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Title:
RADIATION CURABLE INK COMPOSITIONS, PRINTED ARTICLES, AND METHODS OF USING THE SAME
Document Type and Number:
WIPO Patent Application WO/2018/182040
Kind Code:
A1
Abstract:
A radiation curable ink composition that includes (A) a mono-ethylenically unsaturated oligomer, (B) a mono-ethylenically unsaturated monomer, and (C) an acrylate ester of a carboxylic acid ester and which is substantially free of a photoinitiator. A printed article including the radiation curable ink composition in cured form, and a method of forming an image with the radiation curable ink composition are also provided.

Inventors:
CONTRACTOR MUSLIM (US)
CUMMINGS STEPHEN (US)
BUCHANAN STEPHEN (US)
Application Number:
PCT/JP2018/014035
Publication Date:
October 04, 2018
Filing Date:
March 26, 2018
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
KAO CORP (JP)
International Classes:
C09D11/10; B41M7/00; C09D11/30
Foreign References:
US20080090930A12008-04-17
US20100190031A12010-07-29
US20100183819A12010-07-22
US6221137B12001-04-24
US5621022A1997-04-15
US5231135A1993-07-27
US6472523B12002-10-29
US6726755B22004-04-27
US6476219B12002-11-05
US6576747B12003-06-10
US6713614B22004-03-30
US6663703B12003-12-16
US6755902B22004-06-29
US6590082B12003-07-08
US6696552B22004-02-24
US6576748B12003-06-10
US6646111B12003-11-11
US6673139B12004-01-06
US6958406B22005-10-25
US6821327B22004-11-23
US7053227B22006-05-30
US7381831B12008-06-03
US7427323B12008-09-23
Other References:
FONZE ANNIE ET AL: "Versatile versatate - Acrylate esters of glycidyl versatate can outperform conventional monomers in UV curing laminating and pressure-sensitive adhesives", EUROPEAN COATINGS JOUR, VINCENTZ VERLAG, DE, no. 1-2, 1 January 2006 (2006-01-01), pages 42 - 45, XP009186941, ISSN: 0930-3847
Attorney, Agent or Firm:
KATAOKA, Makoto et al. (JP)
Download PDF:
Claims:
CLAIMS

1. A radiation curable ink composition, comprising:

(A) a mono-ethylenically unsaturated oligomer;

(B) a mono-ethylenically unsaturated monomer; and

(C) an acrylate ester of a carboxylic acid ester of formula (I)

wherein R1, R2, and R3 are each independently an alkyl, an aryl, an alkylaryl, an alkoxyaryl, or a cycloaliphatic group having 1 to 10 carbon atoms, and R is a group selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, and alkoxy phenyl;

wherein the radiation curable ink composition is substantially free of a photoinitiator.

2. The radiation curable ink composition according to claim 1, wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a weight of the mono-ethylenically unsaturated monomer (B).

3. The radiation curable ink composition according to claims 1 or 2, wherein the mono-ethylenically unsaturated oligomer (A) is present in an amount of about 8 to about 30 wt.%, based on a total weight of the radiation curable ink composition.

4. The radiation curable ink composition according to any one of claims 1 to 3, wherein the mono-ethylenically unsaturated monomer (B) is present in an amount of about 30 to about 70 wt.%, based on a total weight of the radiation curable ink composition. 5. The radiation curable ink composition according to any one of claims 1 to 4, wherein the acrylate ester of a carboxylic acid ester of formula (I) (C) is present in an amount of about 0.5 to about 15 wt.%, based on a total weight of the radiation curable ink

composition. 6. The radiation curable ink composition according to any one of claims 1 to 5, further comprising (D) a poly-ethylenically unsaturated component.

7. The radiation curable ink composition according to claim 6, wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a combined weight of the mono- ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D).

8. The radiation curable ink composition according to claim 6 or 7, wherein a weight ratio of the combined weight of the mono-ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D) to the combined weight of the mono- ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) ((B+D)/(A+C)) is 2:1 to 5:1.

9. The radiation curable ink composition according to any one of claims 6 to 8, wherein the poly-ethylenically unsaturated component (D) is a mixture of a poly- ethylenically unsaturated monomer (Dl) and a poly-ethylenically unsaturated oligomer (D2). 10. The radiation curable ink composition according to any one of claims 6 to 9, wherein the poly-ethylenically unsaturated component (D) is present in an amount of about 10 to about 40 wt.%, based on a total weight of the radiation curable ink composition.

11. The radiation curable ink composition according to any one of claims 1 to 10, which is substantially free of solvent.

12. The radiation curable ink composition according to any of claims 1 to 11, wherein R1 and R2 combined have 6-8 carbon atoms, R3 is methyl, and R4 is hydrogen. 13. The radiation curable ink composition according to any one of claims 1 to 12, further comprising a colorant (E) and at least one additive (F) selected from the group consisting of a surfactant, a stabilizer, and an adhesion promoter.

14. The radiation curable ink composition according to any one of claims 1 to 13, which exhibits a migration level of less than 10 ppb after being cured on an article.

15. A printed article, comprising: a substrate and a cured ink composition on the substrate, wherein the cured ink composition is formed from the radiation curable ink composition according to any one of claims 1 to 14.

16. The printed article according to claim 15, wherein the printed article is a tag or label, a lottery ticket, a publication, packaging, a folding carton, a cup, a tub, or a point-of- sale display.

17. The printed article according to claim 15 or 16, wherein migration of the cured ink composition is less than 10 ppb.

18. A method of forming an image on a substrate, comprising:

applying a radiation curable ink composition onto a surface of the substrate, wherein the radiation curable ink composition comprises

(A) a mono-ethylenically unsaturated oligomer,

(B) a mono-ethylenically unsaturated monomer, and

(C) an acrylate ester of a carboxylic acid ester of formula (I)

wherein R1, R2, and R3 are each independently an alkyl, an aryl, an alkylaryl, an alkoxyaryl, or a cycloaliphatic group having 1 to 10 carbon atoms, and R4 is a group selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, and alkoxy phenyl; and

exposing the radiation curable ink composition to electron beam radiation to at least partially cure the radiation curable ink composition to form a cured ink composition on the surface of the substrate.

19. The method according to claim 18, wherein the radiation curable ink composition further comprises a poly-ethylenically unsaturated component (D), and wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a combined weight of the mono- ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component

(D).

20. The method according to claim 18 or 19, wherein the cured ink composition exhibits a migration level of less than 10 ppb.

21. A radiation curable ink composition, comprising:

(A) a mono-ethylenically unsaturated oligomer;

(B) a mono-ethylenically unsaturated monomer; and

(C) an acrylate ester of a carboxylic acid ester of formula (I)

(I) wherein R1, R2, and R3 are each independently an alkyl, an aryl, an alkylaryl, an alkoxyaryl, or a cycloaliphatic group having 1 to 10 carbon atoms, and R4 is a group selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, and alkoxy phenyl;

wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a weight of the mono-ethylenically unsaturated monomer (B).

22. The radiation curable ink composition according to claim 21, wherein the mono- ethylenically unsaturated oligomer (A) is present in an amount of about 8 to about 30 wt.%, based on a total weight of the radiation curable ink composition.

23. The radiation curable ink composition according to claim 21 or 22, wherein the mono-ethylenically unsaturated monomer (B) is present in an amount of about 30 to about 70 wt.%, based on a total weight of the radiation curable ink composition.

24. The radiation curable ink composition according to any one of claims 21 to 23, wherein the acrylate ester of a carboxylic acid ester of formula (I) (C) is present in an amount of about 0.5 to about 15 wt.%, based on a total weight of the radiation curable ink

composition.

25. The radiation curable ink composition according to any one of claims 21 to 24, further comprising (D) a poly-ethylenically unsaturated component.

26. The radiation curable ink composition according to claim 25, wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a combined weight of the mono- ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D).

27. The radiation curable ink composition according to claim 25 or 26, wherein a weight ratio of the combined weight of the mono-ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D) to the combined weight of the mono- ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) ((B+D)/(A+C)) is 2: 1 to 5 : 1.

28. The radiation curable ink composition according to any one of claims 25 to 27, wherein the poly-ethylenically unsaturated component (D) is a mixture of a poly- ethylenically unsaturated monomer (Dl) and a poly-ethylenically unsaturated oligomer (D2).

29. The radiation curable ink composition according to any one of claims 25 to 28, wherein the poly-ethylenically unsaturated component (D) is present in an amount of about 10 to about 40 wt.%, based on a total weight of the radiation curable ink composition.

30. The radiation curable ink composition according to any one of claims 21 to 29, which is substantially free of solvent.

31. The radiation curable ink composition according to any one of claims 21 to 30, wherein R1 and R2 combined have 6-8 carbon atoms, R3 is methyl, and R4 is hydrogen.

32. The radiation curable ink composition according to any one of claims 21 to 31, further comprising a colorant (E) and at least one additive (F) selected from the group consisting of a surfactant, a stabilizer, and an adhesion promoter.

33. The radiation curable ink composition according to any one of claims 21 to 32, which exhibits a migration level of less than 10 ppb after being cured on an article.

34. A printed article, comprising:

a substrate and a cured ink composition on the substrate, wherein the cured ink composition is formed from the radiation curable ink composition according to any one of claims 21 to 33.

35. The printed article according to claim 34, wherein the printed article is a tag or label, a lottery ticket, a publication, packaging, a folding carton, a cup, a tub, or a point-of- sale display.

36. The printed article according to claim 34 or 35, wherein migration of the cured ink composition is less than 10 ppb.

Description:
DESCRIPTION

TITLE OF THE INVENTION

RADIATION CURABLE INK COMPOSITIONS, PRINTED ARTICLES, AND METHODS OF USING THE SAME

FIELD OF THE INVENTION [0001]

The present invention relates to radiation curable ink compositions, printed articles, and methods of forming an image on a substrate using the radiation curable ink compositions.

BACKGROUND OF THE INVENTION [0002]

The "background" description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present invention. [0003] Sheetfed offset lithography is the dominant printing process for the printing of food packaging. High reliability of inkjet printing on food packaging is not only required for reasons of productivity in an industrial environment, but also for reasons of food safety. Inks to be used on food packaging should not contaminate the food or impart any unnatural odor.

Contamination, in this context, can result from migration of components of an ink into the foodstuff or other packaged material or from undesirable odors imparted to the packaged material by the ink. Migration of ink components into foodstuffs or pharmaceuticals may present a health risk and consequently should be kept to a minimum. Several food packaging regulations and guidelines exist which provide listings of acceptable ink components as well as stipulations regarding acceptable levels of migration (e.g., the European Printing Ink Association (EuPIA) and associated GMP guidelines EuPIA Inventory List 2012, Swiss Ordinance on Materials and Articles in Contact with Food, SR 817.023.21, Nestle Guidance Notes, FDA Title 21 CFR or FCN - Food Contact Notification). Specific migration limits (SML) of consumer product packaging inks are typically below 50 ppb and sometimes migration levels below 10 ppb are required.

