LED Curable Compositions

Abstract

A composition including at least one component selected from the group consisting of a curable monomer and a curable oligomer; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength. A process of digital offset printing including applying a composition onto a re-imageable imaging member surface at an ink take up temperature, the re-imageable imaging member having dampening fluid disposed thereon; forming an ink image; transferring the ink image from the re-imageable surface of the imaging member to a printable substrate at an ink transfer temperature. A process including combining at least one component selected from the group consisting of a curable monomer and a curable oligomer; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength; optionally, heating; and optionally, filtering; to provide an LED curable composition.

Claims

1. A composition comprising: at least one component selected from the group consisting of a curable monomer and a curable oligomer; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength.

2. The composition of claim 1, wherein the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength is a photoinitiator that absorbs at a wavelength of about 365 nanometers, about 385 nanometers, about 395 nanometers, or about 405 nanometers.

3. The composition of claim 1, wherein the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength absorbs at a selected narrow spectral LED wavelength; and wherein the at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength does not absorb at the selected narrow spectral LED wavelength.

4. The composition of claim 1, wherein the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength absorbs at a selected narrow spectral LED wavelength; and wherein the at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength absorbs over a range of ultra-violet wavelengths wherein the range is broader than the narrow spectral LED wavelength.

5. The composition of claim 1, wherein the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength comprises a Type I photoinitiator, a Type II photoinitiator, or a combination thereof.

6. The composition of claim 5, further comprising a co-initiator.

7. The composition of claim 1, wherein the photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength is selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, benzophenone, and combinations thereof.

8. The composition of claim 1, wherein the photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength is selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4,4-bis(diethylamino)benzophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 2-dimethyl amino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, (2-Methyl-4-(methylthio)-2-morpholinopropiophenone), and combinations thereof.

9. The composition of claim 1, further comprising a co-initiator; wherein the co-initiator is selected from the group consisting of dihydroxyethyl-para-toluidine, ethyl-4-dimethylaminobenzoate, N-methyldiethanolaamine, 2-ethylhexyl-4-dimethylaminobenzoate diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and combinations thereof.

10. The composition of claim 1, wherein the at least one component selected from the group consisting of a curable monomer and a curable oligomer is a component selected from the group consisting of acrylated polyesters, acrylated polyethers, acrylated epoxies, urethane acrylates, and pentaerythritol tetraacrylate, and combinations thereof.

11. The composition of claim 1, wherein the at least one component selected from the group consisting of a curable monomer and a curable oligomer is a component selected from the group consisting of a tetrafunctional polyester acrylate oligomer, a propoxylated trimethylolpropane triacrylate monomer, and combinations thereof.

12. The composition of claim 1, further comprising: at least one non-radiation curable poly-alpha-olefin;

13. The composition of claim 1, wherein the composition is substantially free of colorant.

14. The composition of claim 1, wherein the composition is substantially colorless or is a tinted clear ink upon printing.

15. A process of digital offset printing, the process comprising: applying a composition onto a re-imageable imaging member surface at an ink take up temperature, the re-imageable imaging member having dampening fluid disposed thereon; forming an ink image; transferring the ink image from the re-imageable surface of the imaging member to a printable substrate at an ink transfer temperature; wherein the ink composition comprises: at least one component selected from the group consisting of a curable monomer and a curable oligomer; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength.

16. The process of claim 15, wherein the printable substrate comprises a pre-imaged substrate; and wherein forming an ink image and transferring the ink image comprises forming and transferring over the pre-image on the substrate.

17. The process of claim 15, wherein the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength is a photoinitiator that absorbs at a selected narrow spectral LED wavelength of about 365 nanometers, about 385 nanometers, about 395 nanometers, or about 405 nanometers; and wherein the at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength does not absorb at the selected narrow spectral LED wavelength.

18. The process of claim 15, wherein the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength comprises a Type I photoinitiator, a Type II photoinitiator, or a combination thereof; and wherein the composition further optionally comprises a co-initiator.

19. A composition comprising: at least one component selected from the group consisting of a curable monomer and a curable oligomer; optionally, at least one non-radiation curable poly-alpha-olefin; at least one first photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength, wherein the at least one first photoinitiator comprises a Type I photoinitiator; at least one second photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength, wherein the at least one second photoinitiator comprises a Type II photoinitiator; and optionally, at least one co-initiator.

20. The composition of claim 19, wherein the composition is substantially free of colorant.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0031] FIG. 1 illustrates a schematic representation of a related art ink-based variable image digital printing system with which the ink compositions according to this disclosure may be used.

DETAILED DESCRIPTION

[0032] Compositions useful for digital radiation curable ink applications, in embodiments for digital radiation curable offset ink applications are described. The compositions are able to absorb light and be cured with a light-emitting diode (LED) light source, in embodiments, compositions suitable for absorbing in the narrow spectral wavelength produced by ultra violet (UV) LED light sources, in embodiments, absorbing radiation at 365 nanometers, 385 nanometers, 395 nanometers, or 405 nanometers wavelengths.

[0033] Prints prepared with the present compositions, including, in embodiments, when printed using digital process, in embodiments using offset lithography printing, possess desirable properties including acceptable robustness qualities of adhesion of the ink onto a substrate and solvent resistance.

[0034] It is highly desirable for offset lithography ink compositions to possess adequate, preferably outstanding, characteristics and performance including anilox filling from the ink loader, transfer to the blanket, and ultimately high transfer of the ink image from the blanket to the receiving substrate. The present compositions maintain viscosity and tack properties within a range required to achieve key print functions in digital offset printing applications while being suitable for narrow spectral LED curing.

[0035] The compositions herein can be cured with an ultra violet (UV) LED light source absorbing radiation at a selected LED UV wavelength of from about 360 nanometers to about 410 nanometers. In embodiments, the compositions can be cured with an ultra violet (UV) LED light source absorbing radiation at 365 nanometers, 385 nanometers, 395 nanometers, or 405 nanometers wavelengths. In embodiments, the compositions comprise radiation curable compositions curable with LED light, in embodiments, curable with LED light emitting a peak wavelength centered at about 395 nanometers, in embodiments, emitting a peak wavelength centered at about 365 nanometers, emitting a peak wavelength centered at about 385 nanometers, emitting a peak wavelength centered at about 395 nanometers, or emitting a peak wavelength centered at about 405 nanometers. In certain embodiments, the compositions are suitable for high speed printers and are able to be cured with LED curing at speeds of at least about 500 millimeters per second. The LED curable compositions achieve desirable tack and viscosity characteristics for offset lithographic printing and enable high ink transfer efficiency between the imaged ink on the blanket and the receiving substrate.

[0036] In certain embodiments, the compositions are clear compositions.

[0037] In embodiments, the ink has relatively low viscosity within a temperature range of, in embodiments, from about 45 to about 80 C., such as from about 50 to about 70 C., such as from about 55 to about 65 C., such as about 60 C., at shear rates corresponding to the equivalent angular frequencies from about 50 to about 200 rad/s such as about 100 rad/s. It is also highly advantageous to ensure a high degree of ink transfer from the anilox roller to the blanket such that the ink has relatively high viscosity within a temperature range of, in embodiments, from about 18 to about 35 C., such as from about 18 to about 30 C., such as about 25 C., at shear rates corresponding to the equivalent angular frequencies from about 0.5 to about 2 rad/s such as about 1 rad/s.

[0038] In embodiments, the ink composition has a first viscosity of from about 3,000 to about 90,000 centipoise at an ink take up temperature of from about 45 C. to about 80 C.; and the ink composition has a second viscosity of from about 100,000 to about 2,000,000 centipoise at an ink transfer temperature of from about 18 C. to about 30 C.

[0039] In embodiments, the ink composition has a first viscosity of from about 3,000 to about 90,000 centipoise at an ink take up temperature of from about 45 C. to about 80 C. and a relatively higher shear rate of from about 50 rad/s to about 200 rad/s; and the ink composition has a second viscosity of from about 100,000 to about 2,000,000 centipoise at an ink transfer temperature of from about 18 C. to about 30 C. and a relatively lower angular frequency of from about 0.5 rad/s to about 2 rad/s.

