Phase change inks containing branched triamides

0001The present invention is directed to hot melt or phase change inks. More specifically, the present invention is directed to phase change inks particularly suitable for use in phase change ink jet printers.

0002In general, phase change inks (sometimes referred to as "hot melt inks") are in the solid phase at ambient temperature, but exist in the liquid phase at the elevated operating temperature of on ink jet printing device. At the jet operating temperature, droplets of liquid ink are ejected from the printing device and, when the ink droplets contact the surface of the recording substrate, either directly or via on intermediate heated transfer belt or drum, they quickly solidify to form a predetermined pattern of solidified ink drops. Phase change inks have also been used in other printing technologies, such as gravure printing, as disclosed in, for example, <patcit id="pcit0001" dnum="US5496879A"><text>U.S. Patent 5,496,879</text></patcit> and German Patent Publications <patcit id="pcit0002" dnum="DE4205636A1"><text>DE 4205636A1</text></patcit> and <patcit id="pcit0003" dnum="DE4205713A1"><text>DE 4205713A1</text></patcit>.

0003Phase change inks for color printing typically comprise a phase change ink carrier composition which is combined with a phase change ink compatible colorant. In a specific embodiment, a series of colored phase change inks can be formed by combining ink carrier compositions with compatible subtractive primary colorants. The subtractive primary colored phase change inks can comprise four component dyes, namely, cyan, magenta, yellow and black, although the inks are not limited to these four colors. These subtractive primary colored inks can be formed by using a single dye or a mixture of dyes. For example, magenta can be obtained by using a mixture of Solvent Red Dyes or a composite block can be obtained by mixing several dyes. <patcit id="pcit0004" dnum="US4889560A"><text>U.S. Patent 4,889,560</text></patcit>, <patcit id="pcit0005" dnum="US4889761A"><text>U.S. Patent 4,889,761</text></patcit>, and <patcit id="pcit0006" dnum="US5372852A"><text>U.S. Patent 5,372,852</text></patcit>, teach that the subtractive primary colorants employed can comprise dyes from the classes of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, and Basic Dyes. The colorants can also include pigments, as disclosed in, for example, <patcit id="pcit0007" dnum="US5221335A"><text>U.S. Patent 5,221,335</text></patcit>. <patcit id="pcit0008" dnum="US5621022A"><text>U.S. Patent 5,621,022</text></patcit>, discloses the use of a specific class of polymeric dyes in phase change ink compositions.

0004Phase change inks have also been used for applications such as postal marking, industrial marking, and labelling.

0005Phase change inks are desirable for ink jet printers because they remain in a solid phase at room temperature during shipping, long term storage, and the like. In addition, the problems associated with nozzle clogging as a result of ink evaporation with liquid ink jet inks are largely eliminated, thereby improving the reliability of the ink jet printing. Further, in phase change ink jet printers wherein the ink droplets are applied directly onto the final recording substrate (for example, paper, transparency material, and the like), the droplets solidify immediately upon contact with the substrate, so that migration of ink along the printing medium is prevented and dot quality is improved.