[0004]

Inkjet inks, such as ultraviolet (UV) and electron beam (EB) curable inks, generally require low viscosity in order to jet properly from print heads. Low viscosity inks are typically achieved using low molecular weight monomers, and these monomers often have associated undesirable odors and do not cure as completely as some higher molecular weight monomers, leading to unacceptable migration levels. Therefore, special attention is paid to photoinitiator systems, especially in UV curable inks, to aid complete curing of low molecular weight ink components. However, photoinitiators themselves can also contribute to migration issues, due to migration of non-polymerized photoinitiators and/or photoinitiator fragments.

[0005]

In view of the forgoing, there is a need for curable ink compositions for use in inkjet printing methods that do not require photoinitiators, and which form cured ink compositions with minimal migration. SUMMARY OF THE INVENTION

[0006]

Accordingly, it is one object of the present invention to provide novel radiation curable ink compositions.

It is another object of the present invention to provide novel printed articles which contain cured ink compositions formed from the radiation curable ink compositions.

It is another object of the present invention to provide novel methods of forming an image on a substrate by applying the radiation curable ink compositions onto the substrate and exposing to electron beam radiation.

[0007]

These and other objects, which will become apparent during the following detailed description, have been achieved by the inventors' discovery that the occurrence of migration can be suppressed by the following ink compositions.

Thus, the present invention provides:

(1) A radiation curable ink composition, comprising:

(A) a mono-ethylenically unsaturated oligomer;

(B) a mono-ethylenically unsaturated monomer; and

(C) an acrylate ester of a carboxylic acid ester of formula (I)

wherein R 1 , R 2 , and R 3 are each independently an alkyl, an aryl, an alkylaryl, an alkoxyaryl, or a cycloaliphatic group having 1 to 10 carbon atoms, and R 4 is a group selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, and alkoxy phenyl;

wherein the radiation curable ink composition is substantially free of a photoinitiator.

[0008]

(2) The radiation curable ink composition according to (1), wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a weight of the mono-ethylenically unsaturated monomer (B).

(3) The radiation curable ink composition according to (1) or (2), wherein the mono- ethylenically unsaturated oligomer (A) is present in an amount of about 8 to about 30 wt.%, based on a total weight of the radiation curable ink composition.

(4) The radiation curable ink composition according to any one of (1) to (3), wherein the mono-ethylenically unsaturated monomer (B) is present in an amount of about 30 to about 70 wt.%, based on a total weight of the radiation curable ink composition.

(5) The radiation curable ink composition according to any one of (1) to (4), wherein the acrylate ester of a carboxylic acid ester of formula (I) (C) is present in an amount of about 0.5 to about 15 wt.%, based on a total weight of the radiation curable ink composition.

(6) The radiation curable ink composition according to any one of (1) to (5), further comprising (D) a poly-ethylenically unsaturated component.

[0009] (7) The radiation curable ink composition according to (6), wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a combined weight of the mono- ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D).

(8) The radiation curable ink composition according to (6) or (7), wherein a weight ratio of the combined weight of the mono-ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D) to the combined weight of the mono- ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) ((B+D)/(A+C)) is 2:1 to 5:1.

(9) The radiation curable ink composition according to any one of (6) to (8), wherein the poly-ethylenically unsaturated component (D) is a mixture of a poly-ethylenically unsaturated monomer (Dl) and a poly-ethylenically unsaturated oligomer (D2).

(10) The radiation curable ink composition according to any one of (6) to (9), wherein the poly-ethylenically unsaturated component (D) is present in an amount of about 10 to about 40 wt.%, based on a total weight of the radiation curable ink composition.

[0010]

(11) The radiation curable ink composition according to any one of (1) to (10), which is substantially free of solvent. (12) The radiation curable ink composition according to any one of (1) to (11), wherein R 1 and R 2 combined have 6-8 carbon atoms, R 3 is methyl, and R 4 is hydrogen.

(13) The radiation curable ink composition according to any one of (1) to (12), further comprising a colorant (E) and at least one additive (F) selected from the group consisting of a surfactant, a stabilizer, and an adhesion promoter.

(14) The radiation curable ink composition according to any one of (1) to (13), which exhibits a migration level of less than 10 ppb after being cured on an article.

[0011]

(15) A printed article, comprising:

a substrate and a cured ink composition on the substrate, wherein the cured ink composition is formed from the radiation curable ink composition according to any one of (1) to (14).

(16) The printed article according to (15), wherein the printed article is a tag or label, a lottery ticket, a publication, packaging, a folding carton, a cup, a tub, or a point-of-sale display.

(17) The printed article according to (15) or (16), wherein migration of the cured ink composition is less than 10 ppb.

[0012]

(18) A method of forming an image on a substrate, comprising: applying a radiation curable ink composition onto a surface of the substrate, wherein the radiation curable ink composition comprises

(A) a mono-ethylenically unsaturated oligomer,

(B) a mono-ethylenically unsaturated monomer, and

(C) an acrylate ester of a carboxylic acid ester of formula (I)

wherein R 1 , R 2 , and R 3 are each independently an alkyl, an aryl, an alkylaryl, an alkoxyaryl, or a cycloaliphatic group having 1 to 10 carbon atoms, and R 4 is a group selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, and alkoxy phenyl; and

exposing the radiation curable ink composition to electron beam radiation to at least partially cure the radiation curable ink composition to form a cured ink composition on the surface of the substrate.

[0013]

(19) The method according to (18), wherein the radiation curable ink composition further comprises a poly-ethylenically unsaturated component (D), and wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a combined weight of the mono- ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D). (20) The method according to (18) or (19), wherein the cured ink composition exhibits a migration level of less than 10 ppb.

[0014]

(21) A radiation curable ink composition, comprising:

(A) a mono-ethylenically unsaturated oligomer;

(B) a mono-ethylenically unsaturated monomer; and

(C) an acrylate ester of a carboxylic acid ester of formula (I)

wherein R 1 , R 2 , and R 3 are each independently an alkyl, an aryl, an alkylaryl, an alkoxyaryl, or a cycloaliphatic group having 1 to 10 carbon atoms, and R 4 is a group selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, and alkoxy phenyl;

wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a weight of the mono-ethylenically unsaturated monomer (B).

[0015]

(22) The radiation curable ink composition according to (21), wherein the mono- ethylenically unsaturated oligomer (A) is present in an amount of about 8 to about 30 wt.%, based on a total weight of the radiation curable ink composition. (23) The radiation curable ink composition according to (21) or (22), wherein the mono-ethylenically unsaturated monomer (B) is present in an amount of about 30 to about 70 wt.%, based on a total weight of the radiation curable ink composition. (24) The radiation curable ink composition according to any one of (21) to (23), wherein the aery late ester of a carboxylic acid ester of formula (I) (C) is present in an amount of about 0.5 to about 15 wt.%, based on a total weight of the radiation curable ink

composition. (25) The radiation curable ink composition according to any one of (21) to (24), further comprising (D) a poly-ethylenically unsaturated component.

[0016]

(26) The radiation curable ink composition according to (25), wherein a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) is less than a combined weight of the mono- ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D).

(27) The radiation curable ink composition according to (25) or (26), wherein a weight ratio of the combined weight of the mono-ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D) to the combined weight of the mono- ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) ((B+D)/(A+C)) is 2:1 to 5:1. (28) The radiation curable ink composition according to any one of (25) to (27), wherein the poly-ethylenically unsaturated component (D) is a mixture of a poly- ethylenically unsaturated monomer (Dl) and a poly-ethylenically unsaturated oligomer (D2).

(29) The radiation curable ink composition according to any one of (25) to (28), wherein the poly-ethylenically unsaturated component (D) is present in an amount of about 10 to about 40 wt.%, based on a total weight of the radiation curable ink composition.

[0017]

(30) The radiation curable ink composition according to any one of (21) to (29), which is substantially free of solvent.

(31) The radiation curable ink composition according to any one of (21) to (30), wherein R 1 and R 2 combined have 6-8 carbon atoms, R 3 is methyl, and R 4 is hydrogen.

(32) The radiation curable ink composition according to any one of (21) to (31), further comprising a colorant (E) and at least one additive (F) selected from the group consisting of a surfactant, a stabilizer, and an adhesion promoter.

(33) The radiation curable ink composition according to any one of (21) to (32), which exhibits a migration level of less than 10 ppb after being cured on an article.

[0018]

(34) A printed article, comprising: a substrate and a cured ink composition on the substrate, wherein the cured ink composition is formed from the radiation curable ink composition according to any one of (21) to (33). (35) The printed article according to (34), wherein the printed article is a tag or label, a lottery ticket, a publication, packaging, a folding carton, a cup, a tub, or a point-of-sale display.

(36) The printed article according to (34) or (35), wherein migration of the cured ink composition is less than 10 ppb.

[0019]

The foregoing paragraphs have been provided by way of general introduction, and are not intended to limit the scope of the following claims. The described embodiments, together with further advantages, will be best understood by reference to the following detailed description.

DETAILED DESCRIPTION OF THE INVENTION

[0020]

In the following description, it is understood that other embodiments may be utilized and structural and operational changes may be made without departure from the scope of the present embodiments disclosed herein.

[0021] The term "curable" describes, for example, an ink composition with an ability to polymerize, harden, and/or cross-link in response to a suitable curing stimulus such as actinic radiation (e.g., ultraviolet (UV) energy, infrared (IR) energy, light emitting diode (LED) energy), electron beam (EB) energy, heat energy, or other source of energy. A curable ink composition typically is liquid at 25°C prior to curing. A curable ink composition can be used to print on a substrate, forming a film of printed ink or coating. The film of curable ink is cured by hardening, polymerizing and/or cross-linking the ink or coating to form a cured ink. The term "radiation curable" refers, for example, to all forms of curing upon exposure to a radiation source, including light sources (e.g., actinic radiation, such as ultraviolet (UV) light, for example having a wavelength of 200-400 nm or more rarely visible light), a heat source in the presence or absence of high-temperature thermal initiators, and an accelerated particle source (e.g., electron beam (EB) radiation) in the presence or absence of initiators, and appropriate combinations thereof.

[0022]

As used herein, the term "cured" refers to a curable ink composition whereby curable components present in the curable ink composition have undergone polymerization, crosslinking, or hardening to form a polymerized or cross-linked network, and includes both partially cured and substantially cured ink compositions. When the curable ink composition cures from a liquid state to a solid state, the curable monomers and/or oligomers form (1) chemical bonds, (2) mechanical bonds, or (3) a combination of a chemical and mechanical bonds. As used herein, "partially cured" or "partially cure" refers to a curable ink

composition where 20 to 75 wt.% of the curable functional groups present in the starting composition are polymerized and/or crosslinked, and the term "substantially cured" or "substantially cure" refers to a curable ink composition where more than 75 wt.%, preferably more than 80 wt.%, more preferably more than 90 wt.% of the curable functional groups present in the starting composition undergo conversion (i.e., polymerized and/or crosslinked). Likewise, "at least partially cured" or "at least partially cure" refers to a curable ink composition where at least 20 wt.%, preferably at least 30 wt.%, more preferably at least 40 wt.%, even more preferably at least 50 wt.% (and up to 100 wt.%) of the curable functional groups present in the starting composition have been polymerized and/or crosslinked. The degree of curing described above may be quantified by measuring percent reacted

ethylenically unsaturated groups using Fourier Transform Infrared spectroscopy (FTIR).