[0040] In certain embodiments, the ink compositions herein have a viscosity of from about 10,000 centipoise at a temperature of about 40 C. to about 800,000 centipoise at a temperature of about 20 C.

[0041] In embodiments, the compositions comprise a radiation curable monomer or oligomer, at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; at least one photoinitiator that does not absorb at an ultraviolet light-emitting diode wavelength. The compositions optionally further contain a non-radiation curable poly-alpha-olefin.

[0042] In further embodiments, the compositions comprise at least one component selected from the group consisting of a curable monomer and a curable oligomer; optionally, at least one non-radiation curable poly-alpha-olefin; at least one first photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength, wherein the at least one first photoinitiator comprises a Type I photoinitiator; at least one second photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength, wherein the at least one second photoinitiator comprises a Type II photoinitiator; and optionally, at least one co-initiator. If the optional co-initiator is not present, one or more of the curable monomer or curable oligomer can function as the co-initiator. Suitable curable oligomers that have at least one acrylate functionality can function as reactive amine co-initiators with Type II photoinitiator include: CN386US, CN371 and CN373 from Sartomer Corporation; Ebecryl 7100 and Ebecryl LED 03 from Allnex; and Genomer 5695 from Rahn among others.

[0043] Photoinitiator.

[0044] The compositions herein contain at least one photoinitiator that absorbs at a selected narrow ultraviolet light-emitting diode wavelength. While the compositions can function in prior Hg (D-bulb) curing systems, they are particularly suited for UV light-emitting diodes (LEDs) which have a narrow spectral output centered on a specific wavelength, in embodiments, plus or minus 15 nanometers, in embodiments, plus or minus 5 nanometers. Typical commercial UV LED lamps emit at 365 nanometers, 385 nanometers, 395 nanometers, or 405 nanometers. In embodiments, the compositions can be cured with an ultra violet (UV) LED light source absorbing radiation at 365 nanometers, 385 nanometers, 395 nanometers, or 405 nanometers wavelengths. The present compositions are particularly well suited for such UV LED lamp curing.

[0045] In embodiments, the compositions comprise radiation curable compositions curable with LED light, in embodiments, curable with LED light emitting a peak wavelength centered at about 395 nanometers, in embodiments, emitting a peak wavelength centered at about 365 nanometers, 385 nanometers, 395 nanometers, or 405 nanometers. In certain embodiments, the compositions are suitable for high speed printers and are able to be cured with LED curing at speeds of at least about 500 millimeters per second. In certain embodiments, the LED curable compositions are curable with LED light emitting a peak wavelength centered at 395 plus or minus 5 nanometers at speeds of at least about 500 millimeters per second. The LED curable compositions achieve desirable tack and viscosity characteristics for offset lithographic printing and enable high ink transfer efficiency between the imaged ink on the blanket and the receiving substrate.

[0046] In embodiments, the compositions herein comprise at least one component selected from the group consisting of a curable monomer and a curable oligomer; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength. In embodiments, at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength absorbs over a range of ultra-violet wavelengths wherein the range is broader than the narrow spectral LED wavelength.

[0047] In embodiments, the composition includes at least one photoinitiator that absorbs at a selected narrow spectral LED wavelength and at least one additional photoinitiator, wherein the at least one additional photoinitiator is selected from the group consisting of a photoinitiator that does not absorb at the selected narrow spectral LED wavelength, a photoinitiator that absorbs over a range of ultra-violet wavelengths wherein the range is broader than the narrow spectral LED wavelength, or a combination thereof. In embodiments, the composition includes at least one photoinitiator that absorbs at a selected narrow spectral LED wavelength, in embodiments, a photoinitiator that absorbs at a wavelength of about 365 nanometers, about 385 nanometers, about 395 nanometers, about 405 nanometers, or about 395 nanometers; and the composition further comprises at least one photoinitiator that does not absorb radiation at the selected narrow spectral LED wavelength, such as does not absorb at a wavelength of about 395 nanometers, or does not absorb radiation at a wavelength of 365 nanometers, 385 nanometers, 395 nanometers, 405 nanometers, or about 395 nanometers.

[0048] In further embodiments, the compositions include at least one component selected from the group consisting of a curable monomer and a curable oligomer; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength.

[0049] In certain embodiments, the compositions include at least one component selected from the group consisting of a curable monomer and a curable oligomer; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength; and wherein the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength absorbs at a selected narrow spectral LED wavelength; and wherein the at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength does not absorb at the selected narrow spectral LED wavelength.

[0050] Any suitable or desired photoinitiator or combination of photoinitiators can be selected for the compositions herein providing that they meet the requirements for the selected absorption performance.

[0051] In some embodiments, the ink composition includes a photoinitiator, such as a -hydroxyketone photoinitiator (including -hydroxyketone photoinitators sold under the trade name IRGACURE 184, IRGACURE 500, DAROCUR 1173, and IRGACURE 2959, which are manufactured by BASF), -aminoketone photoinitiators (including -aminoketone photo-initiators IRGACURE 369, IRGACURE 379, IRGACURE 907, and IRGACURE 1300, which are manufactured by BASF) and bisacyl phosphine photoinitiators (including bisacyl phospine photoinitiators sold under the trade name IRGACURE 819, IRGACURE 819DW, and IRGACURE 2022, which are manufactured by BASF). Other suitable photoinitiators include monoacylphosphine oxide and bisacylphosphine oxide, such as 2,4,6-trimethylbenzoybiphenylphosphine oxide (manufactured by BASF under the trade name LUCIRIN TPO); ethyl-2,4,6-trimethylbenzoylphenyl phosphinate (manufactured by BASF under the trade name LUCIRIN TPO-L); mono- and bis-acylphosphine photoinitiators (such IRGACURE 1700, IRGACURE 1800, IRGACURE 1850, and DAROCUR 4265, manufactured by BASF), benzyldimethyl-ketal photoinitiators (such as IRGACURE 651, manufactured by BASF) and oligo [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] (available as Esacure KIP 150 from Lamberti); and the like, as well as mixtures thereof.

[0052] There are 2 classes of photoinitiators: Type I and Type II. Type I photoinitiators are those that undergo unimolecular bond cleavage after absorption of light to render the reactive species. No other species are necessary in order for these photoinitiators to work. Type I photoinitiators absorb a specific wavelength of irradiating incident light such that the hemolytic cleavage of the photoinitiator results in the even scission of a bonding pair of electrons such that two free radical products are formed that can go on to initiate the polymerization reaction to enable the curing of the ink. Type II photoinitiators undergo a bimolecular reaction. After absorption of light, the photoinitiator reaches an excited state from which it reacts with another molecule (co-initiator or synergist) to create the reactive species. Type II photoinitiators, in the present of the co-initiator, such as an amine or alcohol, also absorb a specific wavelength of irradiating incident light which products an excited electron state in the photoinitiator resulting in the abstraction of a hydrogen atom from the co-initiator and consequently splitting a bonding pair of electrons forming the free radical products.

[0053] In embodiments, the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength comprises a Type I photoinitiator, a Type II photoinitiator, or a combination thereof; and, in embodiments, further comprises a co-initiator. In embodiments, the compositions herein include one or more of at least one Type I photoinitiator and at least one a Type II photoinitiator, optionally in combination with one or more co-initiators. In certain embodiments, the compositions comprise a combination of at least one Type I photoinitiator and at least one Type II photoinitiator, and optionally, at least one co-initiator.

