Ink composition comprising humectant blend

Abstract

An ink composition including a humectant blend comprising a first humectant and a second humectant; wherein the first humectant has a freezing point; wherein the second humectant suppresses the freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a desired temperature without solidifying; water; an optional co-solvent; an optional colorant; and a sulfonated polyester. A process of digital offset printing using the ink composition.

Claims

1. An ink composition comprising: a humectant blend comprising a first humectant and a second humectant; wherein the first humectant has a freezing point; wherein the second humectant suppresses the freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a desired temperature without solidifying; water; an optional co-solvent; an optional colorant; and a sulfonated polyester; wherein the ink composition has a first viscosity of from about 3,000 to about 90,000 centipoise at an ink take up temperature of from about 45 C. to about 80 C.; and the ink composition has a second viscosity of from about 100,000 to about 2,000,000 centipoise at an ink transfer temperature of from about 18 C. to about 30 C.

2. The ink composition of claim 1, wherein the first humectant is a solid at or near room temperature, wherein room temperature is from about 20 to about 40 C.; and wherein the second humectant suppresses the freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a temperature of from about 0 to about 4 C. without solidifying.

3. The ink composition of claim 1, wherein the first humectant is selected from the group consisting of tert-butyl alcohol, sulfolane, and combinations thereof.

4. The ink composition of claim 1, wherein the second humectant is selected from the group consisting of methanol, glycerol, ethylene glycol, propylene glycol, diethylene glycol, and combinations thereof.

5. The ink composition of claim 1, wherein the first humectant is present in the ink composition in an amount of from about 10 to about 45 percent by weight based upon the total weight of the ink composition.

6. The ink composition of claim 1, wherein the second humectant is present in the ink composition in an amount of from about 1 to about 20 percent by weight based upon the total weight of the ink composition.

7. The ink composition of claim 1, wherein the sulfonated polyester has a degree of sulfonation of at least about 3.5 mol percent.

8. The ink composition of claim 1, wherein the sulfonated polyester has a degree of sulfonation of at least about 7.5 mol percent.

9. The ink composition of claim 1, wherein the sulfonated polyester comprises a sodium sulfonated polyester.

10. The ink composition of claim 1, wherein the sulfonated polyester comprises a polyol monomer unit selected from the group consisting of trimethylolpropane, 1,2-propanediol, diethylene glycol, and combinations thereof; and wherein the sulfonated polyester comprises a diacid monomer unit selected from the group consisting of terephthalic acid, sulfonated isophthalic acid, and combinations thereof.

11. The ink composition of claim 1, further comprising: a latex emulsion comprising a member selected from the group consisting of an isoprene rubber, a styrene-butadiene, an acrylonitrile-butadiene, an acrylonitrile-butadiene-styrene, a polyurethane, and combinations thereof.

12. The ink composition of claim 1, further comprising: an isoprene rubber.

13. The ink composition of claim 1, further comprising: an isoprene rubber, wherein the isoprene rubber comprises a copolymer comprising a member of the group consisting of styrene-butadiene, styrene-isoprene, isoprene, and combinations thereof.

14. The ink composition of claim 1, wherein the colorant is present and comprises a pigment, a pigment dispersion, or a combination thereof.

15. A process of digital offset printing, the process comprising: applying an ink composition onto a re-imageable imaging member surface at an ink take up temperature, the re-imageable imaging member having dampening fluid disposed thereon; forming an ink image; transferring the ink image from the re-imageable surface of the imaging member to a printable substrate at an ink transfer temperature; wherein the ink composition comprises a humectant blend comprising a first humectant and a second humectant; wherein the first humectant has a freezing point; wherein the second humectant suppresses the freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a desired temperature without solidifying; water; an optional co-solvent; an optional colorant; and a sulfonated polyester; wherein the ink composition has a first viscosity of from about 3,000 to about 90,000 centipoise at an ink take up temperature of from about 45 C. to about 80 C.; and the ink composition has a second viscosity of from about 100,000 to about 2,000,000 centipoise at an ink transfer temperature of from about 18 C. to about 30 C.

16. The process of claim 15, wherein applying the ink composition comprises applying the ink composition using an anilox delivery system.

17. The process of claim 15, wherein the first humectant is selected from the group consisting of tert-butyl alcohol, sulfolane, and combinations thereof; and wherein the second humectant is selected from the group consisting of methanol, glycerol, ethylene glycol, propylene glycol, diethylene glycol, and combinations thereof.

18. The process of claim 15, wherein the substrate is selected from the group consisting of paper, plastic, polymeric film, cardboard, paperboard, folded paperboard, Kraft paper, glass, glass plate, wood, metal, and combinations thereof.

19. The process of claim 15, the substrate comprises a member of the group consisting of food packaging, medicinal packaging, medical devices, cosmetic packaging, cosmetic tools, cosmetic products, and combinations thereof.

20. The process of claim 15, wherein the ink composition has the characteristic of providing substantially 100 percent transfer from the re-imageable imaging member surface to the printable substrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

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

(2) FIG. 2 shows a schematic representation of a method for preparing sulfonated polyester latex materials.

(3) FIG. 3 is an illustration of a 100 percent sulfolane humectant at 5 C. and a sulfolane/diethylene glycol humectant blend at 5 C. in accordance with the present embodiments.

(4) FIG. 4 is a graph showing complex viscosity (y-axis, centipoise) versus angular frequency (x-axis, rad/sec) for an ink in accordance with the present embodiments.

(5) FIG. 5 is an image of three rolled sheets prepared with an ink in accordance with the present embodiments.

(6) FIG. 6 is an image of three rolled sheets prepared with a comparative ink.

DETAILED DESCRIPTION

(7) An ink composition is described comprising a humectant blend comprising a first humectant and a second humectant; wherein the first humectant has a freezing point; wherein the second humectant suppresses the freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a desired temperature without solidifying; water; an optional co-solvent; an optional colorant; and a sulfonated polyester.

(8) In embodiments, the ink composition comprises a humectant blend comprising a first humectant and a second humectant; wherein the first humectant is a solid at or near room temperature, wherein room temperature is from about 20 to about 40 C.; wherein the second humectant suppresses a freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a temperature of from about 0 to about 4 C. without solidifying; water; an optional co-solvent; an optional colorant; and a sulfonated polyester.

(9) The ink compositions can be used for any suitable or desired purpose. In embodiments, the ink compositions herein are particularly suitable for digital offset printing, in embodiments, for printing labels, packaging, and in particular for food grade and medical grade printing. In embodiments, the ink herein is suitable for use as an undercoat in a printing process. The digital offset ink herein containing the particular combination of components, in embodiments, a specific humectant blend comprising at least two distinct humectants wherein at least one first humectant is a solid at or near room temperature and wherein at least one second humectant functions to suppress the freezing point of the first humectant to impart to the ink composition a wide temperature latitude for storage stability at various temperatures while preserving the desired storage qualities such as inert, modest vapour pressure, water miscibility, and desired inking and release properties. The ink compositions further include a sulfonated polyester and, in embodiments, a latex. In certain embodiments, the ink compositions further include a rubber, which provides improved transfer performance over prior digital offset ink compositions.

(10) In order to meet digital offset printing requirements, the ink desirably possesses many physical and chemical properties. The ink is desirably compatible with materials it is in contact with, including printing plate, fountain solution, and other cured or non-cured inks. It also desirably meets functional requirements of the sub-systems, including wetting and transfer properties. Transfer of the imaged inks is challenging, as the ink desirably possesses the combination of wetting and transfer traits, that is, the ink desirably at once wets the blanket material homogeneously, and transfers from the blanket to the substrate. Transfer of the image layer is desirably efficient, desirably at least as high as 90%, as the cleaning sub-station can only eliminate small amounts of residual ink. Any ink remaining on the blanket after cleaning can result in an unacceptable ghost image appearing in subsequent prints.

(11) In embodiments, the ink composition herein has the characteristic of providing substantially 100 percent transfer from the re-imageable imaging member surface to the printable substrate.