[0023]

Suitable ethylenically unsaturated groups that may be cured in the present ink compositions include acrylate, methacrylate, acrylamide, methacrylamide, vinyl, allyl, or other ethylenically unsaturated functional groups. The materials including such groups can be in the form of monomers, oligomers, and/or polymers, or mixtures thereof. As used herein, the term "monomer" is a compound whose molecules can join together to form oligomers or polymers. "Oligomers" as used herein is a polymeric compound containing relatively few repeated structural units (i.e., 2, 3, or 4 repeat units). A "polymer" as used herein is a large molecule, or macromolecule, composed of many repeated structural units (i.e., 5 or more repeat units). Ethylenically unsaturated alkoxylated compounds are excluded from the definition of an oligomer or a polymer and are herein considered monomers unless indicated otherwise. For example, propoxylated neopentyl glycol diacrylate is considered a monomer.

[0024]

As used herein, "mono-ethylenically unsaturated" refers to components (monomers or oligomers) of the radiation curable ink compositions which have one ethylenically

unsaturated group per molecule, while "poly-ethylenically unsaturated" refers to those components (monomers or oligomers) having two or more (e.g., 2, 3, 4, 5, 6, 7, 8, etc. ) ethylenically unsaturated groups per molecule. For example a "mono-ethylenically unsaturated oligomer" refers to an oligomeric material containing one ethylenically unsaturated group that may participate in curing when exposed to a radiation source.

[0025]

When referencing radiation curable ink compositions, the phrase "substantially free", unless otherwise specified, describes an amount of a particular component (e.g., a

photoinitiator) present in the ink composition being less than about 1 wt.%, preferably less than about 0.5 wt.%, more preferably less than about 0.1 wt.%, even more preferably less than about 0.05 wt.%, yet even more preferably 0 wt.%, relative to a total weight of the radiation curable ink composition.

[0026]

Radiation Curable Ink Compositions

The present disclosure is directed to radiation curable ink compositions that possess suitable physical and chemical stability at both ambient temperatures and print head operating temperatures, and after curing, possess advantageous adhesion properties, rub and scratch resistance, and low migration tendencies. Radiation curable ink compositions of the present disclosure comprise radiation curable materials, which are generally liquids of low volatility, both at ambient temperature and at temperatures employed in the print heads. Such compositions generally include the following components: (A) a mono-ethylenically unsaturated oligomer, (B) a mono-ethylenically unsaturated monomer, (C) an acrylate ester of a carboxylic acid, optionally (D) a poly-ethylenically unsaturated component, optionally (E) a colorant, and optionally (F) an additive.

[0027] (A) Mono-Ethylenically Unsaturated Oligomer

Mono-ethylenically unsaturated oligomers generally provide fast curing, strong yet flexible cured films, high elongation, and chemical resistance. Both aliphatic and aromatic mono-ethylenically unsaturated oligomers may be employed herein, for example, acrylates or methacrylates of straight chain, branched chain, or cyclic alkyl alcohols, and aromatic acrylic oligomers, including polyether alcohols thereof. Specific examples include aliphatic monoacrylate oligomers (e.g., CN152, CN130), aromatic monoacrylate oligomers (e.g., CN131), acrylic oligomers (e.g., CN2285) and the like, as well as mixtures thereof. In addition to acrylate or methacrylate groups, the mono-ethylenically unsaturated oligomers employed herein may also possess hydroxyl functionality, for example CN3100 and CN3105. All of the oligomers disclosed above are available from Sartomer Co. Inc. (Exton, Pa.).

Preferably, the mono-ethylenically unsaturated oligomer is at least one selected from the group consisting of CN3100, CN3105, and CN131.

[0028]

The mono-ethylenically unsaturated oligomer may be present in the radiation curable ink composition in an amount of at least about 8 wt.%, preferably at least about 10 wt.%, preferably at least about 11 wt.%, preferably at least about 12 wt.%, more preferably at least about 13 wt.%), even more preferably at least about 14 wt.%, even more preferably at least about 15 wt.%), yet even more preferably at least about 16 wt.%, and up to about 30 wt.%, preferably up to about 28 wt.%, preferably up to about 26 wt.%>, more preferably up to about 24 wt.%, even more preferably up to about 22 wt.%, yet even more preferably up to about 20 wt.%), or in a range of 12-20 wt.%, preferably 14-18 wt.%, more preferably 15-17 wt.% based on a total weight of the radiation curable ink composition.

[0029] In some embodiments, the mono-ethylenically unsaturated oligomer has a number average molecular weight of about 250 g/mol, preferably about 300 g/mol, more preferably about 350 g/mol, and up to about 50,000 g/mol, preferably up to about 30,000 g/mol, preferably up to about 10,000 g/mol, more preferably up to about 5,000 g/mol, even more preferably up to about 1 ,000 g/mol. The viscosity of the mono-ethylenically unsaturated oligomer (A) is typically from about 50 cPs, preferably from about 70 cPs, more preferable from about 90 cPs, and up to about 1,200 cPs, preferably up to about 1,100 cPs, and more preferably up to about 1,000 cPs at 25°C, although viscosities outside of this range are possible and the mono-ethylenically unsaturated oligomers may still function as intended.

[0030]

(B Mono-Ethylenically Unsaturated Monomer

Mono-ethylenically unsaturated monomers (B) may increase the chain length of oligomers and build molecular weight, without excessive crosslinking, contributing to low modulus, high elongation, flexibility, desirable hardness properties, thermal resistance, low shrinkage, improved water resistance, resiliency, and impact resistance of the cured ink compositions. The mono-ethylenically unsaturated monomer may be an acrylate ester monomer having hydroxyl functionality. Suitable acrylate ester monomers include hydroxyl functional monoacrylates, or their mono(meth)acrylates of straight chain, branched chain, or cyclic alkyl alcohols, including polyether alcohols. Suitable acrylate ester monomers having hydroxyl functionality include, but are not limited to, hydroxyalkylacrylates and

hydroxyalkyl(meth)acrylates wherein the hydroxyalkyl group contains 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, preferably 3 to 8 carbon atoms. Examples include hydroxyethylacrylate, hydroxyethyl(meth)acrylate, hydroxypropylacrylate,

hydroxypropyl(meth)acrylate, hydroxybutylacrylate, hydroxybutyl(meth)acrylate, 2-hydroxy- 3-phenyloxypropylacrylate, 2-hydroxy-3-phenyloxypropyl(meth)acrylate, 1 ,4-butanediol monoacrylate, 1 ,4-butanediol mono(meth)acrylate, 4-hydroxycyclohexylacrylate, 4- hydroxycyclohexyl(meth)acrylate, 1 ,6-hexanediol monoacrylate, 1,6-hexanediol

mono(meth)acrylate, 2-[(l ',1 ',1 '-trifluoro-2'-(trifluoromethyl)-2'-hydroxy)propyl]-3- norbornyl methacrylate, and any combination or subset thereof.

[0031]

The mono-ethylenically unsaturated monomer (B) may be an aliphatic mono- ethylenically unsaturated component. Aliphatic mono-ethylenically unsaturated materials for use in radiation curable ink compositions include, for example, acrylates and (meth)acrylates of straight chain, branched chain, or cyclic alkyl alcohols, such as alcohols having 1-20 carbon atoms, preferably 4-16 carbon atoms, including polyether alcohols thereof, as well as acrylates or (meth)acrylates of aromatic, bicyclic or heterocyclic alcohols, optionally containing an aliphatic linking group between the acrylate and the aromatic group, bicycle or heterocycle. Exemplary aliphatic mono-ethylenically unsaturated monomers include 3,3,5- trimethylcyclohexyl acrylate (e.g., SR420), 3,3,5-trimethylcyclohexyl methacrylate (e.g., CD421), 3,5,5-trimethylhexyl acrylate, cyclohexyl methacrylate, phenyl methacrylate, 4-tert- butylcyclohexyl acrylate (Laromer TBCH), dicyclopentadienyl methacrylate (e.g., CD535), diethylene glycol methyl ether methacrylate (e.g., CD545), methoxy polyethylene glycol (550) monoacrylate monomer (CD553), alkoxylated tetrahydrofurfuryl acrylate (e.g., CD611), ethoxylated (4) nonyl phenol methacrylate (e.g., CD612), ethoxylated nonyl phenol acrylate (e.g., CD613), triethylene glycol ethyl ether methacrylate (e.g., CD730),

monofunctional acid ester (e.g., CD9050), alkoxylated lauryl acrylate (e.g., CD9075), alkoxylated phenol acrylate (e.g., CD9087), tetrahydrofurfuryl methacrylate (e.g., SR203), isodecyl methacrylate (e.g., SR242), 2-(2-ethoxyethoxy) ethyl acrylate (e.g., SR256), stearyl acrylate (e.g., SR257), tetrahydrofurfuryl acrylate (e.g., SR285), lauryl methacrylate (e.g., SR313A), stearyl methacrylate (e.g., SR324), lauryl acrylate (e.g., SR335), 2-phenoxylethyl acrylate (e.g., SR339), 2-phenoxylethyl methacrylate (e.g., SR340), isodecyl acrylate (e.g., SR395), isobornyl methacrylate (e.g., SR423A), isooctyl acrylate (e.g., SR440), octadecyl acrylate (SR484), tridecyl acrylate (SR489D), tridecyl methacrylate (SR493), caprolactone acrylate (e.g., SR495), ethoxylated (4) nonylphenol acrylate (e.g., SR504), isobornyl acrylate (e.g., SR506A), cyclic trimethylolpropane formal acrylate (e.g., SR531), methoxy

polyethylene glycol (350) monomethacrylate (e.g., SR550), and the like. These monomers may be used singly or in combination of two or more thereof. All of the monomers disclosed above are available from Sartomer Co. Inc. (Exton, Pa.), BASF Dispersions & Resins, North America, or Sigma Aldrich.

[0032]

In some embodiments, the mono-ethylenically unsaturated monomer is preferably at least one selected from the group consisting of 4-teri-butylcyclohexyl acrylate, isobornyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, and 2-phenoxylethyl acrylate.

The mono-ethylenically unsaturated monomer employed in the radiation curable ink compositions may include an aliphatic, aromatic, alkoxy, aryloxy mono-functional vinyl ether and vinyl ether alcohol. Suitable examples include vinyl ethers such as Rapi-cure HBVE, Rapi-cure CVE, Rapi-cure EHVE, all available from Ashland Specialty Company, 4- hydroxymethyl cyclohexylmethyl vinyl ether (Novachem), dodecylvinyl ether, and octadecylvinylether.