[0054] Any suitable or desired Type I photoinitiator can be selected provided that it meet the requirements for the selected absorption and offset lithography printing characteristics. In embodiments, suitable Type I photoinitiators include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, available as GENORAD TPO available from Rahn AG, OMNIRAD TPO available from IGM Resins, and DOUBLECURE TPO available from Double Bond Chemical Ind. Co. Ltd. The TPO designated photoinitiator has a secondary lambda-max at about 380 nanometers (as diluted in such solvents as methanol, acetonitrile, and the like) useful for absorbing LED radiation in that range and, in embodiments, above to about 405 nanometers, and has a relatively low melting point of about 93 C., has a high solubility in a wide range of functional monomers and oligomers, and is relatively inexpensive compared to other photoinitiator classes. Bisacylphosphine oxides having primary or secondary absorbances at about 380 nanometers can also be selected. Liquid-based photoinitiators such as liquid monoacylphosphine oxides, their liquid mixtures and eutectic mixtures, etc., and solid-based photoinitiators can be selected for the present compositions. In certain embodiments, solid-based photoinitiators, such as solid-based monoacylphosphine oxides, are selected, which do not impact the formulation latitude of the compositions compared to liquid-based photoinitiators which liquid-based photoinitiators can, in some cases, reduce tack and viscosity of the compositions when present in amounts desired to achieve a sufficient cure of the compositions.

[0055] In embodiments, the photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength is selected from the group consisting of monoacylphosphine oxide, and bisacylphosphine oxide, such as 2,4,6-trimethylbenzoybiphenylphosphine oxide (manufactured by BASF under the trade name LUCIRIN TPO); ethyl-2,4,6-trimethylbenzoylphenyl phosphinate (manufactured by BASF under the trade name LUCIRIN TPO-L); mono- and bis-acylphosphine photoinitiators (such IRGACURE 1700, IRGACURE 1800, IRGACURE 1850, and DAROCUR 4265, manufactured by BASF), benzyldimethyl-ketal photo-initiators (such as IRGACURE 651, manufactured by BASF) and oligo [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] (available as Esacure KIP 150 from Lamberti); and the like, as well as mixtures and combinations thereof. In certain embodiments, the photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength is selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, benzophenone, and combinations thereof.

[0056] In embodiments, the photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength is selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4,4-bis(diethylamino)benzophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 2-dimethyl amino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, (2-Methyl-4-(methylthio)-2-morpholinopropiophenone), and combinations thereof.

[0057] Any suitable or desired Type II photoinitiator can be selected provided that it meet the requirements for the selected absorption and offset lithography printing characteristics. In embodiments, suitable Suitable Type II photoinitiators include those that have a secondary lambda-max near or at about 380 to about 400 nanometers, such as 4,4-bis(diethylamino)benzophenone (Ethyl Micheler's Ketone) which has a melting point of about 92 C., 2-isopropylthioxanthone and 4-isopropylthioxanthone (usually found as isomeric mixtures) which have a melting point range of about 56 to about 72 C., and 2,4-diethylthioxanthone (DETX) which has a melting point of from about 68 C. to about 75 C. Another suitable Type II photoinitiator is 1-phenyl-1,2-propanedione (PPD) which is a liquid at room temperature.

[0058] Any suitable or desired co-initiator can be selected for the compositions herein. In embodiments, suitable co-initiators for the compositions including Type II photoinitiators include dihydroxyethyl-para-toluidine, tertiary amines such as ethyl-4-dimethylamino benzoate, methyldiethanol amine, combinations thereof, and the like. Examples of reactive co-initiators for the compositions including Type II photoinitiators include CN374 available from Sartomer, an amine-modified acrylate having a viscosity of about 275 mPa.Math.s at 25 C., and Ebecryl 7100 available from Allnex, an amine-functional acrylate having a viscosity of about 1,200 mPa.Math.s at 25 C. In embodiment, reactive amine co-initiators are selected in that they can be reacted without adversely impacting the cured properties of the coating/print.

[0059] In embodiments, the co-initiator is selected from the group consisting of dihydroxyethyl-para-toluidine, ethyl-4-dimethylaminobenzoate, N-methyldiethanolaamine, 2-ethylhexyl-4-dimethylaminobenzoate diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and combinations thereof.

[0060] The photoinitiator or combination of photoinitiators may be present in the ink composition of the instant disclosure in any suitable or desired amount, in embodiments, in an amount of about 0% to about 8% by weight, such as about 1% to about 7%, by weight such as about 2% to about 6% by weight, based upon the total weight of the ink composition.

[0061] In embodiments, the at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength is present in the ink composition in an amount of from at least about 7 to about 10 percent by weight based upon the total weight of the ink composition.

[0062] In embodiments where the ink composition contains at least one photoinitiator that absorbs at a selected narrow spectral LED wavelength and at least one photoinitiator that does not absorb at the selected LED wavelength, the photoinitiator that absorbs at the selected narrow spectral LED wavelength can be present in an amount of from about 0.5 to about 8 percent by weight, or from at least about 2 to about 7 percent by weight, based upon the total weight of the ink composition, and the at least one photoinitiator that does not absorb at the selected LED wavelength can be present in an amount of from about 0.5 to about 5 percent by weight, or from about 1 to about 3 percent by weight, based upon the total weight of the ink composition.

[0063] The co-initiator, if present, may be present in the ink composition of the instant disclosure in any suitable or desired amount. In embodiments, the co-initiator is present in an amount of from about 1 to about 8, or from about 2 to about 7, or from about 3 to about 6 percent by weight based upon the total weight of the composition.

[0064] In some embodiments, the ink composition of the present disclosure comprises a free radical scavenger, such as IRGASTAB UV10, IRGASTAB UV22 available from BASF, Genorad 20 from Rahn AG, or CN3216 available from Sartomer Co. The free radical scavenger may be present in the ink composition in any suitable or desired amount, in embodiments in an amount of about 0% to about 5% by weight, such as from about 0.5% to about 4% by weight, such as about 2% to about 3% by weight, based upon the total weight of the ink composition.

[0065] Monomers, Oligomers.

[0066] In embodiments, the composition of the present disclosure includes a suitable curable monomer or oligomer. Examples of suitable materials include radically curable monomer compounds, such as acrylate and methacrylate monomer compounds. Specific examples of acrylate and methacrylate monomers include (but are not limited to) isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, isodecylacrylate, isodecylmethacrylate, caprolactone acrylate, 2-phenoxyethyl acrylate, isooctylacrylate, isooctylmethacrylate, butyl acrylate, alkoxylated lauryl acrylate, ethoxylated nonyl phenol acrylate, ethoxylated nonyl phenol methacrylate, ethoxylated hydroxyethyl methacrylate, methoxy polyethylene glycol monoacrylate, methoxy polyethylene glycol monomethacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like, as well as mixtures or combinations thereof.

[0067] In embodiments, the at least one component selected from the group consisting of a curable monomer and a curable oligomer in the ink composition herein is a component selected from the group consisting of acrylated polyesters, acrylated polyethers, acrylated epoxies, urethane acrylates, and pentaerythritol tetraacrylate, and combinations thereof.

[0068] In embodiments, propoxylated trimethylolpropane triacrylate such as SR501 from Sartomer Co. is used.

[0069] The monomers may be present in the ink composition of the present disclosure in any suitable or desired amount, in embodiments in an amount of from about 0% to about 50% by weight, such as about 1% to about 30% by weight, such as about 5% to about 30% by weight, such as about 5% to about 10% by weight, based upon the total weight of the ink composition.

[0070] In embodiments, the composition of the present disclosure includes a curable oligomer. Suitable curable oligomers include, but are not limited to acrylated polyesters, acrylated polyethers, acrylated epoxies, urethane acrylates, and pentaerythritol tetraacrylate. Specific examples of suitable acrylated oligomers include, but are not limited to, acrylated polyester oligomers, such as CN2255, CN2256, CN294E, CN2282 (Sartomer Co.), and the like, acrylated urethane oligomers, acrylated epoxy oligomers, such as CN2204, CN110 (Sartomer Co.) and the like; and mixtures and combinations thereof. In embodiments, the at least one component selected from the group consisting of a curable monomer and a curable oligomer in the composition herein is a component selected from the group consisting of a tetrafunctional polyester acrylate oligomer, a propoxylated trimethylolpropane triacrylate monomer, and combinations thereof.

[0071] In certain embodiments wherein the compositions are free of colorant, oligomers may be present in the ink composition of the present disclosure in any suitable or desired amount, in embodiments in an amount of from about 50 to about 90 percent by weight, or from about 55 to about 85 percent by weight, or from about 60 to about 80 percent by weight, based upon the total weight of the ink composition.

