# Patent

## Title
Hot melt inks

## Abstract

This disclosure includes a hot melt ink composition that includes at least one wax having a freezing point of from about 20° C. to about 45° C. and a melting point of at least about 35° C., and at least one colorant. The composition includes at least about 50 wt % of the at least one wax. This disclosure also relates to a printing process using such a composition and a product containing such a composition.

## Background
TECHNICAL FIELD
This disclosure relates to hot melt ink compositions, as well as related products and processes.
BACKGROUND
Hot melt inks are a solid at ambient temperature and a liquid at temperatures above ambient temperature. Hot melt inks can be used, for example, in digital printing methods. During printing, the ink is typically heated until it becomes a liquid which is then ejected through a printhead onto a substrate. The ink can solidify on the substrate at ambient temperature.
The hot melt ink can be used with an inkjet printer having heating capabilities, which can eject droplets of ink through tiny nozzles to form small dots, which in turn form an image on a substrate. The resolution of the image printed by the ink is typically measured by the number of dots per inch (DPI).
SUMMARY
This disclosure is based on the unexpected discovery that certain waxes having a relatively low freezing point (e.g., having a freezing point lower than a melting point) can be used to form a hot melt ink composition that forms dots having a relatively large average diameter when the hot melt ink composition is printed on a certain substrate (e.g., a cardboard or a film) without external treatment to the dots.
In one aspect, this disclosure features a hot melt ink composition that includes at least one wax having a freezing point of from about 20° C. to about 45° C. and a melting point of at least about 35° C., and at least one colorant. The composition includes at least about 50 wt % of the at least one wax.
In another aspect, this disclosure features a hot melt ink composition capable of forming dots having an average dot diameter of at least about 15% larger than those formed by Markem-Imaje 5005 TOUCH DRY black ink (Ink 5005) when the dots are formed under the same conditions and without external treatment.
In another aspect, this disclosure features a hot melt ink composition capable of forming dots having an average dot diameter of at least about 85 μm when the composition has a melt viscosity of about 10 cP, each dot is formed by using about 70 picoliter of the composition, and the dots are formed at ambient temperature without external treatment.
In another aspect, this disclosure features a printing process that includes melting any of the hot melt ink compositions described herein in a printhead in an inkjet printer (e.g., a hot melt inkjet printer), and ejecting the hot melt ink composition from the printhead onto a substrate to form an image.
In still another aspect, this disclosure features a product that includes a substrate (e.g., a cardboard or a film) and a solid ink defining an image on the substrate. The solid ink includes any of the hot melt ink compositions described herein.
Embodiments can have one or more of the following features.
The at least one wax has a freezing point of from about 30° C. to about 50° C. (e.g., from about 30° C. to about 40° C.).
The melting point of the at least one wax can be at least about 10° C. (e.g., at least about 15° C.) higher than the freezing point of the at least one wax.
The at least one wax can include an amide alcohol wax, a urethane wax, an ether wax, or an ester wax.
The amide alcohol wax can be stearyl diethanolamide, stearyl isopropanolamide, mono isopropanolamide, or coconut monoisopropanolamide.
The urethane wax can be 2,2,4-trimethylpentane-1,3-diyl bis(stearylcarbamate) or [2-ethyl-2-(octadecylcarbamoyloxymethyl)hexyl] N-octadecylcarbamate.
The ether wax can be polyethylene glycol having a weight average molecular weight of from about 540 g/mol to about 1450 g/mol.
The ester wax can be behenyl erucate, glycerol tribehenate, C32-C36 branched alkyl stearate, or polyglyceryl-3 stearate.
The hot melt ink composition can include at least about 70 wt % of the at least one wax.
The hot melt ink composition can further include at least one wax having a freezing point higher than 45° C. The at least one wax having a freezing point higher than 45° C. can be 2-(2-(3-octadecylureido)ethoxy)ethyl octadecylcarbamate or octadecyl octadecylcarbamate.
The hot melt ink composition can include at least one tackifier, at least one resin, at least one plasticizer, at least one antioxidant, or at least one dispersant.
The at least one colorant can include a dye or a pigment.
The hot melt ink composition can have a melt viscosity of from about 5 cP to about 25 cP (e.g., from about 10 cP to about 14 cP).
The hot melt ink composition can be substantially free of a polyethylene (e.g., a polyethylene wax).
The hot melt ink composition can consist of: (1) the at least one wax, (2) the at least one colorant, (3) optionally, at least one tackifier, (4) optionally, at least one resin, (5) optionally, at least one plasticizer, (6) optionally, at least one antioxidant, and (7) optionally, at least one dispersant.
The hot melt ink composition can be capable of forming dots having an average dot diameter of at most about 100% larger than those formed by Ink 5005 when the dots are formed under the same conditions and without external treatment.
The hot melt ink composition can be capable of forming dots having an average dot diameter of at most about 120 μm when the composition has a melt viscosity of about 10 cP, each dot is formed by using about 70 picoliter of the composition, and the dots are formed at ambient temperature without external treatment.
Other features and advantages will be apparent from the description and from the claims.


