STABILIZED CARBONIC ACID METHOD FOR SOLVATION OF

CATIONIC & AMPHOTERIC COMPOUNDS

[001] The present application claims priority to U.S. Provisional Patent Application no. 62/350,915, filed June 16, 2016, which is incorporated herein by reference in its entirety.

Field of the Invention

[002] The present disclosure is directed to stabilized systems comprised of aqueous solutions of carbonic acid that include a solvated cationic and/or amphoteric resin and a stabilizer. Such systems can be used, for example, in cationic printing inks and coatings for application to various substrates, such as cellulose-based substrates (paper towels, tissue, etc.) and polymer- based substrates (e.g., polyethylene, polypropylene, polyethylene terephthalate (PET), and glycol-modified polyethylene terephthalate (PET-G)).

Background of the Invention

[003] Anionic water-based inks and coating provide a good array of desirable ink properties, among them being excellent adhesion, product resistance, lamination and mechanical resistance. However, because anionic inks rely on electrophilic functionality for these properties, in which there is wet attraction to the-COOH acid group of the anionic resin, cohesion forces are elevated within the wet ink or coating, making it difficult for the ink to release cleanly from a

flexographic plate or rotogravure cell. This can result in dirty prints. These same attractions elevate wet viscosity in the ink, which compromises the amount of resin solids deposited on the substrate at certain viscosity.

[004] For example, Casamid 1914 is marketed as a water-based polyamide resin, but in actuality it also contains -COOH groups, and thus it is a polyamide/polyacid resin. The acid groups are presumably incorporated to facilitate solubility of the amine polymer in water. The amide groups of the Casamid resin are attracted to (1) electron-rich surface groups present on most substrates; and, by intramolecular attraction, to (2) the -COOH groups of the polymer. The competing attractions have the effect of lowering the availability of amide groups for substrate anchoring. This decrease in attraction/anchoring efficiency has analogs in urethane/-COOH interactions, and adhesion promoters (e.g. ZnC0 ₃ , silanes, carbodiimides) that are attracted to - COOH.

[005] Sun Chemical Towel & Tissue ink WKSFW5614685:HYDROFIBE PRO CYAN includes Cartaretin F4, a cationic polyamide-amine resin having a low amine number that is readily soluble in water. An ink formulation was prepared that includes, in lieu of Cartaretin F4, Ottopol K-362-A, a low molecular weight cationic acrylic resin neutralized with acetic acid solution. Ottopol K-362-A has a solids content of 29-3 lwt % and is available from Gellner Industrial, LLC, Hometown, PA, US. The two inks were applied to paper towel as a substrate and rub resistance tests were conducted. The Ottopol-based ink containing the cationic acrylic resin exhibited greater resistance to rub transfer than the ink formulation containing the

Cartaretin F4 cationic polyamide-amine resin. The Ottopol-based ink also exhibited better product resistance, that is, resistance to commercial household cleaning products such as Formula 409, Windex, etc. in which resin solvation and/or pigment mobility was not detected. Cartaretin F4 is readily soluble in an aqueous solution at pH 7.6. From this it appears that there is no neutralization of a nucleophile to allow for ionic and hydrogen bonding to provide for solubility at this pH. Apparently, Cartaretin F4 contains anionic functionality that competes with the cationic polyamide groups which anchor/associate to cellulose hydroxyl groups (-OH). The aforementioned Ottopol resin more effectively crosslinks with the hydroxyl groups (-OH) of the cellulose fibers.

[006] While Ottopol K-362-A provides good rub resistance, which suggests there is a good bond between the ink and the substrate, this cationic acrylic resin cannot be used "as is" in printing operations, such as in printing paper towels. This resin dries slowly, and further, since its packaging includes acetic acid, an undesirable odor is associated with this resin. The unpleasant odor of acetic acid odor may last for an extended period, e.g., four (4) weeks or so, after printing.

[007] Most water-based soluble resins used in the ink and coatings industry are anionic. In such anionic inks, the carboxylic acid groups resin are neutralized with amine, e.g., the amine accepts a proton from the carboxylic acid (-COOH) group, yielding a more water soluble salt or neutralized derivative of the original resin. Resins having high acid numbers are more likely to dissolve in an amine-water solution than low acid number resins. While not wishing to be bound by any theory, it is possible that resins having acid numbers below 90 (e.g. BASF 586 resin) are borderline in their capability to dissolve at all. Yet while carboxylic acid group neutralization renders an anionic resin soluble, such acid groups do not contribute to providing properties desired in an ink (other than solubility and printability). The desirable properties that carboxylic acid groups inhibit and diminish are far more numerous. For example, carboxylic acid groups are not attracted to oxygen-containing or electronegative chemical groups present on most non- absorbent print substrates, which diminishes bonding properties. The chemical attraction responsible for lamination bonding, product resistance, chemical resistance, mechanical toughness, water resistance and wet attractions (i.e. carry up) are predominantly rooted in electrophilic groups, qualities not present in the -COOH nucleophilic group.

[008] Resins containing cationic groups, e.g., cationic resins, can be solvated, e.g., dissolved, in water through the neutralization of the cationic groups. A dissociated acid donates a proton to a cationic functional group in the polymer, yielding a more water soluble salt derived from the original resin. The cationic group may be one that contains one or more nitrogen atoms.

[009] Cationic resins are not very water soluble at pH 7. Cationic resins can be solubilized in water when the proton accepting groups are neutralized, such as by including an amount of an acid in aqueous solutions. However, acid neutralization is problematic in that acids can corrode materials that they contact, such as metals and other materials. Further, many acids have an unpleasant, strong odor which further limits the usefulness of a resin that is acid neutralized.

[0010] Many commercial cationic resin products made available in acid neutralized form, such as the Ottopol K-362-A cationic acrylic resin described above. The Ottopol K-362-A acrylic resin is packaged in water and acetic acid, which is known to be malodorous. Thus, due to the way that the Ottopol K-362-A cationic acrylic resin is packaged, it is not suited for use in a printing ink. The malodor deriving from the acid would make an ink containing same unsuited for use in packaged consumer goods, and unsuited for used in patterning paper products such as paper towels, napkins, and paper plates. This problem is not limited to the Ottopol cationic resin, as many cationic resins are formulated with an acid-containing neutralizing solution, such as a formic acid solution. Formic acid also has an unpleasant odor. Formic acid is also corrosive and volatile.

[0011] Many organic acids that can be used to neutralize cationic resins to render them water soluble are volatile. Volatile acids such as formic acid and acetic acid have unpleasant odors, and further are corrosive to metals and other materials, such as those used to fabricate the components of a printing press.

[0012] Amphoteric resins contain chemical functionality to either accept or donate a proton. Amphoteric resins may provide the anchoring, mechanical and product resistant qualities found in cationic chemistries if neutralized. Amphoteric resins are currently held back from attaining that same utility when solvated in water-amine. Amphoterics solvated in water-amine display nucleophilic character. Amphoterics solvated in water-acid display electrophilic character.

[0013] Cationic and amphoteric resins are therefore underutilized in inks and coating compositions. One the one hand, they need to be solubilized in water, and while the addition of an organic acid such as acetic or formic acid can achieve this end, such acids have unpleasant odors and they also have a corrosive effect, which make them unsuited for inclusion in ink formulations, since the acids could corrode the components of a printing press. Further, use of non-volatile acids would neutralize a cationic resin without a persistent odor, although poor water resistance would result, due to the cationic resin remaining indefinitely neutralized.

[0014] Cationic resins represent only a small part of the printing ink market, due in part to the challenges associated with solubilizing them in water. While the odor problem can be resolved by packaging the resins in methanesulphonic acid, this acid can still be corrosive to other materials, such as those used to form the components of the press.

[0015] Many ink-receiving substrates used in printing applications contain a majority of electronegative anchoring sites. Some printing applications cannot use anionic inks because of the nucleophilic nature of the carboxylic acid groups present to provide for anionic solvation with amine. These applications include excellent chemical resistance, bond strength, and mechanical resistance. The anionic resins which do have some electrophilic nature would have those electrophilic groups compromised by the nucleophillic carboxylic acid groups (used for solvation) via association.

[0016] Cationic resins possess electrophilic groups that facilitate anchoring of the ink to the substrate and provide water soluble polymers without anchoring properties (i.e., anchoring to the substrate) and product resistance working against one another (as occurs in anionic resin-based inks).

[0017] The following references may be of interest here: CA 1074729; U.S. Patent No.