[0033]

The mono-ethylenically unsaturated monomer may be present in the radiation curable ink composition in an amount of at least about 30 wt.%, preferably at least about 35 wt.%, preferably at least about 40 wt.%, preferably at least about 42 wt.%, more preferably at least about 44 wt.%, even more preferably at least about 45 wt.%, even more preferably at least about 46 wt.%, yet even more preferably at least about 47 wt.%, and up to about 70 wt.%, preferably up to about 65 wt.%, preferably up to about 60 wt.%, more preferably up to about 55 wt.%, even more preferably up to about 50 wt.%, yet even more preferably up to about 47 wt.%, or in a range of 40-50 wt.%, preferably 42-48 wt.%, more preferably 45-47 wt.% based on a total weight of the radiation curable ink composition.

[0034]

The viscosity of the mono-ethylenically unsaturated monomer (B) is typically from about 2 cPs, preferably from about 3 cPs, more preferable from about 5 cPs, and up to about 300 cPs, preferably up to about 200 cPs, preferably up to about 150 cPs, preferably up to about 145 cPs, and more preferably up to about 140 cPs at 25°C, although viscosities outside of this range are possible and the mono-ethylenically unsaturated monomers may still function as intended.

[0035]

(C) Acrylate Ester of a Carboxylic Acid Ester

The radiation curable ink compositions of the present disclosure include an acrylate ester of a carboxylic acid ester, which are compounds of the general formula (I)

wherein R 1 , R 2 , and R 3 are each independently an alkyl, an aryl, an alkylaryl, an alkoxyaryl, or a cycloaliphatic group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms.

[0036]

The term "alkyl", as used herein, unless otherwise specified, refers to a saturated straight or branched, primary, secondary, or tertiary hydrocarbon and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, 3-methylpentyl, 3-methylbutyl, 1,3-dimethylbutyl, 2,2- dimethylbutyl, and 2,3-dimethylbutyl.

The term "aryl" refers to a carbocyclic aromatic monocyclic group containing 6 carbon atoms which may be further fused to a second 5- or 6-membered carbocyclic group which may be aromatic, saturated or unsaturated. Exemplary aryl groups include, but is not limited to, phenyl, indanyl, 1-naphthyl, 2-naphthyl and tetrahydronaphthyl. "Alkylaryl" or "alkoxyaryl" refers to aryl groups which are substituted with one or more alkyl groups or alkoxy groups, respectively, as defined above.

The term "cycloaliphatic" refers to cyclized alkyl groups having 3-12 carbon atoms (i.e., C3, C4, C5, C7, C8, C9, CIO, CI 1, and C12 cycloaliphatic groups). Exemplary cycloaliphatic groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl. Branched cycloaliphatic groups having alkyl substituents, such as 1 -methylcyclopropyl and 2-methylcyclopropyl, are included in the definition of "cycloaliphatic".

R 4 is a group selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, and alkoxy phenyl. In preferred embodiments, R 4 is hydrogen. [0037]

Although satisfying the definition of a mono-ethylenically unsaturated monomer, the acrylate ester of a carboxylic acid ester is considered to be a separate and distinct component employed in the radiation curable ink compositions of the present disclosure. That is, the acrylate ester of a carboxylic acid ester (C) is not included in the definition of the mono- ethylenically unsaturated monomer (B) herein.

[0038]

The "carboxylic acid ester" moiety in formula (I) is represented by general formula

(Π)

Representative examples of acids from which the carboxylic acid ester moiety can be derived include α,α-dimethyl-caproic acid, α-ethyl-a-methyl-caproic acid, α,α-diethyl-caproic acid, α,α-diethyl-valeric acid, α,α-dimethyl-capric acid, α-butyl-a-ethyl-capric acid, α,α-dimethyl- enanthic acid, α,α-diethyl-pelargonic acid, α-butyl-a-methyl-caproic acid, α,α-dimethyl- caprylic acid, α-methyl-a-propyl-caproic acid, a-ethyl-a-methyl-enanthic acid, a-methyl-a- propyl valeric acid, a-ethyl-a-methyl-caprylic acid, a-butyl-a-methyl-caprylic acid, a-ethyl-a -propyl-caproic acid, a-ethyl-a-propyl-valeric acid, a-butyl-a-ethyl-pelargonic acid, α,α- dimethyl propionic acid (pivalic acid), neodecanoic acid, which includes one or mixtures of 2,2,3,5-tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2- ethylhexanoic acid, 2,2-dimethyloctanoic acid, and 2,2-diethylhexanoic acid, and combinations as well as any subset thereof. Preferred examples of acrylate esters of carboxylic acid esters include but are not limited to acrylate esters of glycidyl esters of neodecanoic acid or acrylate ester of glycidyl ester of pivalic acid and combinations thereof. In preferred embodiments, R 1 and R 2 combined have a total of 2 to 9 carbon atoms, preferably 4 to 8 carbon atoms, more preferably 6 to 8 carbon atoms, even more preferably 7 carbon atoms, while R 3 is methyl, and R 4 is hydrogen, for example ACE™ hydroxyl acrylate monomer available from Momentive (Columbus OH).

[0039]

The acrylate ester of a carboxylic acid ester of formula (I) may provide various advantageous properties to the radiation curable ink compositions. For example, the hydroxyl group may aid adhesion to a variety of substrates, while groups R -R 4 may provide hydrophobicity and increased molecular weight, which generally reduce migration of the cured ink composition from various substrates. The acrylate ester of a carboxylic acid ester of formula (I) may be present in the radiation curable ink composition in an amount of at least about 0.5 wt.%, preferably at least about 1 wt.%, preferably at least about 2 wt.%, preferably at least about 3 wt.%, more preferably at least about 4 wt.%, even more preferably at least about 5 wt.%, even more preferably at least about 6 wt.%, yet even more preferably at least about 7 wt.%, and up to about 50 wt.%, preferably up to about 30 wt.%, preferably up to about 15 wt.%, more preferably up to about 12 wt.%, even more preferably up to about 10 wt.%, yet even more preferably up to about 9 wt.%, or in a range of 3-13 wt.%, preferably 5- 11 wt.%, more preferably 7-9 wt.% based on a total weight of the radiation curable ink composition.

[0040] In some embodiments, an acrylate ester monomer having hydroxyl functionality like caprolactone acrylate (e.g., SR495B, available from Sartomer Co. Inc., Exton, Pa.) is employed in lieu of, or in addition to, the acrylate ester of a carboxylic acid ester of formula (I). When a mixture is employed, the weight ratio of the acrylate ester of a carboxylic acid ester of formula (I) to caprolactone acrylate is 10: 1 to 1 : 10, preferably 8 : 1 to 1 :8, preferably, 6:1 to 1:6, even more preferably 5:1 to 1 :5, yet even more preferably 3:1 to 1 :3.

[0041]

The viscosity of the acrylate ester of a carboxylic acid ester (C) is typically less than about 300 cPs, preferably less than about 250 cPs, preferably less than about 200 cPs, preferably up to about 150 cPs at 25 °C, although viscosities outside of this range are possible and the acrylate ester of a carboxylic acid ester component may still function as intended.

[0042]

(D poly-ethylenically unsaturated component

In some embodiments, the radiation curable ink composition further includes a poly- ethylenically unsaturated component (D), which includes two or more ethylenically unsaturated groups per molecule, for example di-, tri-, terra-, penta-, hexa-, hepta-, and octa- ethylenically unsaturated molecules. Poly-ethylenically unsaturated components for use in the radiation curable ink compositions include, for example, acrylates, (meth)acrylates, or vinyl ethers of straight chain, branched chain, hyperbranched or cyclic alkyl alcohols, including those that are silicone, polyester, or glycol-based acrylates, (meth)acrylates, or vinyl ethers of alcohols. In some embodiments, the radiation curable ink compositions are substantially free of poly-ethylenically unsaturated components (D). However, when present, the amount of poly-ethylenically unsaturated component present in the radiation curable ink compositions is typically at least about 10 wt.%, preferably at least about 15 wt.%, preferably at least about 20 wt.%, preferably at least about 21 wt.%, more preferably at least about 22 wt.%, even more preferably at least about 23 wt.%, even more preferably at least about 24 wt.%, yet even more preferably at least about 25 wt.%, and up to about 40 wt.%, preferably up to about 35 wt.%, preferably up to about 30 wt.%, more preferably up to about 29 wt.%, even more preferably up to about 28 wt.%, yet even more preferably up to about 27 wt.%, or in a range of 21-27 wt.%, preferably 22-26 wt.%, more preferably 23-25 wt.% based on a total weight of the radiation curable ink composition.

[0043]

The poly-ethylenically unsaturated component (D) may be a poly-ethylenically unsaturated monomer (D 1), a poly-ethylenically unsaturated oligomer (D2), or a mixture thereof (D1+D2).

Suitable poly-ethylenically unsaturated monomers (Dl) are typically liquids at a temperature of 25 °C, and may provide advantageous viscosity properties. Exemplary poly- ethylenically unsaturated monomers (Dl) that may be employed herein include

tripropyleneglycol diacrylate, neopentyl glycoldiacrylate, 1 ,6-hexanediol diacrylate (all available from Sigma-Aldrich), acrylates of propoxylated alcohols such as propoxylated (2) neopentyl glycol diacrylate (SR9Q03B, Sartomer Co. Inc.), acrylates of ethoxylated alcohols such as ethoxylated (6) trimethylolpropane triacrylate (e.g., SR499, Sartomer Co. Inc.), triethyleneglycol divinylether (e.g., Rapi-cure DVE 3), cyclohexanedimethanol divinylether, diethyleneglycol divinylether, hexanediol divinylether, butanediol divinylether (all available from Sigma Aldrich), bis[4-(ethenyloxy)butyl]hexanedioic acid ester (VECTOMER 4060), bis [4-(ethenyloxybutyl] ester of 1,3-benzenedicarboxylic acid (VECTOMER 4010), trifunctional vinyl ether monomers (e.g., tris(4-vinyloxybutyl) trimellitate, VECTOMER 5015), all available from Vertellus Performance Materials, Greensboro, NC. Hybrid poly- ethylenically unsaturated monomers containing both acrylate and vinyl ether functionality may also be used, examples of which include, but are not limited to 2-(2-vinylethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)-2 -propyl (meth)acrylate, 2-(2-vinyloxyethoxy)-3- propyl (meth)acrylate, 2-(2-vinyloxyethoxy)-2-butyl (meth)acrylate, 2-(2-vinyloxyethoxy) 4- butyl (meth)acrylate, 2-(2-allyloxyethoxy)ethyl (meth)acrylate, 2-(2-allyIoxyethoxy)-2- propyl (meth)acrylate, 2-(2-allyloxyethoxyxy)-3 -propyl (meth)acrylate, 2-(2-allyloxyethoxy)- 2-butyl (meth)acrylate, 2-(2-allyloxyethoxy)-4-butyl (meth)acrylate, 2-(2- vinyloxypropoxy)ethyl (meth)acrylate, 2-(2-vinyloxypropoxy)-2 -propyl (meth)acrylate, 2-(2- vinyloxypropoxy)-3 -propyl (meth)acrylate, 2-(3-vinyloxypropoxy)ethyl (meth)acrylate, 2-(3- vinyloxypropoxy) 2-propyl (meth)acrylate, 2-(3-vinyloxypropoxy)-3 -propyl (meth)acrylate, and any combinations or subset thereof. Any of the above poly-ethylenically unsaturated monomers may be used singly or in combination of two or more.