DETAILED DESCRIPTION
This disclosure generally relates to a hot melt ink composition that includes at least one wax having a freezing point of from about 20° C. to about 45° C. and a melting point of at least about 35° C., and at least one colorant. The hot melt ink composition can include at least about 50 wt % of the at least one wax. If the wax has more than one freezing point or more than one melting point, at least one of the freezing points is within the range of from about 20° C. to about 45° C. and/or at least one of the melting points is at least about 35° C.
In general, the wax provides the ink composition with the property of being a solid at ambient temperature, but a liquid at an elevated temperature. As mentioned herein, the “ambient temperature” is defined as a temperature from about 20° C. to about 25° C.
In general, the hot melt ink composition should contain enough wax such that the ink composition, as a whole, is a hot melt material. In some embodiments, the ink composition contains at least about 50 wt % (e.g., at least about 55 wt %, at least about 60 wt %, at least about 65 wt %, at least about 70 wt %, at least about 75 wt %, or at least about 80 wt %) and/or at most about 95 wt % (e.g., at most about 90 wt %, at most about 85 wt %, at most about 80 wt %, at most about 75 wt %, or at most about 70 wt %) of the wax. In some embodiments, the hot melt ink composition contains two or more (e.g., three or four) waxes.
In some embodiments, the wax can have a melting point of at least about 35° C. (e.g., at least about 40° C., at least about 45° C., at least about 50° C., at least about 55° C., at least about 60° C., at least about 65° C., at least about 70° C., at least about 75° C., or at least about 80° C.) and/or at most about 150° C. (e.g., at most about 140° C., at most about 130° C., at most about 120° C., at most about 110° C., at most about 100° C., at most about 90° C., or at most about 80° C.). The melting point mentioned herein refers to that measured by Differential Scanning calorimetry. In some embodiments, the wax has a relatively high melting point so that the hot melt ink composition remains as a solid at a relatively high temperature (e.g., about 45° C.) after it is printed on a substrate.
In general, the wax has a freezing point at or above the ambient temperature so that the ink composition can form a solid at ambient temperature after it is printed on a substrate. In some embodiments, the wax can have a freezing point of at least about 20° C. (e.g., at least about 25° C., at least about 30° C., at least about 35° C., or at least about 40° C.) and/or at most about 45° C. (e.g., at most about 40° C., at most about 35° C., at most about 30° C., or at most about 25° C.). The freezing point mentioned herein refers to that measured by Differential Scanning calorimetry. In general, the melting and freezing points of the hot melt ink composition can be similar to those of the wax and can have the ranges described above, respectively. Without wishing to be bound by theory, it is believed that the freezing point of the wax should not be too high (e.g., higher than about 45° C.) because a high freezing point can cause the ink composition to freeze rapidly after it is printed on the substrate, thereby reducing drop spread of the melted composition on the substrate and reducing sizes of the dots printed.
In some embodiments, the wax can exhibit thermal hysteresis in melting and freezing points, i.e., having the freezing point lower than the melting point. In some embodiments, the melting point of the wax can be at least about 10° C. (e.g., at last about 15° C., at least about 20° C., at least about 25° C., or at least about 30° C.) higher than the freezing point. Without wishing to be bound by theory, it is believed that, when a hot melt ink composition contains a wax having a freezing point lower than the melting point, the ink composition is capable of forming dots having a relatively large diameter when it is printed on a substrate without any external treatment (e.g., heating after printing, using a high jetting temperature, or pressing the printed dots with a mechanical pressure roller after printing) to the dots formed because the wax takes longer to freeze compared to the wax in a conventional hot melt ink composition. A disadvantage of using an external treatment is that an additional process is required, which requires more labor, hardware, intervention and/or maintenance and therefore increases manufacturing costs.
In some embodiments, the wax can be an amide alcohol wax, a urethane wax, an ether wax, or an ester wax. Exemplary amide alcohol waxes include stearyl diethanolamide, stearyl isopropanolamide, mono isopropanolamide, and coconut monoisopropanolamide. Exemplary urethane waxes include 2,2,4-trimethylpentane-1,3-diyl bis(stearylcarbamate) (i.e., MS 38-48), and [2-ethyl-2-(octadecylcarbamoyloxy-methyl)hexyl] N-octadecylcarbamate (i.e., MS 38-37). An exemplary ether wax is a polyethylene glycol having a weight average molecular weight of from about 540 g/mol to about 1450 g/mol (commercially available from Dow Chemical Co, Midland, Mich., under the trade name Carbowax). Exemplary ester waxes include behenyl erucate, glycerol tribehenate, C32-C36 branched alkyl stearate (e.g., BK-40 commercially available from Koster Keunen, Watertown, Conn.), and polyglyceryl-3 stearate.
In some embodiments, the hot melt ink composition can include one or more waxes (e.g., amide alcohol waxes, urethane waxes, ether waxes, or ester waxes) having a freezing point higher than 45° C. Examples of such waxes include 2-(2-(3-octadecylureido)ethoxy)ethyl octadecylcarbamate (i.e., MS 36-181) and octadecyl octadecylcarbamate (i.e., MS 37-121). In general, the amount of such waxes in the hot melt ink composition is less than the amount of the waxes having a freezing point of from about 20° C. to about 45° C. In some embodiments, the hot melt ink composition can include at most about 50 wt % (e.g., at most about 45 wt %, at most about 40 wt %, at most about 35 wt %, at most about 30 wt %, or at most about 25 wt %) and/or at least about 1 wt % (e.g., at least about 5 wt %, at least about 10 wt %, at least about 15 wt %, at least about 20 wt %, at least about 25 wt %, or at least about 30 wt %) of the waxes having a freezing point higher than 45° C.
The melting and freezing points of some of certain exemplary waxes described above are summarized in Table 1 below.