(12) The waterborne digital offset ink compositions comprise, in embodiments, a humectant blend comprising at least one first humectant, at least one second humectant, as described herein, an aqueous compatible pigment, self-dispersing sulfonated polyester particles, and, in certain embodiments, a latex emulsion, which provide desired inking and release properties, compatibility with non-aqueous fountain fluids, and function within the ink delivery system (anilox roll). The ink compositions demonstrate good inking from the anilox delivery system, wetting to the blanket substrate, and blanker transfer to the print substrate. The ink compositions demonstrate substantially 100 percent transfer on a digital offset printing fixture. In embodiments, the latex emulsion comprises a polyisoprene rubber latex emulsion.

(13) As described in FIG. 1, it is highly advantageous to ensure inking uniformity and delivery of the ink from the ink loader system (or inker unit) and that the ink has relatively low viscosity within a temperature range of, in embodiments, from about 45 to about 80 C., such as from about 50 to about 70 C., such as from about 55 to about 65 C., such as about 60 C., at shear rates corresponding to the equivalent angular frequencies from about 50 to about 200 rad/s such as about 100 rad/s. It is also highly advantageous to ensure a high degree of ink transfer from the anilox roller to the blanket such that the ink has relatively high viscosity within a temperature range of, in embodiments, from about 18 to about 35 C., such as from about 18 to about 30 C., such as about 25 C., at shear rates corresponding to the equivalent angular frequencies from about 0.5 to about 2 rad/s such as about 1 rad/s.

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

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

(16) The ink composition herein includes a humectant blend comprising a first humectant and a second humectant. In embodiments, the first humectant has a freezing point, and the second humectant is a humectant which suppresses the freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a desired temperature without solidifying. The ink composition may further comprise water; an optional co-solvent; an optional colorant; and a sulfonated polyester. In further embodiments, the ink composition may further comprise a latex.

(17) In embodiments, the first humectant is a solid at or near room temperature. In embodiments, room temperature is a temperature of from about 20 to about 40 C. In embodiments, the second humectant is a humectant that suppresses a freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a cold temperature, such as a refrigerated temperature, without freezing or solidifying. In embodiments, a refrigerated temperature is a temperature of from about 0 to about 4 C.

(18) As used herein, freezing point means, in embodiments, the temperature at which a liquid turns into a solid when cooled.

(19) Any suitable or desired material can be selected for the first humectant. In embodiments, the first humectant is selected from the group consisting of tert-butyl alcohol, sulfolane, and combinations thereof. In a specific embodiment, the first humectant is sulfolane.

(20) Any suitable or desired material can be selected for the second humectant. In embodiments, the second humectant is selected from the group consisting of methanol, glycerol, ethylene glycol, propylene glycol, diethylene glycol, and combinations thereof.

(21) In a specific embodiment, the first humectant is sulfolane and the second humectant is diethylene glycol. In embodiments, sulfolane of the formula

(22) ##STR00001##
is selected for the first humectant. In embodiments, diethylene glycol of the formula

(23) ##STR00002##

(24) Is selected for the second humectant.

(25) The first humectant can be present in the ink composition at any suitable or desired amount. In embodiments, the ink composition is a waterborne ink wherein the total humectant load no greater than about 50 percent by weight, based upon the total weight of the ink composition. In embodiments, the first humectant is present in the ink composition in a first amount and the second humectant is present in the ink composition in a second amount, wherein the first amount is greater than the second amount. That is, in embodiments, the first humectant is present in the ink composition in a greater amount and the second humectant is present in the ink composition in a lesser amount. In embodiments, the first humectant is present in any suitable or desired amount and the second humectant is present in any amount sufficient to suppress the freezing point of the first humectant to a desired degree such that the ink composition can be stored at a desired temperature without freezing or solidifying.

(26) In embodiments, the first humectant is present in the ink composition in an amount of from about 10 to about 45 percent by weight, or from about 18 to about 45 percent by weight, or from about 18 to about 40 percent by weight, or from about 18 to about 20 percent by weight, based upon the total weight of the ink composition. In certain embodiments, the first humectant is present in the ink composition in an amount of from about 18 to about 45 percent by weight, based upon the total weight of the ink composition.

(27) In embodiments, the second humectant is present in the ink composition in an amount suitable to suppress the freezing point of the first humectant. In embodiments, the second humectant is present in an amount of from about 1 to about 20 percent by weight, or from about 1 to about 10 percent by weight, or from about 1 to about 5 percent by weight, based upon the total weight of the ink composition. In certain embodiments, the second humectant is present in the ink composition in an amount of from about 1 to about 5 percent by weight, based upon the total weight of the ink composition.

(28) The ink composition includes a sulfonated polyester. In embodiments, the sulfonated polyester has a high degree of sulfonation, in embodiments, the sulfonated polyester has a degree of sulfonation of at least about 3.5 mol percent, at least about 4 mol percent, at least about 7 mol percent, or at least about 7.5 mol percent. In embodiments, the sulfonated polyester has a degree of sulfonation of from at least about 3.5 mol percent to about 3.75 mol percent, or from at least about 4 mol percent to about 5.5 mol percent, or from at least about 7.0 mol percent to about 7.5 mol percent.

(29) As used herein, mol percent refers, for example, to the percentage of moles of sulfonated monomer present in the final resin and can be calculated, for example, as (moles DMSIP (Dimethyl-5-Sulfoisophthalate Sodium Salt) charged/(total moles charged less excess moles glycol)100 percent).

(30) The use of a sulfonated polyester having a higher degree of sulfonation, such as at least 7.5 mol percent in the ink compositions, permits a higher sulfonated polyester content in the ink composition (i.e., a higher solid loading of sulfonated polyester). In embodiments, the solids loading of sulfonated polyester may be ranged from between about 25 to about 50, between about 30 to about 45, or between about 35 to about 40. The term solids loading used herein, which is interchangeably with the term weight percent solids refers to the sulfonated polyester weight percent in water. In certain embodiment, the sulfonated polyester is present in the ink composition in an amount of about 60 percent by weight, based upon the weight of the sulfonated polyester and the water in the ink composition. In certain other embodiments, the sulfonated polyester is present in the ink composition in an amount of about 30 percent by weight, based upon the total weight of the ink composition.

(31) The sulfonated polyester is a self-dissipatible polymer, meaning that it can be dispersed in water without the need for additional surfactants. In embodiments, the sulfonated polyester is water-dissipatible. Typically, when a polymer is self-dissipatible, it means that the polymer can be dispersed in water without the need for additional surfactants. The term water-dissipatible is used interchangeably with other terms such as water-dispersible, or water-soluble. The term refers to the activity of a water or aqueous solution on the sulfonated polyesters described herein. The term covers situations, including where the sulfonated polyesters dissolved to form a true solution or is dispersed within an aqueous medium. The particle size is a function of the degree of sulfonation. For example, sulfonated polyesters with lower degree of sulfonation (3.5 mole percent or less) do not dissolve in water readily, the solubility of these sulfonated polyesters with lower degree of sulfonation in water is typically less than 10 weight percent based on the total weight of the sulfonated polyesters, which can cause the phenomena of water cloudiness, and the resulting sulfonated polyester particle size of greater than 100 nanometers. In contrast, the present disclosure provide sulfonated polyester with a higher degree of sulfonation, which dissolve readily in water, thus resulting a clear polymer solution, and the resulting sulfonated polyester particle size is in a desirable range of less than 50 nanometers.

(32) The sulfonated polyester can be simultaneously synthesized during the self-assembly or dispersing of polymer in water as indicated in FIG. 2. Referring to FIG. 2, the sulfonated polyester is dispersed in water, for example at a temperature of about 90 C., providing a hydrophobic resin core and hydrophilic surface sulfonate groups. The colloidal latex dispersions prepared in hot water enable moderately high percent solids to be attained.

(33) The sulfonated polyester resins disclosed herein have been selected to have a hydrophobic backbone while presenting hydrophilic sulfonate groups attached along the chain. Without being bound by theory, when placed in water and heated, the hydrophobic portions may interact with each other to form a hydrophobic core with the hydrophilic sulfonate groups facing the surrounding water resulting in the sulfonated polyester self-assembling into a higher order, spherical nanoparticle without the requirement of additional reagents, such as surfactants or dispersants, which are typically required to stabilize colloidal dispersions. Thus, there is a higher order involving the amphiphilic polyester, in which the hydrophobic backbone, which is insoluble in water, and the water-soluble hydrophilic sulfonate groups, operate as macrosurfactants. This results in self-association, self-assembly, self-dispersible nanoparticles in aqueous medium to yield micelle-like aggregates.