4,433,078; U.S. Patent No. 4, 147,680; U.S. Patent No. 4,419,467; U.S. Patent App. Publ. No. 2006/0121204; AU 7 825 801; CN 10 0 540 584; JP 2001-011125; U.S. Patent No. 7,964,665; JP 2003-200652; JP 2002-220558; and JP4048920.

Summary of the Invention

[0018] Described herein are stabilized cationic or amphoteric resin systems comprising: an aqueous solution of carbonic acid; a resin selected from a cationic resin or an amphoteric resin or a combination thereof solvated in the aqueous solution; and a stabilizer; wherein if the resin is an amphoteric resin, the amphoteric resin and the stabilizer may be the same or different.

[0019] In another inventive aspect, described herein are cationic or amphoteric resin-based inks or coatings that include the stabilized cationic or amphoteric resin systems as described above and as further described herein.

[0020] In another inventive aspect, described herein is a method of forming stabilized cationic or amphoteric resin systems comprising the steps of: providing an aqueous solution of carbonic acid; a resin selected from a cationic resin or an amphoteric resin or a combination thereof solvated in the aqueous solution; and a stabilizer; wherein if the resin is an amphoteric resin, the amphoteric resin and the stabilizer may be the same or different. [0021] The present invention describes the solvation of cationic and amphoteric compounds in aqueous solutions without resorting to the use of solvating agents such as odorous acid compounds, non-volatile acids that have poor water resistance, and/or acids that are corrosive, e.g., being corrosive to the components of the printing press, such as metal exhaust ducts.

[0022] The electrophilic nature of cationic resins make them attractive candidates for inclusion of printing inks used in many different printing operations, e.g., flexo, gravure, digital (i.e., ink jet printing), and they could also be used in areas not well supported by anionic-resin containing inks.

[0023] The inventor has surprisingly found that cationic and amphoteric resins can be solvated in stabilized aqueous solutions of carbonic acid and remain stable in solution for long durations of time. Stabilized aqueous solutions of carbonic acid containing cationic and/or amphoteric resins remain stable for periods of one year or longer under normal ink handling conditions. That is, the resin solutions remain clear and stable for long periods of time, without any resin settling out of solution.

[0024] Amphoteric resin compounds such as proteins can be solubilized in aqueous solutions of carbonic acid. Such resin solutions exhibit very good adhesion to printing substrates such as polyester, polyolefins, nylon, and acrylics, and are better than their amine solubilized

counterparts.

[0025] A set of printing applications currently has few or no options in water-based inks due to the chemical nature of anionic resins. Printing inks that include amphoteric and cationic resins solvated in aqueous carbonic acid solutions may solve the problems related to using anionic resin-based systems in printing inks. Until this time, printing applications using cationic based inks have not been widely used due to the difficulties in solvating such resins in solutions that are suited for printing application. Whereas such resins can be solvated in solutions of acid such as formic acid, such acids have an unpleasant odor and are corrosive to components of the printing press. Solvating cationic and amphoteric resins in aqueous carbonic acid solutions solves the odor problem, since carbonic acid does not possess a strong unpleasant odor and/or has no odor, and it is a weak, non-corrosive acid. Cationic and amphoteric resin-based inks form a strong bond with many of the substrates that they are printed on, due to their cationic, electrophilic attraction with many substrates.

[0026] Cationic resin-based inks could be suited for printing materials used in the following classes, some of which present challenges to the printmaker:

[0027] Outdoor bag. This is a class of packaging materials intended to be stored in harsh outdoor environments, and thus the inks printed on outdoor bag packaging has to be able to withstand the those environments. For example, outdoor bag is the packaging used for gardening products such as mulch, topsoil, fertilizer, seed, etc. Such products are typically stored outdoors in the elements at garden centers for long periods of time. The inks for outdoor bag should exhibit exceptional water, chemical and mechanical resistance, which are properties associated with cationic resins. Outdoor bag materials include white or clear polyethylene.

[0028] Towel & tissue. Absorbent paper towels comprised of cellulose fibers often have patterns, texts, and/or designs printed on them. Due to the manner in which such towels are used and to the compositions they are exposed (e.g., household cleaning products), a strong, virtually unbreakable bond should be formed between the printing ink and cellulose substrate in order to resist the potentially degrading effects of exposure to soaps, water, grease, and household cleaners. An ink based on a cationic resin should form strong attractions with the hydroxyl groups of the cellulose (e.g., (crosslinking attractions). The present cationic and amphoteric resin systems are well suited to be used in an ink to meet this objective.

[0029] Confectionary/cold seal, for packaging of candies. Cationic resin-based water-acid soluble inks have not been used for this kind of packaging because of the odor issues discussed herein. The inks of the present disclosure are essentially odor-free, and thus an ink based on polyamide-imide cationic resins (solvated in aqueous carbonic acid solution) may show resistance to cold seal adhesive (e.g., natural rubber latex and acrylic dispersions) while anchoring to the electron rich aldehyde and ketone groups present on oriented polypropylene (OPP) substrate. Aqueous carbonic acid solutions containing amphoteric or cationic resins can be used in ink compositions for cold seal packaging. Polyamide is currently the only overlaquer resin option for inks in the confectionery packaging application. They are a solvent based resin that is dissolved in alcohol and a hydrocarbon, and it would be beneficial to replace such inks.

[0030] Shrink wrap. Cationic resin-based inks are well suited for shrink wrap printing due to their excellent water and mechanical resistance, which are needed to anchor an ink to

polyethylene terephthalate (PET) and oriented polypropylene (OPP) shrink wrap substrates. The present disclosure overcomes the drawbacks associated with cationic resin-based inks.

[0031] High speed printing operations. Many printing substrates are electronegative in nature. Thus, a cationic resin-based ink would have a natural "wetting/gain" property when printed on an electronegative substrate. This in contrast to anionic water-based inks, which are not well suited for printing at high speeds, e.g., speeds of about 3000 feet per minute (fpm) or greater. At such speeds, anionic water-based inks are prone to loss of complete wetting due to limited ink/substrate attractions.

[0032] Amine/ammonia-resistant application - many cationics are unaffected by amines by definition of their solubility character.

[0033] Performance protein: Amphoteric proteins are used in amine-neutralized basic solution for current applications such as when high bio-renewable carbon content is required. Proteins undergo biodegradation and thus contribute to the eco-friendliness of a product that contains such proteins, such as in an ink composition. Soy proteins may be used in this way. Soy proteins dissolved in the manner of anionic resins do not provide adhesion or mechanical advantages when compared to water-amine based inks. Carbonic acid-solvated proteins, solvated in the same manner as the cationic resins are solvated herein, show excellent adhesion and block resistance at, for example, 120°F, 50 psi, 66% relative humidity on corona treated PET, Nylon, OPP, polyethylene and acrylic. Protein solvated in an aqueous carbonic acid solution could take a major role in printing ink and coating formulations. [0034] Reactive layer interaction - alternating layers of anionic colors with a cationic white or overprint varnish can form highly resistant covalent bonds in the interface between the anionic and cationic layers.

[0035] Metallic pigment-containing inks - These inks contain metallic pigments that may undergo oxidation. Currently metallic inks using aluminum or copper or zinc metal pigment require that the pigment be encapsulated by a layer of stearic acid or linoleic acid. There may be a non-oxidation benefit when such inks are at a pH below 7.0, due to natural attraction/anchoring of cationics resins to those metal pigments. With metallic water based inks, the protective layer present on the metal pigments may eventually be lost due to exposure to mechanical shear forces. When unprotected from water-amine, metallic pigments oxidize to their (non-lustrous) metal oxide form. This oxidative process also liberates nitrous oxides (NO _x ) and hydrogen gas. The same oxidative process with metallic pigment does not occur in water-acid.

Detailed Description of the Invention

[0036] The stabilized cationic or amphoteric resin systems of the present disclosure comprise: an aqueous solution of carbonic acid; a resin selected from a cationic resin or an amphoteric resin or a combination thereof solvated in the aqueous solution; and a stabilizer; wherein if the resin is an amphoteric resin, the amphoteric resin and the stabilizer may be the same or different. By "same", it is meant that the amphoteric resin and the stabilizer components may be one and the same, and by "different", it is meant that the amphoteric resin and the stabilizer are individual components that differ from each other, e.g., the cationic or amphoteric resin is a first component and the stabilizer is a second component.