[0072] In embodiments, the at least one component selected from the group consisting of a curable monomer and a curable oligomer is a branched acrylate having from at least about 6 carbon atoms to about 20 carbon atoms.

[0073] In a specific embodiment, at least one of the curable oligomers is a polyester acrylate oligomer. Without wishing to be bound by theory, it is believed that the polyester acrylate oligomer improves the reactivity of the system and enables a more rigid and tougher three-dimensional structure to be realized once cured. A specific example of such a polyester acrylate oligomer is CN2302 (Sartomer Co.), which is a hyper-branched polyester acrylate oligomer designed with low viscosity and high functionality. It is believed that the high degree of hyper-branched functionality (about 16). It is believed that the high degree of hyper-branched functionality (about n=16 acrylate functionality) improves the reactivity of the system and contributes to the more rigid and tough three-dimensional structure achieved upon curing.

[0074] In certain embodiments, the compositions described herein may include the following components: (a) radiation-curable water-dilutable monomer compounds, including mono-, di-, and tri-functional water-dilutable acrylate monomers, oligomers; (b) dispersants; (c) colorant; in embodiments, the compositions are colorant-free; (d) clays or other additives; (e) initiators; (f) additional curable compounds including monomers, oligomers, including oligomers from Sartomer USA, LLC or Cytec Industries, Inc., prepolymers, polymers; (g) at least one UV LED photoinitiator as described herein; (h) secondary additives including surfactants, free-radical scavengers, and the like; and (i) thermal stabilizers.

[0075] In embodiments, the water-diluted curable components may include any water-dilutable acrylate or methacrylate monomer compound(s) suitable for use as a vehicle that may be water dilutable, with an addition of water being available to adjust and/or enhance background performance for use in the variable digital data lithographic printing architecture. In embodiments, the water-diluted curable component is a water-dilutable functional acrylate monomer, a methacrylate monomer, a multifunctional acrylate monomer, a multifunctional methacrylate monomer, or a mixture or combination thereof. Exemplary acrylates may include acrylate monomers or polymers such as polyester acrylates Sartomer CN294E, Sartomer CD-501, Sartomer CN9014, Sartomer CN2282 and Sartomer CN2256. In embodiments, a mixture of the components is water-dilutable.

[0076] In embodiments, further examples of curable monomers and diluting acrylates which can be used in the compositions as vehicles may include trimethylolpropane triacrylate; SR-492, SR-501, SR-444, SR-454, SR-499, SR-502, SR-9035 and SR-415 from Sartomer; EBECRYL 853 and EBECRYL 5500 from Allnex. Trimethylolpropane triacrylate has a refractive index of 1.474, a specific gravity of 1.06 g/cm.sup.3, an APHA Color of less than 300 and a viscosity range of 80 to 120 cps at 25 C. Sartomer SR-492 is a three mole propoxylated trimethylolpropane triacrylate and has a refractive index of 1.459, a specific gravity of 1.05 g/cm.sup.3, a Tg of 15 C., an APHA Color of 30 and a viscosity of 90 cps at 25 C. Sartomer SR-501 is a six mole propoxylated trimethylolpropane triacrylate and has a refractive index of 1.4567, a specific gravity of 1.048 g/cm.sup.3, a Tg of 2 C., an APHA Color of 90 and a viscosity of 125 cps at 25 C. Sartomer SR-444 is a pentaerythritol triacrylate and has a refractive index of 1.4801, a specific gravity of 1.162 g/cm.sup.3, a Tg of 103 C., an APHA Color of 50 and a viscosity of 520 cps at 25 C. Sartomer SR-454 is a three mole ethoxylated trimethylolpropane triacrylate and has a refractive index of 1.4689, a specific gravity of 1.103 g/cm.sup.3, a Tg of 120 C., an APHA Color of 55 and a viscosity of 60 cps at 25 C. Sartomer SR-499 is a six mole ethoxylated trimethylolpropane triacrylate and has a refractive index of 1.4691, a specific gravity of 1.106 g/cm.sup.3, a Tg of 8 C., an APHA Color of 50 and a viscosity of 85 cps at 25 C. Sartomer SR-502 is a nine mole ethoxylated trimethylolpropane triacrylate and has a refractive index of 1.4691, a specific gravity of 1.11 g/cm.sup.3, a Tg of 19 C., an APHA Color of 140 and a viscosity of 130 cps at 25 C. Sartomer SR-9035 is a fifteen mole ethoxylated trimethylolpropane triacrylate and has a refractive index of 1.4695, a specific gravity of 1.113 g/cm3, a Tg of 32 C., an APHA Color of 60 and a viscosity of 168 cps at 25 C. Sartomer SR-415 is a twenty mole ethoxylated trimethylolpropane triacrylate and has a refractive index of 1.4699, a specific gravity of 1.115 g/cm3, a Tg of 40 C., an APHA Color of 55 and a viscosity of 225 cps at 25 C. EBECRYL 853 is a low viscosity polyester triacrylate and has a specific gravity of 1.10 g/cm3, an APHA Color of 200 and a viscosity of 80 cps at 25 C. EBECRYL 5500 is a low viscosity glycerol derivative triacrylate and has a specific gravity of 1.07 g/cm.sup.3, an APHA Color of 62 and a viscosity of 130 cps at 25 C. Other triacrylate, monoacrylate, diacrylate, tetraacrylate and higher functional acrylate monomers, diluting acrylates, and various combinations thereof, can also be used in the ink compositions as vehicles.

[0077] In embodiments, one or more components in a mixture may be non-water dilutable, if the ink is water dilutable, and the reactive component are themselves miscible. In the same way that water may be added, in some embodiments, co-reactive monomers may be added to control polarity of the ink. Specific examples of water-dilutable curable components include, but are not limited to, the functional water soluble aromatic urethane acrylate compound (available from CYTEC as EBECRYL 2003), the di-functional compound polyethylene glycol diacrylate (available from CYTEC as EBECRYL 11), and the tri-functional compound polyether triacrylate (available from CYTEC as EBECRYL 12). The monomer or oligomer can be present in any suitable amount. In embodiments, the monomer or oligomer, or combination thereof is added in an amount of from about 10 to about 85%, or from about 30 to about 80%, or from about 50 to about 70%, by weight based on the total weight of the curable ink composition. Curable oligomers which can be used in the ink compositions as vehicles may include Sartomer CN294E; CN2256; CN2282; CN9014 and CN309. Sartomer CN294E is a tetrafunctional acrylated polyester oligomer. CN294E is a clear liquid having a specific gravity of 0.93 and a viscosity of 4,000 cps at 60 C. Sartomer CN2256 is a difunctional polyester acrylate oligomer and has a refractive index of 1.5062, a Tg of 22 C., a tensile strength of 675 psi, and a viscosity of 11,000 cps at 60 C.

[0078] Sartomer CN2282 is tetrafunctional acrylated polyester and is a clear liquid having a specific gravity of 1.15 and a viscosity of 2,500 cps at 60 C. Sartomer CN9014 is a difunctional acrylated urethane and is a non-clear liquid having a specific gravity of 0.93 and a viscosity of 19,000 cps at 60 C. Sartomer CN309 is an oligomer containing an acrylate ester that derives from an aliphatic hydrophobic backbone, or in other words is an aliphatic acrylate ester. CN309 is a clear liquid having a specific gravity of 0.92, a density of 7.68 pounds/gallon, a surface tension of 26.3 dynes/cm, a viscosity of 150 cps at 25 C., and a viscosity of 40 cps at 60 C.