[0044]

Poly-ethylenically unsaturated oligomers (D2) may be used in the radiation curable ink compositions to offer toughness, flexibility, abrasion resistance, exterior durability, resistance to yellowing, and other desirable properties to the cured ink compositions. In some embodiments, the poly-ethylenically unsaturated oligomers have a number average molecular weight of at least about 300 g mol, preferably at least about 500 g/mol, more preferably at least about 800 g/mol, and up to about 50,000 g mol, preferably up to about 30,000 g/mol, more preferably up to about 10,000 g/mol, even more preferably up to about 5,000 g/mol, yet even more preferably up to about 1,200 g/mol. Exemplary poly-ethylenically unsaturated oligomers (D2) that may be employed herein include diacrylate oligomers (e.g., CN132, CN991, CN962, CN964, and CN966, Sartomer Co. Inc.), tetra-acrylate oligomers (e.g., CN549, Sartomer Co. Inc.), silicone hexa-acrylates (e.g., EBECRYL 1360, Allnex, Belgium), urethane acrylates (e.g., EBECYRL 1290, Allnex, Belgium), polyester acrylate oligomers (e.g., CN2302 and CN2303, Sartomer Co. Inc.), polyester acrylate/polyether acrylate blends (e.g., BDE1025, Dymax Corp.), polyester urethane-based oligomers (e.g., CN966J75, which is an aliphatic polyester based urethane diacrylate oligomer blended with 25wt.% SR506, isobornyl acrylate, available from Sartomer Co. Inc.), aliphatic urethane oligomers (e.g., EBECRYL 8411, which is an aliphatic urethane diacrylate oligomer blended with 20 wt.% isobornyl acrylate, available from Allnex, Belgium, and CN9893, available from Sartomer Co. Inc.), aromatic urethane acrylates (e.g., EBECRYL 220, available from Allnex,

Belgium), polyfunctional vinyl ether oligomers (e.g., VECTOMER 1312, Sigma Aldrich), silicone di-acrylates (e.g., CN9800, available from Sartomer Co. Inc., and EBECRYL 350, available from Allnex, Belgium). These poly-ethylenically unsaturated oligomers may be used singly or in combination of two or more.

[0045]

In preferred embodiments, the poly-ethylenically unsaturated component is at least one selected from the group consisting of propoxylated (2) neopentyl glycol diacrylate (e.g., SR9003B), ethoxylated (6) trimethylolpropane triacrylate (e.g., SR499), EBECRYL 8411 and CN9893.

[0046]

In some embodiments, the poly-ethylenically unsaturated component is a mixture of the poly-ethylenically unsaturated monomer (Dl) and the poly-ethylenically unsaturated oligomer (D2). Under these circumstances, a weight ratio of the poly-ethylenically unsaturated monomer (Dl) to the poly-ethylenically unsaturated oligomer (D2) is typically at least 2:1, preferably at least 3:1, preferably at least 4:1, more preferably at least 5:1, even more preferably at least 6:1, and up to about 10:1, preferably up to about 9:1, more preferably up to about 8:1, even more preferably up to about 7:1, or in a range of about 6:1 to 7:1.

However, weight ratios outside of this range are possible and the poly-ethylenically unsaturated component may still provide suitable radiation curable ink compositions.

[0047]

In radiation curable ink compositions that include the mono-ethylenically unsaturated oligomer (A), the mono-ethylenically unsaturated monomer (B), and the acrylate ester of a carboxylic acid ester of formula (I) (C), and which are substantially free of the poly- ethylenically unsaturated component (D), the proportions of components (A), (B), and (C) described above can be controlled to obtain desirable properties, specifically ink

compositions exhibiting low levels of migration. In some embodiments, a combined weight of the mono-ethylenically unsaturated oligomer and the acrylate ester of a carboxylic acid ester of formula (I) (A+C) is less than a weight of the mono-ethylenically unsaturated monomer (B). In preferred embodiments, a weight ratio of the mono-ethylenically unsaturated monomer (B) to the combined weight of the mono-ethylenically unsaturated oligomer and the acrylate ester of a carboxylic acid ester of formula (I) (A+C) is at least about 1.3:1, preferably at least about 1.4:1, preferably at least about 1.5:1, preferably at least about 1.6:1, and up to about 8:1, preferably up to about 6:1, preferably up to about 5:1, preferably up to about 4:1, more preferably up to about 3:1, even more preferable up to about 2:1, for example 1.4:1 to 3:1, or 1.5:1 to 2:1.

[0048]

In radiation curable ink compositions that also include the poly-ethylenically unsaturated component (D), the proportions of components (A), (B), (C), and (D) described above can be controlled to obtain desirable properties, specifically ink compositions exhibiting low levels of migration. Preferred proportions involve a combined weight of the mono-ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) that is less than a combined weight of the mono-ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D). Preferably, a weight ratio of the combined weight of the mono-ethylenically unsaturated monomer (B) and the poly-ethylenically unsaturated component (D) to the combined weight of the mono- ethylenically unsaturated oligomer (A) and the acrylate ester of a carboxylic acid ester of formula (I) (C) ((B+D)/(A+C)) is at least 1.5:1, preferably at least 2:1, more preferably at least 2.5:1, even more preferably at least 2.9:1, and up to about 10:1, preferably up to about 8: 1 , preferably up to about 6:1, preferably up to about 5:1, more preferably up to about 4:1, even more preferably up to about 3:1.

[0049]

In preferred embodiments, the radiation curable ink composition is substantially free of a photoinitiator, more preferably is completely free of a photoinitiator (e.g., 0 wt.%). Optionally, a photoinitiator may be present in the radiation curable ink compositions. The photoinitiator may be a cationic photoinitiator, for example in applications that involve printing on substrates where adhesion is difficult, for example glass substrates. The photoinitiator may also be a free-radical photoinitiator. When present, the radiation curable ink composition may contain less than about 3 wt.%, preferably less than about 2 wt.%, preferably less than about 1 wt.%, preferably less than about 0.5 wt.% of the photoinitiator.

[0050]

Suitable photocationic initiators that may be optionally included in the radiation curable ink compositions include onium salts, for example, triarylsulfonium salts or diaryl iodonium salts, such as UVI-6974, UVI-6976, UVI-6990 and UVI 6992 (available from the Dow Chemical Company, Midland, Mich.), ADEKA Optomers SP-150, SP-151, SP-170, and SP-171 (Asahi Denka Kogyo, Tokyo, Japan), Omnicat 550, Omnicat 650, Omnicat BL550, Omnicat 440, Omnicat 445, Omnicat 432, Omnicat 430, Omnicat 750, Omnicat 250

(available from IGM resins, Shanghai, China), and DTS-102, DTS-103, NAT-103, NDS-103, TPS- 103, MDS-103, MPI-103, BBI-103 (available from Midori Kagaku, Tokyo, Japan), Chivacure 1176, Chivacure 1190, R-gen BF 1172, R-gen 1130, R-gen 261 (available from Chitec Technology Co. Ltd.,) Uvacure 1600 (available from Allnex), including combinations and sub-sets thereof. Further, in embodiments where a photocationic initiator is present, the radiation curable ink compositions may also optionally include poly-functional alcohol components such as hexafunctional alcohol BOLTORN H 2004 (available from Perstorp Specialty Chemicals Toledo, Ohio) to provide improved flexibility and reactivity, chemical resistance, rheological behavior, and ink transfer at high speeds.

[0051]

Additionally, a photosensitizer may optionally be used, for example, to increase the efficiency of curing by the photocationic initiator. Exemplary photosensitizers include, but are not limited to, Anthracure UVS 1101 (9, 10-diethoxy anthracene) and Anthracure

UVS1331 (9,10-dibutoxy anthracene) made by Kawasaki Kasei, Japan, SpeedCure CPTX( 1- chloro-4-propoxythioxanthone), made by Lambson, Ltd, U.K., Genocure ITX (Isopropyl thioxanthone) and Genocure DETX (2,4-Diethylthioxanthone), both available from Rahn USA. When present, the radiation curable ink composition may contain less than about 3 wt.%, preferably less than about 2 wt.%, preferably less than about 1 wt.% of the

photosensitizer.

[0052]

Suitable free-radical photoinitiators that may be optionally included in the radiation curable ink compositions include 2-benzyl-2-(dimethylamino)-4'-moφholinobutyrophenone, 2-hydroxy-2-methylpropiophenone, trimethylbenzophenone, methylbenzophenone, 1- hydroxycyclohexylphenyl ketone, isopropyl thioxanthone, 2,2-dimethyl-2-hydroxy- acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- 1 -[4-(methylthio)phenyl]-2- morpholino-propan-l-one, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, l-chloro-4- propoxythioxanthone, benzophenone, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl pentyl phosphine oxide, 5,7-diiodo-3-butoxy-6-fluorone, ethyl 2,4,6-trimethylben

zoylphenylphosphinate, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester, l-phenyl-2-hydroxy-2- methyl propanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, camphorquinone, polymeric photoinitiators such as polymeric benzophenone Genopol BP-2 (Rahn U.S.A.), Omnipol BP, Omnipol SZ, Omnipol BL 801 T, Omnipol 801 S, Omnipol BPLV (from IGM resins) and the like. Combinations and sub-sets, comprising one or more the foregoing may also be used. Suitable commercially available photoinitiators include, but are not limited to Omnirad 73, Omnirad 819, Omnirad BDK, Omnirad TPO-L, Omnirad 659, and Omnirad 754 (available from IGM Resins), Methyl benzoylformate (Genocure MBF), Genocure PMP, Genocure BDMM, Genocure CPK, Genocure TPO (available from Rahn U.S.A. Corp, Aurora, 111.), H-Nu 470, H-Nu 535, H-Nu 635, H-Nu 640, and H-Nu 660 (available from Spectra Group Limited, Millbury, Ohio). In some embodiments, the radiation curable ink compositions are substantially non-aqueous, meaning that no water is added to the radiation curable ink compositions other than the incidental amounts of moisture derived from ambient conditions. In preferred embodiments, the radiation curable ink compositions are

substantially free of a solvent, which includes both organic solvents (e.g., alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents) and water. That is, the radiation curable ink compositions have less than about 3 wt.%, preferably less than about 2 wt.%, preferably less than about 1 wt.%, preferably less than about 0.1 wt.%, preferably less than about 0.05 wt.% of a solvent, based on the total weight of the radiation curable ink composition.

[0053]

In some embodiments, the ink compositions of the invention are substantially free of non-reactive oligomers and preferably substantially free of non-reactive oligomers having a number average molecular weight of more than about 10,000 g/mol. Specifically, the ink compositions of the invention are free of oligomers which do not contain ethylenically unsaturated radiation curable functional groups and therefore are non-reactive.

[0054]

(E) Colorants

In some embodiments, the radiation curable ink compositions are substantially free of colorants, wherein a colorless coating composition is formed that may be useful in clear- coating applications. All of the disclosure set forth herein relating to the radiation curable ink compositions, other than the colorant descriptions, is equally applicable to such colorless coating compositions.

