Inks

The present invention is directed to ink compositions and, more specifically, the present invention relates to inks with a melting point of between about 60.degree. C. and about 150.degree. C., and preferably between about 70.degree. C. to about 90.degree. C., which inks are especially useful for acoustic ink printing, processes and apparatuses, reference, for example, U.S. Pat. No. 5,121,141, U.S. Pat. No. 5,111,220, U.S. Pat. No. 5,128,726, U.S. Pat. No. 5,371,531, the disclosures of which are totally incorporated herein by reference, including especially acoustic ink processes as illustrated in the copending applications, such as an acoustic ink printer for printing images on a record medium.

The inks of the present invention in embodiments thereof can be considered (1) a phase change ink, that is for example, an ink that changes from a liquid state to solid state in a suitable period of time, for example from about 1 to about 100 milliseconds and preferably in less than about 10, such as from about 2 to about 7 milliseconds and which inks contain a phase-change color spreading compound, or an additive that can fill the pores of a substrate such as paper, and which compound has a melting point of, for example, lower than about or about equal to 120.degree. C. and preferably between about 60 to about 100.degree. C., and with a low acoustic loss value of below, for example, about 100 dB/mm, (2) a nonaqueous gloss and crease improving alcohol compound having a boiling point, for example, higher than or equal to about 150.degree. C. (Centigrade), and more specifically, having a boiling point from about 150.degree. C. to about 225.degree. C. and preferably from about 170.degree. C. to about 200.degree. C., and a melting point of between about 25 to about 90.degree. C. with low acoustic loss, which enables a reduction, or minimization of energy consumption, and which acoustic loss is in the range of, for example, from about 5 to about 60 dB/mm, and preferably between about 5 to about 40 dB/mm, (3) a lightfast UV absorber, (4) a lightfast antioxidant, (5) and a colorant such as a dye, a pigment or mixtures thereof.

More specifically, the present invention is directed to phase-change acoustic ink compositions comprised of (1) nonaqueous solid phase-change additives with a melting point of lower than about 120.degree. C. and preferably between about 60 and about 100.degree. C., and having a low acoustic loss and which acoustic loss is below about 100 dB/mm, and preferably in the range of between about 25 to about 80 dB/mm at the jetting temperature, (2) a nonaqueous gloss and crease improving alcohol compound having a boiling point of higher than about 150.degree. C. (Centigrade), and more specifically, with a boiling point from about 150.degree. C. to about 225.degree. C. and preferably from about 170.degree. C. to about 200.degree. C., and a melting point of less than about 90.degree. C. with low acoustic loss, which enables a reduction, or minimization of energy consumption, and which acoustic loss is in the range of from about 5 to about 60 dB/mm, and preferably between about 5 to about 40 dB/mm, (3) a UV absorber, (4) an antioxidant, (5) a colorant, and wherein there can be generated with such inks excellent developed images on plain and coated papers with acceptable image permanence, excellent projection efficiency on transparencies without a post fusing step, and excellent crease resistance, and wherein the inks possess acceptable, and in embodiments superior lightfastness between about 90 to about 100 percent, and superior waterfastness values between about 95 to about 100 percent. Moreover, in embodiments of the present invention there is enabled the elimination, or minimization of undesirable paper curl since water need not be present, or minimum amounts less than about 1 percent, for example from about 0.5 to about 0.99 of water may be selected in embodiments, and it is preferred that there be an absence of water. When water is not present in the inks a dryer can be avoided thereby minimizing the cost of the acoustic ink jet apparatus and process.

In acoustic ink printing, the print head produces approximately 0.5 to 8 picoliter and preferably about 2 picoliter droplets by an acoustic energy process. The ink under these conditions should display a melt viscosity of about 10 to about 15 centipoise or less at the jetting temperature. Furthermore, once the ink is jetted onto the paper, the ink image should possess excellent crease properties, and should be nonsmearing and waterfast. In selecting an ink for such applications, it is desirable that the vehicle display a low melt viscosity, such as from about 1 centipoise to about 25 centipoise in the acoustic head, while also displaying solid like properties after being jetted onto paper. Since the acoustic head can usually tolerate a temperature up to about 180.degree. C., and preferably up to a temperature of from about 130.degree. C. to about 160.degree. C., the vehicle for the ink should preferably display liquid like properties such as a viscosity of about 1 to about 10 centipoise at a temperature of from about 75.degree. C. to about 165.degree. C., and solidify or harden after jetting onto paper such that the ink displays a hardness value of from about 0.1 to about 0.5 millimeter utilizing a penetrometer according to the ASTM penetration method D1321.

Ink jet printing processes that employ inks that are solid at room temperature and liquid at elevated temperatures are known. For example, U.S. Pat. No. 4,490,731, the disclosure of which is totally incorporated herein by reference, discloses an apparatus for dispensing certain solid inks for printing on a substrate such as paper. An ink dye vehicle is chosen with a melting point above room temperature so that the ink, which is melted in the apparatus, will not be subject to evaporation or spillage during periods of nonprinting. The vehicle selected possesses a low temperature to permit the use of the solid ink in a thermal ink jet printer. In thermal ink jet printing processes employing phase-change inks, the solid ink is melted by a heater in the printing apparatus and utilized as a liquid in a manner similar to that of conventional thermal or piezoelectric ink jet printing. Upon contact with the printing substrate, the molten ink solidifies rapidly, enabling the dye to remain on the surface instead of being carried into the paper by capillary action, thereby attempting to enable higher print density than is generally obtained with liquid inks. Phase-change ink jets are somewhat similar to thermal ink jets; however, a phase-change ink contains no solvent. Thus, rather than being liquid at room temperature, a phase-change ink is typically a solid or phase-change having a wax-like consistency. These inks usually need to be heated, for example, to approximately 100.degree. C. before the ink melts and converts into a liquid. With phase-change inks, a plurality of ink jet nozzles is provided in a printhead. A piezoelectric vibrating element is located in each ink channel upstream from a nozzle so that the piezoelectric oscillations propel ink through the nozzle. After the phase-change ink is applied to the substrate, freezing on the substrate resolidifies the ink.

Each of these types of known ink jet systems have a number of advantages and disadvantages. One advantage of thermal ink jets is their compact design for the integrated electronics section of the printhead. Thermal ink jets are disadvantageous in that the thermal ink has a tendency to soak into a plain paper medium. This blurs the print or thins out the print locally thereby adversely affecting print quality. Problems have been encountered with thermal ink jets in attempting to rid the ink of moisture fast enough so that the ink does not soak into a plain paper medium. This is particularly the situation when printing with color. Therefore, usually when printing with thermal inks, coated papers are used to obtain photo like quality images.

One advantage of phase-change ink is its ability to print on plain paper since the phase-change ink quickly solidifies as it cools and, since it is waxy in nature, and does not normally soak into paper. However, phase-change ink jet systems can be cumbersome in structure and in design, that is, the associated integrated electronics of a thermal ink jet head are considerably more compact than those of a phase-change ink jet head.

In addition, U.S. Pat. No. 4,751,528, the disclosure of which is totally incorporated herein by reference, discloses a phase-change ink jet system which includes a temperature-controlled platen provided with a heater and a thermoelectric cooler electrically connected to a heat pump and a temperature control unit for controlling the operation of the heater and the heat pump to maintain the platen temperature at a desired level. The apparatus also includes a second thermoelectric cooler to solidify the phase-change ink in a selected zone more rapidly to avoid offset by a pinch roll coming in contact with the surface of the substrate to which phase-change ink has been applied. An airtight enclosure surrounding the platen is connected to a vacuum pump and has slits adjacent to the platen to retain the substrate in thermal contact with the platen.

