# US 7,411,008 B2 · Ink formulations and uses thereof

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- Number: US 7,411,008 B2
- Document ID: US7411008B2
- Status: Granted
- Kind: B2
- Application number: 10/287,730
- Filed: 2002-11-04
- Published: 2003-06-26
- Granted: 2008-08-12
- Earliest claimed: 2001-11-07
- Assignees: Novartis AG
- Inventors: Robert Carey Tucker; Sandra Corti
- Web page: https://patentgrep.com/patent/US7411008B2

## CPC

- C09D 11/30: Inkjet printing inks
- C09D 11/322: Pigment inks
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

The present invention provides a chemical ink comprises a solvent, a binder polymer, a colorant and optionally a crosslinker. The ink of the invention has one or more of the following characteristics: a viscosity lower than about 50 centipoises; a surface tension of from about 20 mN/m to about 60 mN/m; a particle size of less than about 5 μm; prolonged stability; an appropriate color level (visible by eye); uniform drop formation; jet stability; good adhesion to contact lenses; good transfer from a mold to a lens made in the mold; and stability of ink in inkjet nozzles. The ink of the invention is useful for inkjet printing of a high-quality color image on a contact lens or a mold so as to produce a colored contact lens.

## Claims

### Claim 1

An ink comprising: a solvent; a colorant; and a binder polymer, wherein the colorant comprises pigments, wherein the binder polymer is a polymer which comprises multiple olefinically unsaturated groups and is capable of being crosslinked under free radical polymerization conditions in the absence of a crosslinker to form inter- and intra crosslinkages so that a macromolecular matrix is formed to bind and/or trap pigments onto a soft contact lens and to ensure no visible and microscopic (˜10×) observation of colorant bleeding, smearing, or delamination in a color image printed on the contact lens with said ink, wherein each intra-crosslinkage is an intramolecular covalent bond formed between a pair of olefinically unsaturated groups which belong to the same binder polymer molecule, wherein the inter-crosslinkage is an intermolecular covalent bond formed between a pair of olefinically unsaturated groups each belonging to one of two binder polymer molecules, wherein the ink is characterized by having a surface tension of from about 20 mN/m to about 60 mN/m, a viscosity of less than 50 centipoise, and good adhesion to a soft contact lens and by being stable for at least about 4 hours, wherein a color image printed on the soft contact lens with said ink passes a sterilization surviving test, and wherein the binder polymer is a cellulosic resin, polyester, polyurethane, polyurea, or polyamides, wherein the amount of the solvent is from about 60% to 99% by weight, wherein the amount of the binder polymer is from about 1% to about 30% by weight, and wherein the amount of the colorant is from about 0 to about 15% by weight.

### Claim 2 (depends on 1)

The ink of claim 1, wherein the sterilization test is an autoclave-surviving test.

### Claim 3 (depends on 1)

The ink of claim 1, wherein said ink can be used to print a color image on the medical device by using an inkjet printing system.

### Claim 4 (depends on 1)

The ink of claim 1, wherein the medical device is an ophthalmic lens.

### Claim 5 (depends on 4)

The ink of claim 4, wherein the ophthalmic lens is a contact lens.

### Claim 6 (depends on 4)

The ink claim 4, wherein the colorant comprises at least a pigment and/or at least a dye which is either sparingly soluble or insoluble in the solvent.

### Claim 7 (depends on 6)

The ink of claim 6, wherein the colorant comprises at least a pigment and optionally a dye.

### Claim 8 (depends on 6)

The ink of claim 6, wherein the pigment is selected from the group consisting of Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 34, Pigment Yellow 35, Pigment Yellow 37, Pigment Yellow 40, Pigment Yellow 53, Pigment Yellow 65, Pigment Yellow 83, Pigment Yellow 95, Pigment Yellow 97, Pigment Yellow 108, Pigment Yellow 110, Pigment Yellow 120, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 153, Pigment Yellow 154, Pigment Yellow 175, Pigment Yellow 184, Pigment Red 60, Pigment Red 83, Pigment Red 88, Pigment Red 122, Pigment Red 171, Pigment Red 176, Pigment Red 177, Pigment Red 202, Pigment Red 264, Natural Pigment Red 4, Natural Pigment Red 9, Pigment Violet 11, Pigment Violet 19, Pigment Violet 42, Pigment Blue 15:1, Pigment Blue 15:3, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 17, Pigment Blue 27, Pigment Blue 28, Pigment Blue 29, Pigment Blue 33, Pigment Blue 35, Pigment Blue 36, Pigment Blue 60, Pigment Blue 72, Pigment Blue 73, Pigment Blue 74, Pigment Black 1, Pigment Black 6, Pigment Black 7, Pigment Black 8, Pigment Black 9, Pigment Black 10, Pigment Black 11, Pigment Black 19, Pigment Black 31, Pigment White 4, Pigment White 6, D&C Blue No. 6, D&C Green No. 6, D&C Violet No. 2, carbazole violet, phthalocyanine green, copper complexes, chromium oxides, iron oxides, phthalocyanine blue, titanium dioxides, cobalt blue, Toner cyan BG, Permajet blue B2G, chromium sesquioxide, and Monolith black C-K.

