Food packaging ink jet ink compositions

Abstract

Described herein are inkjet ink compositions that are suitable for use in food packaging (e.g., safe for printing on food packages with good adhesion and high color and contrast). Such food packaging inkjet ink compositions include one or more colorants, one or more water insoluble binders, and one or more organic solvents.

Description

FOOD PACKAGING INK JET INK COMPOSITIONSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 616,227 filed December 29, 2024, which is incorporated herein by reference, in its entirety for any and all purposes.FIELD

[0002] The present technology generally relates to inkjet ink compositions that are suitable for use in food packaging (e.g., safe for printing on food packages with good adhesion and high color and contrast). Such food packaging ink jet ink compositions include one or more colorants, one or more water insoluble binders, and one or more organic solvents.BACKGROUND

[0003] Industrial ink jet coding and marking of food products usually occurs during the production process at or near the stage where food is sealed within its packaging. The jetted code is usually printed on the exterior of the package and is thus separated from the food by a package layer with various degrees of permeability. An obvious goal in such food production and packaging is to minimize or eliminate the migration of the code ink component into the food article.

[0004] Continuous inkjet inks for high-speed industrial marking currently rely on synthetic colorants for printing onto food packaging. These colorants have evolved over time to provide improved formulation stability, enhanced compatibility with inkjet printers and better printed ink properties such as heightened durability and improved legibility. When used on food packaging, the use of specialized synthetic colorants has not historically been a safety or compliance concern for various reasons. However, as packaging has evolved and regulations have changed, there is a need for inks that are considered to be safer.

[0005] Colorants are sometimes deemed to be safe because they are reviewed and approved by regulatory entities for a particular industrial use. Various countries or regional entities have different regulatory means of classifying dyes that are safe for use in or on food products orprimary food packaging. For example, for use directly in or on food products there are lists such as FD&C colorants (21 C.F.R. Section 170), GRAS or EC grade colorants defined in Regulation (EC) No. 1333 / 2008 each of which specifies useable food grade dyes which may be of natural or synthetic origin. In certain regions, colorants may be required to be certified food grade or may be considered exempt from certification, particularly those of natural origin. Naturally derived colorants may fall under other exemptions which allow their use when processed by certain means, for example by extraction from a natural source. In many cases any chemical components that are listed as safe for use directly in food such as in regulation 21 C.F.R. may also be used safely in or on food packaging by inference.

[0006] When used on food packaging, it may be necessary to prove that the ink components do not migrate through the food packaging into the food, or migrate so slowly that the food expiration date will pass before a meaningful amount of ink components have migrated through the food packaging. Therefore, there is a need to ensure that inkjet inks will meet regulatory requirements for migrating species. Such regulations, such as EC 10 / 2011 lay out specific migration limits for chemicals that are part of food packaging and various related guidelines and regulations specify different migration tests which are appropriate to conduct to validate specific migrants of concern are below acceptable thresholds. Passing such migration tests on the specific or even on modelled packaging can provide compelling evidence to food producers that the ink will not taint the food contents and that they may produce their food without risk.

[0007] It is also important that the CIJ marks can be delivered with sufficient production speed. Coding and marking of products require fast drying organic solvents along with appropriate solvent compatible resins. The resulting printed images must also achieve a practical level of color development (wetting), reliable adhesion and water resistance on materials in order to meet standard industry requirements. Whatever the adhesion process that is required and whatever type of packaging that is employed, the marking must achieve reliable adhesion. Additionally, dyes must be able to survive after printing- e.g., the printed mark must be able to resist ambient lighting without fading.

[0008] Food grade dyes, however, are typically water soluble and have low or limited solubility in all organic solvents (particularly fast drying ones such as ketones). For CIJ inks, achieving acceptable concentration for all soluble dyes within the ink formulation is important to ensure sufficient contrast and predictable color that is discernible on different coded productswith a high variety of background colors. The inks across a range of environments where products are made must also be conductive enough to operate reliably in the CIJ printer.

[0009] This disclosure provides inkjet ink compositions that are suitable for food packaging that have been formulated with dyes that previously have been inherently incompatible with or are not particularly soluble in the jet ink. In particular, the inkjet ink compositions include one or more colorants, one or more water insoluble binders, and one or more organic solvent. The ink jet ink compositions described herein have sufficient dye concentration and the resulting printed inks have the required adhesion, lightfastness, dark contrast, and general food packaging compliance.SUMMARY

[0010] Provided in one aspect is an inkjet ink composition comprising a colorant, one or more water insoluble binders, and one or more organic solvents, wherein the colorant, the one or more water insoluble binders and the one or more organic solvents are present in a amount of greater than about 60% by weight, based on the total weight of the composition.

[0011] In some embodiments, the colorant comprises one or more water soluble dyes and pigments. In some other embodiments, the colorant comprises one or more water soluble dyes. In still some embodiments, the colorant comprises a water-soluble dye or a mixture of a water- soluble dye and a pigment. In some embodiments, the colorant comprises any one of more of the following: (a) one or more mono-, di-, or trifunctional dyes comprising the ionic functional groups of sulfonate, benzene sulfonate, carboxylate or phenolate; (b) one or more cationic, zwitterionic, or non-ionic dyes; (c) one or more triphenylmethanes, monoazos or disazos. In some embodiments, the colorant is present in an amount of from about 0.3% to about 10% by weight, based on the total weight of the composition. In some embodiments, the colorant is Patent Blue V. In some embodiments, the colorant is carbon black. In some embodiments, the colorant is a metal complex solvent black dye. In In some embodiments, the colorant is present in an amount of from about 0.3% to about 5 % by weight, based on the based on the total weight of the composition.

[0012] In some embodiments, the one or more water insoluble binders comprise any one of polyvinyl butyral binders, polyurethane binders, cellulose ester binders, vinyl chloride binders, vinyl acetate binders, ester binders, and acrylic binders, and tackifier resins. In some embodiments, the one or more water-insoluble binders comprise one or more acrylic binders, cellulose acetate butyrate binders, polyvinyl butyral binders, urethane binders, tackifier resins and vinyl polymers binders. In still some other embodiments, the one or more water-insoluble binders comprise one or more polyvinyl butyral binders, polyurethane binders and tackifier resins. In some embodiments, the one or more water insoluble binders comprise any one of vinyl butyral, cellulose ester, vinyl chloride, vinyl acetate, ester, and acrylic. In some embodiments, the one or more water insoluble binders does not comprise shellac. In some embodiments, the one or more water insoluble binders is present in an amount of from about 3% to about 35% by weight, based on the total weight of the composition.

[0013] In some embodiments, the one or more organic solvents comprises Cl to C4 alcohols or lactates, the one or more organic solvents comprise ethanol, n-propanol, methyl lactate, ethyl lactate, butyl lactate, or any combination thereof. In some embodiments, the one or more organic solvents comprise ethanol. In some embodiments, the one or more organic solvents further comprise a compatibilizing solvent. In some embodiments, the compatibilizing solvent comprises a ketone and an ester. In some embodiments, the compatibilizing solvent comprises acetone, methyl ethyl ketone (MEK), methyl propyl ketone (MPK), or methyl isobutyl ketone (MiBK). In some embodiments, the compatibilizing solvent comprises MEK. In some embodiments, the compatibilizing solvent is present in an amount of at least about 20 wt% by weight, based on the total weight of the composition. In some embodiments, the compatibilizing solvent is present in an amount of from about 20% to about 80% by weight of the composition. In some embodiments, the compatibilizing solvent is present in an amount of from about 20% to about 90% by weight of the composition. In some embodiments, the compatibilizing solvent is present in an amount of from about 45% to about 90% by weight of the composition.

[0014] In some embodiments, the composition comprises water in amount of about 15% or less by weight, based on the total weight of the composition. In some embodiments, the composition comprises water in amount of about 1% or less by weight, based on the total weight of the composition. In some embodiments, water is present in the composition in anamount of from about 0.5% by weight to about 5% by weight, based on the total weight of the composition.

[0015] In some embodiments, the composition comprises one or more selected from glycol, diol or glycerin. In some embodiments, one or more selected from glycol, diol or glycerin is present in amount of less than about 7% by weight, based on the based on the total weight of the composition.

[0016] In some embodiments, the composition comprises one or more water-compatible materials. In some embodiments, the one or more water-compatible materials is present in an amount of at least greater than 1% by weight, based on the total weight of the composition.