Further, U.S. Pat. No. 4,791,439, the disclosure of which is totally incorporated by reference, discloses an apparatus for use with phase-change inks with an integrally connected ink jet head and reservoir system, the reservoir system including a highly efficient heat conducting plate inserted within an essentially nonheat conducting reservoir housing.

Ink compositions for ink jet printing are known. For example, U.S. Pat. No. 4,840,674, the disclosure of which is totally incorporated herein by reference, discloses an ink composition which comprises a major amount of water, an organic solvent selected from the group consisting of tetramethylene sulfone, 1,1,3,3-tetramethyl urea, 3-methyl sulfolane, and 1,3-dimethyl-2-imidazolidone, which solvent has permanently dissolved therein spirit soluble dyes.

U.S. Pat. No. 5,006,170 and U.S. Pat. No. 5,122,187, the disclosures of each of which are totally incorporated herein by reference, disclose ink compositions suitable for ink jet printing, which inks comprise, for example, a colorant, a binder, and a propellant such as hydrazine, cyclic amines, ureas, carboxylic acids, sulfonic acids, aldehydes, ketones, hydrocarbons, esters, phenols, amides, imides, halocarbons, and the like.

U.S. Pat. No. 5,041,161, the disclosure of which is totally incorporated herein by reference, discloses ink jet inks, which can phase-change at room temperature. These inks can comprise vehicles, such as acids, aldehydes and mixtures thereof, which phase-changes at temperatures between about 20.degree. C. and about 45.degree. C.

U.S. Pat. No. 4,853,036 and U.S. Pat. No. 5,124,718 disclose an ink for ink jet recording which comprises a liquid composition essentially comprising a coloring matter, a volatile solvent with a vapor pressure of 1 millimeter Hg or more at 25.degree. C., and a compound being solid at room temperature and having a molecular weight of 300 or more.

While the known ink compositions and processes may be suitable for their intended purposes, a need remains for acoustic phase-change ink compositions suitable for ink jet printing. In addition, there is a need for phase-change ink compositions, which are compatible with a wide variety of plain papers and can generate in some instances photographic quality images on plain and coated papers. Further, there is a need for phase-change ink compositions, which generate high quality, lightfast, and waterfast images on plain papers. There is also a need for phase-change ink jet ink compositions which generate high quality, fast-drying images on a wide variety of plain papers at low cost with high quality text and high quality graphics, and wherein the dye may be retained on the paper surface while the ink vehicle can continue to spread within the paper structure. Further, there is a need for phase-change ink jet ink compositions, which exhibit minimal feathering. Additionally, there is a need for phase-change ink jet ink compositions, which exhibit minimal intercolor bleed. There is also a need for phase-change ink jet ink compositions, which exhibit excellent image permanence. Further, there is a need for phase-change ink jet ink compositions, which are suitable for use in acoustic ink jet printing processes. Additionally, there is a need for phase-change hot ink compositions suitable for ink jet printing processes wherein the substrate is heated prior to printing and is cooled to ambient temperature subsequent to printing (also known as heat and delay printing processes). There is also a need for ink compositions suitable for ink jet printing wherein high optical densities can be achieved with relatively low dye concentrations. A need also remains for ink compositions suitable for ink jet printing wherein curling of the substrate, such as paper, subsequent to printing is minimized, or avoided. These and other needs can be achievable with the inks of the present invention in embodiments thereof.

Aspects of the present invention relate to an ink composition comprised of (1) a carbamate or thiourea each with a melting point of from about 60.degree. C. to about 120.degree. C. and an acoustic-loss value of from about 25 to about 80 dB/mm, (2) an alcohol compound with melting point of about 25.degree. C. to about 90.degree. C. and with an acoustic-loss value of from about 5 to about 40 dB/mm, (3) a lightfastness component, (4) an antioxidant, and (5) a colorant;