TABLE 1






Material designation
Melt point (° C.)
Freeze point (° C.)



















MS 36-181
113
97



MS 37-121
83.2
71.1



MS 38-48
44
31



MS 38-37
66
36



BK-40
38
25









In some embodiments, the hot melt ink composition containing one or more of the waxes described herein can be capable of forming dots on a substrate (e.g., a cardboard or a film) that have an average diameter larger than those formed by Ink 5005 Ink 5005 is a hot melt ink composition commercially available from Markem-Imaje Corporation (Keene, N.H.). For example, the dots can have an average diameter of at least about 15% (e.g., at least about 20%, at least about 25%, at least about 30%, at least about 35%, or at least about 40%) and/or at most about 100% (e.g., at most about 50%, at most about 45%, at most about 40%, at most about 35%, or at most about 30%) larger than those formed by Ink 5005 when the dots are formed under the same conditions and without external treatment (such as those described above) to the dots formed. As used herein, the above average dot diameter increase compared to Ink 5005 is also referred to as “dot gain.”
In some embodiments, the hot melt ink composition containing one or more of the waxes described herein can be capable of forming dots having an average dot diameter of at least about 85 μm (e.g., at least about 90 μm, at least about 95 μm, at least about 100 μm, at least about 105 μm, or at least about 110 μm) and/or at most about 120 μm (e.g., at most about 115 μm, at most about 110 μm, at most about 105 μm, at most about 100 μm, at most about 95 μm, or at most about 90 μm) when the composition has a melt viscosity of about 10 cP, each dot is formed by using about 70 picoliter of the composition, and the dots are formed at ambient temperature without external treatment (such as those described above) to the dots formed. By contrast, when Ink 5005 is used to form dots under the same conditions, the dots formed generally have an average diameter of at most about 75 μm. In other words, the hot melt ink composition described herein can have an increased dot size (i.e., dot gain) compared to a conventional hot melt ink composition (i.e., Ink 5005).
Without wishing to be bound by theory, it is believed that hot melt ink compositions capable of forming dots that have a relatively large dots size without using any external treatment can have a number of advantages, including improved visual darkness, increased drop spread (i.e., dot gain), and improved barcode validation scores. For example, the dots printed would have relatively large ink coverage to block the background color of the substrate, thereby increasing the visual and machine readable contrast of the image on the substrate. As another example, such a hot melt ink composition can have improved contrast at any given print resolution when compared to commercially available dye-based or pigment-based inks that don't exhibit the dot gain phenomena. As another example, such a hot melt ink composition can reduce the necessary print resolution settings while achieving equivalent darkness, thereby reducing the amount of the ink used and reducing costs. As a further example, by reducing print resolution settings, such a hot melt ink composition can reduce the jetting frequency, which can improve performance such as jet sustainability and reduce maintenance costs by requiring fewer maintenance interventions.
Without wishing to be bound by theory, it is believed that, although a liquid ink composition may be used to print images on a substrate with a relatively large dot size, a hot melt ink composition can possess advantages compared to a liquid ink composition. For example, a liquid ink composition is a liquid at room temperature, typically oil based, and is capable of diffusing into the surface of the substrate, causing the images printed to diffuse into the substrate, resulting in blurred lines or low quality images. By contrast, a hot melt ink composition is a solid at room temperature and is typically not diffused into the surface of the substrate, which can result in images with higher qualities (such as better relative line width and edge definition).