0006Compositions suitable for use as phase change ink carrier compositions are known. Some representative examples of references disclosing such materials include <patcit id="pcit0009" dnum="US3653932A"><text>U.S. Patent 3,653,932</text></patcit>, <patcit id="pcit0010" dnum="US4390369A"><text>U.S. Patent 4,390,369</text></patcit>, <patcit id="pcit0011" dnum="US4484948A"><text>U.S. Patent 4,484,948</text></patcit>, <patcit id="pcit0012" dnum="US4684956A"><text>U.S. Patent 4,684,956</text></patcit>, <patcit id="pcit0013" dnum="US4851045A"><text>U.S. Patent 4,851,045</text></patcit>, <patcit id="pcit0014" dnum="US4889560A"><text>U.S. Patent 4,889,560</text></patcit>, <patcit id="pcit0015" dnum="US5006170A"><text>U.S. Patent 5,006,170</text></patcit>, <patcit id="pcit0016" dnum="US5151120A"><text>U.S. Patent 5,151,120</text></patcit>, <patcit id="pcit0017" dnum="US5372852A"><text>U.S. Patent 5,372,852</text></patcit>, <patcit id="pcit0018" dnum="US5496879A"><text>U.S. Patent 5,496,879</text></patcit>, European Patent Publication <patcit id="pcit0019" dnum="EP0187352A"><text>0187352</text></patcit>, European Patent Publication <patcit id="pcit0020" dnum="EP0206286A"><text>0206286</text></patcit>, German Patent Publication <patcit id="pcit0021" dnum="DE4205636A1"><text>DE 4205636A1</text></patcit>, German Patent Publication <patcit id="pcit0022" dnum="DE4205713A1"><text>DE 4205713A1</text></patcit>, and <patcit id="pcit0023" dnum="WO9404619A"><text>PCT Patent Application WO 94/04619</text></patcit>. Suitable carrier materials can include paraffins, microcrystalline waxes, polyethylene waxes, ester waxes, fatty acids and other waxy materials, fatty amide containing materials, sulfonamide materials, resinous materials made from different natural sources (tall oil rosins and rosin esters, for example), and many synthetic resins, oligomers, polymers, and copolymers.

0007While known compositions and processes are suitable for their intended purposes, a need remains for improved phase change inks. In addition, a need remains for phase change inks having ink carriers having improved miscibility with polyethylene waxes. Further, a need remains for phase change inks containing branched, rather than linear, amide carriers. Additionally a need remains for phase change inks containing amide carriers with reduced viscosity. There is also a need for phase change inks containing amide carriers having desirably low melting points compared to other amides of similar molecular weight and similar ratio of amide groups to hydrocarbon portion.

0008The present invention provides a phase change ink composition comprising (a) a colorant and (b) a carrier comprising a polyamide, wherein the polyamide component of the carrier contains at least 10 percent by weight of a branched triamide.

0009The present invention further provides a process which comprises incorporating said phase change ink into an ink jet printing apparatus, melting the ink, and causing droplets of the melted ink to be ejected in an imagewise pattern onto a recording substrate.

0010Preferred embodiments of the invention are set forth in the sub-claims.

0011The ink compositions of the present invention contain on ink carrier which comprises a polyamide, wherein the polyamide component of the carrier contains at least 10 percent by weight of a branched triamide. By "branched triamide" is meant that the structure of the triamide can be drawn so that each amide group is bonded to an atom or group of atoms contained in a branch other than that of the others, and that each amide group is in a different branch. By "each amide group is in a different branch" is meant that the triamide is not linear; by "linear" is meant a molecule wherein all three amide groups can be drawn as being in the same molecular chain or branch, such as linear triamides of the formulae <chemistry id="chem0001" num="0001"><img file="EP1514912B1_D0001.tif" /></chemistry><chemistry id="chem0002" num="0002"><img file="EP1514912B1_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP1514912B1_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP1514912B1_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP1514912B1_D0005.tif" /></chemistry> or the like. For purposes of the present invention, linear triamides include those wherein a line <u>can</u> be drawn through the three amide groups, even if one would ordinarily draw a different line. For example, a compound of the formula <chemistry id="chem0006" num="0006"><img file="EP1514912B1_D0006.tif" /></chemistry> is considered a linear compound for purposes of the present invention, because it <u>can</u> also be drawn as follows: <chemistry id="chem0007" num="0007"><img file="EP1514912B1_D0007.tif" /></chemistry> and accordingly would not be considered to be a branched triamide within the scope of the present invention. For purposes of the present invention, "branched triamines", "branched triacids", branched monoomino diacids", and "branched diamino monoacids" have similar definitions in that each of the three functional groups named can be drawn as being in a different branch from the other two.

