Ink compositions containing malonaldehyde bis (dimethylacetal)

Abstract: Disclosed is an ink composition comprising (a) water, (b) a colorant, and (c) malonaldehyde bis(dimethylacetal).

Description: The present invention is directed to ink compositions and to methods for the use thereof. More specifically, the present invention is directed to ink compositions suitable for use in ink jet printing processes. One embodiment of the present invention is directed to an ink composition comprising (a) water, (b) a colorant, and (c) malonaldehyde bis(dimethylacetal). Ink jet printing systems generally are of two types: continuous stream and drop-on-demand. In continuous stream ink jet systems, ink is emitted in a continuous stream under pressure through at least one orifice or nozzle. The stream is perturbed, causing it to break up into droplets at a fixed distance from the orifice. At the break-up point, the droplets are charged in accordance with digital data signals and passed through an electrostatic field which adjusts the trajectory of each droplet in order to direct it to a gutter for recirculation or a specific location on a recording medium. In drop-on-demand systems, a droplet is expelled from an orifice directly to a position on a recording medium in accordance with digital data signals. A droplet is not formed or expelled unless it is to be placed on the recording medium. Since drop-on-demand systems require no ink recovery, charging, or deflection, the system is much simpler than the continuous stream type. There are two types of drop-on-demand ink jet systems. One type of drop-on-demand system has as its major components an ink filled channel or passageway having a nozzle on one end and a piezoelectric transducer near the other end to produce pressure pulses. The relatively large size of the transducer prevents close spacing of the nozzles, and physical limitations of the transducer result in low ink drop velocity. Low drop velocity seriously diminishes tolerances for drop velocity variation and directionality, thus impacting the system's ability to produce high quality copies. Drop-on-demand systems which use piezoelectric devices to expel the droplets also suffer the disadvantage of a slow printing speed. Another type of drop-on-demand system is known as thermal ink jet, or bubble jet, and produces high velocity droplets and allows very close spacing of nozzles. The major components of this type of drop-on-demand system are an ink filled channel having a nozzle on one end and a heat generating resistor near the nozzle. Printing signals representing digital information originate an electric current pulse in a resistive layer within each ink passageway near the orifice or nozzle, causing the ink in the immediate vicinity to evaporate almost instantaneously and create a bubble. The ink at the orifice is forced out as a propelled droplet as the bubble expands. When the hydrodynamic motion of the ink stops, the process is ready to start all over again. With the introduction of a droplet ejection system based upon thermally generated bubbles, commonly referred to as the "bubble jet" system, the drop-on-demand ink jet printers provide simpler, lower cost devices than their continuous stream counterparts, and yet have substantially the some high speed printing capability. The operating sequence of the bubble jet system begins with a current pulse through the resistive layer in the ink filled channel, the resistive layer being in close proximity to the orifice or nozzle for that channel. Heat is transferred from the resistor to the ink. The ink becomes superheated far above its normal boiling point, and for water based ink, finally reaches the critical temperature for bubble formation or nucleation of around 280°C. Once nucleated, the bubble or water vapor thermally isolates the ink from the heater and no further heat can be applied to the ink. This bubble expands until all the heat stored in the ink in excess of the normal boiling point diffuses away or is used to convert liquid to vapor, which removes heat due to heat of vaporization. The expansion of the bubble forces a droplet of ink out of the nozzle, and once the excess heat is removed, the bubble collapses on the resistor. At this point, the resistor is no longer being heated because the current pulse has passed and, concurrently with the bubble collapse, the droplet is propelled at a high rate of speed in a direction towards a recording medium. The resistive layer encounters a severe cavitational force by the collapse of the bubble, which tends to erode it. Subsequently, the ink channel refills by capillary action. This entire bubble formation and collapse sequence occurs in about 10 microseconds. The channel can be refired after 100 to 500 microseconds minimum dwell time to enable the channel to be refilled and to enable the dynamic refilling factors to become somewhat dampened. Thermal ink jet processes are well known and are described in, for example, U.S. Patent 4,601,777, U.S. Patent 4,251,824, U.S. Patent 4,410,899, U.S. Patent 4,412,224, and U.S. Patent 4,532,530. Acoustic ink let printing orocesses ore also known. As is known, an acoustic beam exerts a radiation pressure against objects upon which it impinges. Thus, when an acoustic beam impinges on a free surface (i.e., liquid/air interface) of a pool of liquid from beneath, the radiation pressure which it exerts against the surface of the pool may reach a sufficiently high level to release individual droplets of liquid from the pool, despite the restraining force of surface tension. Focusing the beam on or near the surface of the pool intensifies the radiation pressure it exerts for a given amount of input power. These principles have been applied to prior ink jet and acoustic printing proposals. For example, K. A. Krause, "Focusing Ink Jet Head," IBM Technical Disclosure Bulletin , Vol. 16, No. 4, September 1973, pp. 1168-1170 describes an ink jet in which an acoustic beam emanating from a concave surface and confined by a conical aperture was used to propel ink droplets out through a small ejection orifice. Acoustic ink printers typically comprise one or more acoustic radiators for illuminating the free surface of a pool of liquid ink with respective acoustic beams. Each of these beams usually is brought to focus at or near the surface of the reservoir (i.e., the liquid/air interface). Furthermore, printing conventionally is performed by independently modulating the excitation of the acoustic radiators in accordance with the input data samples for the image that is to be printed. This modulation enables the radiation pressure which each of the beams exerts against the free ink