an ink wherein said ink yields images with crease values of about 10 to about 20, haze values of about 10 to about 25, gloss values of about 80 to about 85, and which ink possesses an acoustic-loss value of from about 10 to about 80 dB/mm, and a viscosity of from about 1 centipoise to about 15 centipoise at a temperature of from about 125.degree. C. to about 165.degree. C.; an ink composition wherein the carbamate or thiourea compound is present in an amount of from about 1 to about 98 percent by weight, the alcohol is present in an amount of from about 69 to about 1 percent by weight, the lightfastness component is present in an amount of from about 5 to about 0.25 percent by weight, the antioxidant is present in an amount of from about 5 to about 0.25 percent by weight, and the colorant is present in an amount of from about 20 to about 0.5 percent by weight; an ink composition wherein the carbamate is selected from the group consisting of (1) tert-butyl carbamate, (2) tert-butyl-N-(tert-butoxycarbonyloxy) carbamate, (3) tert-butyl-N-[2-hydroxy-2-(hydroxyphenyl)-1-methylethyl] carbamate, (4) tert-butyl-(2,4-dinitrophenoxy) carbamate, (5) benzyl carbamate, (6) benzyl N-hydroxycarbamate, (7) ethyldiphenyl carbamate, (8) 2-chloroethyl carbamate, (9) cyanomethyl-N,N-dimethyl dithiocarbamate, (10) 4,4'-methylene-bis(dibutyldithio carbamate), (11) potassium N-hydroxy methyl-N-methyl-dithiocarbamate, (12) sodium dimethyl dithiocarbamate, (13) disodium ethylenebis-dithio carbamate, (14) diethylammonium diethyldithio carbamate, (15) benzyl(S)-(-)-tetrahydro-5-oxo-3-furanyl carbamate (16) diethyldithiocarbamic acid, ammonium salt, (17) diethyldithiocarbamic acid, diethyl ammonium salt, and (18) diethyldithiocarbamic acid, sodium salt, trihydrate; an ink composition wherein the carbamate is selected from the group consisting of (1) tert-butyl carbamate; (2) tert-butyl-(2,4-dinitrophenoxy) carbamate; (3) benzyl carbamate; (4) benzyl N-hydroxycarbamate; and (5) benzyl (S)-(-)-tetrahydro-5-oxo-3-furanyl carbamate; an ink composition wherein the thiourea compound is selected from the group consisting of (1) 1-allyl-2-thiourea, (2) 1-allyl-3-(2-hydroxyethyl)-2-thiourea, (3) 1-methyl-2-thiourea, (4) 1-methallyl-3-methyl-2-thiourea, (5) 1,3-dibutyl-2-thiourea, (6) 1,1,3,3-tetramethyl-2-thiourea, (7) N,N'-di-n-propyl thiourea, and (8) 1-benzyl-3-methyl-2-thiourea; an ink composition wherein the thiourea is 1-allyl-2-thiourea; 1-allyl-3-(2-hydroxyethyl)-2-thiourea; 1-methallyl-3-methyl-2-thiourea; or 1,1,3,3-tetramethyl-2-thiourea; an ink composition wherein the cyclic alcohol is selected from the group consisting of (1) cycloalkyl alcohols where the number of carbons in the alkyl chain varies from about 6 to about 12, (2) 4-tert-butyl cyclohexanol, (3) 3-aminomethyl-3,5,5-trimethyl cyclohexanol, (4) 2,2,6,6-tetrachloro cyclohexanol, (Aldrich #18,681-3); (5) cycloalkane methanol where the number of carbons in the alkane chain varies from about 5 to about 12, (6) dicyclohexylmethanol, (7) 3-cyclohexyl-1-propanol, (8) 2-amino-3-cyclohexyl-1-propanol, (9) (S)-2-(tert-butoxy carbonylamino)-3-cyclohexyl-1-propanol, (10) cycloalkane diol where the number of carbons in the alkane chain varies from about 5 to about 8, (11) cis-3,5-cyclohexa diene-1,2-diol, (12) .rho.-menthane-3,8-diol, (13) cyclohexane dimethanol, (14) 3-cyclohexene-1,1-dimethanol, (15) 1,3-dioxane-5,5-dimethanol, and (16) piperidinemethanol; an ink composition wherein the alcohol is a linear alcohol selected from the group consisting of (1) alkyl alcohols where the number of carbons in the alkyl chain vary from about 6 to about 22, (2) alkane diols where the number of carbons in the alkane chain vary from about 5 to about 14, (3) 5-amino-1-pentanol, (4) nitromethane trispropanol, (5) 6-amino-1-hexanol, (6) 11-bromo-1-undecanol, (7) 12-bromo-1-dodecanol, (8) 2-methyl-2-propyl-1,3-propane diol, (9) 2,2-diethyl-1,3-propanediol, (10) 2-(hydroxymethyl)-1,3-propanediol, (11) 2,2,4-trimethyl-1,3-pentanediol, (12) 2-butyne-1,4-diol, (13) (.+-.)-3,6-dimethyl-4-octyne-3,6-diol, (14) 3,6-dithia-1,8-octanediol, and (15) 2,4,7,9-tetramethyl-5-decyne-4,7-diol; an ink composition wherein the alcohol is an amino alcohol selected from the group consisting of (1) 2-(2-aminoethoxy)ethanol, (2) 2-(2-amino ethylamino) ethanol, (3) amino-1-propanol, (4) amino-1-butanol, (5) 2-amino-3-methyl-1-butanol, (6) DL-2-amino-1-hexanol, and (7) (S)-(-)-N-(tertbutoxycarbonyl) leucinol; an ink composition wherein the alcohol is an aromatic alcohol selected from the group consisting of benzyl alcohol and its derivatives (1) alkyl benzyl alcohols where the number of carbon atoms in the alkyl group varies from about 0 to about 8, (2) alkoxy and aryloxy benzyl alcohols where the number of carbons in the alkoxy groups varies from about 1 to about 4, (3) alkyl alkyl benzyl alcohols where the number of carbons in the alkyl varies from about 1 to about 4, (4) 2-amino-3-methyl benzyl alcohol, (5) alkoxy alkoxy benzyl alcohols where the number of carbon atoms in the alkoxy group varies from about 1 to about 4, (6) 2-hydroxy-3-methoxy benzyl alcohol, and (7) 3,4,5-trimethoxy benzyl alcohol; an ink composition wherein the alcohol is an aromatic alcohol selected from the group consisting of phenyl alcohol and its derivatives (1) phenylpropanol, (2) 3-(4-hydroxy phenyl)-1-propanol, (3) (S)-(-)-1-phenyl-1-butanol, (4) 2-amino-1-phenyl ethanol, (5) 3,4-dimethoxy phenethyl alcohol, (6) 2-phenyl-1,2-propane diol, (7) 3-phenoxy-1,2-propane diol, (8) 3-methoxy catechol, (9) benzhydrol, (10) methyl benzhydrol, (11) phenethylalcohol, (12) 4-methoxy phenethyl alcohol, (13) 2-hydroxy phenethyl alcohol, and (14) 2-amino phenethylalcohol; an ink wherein the lightfastness component is selected from the group consisting of (1) 1,1-(1,2-ethane diyl) bis(3,3,5,5-tetramethyl piperazinone); (2) 6-ethoxy-1,2-dihydro-2,2,4-trimethyl quinoline; (3) 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate; (4) 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)succinimide; and (5) 1,2,2,6,6-pentamethyl-4-piperidinyl/.beta.,.beta.,.beta.',.beta.'-tetramet hyl-3,9-(2,4,8,10-tetraoxo spiro (5,5) undecane)diethyl]-1,2,3,4-butane tetracarboxylate; an ink wherein the antioxidant compound is selected from the group consisting of (1) antimony dialkyl phosphorodithioate, (2) molybdenum oxysulfide dithio carbamate, (3) nickel-bis(o-ethyl(3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate), and (4) tetra sodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate; a printing process which comprises incorporating into an acoustic ink jet printer the inks illustrated herein; a process which comprises (a) providing an acoustic ink printer having a pool of a liquid ink illustrated herein, and causing droplets of the ink to be ejected in imagewise pattern onto a substrate; an ink wherein the colorant is selected in an amount of from about 0.5 to about 20 percent by weight; an ink wherein the colorant is a pigment, or a dye; an ink wherein the colorant is a pigment of carbon black; an ink wherein the colorant is a pigment of cyan, magenta, yellow, black, or mixtures thereof; an ink with a viscosity of from about 1 centipoise to about 15 centipoise; an ink with a viscosity of from about 1 centipoise to about 10 centipoise, and an acoustic loss of from about 10 to about 80 dB/mm; an ink composition comprised of (1) a solid carbamate or a solid urea compound, (2) an alcohol, (3) a lightfastness UV absorber, (4) a lightfastness antioxidant, and (5) a colorant; an ink wherein the colorant is a pigment, or a dye; an ink which possesses an acoustic-loss value of from about 10 to about 80 dB/mm; an ink comprised of a carbamate, an alcohol, a lightfastness compound, an antioxidant, and a colorant; an ink containing substantially no water; an ink containing no water; and (1) an ink containing a nonaqueous solid phase-change additive with a melting point of lower than about 120.degree. C. and preferably between about 60.degree. C. to about 100.degree. C., with a low acoustic loss value, and which acoustic loss is below about 100 dB/mm, and preferably in the range of about 25 to about 80 dB/mm, (2) a nonaqueous gloss and crease improving alcohol compound with a boiling point of higher than about 150.degree. C. (Centigrade) and more specifically, with a boiling point of from about 150.degree. C. to about 225.degree. C. and preferably from about 170.degree. C. to about 200.degree. C., and a melting point of about 25.degree. C. to about 90.degree. C. with a low acoustic loss, which enables a reduction, or minimization of energy consumption, and which acoustic loss is in the range of from about 5 to about 60 dB/mm, and preferably between about 5 to about 40 dB/mm, (3) a UV absorber, (4) an antioxidant, and (5) a colorant.

A phase-change additive compound with, for example, a melting point of from about 60.degree. C. to about 120.degree. C. is present for example, in an amount of from about 1 to about 98 percent by weight, the gloss and crease improving alcohol compound with an acoustic-loss value of, for example, from about 5 to about 40 dB/mm is present in the ink composition in an amount of, for example, from about 69 to about 1 percent by weight, the lightfastness component, such as a UV absorber, is present, for example, in an amount of from about 5 to about 0.25 percent by weight, the antioxidant is, for example, present in an amount of from about 5 to about 0.25 percent by weight, and the colorant is, for example, present in an amount of from about 20 to about 0.5 percent by weight. The ink composition contains, for example, the following range amounts, respectively, for components (1) to (6), (1) being either a thiourea or a carbamate [1+69+5+5+20=100] to [98+1+0.25+0.25+0.5=100].