0012Examples of suitable branched triamides include those generated from branched triamines, said branched triamides being of the formula <chemistry id="chem0008" num="0008"><img file="EP1514912B1_D0008.tif" /></chemistry> wherein R_f is (i) an alkylene group (including linear, branched, saturated, unsaturated, cyclic, substituted, and unsubstituted alkylene groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkylene group), in embodiments with at least 3, 4, 5, 15 or 21 carbon atoms and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (ii) an arylene group (including unsubstituted and substituted arylene groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the arylene group), in embodiments with at least 6, 10 or 14 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (iii) an arylalkylene group (including unsubstituted and substituted arylalkylene groups, wherein the alkyl portion of the arylalkylene group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkylene group), in embodiments with at least 7, 8 or 9 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as benzylene or the like, or (iv) an alkylarylene group (including unsubstituted and substituted alkylarylene groups, wherein the alkyl portion of the alkylarylene group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylarylene group), in embodiments with at least 7, 8 or 9 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as tolylene or the like, R_a, R_b, and R_c each, independently of the others, is (i) a hydrogen atom, (ii) an alkyl group (including linear, branched, saturated, unsaturated, cyclic, substituted, and unsubstituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in embodiments with at least 1, 2, 7 or 10 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (iii) an aryl group (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the aryl group), in embodiments with at least 6, 10 or 14 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges. (iv) an arylalkyl group (including unsubstituted and substituted arylalkyl groups, wherein the alkyl portion of the arylalkyl group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group), in embodiments with at least 6, 7 or 8 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as benzyl or the like, or (v) an alkylaryl group (including unsubstituted and substituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group), in embodiments with at least 6, 7 or 8 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as tolyl or the like, R_d, R_e, and R_f each, independently of the others, is (i) an alkyl group (including linear, branched, saturated, unsaturated, cyclic, substituted, and unsubstituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in embodiments with at least 1, 2, 6, 17 or 36 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (ii) an aryl group (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the aryl group), in embodiments with at least 6, 10 or 14 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms con be outside of these ranges, (iii) an arylalkyl group (including unsubstituted and substituted arylalkyl groups, wherein the alkyl portion of the arylalkyl group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group), in embodiments with at least 6, 7 or 8 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as benzyl or the like, or (iv) an alkylaryl group (including unsubstituted and substituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group), in embodiments with at least 6, 7 or 8 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as tolyl or the like, those generated from branched triacids, said branched triamides being of the formula <chemistry id="chem0009" num="0009"><img file="EP1514912B1_D0009.tif" /></chemistry> wherein R₂ is (i) an alkylene group (including linear, branched, saturated, unsaturated, cyclic, substituted, and unsubstituted alkylene groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkylene group), in embodiments with at least 3, 4, 5, 15 or 21 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (ii) an arylene group (including unsubstituted and substituted arylene groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the arylene group), in embodiments with at least 6, 10 or 14 carbon atoms, and in embodiments with no more than 200 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (iii) an arylalkylene group (including unsubstituted and substituted arylalkylene groups, wherein the alkyl portion of the arylalkylene group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkylene group), in embodiments with at least 7, 8 or 9 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as benzylene or the like, or (iv) an alkylarylene group (including unsubstituted and substituted alkylarylene groups, wherein the alkyl portion of the alkylarylene group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylarylene group), in embodiments with at least 7, 8 or 9 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as tolylene or the like, R_g. R_i, and R_p each, independently of the others, is (i) a hydrogen atom, (ii) an alkyl group (including linear, branched, saturated, unsaturated, cyclic, substituted, and unsubstituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in embodiments with at least 1, 2, 3, 6 or 18 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (iii) an aryl group (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the aryl group), in embodiments with at least 6, 10 or 14 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (iv) an arylalkyl group (including unsubstituted and substituted arylalkyl groups, wherein the alkyl portion of the arylalkyl group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group), in embodiments with at least 7, 8 or 9 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as benzyl or the like, or (v) an alkylaryl group (including unsubstituted and substituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group), in embodiments with at least 7, 8 or 9 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as tolyl or the like, R_h, R_k, and Rq each, independently of the others, is (i) a hydrogen atom, (ii) an alkyl group (including linear, branched, saturated, unsaturated, cyclic, substituted, and unsubstituted alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the alkyl group), in embodiments with at least 1, 2, 3, 4 or 5 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (iii) an aryl group (including unsubstituted and substituted aryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in the aryl group), in embodiments with at least 6, 7 or 8 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, (iv) an arylalkyl group (including unsubstituted and substituted arylalkyl groups, wherein the alkyl portion of the arylalkyl group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the arylalkyl group), in embodiments with at least 7, 8 or 9 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as benzyl or the like, or (v) an alkylaryl group (including unsubstituted and substituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group can be linear, branched, saturated, unsaturated, and/or cyclic, and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either may or may not be present in either or both of the alkyl portion and the aryl portion of the alkylaryl group), in embodiments with at least 7, 8 or 9 carbon atoms, and in embodiments with no more than 200, 150 or 100 carbon atoms, although the number of carbon atoms can be outside of these ranges, such as tolyl or the like, those generated from branched diamino monoacid compounds, said branched triamides being of the formula <chemistry id="chem0010" num="0010"><img file="EP1514912B1_D0010.tif" /></chemistry> wherein R₁, R_a, R_b, R_d, R_e, R_g, and R_h are as defined hereinabove, those generated from branched monoamino diacid compounds, said branched triamides being of the formula <chemistry id="chem0011" num="0011"><img file="EP1514912B1_D0011.tif" /></chemistry> wherein R₂, R_a, R_d, R_g, R_h, R_j, and R_k are as defined hereinabove, and the like, wherein the substituents on the substituted alkyl, alkylene, aryl, arylene, arylalkyl, arylalkylene, alkylaryl, and alkylarylene groups can be hydroxy groups, halogen atoms, imine groups, ammonium groups, cyano groups, pyridine groups, pyridinium groups, ether groups, aldehyde groups, ketone groups, ester groups, carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acid groups, sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups, phosphate groups, nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfone groups, azide groups, azo groups, cyanato groups, carboxylate groups, mixtures thereof, and the like, wherein two or more substituents can be joined together to form a ring.