(34) In embodiments, the sulfonated polyester matrix is a branched polymer. In embodiments, the sulfonated polyester matrix is a linear polymer. The selection of branched or linear polymer may depend on, inter alia, the downstream application of the composite product. Linear polymers can be used to create strands of fibers or form a strong mesh-like structure. Branched polymers may be useful to confer thermoplastic properties on the resultant composite material.

(35) Both linear amorphous and branched amorphous sulfonated polyester resins are alkali sulfonated polyester resins. The alkali metal in the respective sulfonated polyester resins may independently be lithium, sodium, or potassium. In a specific embodiment, the alkali metal in the respective sulfonated polyester resin is sodium.

(36) In embodiments, the sulfonated polyester matrix is selected from the group consisting of poly(1,2-propylene-5-sulfoisophthalate), poly(neopentylene-5-sulfoisophthalate), poly(diethylene-5-sulfoisophthalate), copoly-(1,2-propylene-5-sulfoisophthalate)-copoly-(1,2-propylene-terphthalate), copoly-(1,2-propylenediethylene-5-sulfoisophthalate)-copoly-(1,2-propylene-diethylene-terephthalatephthalate), copoly(ethylene-neopentylene-5-sulfoisophthalate)-copoly-(ethylene-neopentylene-terephthalatephthalate), and copoly(propoxylated bisphenol A)-copoly-(propoxylated bisphenol A-5-sulfoisophthalate). Thus, in embodiments, the sulfonated polyester matrix is lithium, potassium, or sodium salt, in specific embodiments, a sodium salt, of a polymer selected from the group consisting of poly(1,2-propylene-5-sulfoisophthalate), poly(neopentylene-5-sulfoisophthalate), poly(diethylene-5-sulfoisophthalate), copoly-(1,2-propylene-5-sulfoisophthalate)-copoly-(1,2-propylene-terphthalate), copoly-(1,2-propylenediethylene-5-sulfoisophthalate)-copoly-(1,2-propylene-diethylene-terephthalatephthalate), copoly(ethylene-neopentylene-5-sulfoisophthalate)-copoly-(ethylene-neopentylene-terephthalatephthalate), and copoly(propoxylated bisphenol A)-copoly-(propoxylated bisphenol A-5-sulfoisophthalate).

(37) In general, the sulfonated polyesters may have the following general structure, or random copolymers thereof in which the n and p segments are separated.

(38) ##STR00003##

(39) wherein R is an alkylene of, for example, from 2 to about 25 carbon atoms such as ethylene, propylene, butylene, oxyalkylene diethyleneoxide, and the like; R is an arylene of, for example, from about 6 to about 36 carbon atoms, such as a benzylene, bisphenylene, bis(alkyloxy) bisphenolene, and the like; X is a halogen, in embodiments, be lithium, sodium, or potassium, in embodiments, sodium; and p and n represent the number of randomly repeating segments, such as for example from about 10 to about 100,000.

(40) In embodiments, sulfopolyester materials herein comprise copolymers containing a blend of PET (polyethylene terephthalate) and sulfonated isophthalate moieties. In embodiments, the sulfonated polyester is a sodium sulfonated polyester having the structure

(41) ##STR00004##
wherein R is an alkylene of, for example, from 2 to about 25 carbon atoms such as ethylene, propylene, butylene, oxyalkylene diethyleneoxide, and the like; R.sub.1 is an alkylene of, for example, from 2 to about 25 carbon atoms such as ethylene, propylene, butylene, oxyalkylene diethyleneoxide, and the like; or an arylene of, for example, from about 6 to about 36 carbon atoms, such as a benzylene, bisphenylene, bis(alkyloxy) bisphenolene, and the like; or wherein, in embodiments, R and R.sub.1 are each an alkyene of, for example, from about 2 to about 10 carbon atoms; and x, y and z represent the number of randomly repeating segments, such as for example from about 10 to about 100,000, wherein, in embodiments, y is from about 3.5 mol percent, or greater than about 3.5 mol percent, or from at least about 3.5 mol percent to about 20 mol percent, or from at least about 3.5 mol percent to about 15 mol percent, or from at least about 3.5 mol percent to about 10 mol percent of the resin; or

(42) wherein R is aliphatic having from about 2 to about 10 carbon atoms and R.sub.1 is aliphatic having from about 2 to about 10 carbon atoms; where y is from about 3 to about 7.5 percent. Higher than 7.5 percent is usually water soluble.

(43) Examples further include those disclosed in U.S. Pat. No. 7,312,011 which is hereby incorporated by reference herein in its entirety. Specific examples of amorphous alkali sulfonated polyester based resins include, but are not limited to, copoly(ethylene-terephthalate)-copoly-(ethylene-5-sulfo-isophthalate), copoly(propylene-terephthalate)-copoly(propylene-5-sulfo-isophthalate), copoly(diethylene-terephthalate)-copoly(diethylene-5-sulfo-isophthalate), copoly(propylene-diethylene-terephthalate)-copoly(propylene-diethylene-5-sulfo-isophthalate), copoly(propylene-butylene-terephthalate)-copoly(propylene-butylene-5-sulfo-isophthalate), copoly(propoxylated bisphenol-A-fumarate)-copoly(propoxylated bisphenol A-5-sulfo-isophthalate), copoly(ethoxylated bisphenol-A-fumarate)-copoly(ethoxylated bisphenol-A-5-sulfo-isophthalate), and copoly(ethoxylated bisphenol-A-maleate)-copoly(ethoxylated bisphenol-A-5-sulfo-isophthalate), and wherein the alkali metal is, for example, a sodium, lithium or potassium ion. Examples of crystalline alkali sulfonated polyester based resins include, but are not limited to, alkali copoly(5-sulfoisophthaloyl)-co-poly(ethylene-adipate), alkali copoly(5-sulfoisophthaloyl)-copoly(propylene-adipate), alkali copoly(5-sulfoisophthaloyl)-copoly(butylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), and alkali copoly(5-sulfo-iosphthaloyl)-copoly(octylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-copoly(ethylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-copoly(propylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-co-poly(butylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-copoly(octylene-adipate), alkali copoly(5-sulfoisophthaloyl)-copoly(ethylene-succinate), alkali copoly(5-sulfoisophthaloyl-copoly(butylene-succinate), alkali copoly(5-sulfoisophthaloyl)-copoly(hexylene-succinate), alkali copoly(5-sulfoisophthaloyl)-copoly(octylene-succinate), alkali copoly(5-sulfo-isophthaloyl)-copoly(ethylene-sebacate), alkali copoly(5-sulfo-isophthaloyl)-copoly(propylene-sebacate), alkali copoly(5-sulfo-isophthaloyl)-copoly(butylene-sebacate), alkali copoly(5-sulfo-isophthaloyl)-copoly(pentylene-sebacate), alkali copoly(5-sulfo-isophthaloyl)-copoly(hexylene-sebacate), alkali copoly(5-sulfo-isophthaloyl)-copoly(octylene-sebacate), alkali copoly(5-sulfo-isophthaloyl)-copoly(ethylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-copoly(propylene-adipate), alkali copoly(5-sulfo-iosphthaloyl)-copoly(butylene-adipate), alkali copoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), alkali copoly(5-sulfo-isophthaloyl)copoly(hexylene-adipate), poly(octylene-adipate), and wherein the alkali is a metal such as sodium, lithium or potassium. In specific embodiments, the alkali metal is sodium.

(44) The linear amorphous polyester resins are generally prepared by the polycondensation of an organic diol and a diacid or diester, at least one of which is sulfonated or a sulfonated difunctional monomer being included in the reaction, and a polycondensation catalyst. For the branched amorphous sulfonated polyester resin, the same materials may be used, with the further inclusion of a branching agent such as a multivalent polyacid or polyol.

(45) In embodiments, the sulfonated polyesters of the present disclosure can be prepared from the polymerization reaction of at least one diacid monomer or at least one diester monomer, and at least one alkali sulfonated difunctional monomer. In embodiments, the sulfonated polyesters of the present disclosure can be prepared from the reaction of at least one diacid monomer or at least one diester monomer, and at least one alkali sulfonated difunctional, and at least one diol monomer.