In preferred embodiments the additive with an acoustic-loss value of from about 25 to about 80 dB/mm is present in an amount of from about 15 to about 90 percent by weight, the gloss and crease improving alcohol compound having a melting point of between 25.degree. C. to 90.degree. C. is present in an amount of from about 60 to about 7 percent by weight, the UV absorber is present in an amount of from about 5 to about 1 percent by weight, the antioxidant is present in an amount of from about 5 to about 1 percent by weight, and the colorant is present in an amount of from about 15 to about 1 percent by weight. The ink composition thus contains the following preferred range amounts [15+60+5+5+15=100] to [90+7+1+1+1=100]. These composition ranges, and the others indicated herein were established using a number of known techniques, such as a statistical design based on the analyses of the experimental data of viscosity at 150.degree. C., jettability at 150.degree. C., image quality, lightfast, and waterfast values of images generated with various ink compositions.

Examples of components with a melting point of between about 60 to about of 120.degree. C. and preferably an acoustic-loss value of between about 25 to about 80 dB/mm include (a) carbamate compounds of (1) tertbutyl carbamate, (Aldrich #16,739-8); (2) tert-butyl-N-(tert-butoxycarbonyloxy) carbamate, (Aldrich #41,279-1); (3) tert-butyl-N-[2-hydroxy-2-(hydroxyphenyl)-1-methylethyl] carbamate, (Aldrich #40,429-2); (4) tert-butyl-(2,4-dinitrophenoxy) carbamate, (Aldrich #33,305-0); (5) benzyl carbamate, (Alfa Organics #A11569); (6) benzyl N-hydroxycarbamate, (Aldrich #32,327-6); (7) ethyldiphenyl carbamate, (Aldrich #37,291-9); (8) 2-chloroethyl carbamate, (Aldrich #40,429-2); (9) cyanomethyl-N,N-dimethyl dithiocarbamate, (Aldrich #28,054-2); (10) 4,4'-methylene-bis(dibutyldithio carbamate), Vanlube 7723, Vanderbilt Corporation; (11) potassium N-hydroxy methyl-N-methyl-dithiocarbamate (Busan 40 from Buckman Larboratories Inc.), (12) sodium dimethyl dithiocarbamate, (13) disodium ethylenebis-dithio carbamate, (14) diethylammonium diethyldithio carbamate, (Alfa Organics #A10458); (15) benzyl(S)-(-)-tetrahydro-5-oxo-3-furanyl carbamate, (Aldrich #41,924-9); (16) diethyldithiocarbamic acid, ammonium salt, (Aldrich #35,954-8); (17) diethyldithiocarbamic acid, diethyl ammonium salt, (Aldrich #31,811-6); and (18) diethyldithiocarbamic acid, sodium salt, trihydrate, (Aldrich #22,868-0);

(b) thiourea compounds of (1) 1-allyl-2-thiourea, (Aldrich #10,880-41); (2) 1-allyl-3-(2-hydroxyethyl)-2-thiourea, (Aldrich #A3, 280-2); (3) 1-methyl-2-thiourea, (Aldrich #M8,460-7); (4) 1-methallyl-3-methyl-2-thiourea, (Aldrich #19,046-2); (5) 1,3-dibutyl-2-thiourea, (Aldrich #D4,959-8); (6) 1,1,3,3-tetramethyl-2-thiourea, (Aldrich #11,516-9); (7) N,N'-di-n-propyl thiourea, (Alfa Organics #A17217); and (8) 1-benzyl-3-methyl-2-thiourea, (Aldrich #27,550-6).

Alcohol compound examples are:

(A) cyclic alcohols such as (1) cycloalkyl alcohols where the number of carbons in the alkyl chain vary from 6 to 12 such as cyclohexanol, (Aldrich #10,589-9); cycloheptanol, (Aldrich #C9,880-2); cyclododecanol, (Aldrich #C9,740-7); (2) 4-tert-butyl cyclohexanol, (Aldrich #B9,200-1); (3) 3-aminomethyl-3,5,5-trimethyl cyclohexanol, (Aldrich #19,479-4); (4) 2,2,6,6-tetrachloro cyclohexanol, (Aldrich #18,681-3); (5) cycloalkane methanol where the number of carbons in the alkane chain vary from 5 to about 12 such as cyclopentane methanol, (Aldrich #10,398-5); cyclohexane methanol, (Aldrich #C10,580-5); cycloheptane methanol, (Aldrich #13,865-7); cyclododecane methanol, (Aldrich #11,224-0), (6) dicyclohexylmethanol, (Aldrich #31,772-1); (7) 3-cyclohexyl-1-propanol, (Aldrich #30,440-9); (8) 2-amino-3-cyclohexyl-1-propanol, (Aldrich #42,161-8); (9) (S)-2-(tert-butoxycarbonylamino)-3-cyclohexyl-1-propanol, (Aldrich #42,169-3); (10) cycloalkane diol where the number of carbons in the alkane chain vary from about 5 to about 8 such as 1,2-cyclopentanediol, (Aldrich #36,144-5); 1,3-cyclohexanediol, (Aldrich #C10,110-9); 1,2-cyclohexane diol, (Aldrich #36,126-14,171-2); 1,4-cyclohexane diol, (Aldrich #C10,120-6); cyclooctanediol, (Aldrich #17,903-5; 36,223-9); (11) cis-3,5-cyclohexadiene-1,2diol, (Aldrich #36,506-8); (12) .rho.-methane-3,8-diol, (Aldrich #38,404-6; 38,405-4); (13) cyclohexane dimethanol, (Aldrich #12,559-8; Aldrich #18,908-1); (14) 1,3-dioxane-5,5-dimethanol, (Aldrich #22,062-0); (15) 3-cyclohexene1,1-dimethanol, (Aldrich #16,215-9); and (16) piperidine methanol, (Aldrich #15,522-5; (Aldrich #15,523-3);