In general, the hot melt ink composition described herein can include at least one colorant, such as a dye or a pigment. The dye or pigment can be either an organic or inorganic material. Examples of dyes include anthraquinone and perinone reds such as solvent red 172, solvent red 111, solvent red 222, solvent red 207, and solvent red 135; anthraquinone blues such as solvent blue 104, solvent violet 13; anthraquinone greens such as solvent green 3 and solvent green 5; xanthane, quinoline, quinophthalone, pyrazolone, methine, and anthraquinoid yellows such as solvent yellow 98, solvent yellow 33, disperse yellow 54, solvent yellow 93, disperse yellow 82, and solvent yellow 163. Examples of pigments include pigment blues (PB) 15, 15:3, 15:4, 16, 22, 28, 64, 68; pigment reds (PR) 3, 4, 48, 81, 97, 113, 122, 175, 202, 217; pigment yellows (PY) 2, 7, 53, 111, 155, 151, 175, 194; pigment blacks 7, carbon black, graphite; and pigment white titanium dioxide. Other exemplary dyes or pigments have been described in, e.g., U.S. Pat. Nos. 6,702,884, 5,863,319, and 5,891,228. In some embodiments, the hot melt ink composition can include at least about 1 wt % (e.g., at least about 5 wt %, at least about 10 wt %, or at least about 15 wt %) and at most about 25 wt % (e.g., at most about 20 wt %, at most about 15 wt %, at most about 10 wt %, or at most about 5 wt %) of the colorant.
In some embodiments, the hot melt ink composition described herein can further include at least one tackifier, at least one resin, at least one plasticizer, at least one antioxidant, and/or at least one dispersant.
In some embodiments, the hot melt ink composition described herein can optionally include one or more tackifiers. In general, a tackifier can improve adhesion between the ink composition and a substrate (e.g., a cardboard or a film). Examples of tackifiers include glycerol esters, pentaerythritol esters, hydrocarbons, rosin, rosin esters, modified rosin esters (e.g., hydrogenated, acid, or phenolic-modified rosin esters), cumarone-indene polymers, cyclic ketone polymers, styrene allyl alcohol polymers, polystyrenes, polyvinyl toluene/methylstyrene polymers, polyvinyl chloride, polyvinyl alcohol, ethylene/vinyl acetate, ethylene/acrylic acid, alkyl hydrocarbon polymers, aryl hydrocarbon polymers, alkyl aryl hydrocarbon polymers, terpene polymers, ethylene carbon monoxide copolymers, vinyl chloride/vinyl alcohol copolymers, polyvinyl butyral, polyketones, styrene/acrylic copolymers, polybutenes, polybutadienes, styrene-isoprene-styrene, styrene-butadiene-styrene, polyvinyl pyrrolidone, polyvinyl pyridine, vinyl pyrrolidone/vinyl acetate, polyurethanes, polyesters, polyamides, cellulose esters, cellulose ethers, polyols, styrene-acrylates, polypropylene, chlorinated polypropylene, chlorinated paraffin, gilsonite and other asphaltic materials, cyclic hydrocarbon polymer, halogenated polymers, acrylics, epoxides, novolacs, and other synthetic and natural resins. A commercially available tackifier is polyterpene available from Goodyear under the trade name Wingtack 86. In some embodiments, the ink composition contains at least about 1 wt % (e.g., at least about 5 wt %, at least about 10 wt %, or at least about 15 wt %) and at most about 25 wt % (e.g., at most about 20 wt %, at most about 15 wt %, at most about 10 wt %, or at most about 5 wt %) of the tackifier.