[0017] In some embodiments, the composition further comprises a conductive agent. In some embodiments, the conductive agent comprises an ammonium salt, alkyl ammonium salt or an alkali metal salt. In some embodiments, the conductive agent comprises a secondary, tertiary or quaternary ammonium cation that is further comprised of at least one organic group exhibiting 4 carbon atoms in series. In some embodiments, the conductive agent cation does not comprise tetrabutylammonium. In some embodiments, the conductive agent cation does not comprise tetrabutylammonium hexafluoroposphate or potassium hexafluorophosphate. In some embodiments, the conductive agent comprises one or more of cetyltrimethylammonium bromide and didecyldimethylammonium chloride. In some embodiments, the conductive agent comprises one or more of cetyltrimethylammonium bromide and lithium nitrate. In some embodiments, the conductive agent is present in an amount of from about 0.1% to about 5% by weight, based on the total weight of the composition.

[0018] In some embodiments, the composition further comprises a pH active compound. In some embodiments, the pH active compound comprises an acid or an acidic moiety and / or has at least one pKa of less than about 5. In some embodiments, the pH active compound is present in am amount of 0.1 to about 6% by weight, based on the total weight of the composition.

[0019] In some embodiments, the composition further comprises a comprises a solvent compatible dispersant. In some embodiments, the solvent compatible dispersant comprises a polyvinyl butyral dispersant.

[0020] In some embodiments, the composition comprises:a colorant comprising one or more water-soluble dyes and pigments, one or more water insoluble binders, one or more organic solvents, and a conductive agent comprising a secondary, tertiary or quaternary ammonium cation that is further comprised of at least one organic group exhibiting 4 carbon atoms in series.

[0021] In some embodiments, the composition has a resistivity of less than about 2500 ohm- cm at about 25 °C.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIGS. 1A, IB, and 1C illustrate the printed code using Composition 2 on aqueous paper (1 A), on PET film (IB), and monoPE film (1C).

[0023] FIGS. 2 A and 2B illustrate the printed code using Composition 2 on PET film after soaking in water for 10 minutes (2A) and soaking for 10 minutes followed by lOx thumb rubs (2B).

[0024] FIG. 3 illustrates the Turboscan mean delta backscatter comparison for Compositions 9A and 14A versus comparative composition CE5 at the air-ink meniscus (approximately top 10mm of sample tubes).

[0025] FIG. 4 illustrates the printed code appearance of Composition CE6 (circled area) after adhesion tests on BOPP.

[0026] FIG. 5 illustrates the printed code appearance of Composition 14A (circled area) after adhesion tests on BOPP.

[0027] FIG. 6 illustrates the printed code appearance of Composition 14A (bottom) and comparative composition / control composition (CE 6, top) after the crinkle test as described in Example 6.DETAILED DESCRIPTION

[0028] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broaderaspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment s).

[0029] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term.

[0030] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0031] Inks that are typically used for direct or near direct food contact (e.g., eggshell coding) are those that have similar colorants and have binders are usually water soluble (e.g. cellulosic) or are naturally sourced resins like shellac or Zein (See Imaje U.S. Patent 8,167,990). Commercially available food grade inks typically contain a substantial amount of water (e.g., greater than 20%), and / or glycol (e.g., greater than 10%) and / or ammonia. One example of a food grade ink with little or no water is V497-D, which contains acetone and ethanol. V497- D also contains -1.2% of acid red 51 and shellac resin. Shellac resins, however, generally achieve poor adhesion on plastic materials.

[0032] Described herein are food packaging inkjet ink compositions comprising a colorant, one or more water insoluble binders, and one or more organic solvents. Such ink jet ink compositions have sufficient dye concentration, and the resulting printed inks have the required functionality, such as adhesion, high color and contrast, and general food packagingcompliance. In some instances, the inkjet ink compositions described herein use alcohol as a primary organic solvent with the potential for inclusion of some glycol or water. In some instances, the compositions described herein use applicable dyes with sufficient solubility in the primary solvent of the composition along with the compatibilizing solvent (e.g., a ketone solvent or an ester solvent) and solvent soluble organic binders.

[0033] Also, the compositions described herein may comprise a conductive agent. In still other instances, these conductive agents in combination with the solvent system may have a significant impact on the solubility of the colorant in the composition. It is advantageous to maximize the solubility of the colorant in organic solvents so that the inkjet ink composition can employ a colorant concentration below the saturation limit. Hence, it is preferred to select conductive agents to minimize any negative impact to the initial solubility; or, it is more preferred to select conductive agents which enhance the solubility of the dye in the ink system. In specific embodiments, the conductive agents comprise a cation with an organic central atom substituted with at least one carbon chain with a length of at least 4 carbon atoms. In some embodiments, the conductive agent cation does not comprise tetrabutylammonium. In contrast to the current food grade inks, the food packaging ink jet ink compositions described herein ensure that the colorant or dye remains soluble and enable the use of all needed, potentially incompatible, components including those which lend to adhesion and wetting of polymer substrates.

[0034] Provided in one aspect is an inkjet ink composition comprising: a colorant, one or more water insoluble binders, and one or more organic solvents, wherein the colorant, the one or more water insoluble binders, and the one or more organic solvents are present in a amount of greater than about 60% by weight, based on the total weight of the composition.

[0035] In some embodiments, the colorant, the one or more water insoluble binders, and the one or more organic solvents are present in an amount of greater than about 65% by weight, based on the total weight of the composition. In some embodiments, the colorant, the one or more water insoluble binders, and the one or more organic solvents are present in an amount of greater than about 70% by weight, based on the total weight of the composition. In someembodiments, the colorant, the one or more water insoluble binders, and the one or more organic solvents are present in an amount of greater than about 75% by weight, based on the total weight of the composition. In some embodiments, the colorant, the one or more water insoluble binders, and the one or more organic solvents are present in an amount of greater than about 80% by weight, based on the total weight of the composition.

[0036] Regulatory agencies also provide lists of components which are acceptable for use in applications involving food or food packaging. For instance, such lists include:• Commission Regulation (EU) No 10 / 2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food;• the 21st Ordinance amending the Consumer Goods Ordinance of the German Printing Ink Ordinance covering printing inks for indirect and foreseeable food contact; or• the Swiss Ordinance 817.023.21 regulating printing inks for indirect food contact.The compositions described herein may comprise one or more the components disclosed in these lists.

[0037] The ink jet ink compositions described herein may comprise one or more of the following features:• printed with pigmented printers and are compatible with higher frequency printers that are typically used for dye-based inks (up to about 80 KHz);• exhibit good compatibility with water at levels typical for operating in a CIJ printer;• provide printed marks having good adhesion to various kinds of packaging, including PE, PP, PET, hard plastics, and flexible films; and• provide printed marks having good contrast and color suitable for the intended application;Colorant

[0038] The ink jet ink composition described herein comprises a colorant. As described herein, the colorant comprises one or more water-soluble dyes and pigments. In some embodiments, the colorant comprises one or more water-soluble dyes. The colorant may be used to provide contrast, adjust color or adjust the solution stability of the overall inkcompositions. The colorant may comprise a blend of dyes that promote colors more similar to black and provide darker contrast. In some embodiments, the colorant comprises a water- soluble dye, a pigment, or a mixture of a water-soluble dye and a pigment.