(B) linear alcohols such as (1) alkyl alcohols where the number of carbons in the alkyl chain vary from 6 to 22 such as hexyl alcohol, (Aldrich #H1330-3); heptyl alcohol, (Aldrich #H280-5); octyl alcohol, (Aldrich #29,324-5); nonyl alcohol, (Aldrich #13,121-0); decylalcohol, (Aldrich #23,976-3); undecyl alcohol, (Aldrich #U100-1); 1-dodecanol, (Aldrich #12,679-9); 1-tetra decanol, (Aldrich #18,538-8); 1-pentadecanol, (Aldrich #41,222-8); 1-hexadecanol, (Aldrich #25,874-1); 1-eicosanol, (Aldrich #23,449-4); 1-docosanol, (Aldrich #16,910-2); (2) alkane diols where the number of carbons in the alkane chain vary from 5 to 14 such as 1,5-pentane diol, (Aldrich #P770-3); 1,6-hexane diol, (Aldrich #H1,180-7); 1,7-heptane diol, (Aldrich #H220-1); 1,2-octane diol, (Aldrich #21,370-5); 1,8-octane diol, (Aldrich #O,330-3); 1,9-nonane diol, (Aldrich #N2,960-0); 1,10-decane diol, (Aldrich #D,120-3); 1,2-decane diol, (Aldrich #26,032-0); 1,2-dodecane diol, (Aldrich #21,372-1); 1,12-dodecane diol, (Aldrich #D22,130-9); 1,2-tetradecane diol, (Aldrich #26,029-0); 1,14-tetradecane diol, (Aldrich #29,901-4); (3) 5-amino-1-pentanol, (Aldrich #12,304-8); (4) nitromethane trispropanol, (Aldrich #36,153-4); (5) 6-amino-1-hexanol, (Aldrich #A5,645-0); (6) 11-bromo-1-undecanol, (Aldrich #18,413-6); (7) 12-bromo-1-dodecanol, (Aldrich #22,467-7); (8) 2-methyl-2-propyl-1,3-propane diol, (Aldrich #M7,520-9); (9) 2,2-diethyl-1,3-propanediol, (Aldrich #D10,000-5); (10) 2-(hydroxymethyl)-1,3-propanediol, (Aldrich #39,365-7); (11) 2,2,4-trimethyl1,3-pentanediol, (Aldrich #32,722-0); (12) 2-butyne-1,4-diol, (Aldrich #B10,320-9); (13) (.+-.)-3,6-dimethyl-4-octyne-3,6-diol, (Aldrich #27,840-8); (14) 3,6-dithia-1,8-octanediol, (Aldrich #23,533-4); and (15) 2,4,7,9-tetramethyl-5-decyne-4,7-diol, (Aldrich #27,838-6);

(C) amino alcohols such as (1) 2-(2-aminoethoxy)ethanol, (Aldrich #A5,405-9); (2) 2-(2-amino ethylamino) ethanol, (Aldrich #12,758-2); (3) amino-1-propanol, (Aldrich #23,886-4; 29,768-2; 19,217-1; A7,620-6; 23,984-4); (4) 2-amino-1-butanol, (Aldrich #A4,380-6); (5) 4-amino-1-butanol, (Aldrich #17,833-0); (6) 2-amino-3-methyl-1-butanol, (Aldrich #18,483-7); (7) DL-2-amino-1-hexanol, (Aldrich #23,767-1); and (8) (S)-(-)-N-(tert-butoxycarbonyl) leucinol, (Aldrich #44,119-8);

(D) aromatic alcohols such as (1) alkyl benzyl alcohol where the number of carbon atoms in the alkyl group vary from 0 to 8 such as benzyl alcohol, (Aldrich #10,800-6); 3-methyl benzyl alcohol, (Aldrich #18,821-2); 4-methyl benzyl alcohol, (Aldrich #12,780-9); (14) 2-phenyl benzyl alcohol, (Aldrich #18,882-4); 2-phenethyl benzyl alcohol, (Aldrich #18,478-0); (2) alkoxy and aryloxy benzyl alcohols where the number of carbons in the alkoxy groups vary from 1 to 4 such as 2-methoxy benzyl alcohol, (Aldrich #M1,080-8); 3-methoxybenzyl alcohol, (Aldrich #M1,100-6); 4-methoxy benzyl alcohol, (Aldrich #13,690-5); 2-ethoxy benzyl alcohol, (Aldrich #19,066-7); 4-ethoxy benzyl alcohol, (Aldrich #19,047-0); 4-butoxy benzyl alcohol, (Aldrich #18,424-1); and in the aryloxy groups these vary from 6 to 8 such as 3-benzyloxy benzyl alcohol (3) alkyl alkyl benzyl alcohols where the number of carbons in the alkyl varies from 1 to 4 such as 2,4-dimethyl benzyl alcohol, (Aldrich #18,878-6); 2,5-dimethyl benzyl alcohol, (Aldrich #18,932-4); 3,5-dimethyl benzyl alcohol, (Aldrich #19,999-0); 3,4-dimethyl benzyl alcohol, (Aldrich #18,879-4); (4) 2-amino-3-methyl benzyl alcohol, (Aldrich #33,419-7); 5) alkoxy alkoxy benzyl alcohols where the number of carbon atoms in the alkoxy group varies from 1 to 4 such as 2,4-dimethoxy benzyl alcohol, Aldrich #15,963-8); 3,5-dimethoxy benzyl alcohol, (Aldrich #19,165-5); 2,3-dimethoxy benzyl alcohol, (Aldrich #12,631-4); 3-ethoxy-4-methoxy benzyl alcohol, (Aldrich #30,790-4); 4-ethoxy-3-methoxy benzyl alcohol, (Aldrich #18,914-6); (6) 2-hydroxy-3-methoxy benzyl alcohol, (Aldrich #30,596-0); (7) 3,4,5-trimethoxy benzyl alcohol, (Aldrich #T7,000-9);

(E) phenyl alcohol derivatives such as (1) phenylpropanol, (Aldrich #P3,080-2; Aldrich #14,085-6), (2) 3-(4-hydroxy phenyl)-1-propanol, (Aldrich #19,741-6); (3) (S)-(-)-1-phenyl-1-butanol, (Aldrich #31,731-4); (4) 2-amino-1-phenyl ethanol, (Aldrich #A7,240-5); (5) 3,4-dimethoxy phenethyl alcohol, (Aldrich #19,765-3); (6) 2-phenyl-1,2-propane diol, (Aldrich #21,376-4); (7) 3-phenoxy-1,2-propane diol, (Aldrich #10,819-7); (8) 3-methoxy catechol, (Aldrich #M1,320-3); (9) benzhydrol, (Aldrich #B,485-4); (10) methyl benzhydrol, (Aldrich #18,995-2; Aldrich #18,996-0), (11) phenethylalcohol, (Aldrich #P1,362-2); (12) 4-methoxy phenethyl alcohol, (Aldrich #15,418-0); (13) 2-hydroxy phenethyl alcohol, (Aldrich #18,824-7; Aldrich #19,902-8); (14) 2-amino phenethyl alcohol, (Aldrich #19,260-0); and the like.

Lightfastness compound or component examples that primarily protect the developed images from ultra violet light degradation include (1) N-p-ethoxycarbonylphenyl)-N'-ethyl-N'-phenylformadine, Givaudan Corporation, (2) 1,1-(1,2-ethane-diyl) bis(3,3,5,5-tetramethyl piperazinone), Goodrich Chemicals, (3) 2,2,4-trimethyl-1,2-hydroquinoline, Mobay Corporation, (4) 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, Monsanto-Chemicals, (5) 2,4,6-tris-(N-1,4-dimethylpentyl-4-phenylenediamino)-1,3,5-triazine, Uniroyal Corporation; (6) 2-(4-benzoyl-3-hydroxy phenoxy)ethylacrylate, (7) 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl) succinimide, (8) 2-dodecyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)succinimide, (9) N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecyl succinimide, all four available from Aldrich Chemicals; (10) 2,2,6,6-tetramethyl-4-piperidinyl/.beta.,.beta.,.beta.',.beta.'-tetramethy l-3,9-(2,4,8,10-tetraoxospiro(5,5)-undecane) diethyl]-1,2,3,4-butane tetracarboxylate, (11) [1,2,2,6,6-pentamethyl-4-piperidinyl/.beta.,.beta.,.beta.',.beta.'-tetrame thyl-3,9-(2,4,8,10-tetraoxo-spiro-(5,5)undecane) diethyl]-1,2,3,4-butanetetra carboxylate, (12) [2,2,6,6-tetra methyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate; (13) nickel dibutyl dithio carbamate, available as UV-Chek AM-105, from Ferro Corporation.