[0037] In one inventive aspect, the stabilizer is selected from an acidic amino acid, an acidic protein, and combinations thereof. The acidic amino acid may be, for example, glutamic acid, aspartic acid, and combinations thereof. In general terms, any amphoteric compound which contains more cationic sites (- H ₂ ) than anionic site (-COOH) for the stabilization of bicarbonate ion as carbonic acid dissociates may be used as the amphoteric resin. [0038] In one preferred inventive aspect, the stabilizer is glutamic acid, which has been found to be particularly well suited to the stabilization of aqueous carbonic acid solutions of cationic or amphoteric resins.

[0039] In another inventive aspect, described herein are cationic or amphoteric resin-based inks or coatings that include stabilized cationic or amphoteric resin systems as described herein.

[0040] Advantageously, the cationic or amphoteric resin-based inks or coatings of the present disclosure effectively solubilize the cationic or amphoteric resin component, and are not corrosive to the printing presses in which they are used.

[0041] In another inventive aspect, described herein is a method of forming a stabilized cationic or amphoteric resin system comprising: providing an aqueous solution of carbonic acid; a resin selected from a cationic resin or an amphoteric resin or a combination thereof solvated in the aqueous solution; and a stabilizer; wherein if the resin is an amphoteric resin, the amphoteric resin and the stabilizer may be the same or different, as described above.

[0042] Amphoteric resin compounds such as proteins can be solubilized in aqueous solutions of carbonic acid. Such resin solutions exhibit very good adhesion to printing substrates such as polyester, polyolefins, nylon, and acrylics, and show greater anchoring capabilities than their amine solubilized counterparts. Any polymerized configuration of amino acids containing both acidic amino acids and basic amino acids is acceptable for solvation by the carbonic acid method described herein. A protein is amphoteric when it has the ability to donate or receive a proton, where that transfer elevates water solubility.

[0043] In one aspect of the present disclosure, the carbonic acid solvent for the cationic and amphoteric resins are formed by dissolving carbon dioxide (C0 ₂ ) in water to create an aqueous carbonic acid solution. In a preferred aspect, the C0 ₂ is introduced into water that is preferably stirred for a period of time, e.g., for 15 minutes, for 30 minutes, or for one hour, or for two hours, or for three hours, or for four hours, or for five hours, or for six hours. In another preferred aspect, the vessel in which the C0 ₂ is introduced into water is pressurized, e.g., pressurized to greater than 1.0 atm, preferably >1.0 atmosphere (atm) to 3.0 atm. In a more preferred aspect, the vessel in which the C0 ₂ is introduced into water is pressurized, e.g., pressurized to greater than 1.0 atm, preferably >1.0 atmosphere (atm) to 3.0 atm, and the water is stirred for a period of time. Applicants have found that 2.5 atmospheres, or approximately this value, is well suited for introduction of carbon dioxide into water to form an aqueous carbonic acid solution suited for solvating cationic and amphoteric resins.

[0044] As used herein a "cationic" resin is one containing a net positive-charged atom or atoms or associated group of atoms that are joined covalently to the polymer molecule of which they are constituents.

[0045] Examples of possible cationic compounds considered for solvation in aqueous carbonic acid solutions are those having a polymer backbone structure listed below, covalently bonded to a moiety responsible for accepting a proton. Any polymer or co-polymer with moieties capable of accepting a proton, where the protonated (neutralized) group elevates the dipole character and/or hydrogen bonding character of the resin, leading to greater water solubility, can be used as a cationic resin in the present application.

[0046] Examples of cationic polymer backbone structures include but are not limited to acrylic, imide, acrylate, maleic, polyether, polyester, polyamide, polyurethane, polycarbonate, polyvinyl, polythioether, polysulfone, polyamine, polyimine, and polyurea.

[0047] Examples of cationic moieties responsible for accepting a proton include but are not limited to amine (primary, secondary, tertiary, aromatic, etc.), an ammonia moiety accepting a proton resulting in an ammonium structure; a phosphorus containing moiety accepting a proton resulting in a phosphonium structure; and a sulfur containing moiety accepting a proton resulting in a sulfonium structure.

[0048] As demonstrated in Example 1 of this disclosure, an amphoteric resin compound, e.g., soy protein, can be solvated in carbonic acid. In this arrangement, the soy protein is solvated and further acts as a stabilizer for the aqueous carbonic acid solution. In this arrangement, it appears that the soy protein structure accepts a proton and stabilizes the corresponding bicarbonate on the polymer. Other protein materials may also be solvated with carbonic acid.

[0049] With the stabilized cationic or amphoteric resin systems described herein that comprise, among other components, an aqueous solution of carbonic acid and a cationic or amphoteric resin solvated in the aqueous solution, the carbon dioxide dissolved in water produces carbonic acid that solubilizes the cationic and/or amphoteric resins. The cationic or amphoteric resin is neutralized by the carbonic acid, e.g., the resin is protonated. That is, carbon dioxide forms carbonic acid in the aqueous solution (C0 ₂ + H ₂ 0 — H ₂ C0 ₃ ), dissociating to a proton (H ⁺ ) and a bicarbonate anion (HC0 ₃ ^" ) in solution. The cationic resin in solution is neutralized by protonation, e.g., R- H ₂ + H ⁺ becomes (R- H ₃ ) ⁺ , (with R being resin other than protonated amine moiety). Further, it is believed that solution stability is achieved by the presence of a stabilization sites for the bicarbonate anion (Protein-H~(HC0 ₃ ^" ) or (amino acid-COOH— HC0 ₃ )·

[0050] The present ink and coating compositions that contain stabilized cationic or amphoteric resin systems comprised of a cationic resin solvated in an aqueous carbonic acid solution have several performance advantages over the inks and coating compositions that include stabilized anionic resins. Those advantages flow from the electrophilic attraction of cationic resin to the oxygen and electronegative groups available on the surface of many printing industry substrates. This arrangement provides greater product resistance, stronger anchoring of the ink composition to the substrate, and greater mechanical resistance. The present inks and coatings are not odorous and are not corrosive, since they do not employ volatile acids such as formic and acetic acid. Should the stabilized cationic or amphoteric resin systems used to form the inks and coatings be prepared with excess C0 ₂ , the excess is liberated upon exposure to atmospheric conditions for about 24 hours. What remains is a stable aqueous carbonic solution of solvated cationic resin.

[0051] Unlike most volatile acids, carbonic acid decomposes and thus does not enter the gas phase intact. The liberation of carbonic acid (liquid to gas upon drying) to the atmosphere upon drying yields C0 ₂ and water. Thus, when a wet ink contained the described aqueous solutions of carbonic acid in which cationic or amphoteric resin is solvated is printed on a substrate, water and carbonic acid are removed as the printed substrate moves thru a dryer. Carbonic acid decomposes in the presence of water vapor, instantaneously breaking down into water and carbon dioxide when the ink is dried. No harmful or corrosive residues are left behind.

[0052] Cationic and amphoteric compounds in carbon dioxide solution can be pressurized to aid in solvation. Pressures may be, for example, greater than one atmosphere, more preferably greater than two atmosphere, and more preferably, up to 2.5 atmospheres or approximate thereto (e.g., 35 psi) with in order to dissolve in water.

[0053] In one aspect of the present invention, the concentration of carbon dioxide in the carbonic acid solution is about 1.5 mg C0 ₂ /ml to about 4.4 mg C0 ₂ /ml.

[0054] In one aspect of the present disclosure, the amount of water present in the stabilized carbonic acid solution can be, on weight basis of the solution, 50wt%, 51wt%, 52wt%, 53wt%, 54wt%, 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, or 90wt%.

[0055] Among the aforementioned amounts of water, 65wt% to 75wt% is preferred; more preferably 68wt% to 72wt%.

[0056] In one aspect of the present disclosure, the amount of cationic or amphoteric resin present in the stabilized carbonic acid solution can be, on weight basis of the solution, be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, l lwt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, or 50wt%. One or more resins may be present. One or more cationic resins may be present. One or more amphoteric resins may be present. One or more cationic resins and one or more amphoteric resins may be present. [0057] Among the aforementioned amounts of resins, 10wt% to 45wt% is preferred; more preferably 18wt% to 40wt%; and most preferably 20wt% to 27wt%.

[0058] In one aspect, the stabilizer may be present in an amount of 0.01wt% to 10wt% based on the total amount of solution. Preferred amounts of stabilizer include, for example, lwt% to 8wt%, more preferably, lwt% to 5wt%, and more preferably 2wt% to 4wt%.