surface to make brief, controlled excursions to a sufficiently high pressure level for overcoming the restraining force of surface tension. That, in turn, causes individual droplets of ink to be ejected from the free ink surface on demand at an adequate velocity to cause them to deposit in an image configuration on a nearby recording medium. The acoustic beam may be intensity modulated or focused/defocused to control the ejection timing, or an external source may be used to extract droplets from the acoustically excited liquid on the surface of the pool on demand. Regardless of the timing mechanism employed, the size of the ejected droplets is determined by the waist diameter of the focused acoustic beam. Acoustic ink printing is attractive because it does not require the nozzles or the small ejection orifices which have caused many of the reliability and pixel placement accuracy problems that conventional drop on demand and continuous stream ink jet printers have suffered. The size of the ejection orifice is a critical design parameter of an ink jet because it determines the size of the droplets of ink that the jet ejects. As a result, the size of the ejection orifice cannot be increased, without sacrificing resolution. Acoustic printing has increased intrinsic reliability because there are no nozzles to clog. As will be appreciated, the elimination of the clogged nozzle failure mode is especially relevant to the reliability of large arrays of ink ejectors, such as page width arrays comprising several thousand separate ejectors. Furthermore, small ejection orifices are avoided, so acoustic printing can be performed with a greater variety of inks than conventional ink jet printing, including inks having higher viscosities and inks containing pigments and other particulate components. It has been found that acoustic ink printers embodying printheads comprising acoustically illuminated spherical focusing lenses can print precisely positioned pixels (i.e., picture elements) at resolutions which are sufficient for high quality printing of relatively complex images. It has also has been discovered that the size of the individual pixels printed by such a printer can be varied over a significant range during operation, thereby accommodating, for example, the printing of variably shaded images. Furthermore, the known droplet ejector technology can be adapted to a variety of printhead configurations, including (1) single ejector embodiments for raster scan printing, (2) matrix configured ejector arrays for matrix printing, and (3) several different types of pagewidth ejector arrays, ranging from single row, sparse arrays for hybrid forms of parallel/serial printing to multiple row staggered arrays with individual ejectors for each of the pixel positions or addresses within a pagewidth image field (i.e., single elector/pixel/line) for ordinary line printing. Inks suitable for acoustic ink jet printing typically are liquid at ambient temperatures (i.e., about 25°C), but in other embodiments the ink is in a solid state at ambient temperatures and provision is made for liquefying the ink by heating or any other suitable method prior to introduction of the ink into the printhead. Images of two or more colors can be generated by several methods, including by processes wherein a single printhead launches acoustic waves into pools of different colored inks. Further information regarding acoustic ink jet printing apparatus and processes is disclosed in, for example, U.S. Patent 4,308,547, U.S. Patent 4,697,195, U.S. Patent 5,028,937, U.S. Patent 5,041,849, U.S. Patent 4,751,529, U.S. Patent 4,751,530, U.S. Patent 4,751,534, U.S. Patent 4,801,953, and U.S. Patent 4,797,693. The use of focused acoustic beams to eject droplets of controlled diameter and velocity from a free-liquid surface is also described in J. Appl. Phys ., vol. 65, no. 9 (1 May 1989) and references therein. While known compositions and processes are suitable for their intended purposes, a need remains for improved ink compositions, particularly those suitable for use in ink jet printing. In addition, a need remains for ink compositions that exhibit rapid penetration into recording substrates such as plain paper. Further, a need remains for ink compositions that exhibit reduced intercolor bleed when printed next to images of another color. Additionally, a need remains for ink compositions with desirable viscosity values. The present invention is directed to an ink composition comprising (a) water, (b) a colorant, and (c) malonaldehyde bis(dimethylacetal). Another embodiment of the present invention is directed to a printing process that comprises (1) incorporating into an ink jet printing apparatus an ink composition comprising (a) water, (b) a colorant, and (c) malonaldehyde bis(dimethylacetal), and (2) causing droplets of the ink to be ejected in an imagewise pattern onto a recording sheet. Yet another embodiment of the present invention is directed to a process for reducing intercolor bleed in ink jet printing which comprises (1) incorporating into an ink jet printing apparatus a first ink composition of a first color comprising (a) water, (b) a colorant, and (c) malonaldehyde bis(dimethylacetat), (2) incorporating into the ink jet printing apparatus a second ink composition of a color different from the first color and comprising (a) water, and (b) a pigment colorant, said second ink composition being substantially free of malonaldehyde bis(dimethylacetal), and (3) causing droplets of the first ink and the second to be ejected in an imagewise pattern onto a recording sheet, wherein at least some droplets of the first ink are ejected onto the recording sheet adjacent to at least some droplets of the second ink, and wherein intercolor bleed between the first ink and the second ink is reduced. The inks of the present invention contain an aqueous liquid vehicle. The liquid vehicle can consist solely of water, or it can comprise a mixture of water and a water soluble or water miscible organic component, such as ethylene glycol, propylene glycol, diethylene glycol, glycerine, dipropylene glycol, polyethylene glycol, polypropylene glycol, amides, ethers, urea, substituted ureas, carboxylic acids and their salts, esters, alcohols, organosulfides, organosulfoxides, sulfones (such as sulfolone), alcohol derivatives, carbitol, butyl carbitol, cellusolve, tripropylene glycol monomethyl ether, ether derivatives, amino alcohols, ketones, N-methylpyrrolidinone, 2-pyrrolidinone, cyclohexylpyrrolidone, hydroxyethers, sulfoxides, lactones, polyelectrolytes, methyl sulfonylethanol, imidazole, betaine, and other water soluble or water miscible materials, as well