Examples of lightfast antioxidants which primarily protect the inks from thermal degradation include (1) antimony dialkyl phosphorodithioate, (2) molybdenum oxysulfide dithio carbamate, both available from Vanderbilt Corporation, (3) (nickel-bis(o-ethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, Ciba Geigy Corporation, (4) tetra sodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, American Cyanamid Corporation, and the like.

Suitable colorants, present in an effective amount generally of from about 1 to about 20 percent by weight, include pigments and dyes, with solvent dyes being preferred. As dyes or pigments there may be selected a component that it is capable of being dispersed or dissolved in the vehicle and is compatible with the other ink components. Colorants include pigments, dyes, mixtures thereof, mixtures of dyes, mixtures of pigments, and the like.

Examples of pigments include Violet Toner VT-8015 (Paul Uhlich), Paliogen Violet 5100 (BASF), Paliogen Violet 5890 (BASF), Permanent Violet VT 2645 (Paul Uhlich), Heliogen Green L8730 (BASF), Argyle Green XP-111-S (Paul Uhlich), Brilliant Green Toner GR 0991 (Paul Uhlich), Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada), E.D. Toluidine Red (Aldrich), Lithol Rubine Toner (Paul Uhlich), Lithol Scarlet 4440 (BASF), Bon Red C (Dominion Color Company),Royal Brilliant Red RD-8192 (Paul Uhlich), Oracet Pink RF (Ciba-Geigy), Paliogen Red 3871K (BASF), Paliogen Red 3340 (BASF), Lithol Fast Scarlet L4300 (BASF), Heliogen Blue L6900, L7020 (BASF), Heliogen Blue K6902, K6910 (BASF), Heliogen Blue D6840, D7080 (BASF), Sudan Blue OS (BASF), Neopen Blue FF4012 (BASF), PV Fast Blue B2G01 (American Hoechst), Irgalite Blue BCA (Ciba-Geigy), Paliogen Blue 6470 (BASF), Sudan III (Red Orange), (Matheson, Colemen Bell), Sudan II (Orange), (Matheson, Colemen Bell), Sudan Orange G (Aldrich),Sudan Orange 220 (BASF), Paliogen Orange 3040 (BASF), Ortho Orange OR 2673(Paul Uhlich), Paliogen Yellow 152,1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol Yellow 1840 (BASF), Novoperm Yellow FGL (Hoechst), Permanent Yellow YE 0305 (Paul Uhlich), Lumogen Yellow D0790 (BASF), Suco-Yellow L1250 (BASF), Suco-Yellow D1355 (BASF), Suco Fast Yellow D1355, D1351 (BASF), Hostaperm Pink E (American Hoechst), Fanal Pink D4830 (BASF), Cinquasia Magenta (Du Pont), Paliogen Black L0084 (BASF), Pigment Black K801 (BASF), and carbon blacks such as REGAL 330.RTM. (Cabot), Carbon Black 5250, Carbon Black 5750(Columbia Chemical Company).

Examples of dyes include Pontamine; Food Black 2; Carodirect Turquoise FBL Supra Conc. (Direct Blue 199), available from Carolina Color and Chemical; Special Fast Turquoise 8 GL Liquid (Direct Blue 86), available from Mobay Chemical; Intrabond Liquid Turquoise GLL (Direct Blue 86), available from Crompton and Knowles; Cibracron Brilliant Red 38-A (Reactive Red 4), available from Aldrich Chemical; Drimarene Brilliant Red X-2B (Reactive Red 56), available from Pylam, Inc.; Levafix Brilliant Red E-4B, available from Mobay Chemical; Levafix Brilliant Red E6-BA, available from Mobay Chemical; Procion Red H8B (Reactive Red 31), available from ICI America; Pylam Certified D&C Red #28 (Acid Red 92), available from Pylam; Direct Brill Pink B Ground Crude, available from Crompton and Knowles; Cartasol Yellow GTF Presscake, available from Sandoz, Inc.; Tartrazine Extra Conc. (FD&C Yellow #5, Acid Yellow 23), available from Sandoz, Inc.; Carodirect Yellow RL (Direct Yellow 86), available from Carolina Color and Chemical; Cartasol Yellow GTF Liquid Special 110, available from Sandoz, Inc.; D&C Yellow #10 (Acid Yellow 3), available from Tricon; Yellow Shade 16948, available from Tricon; Basacid Black X 34, available from BASF; Carta Black 2GT, available from Sandoz, Inc.; and the like. Particularly preferred are solvent dyes, and within the class of solvent dyes, spirit soluble dyes are preferred because of their compatibility with the vehicles and dye leveling agents of the present application. Examples of suitable spirit solvent dyes include Neozapon Red 492 (BASF), Orasol Red G (Ciba-Geigy), Direct Brilliant Pink B (Crompton-Knolls), Aizen Spilon Red C-BH (Hodogaya Chemical Company), Kayanol Red 3BL (Nippon Kayaku Company). Levanol Brilliant Red 3BW (Mobay Chemical Company), Levaderm Lemon Yellow (Mobay Chemical Company), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (Hodogaya Chemical Company), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (Sandoz), Pergasol Yellow CGP (Ciba-Geigy), Orasol Black RLP (Ciba-Geigy), Savinyl Black RLS (Sandoz), Dermacarbon 2GT (Sandoz), Pyrazol Black BG (ICI), Morfast Black Conc. A (Morton-Thiokol), Diaazol Black RN Quad (ICI), Orasol Blue GN (Ciba-Geigy), Savinyl Blue GLS (Sandoz), Luxol Blue MBSN (Morton-Thiokol), Sevron Blue 5GMF (ICI), Basacid Blue 750 (BASF), and the like.

The inks of the present invention can be prepared by any suitable method. For example, a colored phase-change ink composition can be prepared by mixing 65 percent by weight of the solid carbamate or thiourea additive having an acoustic-loss value of less than about 60 dB/mm less than about 40 dB/mm and a melting point of point of between about 60 to about 120.degree. C.; 20 percent by weight of the alcohol compound having a melting point between about 25.degree. C. to about 90.degree. C., 5 percent by weight of a lightfastness UV absorber, 5 percent by weight of lightfastness antioxidant and 5 percent by weight of a colorant. The resulting mixture can then be heated to a temperature of about 120.degree. C. and stirred for a period of about 60 minutes until it forms a homogeneous solution, and subsequently was cooled to 25.degree. C.

The inks of the present invention are particularly suitable for printing processes wherein the substrate, such as paper, transparency material, or the like, is heated during the printing process to facilitate formation of the liquid crystalline phase within the ink. When transparency substrates are employed, temperatures typically are limited to a maximum of about 100.degree. C. to about 110.degree. C., since the polyester typically employed, as the base sheet in transparency sheets tends to deform at higher temperatures. Specially formulated transparencies and paper substrates can, however, tolerate higher temperatures, and frequently are suitable for exposure to temperatures of 150.degree. C. or even 200.degree. C. in some instances. Typical heating temperatures are from about 40.degree. C. to about 140.degree. C., and preferably from about 60.degree. C. to about 95.degree. C., although the temperature can be outside these ranges.