[0059] In one aspect, a solvating aid may be present in the stabilized carbonic acid solutions in which cationic and/or amphoteric resins are solvated. Suitable solvating aids includes alcohols, such as alkanols, for example ethanol, propanol, butanol, isopropanol, and mixtures thereof. When present, the solvating aid may be present in an amount of 0.01wt% to 10wt%, based on the total amount of solution. Preferred amounts of solvating agent include, for example, lwt% to 5wt%, more preferably, 2 wt% to 4wt%, and more preferably 2.5wt% to 3.5 wt%.

[0060] In one aspect, a defoaming agent may be present in the stabilized carbonic acid solutions in which cationic and/or amphoteric resins are solvated. Suitable solvating aids include commercially available products such as Dow 62 or Dow 65 defoamer. When present, the defoamer may be present in an amount of 0.01wt% to 5wt%, based on the total amount of solution. Preferred amounts include, for example, 0.01 wt% to 2.5wt%, more preferably, 0.01wt% to lwt%, and more preferably 0.01wt% to 0.5 wt%.

[0061] It is believed that if a stabilizer was not present in the aqueous system, the carbonic acid in the aqueous cationic resin solution would dissociate into carbon dioxide and water, with carbon dioxide escaping from the solution and the solid, resin would precipitate out of solution. The stabilizer is believed to stabilize the carbonic acid. As described herein, the applicants have found that amino acids and proteins may be used as the stabilizer of carbonic acid. In one preferred embodiment, the proteins or amino acid may be those that predominantly contain acidic groups, that is, a majority of acidic groups and minority of basic groups. Suitable amino acids include glutamic acid and aspartic acid. Suitable proteins include soy protein. [0062] The stabilized aqueous carbonic acid solutions containing solvated cationic or amphoteric resin may be included in a color dispersion with cationic properties that is suitable for inclusion in an ink and coating composition. Such color dispersions would further include a pigment composition and may optionally contain other components, such as water, and defoamers. The stabilized aqueous carbonic acid solutions containing solvated cationic or amphoteric resin may be present in the color dispersions in amounts of 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, 51wt%, 52wt%, 53wt%, 54wt%, 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, or 75wt%.

[0063] Of the above, preferred amounts include 25wt% to 75wt%, more preferably, 28wt% to 70wt%, and even more preferably, 30wt% to 65wt%.

[0064] The amount of pigment in the color dispersion may be in an amount of 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, or 50wt%.

[0065] Of the above, preferred amounts include 25wt% to 50wt%, more preferably, 30wt% to 40wt%, and even more preferably, 34wt% to 40wt%.

[0066] In one aspect of the present disclosure, the present ink and coating compositions may include cationic color dispersions as described above in amounts of 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, 51wt%, 52wt%, 53wt%, 54wt%, 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, or 75wt%. [0067] Of the above, preferred amounts include 25wt% to 65wt%, more preferably, 40wt% to 65wt%, and even more preferably, 45wt% to 62wt%.

[0068] In one aspect of the present disclosure, the present ink and coating compositions may include additional stabilized aqueous carbonic acid solutions containing solvated cationic or amphoteric resin. For example, the inks and coatings may contain cationic color dispersions as described, and additional stabilized carbonic aqueous acid solution in which cationic or amphoteric resin is solvated. Such additional stabilized solutions may be present in the inks and coating compositions in amounts of 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, 51wt%, 52wt%, 53wt%, 54wt%, or 55wt%.

[0069] Of the above, preferred amounts include 25wt% to 50wt%, more preferably, 30wt% to 40wt%, and even more preferably, 32wt% to 37wt%.

[0070] In one aspect, the present inks and coating compositions may contain a cross linking agent, such as, for example, Silquest® A- 187, an epoxy functional silane. Cross linking agent may be present in amounts of from 0.01wt% to 10wt%, more preferably lwt% to 7wt%, and even more preferably, 3wt% to 6wt%.

[0071] The inks and coating compositions that are the subject of the present disclosure can be printed according to the flexographic and gravure print processes, as well as other print processes such as lithography, offset printing, screen printing, rod, spray, digital printing (e.g., ink jet printing), and printing employing energy curing (e.g., UV-curing and electron beam curing). It should be further understood that the ink formulation may be modified depending on the printing process, such as by adjusting amounts of the components in the formulation, or adding additional components to same in order to adjust ink viscosity and/or provide for a performance capability (e.g., include ethylenically unsaturated monomers, etc. and photoinitiators to render the inks energy curable). Such adjustments are within the capabilities and know-how of the skilled person. [0072] The stabilized aqueous solutions of cationic or amphoteric resins described herein can be included in other products such as paints, varnishes, adhesives, lubricants, and the process of polymer synthesis.

[0073] Inks and coating compositions that include the stabilized aqueous carbonic acid solutions in which cationic resin or amphoteric resin is solvated may include other components found such compositions. For example, such inks and coating compositions may include colorants, such as dyes and pigments, photoinitiators, viscosity modifiers, and other inks and coatings additives.

[0074] The amount of viscosity modifier that can be included in the ink formulations can vary depending on the type of process used to apply the ink. In some applications, the amount of viscosity modifier based on the weight of the ink composition is between at or about 0.1 wt % to at or about 30 wt %. In some applications, the amount of viscosity modifier based on the weight of the ink composition is in the range of 1 wt % to 25 wt %, or 5 wt % to 20 wt %, or 5 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt %. In some applications, the amount of viscosity modifier present in the ink is 0.1%, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 1.25 wt %, 1.5 wt %, 1.75 wt %, 2 wt %, 2.25 wt %, 2.5 wt %, 2.75 wt %, 3 wt %, 3.25 wt %, 3.5 wt %, 3.75 wt %, 4 wt %, 4.25 wt %, 4.5 wt %, 4.75 wt %, 5%, 5.25 wt %, 5.5%, 5.75 wt %, 6 wt %, 6.25 wt %, 6.5 wt %, 6.75 wt %, 7 wt %, 7.25 wt %, 7.5 wt %, 7.75 wt %, 8 wt %, 8.25 wt %, 8.5 wt %, 8.75 wt %, 9 wt %, 9.25 wt %, 9.5 wt %, 9.75 wt %, 10 wt %, 11 wt %, 11.25 wt %, 11.5 wt %, 11.75 wt %, 12 wt %, 12.25 wt %, 12.5 wt %, 12.75 wt %, 13 wt %, 13.25 wt %, 13.5 wt %, 13.75 wt %, 14 wt %, 14.25 wt %, 14.5 wt %, 14.75 wt %, 15%, 15.25 wt %, 15.5%, 15.75 wt %, 16 wt %, 16.25 wt %, 16.5 wt %, 16.75 wt %, 17 wt %, 17.25 wt %, 17.5 wt %, 17.75 wt %, 18 wt %, 18.25 wt %, 18.5 wt %, 18.75 wt %, 19 wt %, 19.25 wt %, 19.5 wt %, 19.75 wt %, 20 wt %, 21.25 wt %, 21.5 wt %, 21.75 wt %, 22 wt %, 22.25 wt %, 22.5 wt %, 22.75 wt %, 23 wt %, 23.25 wt %, 23.5 wt %, 23.75 wt %, 24 wt %, 24.25 wt %, 24.5 wt %, 24.75 wt %, 25%, 25.25 wt %, 25.5%, 25.75 wt %, 26 wt %, 26.25 wt %, 26.5 wt %, 26.75 wt %, 27 wt %, 27.25 wt %, 27.5 wt %, 27.75 wt %, 28 wt %, 28.25 wt %, 28.5 wt %, 28.75 wt %, 29 wt %, 29.25 wt %, 29.5 wt %, 29.75 wt % or 30 wt %, based on the weight of the ink composition. [0075] The colorants included in the present inks and coating compositions include pigments, dyes, and combinations thereof. Any organic and/or inorganic pigments and dyes can be included. Exemplary pigments suitable for use in the present invention include International Color Index or C.I. Pigment Black Numbers 1, 7, 11 and 31, C.I. Pigment Blue Numbers 15, 15: 1, 15:2, 15:3, 15:4, 15:6, 16, 27, 29, 61 and 62, C.I. Pigment Green Numbers 7, 17, 18 and 36, C.I. Pigment Orange Numbers 5, 13, 16, 34 and 36, C.I. Pigment Violet Numbers 3, 19, 23 and 27, C.I. Pigment Red Numbers 3, 17, 22, 23, 48: 1, 48:2, 57: 1, 81 : 1, 81 :2, 81 :3, 81 :5, 101, 114, 122, 144, 146, 170, 176, 179, 181, 185, 188, 202, 206, 207, 210 and 249, C.I. Pigment Yellow Numbers 1, 2, 3, 12, 13, 14, 17, 42, 65, 73, 74, 75, 83, 93, 109, 110, 128, 138, 139, 147, 142, 151, 154 and 180, D&C Red No. 7, D&C Red No. 6 and D&C Red No. 34, carbon black pigment (such as Regal 330, Cabot Corporation), quinacridone pigments (Quinacridone Magenta (228-0122), available from Sun Chemical Corporation, Fort Lee, N.J.), diarylide yellow pigment (such as AAOT Yellow (274-1788) available from Sun Chemical Corporation); and phthalocyanine blue pigment (such as Blue 15:3 (294-1298) available from Sun Chemical Corporation). The classes of dyes suitable for use in present invention can be selected from acid dyes, natural dyes, direct dyes (either cationic or anionic), basic dyes, and reactive dyes. The acid dyes, also regarded as anionic dyes, are soluble in water and mainly insoluble in organic solvents and are selected, from yellow acid dyes, orange acid dyes, red acid dyes, violet acid dyes, blue acid dyes, green acid dyes, and black acid dyes. European Patent 0745651, incorporated herein by reference, describes a number of acid dyes that are suitable for use in the present invention. Exemplary yellow acid dyes include Acid Yellow 1 International Color Index or C.I. 10316); Acid Yellow 7 (C.I. 56295); Acid Yellow 17 (C.I. 18965); Acid Yellow 23 (C.I. 19140); Acid Yellow 29 (C.I. 18900); Acid Yellow 36 (C.I. 13065); Acid Yellow 42 (C.I. 22910); Acid Yellow 73 (C.I. 45350); Acid Yellow 99 (C.I. 13908); Acid Yellow 194; and Food Yellow 3 (C.I. 15985). Exemplary orange acid dyes include Acid Orange 1 (C.I. 13090/1); Acid Orange 10 (C.I. 16230); Acid Orange 20 (C.I. 14603); Acid Orange 76 (C.I. 18870); Acid Orange 142; Food Orange 2 (C.I. 15980); and Orange B. Exemplary red acid dyes include Acid Red 1. (C.I. 18050); Acid Red 4 (C.I. 14710); Acid Red 18 (C.I. 16255), Acid Red 26 (C.I. 16150); Acid Red 2.7 (C.I. as Acid Red 51 (C.I. 45430, available from BASF Corporation, Mt. Olive, N.J.) Acid Red 52 (C.I. 45100); Acid Red 73 (C.I. 27290); Acid Red 87 (C. I. 45380); Acid Red 94 (C.I. 45440) Acid Red 194; and Food Red 1 (C.I. 14700). Exemplary violet acid dyes include Acid Violet 7 (C.I. 18055); and Acid Violet 49 (C.I. 42640). Exemplary blue acid dyes include Acid Blue 1 (C.I. 42045); Acid Blue 9 (C.I. 42090); Acid Blue 22 (C.I. 42755); Acid Blue 74 (C.I. 73015); Acid Blue 93 (C.I. 42780); and Acid Blue 158A (C.I. 15050). Exemplary green acid dyes include Acid Green 1 (C.I. 10028); Acid Green 3 (C.I. 42085); Acid Green 5 (C.I. 42095); Acid Green 26 (C.I. 44025); and Food Green 3 (C.I. 42053). Exemplary black acid dyes include Acid Black 1 (C.I. 20470); Acid Black 194 (Basantol® X80, available from BASF Corporation, an azo/l :2 CR-complex.