as mixtures thereof. The non-water component of the liquid vehicle generally serves as a humectant or cosolvent which has a boiling point higher than that of water (100°C). In the ink compositions of the present invention, the liquid vehicle is typically present in an amount of from about 80 to about 99.9 percent by weight of the ink, and preferably from about 90 to about 99 percent by weight of the ink, although the amount can be outside these ranges. Preferably, the ink contains water in a minimal amount. More specifically, it is preferred that the ink contain water in an amount of no more than about 80 percent by weight of the ink, more preferably in an amount of no more than about 60 percent by weight of the ink, and even more preferably in an amount of no more than about 50 percent by weight of the ink, although the amount can be outside of these ranges. In a particularly preferred embodiment, the inks of the present invention further contain sulfolane, typically in an amount of from 0 to about 50 percent by weight of the ink, preferably from about 5 to about 40 percent by weight of the ink, and more preferably from about 10 to about 30 percent by weight of the ink, although the amount can be outside of these ranges. The inks of the present invention also contain a colorant. 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 Block 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), anthraquinone dyes, monoazo dyes, disazo dyes, phthalocyanine derivatives, including various phthalocyanine sulfonate salts, aza(18)annulenes, formazan copper complexes, triphenodioxazines, Reactive Red 4, Reactive Red 56, Reactive Red 31, the Pro-Jet® series of dyes available from ICI, Reactive Black 31, Reactive Yellow 37, Reactive Red 180, various Reactive dyes, including Reactive Black dyes, Reactive Blue dyes, Reactive Red dyes, Reactive Yellow dyes, and the like, as well as mixtures thereof. The dye is present in the ink composition in any desired or effective amount, typically from about 0.05 to about 15 percent by weight of the ink, preferably from about 0.1 to about 10 percent by weight of the ink, and more preferably from about 1 to about 5 percent by weight of the ink, although the amount can be outside of these ranges. Examples of suitable pigments include various carbon blacks such as channel block, furnace black, lamp black, and the like. Colored pigments include red, green, blue, brown, magenta, cyan, and yellow particles, as well as mixtures thereof. Preferably, the pigment particle size is 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. Preferred particle average diameters are generally from about 0.001 to about 5 microns, and more preferably from about 0.1 to about 1 micron, although the particle size can be outside these ranges. Within the ink compositions of the present invention, the pigment is present in any effective amount to achieve the desired degree of coloration. Typically, the pigment is present in an amount of from about 0.1 to about 8 percent by weight of the ink, and preferably from about 2 to about 7 percent by weight of the ink, although the amount can be outside these ranges. In one preferred embodiment of the present invention, the colorant comprises a mixture of an anionic dye and a polyquatemary amine compound, and preferably the ink further contains a monomeric salt comprising at least one cation and at least one anion. Any desired or suitable anionic dye can be employed, including (but not limited to) those listed hereinabove. In this embodiment, the anionic dye is present in the ink composition in any desired or effective amount, typically from about 0.05 to about 10 percent by weight of the ink, preferably from about 0.1 to about 7 percent by weight of the ink, and more preferably from about 1 to about 5 percent by weight of the ink, although the amount can be outside of these ranges. The polyquaternary amine compound, which generally is believed to be complexed with the anionic dye, is a polymer containing quaternary groups in the repeat units thereof. The polymer typically has a weight average molecular weight of from about 1,000 to about 10,000,000, preferably from about 3,000 to about 1,000,000, and more preferably from about 5,000 to about 400,000, although the value can be outside of these ranges. The polymer typically has a number average molecular weight of from about 800 to about 11,000,000, preferably from about 3,300 to about 1,100,000, and more preferably from about 5,600 to about 450,000, although the value can be outside of these ranges. The polymer typically has from about 5 to about 70,000 repeat monomer units therein, preferably from about 21 to about 7,000 repeat monomer units, and more preferably from about 35 to about 2,800 repeat monomer units, although the number of repeat monomer units can be outside of this range. Suitable polyquaternary amine compounds typically are of the general formulae or wherein n is an integer representing the number of repeat monomer units, R 1 is an alkylene group, including saturated, unsaturated, cyclic, and substituted alkylene groups (including polymethylene oxide groups, polyethylene oxide groups, polypropylene oxide groups, and the like), typically with from 1 to about 30 carbon atoms and preferably with from 1 to about 6 carbon atoms, an arylene group, including substituted arylene groups, typically with from 6 to about 50 carbon atoms and preferably with from 6 to about 18 carbon atoms, or an arylalkylene group, including substituted arylalkylene groups, typically with from 7 to about 60 carbon atoms and preferably with from 7 to about 20 carbon atoms, and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each, independently of the others, are hydrogen atoms, alkyl groups, including saturated, unsaturated, cyclic, and substituted alkyl groups (including polymethylene oxide groups, polyethylene oxide groups, polypropylene oxide groups, and the like), typically with from 1 to about 30 carbon atoms and preferably with from 1 to about 6 carbon atoms, aryl groups, including substituted aryl groups, typically with from 6 to about 50 carbon atoms and preferably with from 6 to about 18 carbon atoms, arylalkyl groups, including substituted arylalkyl groups, typically with from 7 to about 60 carbon atoms and preferably with from 7 to about 20 carbon atoms, wherein the substituents on the substituted alkyl, alkylene, aryl, arylene, arylalkyl, and arylalkylene groups can be (but are not limited to) hydroxy groups, amine groups, ammonium groups, cyano groups, pyridine groups, pyridinium groups, ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carbonyl groups, sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups, nitrile