[0039] Examples of suitable colorants include one or more of mono-, di-, or trifunctional dyes comprising the ionic functional groups of sulfonate, benzene sulfonate, carboxylate or phenolate. Dyes can be instead cationic or zwitterionic, or, even non-ionic and be soluble by the fact that they contain sufficient and appropriate functionalization to be water soluble at some proportion. Suitable dyes include triphenylmethanes, xanthenes, triphenylmethanes, monoazos or disazos, quinolines, tartrazines, erythrosines, rhodamines, anthraquinones, phthalocyanines or dyes of natural origin with various structures. Suitable examples, include but are not limited to, Acid Red 51 (Erythrosin) (CAS No. 12227-78-0), Genuine Carmine (Natural Red 4, E 120), carminic acid (CAS No. 1260-17-9), Real carmine (CAS No. 1390-65- 4), Annatto (natural orange 4) (CAS No. 1393-63-1), Chlorophylls (CAS No. 1406-65-1), copper-containing complexes of chlorophylls (CAS No. 15739-09-0), Acid Red 51 (Erythrosin) (CAS No. 16423-68-0), Acid yellow 23 (Tartrazine) (CAS No. 1934-21-0), Patent Blue V (Na-salt) (CAS No. 20262-76-4), copper-containing complexes of chlorophylls (CAS No. 24111-17-9), Brilliant black BN (E 151) (CAS No. 2519-30-4), Allura Red AC (E 129) (CAS No. 25956-17-6), Food Red 7 (Ponceau 4R) (CAS No. 2611-82-7), Patent Blue V (Acid Blue 3, E131) (CAS No. 3536-49-0), Carotenes (i) mixed carotenes (ii) beta-carotene (CAS No. 36-88-4), Braun HAT (Food Brown 3, E 155) (CAS No. 4553-89-3), Curcumin (CAS No. 458-37-7), Capsanthin (paprika) (CAS No. 465-42-9), Capsorubin (CAS No. 470-38-2), Natural Blue 1 (CAS No. 482-89-3), beet red (CAS No. 7659-95-2), ammonesulfite caramel (CAS No. 8028-89-5), Simple caramel (CAS No. 8028-89-5), Sulphite Liquor Caramel (CAS No. 8028-89-5), copper-containing complexes of chlorophylls (CAS No. 8049-84-1), Food red 9 (Amar-anth) (CAS No. 915-67-3), coumarin (CAS No. 91-64-5), and Acid yellow 3 (quinoline yellow) (CAS No. 95193-83-2),. In some embodiments, the colorant is one or more of Acid Red 51 (Erythrosin) (CAS No. 12227-78-0), Acid Blue 9 and Patent Blue V (Na-salt) (CAS No. 20262-76-4), and metal complex solvent black dyes. In some embodiments, the colorant is Patent Blue V. In some embodiments, the colorant is a metal complex solvent black dye.

[0040] Examples of suitable colorants include, but are not limited to, Allura Red AC (E 129) / FD&C Red No. 40 (CAS No. 0025956-17-6), Brilliant black BN (E 151) (CAS No. 0002519-30-4), Food Blue 2 (Brilliant Blue FCF) / FD&C Blue No. 1 or Acid Blue 9 (CAS No. 0003844-45-9), Patent Blue V (Na-salt) (CAS No. 20262-76-4), Green S / Acid green 50 (CAS No. 0003087-16-9), Natural Blue 1 / indigo (CAS No. 0000482-89-3), Genuine Carmine (Natural Red 4, E 120) / Carminic acid (CAS No. 1260-17-9), yellow-orange S / Sunset Yellow FCF (CAS No. 2783-94-0), Acid Yellow 3 (quinoline yellow) (CAS No. 8004-92-0), Anthocyanins / purple red, natural dye (CAS No. 11029-12-2), FD&C Red 3 / red, Food Red 3 (Azoru- bin) / CI FOOD Red 3; E122;carmoisine, acid red 14 (CAS No. 3567-69-9), Food Red 7 (Ponceau 4R) / New Coccine, Acid Red 18, Ponceau 4 R (CAS No. 0002611-82- 7), and Food Red 9 (Amar- anth) / CI FOOD Red 9; E123 (CAS No. 915-67-3).

[0041] In some embodiments, the colorant may comprise one or more pigments, which may be inorganic or organic pigments. In some embodiments, the colorant may comprise a mixture comprising one or more pigments and one or more water-soluble dyes. For embodiments, where one or more pigments and one or more water-soluble dyes are present in the colorant, the one or more pigments and one or more water-soluble dyes are present in suitable amounts that minimize the pigment content within the ink. Without being bound by theory, it is believed that adding one or more pigments to the ink jet ink compositions described herein reduce the amount of one or more dyes required as a relative proportion in the colorant. Since dyes are well known to have relatively high migration potential as compared with pigments, the inkjet ink compositions comprising one or more pigments have a lower migration potential. Examples of suitable pigments include but are not limited to carbon black pigment and organic pigments. Also, suitable pigments include those having a mean particle size of from about 0.1 microns to about 0.2 microns.

[0042] Carbon black is a preferred pigment and may be any conventional form of carbon black including soot, furnace black, acetylene black, lamp black, C.I. Pigment Black 7 and channel black. Suitable carbon blacks may be milled or processes to yield pigments with suitable primary and secondary structures for stable dispersion within inkjet inks. Especially preferred carbon black pigments are ones that contain low polycyclic aromatic hydrocarbon impurities (PAHs) as PAHs are known to be harmful to human health and may migrate easilythrough food packaging. These conforms generally to the requirements set-forth in EC 10 / 2011 namely: a. Primary particles of 10-300 nm, aggregated to 100-1200 nm, which can form agglomerates of 300 nm-mm. b. Toluene-soluble substances: maximum 0.1 %, determined according to ISO method 6209. c. UV absorption of cyclohexane extract at 386 nm: < 0.02 AU for a cell of 1 cm or < 0.1 AU for a cell of 5 cm, determined by a generally accepted method of analysis. d. Benzo(a)pyrene content: max. 0.25 mg / kg carbon black.Different PAHs may be tested for during GC-MS analysis including but not limited to: naphthalene; acenaphthylene; acenaphthene; fluorene; phenanthrene; anthracene; fluoranthene; pyrene; benzo[c]fluorene; benzo[a]anthracene; cylopenta[cd]pyrene; chrysene; 5-methylchrysene; benzo[b]fluoranthene; benzo[k]fluoranthene; benzo[j]fluoranthene; benzo[a]pyrene; benzo[e]pyrene; indeno[l,2,3-cd]pyrene; dibenz(a,h)anthracene; benzo[ghi]perylene; dibenzo[al]pyrene; dibenzo[ae]pyrene; dibenzo[ai]pyrene; dibenzo[ah]pyrene]. It is preferred that cumulative PAH content is below 100 ppm or even below 10 ppm.