In some embodiments, the hot melt ink composition described herein can optionally include one or more resins. The resin can provide the ink composition with a desired viscosity, thermal stability, flexibility, and adhesion properties. Examples of resins include acacia (gum arabic); gum ghatti; guar gum; locust (carob) bean gum; karaya gum (sterculia gum); gum tragacanth; chicle; highly stabilized rosin ester; tall oil; manila copais; corn gluten; coumarone-indene resins; crown gum; damar gum; p, alpha-dimethylstyrene; gum elemi; ethylene oxide polymer and its adducts; ethylene oxide/propylene oxide copolymer and its adducts; galbanum resin; gellan gum; ghatti gum; gluten gum; gualac gum; guarana gum; heptyl paraben; cellulose resins, including methyl and hydroxypropyl; hydroxypropyl methylcellulose resins; isobutylene-isoprene copolymer; mastic gum; oat gum; opopanax gum; polyacrylamide; modified polyacrylamide resin; polylimonene; polyisobutylene; polymaleic acid; polyoxyethylene derivatives; polypropylene glycol; polyvinyl acetate; polyvinyl alcohol; polyvinyl polypyrrolidone; polyvinyl pyrrolidone; rosin, adduct with fumaric acid, pentaerythritol ester; rosin, gum, glycerol ester; rosin, gum or wood, pentaerythritol ester; rosin, gum or wood, partially hydrogenated, glycerol ester; rosin, gum or wood, partially hydrogenated, pentaerythritol ester; rosin, methyl ester, partially hydrogenated; rosin, partially dimerized, glycerol ester; rosin, partially hydrogenated; rosin and rosin derivatives; rosin, polymerized, glycerol ester; rosin, tall oil, glycerol ester; rosin, wood; rosin, wood, glycerol ester; purified shellac; styrene; styrene terpolymers; styrene copolymers; sucrose acetate isobutyrate; terpene resins, natural and synthetic; turpentine gum; vinylacetate; vinyl chloride-vinylidene chloride copolymer; zanthan gum; and zein.
In general, the hot melt ink composition includes enough resin to achieve the desired viscosity, stability, flexibility, and adhesion. In some embodiments, the ink composition contains at least about 1 wt % (e.g., at least about 5 wt %, at least about 10 wt %, or at least about 15 wt %) and at most about 25 wt % (e.g., at most about 20 wt %, at most about 15 wt %, at most about 10 wt %, or at most about 5 wt %) of the resin. In some embodiments, the ink composition contains no resin.
In some embodiments, the hot melt ink composition described herein can optionally include one or more plasticizers. In general, a plasticizer can reduce the viscosity of the ink composition. Examples of plasticizers include aromatic sulfonamides, phthalates, acetates, adipates, amides, azelates, epoxides, glutarates, laurates, oleates, sebacates, stearates, sulfonates, tallates, phosphates, benzoin ethers, and trimellitates. In some embodiments, the ink composition contains at least about 1 wt % (e.g., at least about 2 wt %, at least about 4 wt %, at least about 6 wt %, or at least about 8 wt %) and at most about 10 wt % (e.g., at most about 9 wt %, at most about 7 wt %, at most about 5 wt %, or at most about 3 wt %) of the plasticizer.
In some embodiments, the hot melt ink composition described herein can optionally include one or more antioxidants. In general, an antioxidant can inhibit oxidation (e.g., thermally induced oxidation) of the ink composition (e.g., when the ink composition is in a hot molten state during jetting). Examples of antioxidants include butylated hydroxyanisole (BHA); butylated hydoxytoluene (BHT); propyl gallate; tert-butyl hydroquinone (TBHQ); ethylenediaminetetraacetic acid (EDTA); methyl paraben; and propyl paraben. A commercial example of the antioxidant is Irganox 1010 (i.e., a hindered phenol) available from BASF Corporation (Florham Park, N.J.). In some embodiments, the ink composition contains at least about 0.1 wt % (e.g., at least about 0.5 wt %, at least about 1 wt %, or at least about 3 wt %) and at most about 5 wt % (e.g., at most about 4 wt %, at most about 3 wt %, at most about 2 wt %, or at most about 1 wt %) of the antioxidant.