groups, mercapto groups, nitroso groups, halogen atoms, nitro groups, sulfone groups, acyl groups, mixtures thereof, and the like, wherein two or more substituents can be joined together to form a ring. Examples of suitable polyquaternary amine compounds include polydiallyl ammonium compounds, of the general formula wherein n is an integer representing the number of repeat monomer units, R 1 and R 2 each, independently of the other, are hydrogen atoms, alkyl groups, including saturated, unsaturated, cyclic, and substituted alkyl groups (including polymethylene oxide groups, polyethylene oxide groups, polypropylene oxide groups, and the like), typically with from 1 to about 30 carbon atoms and preferably with from 1 to about 6 carbon atoms, aryl groups, including substituted aryl groups, typically with from 6 to about 50 carbon atoms and preferably with from about 6 to about 18 carbon atoms, or arylalkyl groups, including substituted arylalkyl groups, typically with from about 7 to about 60 carbon atoms and preferably with from 7 to about 20 carbon atoms, wherein the substituents on the substituted alkyl aryl, and arylalkyl groups can be (but are not limited to) hydroxy groups, amine groups, ammonium groups, cyano groups, pyridine groups, pyridinium groups, ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carbonyl groups, sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups, nitrile groups, mercapto groups, nitroso groups, halogen atoms, nitro groups, sulfone groups, acyl groups, mixtures thereof, and the like, wherein two or more substituents can be joined together to form a ring, and A is an anion, such as Cl - , Br - , I - , HSO 4 - , HSO 3 - , SO 4 2- , SO 3 2- , CH 2 SO 3 - , CH 3 SO 3 - , CH 3 C 6 H 4 SO 3 - , NO 3 - , HCOO - , CH 3 COO - , HCO 3 - , CO 3 2- , H 2 PO 4 - , HPO 4 2- , PO 4 3- , SCN - , BF 4 - , ClO 4 - , SSO 3 - , or the like, such as polydiallyl dimethyl ammonium compounds, including polydiallyl dimethyl ammonium chloride, of the formula wherein n is an integer representing the number of repeat monomer units, commercially available with a molecular weight of about 400,000 (wherein n is an integer of about 2,500) from Calgon Corp. as 261-RV, and with a molecular weight of about 5,000 (wherein n is an integer of about 31) from Calgon Corp. as VARIKEM 110 or E2253. Also suitable are polyquaternized polyvinylamines, of the general formula wherein n is on integer representing the number of repeat monomer units, R 1 , R 2 , and R 3 each, independently of the others, are hydrogen atoms, alkyl groups, including saturated, unsaturated, cyclic, and substituted alkyl groups (including polymethylene oxide groups, polyethylene oxide groups, polypropylene oxide groups, and the like), typically with from 1 to about 30 carbon atoms and preferably with from 1 to about 6 carbon atoms, aryl groups, including substituted aryl groups, typically with from 6 to about 50 carbon atoms and preferably with from about 6 to about 18 carbon atoms, arylalkyl groups, including substituted arylalkyl groups, typically with from 7 to about 60 carbon atoms and preferably with from 7 to about 20 carbon atoms, wherein the substituents on the substituted alkyl, aryl and arylalkyl groups can be (but are not limited to) hydroxy groups, amine groups, ammonium groups, cyano groups, pyridine groups, pyridinium groups, ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carbonyl groups, sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups, nitrile groups, mercapto groups, nitroso groups, halogen atoms, nitro groups, sulfone groups, acyl groups, mixtures thereof, and the like, wherein two or more substituents can be joined together to form a ring, and A is an anion, such as Cl - , Br - , I - , HSO 4 - , HSO 3 - , SO 4 2- , SO 3 2- , CH 2 SO 3 - , CH 3 SO 3 - , CH 3 C 6 H 4 SO 3 - , NO 3 - , HCOO - , CH 3 COO - , HCO 3 - , CO 3 2- , H 2 PO 4 - , HPO 4 2- , PO 4 3- , SCN - , BF 4 - , ClO 4 - , SSO 3 - , or the like. Also suitable are polyquaternized polyallylamines, of the general formula wherein n is an integer representing the number of repeat monomer units, R 1 , R 2 , and R 3 each, independently of the others, are hydrogen atoms, alkyl groups, including saturated, unsaturated, cyclic, and substituted alkyl groups (including polymethylene oxide groups, polyethylene oxide groups, polypropylene oxide groups, and the like), typically with from 1 to about 30 carbon atoms and preferably with from 1 to about 6 carbon atoms, aryl groups, including substituted aryl groups, typically with from 6 to about 50 carbon atoms and preferably with from about 6 to about 18 carbon atoms, arylalkyl groups, including substituted arylalkyl groups, typically with from 7 to about 60 carbon atoms and preferably with from 7 to about 20 carbon atoms, wherein the substituents on the substituted alkyl, aryl and arylalkyl groups can be (but are not limited to) hydroxy groups, amine groups, ammonium groups, cyano groups, pyridine groups, pyridinium groups, ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carbonyl groups, sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups, nitrile groups, mercapto groups, nitroso groups, halogen atoms, nitro groups, sulfone groups, acyl groups, mixtures thereof, and the like, wherein two or more substituents can be joined together to form a ring, and A is an anion, such as Cl - , Br - , I - , HSO 4 - , HSO 3 - , SO 4 2- , SO 3 2- , CH 2 SO 3 - , CH 3 SO 3 - , CH 3 C 6 H 4 SO 3 - , NO 3 - , HCOO - , CH 3 COO - , HCO 3 - , CO 3 2- , H 2 PO 4 - , HPO 4 2- , PO 4 3- , SCN - , BF 4 - , ClO 4 - , SSO 3 - , or the like. Also suitable are epichlorohydrin/amine copolymers, including those of the general formula wherein n is an integer of from about 3 to about 3,000, and preferably from about 5 to about 100, although the value can be outside of these ranges, and A is any suitable or desired anion, such as Cl - , Br, I - , HSO 4 - , HSO 3 - , SO 4 2- , SO 3 2- , CH 2 SO 3 - , CH 3 SO 3 - , CH 3 C 6 H 4 SO 3 - , NO 3 - , HCOO - , CH 3 COO - , HCO 3 -, CO 3 2- , H 2 PO 4 - , HPO 4 2- , PO 4 3- , SCN - , BF 4 - , ClO 4 - , SSO 3 - , or the like. Polymers of this formula are commercially available from Hercules, Wilmington, DE as RETEN 200 or RETEN 201 (molecular weight generally less than 10,000), and from Cytex, Inc., West Patterson, NJ, as CYPRO 514, 515, and 516 (wherein the polymers have a molecular weight range of from about 75,000 to about 250,000 and n is from about 870 to about 3,000), and as SUPERFLOC C567 (wherein the polymer has a molecular weight of about 10,000 and n is from about 110 to about 120, typically about 116). Also suitable are cationic amido amine copolymers. Examples