0013In one specific embodiment, when the triamide is of the formula <chemistry id="chem0012" num="0012"><img file="EP1514912B1_D0012.tif" /></chemistry> the total number of carbon atoms in R₁ + R_a +R_b + R_c +R_d + R_e + R_f is at least 7, 10 or 12, and in embodiments no more than 500, 350, or 300, although the total number of carbon atoms can be outside of these ranges.

0014In one specific embodiment, when the triamide is of the formula <chemistry id="chem0013" num="0013"><img file="EP1514912B1_D0013.tif" /></chemistry> the total number of carbon atoms in R₂ + R_g +R_h + R_j +R_k + Rp + R_q is at least 7, 10, or 12, and in embodiments no more than 500, 350, or 300, although the total number of carbon atoms can be outside of these ranges.

0015In one specific embodiment, when the triamide is of the formula <chemistry id="chem0014" num="0014"><img file="EP1514912B1_D0014.tif" /></chemistry> the total number of carbon atoms in R₁ + R_a +R_b + R_d +R_e + R_g + R_h is at least 7, 10, or 12, and in embodiments no more than 500, 350, or 300, although the total number of carbon atoms can be outside of these ranges.

0016In one specific embodiment, when the triamide is of the formula <chemistry id="chem0015" num="0015"><img file="EP1514912B1_D0015.tif" /></chemistry> the total number of carbon atoms in R₂ + R_a +R_d + R_g +R_h + R_j + R_k is at least 7, 10, or 12, and in embodiments no more than 500, 350, or 300, although the total number of carbon atoms can be outside of these ranges.

0017It must be emphasized that not all of the amide groups in the first formula need to be directly bonded to the same atom in the R₁ or R₂ group, and in one specific embodiment of the present invention, each amide group is bonded to a different atom in the R₁ or R₂ group.

0018Compounds of the formula <chemistry id="chem0016" num="0016"><img file="EP1514912B1_D0016.tif" /></chemistry> can be prepared by reacting a branched triamine with at least one monoacid. When only one monoacid is used, the reaction proceeds as follows: <chemistry id="chem0017" num="0017"><img file="EP1514912B1_D0017.tif" /></chemistry> When a mixture of monoacids is used, such as a mixture containing R_d-COOH, R_e-COOH, and R_f-COOH, products of the formula <chemistry id="chem0018" num="0018"><img file="EP1514912B1_D0018.tif" /></chemistry> can be obtained. The triamine and monoacid are present in any desired or effective relative amounts, in embodiments at least 3, 3.1 or 4 moles of monoacid per every one mole of triamine, and in embodiments no more than 30, 25, 20 or 5 moles of monoacid per every one mole of triamine, although the relative amounts can be outside of these ranges.