(46) The term diacid used herein, refers to compounds containing dicarboxylic acids or the source compounds of the dicarboxylic acids derived from (i.e., acid anhydrides or esters of the diacid). Examples of diacid include dicarboxylic acids of terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, succinic acid, succinic anhydride, dodecenylsuccinic acid, dodecenylsuccinic anhydride (DDSA), glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelic acid, dodecanediacid, dimethyl terephthalate, diethyl terephthalate, dimethylisophthalate, diethylisophthalate, dimethylphthalate, phthalic anhydride, diethylphthalate, dimethylsuccinate, dimethylfumarate, dimethylmaleate, dimethylglutarate, dimethyladipate, dimethyl dodecylsuccinate, and mixtures thereof. The term diesters used herein, refers to esters of the diacids used herein, where the alkyl groups of the diesters (the carbon group of the diol) may contain from 2 to about 10 carbon atoms, which may be branched or unbranched.

(47) In embodiments, the diacid or diester used in the preparation of the sulfonated polyester may be from about 40 to about 48, from about 43 to about 45, or from about 42.5 to about 46.5 mole percent, based on the total weight of the sulfonated polyester.

(48) Alkali sulfonated difunctional monomer examples, wherein the alkali is lithium, sodium, or potassium, and in particular embodiments wherein the alkali is sodium, include dimethyl-5-sulfo-isophthalate, dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride, 4-sulfo-phthalic acid, 4-sulfophenyl-3,5-dicarbomethoxybenzene, 6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid, dimethyl-sulfo-terephthalate, dialkyl-sulfo-terephthalate, sulfo-ethanediol, 2-sulfo-propanediol, 2-sulfo-butanediol, 3-sulfo-pentanediol, 2-sulfo-hexanediol, 3-sulfo-2-methylpentanediol, N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonate, 2-sulfo-3,3-dimethylpentanediol, sulfo-p-hydroxybenzoic acid, mixtures thereof, and the like. In embodiments, the alkali sulfonated difunctional monomer used in the preparation of the sulfonated polyester may be from about 3.0 to about 7.5 mole percent in embodiments, from about 4 to about 10, from about 5 to about 9, or from about 6 to about 8 mole percent.

(49) Examples of diacid or diesters selected for the preparation of amorphous polyesters include dicarboxylic acids or diesters selected from the group consisting of terephthalic acid, phthalic acid, isophthalic acid, sulfonated isophthalic acid, fumaric acid, maleic acid, itaconic acid, succinic acid, succinic anhydride, dodecylsuccinic acid, dodecylsuccinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelic acid, dodecanediacid, dimethyl terephthalate, diethyl terephthalate, dimethylisophthalate, diethylisophthalate, dimethylphthalate, phthalic anhydride, diethylphthalate, dimethylsuccinate, dimethylfumarate, dimethylmaleate, dimethylglutarate, dimethyladipate, dimethyl dodecylsuccinate, and mixtures thereof. The organic diacid or diester are selected, for example, from about 45 to about 52 mole percent of the resin.

(50) Examples of diols utilized in generating the amorphous polyester include trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, 2,2-dimethylpropanediol, 2,2,3-trimethylhexanediol, heptanediol, dodecanediol, bis(hydroxyethyl)-bisphenol A, bis(2-hydroxypropyl)-bisphenol A, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, xylenedimethanol, cyclohexanediol, diethylene glycol, bis(2-hydroxyethyl) oxide, dipropylene glycol, dibutylene, and mixtures thereof. The amount of organic diol selected can vary, and more specifically, is, for example, from about 45 to about 52 mole percent of the resin.

(51) In embodiments, the diol used in the preparation of the sulfonated polyester may be from about 40 to about 48, from about 43 to about 45, or from about 42.5 to about 46.5 mole percent based on the total weight of the sulfonated polyester. In embodiments, an extra amount (or excess amount) of diol may be used to drive the reaction to completion, where the excess amount of diol is then distilled off or removed.

(52) In certain embodiments, the sulfonated polyester matrix comprises a polyol monomer unit selected from the group consisting of trimethylolpropane, 1,2-propanediol, diethylene glycol, and combinations thereof. In embodiments, the sulfonated polyester matrix comprises a polyol monomer unit selected from the group consisting of trimethylolpropane, 1,2-propanediol, diethylene glycol, and combinations thereof. In embodiments, the sulfonated polyester comprises a polyol monomer unit selected from the group consisting of trimethylolpropane, 1,2-propanediol, diethylene glycol, and combinations thereof; and the sulfonated polyester comprises a diacid monomer unit selected from the group consisting of terephthalic acid, sulfonated isophthalic acid, and combinations thereof.

(53) Alkali sulfonated difunctional monomer examples, wherein the alkali is lithium, sodium, or potassium, and in particular embodiments wherein the alkali is sodium, include dimethyl-5-sulfo-isophthalate, dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride, 4-sulfo-phthalic acid, 4-sulfophenyl-3,5-dicarbomethoxybenzene, 6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid, dimethyl-sulfo-terephthalate, dialkyl-sulfo-terephthalate, sulfo-ethanediol, 2-sulfo-propanediol, 2-sulfo-butanediol, 3-sulfo-pentanediol, 2-sulfo-hexanediol, 3-sulfo-2-methylpentanediol, N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonate, 2-sulfo-3,3-dimethylpentanediol, sulfo-p-hydroxybenzoic acid, mixtures thereof, and the like. Effective difunctional monomer amounts of, for example, from about 0.1 to about 2 weight percent of the resin can be selected.

(54) Branching agents for use in forming the branched amorphous sulfonated polyester include, for example, a multivalent polyacid such as 1,2,4-benzene-tricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylene-carboxylpropane, tetra(methylene-carboxyl)methane, and 1,2,7,8-octanetetracarboxylic acid, acid anhydrides thereof, and lower alkyl esters thereof, 1 to about 6 carbon atoms; a multivalent polyol such as sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitane, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, mixtures thereof, and the like. The branching agent amount selected is, for example, from about 0.1 to about 5 mole percent of the resin.

(55) Polycondensation catalyst examples for amorphous polyesters include tetraalkyl titanates, dialkyltin oxide such as dibutyltin oxide, tetraalkyltin such as dibutyltin dilaurate, dialkyltin oxide hydroxide such as butyltin oxide hydroxide, aluminum alkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, or mixtures thereof; and which catalysts are selected in amounts of, for example, from about 0.01 mole percent to about 5 mole percent based on the starting diacid or diester used to generate the polyester resin.

(56) In embodiments, after polymerization, the resulting sulfonated polyesters may comprise an aryl unit, a sulfonated unit, and a aliphatic unit having the following formulae:

(57) ##STR00005##
wherein each R.sub.1 and each R.sub.2 may be independently an alkylene of, for example, from 2 to about 25 carbon atoms such as ethylene, propylene, butylene, oxyalkylene diethyleneoxide, and the like; each R.sub.3 may be independently an alkyl group of, for example, from 1 to 15 carbon atoms, branched or unbranched, such as, methyl, ethyl, propyl, isopropyl, butyl, and the like; each R may be independently an arylene of, for example, from about 6 to about 36 carbon atoms, such as a benzylene, bisphenylene, bis(alkyloxy) bisphenolene, and the like; each X.sup.+ may be independently Na.sup.+, Li.sup.+, K.sup.+, and the like; and each n, each p and each q represent the number of randomly repeating segments, each of which may be independently from about 10 to about 100,000. In embodiments, n is from about 40 to about 50 mol percent, from about 42.5 to about 46.5 mol percent, or from about 43 to about 45 mol percent. In embodiments, p is from about 7.5 to about 15 mol %, from about 8 to about 12 mol percent. In embodiments, q is from about 0.1 to about 4 mol percent, 0.1 to about 2.5 mol percent, or from about 0.2 to about 1.5; p represents the amount of sulfonation in the sulfonated polyester; q represents the amount of crosslinker in the sulfonated polyester; and n is 100(p+q).