of suitable cationic amido amine copolymers include those of the general formula (A-B) n 2n+ •2nX - wherein X is an anion, such as Cl - , Br - , I - , HSO 4 - , HSO 3 - , SO 4 2- , SO 3 2- , CH 2 SO 3 - , CH 3 SO 3 - , CH 3 C 6 H 4 SO 3 - , NO 3 - , HCOO - , CH 3 COO - , HCO 3 - , CO 3 2- , H 2 PO 4 - , HPO 4 2- , PO 4 3- , SCN - , BF 4 - , ClO 4 - , SSO 3 - , or the like, n is an integer representing the number of repeating monomer units, and typically is from about 2 to about 1,000, preferably from about 3 to about 200, more preferably from about 3 to about 100, and even more preferably from about 3 to about 10, although the value can be outside of these ranges, "A" is and "B" is selected from the group consisting of (a) monomers of the formula wherein p is an integer representing the number of repeat monomer units, and typically is from 1 to about 12, preferably from I to about 7, and more preferably from 1 to about 4, although the value can be outside of these ranger such as (i) azelaic acid diamide, wherein p is 7 of the formula or (ii) adipic acid diamido, wherein p is 4, of the formula and (b) ureido, of the formula Mixtures of two or more "B" monomers can also be used within the polymer. In a preferred embodiment, these specific polymers typically are condensation polymers, with alternating "A" and "B" monomer units. The weight average molecular weight of the polymer typically is from about 1,000 to about 100,000, preferably from about 1,000 to about 30,000, and more preferably from about 2,000 to about 5,000, although the value can be outside of these ranges. Copolymers of an amine and an amide are commercially available from, for example, Rhone-Poulenc, Cranbury, NJ, as, for example, MIRAPOL AZ-1, of the above formula wherein the "B" monomer is azelaic acid diamido, n has an average value of about 100, and the molecular weight is about 50,000, MIRAPOL AD-1, of the above formula wherein the "B" monomer is adipic acid diamido, n has on average value of about 100, and the molecular weight is about 50,000, and MIRAPOL A-15, of the above formula wherein the "B" monomer is ureido, n has an average value of about 6, and the molecular weight is about 2,260. Also suitable are copolymers of vinyl pyrrolidinone and a vinyl imidazolium salt. In one embodiment, the copolymer is of a vinyl imidazolium salt of the formula wherein X is an anion and R is a hydrogen atom or an alkyl group, typically with from 1 to about 8 carbon atoms and preferably with from 1 to about 3 carbon atoms, and vinyl pyrrolidinone, of the formula wherein the copolymer is of the general formula wherein X is any suitable or desired anion, such as Cl - , Br - , I - , HSO 4 - , HSO 3 - , SO 4 2- , SO 3 2- , CH 2 SO 3 - , CH 3 SO 3 - , CH 3 C 6 H 4 SO 3 - , NO 3 - , HCOO - , CH 3 COO - , HCO 3 - , CO 3 2- , H 2 PO 4 - , HPO 4 2- , PO 4 3- , SCN - , BF 4 - , ClO 4 - , SSO 3 - , or the like, R is a hydrogen atom or an alkyl group, typically with from 1 to about 8 carbon atoms, and preferably with from 1 to about 3 carbon atoms, m is a integer representing the number of repeat vinyl imidazolium units, and n is an integer representing the number of repeat vinyl pyrrolidinone units. When R is a hydrogen atom, the pH of the ink can be adjusted to provide optimal ink-paper interaction; for example, the hydrogen atom can be extracted upon contact with the paper, or the cationic character of the polymer can be adjusted with ink pH. Random copolymers of the above formula generally are preferred, although alternating and block copolymers are also suitable. The weight average molecular weight of the polymer typically is from about 1,000 to about 1,000,000, preferably from about 1,000 to about 100,000, and more preferably from about 2,000 to about 5,000, although the value can be outside of these ranges. The ratio of vinyl imidazolium monomers to vinyl pyrrolidinone monomers typically is from about 99:1 to about 5:95, preferably from about 95:5 to about 20:80, more preferably from about 95:5 to about 30:70, and even more preferably from about 95:5 to about 50:50, although the value can be outside of these ranges. Vinyl pyrrolidinone/vinyl imidazolium salt copolymers are commercially available; for example, BASF, Parsippany, NJ, provides vinyl imidazolium chloride/vinyl pyrrolidinone copolymers (of the above formula wherein R is CH 3 ) with a molecular weight of about 100,000 in three monomer ratios: LUVIQUAT® FC905 has a vinyl imidazolium chloride:vinyl pyrrolidinone ratio of 95:5 with 6.7 milliequivalents per gram of cationic groups, LUVIQUAT® FC550 has a vinyl imidazolium chloride:vinyl pyrrolidinone ratio of 50:50 with 3.0 milliequivalents per gram of cationic groups, and LUVIQUAT® FC370 has a vinyl imidazolium chloride:vinyl pyrrolidinone ratio of 30:70 with 1.8 milliequivalents per gram of cationic groups. Also available from BASF is LUVIQUAT® HM552, with a molecular weight of about 800,000 and a vinyl imidazolium chloride:vinyl pyrrolidinone ratio of 50:50. Mixtures of two or more polyquaternary amine compounds can also be present in the ink. The polyquaternary amine compound is present in the ink in any desired or effective amount, typically from about 0.01 to about 50 percent by weight of the ink, more typically from about 0.05 to about 40 percent by weight of the ink, preferably from about 1 to about 10 percent by weight of the ink, more preferably from about 1 to about 9 percent by weight of the ink, and even more preferably from about 1 to about 5 percent by weight of the ink, although the amount can be outside of these ranges. The preferred relative amounts of polyquaternary amine and anionic dye in the ink can also be expressed as a stoichiometric ratio, with the molar ratio of anionic dye groups to cationic polyquaternary groups typically being from about 1:0.33 to about 1:300, preferably from about 1:1 to about 1:20, more preferably from about 1:2 to about 1:6, and most preferably about 1:3, although the relative amounts can be outside of these ranges. While not being limited to any particular theory, it is believed that the polyquaternary amine and the dye form a multidentate ionic complex upon admixing of the ink ingredients. While the ink ingredients can be mixed in any desired order, it is preferred that any salts present in the ink be added prior to addition of the dye or the polyquaternary amine. The structure of the polyquaternary complex generally is independent of ink pH over the normal pH range of the ink. In embodiments of the present invention wherein the colorant is a mixture of an anionic dye and a polyquaternory amine, the inks further contain a nonpolymeric salt comprising at least one cation and at least