[0043] Examples of suitable organic pigments include Pigment Violet 19 (CAS No.1047-16- 1), Pigment Red 49:2 (CAS No. 1103-39-5), Pigment Red 176 (CAS No. 12225-06-8), Pigment Violet 32 (CAS No. 12225-08-0), Pigment Yellow 97 (CAS No. 12225-18-2), Pigment Black 11 (CAS No. 12227-89-3), Pigment Orange 36 (CAS No. 12236-62-3), Pigment Orange 38 (CAS No. 12236-64-5), Pigment Violet 27 CAS No. 12237-62-6), Pigment Red 169 (CAS No. 12237-63-7), Pigment Blue 27 (CAS No. 12240-15-2), Pigment Yellow 62 (CAS No. 12286-66-7), Pigment Yellow 180 (CAS No. 77804-81-0), Pigment Orange 72 (CAS No. 78245-94-0), Pigment Yellow 174 (CAS No. 78952-72-4), Pigment Yellow 128 (CAS No. 79953-85-8), Acid yellow 3 (quinoline yellow) (CAS No. 8004-92-0), Pigment Yellow 53 (CAS No. 8007-18-9), Pigment Red 81 : 1 (CAS No. 80083-40-5), Iron(III) oxide (Pigment Red 101) (CAS No. 1309-37-1), Pigment Black 11 (CAS No. 1317-61-9), Pigment Blue 61 (CAS No. 1324-76-1), Pigment Blue 1 (CAS No. 1325-87-7), Pigment Green 7 (CAS No. 1328-53- 6), Pigment Green 37 (CAS No. 1330-37-6), Pigment Blue 79 (CAS No. 14154-42-8), PigmentGreen 36 (CAS No. 14302-13-7), Pigment Blue 15 (also Pigment Blue 15: 1, Pigment Blue 15:3, Pigment Blue 15:6) (CAS No. 147-14-8), Pigment Red 48:3 (CAS No. 15782-05-5), Yellow-orange S (CAS No. 15790-07-5), Pigment Orange 34 (CAS No. 15793-73-4), Pigment Yellow 111 (CAS No. 15993-42-7), Pigment Red 268 (CAS No. 16403-84-2), Indigotine I (CAS No. 16521-38-3), Pigment Yellow 4 (CAS No. 1657-16-5), Pigment Violet 37 (CAS No. 17741-63-8), Pigment Red 52: 1 (CAS No. 17852-99-2), Pigment Violet 23 (CAS No. 215247- 95-3), Pigment Yellow 188 (CAS No. 23792-68-9), Pigment Red 3 (CAS No. 2425-85-6), Pigment Yellow 1 (CAS No. 2512-29-0), Pigment Yellow 150 (CAS No. 25157-64-6), Yellow-orange S (CAS No. 2783-94-0), Pigment Red 170 (CAS No. 2786-76-7), Pigment Red 4 (CAS No. 2814-77-9), Pigment Yellow 120 (CAS No. 29920-31-8), Pigment Yellow 138 (CAS No. 30125-47-4), Green S (CAS No. 3087-16-9), Pigment Red 202 (CAS No. 3089-17- 6), Pigment Red 208 (CAS No. 31778-10-6), Pigment Yellow 151 (CAS No. 31837-42-0), Pigment Red 200: 1 (CAS No. 32041-58-0), Pigment Orange 13 (CAS No. 3520-72-7), Pigment Yellow 175 (CAS No. 35636-63-6), Food red 3 (Azoru- bin) (CAS No. 3567-69-9), Pigment Brown 23 (CAS No. 35869-64-8), Pigment Yellow 139 (CAS No. 36888-99-0), Pigment Red 266 (CAS No. 36968-27-1), Food Blue 2 (Brilliant Blue FCF) (CAS No. 3844-45-9), Pigment Red 166 (CAS No. 3905-19-9), Pigment Red 177 (CAS No. 4051-63-2), Pigment Red 214 (CAS No. 40618-31-3), Pigment Orange 61 (CAS No. 40716-47-0), Pigment Orange 43 (CAS No. 4424-06-0), Pigment Yellow 17 (CAS No. 4531-49-1), Pigment Blue 60 (CAS No. 81-77- 6), Pigment Black 32 (CAS No. 83524-75-8), Pigment Orange 71 (CAS No. 84632-50-8), Pigment Orange 73 (CAS No. 84632-59-7), Pigment Red 254 (CAS No. 84632-65-5), Pigment Red 272 (CAS No. 84632-66-6), Indigotine I (CAS No. 860-22-0), Pigment Yellow 150 (CAS No. 86249-83-4), Pigment Yellow 150 (CAS No. 872613-79-1), Pigment Red 264 (CAS No. 88949-33-1), Pigment Yellow 126 (CAS No. 90268-23-8), Pigment Red 149 (CAS No. 4948- 15-6), Pigment Yellow 109 (CAS No. 5045-40-9), Pigment Yellow 13 (CAS No. 5102-83-0), Iron(III) hydroxide oxide (Pigment Yellow 42) (CAS No. 51274-00-1), Canthaxanthin (CAS No. 514-78-3), Pigment Red 185 (CAS No. 51920-12-8), Pigment Red (CAS No. 242 52238- 92-3), Pigment Red 48:4 (CAS No. 5280-66-0), Pigment Red 146 (CAS No. 5280-68-2), Pigment Red 144 (CAS No. 5280-78-4), Pigment Yellow 95 (CAS No. 5280-80-8), Litholrubin BK (CAS No. 5281-04-9), Pigment Yellow 14 (CAS No. 5468-75-7), Pigment Yellow 83 (CAS No. 5567-15-7), Pigment Yellow 93 (CAS No. 5580-57-4), Pigment Yellow 110 (CAS No. 5590-18-1), Pigment Blue 29 (CAS No. 57455-37-5), Pigment Blue 16 (CASNo. 574-93-6), Pigment Red 200 (CAS No. 58067-05-3), Pigment Yellow 16 (CAS No. 5979- 28-2), Pigment Red 2 (CAS No. 6041-94-7), Pigment Red 210 (CAS No. 61932-63-6), Pigment Violet 23 (CAS No. 6358-30-1), Pigment Yellow 74 (CAS No. 6358-31-2), Pigment Yellow 55 (CAS No. 6358-37-8), Pigment Yellow 12 (CAS No. 6358-85-6), Pigment Red 12 (CAS No. 6410-32-8), Pigment Red 63: 1 (CAS No. 6417-83-0), Pigment Yellow 3 (CAS No. 6486- 23-3), Pigment Orange 16 (CAS No. 6505-28-8), Pigment Red 112 (CAS No. 6535-46-2), Pigment Orange 46 (CAS No. 67801-01-8), Pigment Red 269 (CAS No. 67990-05-0), Pigment Yellow 154 (CAS No. 68134-22-5), Pigment Red 147 (CAS No. 68227-78-1), Pigment Red 220 (CAS No. 68259-05-2), Pigment Yellow 150 (CAS No. 68511-62-6), Pigment Yellow 155 (CAS No. 68516-73-4), Pigment Yellow 127 (CAS No. 68610-86-6), Pigment Red 48:2 (CAS No. 7023-61-2), Pigment Orange 64 (CAS No. 72102-84-2), Pigment Yellow 181 (CAS No. 74441-05-7), Pigment Red 81 :2 (CAS No. 75627-12-2), Pigment Yellow 185 (CAS No. 76199- 85-4), Pigment Red 282 (CAS No. 938065-79-3), Pigment Red 148 (CAS No. 94276-08-1), Pigment Red 122 (CAS No. 980-26-7), and Pigment Red 184 (CAS No. 99402-80-9)

[0044] In some embodiments, the colorant is present in an amount of from about 0.3% to about 15% by weight of the composition, including about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, about 5%, about 5.5%, about 6%, about 6.5%, about 7%, about 7.5%, about 8%, about 8.5%, about 9%, about 9.5%, about 10%, about 10.5%, about 11%, about 11.5%, about 12%, about 12.5%, about 13%, about 13.5%, about 14%, about 14.5%, about 15% by weight of the composition. In some embodiments, the colorant is present in an amount of from about 0.3% to about 5% by weight of the composition, including about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, and about 5% by weight of the composition. In some embodiments, the colorant is present in an amount of from about 0.5% to about 15% by weight of the composition. In some embodiments, the colorant is present in an amount of from about 0.5% to about 2.5% by weight of the composition. In some embodiments, the colorant is present in an amount of from about 2.5% to about 12% by weight of the composition.

[0045] In some embodiments, when the colorant is a water-soluble colorant, the water-soluble colorant is more water-soluble than it is soluble in one or more organic solvents. In someembodiments, the water-soluble colorant has a solubility in water of less than 5%, particularly if it is a naturally derived colorant, or the acid form of the water-soluble colorant.Water Insoluble Binders

[0046] The inkjet ink compositions described herein comprise one or more water insoluble binders (e.g., binders that soluble only in organic solvents). As described in more detail below, other binders or materials may be present that have partial or complete water solubility. However, the water-soluble components are present in low enough amounts such that the one or more binders present in the composition do not dissolve or disperse in water.

[0047] Suitable examples of one or more water insoluble binders comprised of monomers from any of the categories of vinyl butyral, cellulose ester, vinyl chloride, vinyl acetate, ester, and acrylic. These may further include natural resins such as shellac or modified natural resins such as rosin esters. Other suitable examples include polyurethane binders and tackifier resins. More specific examples include cellulose esters such as cellulose acetate butyrate and cellulose acetate propionate, polyvinyl butyral (PVB), and any combinations thereof.

[0048] Examples of polyvinyl butyral binders include PIOLOFORM® BN 18, available from Wacker Chemie AG, MOWITAL® B20H or MOWITAL® B 14 S available from Kuraray America, Inc., and S-LEC B Polyvinyl Butyral from Sekisui Products LLC. An example of cellulose acetate propionate binders includes CAP-482-0.5 (cellulose acetate propionate) from Eastman Chemical. Examples of cellulose acetate butyrate binders include CAB 553-0.4, CAB 551-0.01, and CAP 482-0.5, all of which are available from Eastman Chemical.

[0049] Rosin ester resins include SUPERESTER 75 available from Arakawa Chemical and STAYB ELITE® Ester 10, which is the glycerol ester of partially hydrogenated wood rosin from Pinova Incorporated or Eastman Chemical Incorporated.

[0050] In some embodiments, the one or more water-insoluble binders comprise rosin esters (e.g, STAYB ELITE® Ester 10). In some embodiments, the one or more water-insoluble binders comprise polyvinyl butyral binders (MOWITAL® B 14 S). In some embodiments, the one or more water-insoluble binders comprise cellulose acetate butyrate binders (e.g., CAB 553-0.4, CAB 551-0.01, and CAP 482-0.5). In some embodiments, the one or more waterinsoluble binders does not comprise shellac. In some embodiments, the one or more waterinsoluble binders comprise one or more acrylic binders, cellulose acetate butyrate binders, polyvinyl butyral binders, urethane binders, tackifier resins and vinyl polymers binders. In some embodiments, the one or more water-insoluble binders comprise one or more polyvinyl butyral binders, polyurethane binders and tackifier resins.