(58) In embodiments, the sulfonated polyesters suitable for use in the present disclosure may have a glass transition (Tg) temperature of from about 45 C. to about 95 C., or from about 52 C. to about 70 C., as measured by the Differential Scanning calorimeter. In embodiments, the sulfonated polyesters may have a number average molecular weight of from about 2,000 grams per mole to about 150,000 grams per mole, from about 3,000 grams per mole to about 50,000 grams per mole, or from about 6,000 grams per mole to about 15,000 grams per mole, as measured by the Gel Permeation Chromatograph. In embodiments, the sulfonated polyesters may have a weight average molecular weight of from about 3,000 grams per mole to about 300,000 grams per mole, from about 8,000 grams per mole to about 90,000 grams per mole, or from about 10,000 grams per mole to about 60,000 grams per mole, as measured by the Gel Permeation Chromatograph. In embodiments, the sulfonated polyesters may have a polydispersity of from about 1.6 to about 100, from about 2.0 to about 50, or from about 5.0 to about 30, as calculated by the ratio of the weight average to number average molecular weight.

(59) As used herein, references to particle size will generally refer to D50 mass-median-diameter (MMD) or the log-normal distribution mass median diameter. The MMD is considered to be the average particle diameter by mass.

(60) In embodiments, the polyester has a particle size in a range of from about 5 nanometers (nm) to about 500 nm or from about 10 to about 200 nm, or from about 20 to about 100 nm. A particle size of less than 100 nm may be useful for reinforcement of polymer matrices without disturbing transparency and other properties of coatings.

(61) In embodiments, the polyester has a particle size of from about 5 nanometers to about 55 nanometers. In further embodiments, the polyester has a particle size of from about 10 nanometers to about 15 nanometers.

(62) In embodiments, there are provided methods comprising heating a sulfonated polyester resin in water, thereby forming an emulsion of composite particles comprising a sulfonated polyester.

(63) In embodiments, heating is conducted at a temperature of from about 65 C. to about 90 C.

(64) In certain embodiments, a method herein comprises heating a sulfonated polyester resin in water, in embodiments a sulfonated polyester resin, wherein the sodium sulfonated polyester has a degree of sulfonation of at least about 3.5 mol percent, or at least about 7.5 mol percent, or of from about 3.5 weight percent to about 12 weight percent; and forming an emulsion of particles comprising the sulfonated polyester. In embodiments, the method further comprises combining the polyester particles with water, an optional colorant, an optional co-solvent, and an isoprene rubber to form an aqueous ink composition.

(65) The sulfonated polyester may be present in the ink composition in any suitable or desired amount. In embodiments, the sulfonated polyester may be present in the ink composition in an amount of from about 10 to about 60 weight percent, from about 20 to about 50 weight percent, or from about 35 to about 45 weight percent, of the sulfonated polyester based on the total weight of the ink.

(66) The ink compositions may include a latex resin or emulsion. Any suitable or desired latex emulsion or dispersion can be selected. The latex can comprise any suitable colloidal dispersion of polymer particles in a liquid. The latex may be the product of an emulsion or dispersion polymerization. For example, the latex may be prepared by polymerizing a monomer that has been emulsified with surfactants.

(67) As used herein, the term dispersion means a two phase system where one phase consists of finely divided particles (often in the colloidal size range) distributed throughout a bulk substance, the particles being the dispersed or internal phase and the bulk substance being the continuous or external phase. The bulk system is often an aqueous system.

(68) In embodiments, the latex emulsion is selected from the group consisting of a latex emulsion comprising a member of the group consisting of an isoprene rubber, a styrene-butadiene, an acrylonitrile-butadiene, an acrylonitrile-butadiene-styrene, a polyurethane, and combinations thereof.

(69) In certain embodiments, the polymer additive comprises a waterborne emulsion of acrylonitrile-butadiene, acrylonitrile-butadiene-styrene, or styrene-butadiene. Examples of commercially available butadiene acrylonitrile, acrylonitrile-butadiene-styrene, and styrene-butadiene dispersions include Nychem 1578x1 available from Emerald Performance Materials. Nychem 1578x1 is a carboxylated butadiene acrylonitrile polymer latex. Other suitable materials include those having high and medium acrylonitrile content such as Nychem 1561X87; Nychem 1561X98; Nychem 1571X12; Nychem 1571X8; Nychem 1552; Nychem 152X103; Nychem 1562X117; Nychem 1562X28; Nychem 1570X79; Nychem 1572; Nychem 1572X32; Nychem 1572X64; Nychem XPE 140, as well as those with acrylonitrile-butadiene-styrene (ABS) content, such as Nychem 1562X170; Nychem 1570X75; Nychem 1577; Nychem 1578X1; and Nychem XPE 130. Further, suitable specialty butadiene products include Nychem 1561; Nychem 1562; Nychem 1562X160; Nychem 1563; Nychem 1581; Nychem 1800X73; Nychem 1871X3; Nychem 2570X59; Nychem 552; Nychem N2000 and Nychem N4000.

(70) Cariflex is the tradename for a class of styrene/butadiene (SBS), styrene/isoprene (SIS), and isoprene rubber (IR) copolymers available from Kraton Corporation. The cis-configuration of the polyisoprene provides an elastic property to the described formulations, which imparts more cohesion to the ink. It is available as an aqueous latex emulsion, enabling incorporation into waterborne inks. Moreover, Kraton polymer segment products are used as components in food packaging applications and meet the exemption for food contact substances. In embodiments, the latex can include an isoprene rubber. In embodiments, polyisoprene available as Cariflex IR040SU isoprene rubber dispersion, available from Kraton Corporation, can be selected.

(71) The latex can be present in the ink composition in any suitable or desired amount. In embodiments, the latex is present in the ink composition in an amount of from about 1 to about 45 percent by weight, or from about 5 to about 40 percent by weight, or from about 5 to about 35 percent by weight, based upon the total weight of the ink composition.

(72) Thus, the ink compositions herein may include a polymer additive, in embodiments, a polymer additive provided in the form of a polymer latex, a polymer dispersion, or a polymer emulsion, wherein the polymer additive is selected from a member of the group consisting of styrene-butadiene, acrylonitrile-butadiene, acrylonitrile-butadiene-styrene, and combinations thereof.

(73) The polymer additive may be carboxylated or noncarboxylated. In embodiments, the polymer additive is selected from a member of the group consisting of carboxylated styrene-butadiene, carboxylated acrylonitrile-butadiene, carboxylated acrylonitrile-butadiene-styrene, noncarboxylated styrene-butadiene, noncarboxylated acrylonitrile-butadiene, noncarboxylated acrylonitrile-butadiene styrene, and combinations thereof.

(74) In embodiments, the polymer additive is provided in the form of a dispersion. The polymer additive dispersions may include any suitable or desired percent solids in water. In embodiments, the polymer additive dispersions comprise from about 30 to about 60 percent solids, or from about 33 to about 54 percent solids, or from about 43 to about 49 percent solids.

(75) The polymer additive can be present in the ink composition in any suitable or desired amount. In embodiments, the polymer additive is present in an amount of from about 1 to about 35 percent by weight, or from about 10 to about 30 percent by weight, or from about 15 to about 25 percent by weight, based upon the total weight of the ink composition.

(76) In embodiments, the ink compositions herein include a polyurethane dispersion (PUD).

(77) A urethane prepolymer can comprise a polyol, a polyisocyanate, and an optional internal surfactant. In embodiments, the polyurethane dispersion herein contains a reaction product of the urethane prepolymer.

(78) In embodiments, the urethane prepolymer can be prepared by reacting a polyol, a polyisocyanate, and an optional internal surfactant in the presence of a catalyst. The internal surfactant may be dissolved in an organic solvent, such as N-Methyl-2-pyrrolidone (NMP), dimethylol propionic acid (DMP), or other polar aprotic solvents, prior to the addition of the polyol and polyisocyanate.

(79) In embodiments, any suitable or desired polyurethane can be selected for the ink compositions herein. In certain embodiments, the polyurethane comprises a waterborne emulsion of polyurethane. Examples of commercially available polyurethane dispersions include U410 and U615 available from Alberdingk Boley, Bayhydrol U355, U2757, UH420, UH2558, UXP2698, UXP2755, UA2586, UHXP2648, and UH2952/1 available from Covestro, and Impranil DL1380 and DL1537 available from Covestro.