### Claim 9 (depends on 6)

The ink of claim 6, wherein the solvent is one or more organic solvents.

### Claim 10 (depends on 9)

The ink of claim 9, wherein the organic solvents are selected from the group consisting of acetone, methanol, ethanol, propanol, isopropanol, 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 alchol, methyl ethyl ketone, acetone, 2-nitropropane, ethylene glycol monoethyl ether, propylene carbonate, cyclohexanol, chloroform, trichloroethylene, 1,4-dioxane, ethyl acetate, 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.

### Claim 11 (depends on 1)

The ink of claim 1, wherein the solvent which is methyl ethyl ketone, cyclohexanone, cyclopentanone or a mixture of thereof.

### Claim 12 (depends on 1)

The ink of claim 1, wherein the ink has a good transferability from a mold to a medical device molded in the mold.

### Claim 13 (depends on 1)

The ink of claim 1, wherein the ink is stable for at least 8 hours.

### Claim 14 (depends on 1)

The ink of claim 1, wherein the ink is stable for at least 24 hours.

### Claim 15 (depends on 1)

The ink of claim 1, wherein the ink is stable for at least 2 days.

### Claim 16 (depends on 13)

The ink of claim 13, wherein said ink can be used to print a color image on the medical device by using an inkjet printing system.

### Claim 17 (depends on 1)

The ink of claim 1, wherein the ink further comprises 0 to 4% by weight glycerol and/or 0 to 15% by weight diethylene glycol.

### Claim 18 (depends on 1)

The ink of claim 1, further comprising a crosslinker.

### Claim 19 (depends on 18)

The ink of claim 18, wherein the crosslinker is selected from the group consisting of diaziridine-containing compounds, ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate, ethyleneglycol diacrylate, allyl methacrylates, allyl acrylates, 1,3-propanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, polyethyleneoxide mono- and diacrylates, and 1,4-butanediol diacrylate (BDDA).

### Claim 20 (depends on 18)

The ink of claim 18, wherein the amount of the crosslinker is from 0 to about 10% by weight.

### Claim 21 (depends on 1)

The ink of claim 1, wherein the ink has a good transferability from a mold to an ophthalmic lens made from the mold.

### Claim 22 (depends on 1)

The ink of claim 1, wherein the solvent is water or a mixture of water and one or more organic solvent.

### Claim 23 (depends on 1)

The ink of claim 1, wherein the ink further comprises 0 to 2% by weight glycerol and/or 2% to 5% by weight diethylene glycol.

### Claim 24 (depends on 1)

The ink of claim 1, wherein the ink further comprises one or more components selected from the group consisting of polymerization initiators, antimicrobial agents, antioxidant agents, and anti-kogating agents.

### Claim 25 (depends on 24)

The ink of claim 24, wherein the ink is stable for at least 8 hours.

### Claim 26 (depends on 23)

The ink of claim 23, wherein the ink is stable for at least 8 hours.

### Claim 27 (depends on 26)

The ink of claim 26, wherein said ink can be used to print a color image on the medical device by using an inkjet printing system.

### Claim 28 (depends on 1)

The ink of claim 1, wherein the binder polymer is a poly(vinyl alcohol).

### Claim 29 (depends on 28)

The ink of claim 28, wherein the poly(vinyl alcohol) has a molecular weight of at least about 2000 and comprises from about 0.5 to about 80%, based on the number of hydroxyl groups in the poly(vinyl alcohol), of units of the formula I, I and II, I and III, or I and II and III
in which R is alkylene having up to 12 carbon atoms, R1 is hydrogen or lower alkyl, R2 is an olefinically unsaturated, electron-withdrawing, crosslinkable radical, and R3 is hydrogen, a C1-C6 alkyl group or a cycloalkyl group,
wherein R and R3 are as defined above, and R7 is a primary, secondary or tertiary amino group or a quaternary amino group of the formula N+(R′)3X−, in which each R′, independently of the others, is hydrogen or a C1-C4 alkyl radical and X is a counterion,
in which R and R3 are as defined above, and R8 is the radical of a monobasic, dibasic or tribasic, saturated or unsaturated, aliphatic or aromatic organic acid or sulfonic acid.

### Claim 30 (depends on 29)

The ink of claim 29, wherein R2 is a radical of the formula IV or V
—CO—NH—(R5—NH—CO—O)q—R6—O—CO—R4 (IV)
—[CO—NH—(R5—NH—CO—O)q—R6—O]p—CO—R4 (V)
in which p and q, independently of one another, are zero or one, and R5 and R6, independently of one another, are lower alkylene having 2 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, a saturated bivalent cycloaliphatic group having 6 to 10 carbon atoms, arylenealkylene or alkylenearylene having 7 to 14 carbon atoms or arylenealkylenearylene having 13 to 16 carbon atoms, and in which R4 is an olefinically unsaturated copolymerizable radical having 2 to 24 carbon atoms.

### Claim 31 (depends on 29)

The ink of claim 29, further comprising one or more components selected from the group consisting of a crosslinker, a surfactant, a humectant, a polymerization initiator, an antimicrobial agent, an antioxidant agent, and an anti-kogating agents.