one anion. Examples of suitable cations include alkali metal cations, such as Li + , Na + , and K + , alkaline earth metal cations, such as Mg 2+ and Ca 2+ , nonpolymeric or monomeric ammonium and quaternary amine cations, with specific examples of ammonium and quaternary amine cations including NH 4 + , N(CH 3 ) 4 + , H 3 NCH 2 CH 2 NH 3 2+ , (H 3 C) 3 NCH 2 CH 2 N(CH 3 ) 3 2+ , imidazolium, quaternized 1,4-diazobicyclo(2.2.2)octane, choline, of the formula alkyl amine quaternary salts such as ETHOQUAD C/12, of the formula wherein R is a long chain alkyl group with 12 carbon atoms, x and y are integers of 0, 1, or 2 representing the number of ethoxy groups, wherein x+y=2, and A is an anion, such as chloride, commercially available from Akzo Chemie, Chicago, IL, and the like, as well as mixtures thereof. Any desired anion can be employed. Examples of suitable anions include sulfate, sulfonate, sulfamate (NH 2 SO 3 - ), carbonate, nitrate, perchlorate, organic acid anions, such as formate, acetate, propionate, and the like, acetylacetonate, of the formula squarate, of the formula halides, including chloride, bromide, and iodide, and the like, as well as mixtures thereof. Specific examples of suitable salts include lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium formate, lithium acetate, lithium propionate, lithium sulfate, lithium sulfonate, lithium sulfamate, lithium carbonate, lithium perchlorate, lithium acetylacetonate, lithium squarate, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium perchlorate, sodium formate, sodium acetate, sodium propionate, sodium sulfate, sodium sulfonate, sodium sulfamate, sodium carbonate, sodium perchlorate, sodium acetylacetonate, sodium squarate, potassium chloride, potassium bromide, potassium iodide, potassium formate, potassium acetate, potassium propionate, potassium sulfate, potassium sulfonate, potassium sulfamate, potassium carbonate, potassium perchlorate, potassium acetylacetonate, potassium squarate, calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium propionate, calcium sulfate, calcium sulfonate, calcium sulfamate, calcium carbonate, calcium perchlorate, calcium acetylacetonate, calcium squarate, magnesium chloride, magnesium sulfate, magnesium formate, magnesium acetate, magnesium propionate, magnesium sulfate, magnesium sulfonate, magnesium sulfamate, magnesium carbonate, magnesium perchlorate, magnesium acetylacetonate, magnesium squarate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium acetate, ammonium formate, ammonium nitrate, ammonium sulfate, ammonium propionate, ammonium sulfonate, ammonium sulfamate, ammonium carbonate, ammonium perchlorate, ammonium acetylacetonote, ammonium squarate, tetramethylammonium chloride, tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium sulfate, tetramethylammonium sulfonate, tetramethylammonium sulfamate, tetramethylammonium carbonate, tetramethylammonium perchlorate, tetramethylammonium acetylacetonate, tetramethylammonium squarate, ethylene diamine dihydrochloride, 1,4-diazabicyclo(2.2.2)octane salts, such as hexamethonium bromide, of the formula imidazole salts, such as imidazolium chloride, acetylacetonate salts, such as lithium acetylacetonate, squarate salts, such as tetramethylammonium squarate, choline salts, such as choline chloride, ETHOQUAD C/12, and the like. The salt can also be a complex salt, including transition metal complexes such as Zn(NH 3 ) 4 or the like. The salt is present in the ink in any desired or effective amount, typically from about 0.1 to about 40 percent by weight of the ink, preferably from about 0.1 to about 30 percent by weight of the ink, more preferably from about 0.5 to about 20 percent by weight of the ink, and even more preferably from about 2 to about 15 percent by weight of the ink, although the amount can be outside of these ranges. The preferred relative amounts of salt and anionic dye in the ink can also be expressed as a stoichiometric ratio, with the molar ratio of onions in the added salt to anionic dye groups typically being from about 0:1 to about 100:1 for anionic dyes and from about 0:1 to about 500:1 for direct dyes. For all anionic dyes (acid dyes, direct dyes, reactive dyes, and the like), the preferred molar ratio of anions in the added salt to anionic dye groups from about 5:1 to about 100:1, more preferably from about 10:1 to about 80:1. The molar ratio of anions in the added salt to anionic dye groups can, however, be outside of these ranges. In addition, when the anions in the added salt are multivalent, a lesser amount can be employed if desired; for example, if the anions in the added salt are bivalent, the amount added can be reduced to approximately one half of the amount desired for a monovalent anion. While not being limited to any particular theory, it is believed that the presence of the salt improves the solubility or stability in the ink vehicle of the dye/polyquaternary amine compound complex which is employed as a colorant in the inks of the present invention. More specifically, it is believed that the salt electrostatically shields charges within the polyelectrolye complex constituting the colorant, thereby enabling a more compact structure which in turn is more soluble or stable in the ink vehicle. Again, while not being limited to any particular theory, it is believed that within the ink, the polyquaternary amine is associated with the anionic dye, with the dye playing the role of a counterion. The adjacent charge centers in the polyquaternary amine repel each other and force the polyquaternary amine into a more stretched-out and less soluble backbone configuration. The presence of the salt in the ink is believed to reduce these repulsions, compact the electrical double layer, and promote a more compact, more soluble polyquaternary amine complex. The presence of the salt in the ink can also reduce jitter when the ink is jetted and increase ink surface tension. In another preferred embodiment, the polyquaternary amine compound is present in the ink in an amount such that the number of quaternary amine groups on the polyquaternary amine compound exceeds the number of anionic groups on the dye. In some instances, particularly when the ink vehicle contains cosolvents such as sulfolane and/or urea and a salt, when the dye and polyquaternary amine compound are present in relative amounts such that the number of anionic groups on the dye exceeds the number of cationic quaternary amine groups on the polymer, precipitation of the dye/polyquaternary amine complex from the ink vehicle can occur. Increasing the amount of polyquaternary amine compound in the ink in these instances enables an ink with excellent