[0079] Examples of curable oligomers which can be used in the compositions as vehicles may include CN294E, CN2256, CN2282, CN9014 and CN309 from Sartomer; EBECRYL 8405, EBECRYL 8411, EBECRYL 8413, EBECRYL 8465, EBECRYL 8701, EBECRYL 9260, EBECRYL 546, EBECRYL 657, EBECRYL 809, and the like from Allnex. EBECRYL 8405 is a tetrafunctional urethane acrylate diluted as 80 wt % by weight in 1,6-Hexanediol diacrylate (HDDA). EBECRYL 8405 is a clear liquid having a Gardner Color of 2 and a viscosity of 4,000 cps at 60 C. EBECRYL 8411 is a difunctional urethane acrylate diluted as 80 wt % by weight in isobornylacrylate (IBOA). EBECRYL 8411 is a clear liquid having a viscosity range of 3,400 to 9,500 cps at 65 C. EBECRYL 8413 is a difunctional urethane acrylate diluted as 67 wt % by weight in IBOA. EBECRYL 8413 is a clear liquid having a viscosity of 35,000 cps at 60 C. EBECRYL 8465 is a trifunctional urethane acrylate. EBECRYL 8465 is a clear liquid having a Gardner Color of 2 and a viscosity of 21,000 cps at 60 C. EBECRYL 8701 is a trifunctional urethane acrylate. EBECRYL 8701 is a clear liquid having a Gardner Color of 2 and a viscosity of 4,500 cps at 60 C. EBECRYL 9260 is a trifunctional urethane acrylate. EBECRYL 9260 is a clear liquid having a Gardner Color of 2 and a viscosity of 4,000 cps at 60 C. EBECRYL 546 is a trifunctional polyester acrylate. EBECRYL 546 is a clear liquid having a Gardner Color of 1.5 and a viscosity of 350,000 cps at 25 C. EBECRYL 657 is a tetrafunctional polyester acrylate. EBECRYL 657 is a clear liquid having a Gardner Color of 4 and a viscosity of 125,000 cps at 25 C. EBECRYL 809 is a trifunctional polyester acrylate. EBECRYL 809 is a clear liquid having a Gardner Color of 3 and a viscosity of 1,300 cps at 60 C.

[0080] In certain embodiments, Sartomer CN2282, tetra-functional polyester acrylate oligomer having a viscosity of about 2,500 mPa.Math.s at 60 C. and a water-white appearance, Ebecryl 80 (Allnex), amine-modified polyether tetra-acrylate having a viscosity of about 3,000 mPa.Math.s at 60 C. and a straw-like color, Sartomer CN 299, tetra-functional polyester acrylate having a viscosity of about 5,200 mPa.Math.s at 60 C. and a light straw appearance, and combinations thereof, can be selected for the present compositions. In certain embodiments, one or more of these oligomers are selected for clear, colorant-free, compositions herein.

[0081] Poly-alpha-olefin.

[0082] The ink compositions can include at least one poly-alpha-olefin. Polyolefins are polymers derived from simple olefins (also called alkenes). Poly-alpha-olefins are prepared by polymerizing an alpha-olefin. An alpha-olefin (or -olefin) is an alkene where the carbon-carbon double bond starts at the -carbon atom. Alpha-olefins such as 1-hexene may be used as co-monomers to give an alkyl branched polymer. Many poly-alpha-olefins have flexible alkyl branching groups on every other carbon of their polymer backbone chain. These alkyl groups, which can shape themselves in numerous conformations, make it very difficult for the polymer molecules to align themselves up side-by-side in an orderly way. This results in lower contact surface area between the molecules and decreases the intermolecular interactions between molecules. See, for example, https://en.wikipedia.org/wiki/Polyolefin.

[0083] The compositions can include at least one poly-alpha-olefin. In embodiments, the poly-alpha-olefin is a non-curable material that is a solid at or near room temperature, in embodiments, at a temperature of from about 20 C. to about 40 C., or from about 20 C. to about 30 C., or from about 20 C. to about 25 C.

[0084] By non-curable it is meant that the material in the ink is not cross-linkable by such means as from exposure to, for example, heat, electromagnetic radiation, electron beam energies, and the like.

[0085] Without wishing to be bound by theory, it is believed that the presence of the poly-alpha-olefin imparts hardness to the cured print and acts as a barrier to oxygen when the ink or composition is imaged and transferred to the receiving substrate before curing radiation is applied. The presence of oxygen, especially at the imaged ink surface but also to some degree in the ink layer, is known to inhibit a high level of cure in radiation-curable systems, such as radiation curable acrylate systems, due to its ability, when the ink is subject to UV and visible radiation, to react with light-generated free radicals in the ink to form peroxy radicals which have relatively long lifetimes but very low reactivity thus negatively affecting the extend of cure and consequently, the robustness of cure. In embodiments, the poly-alpha-olefin, when present in the inks herein, enhances cured robustness properties of the cured print.

[0086] In embodiments, the poly-alpha-olefin is selected from the group consisting of branched synthetic based poly-alpha-olefin, branched bio-based poly-alpha-olefin, and combinations thereof. Bio-based monomers are derived from or otherwise are sourced from a natural source (e.g. plants, algae, protozoa, animals, microbes and so on), and a bio-based poly-alpha-olefin herein can comprise at least one bio-based moiety or be completely comprised of bio-based components.

[0087] In embodiment, the poly-alpha-olefin can be selected from the materials sold under the tradename Vybar. Vybar grades of materials, available from Baker Hughes, are hyper-branched aliphatic polymers with varying molecular weights and degrees of branching. By hyper-branched it is meant that the polymer is a highly branched macromolecule and can have imperfect or perfect branching, the latter that describes dendrimers.

[0088] The poly-alpha-olefin can be present in the ink composition in any suitable or desired amount. In embodiments, the poly-alpha-olefin is present in the ink composition in an amount of from about 1 to about 10 percent by weight, or from about 1 to about 6 percent by weight, or from about 1 to about less than about 5 percent by weight based upon the total weight of the ink composition. In embodiments, the poly-alpha-olefin is present in the ink composition in an amount of from about at least about 1 to about 10 percent by weight, or from at least about 1.5 to about 10 percent by weight based upon the total weight of the ink composition.

[0089] Filler.

[0090] In some embodiments, the composition of the present disclosure includes a filler or fillers. Suitable fillers may include, but are not limited to, amorphous, diatomaceous, fumed quartz and crystalline silica, clays, aluminum silicates, magnesium aluminum silicates, talc, mica, delaminated clays, calcium carbonates and silicates, gypsum, barium sulfate, zinc, calcium zinc molybdates, zinc oxide, phosphosilicates and borosilicates of calcium, barium and strontium, barium metaborate monohydrate, and the like. In specific embodiments, the filler may be clays from Southern Clay Products CLAYTONE HA and CLAYTONE HY. In embodiments, the clay may be present or provided in the form of clay or in the form of a clay dispersion. In some embodiments, filler may be present in the ink composition of the present disclosure in an amount from about 0% to about 50% by weight, such as about 1% to about 20% by weight, such as from about 2% to about 10% by weight, based upon the total weight of the composition.

[0091] Colorant.

[0092] The ink composition herein may also contain a colorant. Any suitable or desired colorant can be used in embodiments herein, including pigments, dyes, dye dispersions, pigments dispersions, and mixtures and combinations thereof.

[0093] In certain embodiments, the ink compositions are colorant free.

[0094] The colorant may include any suitable or desired color including cyan, magenta, yellow, black, and combinations thereof. The robustness properties of the ink compositions herein are achieved with the additives described for any color or combination selected, including cyan, magenta, yellow, black, and combinations thereof. In embodiments, the colorant comprises a pigment. In further embodiments, the colorant is provided in the form of a pigment dispersion. In certain embodiments, the ink compositions contain a pigment, in embodiments provided in the form of a pigment dispersion, and a clay.

[0095] The colorant may be provided in the form of a colorant dispersion. In embodiments, the colorant dispersion has an average particle size of from about 20 to about 500 nanometers (nm), or from about 20 to about 400 nm, or from about 30 to about 300 nm. In embodiments, the colorant is selected from the group consisting of dyes, pigments, and combinations thereof, and optionally, the colorant is a dispersion comprising a colorant, an optional surfactant, and an optional dispersant.