### Claim 32 (depends on 31)

The ink of claim 31, comprising at least one surfactant in an amount of from about 0 to about 2% by weight.

### Claim 33 (depends on 32)

The ink of claim 32, wherein the surfactant is 2,4,7,9-tetramethyl-5-decyne-4,7-diol, ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol, a mixture of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol, or a block copolymer of ethylene oxide and propylene oxide.

### Claim 34 (depends on 32)

The ink of claim 32, comprising a humectant in an amount of from about 0 to about 30% by weight.

### Claim 35 (depends on 34)

The ink of claim 34, wherein the humectant is glycerol, ethylene glycol, diethylene glycol, 1 ,3-dioxane-5,5-dimethanol, or a mixture thereof.

### Claim 36 (depends on 35)

The ink of claim 35, wherein the humectant is glycerol and/or diethylene glycol.

### Claim 37 (depends on 31)

The ink of claim 31, comprising a crosslinker in an amount of from 0 to about 10% by weight.

### Claim 38 (depends on 37)

The ink of claim 37, wherein the crosslinker is selected from the group consisting of diaziridine-containing compounds, ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate, ethyleneglycol diacrylate, allyl methacrylates, allyl acrylates, 1,3-propanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, polyethyleneoxide mono- and diacrylates, and 1,4-butanediol diacrylate (BDDA).

### Claim 39 (depends on 29)

The ink of claim 29, wherein the ink has a good transferability from a mold to a contact lens molded with the mold.

### Claim 40 (depends on 39)

The ink of claim 39, wherein the ink is stable for at least 4 hours.

### Claim 41 (depends on 40)

The ink of claim 40, wherein the ink is stable for at least 8 hours.

### Claim 42 (depends on 41)

The ink of claim 41, wherein the ink is stable for at least 24 hours.

### Claim 43 (depends on 42)

The ink of claim 42, wherein the ink is stable for at least 7 days.

### Claim 44 (depends on 43)

The ink of claim 43, wherein the ink is stable for at least three weeks.

### Claim 45

A method for making an inkjet ink, comprising grinding pigments in a liquid mixture comprising water and a binder polymer, wherein the binder polymer is a crosslinkable, water-soluble poly(vinyl alcohol) and comprises olefinically unsaturated groups which are capable of being crosslinked under free radical polymerization conditions in the absence of a crosslinker to form inter—and intra crosslinkages so that a macromolecular matrix is formed to bind and/or trap pigments onto a soft contact lens and to ensure no visible and microscopic (˜10×) observation of colorant bleeding, smearing, or delamination in a color image printed on the soft contact lens with said ink, wherein each intra-crosslinkage is an intramolecular covalent bond formed between a pair of olefinically unsaturated groups which belong to the same binder polymer molecule, wherein the inter-crosslinkage is an intermolecular covalent bond formed between a pair of olefinically unsaturated groups each belonging to one of two binder polymer molecules, and wherein the ink is characterized by having a surface tension of from about 20 mN/m to about 60 mN/m, a viscosity of less than 50 centipoise, and good adhesion to the soft contact lens without and by being stable for at least about 4 hours.

### Claim 46 (depends on 45)

The method of claim 45, wherein the crosslinkable, water-soluble poly(vinyl alcohol) has a molecular weight of at least about 2000 and comprises from about 0.5 to about 80%, based on the number of hydroxyl groups in the poly(vinyl alcohol), of units of the formula I, I and II, I and III, or I and II and III
in which R is alkylene having up to 12 carbon atoms, R1 is hydrogen or lower alkyl, R2 is an olefinically unsaturated, electron-withdrawing, crosslinkable radical, and R3 is hydrogen, a C1-C6 alkyl group or a cycloalkyl group,
wherein R and R3 are as defined above, and R7 is a primary, secondary or tertiary amino group or a quaternary amino group of the formula N+(R′)3X−, in which each R′, independently of the others, is hydrogen or a C1-C4 alkyl radical and X is a counterion,
in which R and R3 are as defined above, and R8 is the radical of a monobasic, dibasic or tribasic, saturated or unsaturated, aliphatic or aromatic organic acid or sulfonic acid.

### Claim 47 (depends on 46)

The method of claim 46, wherein the grinding step is performed using a technique selected from the group consisting of high speed mixers, Kady Mills, colloid mills, homogenizers, microfluidizers, sonalators, ultrasonic mills, roll mills, ball mills, roller mills, vibrating ball mills, attritors, sand mills, varikinetic dispensers, three-roll mills, Ban bury mixers, and vertical mill.

### Claim 48 (depends on 1)

The ink of claim 1, wherein said ink can be used to print a color image on the medical device by using an inkjet printing system.

### Claim 49 (depends on 22)

The ink of claim 22, wherein the colorant comprises at least a pigment and/or at least a dye which is either sparingly soluble or insoluble in the solvent.

### Claim 50 (depends on 22)

The ink of claim 22, wherein said ink can be used to print a color image on the medical device by using an inkjet printing system.