[0076] Exemplary direct dyes for use in the present invention include Direct Blue 86 (C.I. 74180); Direct Blue 199; Direct Black 168; Direct Red 253; and Direct Yellow 107/132 (C.I. Not Assigned).

[0077] Exemplary natural dyes for use in the present invention include Alkanet (C.I. 75520, 75530); Annafto (C.I. 75120); Carotene (C.I. 75130); Chestnut; Cochineal (C.I. 75470); Cutch (C.I. 75250, 75260); Divi-Divi; Fustic (C.I. 75240); Hypernic (C.I. 75280); Logwood (C.I. 75200); Osage Orange (C.I. 75660); Paprika; Quercitron (C.I. 75720); Sanrou (C.I. 75100); Sandal Wood (C.I. 75510, 75540, 75550, 75560); Sumac; and Tumeric (C.I. 75300). Exemplary reactive dyes for use in the present invention include Reactive Yellow 37 (monoazo dye); Reactive Black 31 (disazo dye); Reactive Blue 77 (phthalo cyanine dye) and Reactive Red 180 and Reactive Red 108 dyes. Suitable also are the colorants described in The Printing Ink Manual (5th ed., Leach et al. eds. (2007), pages 289-299. Other organic and inorganic pigments and dyes and combinations thereof can be used to achieve the colors desired.

[0078] For non-white inks, the amount of pigment/dye generally is present in an amount of from at or about 0.1 wt % to at or about 20 wt % based on the weight of the ink composition. In some applications, a non-white ink may include 15 wt % or less pigment/dye, or 10 wt % or less pigment/dye or 5 wt % pigment/dye, or 1 wt % pigment/dye based on the weight of the ink composition. In some applications, a non-white ink may include 1 wt % to 10 wt %, or 5 wt % to 15 wt %, or 10 wt % to 20 wt % pigment/dye based on the weight of the ink composition. In some applications, a non-white ink can contain an amount of dye/pigment that is 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5%, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15%, 16 wt %, 17 wt %, 18 wt %, 19 wt % or 20 wt % based on the weight of the ink composition.

[0079] For white ink compositions, the amount of white pigment generally is present in an amount of from at or about 1 wt % to at or about 60 wt % based on the weight of the ink composition. In some applications, greater than 60 wt % white pigment can be present. Preferred white pigments include titanium dioxide (anatase and rutile), zinc oxide, lithopone (calcined coprecipitate of barium sulfate and zinc sulfide), zinc sulfide, blanc fixe and alumina hydrate and combinations thereof, although any of these can be combined with calcium carbonate. In some applications, a white ink may include 60 wt % or less white pigment, or 55 wt % or less white pigment, or 50 wt % white pigment, or 45 wt % white pigment, or 40 wt % white pigment, or 35 wt % white pigment, or 30 wt % white pigment, or 25 wt % white pigment, or 20 wt % white pigment, or 15 wt % white pigment, or 10 wt % white pigment, based on the weight of the ink composition. In some applications, a white ink may include 5 wt % to 60 wt %, or 5 wt % to 55 wt %, or 10 wt % to 50 wt %, or 10 wt % to 25 wt %, or 25 wt % to 50 wt %, or 5 wt % to 15 wt %, or 40 wt % to 60 wt % white pigment based on the weight of the ink composition. In some applications, a non-white ink can an amount of dye/pigment that is 5%, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15%, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25%, 26 wt %, 27 wt %, 28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35%, 36 wt %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 wt %, 45%, 46 wt %, 47 wt %, 48 wt %, 49 wt %, 50 wt %, 51 wt %, 52 wt %, 53 wt %, 54 wt %, 55%, 56 wt %, 57 wt %, 58 wt %, 59 wt % or 60 wt % based on the weight of the ink composition.

[0080] For clear coatings, colorants such as optical brighteners can be included. In some applications, no colorant, pigment or dye is included in the clear coatings. When present, the amount of colorant, pigment or dye generally is 10 wt % or less based on the weight of the ink composition.

[0081] The ink, white ink and clear coating compositions may include one or more of various additives, such as, e.g., anti-misting agents {e.g., silica and microtalc), clay, defoamers, dispersants, flow agents, inhibitors, lubricants {e.g., wax), plasticizers, silicones, stabilizers, talc, wetting agents, surface tension modifiers, rheology (wet adhesion/cohesion) modifiers, print quality modifiers, anchoring/bonding/adhesion modifiers, specific chemical resistance modifying resins or additives, slip (COF) and scuff additives, texture modifiers, gloss modifiers, transparency modifiers, opacity modifiers reactivity modifiers, and combination thereof

[0082] Each of these additives can be used in an ink or coating of this disclosure at a level of from about 0.001% to about 10% or more based on the weight of the ink composition.