[0096] As noted, any suitable or desired colorant can be selected in embodiments herein. The colorant can be a dye, a pigment, or a mixture thereof. Examples of suitable dyes include anionic dyes, cationic dyes, nonionic dyes, zwitterionic dyes, and the like. Specific examples of suitable dyes include Food dyes such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, Food Yellow No. 7, and the like, FD & C dyes, Acid Black dyes (No. 1, 7, 9, 24, 26, 48, 52, 58, 60, 61, 63, 92, 107, 109, 118, 119, 131, 140, 155, 156, 172, 194, and the like), Acid Red dyes (No. 1, 8, 32, 35, 37, 52, 57, 92, 115, 119, 154, 249, 254, 256, and the like), Acid Blue dyes (No. 1, 7, 9, 25, 40, 45, 62, 78, 80, 92, 102, 104, 113, 117, 127, 158, 175, 183, 193, 209, and the like), Acid Yellow dyes (No. 3, 7, 17, 19, 23, 25, 29, 38, 42, 49, 59, 61, 72, 73, 114, 128, 151, and the like), Direct Black dyes (No. 4, 14, 17, 22, 27, 38, 51, 112, 117, 154, 168, and the like), Direct Blue dyes (No. 1, 6, 8, 14, 15, 25, 71, 76, 78, 80, 86, 90, 106, 108, 123, 163, 165, 199, 226, and the like), Direct Red dyes (No. 1, 2, 16, 23, 24, 28, 39, 62, 72, 236, and the like), Direct Yellow dyes (No. 4, 11, 12, 27, 28, 33, 34, 39, 50, 58, 86, 100, 106, 107, 118, 127, 132, 142, 157, and the like), Reactive Dyes, such as Reactive Red Dyes (No. 4, 31, 56, 180, and the like), Reactive Black dyes (No. 31 and the like), Reactive Yellow dyes (No. 37 and the like); anthraquinone dyes, monoazo dyes, disazo dyes, phthalocyanine derivatives, including various phthalocyanine sulfonate salts, aza(18)annulenes, formazan copper complexes, triphenodioxazines, and the like; as well as mixtures thereof.

[0097] Examples of suitable pigments include black pigments, white pigments, cyan pigments, magenta pigments, yellow pigments, and the like. Further, pigments can be organic or inorganic particles. Suitable inorganic pigments include carbon black. However, other inorganic pigments may be suitable such as titanium oxide, cobalt blue (CoOAl.sub.2O.sub.3), chrome yellow (PbCrO.sub.4), and iron oxide. Suitable organic pigments include, for example, azo pigments including diazo pigments and monoazo pigments, polycyclic pigments (e.g., phthalocyanine pigments such as phthalocyanine blues and phthalocyanine greens), perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, pyranthrone pigments, and quinophthalone pigments), insoluble dye chelates (e.g., basic dye type chelates and acidic dye type chelate), nitro pigments, nitroso pigments, anthanthrone pigments such as PR168, and the like. Representative examples of phthalocyanine blues and greens include copper phthalocyanine blue, copper phthalocyanine green, and derivatives thereof (Pigment Blue 15, Pigment Green 7, and Pigment Green 36). Representative examples of quinacridones include Pigment Orange 48, Pigment Orange 49, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19, and Pigment Violet 42. Representative examples of anthraquinones include Pigment Red 43, Pigment Red 194, Pigment Red 177, Pigment Red 216 and Pigment Red 226. Representative examples of perylenes include Pigment Red 123, Pigment Red 149, Pigment Red 179, Pigment Red 190, Pigment Red 189 and Pigment Red 224. Representative examples of thioindigoids include Pigment Red 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36, and Pigment Violet 38. Representative examples of heterocyclic yellows include Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 90, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 155, and Pigment Yellow 213. Such pigments are commercially available in either powder or press cake form from a number of sources including, BASF Corporation, Engelhard Corporation, and Sun Chemical Corporation. Examples of black pigments that may be used include carbon pigments. The carbon pigment can be almost any commercially available carbon pigment that provides acceptable optical density and print characteristics. Carbon pigments suitable for use in the present system and method include, without limitation, carbon black, graphite, vitreous carbon, charcoal, and combinations thereof. Such carbon pigments can be manufactured by a variety of known methods, such as a channel method, a contact method, a furnace method, an acetylene method, or a thermal method, and are commercially available from such vendors as Cabot Corporation, Columbian Chemicals Company, Evonik, and E.I. DuPont de Nemours and Company. Suitable carbon black pigments include, without limitation, Cabot pigments such as MONARCH 1400, MONARCH 1300, MONARCH 1100, MONARCH 1000, MONARCH 900, MONARCH 880, MONARCH 800, MONARCH 700, CAB-O-JET 200, CAB-O-JET 300, REGAL, BLACK PEARLS, ELFTEX, MOGUL, and VULCAN pigments; Columbian pigments such as RAVEN 5000, and RAVEN 3500; Evonik pigments such as Color Black FW 200, FW 2, FW 2V, FW 1, FW18, FW S160, FW S170, Special Black 6, Special Black 5, Special Black 4A, Special Black 4, PRINTEX U, PRINTEX 140U, PRINTEX V, and PRINTEX 140V. The above list of pigments includes unmodified pigment particulates, small molecule attached pigment particulates, and polymer-dispersed pigment particulates. Other pigments can also be selected, as well as mixtures thereof. The pigment particle size is desired to be as small as possible to enable a stable colloidal suspension of the particles in the liquid vehicle and to prevent clogging of the ink channels when the ink is used in a thermal ink jet printer or a piezoelectric ink jet printer. In embodiments, the colorant is a magenta colorant. In embodiments, the colorant is a magenta pigment.

[0098] The colorant can be present in the ink composition in any desired or effective amount, in embodiments, the colorant can be present in an amount of from about 0.05 to about 15 percent, or from about 0.1 to about 10 percent, or from about 1 to about 5 percent by weight, based on the total weight of the ink composition.

[0099] In embodiments, the ink composition herein further enables use of a high colorant concentration, in embodiments a colorant or pigment concentration of greater than 50 percent, in embodiments, greater than 60 percent, by weight based on the total weight of the ink composition, while maintaining desired characteristics of desired viscosity at room temperature and desired viscosity at heated temperature for ink transfer.

[0100] In embodiments, the compositions herein are clear or substantially colorless. As used herein, clear or substantially colorless refers to the ink composition being substantially or completely transparent or clear prior to and after undergoing curing or successive curing steps such as by radiation curing such as by UV light such as by UV LED light, drying, thermal curing, and the like. For this, the composition may be substantially free of colorants, in embodiments, substantially free of dye or pigment. The composition herein does not yellow upon drying and remains substantially or completely transparent and clear; that is, little or no measurable difference in any of L* a* b* values, or k, c, m, y is observed. Being substantially non-yellowing or substantially or completely transparent or clear refers to the composition changing color or hue upon curing in an amount of less that about 15 percent, or less than about 10 percent, or less than about 5 percent, or less than about 2 percent, or less than about 1 percent, for example, about zero percent.

[0101] In embodiments, the composition is substantially or completely free of colorants, such as pigments, dyes, or mixtures thereof.

[0102] In embodiments, the composition may include a small amount of colorant sufficient to provide a clear tinted ink. In these embodiments, the colorant is selected in a small amount suitable to impart the desired tint while maintaining the clarity of the ink composition and while not adversely affecting the ink viscosity, wetting, or transfer properties. In embodiments, the ink composition is substantially colorless or is a tinted clear ink upon printing.

[0103] In embodiments, the optional tinted clear compositions include a colorant in an amount of from about 0.0001 to about 0.3, or from about 0.001 to about 0.2, or from about 0.01 to about 0.1 percent by weight, based on the total weight of the ink composition.

[0104] If a small amount of colorant is included to provide a clear, tinted ink, the colorant can be selected from any suitable or desired colorant including pigments, dyes, dye dispersions, pigments dispersions, and mixtures and combinations thereof, including those described herein.

[0105] The radiation-cured prints made from clear compositions described herein, after being exposed to and cured by LED radiation, have desired aesthetic attributes and robustness qualities about them.