0019Compounds of the formula <chemistry id="chem0019" num="0019"><img file="EP1514912B1_D0019.tif" /></chemistry> can be prepared by reacting a branched triacid with at least one monoamine. When only one monoamine is used, the reaction proceeds as follows: <chemistry id="chem0020" num="0020"><img file="EP1514912B1_D0020.tif" /></chemistry> When a mixture of monoamines is used, such as a mixture containing <chemistry id="chem0021" num="0021"><img file="EP1514912B1_D0021.tif" /></chemistry> products of the formula <chemistry id="chem0022" num="0022"><img file="EP1514912B1_D0022.tif" /></chemistry> can be obtained. The triacid and monoamine are present in any desired or effective relative amounts, in embodiments at least 2.5, 2.9 or 3 moles of monoamine per every one mole of triacid, and in embodiments no more than 15, 12, 10 or 4 moles of monoamine per every one mole of triacid, although the relative amounts can be outside of these ranges.

0020The compounds of the formulae <chemistry id="chem0023" num="0023"><img file="EP1514912B1_D0023.tif" /></chemistry> and <chemistry id="chem0024" num="0024"><img file="EP1514912B1_D0024.tif" /></chemistry> can be prepared by similar methods, in one embodiment in a process in which the amine group or groups are first protected by any desired or effective method, such as reaction with phosgene derivatives of the formula <chemistry id="chem0025" num="0025"><img file="EP1514912B1_D0025.tif" /></chemistry> followed by reacting the acid group or groups with the monoamine, followed by deprotection of the protected amine groups, followed by reacting the amine group or groups with the monoacid.

0021The reaction between the acid and the amine can take place neat in the absence of a solvent, or, optionally in the presence of a solvent. Particularly desirable solvents are those that can form an azeotrope with water and carry out the water byproduct of the amidation reaction, such as toluene, xylene, or the like. When present, the solvent is present in any desired or effective amount, in one embodiment up to 5 parts by weight per every one part by weight of the total reactants, although the amount can be outside of this range. When no solvent is used, it can be useful to remove the water byproduct from the reaction mixture by other means, such as by blowing a gas through the reaction mixture, pulling a vacuum on the reaction mixture, or the like to drive the reaction to completion.

0022While not required, the amine and the acid can be reacted in an inert atmosphere, particularly when it is desired to reduce or eliminate color in the triamide product.

0023The amine and the acid are admixed with each other. In one specific embodiment, the acid is heated, followed by addition of the amine to the heated acid, which enables production of less colored products, although the reaction can also be performed by adding the acid to the amine.

0024The amine and the acid are allowed to react at any desired or effective temperature, in embodiments at least 120°C, 150°C, or 180°C, and in embodiments no more than 300°C, 260°C, or 240°C, although the reaction temperature can be outside of these ranges.

0025The amine and the acid are allowed to react for any desired or effective period of time, in embodiments at least 1, 3 or 4 hours, and in embodiments no more than 12, 10 or 8 hours, although the reaction time can be outside of these ranges.

0026Optionally, the reaction mixture can also contain ingredients that do not react with the acid, the amine, or the reaction product thereof, such as antioxidants commonly used in phase change inks (which, when present in the reaction mixture, can in some cases reduce coloration of the reaction product), waxes, such as polyethylene waxes commonly used in phase change inks, or the like.