[0083] Wetting agents can be included in the inks or coatings, e.g., to modify surface tension. Exemplary wetting agents include polyether modified polydimethylsiloxane (BYK®307), xylene, ethylbenzene, a blend of xylene and ethylbenzene (BYK0310), octamethylcyclo- tetrasiloxane (BYK0331) and alcohol alkoxylates {e.g., BYK® DYNWET). Any foam destroying or foam mitigating polymer or compound can be included in the inks as a defoamer. Examples of these include polysiloxanes, oxyalkylene amines, silicone oils and fluids, polyacrylates, polyglycol, polyols, and polyether modified methylalkyl polysiloxane copolymers and combinations thereof.

[0084] In some applications, the inks or coatings may include one or more polymerization inhibitors or stabilizers for radically curable inks or both. Examples of these include benzoquinone, benzotriazolealuminium salt amine complexes, butylated hydroxytoluene, hydroquinone, hydroquinone monom ethyl ether, Florstab® UV-1 (Kromachem LTD), Genorad® 16 inhibitor compound (Rahn Corporation), Irgastab® UV-10 and Irgastab® UV-22 (Ciba Specialty Chemicals Inc.), naphthoquinone, t-butyl catechol, t-butylhydroquinone and combinations thereof.

[0085] The inks or coatings may include a flow agent. Examples of flow agents that can be included in the inks or coatings include, e.g., butyrates, celluloses, polyacrylates, surfactants, silicones and waxes. Examples of surfactants include siloxanes, polyalkyleneoxide siloxanes, polyalkyleneoxide polydimethylsiloxanes, polyester polydimethylsiloxanes, ethoxylated nonylphenols, nonylphenoxy polyethyleneoxy-ethanol, fluorocarbon esters, fluoroaliphatic polymeric esters, fluorinated esters, alkylphenoxy alkyleneoxides, cetyl trimethyl ammonium chloride, carboxymethyl-amylose, ethoxylated acetylene glycols, betaines, N-dodecyl-N,N- dimethylbetaine, dialkyl sulfosuccinate salts, alkylnaphthalene-sulfonate salts, fatty acid salts, polyoxyethylene alkylethers, polyoxyethylene alkylallyl-ethers, polyoxyethylene- polyoxypropylene block copolymers, alkylamine salts, quaternary ammonium salts, and mixtures thereof.

[0086] The inks or coatings may include a plasticizer. Examples of plasticizers include alkyl benzyl phthalates, butyl benzyl phthalates, di-2-ethylhexy-adipates, diethyl phthalates, dimethyl phthalates, dioctyl phthalates, diisobutyl phthalates, dicyclohexyl phthalates, diisobutyl adipates, glycerol tribenzoates, polypropylene glycol dibenzoates, neopentyl glycol dibenzoates, dimethyl isophthalates, dibutyl phthalates, dibutyl sebacates, sucrose benzoates, tri-n-hexyltrimellitates, and mixtures thereof.

[0087] The inks or coatings may include one or more dispersant. Examples of a dispersant include acrylic block copolymers, acrylate block copolymers, graft polymers, hydrophilic- hydrophobic block copolymers, a polymer dispersant, a surfactant, and mixtures thereof.

[0088] The following examples illustrate specific aspects of the present invention and are not intended to limit the scope thereof in any respect and should not be so construed.

Examples

[0089] In the following examples, stable aqueous carbonic acid solutions containing solvated cationic or amphoteric resins were prepared in a Hamilton Beach Soda Station. About 35 psi (approximately 2.5 atmospheres) of carbon dioxide (C0 ₂ ) is introduced into the water in the sealed chamber of the soda station. The soda station holds about 520 grams of water at the minimum fill line of the soda station, and holds about 800 grams of water at the maximum fill line. [0090] A magnetic mixing pill was placed inside the soda station and the soda station was placed on a magnetic mixer, which when operated, spins the mixing pill to mix the solution in the soda station.

[0091] In the examples, cationic resins are solvated in the stable aqueous carbonic acid solutions. Three of the cationic resins are commercially available products that are packaged in solutions of water and formic acid (or water and another acid). As such, these commercially available products are unsuited from inclusion in inks and coating compositions because the

aforementioned drawbacks. The resins are Ottopol K-362-A (aforedescribed herein), DVK.4171 from Vanora AG, an acrylate cationic dispersion, and Syntran® 6302, a water-based cationic acrylic copolymer available from Interpolymer Corporation.

[0092] Before performing the experiments, the resins were air dried thoroughly at 70°F (21°C) at ambient pressure for 96 hours, yielding cationic resins essentially free of volatile acids.

Complete loss of water and volatile acids is verified by vacuum solids testing, with no additional weight being lost at 250°C and 0.2 atm for 30 minutes. A typical procedure for C0 ₂ solvation for a resin requires mixing the aqueous solutions for about 1 to 2 hours in the soda station.

[0093] Also used in the examples are the following non-neutralized cationic and amphoteric compounds, available as 100% solids (e.g., no solvent packaging): SMA® Imide 10001 and Sobind™ Impression soy protein.

[0094] Stabilizing agents used in the examples are Nutrabio L-Glutamic Acid and Sobind™ Impression soy protein.

Comparative Example 1: Solvation of SMA® Imide 10001 (cationic imide)

[0095] Using a clean, dry soda station, the following components are loaded into the soda chamber, at room temperature:

[0096] 395.2 grams tap water; [0097] 106.6 grams SMA® Imide 10001— a copolymer resin of styrene and

dimethylaminopropylamine (MDAPA) maleimide in a l : lmonomer ratio. (3.5 meq/gram amine index, Tg is 85°C. Mw is 5,000 to 10,000. This copolymer is available from Cray Valley, Exton, PA, US;

[0098] 15.6 grams Isopropanol, present as a solvating aid;

[0099] 2.6 grams Rhodoline 679 (a defoaming agent); and

[00100] a magnetic stirring pill.

[00101] The top of the soda machine was sealed after loading in the above components. An 8.0 gram C0 ₂ charger was placed in the soda station and activated to pressurize the soda chamber with C0 ₂ . The mixing station was activated and set to the high mix setting. Mixing continued at this setting for setting for 2 hours, or until the solution was clear, evidencing that the resin dissolved. If needed, the soda station was shaken if the magnetic stirring pill gets stuck in the resin. The aqueous solution of Example 1 and all other examples were prepared at room temperature.

[00102] Due to the lack of a stabilizing agent, the Comparative Example 1 formula was found to continuously liberate C0 ₂ over time, eventually causing the resin to precipitate out of solution when exposed to the atmosphere. Stabilization of the carbonic acid was preferred for greater shelf life.

Example 1 : CO2 Solvation of Amphoteric Soy Protein ( Amphoteric Soy Polymer)

[00103] The soda station described in Comparative Example 1 was loaded with the following components:

[00104] 448.7 grams tap water;

[00105] 68.7 grams Sobind™ Impression soy protein;

[00106] 2.6 grams Rhodoline 679; and

[00107] a magnetic stirring pill.

[00108] The top of the soda machine was sealed after loading in the above components. An 8.0 gram C0 ₂ charger was placed in the soda station and activated to pressurize the soda chamber with C0 ₂ . The mixing station was activated and set to the high mix setting. Mixing was continued until the initial opaque solution fully dissolved, e.g., when particles were no longer present. The pH of the solution is 6.1.

[00109] In Example 1, only excess C0 ₂ is released over time in a closed container. Solvated carbonic acid remains for neutralizing the resin.

[00110] In Example 1, the system of an amphoteric resin solvated in an aqueous solution of carbonic acid did not liberate resin-bound bicarbonate anion with time. It is believed that the amphoteric soy protein stabilizes the carbonic acid in solution. In Example 1, the soy protein serves as both a resin and a stabilizing agent. More specifically, the excess acid groups on the protein polymer stabilize bicarbonate anion. The excess acid groups on protein are due to acidic amino acids Aspartic acid (Asp) and Glutamic acid (Glu). Proteins whose amino acid building blocks are more acidic than basic are effective stabilizers, i.e., neutralizers.

Example 2: Aqueous Carbonic Acid Solution Including Solvated

Cationic Resin (SMA-Imide lOOOi)., Stabilized with Soy Protein Resin

[00111] The soda station described in Comparative Example 1 was loaded with the following components:

[00112] 374.4 grams tap water;

[00113] 106.6 grams SMA-Imide lOOOi, a copolymer cationic resin that is described above;

[00114] 20.8 grams Sobind™ Impression soy protein;

[00115] 15.6 grams Isopropanol;

[00116] 2.6 grams Rhodoline 679; and

[00117] A magnetic stirring pill.

[00118] The top of the soda machine was sealed after loading in the above components.