[0106] A digitally printed clear ink composition acting as an overcoat or over-print to an underlying CMYK (cyan, magenta, yellow, black) image ultimately results in a toughened print image such as when the printed page or area is substantially or completely covered with digital ink (the present composition) effectively acts as a protective laminating layer. A stress test for solvent resistance is employed with methyl ethyl ketone (MEK) solvent where it is desirable that the print can withstand at least 15 double rubs of MEK applied at room temperature before the supporting substrate becomes visible. Theoretically, a highly cross-linked ink matrix is more solvent-resistant than one that is less cross-linked but too high a cross-linking density can lead to brittleness of the printing layer and consequently poor adhesion can occur between the cured ink and the printed substrate. It is desirable that both solvent resistant and adhesion properties are balanced such that the print can withstand at least 15 double rubs of MEK before the supporting substrate becomes visible and achieve an adhesion rating of at least 3B as determined using the method prescribed in ASTM D-3359-09, Measuring Adhesion by Tape Test.

[0107] Various aesthetic attributes of digitally printed clear inks include tonal and textural enhancements of the image. The high optical transmission and gloss attributes of the clear compositions herein can be used to enhance the saturation of the under-printed CMYK images and solid fills allowing for a selective professional looking dazzling and varnished effect for the viewer. Digital clear inks can be used to focus attention on certain text or graphics or be added to personalize an image, document, etc. Clear inks can also be formulated to achieve lower gloss than the under-printed CMYK images and solid fills but still have high optical transmission for those applications that require more matted finishes.

[0108] Textural features of printed clear inks include raised printing or embossed effects such a by textured printing that can result in both a visual and tactile appeal. Depending on the nature of the desired look and texture of the over-printed clear ink, clear ink can be applied with additional colors to create a shadow effect. For those architectures capable of printing many layers of clear ink, tactile prints can be made with varying degrees of optical transmission, especially if it is printed with one or more of CMYK and white inks.

[0109] In embodiments, clear ink compositions herein have water-white or near water-white optical characteristics. While it is not essential that the clear inks herein be exclusively water-white owing to the, in embodiments, very thin printed pile height of about 1 micron in thickness or less once cured, it is an advantageous feature that the printed clear inks do not yellow, blister, haze, etc. over time which would negatively affect the aesthetic quality of the cured print in terms of the observed surface quality and of the underlying image in general. The ink compositions are printed with a printed pile height of, in embodiments, from about 0.3 to about 4 microns, or from about 0.5 to about 3 microns, or from about 0.8 to about 2 microns in thickness, or about 1.5 microns, or about 1 micron, in thickness or less once cured.

[0110] Gloss, a substrate surface property, involves specular reflection, which may be illustrated by a sharply defined light beam reflecting off a smooth, uniform surface. Human perception of gloss is related to the physics of light reflection. That is, when a ray of light reflects off a surface, its angle of incidence is equal to its angle of reflection.

[0111] Gloss properties are generally determined via so-called Gardner Gloss Unit (GGU) values, using a conventional gloss meter equipped with 20/60/85 geometries such as specified in ISO2813/ASTM D523. It is established practice that when determining the gloss of prints, coatings or the like to change the measurement angle of the gloss meter depending on the 60 gloss value. Typically, for relatively low 60 gloss values of less than about 10 GGU, a gloss meter measurement angle of 85 is used while for intermediate 60 gloss values of from about 10 to about 70 GGU, those 60 GGU values are retained while for higher 60 gloss values of more than about 70 GGU, a gloss meter measurement angle of 20 is used. Thus, measurement angles are selected to preserve the linear relationship between the gloss meter results and human perception. Acceptable gloss levels for copies and prints are generally dependent upon a particular market segment involved. Thus, while certain consumers (hereinafter customers) may prefer glossy prints, e.g., with values above 80 GGU units, other customers may prefer a so-called matte look, e.g., with values below 40 GGU units, and still other customers may prefer that a particular image gloss value match the gloss value of an underlying substrate.

[0112] In embodiments, prints prepared with the compositions herein have a gloss value of from about 20 to about 100 GGU, or from about 30 to about 90 GGU, or from about 40 to about 80 GGU.

[0113] Dispersant.

[0114] In some embodiments, if the colorant is present, the colorant is dispersed in a suitable dispersant. In embodiments, suitable dispersants include copolymers and block copolymers containing pigment affinic groups, such as amines, esters, alcohols and carboxylic acids and salts thereof. Illustrative examples of suitable dispersants include dispersants selected from Efka 4008, Efka 4009, Efka 4047, Efka 4520, Efka 4010, Efka 4015, Efka 4020, Efka 4050, Efka 4055, Efka 4080, Efka 4300, Efka 4330, Efka 4400, Efka 4401, Efka 4403, Efka 4406, Efka 4800, all available from BASF, Charlotte, N.C., Disperbyk 101, Disperbyk 102, Disperbyk 107, Disperbyk 108, Disperbyk 109, Disperbyk 110, Disperbyk 111, Disperbyk 112, Disperbyk 115, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 2001, all available from BYK Additives & Instruments, Wesel Germany, Solsperse 24000 SC/GR, Solsperse 26000, Solsperse 32000, Solsperse 36000, Solsperse 39000, Solsperse 41000, Solsperse 71000 all available from Lubrizol Advanced Materials, Inc. Cleveland, Ohio or mixtures or combinations thereof.

[0115] In specific embodiments, the dispersant includes K-Sperse XDA-504 from King Industries, Norfolk, Conn. The dispersant may be present in the ink composition of the instant disclosure in an amount of about 0% to about 30% by weight, or from about 0% to about 20% by weight, or from about 1% to about 10% by weight, or from about 6% to about 10% by weight, based upon the total weight of the white ink composition.

[0116] In certain embodiments, the colorant and the dispersant together are present in the ink composition in an amount of from about 50 percent to about 85 percent by weight based on the total weight of the ink composition.

[0117] The ink compositions can be prepared by any suitable process, such as by simple mixing of the ingredients. One process entails mixing all of the ink ingredients together and optionally filtering the mixture to obtain an ink. Inks can be prepared by mixing the ingredients, heating if desired, and optionally filtering, followed by adding any desired additional additives to the mixture and mixing at room temperature with moderate shaking until a homogeneous mixture is obtained, in embodiments from about 5 to about 10 minutes. Alternatively, the optional ink additives can be mixed with the other ink ingredients during the ink preparation process, which takes place according to any desired procedure, such as by mixing all the ingredients, heating if desired, and optionally filtering.

[0118] In embodiments, a process herein comprises combining at least one component selected from the group consisting of a curable monomer and a curable oligomer, wherein at least one of the curable oligomers is a polyester acrylate oligomer; optionally, at least one non-radiation curable poly-alpha-olefin; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength; optionally, heating; and optionally, filtering; to provide an ink composition.

[0119] The compositions herein can be employed in any suitable or desired apparatus. The present disclosure further provides a method of digital offset printing, which includes applying the ink composition of the present disclosure onto a re-imageable imaging member surface, the re-imageable imaging member having dampening fluid disposed thereon; forming an ink image; and transferring the ink image from the re-imageable surface of the imaging member to a printable substrate.

[0120] An exemplary digital offset printing architecture is shown in FIG. 1 described above. In embodiments, the ink compositions herein can be employed in a device such as the one described in FIG. 1.

[0121] In embodiments, a process of digital offset printing herein comprises applying a composition onto a re-imageable imaging member surface at an ink take up temperature, the re-imageable imaging member having dampening fluid disposed thereon; forming an ink image; transferring the ink image from the re-imageable surface of the imaging member to a printable substrate at an ink transfer temperature; wherein the ink composition comprises at least one component selected from the group consisting of a curable monomer and a curable oligomer; at least one photoinitiator that absorbs at an ultraviolet light-emitting diode wavelength; and at least one photoinitiator that does not absorb radiation at the ultraviolet light-emitting diode wavelength.

[0122] In embodiments, applying the ink composition comprises applying the ink composition using an anilox delivery system.

[0123] In embodiments, the compositions herein function as a digital varnish or overcoat. In embodiments, the printable substrate comprises a pre-imaged substrate; and wherein forming an ink image and transferring the ink image comprises forming and transferring over the pre-image on the substrate.