[0055]

The radiation curable ink compositions may optionally contain a colorant which may comprise pigment, dye, or a combination of pigments and/or dyes to provide the desired color. It is to be readily appreciated by those of ordinary skill in the art that colorants may be included in the radiation curable ink compositions to provide colored inks that may be used for a variety of printing purposes and the radiation curable ink compositions are not limited to any particular color. Suitable colors include, for example, cyan, magenta, yellow, and key ("CMYK"), black, white, orange, green, light cyan, light magenta, violet, and the like. In general, the colorants may be employed in amounts of up to about 25 wt.%, preferably up to about 15 wt.%, preferably up to about 10 wt.%, preferably up to about 8 wt.%, preferably up to about 6 wt.%, preferably up to about 4 wt.%, preferably up to about 3 wt.%, preferably up to about 2 wt.%, preferably up to about 1 wt.%, relative to the total weight of the radiation curable ink compositions. Any desired or effective colorant can be employed in the ink compositions, including dyes, pigments, mixtures thereof, and the like, provided that the colorant can be dissolved or dispersed in the ink compositions. Pigments, which are typically cheaper and more robust than dyes, may be included in some embodiments. The

compositions can be used in combination with conventional ink-colorant materials such as Color Index (C.I.) solvent dyes, disperse dyes, modified acid and direct dyes, basic dyes, sulfur dyes, vat dyes, and the like.

[0056]

Examples of suitable dyes include Neozapon Red 492 (Pylam Products Co., Inc.); Orasol Red G (BASF); Direct Brilliant Pink B (Zibo Hongwei Industry Co.); Direct Red 3BL (Classic Dyestuffs); Supranol Brilliant Red 3BW (Bayer AG); Lemon Yellow 6G (United Chemie); Light Fast Yellow 3G (Shaanxi); Aizen Spilon Yellow C-GNH (Hodogaya Chemical); Bemachrome Yellow GD Sub (Classic Dyestuffs); Cartasol Brilliant Yellow 4GF (Clariant); Orasol Black CN (BASF); Savinyl Black RLSN (Clariant); Pyrazol Black BG (Clariant); Morfast Black 101 (Keystone); Orasol Blue GN (BASF); Savinyl Blue GLS (Clariant); Luxol Fast Blue MBSN (ACROS); Sevron Blue 5GMF (Classic Dyestuffs);

Basacid Blue 750 (BASF), Neozapon BlackX51 (BASF), Classic Solvent Black 7 (Classic Dyestuffs), Sudan Blue 670 (C.I. 61554) (BASF), Sudan Yellow 146 (C.I. 12700) (BASF), SudanRed462 (C.I. 26050) (BASF), C.I. Disperse Yellow 238, Neptune Red Base NB543 (BASF, C.I. Solvent Red 49), Neopen Blue FF-4012 from BASF, Lampronol Black BR from ICI (C.I. Solvent Black 35), Morton Morplas Magenta 36 (C.I. Solvent Red 172), metal phthalocyanine colorants such as those disclosed in U.S. Pat. No. 6,221,137, which is incorporated herein by reference in its entirety, and the like. Polymeric dyes can also be used, such as those disclosed in, for example, U.S. Pat. No. 5,621,022 and U.S. Pat. No. 5,231,135, which are each incorporated herein by reference in its entirety, and commercially available from, for example, Milliken & Company as Milliken Ink Yellow 869, Milliken Ink Blue 92, Milliken Ink Red 357, Milliken Ink Yellow 1800, Milliken Ink Black 8915-67, uncut

Reactant Orange X-38, uncut Reactant Blue X-17, Solvent Yellow 162, Acid Red 52, Solvent Blue 44, and uncut Reactant Violet X-80.

[0057]

Pigments are also suitable colorants for the radiation curable ink compositions.

Exemplary pigments include those having the following Color Index classifications: Green PG 7 and 36; Orange PO 5, 34, 36, 38, 43, 51, 60, 62, 64, 66, 67 and 73; Red PR112, 122, 146, 149, 150, 170, 178, 179, 185, 187, 188, 207, 208, 214, 220, 224, 242, 251, 254, 255, 260 and 264; Magenta/Violet PV 19, 23, 31, and 37, and PR 122, 181 and 202; Yellow PY 12, 13, 17, 120, 138, 139, 155, 151, 168, 175, 179, 180, 181 and 185; Blue PB 15, 15:3, 15:4, 15:6; Black PB 2, 5 and 7; carbon black; titanium dioxide (including rutile and anatase); zinc sulfide, and the like. Examples of suitable pigments include PALIOGEN Violet 5100

(commercially available from BASF); PALIOGEN Violet 5890 (commercially available from BASF); HELIOGEN Green L8730 (commercially available from BASF); Irgalite

Scarlet D3700 (commercially available from BASF); SUNFAST Blue 15:4 (commercially available from Sun Chemical); Hostaperm Blue B2G-D (commercially available from

Clariant); Hostaperm Blue B4G (commercially available from Clariant); Permanent Red P- F7RK; Hostaperm Violet BL (commercially available from Clariant); LITHOL Scarlet 4440 (commercially available from BASF); Bon Red C (commercially available from Dominion Color Company); PALIOGEN Red 3871 K (commercially available from BASF); SUNFAST Blue 15:3 (commercially available from Sun Chemical); PALIOGEN Red 3340

(commercially available from BASF); SUNFAST Carbazole Violet 23 (commercially available from Sun Chemical); LITHOL Fast Scarlet L4300 (commercially available from BASF); SUNBRITE Yellow 17 (commercially available from Sun Chemical); HELIOGEN Blue L6900, L7020 (commercially available from BASF); SUNBRITE Yellow 74

(commercially available from Sun Chemical); SPECTRA PAC C Orange 16 (commercially available from Sun Chemical); HELIOGEN Blue K6902, K6910 (commercially available from BASF); SUNFAST Magenta 122 (commercially available from Sun Chemical);

HELIOGEN Blue D6840, D7080 (commercially available from BASF); Sudan Blue OS (commercially available from BASF); NEOPEN Blue FF4012 (commercially available from BASF); PV Fast Blue B2GO 1 (commercially available from Clariant); IRGALITE Blue BCA, GLSM, or GLVO (commercially available from BASF); PALIOGEN Blue 6470 (commercially available from BASF); MONASTRAL BLUE FGX, GBX, GLX, a 6Y, Sudan Orange G (commercially available from Aldrich), Sudan Orange 220 (commercially available from BASF); PALIOGEN Orange 3040 (BASF); PALIOGEN Yellow 152, 1560

(commercially available from BASF); LITHOL Fast Yellow 0991 K (commercially available from BASF); PALIOTOL Yellow 1840 (commercially available from BASF); NOVO PERM Yellow FGL (commercially available from Clariant); Ink Jet Yellow 4G VP2532

(commercially available from Clariant); Toner Yellow HG (commercially available from Clariant); Lumogen Yellow D0790 (commercially available from BASF); Suco- Yellow L1250 (commercially available from BASF); Suco-Yellow D1355 (commercially available from BASF); Suco Fast Yellow DI 355, DI 351 (commercially available from BASF); HOSTAPERM Pink E 02 (commercially available from Clariant); Hansa Brilliant Yellow 5GX03 (commercially available from Clariant); Permanent Yellow GRL 02 (commercially available from Clariant); Permanent Rubine L6B 05 (commercially available from Clariant); FANAL Pink D4830 (commercially available from BASF); CINQUASIA Magenta

(commercially available from BASF); PALIOGEN Black L0084 (commercially available from BASF); Pigment Black K801 (commercially available from BASF); and carbon blacks such as REGAL 330 (commercially available from Cabot), NIPEX 150, NIPEX 160, NIPEX 180 (commercially available from Orion Engineered Carbons), SPECIAL BLACK 100, SPECIAL BLACK 250, SPECIAL BLACK 350, FW1, FW2 FW200, FW18, SPECIAL BLACK 4, SPECIAL BLACK 5, SPECIAL BLACK 6, PRJNTEX 80, PRINTEX 90, PRJNTEX 140, PRINTEX 150T, PRINTEX 200, PRINTEX U, and PRINTEX V, all available from Orion Engineered Carbons, MOGUL L, REGAL 400R, REGAL 330, and MONARCH 900, available from Cabot Chemical Co., Boston, Mass., MA77, MA7, MA8, MAI 1, MA100, MA100R, MA100S, MA230, MA220, MA200RB, MA14, #2700B, #2650, #2600, #2450B, #2400B, #2350, #2300, #2200B, #1000, #970, #3030B, and #3230B, all available from Mitsubishi, Tokyo, Japan, RAVEN 2500 ULTRA, from Birla Carbon - Columbian, and the like, as well as mixtures thereof.

[0058]

A number of titanium oxide pigments are also known. Nanostructured titania powders may be obtained, for example, from Nanophase Technologies Corporation, BurrRidge, III, or under the trade names KRONOS 1171 from Kronos Titan, Cranbury, N.J. Surface treated or surface coated titania, for example titania coated with alumina or silica, may also be used. This type of coated titanium oxide is commercially available from E.I. du Pont de Nemours and Company, Wilmington, Del., under the trade name R960 or R902. [0059]

The pigments generally are of a size that can be jetted from a print head without substantially clogging print nozzles, capillaries, or other components of print equipment. Pigment size can also have an effect on the final ink viscosity. The average particle size of the pigment is generally at least about 10 nm, preferably at least about 25 nm, more preferably at least about 50 nm, and less than about 750 nm, preferably less than about 500 nm, and more preferably less than about 350 nm. For example, the pigments can have a D50 of less than or equal to 350 nm.

[0060]

Also suitable are the colorants disclosed in U.S. Pat. No. 6,472,523, U.S. Pat. No.

6,726,755, U.S. Pat. No. 6,476,219, U.S. Pat. No. 6,576,747, U.S. Pat. No. 6,713,614, U.S.

Pat. No. 6,663,703, U.S. Pat. No. 6,755,902, U.S. Pat. No. 6,590,082, U.S. Pat. No.

6,696,552, U.S. Pat. No. 6,576,748, U.S. Pat. No. 6,646,1 1 1 , U.S. Pat. No. 6,673,139, U.S.

Pat. No. 6,958,406, U.S. Pat. No. 6,821 ,327, U.S. Pat. No. 7,053,227, U.S. Pat. No. 7,381 ,831 and U.S. Pat. No. 7,427,323, which are each incorporated herein by reference in their entirety.

[0061]

(F) Additives

In some embodiments, the radiation curable ink compositions also contain at least one additive selected from the group consisting of a surfactant, a stabilizer, and an adhesion promoter.