[00119] An 8.0 gram C0 ₂ charger was placed in the soda station and activated to pressurize the soda chamber with C0 ₂ . The mixing station was activated and set to the high mix setting.

Mixing continued at this setting for setting for 2 hours, or until the solution was clear, evidencing that the resin was dissolved. The pH of this system is 6.8. [00120] The aqueous carbonic acid solution containing solvated cationic resin of Example 2 is stabilized with a relatively small amount of soy protein. It is believed that the protein stabilizes the bicarbonate anion. The aqueous carbonic acid solution has a longer shelf life (no gassing or loss of solubility), believed to be due to the protein stabilization of the bicarbonate anion.

Example 3: Aqueous Carbonic Acid Solution Including

Solvated Cationic Resin (SMA-Imide lOOOi), Stabilized with Amino acid

[00121] The soda station described in Comparative Example 1 was loaded with the following components:

[00122] 384.8 grams tap water;

[00123] 106.6 grams SMA-Imide lOOOi (as described above);

[00124] 10.4 grams L-Glutamic Acid;

[00125] 15.6 grams Isopropanol;

[00126] 2.6 grams Rhodoline 679; and

[00127] a magnetic stirring pill.

[00128] An 8.0 gram C0 ₂ charger was placed in the soda station and activated to pressurize the soda chamber with C0 ₂ . The mixing station was activated and set to the high mix setting. Mixing continued at this setting for setting for 2 hours, or until the solution was clear, evidencing that the resin dissolved. The pH of this system is 7.0.

[00129] The aqueous carbonic acid solution of Example 3 ceased liberating excess C0 ₂ within 48 hours of exposure to air, without any cationic resin precipitating out of solution.

[00130] Glutamic acid is the stabilizer component employed in the aqueous carbonic acid cationic resin-solvated solution of Example 3. A lesser amount of glutamic acid (2wt% of the total solution) may be used as stabilizer, when compared to the amount of soy protein used in Example 2 (4wt% of the total solution). Glutamic acid may be a more effective stabilizer for the bicarbonate ion, when compared to a protein in which this amino acid is a building block.

[00131] A color dispersion was prepared that includes the aqueous carbonic acid solution of Example 3 and a blue pigment 15:3, thereby providing a cationic base colorant option comprising 38.0% blue pigment 15:3 and 62.0% of the Example 3 aqueous carbonic acid solution in which cationic resin is solvated.

[00132] This cationic dispersion is included in several formulations of cationic finished inks in which 50wt% of the finished ink is the dispersion, and 50wt% of the ink is a cationic letdown varnishes solvated with C0 ₂ . Those letdown cationic varnishes would carry their own specific performance properties. Letdown varnish compositions are disclosed in the examples of Table 2.

Example 4: Aqueous Carbonic Acid Solution Including

Solvated Cationic Resin (Interpolymer Syntran 6302), Stabilized with Amino acid

[00133] The soda station described in Comparative Example 1 was loaded with the following components:

[00134] 358.3 grams tap water;

[00135] 133.1 grams dried Syntran® 6302 - a cationic acrylic resin;

[00136] 10.4 grams L-Glutamic Acid;

[00137] 15.6 grams Isopropanol;

[00138] 2.6 grams Rhodoline 679; and

[00139] a magnetic stirring pill.

[00140] An 8.0 gram C0 ₂ charger was placed in the soda station and activated to pressurize the soda chamber with C0 ₂ . The mixing station was activated and set to the high mix setting. Mixing continued at this setting for setting for 2 hours, or until the solution was clear, evidencing that the resin dissolved. The pH of this system is 5.5.

[00141] Example 4 shows that Syntran® 6302, a commercially available cationic acrylic resin product available from Interpolymer, typically used for wood protection, can be separated from a corrosive volatile component (e.g. formic acid) and solvated in aqueous solutions of carbonic acid and stabilizer. These cationic resin solutions can be included in ink and coating

compositions used in printing processes such as flexographic, rotogravure, and ink jet applications without being corrosive to press components and/or be unpleasantly odorous.

Syntran® 6302 also has potential use as a lamination option for polyester where solvent less adhesive is employed. Example 5: Aqueous Carbonic Acid Solution Including

Solvated Cationic Resin (Gellner Ottopol K-362-A), Stabilized with Amino acid

[00142] Gellner Ottopol K-362-A is a commercially cationic acrylic resin packaged in an aqueous acetic acid solution. Before being prepared in an aqueous carbonic acid solution, the resin was vacuum dried in three drying procedures and then dried in ambient conditions for four (4) weeks to remove the odor of acetic acid form the resin.

[00143] The soda station described in Comparative Example 1 was loaded with the following components:

[00144] 384.8 grams tap water;

[00145] 106.6 grams dried Gellner Ottopol K-362-A;

[00146] 10.4 grams L-Glutamic Acid;

[00147] 15.6 grams Isopropanol;

[00148] 2.6 grams Rhodoline 679; and

[00149] a magnetic stirring pill.

[00150] An 8.0 gram C0 ₂ charger was placed in the soda station and activated to pressurize the soda chamber with C0 ₂ . The mixing station was activated and set to the high mix setting.

Mixing continued at this setting for setting for 2 hours, or until the solution was clear, evidencing that the resin dissolved. The pH of this system is 4.0

[00151] The aqueous solution of carbonic acid in which Gellner Ottopol K-362-A is solvated has little to no detectable odor.

Example 6: Aqueous Carbonic Acid Solution Including Solvated

Cationic Resin (Alberdingk Boley Vanora DKV.4171), Stabilized with Amino acid

[00152] The soda station described in Comparative Example 1 was loaded with the following components:

[00153] 133.6 grams dried DKV.4171, a commercially available cationic acrylic resin described above;

[00154] 10.4 grams L-Glutamic Acid; and

[00155] 15.6 grams Isopropanol.

[00156] Let first 3 ingredients sit for 12 hours, then add: [00157] 357.8 grams tap water;

[00158] 2.6 grams Rhodoline 679; and

[00159] a magnetic stirring pill.

[00160] An 8.0 gram C0 ₂ charger was placed in the soda station and activated to pressurize the soda chamber with C0 ₂ . The mixing station was activated and set to the high mix setting. Mixing continued at this setting for setting for 6 hours, or until the opaque solution no longer has particulates.

[00161] The solvation of DKV.4171 resin in an aqueous solution of carbonic acid

demonstrates that higher molecular weight emulsion cationic resins can also be separated from the acid solvents (in this case, methanesulfonic acid) and included in the carbonic acid aqueous solution vehicles described herein. The DKV.4171 resin has exceptional mechanical and water resistance properties. A recent evaluation on recycled board showed that the DKV.4171 resin coating applied with Rod-3 increased the mass per area of the board by 8.96g/m ² and increased the stiffness of the board by 8%. It would be expected that solvated DKV.4171 resin in an aqueous solution of carbonic acid as described herein, should exhibit the same advantageous properties when incorporated into a printing ink or coating. The solvated cationic resin

DKV.4171 cross-links with the the available -OH groups in the paperboard, leading to a greater weight support, with relatively low weight addition to the board.

Example 7 - Aqueous Carbonic Acid Solution Including

Solvated Cationic Resin (Gellner Ottopol KX-99), Stabilized with Amino Acid

[00162] The soda station of Comparative Example 1 was loaded with the following components:

[00163] 133.6 grams dried Gellner Ottopol KX-99, a commercially available hydroxyl functional cationic acrylic resin solution, available from Gellner Industries LLC (place of business previously mentioned);

[00164] 3.2 grams L-Glutamic Acid; and

[00165] 15.6 grams Isopropanol.

[00166] Let the above ingredients sit for 12 hours, then add: [00167] 357.8 grams tap water;

[00168] 2.6 grams Rhodoline 679; and

[00169] a magnetic stirring pill.

[00170] An 8.0 gram C0 ₂ charger was placed in the soda station and activated to pressurize the soda chamber with C0 ₂ . The mixing station was activated and set to the high mix setting. Mixing continued at this setting for 20 minutes, or until the solution no longer has particulates.

[00171] A lesser amount of L-Glutamic acid was required to stabilize the KX-99 cationic resin, which includes both proton accepting nitrogen functionality and hydroxyl functionality, as there is the possibility that hydroxyl groups (-OH) present on a neutralized cationic resin may also stabilize the bicarbonate anion.

[00172] There is the possibility that if enough hydroxyl functionality is present on a cationic resin, no acidic amino acid would be required to stabilize the dissociated bicarbonate anion.