0027The triamide can, if desired, function as the sole ink carrier. Optionally, the triamide can be admixed with other materials to create an ink carrier. Any desired or effective carrier composition can be used. Examples of suitable ink carrier materials include fatty amides, such as monoamides, tetra-amides, mixtures thereof, and the like. Further information on fatty amide carrier materials is disclosed in, for example, <patcit id="pcit0024" dnum="US4889560A"><text>U.S. Patent 4,889,560</text></patcit>, <patcit id="pcit0025" dnum="US4889761A"><text>U.S. Patent 4,889,761</text></patcit>, <patcit id="pcit0026" dnum="US5194638A"><text>U.S. Patent 5,194,638</text></patcit>, <patcit id="pcit0027" dnum="US4830671A"><text>U.S. Patent 4,830,671</text></patcit>, <patcit id="pcit0028" dnum="US6174937B"><text>U.S. Patent 6,174,937</text></patcit>, <patcit id="pcit0029" dnum="US5372852A"><text>U.S. Patent 5,372,852</text></patcit>. <patcit id="pcit0030" dnum="US5597856A"><text>U.S. Patent 5,597,856</text></patcit>, <patcit id="pcit0031" dnum="US6174937B"><text>U.S. Patent 6,174,937</text></patcit>, and British Patent <patcit id="pcit0032" dnum="GB2238792A"><text>GB 2 238 792</text></patcit>. When the ink carrier contains other polyamides, such as tetra-amides or the like, the polyamide component of the carrier contains at least 10 percent by weight of the branched triamide. In specific embodiments, the polyamide component of the ink carrier contains at least 20, 50, 60, 70, 80, 90 or 100 percent by weight of the branched triamide.

0028Also suitable as phase change ink carrier materials are isocyanate-derived resins and waxes, such as urethane isocyanate-derived materials, urea isocyanate-derived materials, urethane/urea isocyanate-derived materials, mixtures thereof, and the like. Further information on isocyanate-derived carrier materials is disclosed in, for example, <patcit id="pcit0033" dnum="US5750604A"><text>U.S. Patent 5,750,604</text></patcit>, <patcit id="pcit0034" dnum="US5780528A"><text>U.S. Patent 5,780,528</text></patcit>, <patcit id="pcit0035" dnum="US5782966A"><text>U.S. Patent 5,782.966</text></patcit>, <patcit id="pcit0036" dnum="US5783658A"><text>U.S. Patent 5,783,658</text></patcit>, <patcit id="pcit0037" dnum="US5827918A"><text>U.S. Patent 5,827,918</text></patcit>, <patcit id="pcit0038" dnum="US5830942A"><text>U.S. Patent 5,830,942</text></patcit>, <patcit id="pcit0039" dnum="US5919839A"><text>U.S. Patent 5,919,839</text></patcit>, <patcit id="pcit0040" dnum="US6255432B"><text>U.S. Patent 6,255,432</text></patcit>, <patcit id="pcit0041" dnum="US6309453B"><text>U.S. Patent 6,309,453</text></patcit>, British Patent <patcit id="pcit0042" dnum="GB2294939A"><text>GB 2 294 939</text></patcit>, British Patent <patcit id="pcit0043" dnum="GB2305928A"><text>GB 2 305 928</text></patcit>, British Patent <patcit id="pcit0044" dnum="GB2305670A"><text>GB 2 305 670</text></patcit>, British Patent <patcit id="pcit0045" dnum="GB2290793A"><text>GB 2 290 793</text></patcit>, <patcit id="pcit0046" dnum="WO9414902A"><text>PCT Publication WO 94/14902</text></patcit>, <patcit id="pcit0047" dnum="WO9712003A"><text>PCT Publication WO 97/12003</text></patcit>, <patcit id="pcit0048" dnum="WO9713816A"><text>PCT Publication WO 97/13816</text></patcit>, <patcit id="pcit0049" dnum="WO9614364A"><text>PCT Publication WO 96/14364</text></patcit>, <patcit id="pcit0050" dnum="WO9733943A"><text>PCT Publication WO 97/33943</text></patcit>. and <patcit id="pcit0051" dnum="WO9504760A"><text>PCT Publication WO 95/04760</text></patcit>.

0029Mixtures of fatty amide materials and isocyanate-derived materials can also be employed in the ink carrier composition for inks of the present invention.

