component Ink Base 8A PVP K60 0 PVP K30 22.5 Binding Polymer 7.5 Glycerol 1 HEP 0 IPL 24.0 1E2P 45.0 Total 100

[0137] Front curve molds were printed using a pad printer first with a clear coating (Clear Coat 7B from example 7) and then with clich? patterns using Ink set 8A. Printed contact lenses were fabricated on a pilot facility production line wherein the oxygen gas level was maintained between 0.5 and 5%. About 100 microliters of RMM#2 listed in Table 9 were dosed into the printed front curve molds at ambient temperature. The time between dosing RMM#2 and placing the BC is termed Dwell 1. The nominal Dwell 1 time was not more than 5 seconds unless noted otherwise. The base curve molds were then placed over the RMM#2. Next, precure weights were placed on top of the mold assemblies. The pallets containing the mold assemblies were then moved into the heated precure tunnel at 30? C. The time between placing the weight and starting cure is termed Dwell 2. The nominal Dwell 2 was not less than 5 minutes unless noted otherwise. Cure is started via irradiation of the pallets containing the mold assemblies with TL 20W/03 T fluorescent bulbs (Philips) and positioned to achieve an intensity of 4.0 mW/cm.sup.2 for 8 minutes.

[0138] The printed lenses were de-molded with most lenses adhering to the FC and released by submerging the lenses in 70 percent IPA for about one or two hours, followed by washing two times with 70 percent IPA, optionally two times with 25 percent IPA, two times with DI, and finally once with borate buffered packaging solution. Each washing step lasted about 30 minutes. A person of ordinary skill recognizes that the exact lens release process can be varied depending on the lens formulation and mold materials, regarding the concentrations of the aqueous isopropanol solutions, the number of washings with each solvent, and the duration of each step. The purpose of the lens release process is to release all lenses without defects and transition from diluent swollen networks to the packaging solution swollen hydrogels. The lenses were inspected and packaged in heat sealed blisters and subsequently sterilized by autoclaving at 121? C. for 18 minutes. The sterile printed lenses (78A, made from clear coat 7B and ink composition set 8A respectively) were evaluated for haze, smear, durability, shape, and wettability and the results listed in Table 3 (Dwell 1=5 seconds; Dwell 2=300 seconds).

TABLE-US-00012 TABLE 12 Test Printed Lens 8A Colored layers 3 Haze None Smear None Durability No Rub Off Shape Round DCA 50(6) Sessile Drop 100(11)

[0139] As shown in Table 12, printed lenses 8A using dissimilar ink layer compositions, were transparent, round, exhibited no print rub off or smear, and were wettable.