In some embodiments, the hot melt ink composition described herein can optionally include one or more dispersants. In general, a dispersant can assist in stabilizing an insoluble component (e.g., a colorant) in the hot melt ink composition. For example, the dispersant can prevent agglomeration of a colorant (e.g., a pigment) in the ink composition. Examples of dispersants include Solsperse 13,650, 13,940, 17,000, J910; Byk 108; Tego Dispers 700; UNIQEMA 5543; and EFKA 5244, 5207, 6750; which are all commercially available from Lubrizol; Byk Chemie; Tego Chemie; Croda; and BASF, respectively. In some embodiments, the ink composition contains at least about 1 wt % (e.g., at least about 2 wt %, at least about 4 wt %, at least about 6 wt %, or at least about 8 wt %) and at most about 10 wt % (e.g., at most about 9 wt %, at most about 7 wt %, at most about 5 wt %, or at most about 3 wt %) of the dispersant.
In general, the hot melt ink composition can have any suitable melt viscosity. As mentioned herein, the term “melt viscosity” refers to the shear viscosity of an ink composition in its molten state. In some embodiments, the ink composition can have a melt viscosity of at least about 5 centiPoise (cP) (e.g., at least about 10 cP, at least about 15 cP, or at least about 20 cP) and/or at most about 25 cP (e.g., at most about 20 cP, at most about 15 cP, or at most about 10 cP) measured at 125° C. For example, the ink composition can have a melt viscosity from about 10 cP to about 14 cP measured at 125° C.
In some embodiments, the hot melt ink composition is substantially free of a certain material. For example, the hot melt ink composition can be substantially free of a polyethylene (e.g., a polyethylene wax).
The hot melt ink composition described herein can be used with a drop-on-demand inkjet printer (e.g., a hot melt piezo inkjet printer). An example of a commercial drop-on-demand inkjet printer is a Markem-Imaje model 5200 inkjet printer.
In some embodiments, the hot melt ink composition described herein can be used in a printing process that includes melting the hot melt ink composition in a printhead in an inkjet printer, and ejecting the hot melt ink composition from the printhead onto a substrate to form an image.
This disclosure also features a product that includes a substrate and a solid ink defining an image on the substrate, in which the solid ink includes the hot melt ink composition described herein. The substrate can be any suitable materials (e.g., porous or non-porous materials), such as films, coated papers, plastics, metals, and cardboards. In some embodiments, the substrate can be a package material, such as a cardboard (e.g., a corrugated cardboard) or a film (e.g., a shrink wrap).
The contents of all publications cited herein (e.g., patents, patent application publications, and articles) are hereby incorporated by reference in their entirety.
The following examples are illustrative and not intended to be limiting.
Examples 1-6 and Comparative Example 1
The waxes used in Examples 1-6 were prepared by the following methods: Stearyl isocyanate was first added to a heated vessel. The vessel was then heated to 100° C. while a mixing vortex was generated in the vessel. A stoichiometric amount of a suitable alcohol was then added into the vessel so that the isocyanate and alcohol functional groups had stoichiometric molar ratio. After addition of the alcohol was completed, the reaction was monitored by using FTIR. The reaction was considered completed once the peak in the 2260-2270 cm−1 region (which corresponds to the isocyanate group) was no longer evident. The reactants and the waxes produced are summarized in Table 2 below.