shelf stability, excellent waterfastness, excellent smear resistance, and reduced intercolor bleed. Ink compositions containing increased amounts of polyquaternary amine compound and salt, i.e., at least about 6 percent by weight polyquaternary amine compound and at least about 12 percent by weight salt, also enable advantages such as the ability to formulate inks in the absence of stabilizing cosolvents such as sulfolane and urea. The ability to formulate inks without cosolvents or humectants such as these enables advantages such as increased compatibility of the ink with materials from which printheads are commonly made, improved shelf stability, and the like. Inks containing glycol cosolvents such as dipropylene glycol, tripropylene glycol monomethyl ether, and the like can be formulated without resulting colorant destabilization. The inks of the present invention further contain malonaldehyde bis(dimethylacetal). Malonaldehyde bis(dimethylacetal) is a polar aprotic compound of the formula This material is commercially available from, for example, Aldrich Chemical Co., Milwaukee, WI. The malonaldehyde bis(dimethylacetal) is present in the ink in any desired or effective amount, typically at least about 1 percent by weight of the ink, preferably at least about 5 percent by weight of the ink, and more preferably at feast about 10 percent by weight of the ink, and typically no more than about 70 percent by weight of the ink, preferably no more than about 50 percent by weight of the ink, and more preferably no more than about 40 percent by weight of the ink, although the amount can be outside of these ranges. In a particularly preferred embodiment the malonaldehyde bis(dimethylacetal) is present in the ink in an amount of at least about 10 percent by weight of the ink and is present in the ink in an amount of no more than about 40 percent by weight of the ink. While not being limited to any particular theory, it is believed that the malonaldehyde bis(dimethylacetal), in addition to enabling superior ink penetration and reduced intercolor bleed, also enables these advantages without unduly raising the ink viscosity to an undesirable level. With no hydrogen-bondable hydrogens and a relatively low molecular weight, malonaldehyde bis(dimethylacetal) imports minimal additional viscosity to the ink. The high ratio of electron lone pairs to molecular weight of this material is also believed to increase its hydrogen bonding capability to water. Again, while not being limited to any particular theory, it is believed that when the ink containing the malonaldehyde bis(dimethylacetal) contacts another ink containing a pigment colorant (either self-dispersing, i.e., pigment particles surface treated to render them more easily dispersed in an ink, or with pigment particles and a dispersant), the presence of the malonaldehyde bis(dimethylacetal) in the first ink causes removal of water hydrogen bonds from the pigment particles in the second ink to the malonaldehyde bis(dimethylacetal) in the first ink, thereby destabilizing the pigment in the second ink, causing it to precipitate onto the paper and reducing its ability to migrate on paper. Intercolor bleed is accordingly reduced. The malonaldehyde bis(dimethylacetal) can also be included in an ink containing a pigment colorant (either self-dispersing, i.e., pigment particles surface treated to render them more easily dispersed in an ink, or with pigment particles and a dispersant). The presence of the malonaldehyde bis(dimethylacetal) in the ink, generally in relatively lesser amounts than would be used in a dye-based ink, tends to destabilize the pigment colorant. The amount of malonaldehyde bis(dimethylocetal) is selected so that the pigment, while destabilized, is still sufficiently stably dispersed to enable functioning of the ink. When the ink contacts the paper, the pigment is immediately further destabilized, causing it to precipitate onto the paper and reducing its ability to migrate on paper. Intercolor bleed is accordingly reduced. In this embodiment, the malonaldehyde bis(dimethylocetal) is present in the ink in any desired or effective amount, typically from about 5 to about 40 percent by weight of the ink, preferably from about 10 to about 30 percent by weight of the ink, and more preferably from about 15 to about 25 percent by weight of the ink, although the amount can be outside of these ranges. The ink compositions are generally of a viscosity suitable for use in thermal ink jet printing processes. At room temperature (i.e., about 25°C), typically, the ink viscosity is no more than about 10 centipoise, and preferably is from about 1 to about 5 centipoise, more preferably from about 1 to about 4 centipoise, although the viscosity can be outside this range, particularly for applications such as acoustic ink jet printing. Ink compositions of the present invention can be of any suitable or desired pH. For some embodiments, such as thermal ink jet printing processes, typical pH values are from about 3 to about 11, preferably from about 5 to about 10, and more preferably from about 6 to about 8.5, although the pH can be outside of these ranges. Ink compositions suitable for ink jet printing can be prepared by any suitable process. Typically, the inks are prepared by simple mixing of the ingredients. One process entails mixing all of the ink ingredients together and filtering the mixture to obtain an ink. Inks can be prepared by mixing the ingredients, heating if desired, and filtering, followed by adding any desired additional additives to the mixture and mixing at room temperature with moderate shaking until a homogeneous mixture is obtained, typically from about 5 to about 10 minutes. Alternatively, the optional ink additives can be mixed with the other ink ingredients during the ink preparation process, which takes place according to any desired procedure, such as by mixing all the ingredients, heating if desired, and filtering. The present invention is also directed to a process which entails incorporating an ink of the present invention into an ink jet printing apparatus and causing droplets of the ink to be ejected in an imagewise pattern onto a recording sheet. In one preferred embodiment, the printing apparatus employs a thermal ink jet process wherein the ink in the nozzles is selectively heated in an imagewise pattern, thereby causing droplets of the ink to be ejected in imagewise pattern. In another preferred embodiment, the printing apparatus employs an acoustic ink jet process, wherein droplets of the ink are caused to be ejected in imagewise pattern by acoustic beams. The present invention further relates to a process for reducing intercolor