[0062]

Surfactants A surfactant is generally used to lower the surface tension of the composition to allow wetting and leveling of the substrate surface, if necessary, before curing. The surfactant can be selected by both its hydrophobic and hydrophilic properties. In some embodiments, the surfactants may be miscible with the radiation curable material (i.e., acrylate or methacrylate miscible). Surfactants suitable for use in the radiation curable ink compositions include, but are not limited to, polysiloxanes, polyacrylic copolymers, fluorine containing polymers, and the like. These surfactants may include one or more functional group such as carbinol, alkyl, aryl, glycol, polyether, siloxane, and mixtures thereof. In some embodiments, these materials contain reactive groups that allow them to become part of the cured network. Suitable surfactants may include, but are not limited to polydimethylsiloxane copolymer (Siltech C- 20, C-42, C-468), alkyl and aryl modified polydimethylsiloxane (Siltech C-32), silicone polyether (Siltech C-101, 442), block copolymer of dimethylsiloxane and a polyoxyalkylene (Siltech C-241, available from Siltech Corporation), Rad 2100, Rad 2200, Rad 2250, Rad 2300, Rad 2500, Rad 2600, and Rad 2700 commercially available from Evonik Industries AG; CoatOSil 1211, CoatOSil 1301, CoatOSil 3500, CoatOSil 3503, CoatOSil 3509, and CoatOSil 3573 commercially available from Momentive; Byk-381, Byk-333, Byk-377, Byk- UV 3500, Byk-UV 3510, and Byk-UV 3530 commercially available from Byk Chemie; and FC-4430 and FC-4432 commercially available from 3M Corporation, and the like, and mixtures thereof.

[0063]

The surfactants may be employed in an amount of about 0 wt.%, preferably from about 0.001 wt.%, more preferably from about 0.005 wt.%, even more preferably from 0.1 wt.%, and up to about 10 wt.%, preferably up to 5 wt.%, preferably up to about 4 wt.%, more preferably up to about 3 wt.%, even more preferably up to about 2 wt.%, based on the total weight of the radiation curable ink composition.

[0064]

Stabilizer

The ink formulations of the present invention may also optionally include a stabilizer to aid aerobic and/or anaerobic stability. Examples include but are not limited to Irgastab UV 10, Irgastab UV 22, Irgaiiox 1010, Irganox 1035, and Tinuvin 292 (available from BASF), Omnistab LS292 (available from IGM Resins, Shanghai, China), 4-methoxyphenol, HQ (hydroquinone) and BHT (butylated hydroxyl toluene) commercially available from Sigma- Aldrich Corp. Other types of stabilizers, such as ultraviolet light absorbing ("UVA") materials and hindered amine light stabilizers ("HALS") can be included in the radiation curable ink compositions to provide photolytic stability to the ink, improve the weatherability of the cured ink compositions, and to provide color retention through the lifetime of the cured ink composition. Exemplary UVAs which can be employed herein include, but are not limited to, Tinuvin 384-2, Tinuvin 1130, Tinuvin 405, Tinuvin 41 IL, Tinuvin 171, Tinuvin 400, Tinuvin 928, Tinuvin 99, combinations thereof, and the like. Examples of suitable HALS include, but are not limited to, Tinuvin 123, Tinuvin 292, Tinuvin 144, Tinuvin 152, combinations thereof, and the like. Combination materials having both UVA and HALS may also be used in the radiation curable ink compositions, such as Tinuvin 5055, Tinuvin 5050, Tinuvin 5060, Tinuvin 5151, and the like. All Tinuvin products are commercially available from BASF.

[0065] Thermal stabilizers such as hindered phenols may optionally be used as an additive in the radiation curable ink compositions. An example of a suitable thermal stabilizer includes, but is not limited to, Irganox 1076, which is commercially available from BASF.

The stabilizers can be present in the radiation curable ink compositions in an amount of about 0 to about 10 wt.%, preferably from about 0.001 wt.%, preferably from about 0.01 wt.%, more preferably from about 0.1 wt.%, and even more preferably from about 0.5 wt.%, and up to about 10 wt.%, preferably up to about 5 wt.%, preferably up to about 3 wt.%, more preferably up to about 2 wt.%, even more preferably up to about 1 wt.%, yet even more preferably up to about 0.3 wt.%, based on the total weight of the radiation curable ink composition.

[0066]

Adhesion promoter

The radiation curable ink composition may optionally include one or more adhesion promoters. In some instances, the adhesion promoter contains one or more acrylate groups. The adhesion promoter can be an acidic modified adhesion promoter or an amine modified adhesion promoter. Exemplary acidic modified adhesion promoters include acidic acrylate oligomer, acrylic acid, polyester acrylate oligomer, β-carboxyethyl acrylate and acid functional acrylic resins, such as Joncryl 678 acid functional acrylic resin (BASF Resins, Heerenveen, The Netherlands). A preferred acidic modified adhesion promoter is Sartomer Co. Inc. CN147, which is an acidic acrylate oligomer. Exemplary amine modified adhesion promoters include amine modified polyether acrylate oligomer (e.g., Laromer PO 94 F (BASF Corp.) and EB 80 (Cytec Surface Specialties)), amine modified polyester tetraacrylate (e.g., EB81 (Cytec Surface Specialties)), and amine modified epoxy acrylate. The adhesion promoter may be a polyurethane, for example polyurethanes sold by Henry Company under the trade names PERMAX 20, PERMAX 200, PERM AX 100, PERM AX 120, and SANCURE 20025, or SANCURE commercially available from Lubrizol.

[0067]

Generally, if present, the amount of adhesion promoter is from about 0.05 wt.%, preferably from about 1 wt.%, more preferably from about 3 wt.%, and up to about 15 wt.%, preferably up to about 10 wt.%, more preferably up to about 5 wt.%. based on the weight of the radiation curable ink composition.

[0068]

In preferred embodiments, the radiation curable ink composition includes (A) 12-20 wt.% of a hydroxyl-functionalized mono-ethylenically unsaturated oligomer (e.g., CN3100), (B) 40-50 wt.% of a mono-ethylenically unsaturated monomer, which is an acrylate of a cyclic alkyl alcohol (e.g., SR420), (C) 4-12 wt.% of the acrylate ester of a carboxylic acid ester of formula (I), (D) 20-30 wt.% of a poly-ethylenically unsaturated component, which is (Dl) an acrylate monomer of a propoxylated alcohol (e.g., SR9003B), with a balance being (E) colorants and at least one (F) additive (e.g., surfactant, a stabilizer, and/or an adhesion promoter), each relative to the total weight of the radiation curable ink composition.

[0069]

In other preferred embodiments, the radiation curable ink composition includes (A) 12-20 wt.%) of a hydroxyl-functionalized mono-ethylenically unsaturated oligomer (e.g., CN3100), (B) 40-50 wt.% of a mono-ethylenically unsaturated monomer, which is an acrylate of a cyclic alkyl alcohol (e.g., SR420), (C) 4-12 wt.% of the acrylate ester of a carboxylic acid ester of formula (I), (D) 20-30 wt.% of a poly-ethylenically unsaturated component, which is a 5:1 to 10:1 wt.% mixture of (Dl) an acrylate monomer of a propoxylated alcohol (e.g., SR9003B) and (D2) a polyester urethane-based oligomer (e.g., CN966J75), with a balance being (E) colorants and at least one (F) additive (e.g., surfactant, a stabilizer, and/or an adhesion promoter), each relative to the total weight of the radiation curable ink composition.

[0070]

In other preferred embodiments, the radiation curable ink composition includes (A)

12-20 wt.% of a hydroxyl-functionalized mono-ethylenically unsaturated oligomer (e.g., CN3100), (B) 40-50 wt.% of a mono-ethylenically unsaturated monomer, which is an acrylate of a cyclic alkyl alcohol (e.g., SR420), (C) 4-12 wt.% of the acrylate ester of a carboxylic acid ester of formula (I), (D) 20-30 wt.% of a poly-ethylenically unsaturated component (e.g., SR9003B), (E) 1-5 wt.% of a colorant, and (F) 1-5 wt.% of at least one additive (e.g., surfactant, a stabilizer, and/or an adhesion promoter), each relative to the total weight of the radiation curable ink composition.

[0071]

Embodiments of the radiation curable ink compositions described herein may be prepared by any suitable technique known to those of ordinary skill in the art, for example by combining components (A), (B), (C), and optionally (D) in any order and stirring at a temperature between 20 and 100°C until a homogeneous solution is formed. Any desired colorants (E) and an additives (F) may also be included in this mixture, or alternatively be mixed into the homogeneous solution with optional stirring, agitating, and/or

homogenization. The formed radiation curable ink compositions may then be filtered, optionally at an elevated temperature, to remove extraneous particles.

[0072]

Properties As used herein, the term "viscosity" refers to a complex viscosity, which is the typical measurement provided by a mechanical rheometer that is capable of subjecting a sample to a steady shear strain or a small amplitude sinusoidal deformation. In this type of instrument, the shear strain is applied by the operator to the motor and the sample deformation (torque) is measured by the transducer. Examples of such instruments are the Rheometrics Fluid

Rheometer RFS3, ARES rheometer, both made by Rheometrics, a division of TA

Instruments, or a Haake Roto Visco 1 rheometer, Brookfield DV-E Viscometer made by AMETEK Brookfield and a TCP/P-Peltier Temperature Control Unit. The results are provided in centipoise (cP). In some embodiments, the radiation curable ink compositions exhibit a desirable combination of low viscosity in liquid form and high elongation once cured, i.e., they have a viscosity at 25 °C of from about 4 cPs, preferably from about 5 cPs, more preferably from about 8 cPs, even more preferably from about lOcPs, and not greater than about 70 cPs, preferably not greater than 50 cPs, more preferably not greater than 30 cPs, even more preferably not greater than about 25 cPs, yet even more preferably not greater than about 20 cPs, yet even more preferably not greater than about 15cPs.

[0073]

The radiation curable ink compositions of the present disclosure provide suitable rub resistance after being cured. Inks exhibiting rub resistance exhibit improved processability, in which the printed substrate can be subjected to further processing without detrimental effect to the printed ink. Rub resistance may be analyzed for example with a Gakushin-type rubbing tester manufactured by Daiei Kagaku, based on reference standard JIS L-0849. The test typically involves placing a reference white cloth on rubbing heads of the rubbing tester. The rubbing heads exert pressure for a number of cycles on the cured ink due to their weight. Depending upon the rub resistance of the ink, the color of the ink will transfer to the reference cloth to a lesser or greater extent. The rub resistance is quantified by measuring the color difference ΔΕ after rubbing on the reference cloth by a Spectrophotometer, such as the X-Rite Ci64. A ΔΕ value less than 3.0 is generally regarded as acceptable, though preferably a ΔΕ value should be less than 2.0, and even more preferably less than 1.0.

[0074]

Adhesion can be measured by a cross hatch adhesion tape test according to ASTM D3359 and quantified on a 0-5 scale. The radiation curable ink compositions provide advantageous adhesion properties on a variety of substrates, with adhesion performance ratings of 4 or 5.

The scratch resistance properties of the radiation curable ink compositions, after being cured, may be analyzed by pencil hardness tests, for example with standard ASTM3363-92a, and rated on a scale of softest to hardest: 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H. In some embodiments, the radiation curable ink compositions provide suitable scratch resistance ratings of at least "B" hardness, preferably at least "HB", more preferably at least "F", even more preferably at least "H", yet even more preferably at least "2H".