TABLE 2







Resulting


Reactant 1
Reactant 2
wax material







stearyl isocyanate
2,2,4-trimethylpentane-1,3-diol
MS38-48


stearyl isocyanate
stearyl alcohol
MS37-121


stearyl isocyanate
2-(2-aminoethoxy)ethan-1-ol
MS36-181









BK-40 and PELEMOL GTB used in Examples 1-6 were purchased from Koster Keunen, Watertown, Conn. and Phoenix Chemical, Somerville, N.J., respectively.
The colorant dispersions used in Examples 1-6 were manufactured by mixing a wax medium, a suitable dispersant, and a pigment such that an ink jet quality dispersion was achieved, as determined by particle size. After the ingredients were melted and pre-mixed, the particle size of the pigment was reduced utilizing a bead mill.
The wax materials and the colorant dispersions were then mixed to form the inks of Examples 1-6. The compositions of the inks of Examples 1-6 are summarized in Table 3 below.













TABLE 3







Wax #1

Wax #2
Colorant
Colorant


Example #
Wax #1
(wt %)
Wax #2
(wt %)
dispersion
(wt %)





















Example 1
MS 38-48
85
None
N/A
GT09-34
15


Example 2
MS 38-48
17.5
BK-40
57.5
GT09-34
25


Example 3
MS 38-48
67.37
BK-40
11.58
GT09-47
21.05


Example 4
MS 38-48
55
MS 37-121
20
GT09-34
25


Example 5
BK-40
50
MS 36-181
25
GT09-34
25


Example 6
MS 38-48
66.67
PELEMOL GTB
11.46
GT09-34
20.83








Comparative
Markem-Imaje 5005 TOUCH DRY Black Ink


Example 1









In Table 1, MS 38-48 is 2,2,4-trimethylpentane-1,3-diyl bis(stearylcarbamate); MS 37-121 is octadecyl octadecylcarbamate; MS 36-181 is 2-(2-(3-octadecylureido)ethoxy)ethyl octadecylcarbamate; BK-40 is a C32-C36 branched alkyl stearate; PELEMOL GTB is a glycerol tribehenate; GT09-34 is a mixture containing MS37-121 (50 wt %), Irganox 1010 (2 wt %), Solsperse J910 (Lubrizol Limited, Cleveland, Ohio) (16 wt %), and Special Black 4A (Evonik Corporation, Theodore, Ala.) (32 wt %); GT09-47 is a mixture containing MS38-48 (50 wt %), Irganox 1010 (2 wt %), Solsperse J910 (16 wt %), and Special Black 4A (32 wt %).
The properties of the inks in Examples 1-6 and Comparative Example 1 were tested using the following methods:
Melting and freezing points are obtained using a Perkin Elmer Pyris 7e DSC using the programmed run sequence summarized in Table 4:










TABLE 4






Starting
Ending Temperature
Ramp Rate


Step #
Temperature (° C.)
(° C.)
(° C.)


















1
0
140
50/minute


2
140
0
50/minute


3
0
0
0/1 minute


4
0
140
20/minute


5
140
0
20/minute









Melting point values taken were the peak heights found during the second melt and freeze cycle.
Melt viscosity was measured by using a Brookfield viscometer (Model DVII) with an attached thermal cell. 8.0 grams of an ink was heated in the ink cup to melt the ink. A #18 spindle running at 60 RPM was used to take viscosity measurement after shearing for 10 minutes minimum.
Dot gain measurements are measured by utilizing an Olympus SZX12 microscope, with Olympus Stream Essentials software, version 1.9. Microphotographs were taken after calibration. The resulting drop diameters were measured with the software accompanying the microscope, and contrasted to the comparative example.
The results are summarized in Table 5 below.











TABLE 5






Viscosity
Melt Point
Freezing



Example #
(cP)
(° C.)
Point (° C.)
Dot Gain



















Example 1
12.8
43
32
15%


Example 2
10.1
36, 66
21.6, 52
53%


Example 3
12.9
41
32
30%


Example 4
12.6
43, 75
30, 57
21%


Example 5
11.5
38
23
24%


Example 6
13.9
42
33
30%


Comparative
9
58
51
Control


Example 1









The dot gain values in Table 2 are the percentage increases of the dot diameters obtained from inks in Examples 1-6 compared to the dot diameter obtained from the ink in Comparative Example 1. These dot gains are average values obtained from 7 to 10 measurements.
Other embodiments are within the scope of the following claims.