[0051] In some embodiments, the one or more water-insoluble binders is present in an amount of from about 3% to about 35% by weight of the composition, including about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, and 35% by weight of the composition. In some embodiments, the one or more water-insoluble binders is present in an amount of from about 5% to about 16% by weight of the composition.

[0052] In some embodiments, the one or more water-insoluble binders is soluble to greater than 10% on a weight / weight basis in a compatibilizing solvent.

[0053] As discussed below, the compositions described herein may further comprise one or more water-soluble binders. If the composition comprises one or more water-soluble binders, then the composition comprises one or more water insoluble binders in an amount that is greater than about 30% of the total binders present in the composition or greater than about 50% of the total binders present in the composition.Organic Solvents

[0054] The ink jet ink compositions described herein comprise one or more protic organic solvents which serve to help solubilize the colorant. Suitable examples include Cl to C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol. Methanol is typically undesirable from a safety perspective, but in some cases it may be permissible because it is a completely volatile component. Other suitable examples include lactates, such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, and n-butyl lactate. In some embodiments, the one or more organic solvents comprise ethanol, n-propanol, or any combination thereof. In some embodiments, the one or more organic solvents comprise ethanol.

[0055] In some embodiments, the one or more organic solvents may comprise one or more compatibilizing solvents (e.g., a ketone solvent or an ester solvent) which enables the use of a wider variety of suitable binder resins with suitable Hansen solubility parameters (e.g., non polar > about 7 and hydrogen bonding < about 5). Suitable examples of ketone solvents include but are not limited to acetone, methyl ethyl ketone, 3-methyl-2-butanone (methyl isopropyl ketone), 2-pentanone (methyl propyl ketone), diethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Suitable examples of ester solvents include but are not limited to methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, t- butyl acetate, amyl acetate, and methoxypropyl acetate. In some embodiments, the compatibilizing solvent is a C3 to C6 ketone and / or an C3 to C7 ester. In some embodiments, the compatibilizing solvent is dimethyl carbonate, some embodiments, the compatibilizing solvent comprises acetone, methyl ethyl ketone (MEK), or methyl isobutyl ketone (MiBK). In some embodiments, the compatibilizing solvent comprises MEK.

[0056] In some embodiments, the compatibilizing solvent is present in an amount of at least about 20% by weight, based on the total weight of the composition, including at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80% by weight and at least about 85% by weight, based on the total weight of the composition. In some embodiments, the compatibilizing solvent is present in an amount of from about 20% to about 80% by weight of the composition. In some embodiments, the compatibilizing solvent is present in an amount of from about 20% to about 90% by weight of the composition. In some embodiments, the compatibilizing solvent is present in an amount of from about 45% to about 90% by weight of the composition.

[0057] In some embodiments, the one or more organic solvents are present in an amount of at least about 50% by weight of the composition, including at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%. In some embodiments, the one or more organic solvents are present in an amount of from about 50% to about 95% by weight of the composition, including about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, and about 95% by weight of the composition.

[0058] In some embodiments, water is present in the composition in an amount of less than about 15% by weight, based on the total weight of the composition, including less than about 14%, less than about 13%, less than about 12%, less than about 11%, less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, and less than about 1% by weight, based on the total weight of the composition. In some embodiments, water is present in the composition in an amount of less than about 1% by weight, based on the total weight of the composition. In some embodiments, water is present in the composition in an amount of from about 0.5% by weight to about 5% by weight, based on the total weight of the composition.Additional Components

[0059] In some embodiments, any one of the inkjet ink compositions described herein further comprises one or more of glycol, diol, glycerin, a water-compatible material, a conductive agent and a pH active compound.

[0060] The inkjet ink compositions described herein may comprise glycol, diol, glycerin, or any combination thereof. Examples of glycol include but are not limited to ethylene glycol and propylene glycol. The glycol, diol, glycerin, or any combination thereof may be present in amount of less than about 7% by weight, based on the total weight of the composition, including less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1% by weight based on the total weight of the composition. The glycol, diol, glycerin, or any combination thereof may be present in amount of from 0.5% to about 7% by weight, based on the total weight of the composition.

[0061] The inkjet ink compositions described herein may comprise one or more potentially water-compatible materials which may effectively be binders, stabilizers, surfactants, emulsifiers or have entirely other functions within the formulation. Examples of watercompatible binders include, but are not limited to, polyvinylpyrrolidone binder, polyvinylpyrrolidone vinylacetate copolymers, and hydroxypropylcellulose. In some embodiments, the composition comprises a polyvinylpyrrolidone binder.

[0062] The one or more water-compatible materials (e.g., water-compatible binders) may be present in an amount of from about 1% to about 5% by weight, based on the total weight of the composition. In some embodiments, the one or more water-compatible materials (e.g., water-compatible binders) is present in an amount of about 2% by weight, based on the based on the total weight of the composition.

[0063] The ink jet ink compositions described herein may comprise one or more light stabilizers to improve lightfastness. These may include UV absorbing types stabilizers, radical scavenging type stabilizers, or any combination thereof.

[0064] The inkjet ink compositions described herein may comprise one or more conductive agents. Suitable conductive agents include one or more of an ammonium salt, alkyl ammonium salt or an alkali metal salt. The alkyl ammonium salt may comprise an aliphatic alkyl chain having at least three carbon atoms. The alkali metal salt comprises a sodium or lithium salt. A blend of conductive agents may be used to improve processibility or stability.

[0065] In some instances, the conductive agent may be used to reduce the migration potential of the printed marks provided by any one of the inkjet ink compositions described herein. In some embodiments, the conductive agent comprises a secondary, tertiary or quaternary ammonium cation that is further comprised of at least one organic group exhibiting 4 carbon atoms in series. In some embodiments, the conductive agent cation does not comprise tetrabutylammonium. In some embodiments, the conductive agent is the reaction product of a methylated amine and alkyl halide salt.

[0066] In some embodiments, the conductive agent comprises one or more of didecyldimethylammonium chloride (DDAC), diallyldimethylammonium chloride (DADMAC), sodium salicylate, lithium salicylate, lithium formate, sodium benzoate, lithium benzoate, ammonium formate, lithium nitrate, lithium iodide, sorbitan monostearate, cetyltrimethylammonium bromide (CTAB), and tetrabutylammonium hexafluorophosphate (TBAPFe). In some embodiments, the conductive agent comprises one or more of cetyltrimethylammonium bromide and lithium nitrate. In some embodiments, the conductive agent comprises one or more of cetyltrimethylammonium bromide and di decyl dimethyl ammonium chlori de .

[0067] In some embodiments, the conductive agent is present in an amount of from about 0.1% to about 5% by weight, based on the total weight of the composition, including about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, and about 5% by weight, based onthe total weight of the composition. In some embodiments, the conductive agent is present in an amount of from about 0.1% to about 3% by weight, based on the total weight of the composition.

[0068] In some embodiments, the conductive agent is present in amount of from about 0.1 to about 2-fold of the colorant on a weight basis, including from about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9 and about 2 fold of the colorant on a weight basis.

[0069] The inkjet ink compositions described herein may comprise a pH active compound. The pH active compound comprises an acid or an acidic moiety. The pH active compound may also potentially conjugate a base to form a buffer. The pH active compound may also have at least one pKa of less than about 5. Examples of suitable pH active compounds include, but are not limited to, acetic acid, 11-aminoundecanoic acid, 4-hydroxybenzoic acid, L-ascorbic acid, formic acid, DL-malic acid, chloroacetic acid and dodecylbenzenesulfonic acid. Alternatively, if a conjugate base is the anion for the conductive agent, the latter may also be pH active within the compositions described herein.

[0070] In some embodiments, the pH active compound is present in an amount of from about 0.1% to about 6% by weight, based on the total weight of the composition, including about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, about 5%, about 5.5%, and about 6% by weight, based on the total weight of the composition.

[0071] The ink jet ink compositions described herein may comprise a polymeric surfactant to adjust surface wetting properties or to interact with the colorant. This may be a polysiloxane, a modified polysiloxane, a polyether modified polysiloxane and the like. Specific examples include Tegoglide 450 and Tegoglide 432 available from Evonik Incorporated. The surfactant may also comprise a polyethoxylated and fatty acid. The surfactant may further comprise sorbitan.