The inks of the present invention are particularly suitable for use in acoustic ink jet printing processes. In acoustic ink jet printing, reference a number of the copending applications and patents recited here, the disclosures of which have been totally incorporated herein by reference, an acoustic beam exerts a radiation pressure against objects upon which it impinges. Thus, when an acoustic beam impinges on a free surface of the ink 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, reference, for example, IBM Technical Disclosure Bulletin, Vol. 16, No. 4, September 1973, pages 1168 to 1170, the disclosure of which is totally incorporated herein by reference. 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 an important 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 since usually there are no nozzles to clog. 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. Acoustic ink printers embodying printheads comprising acoustically illuminated spherical focusing lenses can print precisely positioned pixels (picture elements) at resolutions which are sufficient for high quality printing of relatively complex images. It has also been determined 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 (i) single lo row, sparse arrays for hybrid forms of parallel/serial printing to (ii) multiple row staggered arrays with individual ejectors for each of the pixel positions or addresses within a pagewidth image field (i.e., single ejector/pixel/line) for ordinary line printing. Inks suitable for acoustic ink jet printing typically are liquid at ambient temperatures (i.e., about 25.degree. C.), however 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. Pat. No. 4,308,547, U.S. Pat. No. 4,697,195, U.S. Pat. No. 5,028,937, U.S. Pat. No. 5,041,849, U.S. Pat. No. 4,751,529, U.S. Pat. No. 4,751,530, U.S. Pat. No. 4,751,534, U.S. Pat. No. 4,801,953, and U.S. Pat. No. 4,797,693, the disclosures of each of which are totally incorporated herein by reference. 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, the disclosure of which is totally incorporated herein by reference.

Acoustic-loss measurements recited can be measured as follows: samples of various liquid vehicles and solid compounds are placed between the two transducers, with the temperature set at 150.degree. C. The samples are allowed to equilibrate at 150.degree. C. for five minutes, and the two transducers are brought together to maximize the acoustic signal. The amplitude and the position of the signals are recorded, and the transducers are separated by a distance varying from about 25.4 microns about 125.4 microns recording each time the amplitude and the position of the signal. Each measurement is performed three times and three samples of the same material are measured. The attenuation dB/mm was then calculated by ratioing the amplitude values obtained at different separation distances. The liquid measured carbamate compounds had dB/mm values of about 15 to 40 whereas the solid carbamate compounds had dB/mm values of about 35 to about 65. A value of less than about 80 dB/mm for the ink composition is an important need for acoustic jetting of these inks.

The optical density values of black ink were measured to be between about 1.55 to about 1.65, cyan between about 1.50 to about 1.6, magenta between about 1.35 to about 1.45, and yellow between about 0.90 to about 1.00, generated by a Pacific Spectrograph Color System. The system consists of two major components, an optical sensor and a data terminal. The optical sensor employs a 6-inch integrating sphere to provide diffuse illumination and 8 degrees viewing. This sensor can be used to measure both transmission and reflectance samples. When reflectance samples are measured, a specular component may be included. A high resolution, full dispersion, grating monochromator was used to scan the spectrum from 380 to 720 nanometers. The data terminal features a 12 inch CRT display, numerical keyboard for selection of operating parameters and the entry of tristimulus values, and an alphanumeric keyboard for entry of product standard information p The lightfast values of ink jet images between about 90 to 100 percent and preferably between about 95 to 100 percent were measured in the Mark V Lightfast Tester obtained from Microscal Company, London, England; the waterfast values of the ink jet images of, for example, between about 90 to about 100 percent and preferably between about 95 to about 100 percent were obtained from the above optical density data and after washing with water at 25.degree. C. for five minutes; the average width of the creased image due to pressure was obtained on colored and black solid area images printed on paper by (a) folding inwards the printed area of the image, (b) passing on the folded image a standard TEFLON.RTM. coated copper roll 2 inches in width, 3 inches in outer diameter, 2.25 inches in inner diameter and weighing 860 grams, (c) unfolding the paper and wiping the loose toner from the creased imaged surface with a cotton swab, (d) measuring the average width of the toner free creased area with an image analyzer; and the haze values of images of, for example, between about 10 to about 30 and preferably between about 10 to about 20 were measured on images printed on uncoated polyester such as MYLAR.RTM. with a Haze meter XL-211, HAZEGARD.RTM. System obtained from Pacific Scientific Company.

Specific embodiments of the invention will now be described in detail. These examples are intended to be illustrative, and the invention is not limited to the materials, conditions, or process parameters set forth in these embodiments. All parts and percentages are by weight unless otherwise indicated.

A black phase-change ink composition was prepared by mixing 65 percent by weight of the solid additive tert-butyl carbamate (Aldrich #16,739-8) having a melting point of 106.degree. C. and an acoustic-loss value of 40 dB/mm; 20 percent by weight of the gloss and crease improving alcohol compound 3-cyclohexene-1,1-dimethanol, (Aldrich #16,215-9) with an acoustic-loss value of 25 dB/mm and a melting point of 89.degree. C.; 5 percent by weight of the UV absorber 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl) succinimide, (Aldrich #41,317-8); 5 percent by weight of the antioxidant tetra sodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, Aerosol 22N, American Cyanamid Corporation, and 5 percent by weight of the colorant Orasol Black RLP (Ciba-Geigy). The mixture was heated to a temperature of about 120.degree. C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently, the mixture was cooled to 25.degree. C. This black ink had an acoustic loss value of 39 dB/mm and a viscosity measured with a known viscometer of 5.2 cps at 150.degree. C.

A blue phase-change ink composition was prepared by mixing 65 percent by weight of benzyl (S)-(-)-tetrahydro-5-oxo-3-furanyl carbamate, (Aldrich #41,924-9) having a melting point of 104.degree. C. and an acoustic-loss value of 38 dB/mm; 20 percent by weight of dicyclohexylmethanol, (Aldrich #31,772-1), with an acoustic-loss value of 33 dB/mm and a melting point of 62.degree. C.; 5 percent by weight of the UV absorber 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl) succinimide, (Aldrich #41,317-8), 5 percent by weight of the antioxidant tetra sodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, Aerosol 22N, American Cyanamid Corporation, and 5 percent by weight of the colorant Sudan Blue (BASF). The mixture was heated to a temperature of about 120.degree. C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently it was cooled to 25.degree. C. This blue ink had an acoustic loss value of 39 dB/mm and a viscosity of 5.25 cps at 150.degree. C.

A yellow phase-change ink composition was prepared by mixing 65 percent by weight of the tert-butyl-(2,4-dinitrophenoxy) carbamate, (Aldrich #33, 305-0) having a melting point of 79.degree. C. and an acoustic-loss value of 37 dB/mm; 20 percent by weight of 1,2-tetradecane diol, (Aldrich #26,029-0) having an acoustic-loss value of 40 dB/mm and a melting point of 63.degree. C.; 5 percent by weight of the UV absorber 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl) succinimide (Aldrich #41,317-8), 5 percent by weight of the antioxidant tetrasodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, Aerosol 22N, American Cyanamid Corporation, and 5 percent by weight of the colorant Sudan yellow (BASF). The resulting mixture was heated to a temperature of about 100.degree. C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently was cooled to 25.degree. C. This yellow ink had an acoustic loss value of 38 dB/mm and a viscosity of 5.05 cps at 150.degree. C.