## Claims

1. A hot melt ink composition, comprising:
at least one wax having a freezing point of from about 20° C. to about 45° C. and a melting point of at least about 35° C., and
at least one colorant,
wherein the composition comprises at least about 50 wt % of the at least one wax and the at least one wax comprises an amide alcohol wax, a urethane wax, an ether wax, or an ester wax.

2. The composition of claim 1, wherein the at least one wax has a freezing point of from about 30° C. to about 45° C.

3. The composition of claim 1, wherein the at least one wax has a freezing point of from about 30° C. to about 40° C.

4. The composition of claim 1, wherein the melting point of the at least one wax is at least about 10° C. higher than the freezing point of the at least one wax.

5. The composition of claim 1, wherein the melting point of the at least one wax is at least about 15° C. higher than the freezing point of the at least one wax.

6. The composition of claim 1, wherein the amide alcohol wax is stearyl diethanolamide, stearyl isopropanolamide, mono isopropanolamide, or coconut monoisopropanolamide.

7. The composition of claim 1, wherein the urethane wax is 2,2,4-trimethylpentane-1,3-diyl bis(stearylcarbamate) or [2-ethyl-2-(octadecylcarbamoyloxy-methyl)hexyl]N-octadecylcarbamate.

8. The composition of claim 1, wherein the ether wax is polyethylene glycol having a weight average molecular weight of from about 540 g/mol to about 1450 g/mol.

9. The composition of claim 1, wherein the ester wax is behenyl erucate, glycerol tribehenate, C32-C36 branched alkyl stearate, or polyglyceryl-3 stearate.

10. The composition of claim 1, wherein the composition comprises at least about 70 wt % of the at least one wax.

11. The composition of claim 1, further comprises at least one tackifier, at least one resin, at least one plasticizer, at least one antioxidant, or at least one dispersant.

12. The composition of claim 1, wherein the at least one colorant comprises a dye or a pigment.

13. The composition of claim 1, wherein the composition has a melt viscosity of from about 5 cP to about 25 cP measured at 125° C.

14. The composition of claim 1, wherein the composition has a melt viscosity of from about 10 cP to about 14 cP measured at 125° C.

15. The composition of claim 1, wherein the composition is substantially free of a polyethylene.

16. The composition of claim 1, wherein the composition consists of:
(1) the at least one wax,
(2) the at least one colorant,
(3) optionally, at least one tackifier,
(4) optionally, at least one resin,
(5) optionally, at least one plasticizer,
(6) optionally, at least one antioxidant, and
(7) optionally, at least one dispersant.

17. The composition of claim 1, wherein the hot melt ink composition capable of forming dots having an average dot diameter of at least about 15% larger than those formed by Ink 5005 when the dots are formed under the same conditions and without external treatment.

18. The composition of claim 17, wherein the composition is capable of forming dots having an average dot diameter of at most about 100% larger than those formed by Ink 5005 when the dots are formed under the same conditions and without external treatment.

19. The composition of claim 1, wherein the hot melt ink composition capable of forming dots having an average dot diameter of at least about 85 μm when the composition has a melt viscosity of about 10 cP, each dot is formed by using about 70 picoliter of the composition, and the dots are formed at ambient temperature without external treatment.

20. The composition of claim 19, wherein the composition is capable of forming dots having an average dot diameter of at most about 120 μm.

21. A printing process, comprising:
melting the hot melt ink composition of claim 1 in a printhead in an inkjet printer, and
ejecting the hot melt ink composition from the printhead onto a substrate to form an image.

22. A product, comprising a substrate and a solid ink defining an image on the substrate, the solid ink comprising the hot melt ink composition of claim 1.

23. The product of claim 22, wherein the substrate is a cardboard or a film.

24. A hot melt ink composition, comprising:
at least one wax having a freezing point of from about 20° C. to about 45° C. and a melting point of at least about 35° C. in an amount of at least about 50 wt % of the composition,
at least one colorant, and
at least one wax having a freezing point higher than 45° C.

25. The composition of claim 24, wherein the at least one wax having a freezing point higher than 45° C. is 2-(2-(3-octadecylureido)ethoxy)ethyl octadecylcarbamate or octadecyl octadecylcarbamate.