(80) The polyurethane dispersion can be present in the ink composition in any suitable or desired amount. In embodiments, the polyurethane dispersion is present in an amount of from about 5 to about 40 percent by weight, or from about 5 to about 35 percent by weight, based upon the total weight of the ink composition.

(81) In embodiments, the ink compositions further comprise an isoprene rubber. Any suitable or desired isoprene rubber can be selected. The isoprene rubber can be provided in the form of a rubber latex emulsion.

(82) In embodiments, the isoprene rubber comprises cis-polyisoprene. The cis-configuration of the polyisoprene is believed to provide an elastic property to the ink composition which imparts increased cohesion to the ink. In embodiments, the isoprene rubber comprises cis-polyisoprene of the formula

(83) ##STR00006##
wherein n is from about 1,400 to about 15,000.

(84) In embodiments, wherein Mw is from 100,000 to 1,000,000, and the unit Mw is 68.12, n is from 1,467 to 14,669.

(85) In embodiments, the isoprene rubber comprises a copolymer comprising a member of the group consisting of styrene-butadiene, styrene-isoprene, isoprene, and combinations thereof.

(86) The isoprene rubber can be present in the ink composition in any suitable or desired amount. In embodiments, the isoprene rubber is present in the ink composition in an amount of from about 1.5 to about 6.5 percent, or from about 1.5 to about 6.6 percent, or from about 1.5 to about 3 percent by weight, based upon the total weight of the ink composition. In embodiments, where a latex is provided as a 30 weight percent latex dispersion in water, 5%0.30=1.5% and 20%0.3=6%.

(87) In other embodiments, the isoprene rubber is present in the ink composition in an amount of from about 5 to about 15 percent by weight based upon the total weight of the ink composition.

(88) The ink can be used in any suitable or desired printing application. The ink herein is particularly useful for indirect printing applications wherein the ink wets the intermediate receiving member enabling formation of a transient image on the intermediate receiving followed by release from the intermediate receiving member in the transfer printing step. In embodiments, the ink undergoes partial or complete drying while on the intermediate transfer member.

(89) Ink compositions herein specifically suitable for indirect printing systems, are also compatible with different printing subsystems including jetting and transfer subsystems, and enable high quality printing at high speed. In embodiments, ink compositions herein enable and perform well in both wetting and transfer subsystems, displaying both acceptable wettability characteristics in combination with acceptable release and transfer characteristics.

(90) In addition to the humectant blend described herein, the ink compositions herein can include an additional solvent or solvents. The ink composition solvent can consist solely of water, or can comprise a mixture of water and a water soluble or water miscible component, referred to as a co-solvent, humectant, or the like (hereinafter co-solvent) such as alcohols and alcohol derivatives, including aliphatic alcohols, aromatic alcohols, dials, glycol ethers, polyglycol ethers, long chain alcohols, primary aliphatic alcohols, secondary aliphatic alcohols, 1,2-alcohols, 1,3-alcohols, 1,5-alcohols, ethylene glycol alkyl ethers, propylene glycol alkyl ethers, methoxylated glycerol, ethoxylated glycerol, higher homologues of polyethylene glycol alkyl ethers, and the like, with specific examples including ethylene glycol, propylene glycol, diethylene glycols, glycerine, dipropylene glycols, polyethylene glycols, polypropylene glycols, trimethylolpropane, 1,5-pentanediol, 2-methyl-1,3,-propanediol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 3-methoxybutanol, 3-methyl-1,5-pentanediol, 1,3-propanediol, 1,4-butanediol, 2,4-heptanediol, and the like; also suitable are amides, ethers, urea, substituted ureas such as thiourea, ethylene urea, alkylurea, alkylthiourea, dialkylurea, and dialkylthiourea, carboxylic acids and their salts, such as 2-methylpentanoic acid, 2-ethyl-3-propylacrylic acid, 2-ethyl-hexanoic acid, 3-ethoxyproponic, acid, and the like, esters, organosulfides, organosulfoxides, sulfones (such as sulfolane), carbitol, butyl carbitol, cellusolve, ethers, tripropylene glycol monomethyl ether, ether derivatives, hydroxyethers, amino alcohols, ketones, N-methylpyrrolidinone, 2-pyrrolidinone, cyclohexylpyrrolidone, amides, sulfoxides, lactones, polyelectrolytes, methyl sulfonylethanol, imidazole, 1,3-dimethyl-2-imidazolidinone, betaine, sugars, such as 1-deoxy-D-galactitol, mannitol, inositol, and the like, substituted and unsubstituted formamides, substituted and unsubstituted acetamides, and other water soluble or water miscible materials, as well as mixtures thereof. In embodiments, the co-solvent is selected from the group consisting of ethylene glycol, N-methylpyrrolidone, methoxylated glycerol, ethoxylated glycerol, and mixtures thereof.

(91) When mixtures of water and water soluble or miscible organic solvent liquids are selected as the liquid vehicle, the water to organic co-solvent ratio ranges can be any suitable or desired ratio, in embodiments from about 100:0 to about 30:70, or from about 97:3 to about 40:60, or from about 95:5 to about 60:40. The non-water component of the liquid vehicle generally serves as a humectant or co-solvent which has a boiling point higher than that of water (100 C.). The co-solvent selected is one that will mix with water without phase separation; thus, a co-solvent having a polarity that is compatible with water is selected. The organic component of the ink vehicle can also serve to modify ink surface tension, modify ink viscosity, dissolve or disperse the colorant, and/or affect the drying characteristics of the ink. In embodiments, the ink is more attracted to paper substrates than plastic media as in solvent-based inks.

(92) The water soluble or water miscible organics which are used in the ink formulation can help with surface tension, drying, leveling, etc. In embodiments, water makes up over 50% of the formulation, in embodiments water comprises from about 60 to about 70% of the ink composition. Thus, the ink compositions herein are mainly aqueous. In embodiments, water comprises about 30% of the ink composition.

(93) In certain embodiments, the co-solvent is selected from the group consisting of sulfolane, methyl ethyl ketone, isopropanol, 2-pyrrolidinone, polyethylene glycol, and mixtures thereof. In embodiments, sulflane is present in an additional amount as a co-solvent as well as being present as a part of the humectant blend.

(94) The total amount of liquid vehicle can be provided in any suitable or desired amount. In embodiments, the liquid vehicle is present in the ink composition in an amount of from about 40 to about 60 percent by weight, based on the total weight of the ink composition. In embodiments, the total amount of liquid in the ink composition is from about 40 to about 60 percent weight based on the total weight of the ink composition, the liquid including water, sulfolane, and DEG.