[0072] The ink jet ink compositions described herein may comprise a solvent compatible dispersant, which is compatible with a wide variety of polymeric resins. Examples of suitable dispersants include but are not limited to acidic acid esters of higher molecular weight alcoholsthat contain polymeric segments of poly)oxy-l,2-ethanediyl), alkyl ethers, or succinates; lecithins; acidic polyesters comprising starting materials derived from organic acids, such as lauric acid, adipic acid or benzenedicarboxylic acid anhydride; polyglycol polyesters modified with polyalkene imine; amine modified alkyl or alkoxy polymers; and phosphoric acid esters. Specific examples include Tegosperse 690 (from Evonik Incorporated), Byk 2023 or Byk 9077, or Solsperse 87000 (from Lubrizol, Inc). In some embodiments, the solvent compatible dispersant comprises a polyvinyl butyral dispersant.

[0073] As shown in the Examples, a solvent compatible dispersant may be added to one or more pigments in a suitable organic solvent (e.g., ethyl acetate) to provide a pigment dispersion, which then may be used as the colorant in the ink jet ink compositions described herein. Suitable specific pigments include a carbon black pigment and suitable dispersants include a polyvinyl butyral dispersant. The mean pigment particle size of the pigments in the dispersion is from about 0.1 microns and about 0.2 microns.Ink Jet Ink Compositions

[0074] In some embodiments, the inkjet ink composition comprises: about 0.3% to about 10% by weight of a colorant, about 3% to about 35% by weight one or more water insoluble binders, and about 50% to about 95% by weight of one or more organic solvents, wherein the colorant, the one or more water insoluble binders, and the one or more organic solvents are present in a amount of greater than about 60% by weight, based on the total weight of the composition.

[0075] In some embodiments, the inkjet ink composition comprises: about 0.3% to about 5 % by weight of a colorant, about 3% to about 35% by weight one or more water insoluble binders, and about 50% to about 95% by weight of one or more organic solvents, wherein the colorant, the one or more water insoluble binders, and the one or more organic solvents are present in a amount of greater than about 60% by weight, based on the total weight of the composition.

[0076] In some embodiments, the inkjet ink composition comprises: about 0.3% to about 10% by weight of a colorant,about 3% to about 35% by weight one or more water insoluble binders, about 50% to about 95% by weight of one or more organic solvents, and about 0.1% to about 5% by weight of a conductive agent; wherein the colorant, the one or more water insoluble binders, and the one or more organic solvents are present in a amount of greater than about 60% by weight, based on the total weight of the composition; wherein the conductive agent comprises secondary, tertiary or quaternary ammonium cation that is further comprised of at least one organic group exhibiting 4 carbon atoms in series; and wherein the colorant comprises one or more water-soluble dyes and pigments.

[0077] In some embodiments, any one of the ink jet ink compositions described herein composition has a viscosity of from about 2.0 to about 6.0 cP at about 25°C, including about 2.0 cP, about 2.1 cP, about 2.2 cP, about 2.3 cP , about 2.4 cP, about 2.5 cP, about 2.6 cP, about 2.7 cP, about 2.8 cP, about 2.9 cP, about 3.0 cP, about 3.1 cP, about 3.2 cP, about 3.3 cP , about 3.4 cP, about 3.5 cP, about 3.6 cP, about 3.7 cP, about 3.8 cP, about 3.9 cP, about 4.0 cP, about 4.1 cP, about 4.2 cP, about 4.3 cP, about 4.4 cP, about 4.5 cP, about 4.6 cP, about 4.7 cP, about 4.8 cP, about 4.9 cP, about 5.0 cP, about 5.1 cP, about 5.2 cP, about 5.3 cP , about 5.4 cP, about 5.5 cP, about 5.6 cP, about 5.7 cP, about 5.8 cP, about 5.9 cP, and about 6.0 cP at about 25°C. In some embodiments, any one of the inkjet ink compositions described herein composition has a viscosity of from about 3.5 to about 5.0 cP at about 25°C or from about 3.9 to about 4.8 cP at about 25°C.

[0078] In some embodiments, any one of the inkjet ink compositions described herein has an electrical resistivity of less than about 2500 ohm-cm at about 25°C, including less than about 2400, less than about 2300, less than about 2200, less than about 2100, less than about 2000, less than about 1900, less than about 1800, less than about 1700, less than about 1600, and less than about 1500 at about 25°C.

[0079] In some embodiments, any one of the inkjet ink compositions described herein has an electrical resistivity of from about 1000 to about 2000 ohm-cm at about 25°C, including about 1000, about 1050, about 1100, about 1150, about 1200, about 1250, about 1300, about 1350, about 1400, about 1450, about 1500, about 1550, about 1600, about 1650, about 1700, about 1750, about 1800, about 1850, about 1900, about 1950, and about 2000 ohm-cm. Insome embodiments, any one of the inkjet ink compositions described herein has an electrical resistivity of from about 1200 to about 1500 ohm-cm at about 25°C.

[0080] In some embodiments, any one of the inkjet ink compositions described herein has one or more properties selected from:(a) where the individually selected solvents exhibit a weighted evaporation rate relative to n-butyl acetate of 1.5 or greater to promote fast drying behavior of the printed codes. (To calculate this weighted evaporation rate, each solvents evaporation rate is simply multiplied by the formulation fraction of the solvent. So for example if a formulation is 40% ethanol (evaporation rate = 1.7) and 40% isopropyl acetate (evaporation rate = 3.0) it would yield a weighted rate of 1.88.)(b) exhibits an L value against a white background of at most 60 and preferably at most 50 and more preferably at most 40 when applied with a #4 draw down bar on a Leneta card, and

[0081] The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.EXAMPLES

[0082] Example 1.

[0083] The below table summarizes the materials used in this Example.Table 1.

[0084] The other component for materials at <100% concentration was water except for DDDMA Cl, which was a 50% solution in 2-propanol / water 2:3.

[0085] A series of saturated dye and / or additive compositions were prepared by adding a dye to a solvent (-94:5: 1 MEK / Ethanol / water). Two different dye solutions were used: Acid red 51 at about 5% concentration and Patent Blue V at about 3% concentration. To the solution about 1% of an additive (w / w) active basis shown in Table 1 were added as well.

[0086] The resulting test solutions were agitated by shaking for 30 minutes and were cooled to -15 °C for 14 hours and allowed to warm to about 20 °C at which point the solution resistivity was measured. The supernatant was sampled for each sample followed by a visible light absorption spectroscopic measurement after a dilution by 0.00125x of original concentration using pure ethanol as the diluent. The series of results representing the optically determined relative colorant saturation levels are provided in Table 2 along with the relative solution resistivity measures.Table 2.

[0087] The above table shows that the conductive agent additives were effective at reducing the solution resistivity to ‘good’ levels (below about 2 kohms cm). In many cases the saturation concentration (based on the absorbances and Beer’s Lambert’s relationship) was higher for some of the additives selected. The above results demonstrate that salts comprising long chain alkyl quaternary ammonium salts, lithium cation or iodide anion performed particularly well, as well though other salts such as sodium salts also performed well.

[0088] A similar set of tests was performed exactly the same as above, but using ethanol: water (~99: 1) with some of the same additives. The results are provided in Table 3.Table 3.

[0089] The saturation concentration governed by salt type was less for the protic solvent ethanol versus the solutions using a high level of compatibilizing solvent (MEK).

[0090] Another set of tests were performed to validate that similar solubility improvements might be realized with different kinds of dyes by attempting to dissolve other dyes at 1% (w / w) level in both MEK and ethanol. A summary of these results is presented in Table 4.Table 4.

[0091] In several cases where a conductive agent was used, dyes were rendered more soluble as a result.

[0092] Example 2.

[0093] The below table summarizes the materials used in this Example.Table 5.

[0094] Another series of compositions employing Patent Blue V were prepared with pH active additives / compounds. A pure MEK solution of approximately 3% dye solutions were tested with 1% (w / w) of the active additives shown in Table 5. The absorbances as measured by visible absorption after dilution in the same manner as in Example 1 are provided in Table 6.Table 6.

[0095] As shown above, specific pH active additives / compounds were better than others at increasing the saturation concentration. Without wishing to be bound by theory, it is presumed that relative acidity (pKa) and / or relative molar concentration were the most important factors.

[0096] Example 3.

[0097] Ink jet ink formulations Compositions 1-6 were prepared in accordance with the components and amounts listed in the below table. The general procedures for preparing these inkjet ink formulations included the following steps: 1) dissolving all of the components one by one in the ink vehicle with mixing; and 2) filtering the ink solution through a Cuno 30A prefilter and at least a 1 micron absolute polyester membrane.Table 7.