Example 8 ~ Blue Ink Formulation Containing Aqueous Carbonic

Acid Solution Including Solvated Cationic Resin Stabilized with Amino Acid

[00173] The following components were prepared in a blue ink formulation:

[00174] 15.0wt% Example 8 A Intermediate Blue Dispersion, described below;

[00175] 4.0wt% glycerin;

[00176] 80.8wt% aqueous carbonic acid solution of Example 7;

[00177] 0.2wt% Dow 62 defoamer.

Example 8A Intermediate Blue Dispersion

[00178] The intermediate blue dispersion used in the present example was formulated with the following components:

[00179] 42.0wt% aqueous carbonic acid solution including solvated cationic resin

(Interpol ymer Syntran® 6302) of Example 4;

[00180] 38.0wt% blue pigment 15:3;

Γ00181] 0.3wt% Dow 62 Defoamer; and [00182] 19.7wt% water.

Example 9 - Towel & Tissue Test

[00183] The ink formulation of Example 8 was compared to the commercial inks identified in Table 1 and evaluated for performance. Color density measured with X-rite 938. In this regard, inks are applied to substrate using a 180 line 9.0 BCM hand proofer. Printed towel sample is placed on flat white surface with ink facing up. X-rite 938 is set to Density mode. Three separate reading are taken near mid-point of printed area. Noted density is an average of three values.

[00184] The Sutherland crock rub test uses a modified sled with an elevated ½" x ¾" rubber pad. The rubber pad is placed over a printed paper towel (ink down), with paper mounted to the base of the Sutherland Rub tester. The paper towel is wetted with tap water. Number of cycles to towel destruction in ink area is noted. This shows the mechanical reinforcement by ink resin via attractions to the cellulose in the paper towel.

[00185] In the product resistance test, printed paper towels are soaked in pools of

commercially available liquid household products, specifically Formula 409® and Windex®. A further test was performed in a pool of water and ethanol. A Passing result shows no color bleed or movement of color for 30 minutes.

Table 1

[00186] The following resins solvated in aqueous carbonic acid solutions can be included in printing inks and coating compositions. These resins are not believed to be used in inks and coatings used in printing flexible packaging, due in part to the packaging of these cationic resins in corrosive and odorous acids that are not sufficiently volatile (e.g. formic, acetic, phosphoric, hydrochloric, etc.). Including these resins in aqueous carbonic acid solutions allows them to be used in printing inks and coating applied in print processes such as flexographic, rotogravure, and inkjet.

[00187] Again, such aqueous carbonic acid solutions include the following resins, in the following suggested amounts:

[00188] 13.2wt% solids solution of Soy Protein, an amphoteric resin;

[00189] 20.5% solids solution of SMA-Imide lOOOi;

[00190] 25.7% solids solution of Syntran 6302;

[00191] 21.5% solids solution of Ottopol K-362-A;

[00192] 25.7% solids Alberdingk Acrylic Vanora 4171; and

[00193] SMA-Imide color dispersion of Blue pigment 15:3.

Example 10 - Odor Test

[00194] A SMA-Imide solvated with formic acid was rated for odor, in comparison to aqueous carbonic acid solution in which this same resin is solvated. An average of three individuals were asked to rate the odor in a blind smell test, on a scale of 1 to 5, with each value having the following score:

[00195] 1= no perceptible odor;

[00196] 2= slight odor;

[00197] 3= moderate odor;

[00198] 4= strong odor; and

[00199] 5= extreme odor.

[00200] The resin solvated in aqueous carbonic acid solution had an average score of 2.3. The resin solvated in formic acid had an average score of 3.9.

Example 11 - Water Resistance Test

[00201] A blue ink composition including 50% Syntran® 6302 and 50% SMA-Imide Blue dispersion was prepared and solvated in aqueous carbonic acid solution. The same composition was again prepared, and to it l .Owt % non-volatile phosphoric acid was added. The compositions were applied side-by-side with a 360 line 3.6 BCM analox hand proofer on treated polyethylene and fried at 120°F for 30 seconds. Water was run over the side-by-side print for 15 seconds, followed by a wipe with paper towel. The results showed that most of the ink composition that included phosphoric acid was removed by the wiping. The side wiped by the formulation that did not contain phosphoric acid showed only a small amount ink removal, demonstrating increased water resistance). When a non-volatile acid such as phosphoric acid is used, water resistance may be lowered.

Example 12 - Corrosion Resistance Test

[00202] A blue steel rotogravure blade was suspended above a solution of SMA-Imide solvated with acetic acid for 7 days in a closed container. A second identical blade was suspended above the Example 3 solution of SMA-Imide solvated with C0 ₂ for 7 days in a closed container without acetic acid. Both samples were heated to 120°F to liberate solvating acid. The sample without acetic acid showed no corrosion on the blade in proximity to the C0 ₂ solvated resin. The blade in proximity to the acetic acid solvated resin showed considerable surface corrosion.

Examples 13-16

[00203] The stabilized aqueous carbonic acid solutions of Examples 13-16 in which cationic resin is solvated, the compositions of which are given in Table 2, were prepared as indicated for the above examples and have the following compositions:

Table 2

Resin and Water L-Glutamic Isopropan Rhodoline C0 ₂ Amount Acid ol 679 cartridge

Stabilizer Defoamer

Example WorieeCryl® 413.8 12 g. 15.6 g. 2.6 g. l- 8 g.

13 7712 W g- cartridge

156 g.

Example Ecronova RA 305.8 12 g. 15.6 g. 2.6 g. l- 8 g.

14 180 Plus g- cartridge

264 g.

[00204] WorleeCryl® 7712 W is a cationic pure resin solution, 6\γί% solids in water and acid, available from Worlee-Chemie G.m.b.H. It is described as being suitable for use in pigmented wood sealants.

[00205] Ecronova RA 180 plus is a cationic acrylic resin dispersion supplied by Michelman made available in a water and acid formulation.

[00206] Ottopol KX-101 is supplied by Gellner Industrial, LLC and is described as a hydroxyl functional cationic acrylic emulsion polymer made available in a water arid acid formulation . This polymer will crosslink at room temperature with polyisocyanates and epoxy silanes. Ambient curing happens very quickly, in 15 minutes the film will have water resistance. Allowing the film to cure for four hours will result in a film that has over 100 double rubs acetone resistance. Detergents and cleaners will not remove this film. Water resistance is excellent. The dried film will also resists staining.

[00207] Duroxyn 2410/40WA is supplied by Allnex and is described as an aqueous, cationic epoxy-resin-ester made available in a water and acid formulation. This material has been developed for the production of one component primers, with quick drying and high film hardness.

Example 17 - Cationic Color Dispersion

[00208] This color dispersion formulation is comprised of the following, and is passed through a media mill to produce sub-micron pigment particle size. The finished color dispersion is pH- suitable for use with a cationic let down resin. All amounts are in weight percent.

[00209] 32wt% Solution of Example 13;

[00210] 32wt% Water; [0021 1] lwt% BYK-094 Defoamer;

[00212] 35 wt% HELIOGEN BLUE D71 1 OF : Pigment blue 15 : 3.

Example 18 - Outdoor Bag Finished Ink on Polyethylene

[00213] 60 wt% Cationic Color Dispersion of Example 17;

[00214] 35wt% solution of Example 14;

[00215] 4wt% Cationic Wax Aquacer 840 (BYK Additives);

[00216] lwt% Dow 65 additive defoamer.

[00217] The above formulation was printed on polyethylene outdoor bag material and showed excellent resistance to the outdoor environment (harsh elements), and to withstanding the wear and tear placed on such packaging due to friction (rubbing), impact forces, stacking, etc. Inks remained on the packaging without any noticeable removal for a period of three months or longer.

Example 19 - Line-Lube Resistant Ink

[00218] Line lube resistant ink is used to label bottles, for example, without use of aziridene.

Line lube is a pH 12.0 soap, which is applied to most in-line bottle fill operations for lubrication.

Anionic resins cannot withstand pH 12 environment, as it will dissolve the material.

[00219] 50wt% Example 17 color dispersion:

[00220] 20wt% Example 15 solution;

[00221] 14wt% Example 16 solution;

[00222] 4wt% Cationic Wax Aquacer 840 (BYK Additives);

[00223] lwt% Dow 62 additive defoamer.

[00224] Optionally, 5.0wt% Silquest® A- 187 epoxy silane, available from Momentive Performance Materials, may be included as a cross linking agent.

[00225] The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention that fall within the scope and spirit of the invention.