[0075]

Migration testing is often used to determine the potential for ink components to enter a package and adulterate the packaged product. The migration levels of the radiation curable ink compositions disclosed herein may be determined using migration testing standards known to those of ordinary skill in the art. Briefly, such analyses may involve stacking several sheets of printed samples, or alternatively cutting a printed sample from the rewind side of a substrate in a roll form web as the test specimen, and conditioning the test specimen in an extraction cell (generally ranging from 30 minutes to 2 days) filled with a food simulant (e.g., water, heptane, isooctane, vegetable oil, ethanol or acetic acid solutions, etc.) according to FDA "Conditions of Use" regulations as defined in Title 21 Code of Federal Regulations (C.F.R.) Section 176.170(c)-(d), April 1, 2000, which specify the testing conditions (e.g., temperature and length of time) for which the test specimen is stored in the extraction cell depending on the intended use of a particular packaged product. After conditioning, any ink components from the test specimen may optionally be extracted with an extraction solvent (e.g., chloroform, methylene chloride). The levels of migration of the ink components may then be quantified with various analytical techniques, such as by weight, gas

chromatography, liquid chromatography, mass spectrometry, elemental analysis, and the like. The exact technique used to measure the amount of migration will depend on the intended use of a particular packaged product. For example, if the package is intended to be used for frozen storage (no thermal treatment in the container), the migration is measured by condition of use "G" according to Table 2 of Title 21 Code of Federal Regulations (C.F.R.) Section 176.170(c) and Section 176.170(d). If the package has multiple intended uses, the package satisfies the migration level for the appropriate test for at least one of the intended uses.

[0076]

In some embodiments, the radiation curable ink compositions disclosed herein exhibit a migration level of less than 50 ppb, preferably less than 40 ppb, preferably less than 30 ppb, preferably less than 20 ppb, more preferably less than 10 ppb, even more preferably less than 5 ppb, yet even more preferably less than 1 ppb, after being cured on an article. In some embodiments, the radiation curable ink compositions, after being cured, exhibit no migration and/or the ink components cannot be detected above the detection limit of the analytical technique employed.

[0077] In some embodiments, the radiation curable ink composition has a surface tension of at least about 20 mN/m, more preferably at least about 22 mN/m, and up to about 50 mN/m, preferably up to about 40 mN/m, more preferably up to about 30 mN/m at a jetting temperature of from about 25°C, preferably from about 35°C, more preferably from about 40°C and less than about 100°C, preferably less than about 95 °C, more preferably less than about 90°C.

[0078]

Printed Article

The radiation curable ink compositions can be cured on a substrate, which includes three dimensional parts as well as flat sheets or webs that are supplied in roll form, for the manufacture of printed articles having advantageous properties, such as printed articles that are rub and scratch resistant, have suitable ink adhesion, and migration levels of less than 10 ppb. Such printed articles may be suitable in the graphic arts, textiles, packaging, lottery, business forms and publishing industries, examples of which include a tag or label, a lottery ticket, a publication, packaging (e.g., flexible packaging), a folding carton, a rigid container (e.g., a plastic cup or tub, glass containers, metal cans, bottles, jars, and tubes), a point-of-sale display, and the like. In embodiments where electron beam curing is used, the depth of penetration of the electron beam radiation enables the radiation curable ink composition to be cured on substrates having various surface types, for example, a flat surface, a structured surface, such as grained surfaces, and a three-dimensional surface, such as curved surfaces.

[0079]

The radiation curable ink compositions may be printed on porous substrates, examples of which include, but are not limited to, paper, wood, membranes, and fabrics (including, for example, but not limited to, woven fabric, non-woven fabric, and foil-laminated fabric). The radiation curable ink compositions may also be printed on non-porous substrates, for example, various plastics, glass, metals, and/or coated papers. These may include, but are not limited to, molded plastic parts as well a flat sheets or rolls of plastic films. Examples include those containing polyethylene terephthalate (PET), biaxially oriented polystyrene (OPS), polyethylene (PE), polypropylene (PP), oriented polypropylene (OPP), polylactic acid (PLA), oriented nylon, polyvinyl chloride (PVC), polyester, cellulose triacetate (TAC),

polycarbonate, polyolefin, acrylonitrile butadiene styrene (ABS), polyacetal and polyvinyl alcohol (PVA), and the like.

[0080]

Flexible substrates used in flexible packaging manufacture are typically challenging substrates for conventional inks due to poor adhesion properties. In order to improve adhesion, many conventional inks employ solvents and/or pretreatment steps, however such solvents and/or pretreatment steps often require thermal processes, for example thermal drying processes for drying the solvent, which may cause melting or distortion of the non- porous substrate.

[0081]

The radiation curable ink compositions disclosed herein are advantageously used for printing flexible packaging, preferably food/product packaging (e.g., primary, secondary, or tertiary food packaging) which may contain food products, non-food products,

pharmaceutical, and/or personal care items, due to the ability to cure the radiation curable ink composition with electron beam radiation with minimal heat and substrate distortion, suitable adhesion, and preferably a migration of less than 10 ppb of the cured ink composition into the packaged product/item.

[0082] Method of Forming an Image

The present disclosure provides a method of forming an image by applying the radiation curable ink composition onto a surface of a substrate and exposing the radiation curable ink composition to electron beam radiation or actinic radiation to at least partially cure the radiation curable ink composition to form a cured ink composition on the surface of the substrate.

[0083]

The radiation curable ink compositions described above may be applied in any suitable manner. In some embodiments, one or more radiation curable ink compositions are jetted onto the desired substrate at temperatures of less than about 100°C, such as from about 25°C to about 100°C, or from about 30°C to about 95°C. The radiation curable ink compositions can be applied in a multi-pass or in a single-pass-method. With the multi-pass method, every line to be printed is coated several times by a printing unit, where a pattern or picture is constructed in several steps, forming a high picture quality. In industrial processes, the single-pass method is used preferably, in which every line to be printed is only coated once by the printing unit, which enables high printing speeds, above 100 m/min.

[0084]

Any print head known to those of ordinary skill in the art of inkjet printing can be used as printing units in the present method, including continuous print heads and thermal, electrostatic and acoustic drop on demand print heads, preferably a piezoelectric print head is used. Typical parameters, such as, for example, drop speed, print head temperature, control voltage and control pulse width, can be adjusted according to the specification of the print head. Print heads which are generally suitable for usage in the method according to the present invention have a droplet size in the range of 2 to 80 pL and a droplet frequency in the range of 10 to 100 kHz, although values above or below these ranges may also be used.

[0085]

The radiation curable ink compositions can be employed in direct printing or indirect (offset) printing applications (e.g., sheetfed offset lithography). When employed in indirect printing, droplets of the ink are ejected in an imagewise pattern onto a recording substrate, the recording substrate is an intermediate-transfer member and the ink in the imagewise pattern is subsequently transferred from the intermediate-transfer member to a final recording substrate. When an indirect-printing process is used, the intermediate-transfer member can be of any desired or suitable configuration, such as a drum or roller, a belt or web, a flat surface or platen, or the like.

[0086]

After applying the radiation curable ink composition onto the substrate, the radiation curable ink composition can be cured by exposing to actinic radiation and/or by electron beam curing. In some embodiments, the radiation curable ink composition includes a photoinitiator, and is cured using actinic radiation, preferably UV radiation, preferably UV radiation having a wavelength of 200-400 nm. In preferred embodiments, the radiation curable ink composition is substantially free of a photoinitiator and is cured by exposure to electron beam radiation. In electron beam curing methods, electrons emerge from a vacuum chamber through a metal foil and reach the radiation curable ink composition on the substrate in a reaction chamber. Electron beam curing processes typically generate little heat and thus are advantageously used for forming an image onto flexible packaging or other substrates that are susceptible to distortion from thermal processing or processes requiring raised

temperatures. The radiation curable ink compositions may be exposed to electron beams using any electron beam generator, such as electron beam generators available from Electron Crosslinking AB (Sweden), Comet AG (Switzerland) or Energy Sciences, Inc. (ESI) (USA). The electron beam generator may be arranged in combination with the print head of the inkjet printer, so that the radiation curable ink composition is exposed to curing radiation shortly after being jetted.

[0087]

In some embodiments, the radiation curable ink composition is exposed to a low dose of electron beam radiation to form an image, such as from about 0.1 Mrad, preferably from about 0.2 Mrad, preferably from about 0.3 Mrad, preferably from about 0.4 Mrad, preferably from about 0.5 Mrad, and up to about 1.3 Mrad, preferably up to about 1.2 Mrad, preferably up to about 1.1 Mrad, or more preferably up to about 1.0 Mrad. In some embodiments, an image is formed by exposing the radiation curable ink composition to a higher dose of electron beam radiation, for example, from about 1 Mrad, preferably from about 1.2 Mrad, preferably from about 1.5 Mrad, preferably from about 1.6 Mrad, preferably from about 1.7 Mrad, up to about 10 Mrad, preferably up to about 8 Mrad, preferably up to about 6 Mrad, or more preferably up to about 3 Mrad, or a combination of low dose and high dose electron beam radiation.

[0088]

Various electron beam accelerating potentials may be employed in the methods disclosed herein, however, an accelerating potential of less than 300 kV is typically used, preferably less than 260 kV, more preferably less than 240 kV, more preferably less than 220 kV, for example in the range of about 70 to about 200 kV.

[0089] The method of the present disclosure may optionally include supplying an inert gas during electron beam curing to displace oxygen ("inerting") which inhibits free-radical polymerization. In some embodiments, less than about 200 ppm, preferably less than about 180 ppm, preferably less than about 160 ppm, preferably less than about 140 ppm oxygen is present in the reaction chamber during curing. Any suitable inert gas may be used including, but not limited to, nitrogen gas and argon gas.

[0090]

Further, it is noted that after application of the radiation curable ink composition, a drying step is optional, i.e., no drying step is required in the methods herein, as the radiation curable ink composition of the present disclosure is preferably non-aqueous.

It should also be recognized that substrate surface treatments such as corona treatment, atmospheric plasma treatment, and flame treatment may optionally be employed in the methods herein prior to application of the radiation curable ink compositions to improve printed article characteristics, for example ink adhesion. The parameters of such substrate surface treatments may be varied greatly depending on the substrate material to be printed, the specific radiation curable ink compositions utilized, the printing method applied, and the desired properties and applications of the printed article.

The examples below are intended to further illustrate radiation curable ink

compositions and are not intended to limit the scope of the claims.

EXAMPLES

[0091]

EXAMPLE 1

100.00

Ratio of [(B)+(D)]:[(A)+(C)] = 2.91 [0092]

EXAMPLE 2

100.00

Ratio of [(B)+(D)]:[(A)+(C)] = 2.91

[0093] Where a numerical limit or range is stated herein, the endpoints are included. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out.

As used herein the words "a" and "an" and the like carry the meaning of "one or more."

Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

All patents and other references mentioned above are incorporated in full herein by this reference, the same as if set forth at length.