[0098] The ink adhesion of ink jet ink formulations Compositions 1-2 on various plastic substates was assessed versus existing ink V497-D. The printed codes ranged from a reddish violet to a bluish violet shade and were adequately contrasting against the printed background so as to be readable. Based on the draw downs, the contrast of the inventive ink was in fact far greater than the comparative example as the L value was nearly 50% of the latter.Table 8.

[0099] The below table summarizes the adhesion results on relatively difficult to adhere to BOPP film for examples 1 and 2 versus V497-D. The codes were assessed 18 hours after printing by both a cardboard abrasion and tape transfer test. The cardboard abrasion test was performed by rubbing a piece of kraft paper across the code back-and-forth ten times with approximately 500 grams of downward force. The tape test was performed by using Scotch™ Tape 600 by first applying it firmly onto the code, after which removing the tape abruptly at a 90-degree angle, looking for signs of code fading or removal. A ‘Fail’ indicated that the codes were completely unreadable.Table 9.

[0100] The above results showed that Compositions 1-2 showed that comparable or better adhesion was achieved with the formulations in accordance with this disclosure.

[0101] The dry time of ink jet ink formulation Composition 2 was measured by lightly touching the printed codes immediately after printing and checking for any signs of smearing. The threshold in 0.1 second increments where no smearing was noted was considered to be the drying time. On BOPP, the drying time for Composition 2 was 1.5 seconds.

[0102] The ink stability of ink jet ink formulations Compositions 1 and 3 was assessed under the conditions noted in the below table. The below table summarizes the results and show that Compositions 1 and 3 passed all stability tests.Table 10.

[0103] FIGS. 1A, IB, and 1C illustrate the printed code using Composition 2 on aqueous paper (1 A), on PET film (IB), and monoPE film (1 C).

[0104] FIGS. 2 A and 2B illustrate the printed code using Composition 2 on PET film after soaking in water for 10 minutes (2A) and soaking for 10 minutes followed by lOx thumb rubs (2B).

[0105] Example 4.

[0106] Making of pigment dispersion'. Pigment dispersions were prepared by employing a high-speed media mill, such as a Ml 00 Lab Mill by EMI Mills, Inc. The components used to prepare these dispersions are shown below (Table 11) with the indicated particle sizes.Table 11. Pigment dispersion summary.Inc.

[0107] Carbon black pigment was a variety that exhibited low PAH content and conformed to the following: Benzo(a)pyrene content (limit value 0.25 mg / kg carbon black); Toluene extractable fraction (limit value 0.1%) ISO 6209 method; and UV absorption of the cyclohexane at 386 nm (limit value 0.02 AU) for 1cm cell or <0.1 for 5cm cell.

[0108] The particle size was measured by a Microtrac Naotrac Wave dynamic light scattering instrument, and the mean was determined from the volume weighted distribution.

[0109] Example 5.

[0110] Ink Performance Based on Salt-Based Conductive Agents'. For screening purposes, the inks for this example were prepared by combining the components shown in Table 12.Table 12. Base formulation (CE2) for comparing conductive agents.Polyurethane solution is a 74% active plasticizing aromatic urethane resin; Valifast 3878 is C.I. index Solvent Black 27 from Orient Chemical, Inc.[OHl] To the base formulation, one of the conductive agents from the below table at the indicated amount was added to prepare inkjet ink formulations Compositions 3 A-8A as shown in Table 13. To prepare the ink compositions, the inks were agitated until the solid components were dissolved. CE1 was used as a control and was a commercially available product that exhibited good plastics adhesion and employed a PVB resin. The ink compositions and control compositions were each cast from separate 0.3 mm glass capillary tube by momentarily spotting the tube onto untreated PET and BOPP materials to simulate a printed mark (<500 micron spot sizes). The marks were subjected to a pasteurization water bath of about 95 °C by submerging the samples together, simultaneously, and exposing them for a total of 30 minutes.Table 13. Comparison of different salt impact on adhesion after pasteurization.

[0112] Surprisingly, the results of this example show that the use of certain salts as the conductive agent at approximately the same weight percentage improved ink adhesion after extreme pasteurization and hydrolytic conditions.

[0113] Example 5.

[0114] The inkjet ink compositions for this example were formulated for screening by combining the components as shown below in Tables 14A and 14B. The inkjet compositions were processed and filtered according to known methods generally used for inkjet ink compositions.Table 14A. Exemplary formulations.Table 14B. Exemplary formulations.TBAPFe , a conventional conductive agent, was sourced from Ultimate Pharmachem, Inc. (India); BTC-1010-80% is an 80% active solution of DDAC in water from Stepan, Inc.; CTAB was obtained from TCI, Inc.; Fluorescent brightener 61 is an efficient fluorescent colorant; BYK 3764 was sourced from Altana, Inc.; Patent Blue V was sourced from Sensient, Inc.

[0115] Select inkjet ink formulations compositions were subjected to a battery of stability tests, in which changes to their physical properties were evaluated after various environmental stresses including:• An oven test at 60°C to accelerate and evaluate energetically driven processes.• As these compositions are meant for use in a printer, such inkjet ink compositions will usually absorb water from the humidity in the air. To study this, the inkjet ink compositions were spiked with a small percentage of water and subjected to oven testing as described above.

[0116] Tests were performed on inks, both initially to establish a baseline; and after stressing to evaluate stability. Such tests included resistivity, viscosity, pH, and contamination level (C / L). In the C / L test, a predetermined volume of an ink was passed through a filter membrane that was attached to a vacuum funnel.

[0117] Below are stability results for Composition 9A, which was determined to be stable enough for use as a continuous inkjet ink composition (Table 15).Table 15.

[0118] The inkjet ink compositions were also evaluated for print quality and reliability by assessing the number of good phases in a Videojet Simplicity™ series printer with a 60-micron nozzle operating at about 76-80 kHz. Phasing was performed as part of printer operation to align the special disposition of the drops at the point of breakoff with the electrical charge pulse waveform applied at the within the charging region. The results are summarized in the below for the various inkjet ink compositions and comparative examples (Table 16).Table 16. Printer phasing summary.

[0119] For acceptance criteria, an inkjet ink composition that exhibits more than 4 good phases is considered suitable for good CIJ operation. As shown above, each of the tested inkjet ink compositions showed a higher number of acceptable phases as compared to the comparative dye (CE1) and pigment (CE5) based inkjet ink compositions.

[0120] Pigment settling is related to the tendency for pigmented particles to flocculate, aggregate or otherwise depart from ideal stability. Inkjet inks in particular perform best when pigment particles are well dispersed and do no settle over time. Inkjet ink compositions were evaluated for their resistance to settling using a Turbiscan Trilab spacial optical spectrometer which scans for optical changes in a sample over the full length of a standardized small sample tube. The results showed that the inventive inks showed less mean settling near the ink-air meniscus than a conventional pigmented CIJ ink (CE5).Table 17

[0121] The adhesion of the inks as checked versus another relevant dye-based inks that is a common ink for similar applications (CE6). A fingernail scratch and kraft test failed for CE6 (FIG. 4) while for the Composition 14a both tests passed (FIG. 5).

[0122] A crinkle test was performed as well to demonstrate the flexibility of the ink and suitability for printing onto films. A small piece of a printed code was cut from the larger substrate. The piece was crinkled between the thumb and forefinger using moderate pressure. Composition 14A was relatively unaffected (FIG. 6, bottom), but the CE6 showed a significant loss of adhesion (FIG. 6, top).

[0123] Para. 1. An ink jet ink composition comprising: a water-soluble colorant,one or more water insoluble binders, and one or more organic solvents, wherein the water-soluble colorant, the one or more water insoluble binders and the one or more organic solvents are present in an amount of greater than about 60% by weight, based on the total weight of the composition.

[0124] Para. 2. The composition of Para.1, wherein the water-soluble colorant comprises one or more water soluble dyes.

[0125] Para. 3. The composition of Paras.1 or 2, wherein the water-soluble colorant comprises any one of more of the following:(a) one or more mono-, di-, or trifunctional dyes comprising the ionic functional groups of sulfonate, benzene sulfonate, carboxylate or phenolate;(b) one or more cationic, zwitterionic, or non-ionic dyes;(c) one or more triphenylmethanes, monoazos or disazos.