bleed in ink jet printing which comprises (1) incorporating into an ink jet printing apparatus a first ink composition of a first color comprising (a) water, (b) a colorant, and (c) malonaldehyde bis(dimethylacetal), (2) incorporating into the ink jet printing apparatus a second ink composition of a color different from the first color and comprising (a) water, and (b) a pigment colorant, said second ink composition being substantially free of malonaldehyde bis(dimethylacetal), and (3) causing droplets of the first ink and the second to be ejected in an imagewise pattern onto a recording sheet, wherein at least some droplets of the first ink are ejected onto the recording sheet adjacent to at least some droplets of the second ink, and wherein intercolor bleed between the first ink and the second ink is reduced. Preferably the colorant in the first ink is a dye. Any suitable substrate or recording sheet can be employed, 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, and the like, transparency materials, fabrics, textile products, plastics, polymeric films, inorganic substrates such as metals and wood, and the like. in a preferred embodiment, the process entails printing onto a porous or ink absorbent substrate, such as plain paper. Specific embodiments of the invention will now be described in detail. All parts and percentages are by weight unless otherwise indicated. EXAMPLE I An ink composition was prepared by simple mixing of the following ingredients: The resulting ink was filtered through a 1.2 micron filter. The ink exhibited a viscosity of 4.28 centipoise at 25°C, a pH of 7.75 at 25°C, a surface tension of 32.2 dynes per centimeter, and a conductivity of 22.8 millimhos. The ink composition thus prepared was incorporated into a LEXMARK® 7200 thermal ink jet printer. Also incorporated into the printer was a black ink prepared by simple mixing of the following ingredients: The ink exhibited a viscosity of 1.9 centipoise at 25°C, a pH of 7.27 at 25°C, a surface tension of 36.1 dynes per centimeter, and a conductivity of 0.298 millimhos. The black and yellow inks were used to generate adjacent black and yellow images on Courtland® 4224 DP paper and Fuji Xerox Multiace AK701 paper. Intercolor bleed was measured as the average MFLEN ( M id F requency L ine E dge N oise, Horizontal lines) of the interface between the two inks. Intercolor bleed usually is caused by undesirable mixing of inks near the bordering areas and results in a distorted line image with irregular edges and large MFLEN values. The smaller MFLEN number is desirable because it shows sharper line image with reduced intercolor bleed. The MFLEN number was obtained by equipment consisting of a personal computer, an illuminating light source, a filter, and an imaging microscope with a CDD sensor. The equipment was calibrated with a standard image (line with sharp edges). Software using a Fourier Transform technique was used to calculate the MFLEN data and line width. The average MFLEN was 9.3 on Courtland® 4224 DP paper and 19.9 on Fuji Xerox Multiace AK701 paper. EXAMPLE II An ink composition was prepared by simple mixing of the following ingredients: The resulting ink was filtered through a 1.2 micron filter. The ink exhibited a viscosity of 3.29 centipoise at 25°C, a pH of 8.58 at 25°C, a surface tension of 36.7 dynes per centimeter, and a conductivity of 3.4 millimhos. The ink composition thus prepared was incorporated into a LEXMARK® 7200 thermal ink jet printer. Also incorporated into the printer was a black ink prepared as described in Example I. The black and yellow inks were used to generate adjacent black and yellow images on Courtland® 4224 DP paper and Fuji Xerox Multiace AK701 paper. Intercolor bleed was measured as the average MFLEN ( M id F requency L ine E dge N oise, Horizontal lines) of the interface between the two inks. The average MFLEN was 17.4 on Courtland® 4224 DP paper and 22.2 on Fuji Xerox Multiace AK701 paper. EXAMPLE III An ink composition was prepared by simple mixing of the following ingredients: COMPARATIVE EXAMPLE A An ink composition was prepared by simple mixing of the following ingredients: The resulting ink was filtered through a 1.2 micron filter. The ink exhibited a viscosity of 3.61 centipoise at 25°C, a pH of 8.27 at 21°C, a surface tension of 36.6 dynes per centimeter, and a conductivity of 4.25 millimhos. The ink composition thus prepared was incorporated into a LEXMARK® 7200 thermal ink jet printer. Also incorporated into the printer was a black ink prepared as described in Example I. The black and yellow inks were used to generate adjacent black and yellow images on Courtland® 4224 DP paper. Intercolor bleed was measured as the average MFLEN ( M id F requency L ine E dge N oise, Horizontal lines) of the interface between the two inks. The average MFLEN was 54.

Claims: An ink composition comprising (a) water, (b) a colorant, and (c) malonaldehyde bis(dimethylacetal). An ink composition according to claim 1 wherein the water is present in an amount of no more than about 80 percent by weight of the ink. An ink composition according to claim 1 wherein the water is present in an amount of no more than about 60 percent by weight of the ink. An ink composition according to any of claims 1 to 3 wherein the colorant is a dye, a pigment or a mixture thereof. An ink composition according to any of claims 1 to 3 wherein the colorant is a mixture of an anionic dye and a polyquatemary amine. An ink composition according to claim 5 wherein the ink further contains a monomeric salt having at least one cation and at least one anion. An ink composition according to any of claims 1 to 6 wherein the malonaldehyde bis(dimethylacetal) is present in the ink in an amount of at least about 1 percent by weight of the ink and is present in the ink in an amount of no more than about 70 percent by weight of the ink. An ink composition according to any of claims 1 to 7 wherein the malonaldehyde bis(dimethylacetal) is present in the ink in an amount of at least about 5 percent by weight of the ink and is present in the ink in an amount of no more than about 50 percent by weight of the ink. An ink composition according to any of claims 1 to 8 further containing sulfolane. A printing process that comprises (1) incorporating into an ink jet printing apparatus an ink composition according to any of claims 1 to 9, and (2) causing droplets of the ink to be ejected in an imagewise pattern onto a recording sheet.

Inventors: COLT RICHARD L, GUNDLACH KURT B, COLT, RICHARD L., GUNDLACH, KURT, B.
Applicants: XEROX CORP, XEROX CORPORATION
Application year: 2000
Main classification: C09D11
IPC codes: B41M5, B41J2, C09D11