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

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

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

(98) Examples of suitable pigments include black pigments, white pigments, cyan pigments, magenta pigments, yellow pigments, and the like. Further, pigments can be organic or inorganic particles. Suitable inorganic pigments include carbon black. However, other inorganic pigments may be suitable such as titanium oxide, cobalt blue (CoOAl.sub.20.sub.3), chrome yellow (PbCr0.sub.4), and iron oxide. Suitable organic pigments include, for example, azo pigments including diazo pigments and monoazo pigments, polycyclic pigments (e.g., phthalocyanine pigments such as phthalocyanine blues and phthalocyanine greens), perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, pyranthrone pigments, and quinophthalone pigments), insoluble dye chelates (e.g., basic dye type chelates and acidic dye type chelate), nitro pigments, nitroso pigments, anthanthrone pigments such as PR168, and the like. Representative examples of phthalocyanine blues and greens include copper phthalocyanine blue, copper phthalocyanine green, and derivatives thereof (Pigment Blue 15, Pigment Green 7, and Pigment Green 36). Representative examples of quinacridones include Pigment Orange 48, Pigment Orange 49, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19, and Pigment Violet 42. Representative examples of anthraquinones include Pigment Red 43, Pigment Red 194, Pigment Red 177, Pigment Red 216 and Pigment Red 226. Representative examples of perylenes include Pigment Red 123, Pigment Red 149, Pigment Red 179, Pigment Red 190, Pigment Red 189 and Pigment Red 224. Representative examples of thioindigoids include Pigment Red 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36, and Pigment Violet 38. Representative examples of heterocyclic yellows include Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 90, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 155, and Pigment Yellow 213. Such pigments are commercially available in either powder or press cake form from a number of sources including, BASF Corporation, Engelhard Corporation, and Sun Chemical Corporation. Examples of black pigments that may be used include carbon pigments. The carbon pigment can be almost any commercially available carbon pigment that provides acceptable optical density and print characteristics. Carbon pigments suitable for use in the present system and method include, without limitation, carbon black, graphite, vitreous carbon, charcoal, and combinations thereof. Such carbon pigments can be manufactured by a variety of known methods, such as a channel method, a contact method, a furnace method, an acetylene method, or a thermal method, and are commercially available from such vendors as Cabot Corporation, Columbian Chemicals Company, Evonik, and E.I. DuPont de Nemours and Company. Suitable carbon black pigments include, without limitation, Cabot pigments such as MONARCH 1400, MONARCH 1300, MONARCH 1100, MONARCH 1000, MONARCH 900, MONARCH 880, MONARCH 800, MONARCH 700, CAB-O-JET 200, CAB-O-JET 300, REGAL, BLACK PEARLS, ELFTEX, MOGUL, and VULCAN pigments; Columbian pigments such as RAVEN 5000, and RAVEN 3500; Evonik pigments such as Color Black FW 200, FW 2, FW 2V, FW 1, FW18, FW S160, FW S170, Special Black 6, Special Black 5, Special Black 4A, Special Black 4, PRINTEX U, PRINTEX 140U, PRINTEX V, and PRINTEX 140V. The above list of pigments includes unmodified pigment particulates, small molecule attached pigment particulates, and polymer-dispersed pigment particulates. Other pigments can also be selected, as well as mixtures thereof. The pigment particle size is desired to be as small as possible to enable a stable colloidal suspension of the particles in the liquid vehicle and to prevent clogging of the ink channels when the ink is used in a thermal ink jet printer or a piezoelectric ink jet printer.

(99) The colorant can be present in the ink composition in any desired or effective amount, in embodiments, the colorant can be present in an amount of from about 1 to about 20 percent, or from about 1 to about 15 percent, or from about 1 to about 5 percent by weight, based on the total weight of the ink composition. In embodiments, the colorant is present in an amount of from about 10 to about 20 percent by weight, based on the total weight of the ink composition.

(100) In embodiments, the ink composition herein comprises any suitable or desired colorant amount, while maintaining desired characteristics of desired viscosity at room temperature and desired viscosity at heated temperature for ink transfer.

(101) The inks disclosed may also contain a surfactant. Examples of suitable surfactants include ionic surfactants, anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and the like, as well as mixtures thereof. Examples of suitable surfactants include alkyl polyethylene oxides, alkyl phenyl polyethylene oxides, polyethylene oxide block copolymers, acetylenic polyethylene oxides, polyethylene oxide (di)esters, polyethylene oxide amines, protonated polyethylene oxide amines, protonated polyethylene oxide amides, dimethicone copolyols, substituted amine oxides, and the like, with specific examples including primary, secondary, and tertiary amine salt compounds such as hydrochloric acid salts, acetic acid salts of laurylamine, coconut amine, stearylamine, rosin amine; quaternary ammonium salt type compounds such as lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, etc.; pyridinium salty type compounds such as cetylpyridinium chloride, cetylpyridinium bromide, etc.; nonionic surfactant such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, acetylene alcohols, acetylene glycols; and other surfactants such as 2-heptadecenyl-hydroxyethylimidazoline, dihydroxyethylstearylamine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine; fluorosurfactants; and the like, as well as mixtures thereof. Additional examples of nonionic surfactants include polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly(ethyleneoxy) ethanol, available from Rhone-Poulenc as IGEPAL CA-210 IGEPAL CA-520, IGEPAL CA-720, IGEPAL CO-890, IGEPAL C0-720, IGEPAL C0-290, IGEPAL CA-21O, ANTAROX 890, and ANTAROX 897. Other examples of suitable nonionic surfactants include a block copolymer of polyethylene oxide and polypropylene oxide, including those commercially available as SYNPERONIC PE/F, such as SYNPERONIC PE/F 108. Other examples of suitable anionic surfactants include sulfates and sulfonates, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl sulfates and sulfonates, acids such as abitic acid available from Sigma-Aldrich, NEOGEN R, NEOGEN SC available from Daiichi Kogyo Seiyaku, combinations thereof, and the like. Other examples of suitable anionic surfactants include DOWFAX 2A1, an alkyldiphenyloxide disulfonate from Dow Chemical Company, and/or TAYCA POWER BN2060 from Tayca Corporation (Japan), which are branched sodium dodecyl benzene sulfonates. Other examples of suitable cationic surfactants, which are usually positively charged, include alkylbenzyl dimethyl ammonium chloride, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C 12, C15, C17 trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOL and ALKAQUAT, available from Alkaril Chemical Company, SANIZOL (benzalkonium chloride), available from Kao Chemicals, and the like, as well as mixtures thereof. Mixtures of any two or more surfactants can be used.

(102) The optional surfactant can be present in any desired or effective amount, in embodiments, the surfactant is present in an amount of from about 0.01 to about 5 percent by weight, based on the total weight of the ink composition. It should be noted that the surfactants are named as dispersants in some cases.

(103) The ink composition can further comprise additives. Optional additives that can be included in the ink compositions include biocides, fungicides, pH controlling agents such as acids or bases, phosphate salts, carboxylates salts, sulfite salts, amine salts, buffer solutions, and the like, sequestering agents such as EDTA (ethylenediamine tetra acetic acid), viscosity modifiers, leveling agents, and the like, as well as mixtures thereof.

(104) In embodiments, a process herein comprises combining a sulfonated polyester resin, a humectant blend comprising a first humectant and a second humectant as described herein, water, an optional co-solvent, an optional colorant, and an optional isoprene rubber to form an aqueous ink composition. In a specific embodiment, the inks are prepared as follows: 1) preparation of a sulfonated polyester; 2) preparation of a dispersion of a colorant optionally stabilized with a surfactant; 3) mixing of the sulfonated polyester with the colorant dispersion and an isoprene rubber; and 4) addition of the humectant blend and other components such as water, co-solvents, and optional additives.

(105) In embodiments, a method of digital offset printing herein includes applying the ink composition of the present disclosure onto a re-imageable imaging member surface, the re-imageable imaging member having dampening fluid disposed thereon; forming an ink image; and transferring the ink image from the re-imageable surface of the imaging member to a printable substrate.

(106) The ink composition in accordance with the present disclosure is not limited to use in digital offset printing. The ink composition disclosed herein may also be useful in conventional offset printing or hybrid conventional offset and digital offset printing systems. Nonetheless, the ink compositions of the present disclosure meet systems requirements that are unique to digital offset printing systems.

(107) In embodiments, a process of digital offset printing herein comprises applying an ink composition onto a re-imageable imaging member surface at an ink take up temperature, the re-imageable imaging member having dampening fluid disposed thereon; forming an ink image; transferring the ink image from the re-imageable surface of the imaging member to a printable substrate at an ink transfer temperature; wherein the ink composition comprises a humectant blend comprising a first humectant and a second humectant; wherein the first humectant is a solid at or near room temperature, wherein room temperature is from about 20 to about 40 C.; wherein the second humectant suppresses a freezing point of the first humectant such as to impart to the ink composition the characteristic of being able to be stored at a temperature of from about 0 to about 4 C. without solidifying; water; an optional co-solvent; an optional colorant; and a sulfonated polyester.