[0124] Curing of the ink can be effected by exposure of the ink image to actinic radiation at any desired or effective wavelength, in embodiments from about 200 nanometers to about 480 nanometers, although the wavelength can be outside of this range. Exposure to actinic radiation can be for any desired or effective period of time, in embodiments for about 0.2 second to about 30 seconds, or from about 1 second to 15 seconds, although the exposure period can be outside of these ranges. By curing is meant that the curable compounds in the ink undergo an increase in molecular weight upon exposure to actinic radiation, such as (but not limited to) crosslinking, chain lengthening, or the like.

[0125] In embodiments, curing comprises curing at a selected narrow UV LED wavelength, as described herein, in embodiments, at an LED wavelength of 365 nanometers, 385 nanometers, 395 nanometers, or 405 nanometers.

[0126] The printed substrate can be cured by exposure to radiation, in embodiments ultraviolet radiation, in embodiments, an LED wavelength as described herein, at any point in the fabrication process resulting in robust prints.

[0127] Any suitable substrate, recording sheet, or removable support, stage, platform, and the like, can be employed for depositing the ink compositions herein, including plain papers such as XEROX 4024 papers, XEROX Image Series papers, Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coated papers such as Sharp Company silica coated paper, JuJo paper, HAMMERMILL LASERPRINT paper, and the like, glossy coated papers such as XEROX Digital Color Gloss, Sappi Warren Papers LUSTROGLOSS, and the like, transparency materials, fabrics, textile products, plastics, polymeric films, glass, glass plate, inorganic substrates such as metals and wood, as well as meltable or dissolvable substrates, such as waxes or salts, in the case of removable supports for free standing objects, and the like. In certain embodiments, the substrate is selected from the group consisting of paper, plastic, folded paperboard, Kraft paper, and metal.

EXAMPLES

[0128] The following Examples are being submitted to further define various species of the present disclosure. These Examples are intended to be illustrative only and are not intended to limit the scope of the present disclosure. Also, parts and percentages are by weight unless otherwise indicated.

[0129] Various clear compositions including Type I and Type II photoinitiators are prepared that exhibit sufficiently high viscosity and tack to enable the substantial transfer of the clear compositions in digital offset lithography printing processes. Table 1 provides components and amounts (weight percent) for the clear ink compositions with Type I photoinitiators of Examples 1-4. Table 1 provides components and amounts (weight percent) for the clear ink compositions with Type II photoinitiators of Examples 5-8.

[0130] Sartomer CN2282 is tetrafunctional acrylated polyester and is a clear liquid having a specific gravity of 1.15 and a viscosity of 2,500 cps at 60 C. available from Sartomer.

[0131] Ebecryl 80 is an amine modified polyester tetraacrylate available from Allnex.

[0132] Ebecryl 7100 is an oligomeric amine modified acrylate functional resin available from Allnex.

[0133] CN299 is a tetrafunctional acrylated polyester oligomer available from Sartomer.

[0134] CN2302 is a hyperbranched polyester acrylate oligomer available from Sartomer.

[0135] Vybar 260 is a hyper-branched aliphatic polymer available from Baker Hughes.

[0136] OMNIRAD TPO is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide photoinitiator available from IGM Resins.

[0137] OMNIRAD 184 is 1-Hydroxy-cyclohexyl-phenyl-ketone photoinitiator available from IGM Resins.

[0138] GENOCURE DETX is 2,4-diethylthioxanthone available from Rahn AG.

[0139] GENOCURE EMK is a thioxanthone photoinitiator available from Rahn AG.

[0140] Esstech PL-EDB is ethyl-4-dimethylamino benzoate available from ESSTECH, Inc.

[0141] CN3216 is an in-can stabilizer from Sartomer.

Example 1

[0142] Based on a 300 gram total scale of preparation of the clear ink composition, the formulation of the components shown in Table 1, the first set of ink base components (including the oligomers and thermal stabilizer) are added in a 1 Liter stainless steel vessel. The vessel is placed on a heating mantel, available from IKA equipped with a thermocouple and stirrer apparatus also available from IKA and with an anchor impeller. The components in the vessel are stirred at about 200 revolutions per minute (RPM) for about 30 minutes at about 85 C. With the vehicle base components solubilized, the given quantity of OMNIRAD TPO and OMNIRAD 184 are added slowly while stirring. The preparation is allowed to stir for about 60 minutes at about 200 RPM at about 85 C. at which point it is discharged into glass amber jars.

Example 2

[0143] Based on the formulation of the components shown in Table 1, the Example 2 preparation proceeds as that of Example 1.

Example 3

[0144] Based on the formulation of the components shown in Table 1, the Example 2 preparation proceeds as that of Example 1, except that after the stirring of the photoinitiators, the given quantity of Vybar 260 is slowly added to the mixing preparation and stirred for an additional 60 minutes at 200 RPM at about 85 C.

Example 4

[0145] Based on the formulation of the components shown in Table 1, the Example 2 preparation proceeds as that of Example 1, except that after the stirring of the photoinitiators, the given quantity of Vybar 260 is slowly added to the mixing preparation and stirred for an additional 60 minutes at 200 RPM at about 85 C.

Example 5

[0146] Based on a 300 gram total scale of preparation of the clear ink composition, the formulation of the components shown in Table 2, the first set of ink base components (including the oligomers, the Esstech PL-EDB co-initiator, and thermal stabilizer) are added in a 1 Liter stainless steel vessel. The vessel is placed on a heating mantel, available from IKA equipped with a thermocouple and stirrer apparatus also available from IKA and with an anchor impeller. The components in the vessel are stirred at about 200 revolutions per minute (RPM) for about 30 minutes at about 85 C. With the vehicle base components solubilized, the given quantity of GENOCURE EMK is added slowly while stirring. The preparation is allowed to stir for about 60 minutes at about 200 RPM at about 85 C. The given quantity of Vybar 260 is slowly added to the mixing preparation and stirred for an additional 60 minutes at 200 RPM at about 85 C. at which point it is discharged into glass amber jars.

Example 6

[0147] Based on the formulation of the components shown in Table 2, the Example 6 ink proceeds in the same manner as the Example 5 ink except that the Allnex Ebecryl 7100 co-initiator replaces the Esstech PL-EDB co-initiator.

Example 7

[0148] Based on the formulation of the components shown in Table 2, the Example 7 ink proceeds in the same manner as the Example 5 ink except that the GENOCURE DETX photoinitiator replaces the GENOCURE EMK photoinitiator.

Example 8

[0149] Based on the formulation of the components shown in Table 2, the Example 8 ink proceeds in the same manner as the Example 5 ink except that the GENOCURE DETX photoinitiator replaces the GENOCURE EMK photoinitiator and the Allnex Ebecryl 7100 co-initiator replaces the Esstech PL-EDB co-initiator.

TABLE-US-00001 TABLE 1 Weight Percent Component Example 1 Example 2 Example 3 Example 4 Sartomer 45 25 40 20 CN2282 Ebecryl 80 25 35 25 35 Sartomer 21 31 21 31 CN299 Sartomer 5 5 5 5 CN2302 Vybar 260 5 5 OMNIRAD 3 3 3 3 TPO OMNIRAD 0.5 0.5 0.5 0.5 184 Sartomer 0.5 0.5 0.5 0.5 CN3216 Total 100 100 100 100

TABLE-US-00002 TABLE 2 Weight Percent Component Example 5 Example 6 Example 7 Example 8 Sartomer 37.5 25 37.5 25 CN2282 Ebecryl 80 21 23.5 21 23.5 Sartomer 21 31 21 31 CN299 Sartomer 5 5 5 5 CN2302 Vybar 260 5 5 5 5 GENOCURE 4 4 EMK GENOCURE 4 4 DETX Esstech PL- 6 6 EDB Ebecryl 6 6 7100 Sartomer 0.5 0.5 0.5 0.5 CN3216 Total 100 100 100 100

[0150] It will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims. Unless specifically recited in a claim, steps or components of claims should not be implied or imported from the specification or any other claims as to any particular order, number, position, size, shape, angle, color, or material.