A red phase-change ink composition was prepared by mixing 65 percent by weight of the cyanomethyl-N, N-dimethyl dithiocarbamate (Aldrich #28, 054-2) having a melting point of 75.degree. C. and an acoustic-loss value of 37 dB/mm; 20 percent by weight of 3,6-dithia-1,8-octanediol, (Aldrich #23,533-4) having an acoustic-loss value of 35 dB/mm and a melting point of 64.degree. C.; 6 percent by weight of the UV absorber 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl) succinimide, (Aldrich #41,317-8), 5 percent by weight of the antioxidant tetra sodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, Aerosol 22N, American Cyanamid Corporation, and 5 percent by weight of the colorant Sudan Red (BASF). The mixture was heated to a temperature of about 120.degree. C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently it was cooled to 25.degree. C. This red ink had an acoustic loss value of 38 dB/mm and a viscosity of 5.02 cps at 150.degree. C.

Each of the above four ink was incorporated into an acoustic ink jet printing test fixture utilizing the ejection mechanism disclosed in J. Appl. Phys. 65(9), 1 May 1989, and references therein, the disclosure of which are totally incorporated herein by reference. A jetting frequency of 160 MHz was used to generate drops of about 2 picoliters, up to 12 drops per pixel at 600 spi. The images formed on paper exhibited excellent color quality with optical density values of 2.20 (black), 1.85 (cyan), 1.95 (magenta), 1.40 (yellow), sharp edges, with lightfast values of black (98.5 percent), cyan (99 percent), magenta (96 percent), yellow (99 percent), waterfast values of black (98.5 percent), cyan (99 percent), magenta (99 percent), yellow (100 percent). The crease values of black, cyan, magenta and yellow ink images were measured at black (19), cyan (18), magenta (16), yellow (18). The images formed on uncoated MYLAR.TM. exhibited excellent color quality with optical density values of 1.58 (black), 1.53 (cyan), 1.40 (magenta), 0.95 (yellow), sharp edges. The haze values of black, cyan, magenta and yellow ink images were measured at black (21), cyan (22), magenta (12), yellow (23), and the gloss values of the images were measured at 83 for all inks.

A black phase-change ink composition was prepared by mixing 65 percent by weight ethyldiphenyl carbamate, (Aldrich #37,291-9) having a melting point of 71.degree. C. and an acoustic-loss value of 36 dB/mm; 20 percent by weight of benzhydrol, (Aldrich #B,485-4); having an acoustic-loss value of 37 dB/mm and a melting point of 66.degree. C.; 5 percent by weight of the UV absorber [1,2,2,6,6-pentamethyl-4-piperidinyl/.beta.,.beta.,.beta.',.beta.'-tetrame thyl-3,9-(2,4,8,10-tetraoxo spiro (5,5) undecane)diethyl]-1,2,3,4-butane tetracarboxylate, Mixxim HALS 63, Fairmount Corporation, 5 percent by weight of the antioxidant tetra sodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, Aerosol 22N, American Cyanamid Corporation, and 5 percent by weight of the colorant Orasol Black RLP (Ciba-Geigy). The resulting mixture was heated to a temperature of about 120.degree. C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently it was cooled to 25.degree. C. This black ink had an acoustic loss value of 39 dB/mm and a viscosity of 5.15 cps at 150.degree. C.

A blue phase-change ink composition was prepared by mixing 65 percent by weight of the solid additive 1-allyl-3-(2-hydroxyethyl)-2-thiourea, (Aldrich #A3, 280-2), having a melting point of 78.degree. C. and an acoustic-loss value of 36 dB/mm; 20 percent by weight of the gloss and crease improving alcohol compound 1-eicosanol, (Aldrich #23,449-4 having an acoustic-loss value of 39 dB/mm and a melting point of 65.degree. C.; 5 percent by weight of the UV absorber 2-dodecyl-N-(2,2,6,6-tetra methyl-4-piperidinyl) succinimide, (Aldrich #41,317-8), 5 percent by weight of the antioxidant tetra sodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, Aerosol 22N, American Cyanamid Corporation, and 5 percent by weight of the colorant Neopan blue (American Hoechst). The mixture resulting was heated to a temperature of about 120.degree. C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently it was cooled to 25.degree. C. This blue ink had an acoustic loss value of 39 dB/mm and a viscosity of 5.35 cps at 150.degree. C.

A yellow phase-change ink composition was prepared by mixing 65 percent by weight of the solid additive 1,1,3,3-tetramethyl-2-thiourea (Aldrich #11,516-9), having a melting point of 76.degree. C. and an acoustic-loss value of 35 dB/mm; 20 percent by weight of the gloss and crease improving alcohol compound 2,2-diethyl-1,3-propanediol, (Aldrich #D10,000-5); having an acoustic-loss value of 36 dB/mm and a melting point of 46.degree. C.; 5 percent by weight of the UV absorber 2-dodecyl-N-(2,2,6,6-tetra methyl-4-piperidinyl) succinimide, (Aldrich #41,317-8), 5 percent by weight of the antioxidant tetrasodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, Aerosol 22N, American Cyanamid Corporation, and 5 percent by weight of the colorant Sudan Yellow (BASF). The resulting mixture was heated to a temperature of about 120.degree. C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently it was cooled to 25.degree. C. This yellow ink had an acoustic loss value of 38 dB/mm and a viscosity of 5.45 cps at 150.degree. C.

A red phase-change ink composition was prepared by mixing 65 percent by weight of the solid additive tert-butyl carbamate, (Aldrich #16,739-8) having a melting point of 106.degree. C. and an acoustic-loss value of 40 dB/mm; 20 percent by weight of the gloss and crease improving alcohol compound dicyclohexylmethanol, (Aldrich #31,772-1); having an acoustic-loss value of 33 dB/mm and a melting point of 62.degree. C.; 5 percent by weight of the UV absorber 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl) succinimide, (Aldrich #41,317-8), 5 percent by weight of the antioxidant tetrasodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, Aerosol 22N, American Cyanamid Corporation, and 5 percent by weight of the colorant Hostaperm Pink E (American Hoechst). The mixture resulting was heated to a temperature of about 120.degree. C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently was cooled to 25.degree. C. This red ink had an acoustic loss value of 38 dB/mm and a viscosity of 5.12 cps at 150.degree. C.

Each of the above four inks was incorporated into an acoustic ink jet printing test fixture utilizing the ejection mechanism disclosed in J. Appl. Phys. 65(9), May 1, 1989, and references therein, the disclosure of which are totally incorporated herein by reference. A jetting frequency of 160 MHz was used to generate drops of about 2 picoliters, up to 12 drops per pixel at 600 spi. The images formed on paper exhibited excellent color quality with optical density values of 2.16 (black), 1.82 (cyan), 1.98 (magenta), 1.37 (yellow), sharp edges, lightfast values of black (98.5 percent), cyan (99 percent), magenta (96 percent), yellow (99 percent), waterfast values of black (100 percent), cyan (99 percent), magenta (99.5 percent), yellow (100 percent). The crease values of black, cyan, magenta and yellow ink images were measured at black (17), cyan (19), magenta (16), yellow (12). The images formed on uncoated MYLAR.TM. exhibited excellent color quality with transmitted optical density values of 1.66 (black), 1.55 (cyan), 1.46 (magenta), 0.92 (yellow), sharp edges, the haze values of the black, cyan, magenta and yellow ink images were measured at black (22), cyan (21), magenta (15), yellow (24); and the gloss values of the images were measured at 85 for the inks.

Other modifications of the present invention may occur to those of ordinary skill in the art subsequent to a review of the present application, and these modifications, including equivalents thereof, are intended to be included within the scope of the present invention.