(108) Any suitable substrate, recording sheet, or removable support, stage, platform, and the like, can be employed for depositing the ink compositions herein, including plain papers such as XEROX 4024 papers, XEROX Image Series papers, Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coated papers such as Sharp Company silica coated paper, JuJo paper, HAMMERMILL LASERPRINT paper, and the like, glossy coated papers such as XEROX Digital Color Gloss, Sappi Warren Papers LUSTROGLOSS, and the like, transparency materials, fabrics, textile products, plastics, polymeric films, glass, glass plate, inorganic substrates such as metals and wood, as well as meltable or dissolvable substrates, such as waxes or salts, in the case of removable supports for free standing objects, and the like. In certain embodiments, the substrate is selected from the group consisting of paper, plastic, polymeric film, cardboard, paperboard, folded paperboard, Kraft paper, glass, glass plate, wood, metal, and combinations thereof. In a specific embodiments, the substrate is a label. The label can be selected from any of the aforementioned types of substrate. In embodiments, the substrate comprises food packaging, medicinal packaging, and the like. In certain embodiments, the ink compositions herein form an undercoat. In embodiments, the substrate comprises a three-dimensional substrate. In embodiments, the substrate comprises medical devices such as catheters, thermometers, cardiac stents, programmable pace makers, other medical devices, menus, food packaging materials, cosmetic tools and products, and any other desired three-dimensional substrate. In further embodiments, the substrate comprises customizable digitally printed ID codes, short-run printable materials three-dimensional medical and any other desired three-dimensional substrate. In certain embodiments, the substrate comprises a member of the group consisting of food packaging, medicinal packaging, medical devices, cosmetic packaging, cosmetic tools, cosmetic products, and combinations thereof.

EXAMPLES

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

Example 1

(110) Highly sulfonated polyester synthesis (7.5 weight percent sulfonation).

(111) A 5 gallon Parr reactor equipped with a mechanical stirrer, distillation apparatus and bottom drain valve was charged with dimethyl terephthalate (3.492 kilograms), dimethyl-5-sulfo-isophthalate sodium salt (940 grams), 1,2-propanediol (2.9 kilograms), diethylene glycol (449 grams) and FASCAT 4100 (7.2 grams). The mixture was heated under nitrogen flow (3 SCFH) to 120 C., after which stirring at 50 rpm was initiated. The mixture was then heated at 0.5 C./minute for the next two hours until a temperature of 180 C. was attained, during which the methanol byproduct was collected in the distillation receiver. The mixture was then heated at a rate of 0.25 C., until a temperature of 210 C. was attained, during which both methanol and excess 1, 2-propanediol was collected in the distillation receiver. Vacuum was then applied gradually until 4.4 mm-Hg was attained at 210 C. over a 1 hour period. The mixture was then re-pressurized to atmospheric pressure with nitrogen, and the content was discharged through the bottom drain into a container. The product was then allowed to cool to room temperature overnight, followed by granulation using a FitzMill. The product, displayed an onset glass transition temperature of 55.4 C., number average molecular weight of 1,326 grams/mole, a weight average molecular weight of 2,350 grams/mole, and a softening point of 135.9 C.

Example 2

(112) Humectant Blend.

(113) The effectiveness of a blended humectant was tested by taking a quantity of sulfolane in a vial, and then a 90% mixture of sulfolane plus 10% DEG (diethylene glycol) blend in a vial. Both vials were stored in a refrigerator at 5 C. for an hour. After removal from the refrigerator, the pure sulfolane vial had frozen, but the sulfolane/DEG blend remained liquid, demonstrating enhanced storage stability. FIG. 3 provides an illustration of a side-by-side Comparison of 100% Sulfolane vs. Sulfolane/10% DEG humectant blend at 5 C.

Examples 3, 4, 5, and 6

(114) Examples 3, 4, 5, and 6 having the components as shown in Table 1 were formulated into an ink as follows. The total percentage of components may not sum to 100 due to rounding errors. To a 250 milliliter beaker fitted with a heating jacket and overhead mixer fitted with a Cowles blade, was added 38.7 grams of an aqueous 45% cyan pigment dispersion (45% solids in water) and heated to 90 C. Next, a mixture of 15.5 grams sulfolane and 1.7 grams diethyleneglycol (DEG) was added. Sulfopolyester (as prepared in Example 1) is gradually added to the heated dispersion. The mixture is covered with foil and allowed to mix for 20-30 minutes at 90 C., then allowed to cool to room temperature. Finally, 4.3 g of the Cariflex IR040SU (about 63 to 65 percent solids in water, Kraton Corporation) dispersion is gradually added during mixing. The mixture is allowed to stir for 30-45 minutes to furnish the final ink, with the beaker warming to 30-35 C. during the addition, to afford the final ink (Example 3). Control ink (Sulfolane only, Example 4) and counter-example (DEG only, Example 5) ink were prepared in the same manner. The viscosity of the prepared inks is shown in FIG. 4. The key observation is that the substitution of 2% of the sulfolane for DEG had a minimal impact on the viscosity of the ink, as the 2 curves are nearly superimposed.

(115) TABLE-US-00001 TABLE 1 Example 3 4 (Control) 5 (Counter-Example) 6 Weight Mass Weight Mass Weight Mass Weight Mass Component Percent (grams) Percent (grams) Percent (grams) Percent (grams) Cyan Aqueous Pigment 45.0 38.7 45.0 54.0 45.0 33.75 30 18.0 Dispersion Sulfonated Polyester 30.0 25.8 30.0 36.0 30.0 22.5 30 18.0 of Example 1 Diethylene Glycol 2.0 1.72 2.0 24.0 20.0 15 2 1.2 Sulfolane 18.0 15.48 20.0 0 0.0 0 18 10.8 Cariflex IR040SU 5.0 4.3 5.0 6.0 5.0 3.75 Nychem 1578x1 20 12 TOTAL 100 86 102 120 100 75 100 60

(116) Testing of inks on lithographic print fixture. Ink Example 3 and Counter Example 5 was tested on a digital offset printing fixture to evaluate the efficiency of ink transfer from the blanket under typical lithographic print conditions. An anilox roll was filled with ink, transferred to the blanket, then offset pressed onto Sterling Gloss #80 paper, followed by a second and third offset event between fresh paper and the previously inked blanket to monitor the residual ink that may remain on the blanket (chase sheet).

(117) FIG. 5 shows the offset printing results for the 3 ink samples. Samples 1 and 2 showed 100% ink transfer with no residue ink observed on the chase sheet. With this mixed humectant, we observe no drop-off in the 100% transfer property, meaning that we have preserved the benchmark performance of the control ink.

(118) FIG. 6 shows the prints of Counter-example ink 5 with 100% DEG humectant. The ink performed very poorly in the lithographic print fixture test, as there was chase ink on chase sheets #1 and #2, due to incomplete drying.

(119) Dried prints on coated paper were subjected to preliminary robustness testing. The results are summarized as follows.

(120) The prints were robust to tape test, where Scotch tape was applied with pressure to the print surface and removed cleanly.

(121) The prints were robust to a water swab test, where a cotton swab was dipped in water and rubbed with pressure across the print surface 20 times, with only a faint trace of coloration on the wet swab. After 20 double rubs, there was no evidence of ink removal.

(122) A waterborne digital offset printing ink is therefore provided containing a performance blend of humectants for enhanced temperature latitude storage for robust performance across various print temperature conditions. The highly robust waterborne digital offset printing ink compositions contain, in embodiments, highly sulfonated polyester having greater than 3.5 percent sulfonation in combination with the blend of humectants described herein. Thus, in certain embodiments, waterborne digital offset lithographic printing ink compositions are provided containing aqueous compatible pigment, self-dispersing sulfo-polyester particles, and a blend of diethylene glycol (DEG)-sulfolane humectants. By adding a small amount of DEG to the sulfolane, the freezing point of sulfolane is suppressed, allowing refrigeration storage without solidifying and causing phase separation. Digital offset lithographic printing ink compositions must meet specific sub-system requirements that are unique to digital offset printing architecture. The most important requirements are wetting and release properties from the offset plate and compatibility with non-aqueous fountain fluids. Another requirement is adequate function within the ink delivery system (anilox roll). The aqueous ink compositions herein demonstrate good inking from the anilox delivery system, wetting to the blanket substrate, and blanket transfer to the print substrate (such as paper or film). The use of a blended humectant composition enables wider operating and storage temperature windows for the ink composition. The ink compositions are suitable for a variety of applications including food labels and packaging.

(123) In certain embodiments, a performance blend of humectants, in embodiments, a blend of sulfolane/DEG co-solvents as the humectants are provided in a digital offset printing ink, further including water dissipatible sulfopolyester materials which provide a polymer matrix for the ink while an isoprene latex additive is included to provide increased internal cohesion, enabling 100 percent ink transfer from the central imaging cylinder and imparting robustness to the final print. In embodiments, water dispersible pigment dispersions are included to achieve CMYK (cyan, magenta, yellow, black) inks as well as specialty colors.

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