[0126] Para. 4. The composition of any one of Paras. 1-3, wherein the water-soluble colorant is present in an amount of from about 0.3% to about 5 % by weight, based on the based on the total weight of the composition.

[0127] Para. 5. The composition of any one of Paras. 1-4, wherein the one or more water insoluble binders comprise any one of vinyl butyral, cellulose ester, vinyl chloride, vinyl acetate, vinyl pyrrolidone, ester, vinyl pyrrolidone and acrylic.

[0128] Para. 6. The composition of any one of Paras. 1-5, wherein the one or more water insoluble binders does not comprise shellac.

[0129] Para. 7. The composition of any one of Paras. 1-6, wherein the one or more water insoluble binders is present in an amount of from about 3% to about 35% by weight, based on the total weight of the composition.

[0130] Para. 8. The composition of any one of Paras. 1-7, wherein one or more organic solvents comprises Cl to C4 alcohols or lactates.

[0131] Para. 9. The composition of Para. 8, wherein the one or more organic solvents comprise ethanol, n-propanol, methyl lactate, ethyl lactate, butyl lactate, or any combination thereof.

[0132] Para. 10. The composition of any one of Paras. 1-9, wherein the one or more organic solvents further comprise a compatibilizing solvent.

[0133] Para. 11. The composition of Para. 10, wherein the compatibilizing solvent comprises a ketone, an ester, or dimethyl carbonate.

[0134] Para. 12. The composition of Para. 10, wherein the compatibilizing solvent comprises acetone, methyl ethyl ketone (MEK), methyl propyl ketone (MPK), or methyl isobutyl ketone (MiBK).

[0135] Para. 13. The composition of any one of Paras. 10-12, wherein the compatibilizing solvent is present in an amount of at least about 20 wt% by weight, based on the total weight of the composition.

[0136] Para. 14. The composition of any one of Paras. 1-13, wherein the composition comprises water in amount of about 15% or less by weight, based on the total weight of the composition.

[0137] Para. 15. The composition of Para. 14, wherein the composition comprises water in amount of about 1% or less by weight, based on the total weight of the composition.

[0138] Para. 16. The composition of any one of Paras. 1-15, wherein the composition comprises one or more selected from glycol, diol or glycerin.

[0139] Para. 17. The composition of claim Para. 16, wherein one or more selected from glycol, diol or glycerin is present in amount of less than about 7% by weight, based on the based on the total weight of the composition.

[0140] Para. 18. The composition of any one of Paras. 1-17, wherein the composition comprises one or more water-compatible materials.

[0141] Para. 19. The composition of Para. 18, wherein the one or more water-soluble materials are present in an amount of at least greater than 1% by weight, based on the total weight of the composition.

[0142] Para. 20. The composition of any one of Paras. 1-19, further comprising a conductive agent.

[0143] Para. 21. The composition of Para. 20, wherein the conductive agent comprises an ammonium salt, alkyl ammonium salt or an alkali metal salt.

[0144] Para. 22. The composition of Para. 21, wherein the conductive agent is present in an amount of from about 0.1% to about 5% by weight, based on the total weight of the composition.

[0145] Para. 23. The composition of any one of Paras. 1-22, wherein the composition further comprises a pH active compound.

[0146] Para. 24. The composition of Para. 23, wherein the pH active compound comprises an acid or an acidic moiety and / or has at least one pKa of less than about 5.

[0147] Para. 25. The composition of any one of Paras. 23-24, wherein the pH active compound is present in an amount of 0.1 to about 6% by weight, based on the total weight of the composition.

[0148] Para. 26. The composition of any one of Paras. 1-25, wherein the composition has a resistivity of less than about 2500 ohm-cm at about 25 °C.

[0149] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0150] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed hereinhave been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of’ will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of’ excludes any element not specified.

[0151] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, or compositions, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0152] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0153] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0154] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0155] Other embodiments are set forth in the following claims.

Claims

WHAT IS CLAIMED IS:

1. An inkjet ink composition comprising: a colorant, one or more water insoluble binders, and one or more organic solvents, wherein the colorant, the one or more water insoluble binders and the one or more organic solvents are present in a amount of greater than about 60% by weight, based on the total weight of the composition.

2. The composition of claim 1, wherein the colorant comprises one or more water soluble dyes and pigments.

3. The composition of claim 1, wherein the colorant comprises any one of more of the following:(a) one or more mono-, di-, or trifunctional dyes comprising the ionic functional groups of sulfonate, benzene sulfonate, carboxylate or phenolate;(b) one or more cationic, zwitterionic, or non-ionic dyes;(c) one or more triphenylmethanes, monoazos or disazos.

4. The composition of claim 1, wherein the colorant is present in a amount of from about 0.3% to about 10% by weight, based on the based on the total weight of the composition.

5. The composition of claim 1, wherein the one or more water insoluble binders comprise any one of polyvinyl butyral binders, polyurethane binders, cellulose ester binders, vinyl chloride binders, vinyl acetate binders, ester binders, acrylic binders, and tackifier resins.

6. The composition of claim 1, wherein the one or more water insoluble binders does not comprise shellac.

7. The composition of claim 1, wherein the one or more water insoluble binders is present in an amount of from about 3% to about 35% by weight, based on the total weight of the composition.

8. The composition of claim 1, wherein one or more organic solvents comprises Cl to C4 alcohols or lactates.

9. The composition of claim 8, wherein the one or more organic solvents comprise ethanol, n-propanol, methyl lactate, ethyl lactate, butyl lactate, or any combination thereof.

10. The composition of claim 1, wherein the one or more organic solvents further comprise a compatibilizing solvent.

11. The composition of claim 10, wherein the compatibilizing solvent comprises a ketone and an ester.

12. The composition of claim 10, wherein the compatibilizing solvent comprises acetone, methyl ethyl ketone (MEK), methyl propyl ketone (MPK), or methyl isobutyl ketone (MiBK).

13. The composition of claim 10, wherein the compatibilizing solvent is present in an amount of at least about 20 wt% by weight, based on the total weight of the composition.

14. The composition of claim 1, wherein the composition comprises water in amount of about 15% or less by weight, based on the total weight of the composition.

15. The composition of claim 14, wherein the composition comprises water in amount of about 1% or less by weight, based on the total weight of the composition.

16. The composition of claim 1, wherein the composition comprises one or more selected from glycol, diol or glycerin.

17. The composition of claim 16, wherein one or more selected from glycol, diol or glycerin is present in amount of less than about 7% by weight, based on the based on the total weight of the composition.

18. The composition of claim 1, wherein the composition comprises one or more watercompatible materials.

19. The composition of claim 18, wherein the one or more water-soluble materials are present in an amount of at least greater than 1% by weight, based on the total weight of the composition.

20. The composition of claim 1, further comprising a conductive agent.

21. The composition of claim 20, wherein the conductive agent comprises an ammonium salt, alkyl ammonium salt or an alkali metal salt.

22. The composition of claim 20, wherein the conductive agent comprises a secondary, tertiary or quaternary ammonium cation that is further comprised of at least one organic group exhibiting 4 carbon atoms in series.

23. The composition of claim 22, wherein the conductive agent cation does not comprise tetrabutylammonium.

24. The composition of claim 20, wherein the conductive agent comprises one or more of cetyltrimethylammonium bromide and didecyldimethylammonium chloride.

25. The composition of claim 20, wherein the conductive agent is present in an amount of from about 0.1% to about 5% by weight, based on the total weight of the composition.

26. The composition of claim 1, wherein the composition further comprises a pH active compound.

27. The composition of claim 26, wherein the pH active compound comprises an acid or an acidic moiety and / or has at least one pKa of less than about 5.

28. The composition of claim 26, wherein the pH active compound is present in an amount of 0.1 to about 6% by weight, based on the total weight of the composition.

29. The composition of claim 1, wherein the composition further comprises a solvent compatible dispersant.

30. The composition of claim 29, wherein the solvent compatible dispersant comprises a polyvinyl butyral dispersant.

31. The composition of claim 1, wherein the composition comprises: the colorant comprising one or more water-soluble dyes and pigments, the one or more water insoluble binders, the one or more organic solvents, and a conductive agent comprising a secondary, tertiary or quaternary ammonium cation that is further comprised of at least one organic group exhibiting 4 carbon atoms in series.

32. The composition of claim 1, wherein the composition has a resistivity of less than about2500 ohm-cm at about 25 °C.

Images