0030Additional suitable phase change ink carrier materials for the present invention include paraffins, microcrystalline waxes, polyethylene waxes, ester waxes, amide waxes, fatty acids, fatty alcohols, fatty amides and other waxy materials, sulfonamide materials, resinous materials made from different natural sources (such as, for example, tall oil rosins and rosin esters), and many synthetic resins, oligomers, polymers and copolymers, such as ethylene/vinyl acetate copolymers, ethylene/acrylic acid copolymers, ethylene/vinyl acetate/acrylic acid copolymers, copolymers of acrylic acid with polyamides, and the like, ionomers, and the like, as well as mixtures thereof. One or more of these materials can also be employed in a mixture with a fatty amide material and/or an isocyanate-derived material.

0031When the triamide or a mixture of triamide with other polyamides is present in combination with other materials to make up the ink carrier, the polyamide component is present in any desired or effective amount, in embodiments at least 5, 15 or 25 percent by weight of the carrier, and in embodiments no more than 90, 80 or 70 percent by weight of the carrier, although the amount of triamide or polyamide mixture can be outside of these ranges.

0032The ink carrier is present in the phase change ink of the present invention in any desired or effective amount, in embodiments of at least 0.1, 50 or 90 percent by weight of the ink, and in embodiments of no more than 99, 98 or 95 percent by weight of the ink, although the amount can be outside of these ranges.

0033While not being limited to any particular theory, it is believed that, in contrast to polyamides such as tetra-amides, which tend to be linear and of general formulae such as <chemistry id="chem0026" num="0026"><img file="EP1514912B1_D0026.tif" /></chemistry> the triamides used in the present invention are branched or star-shaped. Again, while not being limited to any particular theory, it is believed that the branched or star shape of these materials enables the triamides to have reduced viscosity compared to, for example, tetra-amides of comparable molecular weight and comparable ratio of amide groups to hydrocarbon in the molecule. In addition, while not being limited to any particular theory, it is believed that the branched or star shape of these materials enables the triamides to exhibit miscibility with polyethylene waxes over a wider mixing range; for example, when a tetra-amide might exhibit a miscibility with polyethylene waxes over a range of only 20 percent by weight or more amide in the wax, a triamide might exhibit a miscibility with polyethylene waxes over a range of from 10 to 70 percent by weight amide in the wax. These characteristics of the triamides provide another level of freedom in optimizing phase change ink formulations having desirable viscosity values and desirable performance in automatic document handlers and feeders.

0034The phase change ink compositions of the present invention also contain a colorant. Any desired or effective colorant can be employed in the inks of the present invention, including dyes, pigments, mixtures thereof, and the like, provided that the colorant can be dissolved or dispersed in the ink vehicle. The phase change carrier compositions of the current invention can be used in combination with conventional phase change ink colorant materials, such as Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, Basic Dyes, Sulphur Dyes, Vat Dyes, and the like. Polymeric dyes can also be used, such as those disclosed in, for example, <patcit id="pcit0052" dnum="US5621022A"><text>U.S. Potent 5,621,022</text></patcit> and <patcit id="pcit0053" dnum="US5231135A"><text>U.S. Patent 5,231,135</text></patcit>.

0035Pigments are also suitable colorants for the phase change inks of the present invention.

0036Other ink colors besides the subtractive primary colors can be desirable for applications such as postal marking or industrial marking and labelling using phase change printing, and the present invention is applicable to these needs. Further, infrared (IR) or ultraviolet (UV) absorbing dyes can also be incorporated into the inks of the present invention for use in applications such as invisible" coding or marking of products. Examples of such infrared and ultraviolet absorbing dyes are disclosed in, for example, <patcit id="pcit0054" dnum="US5378574A"><text>U.S. Potent 5,378,574</text></patcit>, <patcit id="pcit0055" dnum="US5146087A"><text>U.S. Patent 5,146,087</text></patcit>, <patcit id="pcit0056" dnum="US5145518A"><text>U.S. Patent 5,145,518</text></patcit>, <patcit id="pcit0057" dnum="US5543177A"><text>U.S. Patent 5,543,177</text></patcit>, <patcit id="pcit0058" dnum="US5225900A"><text>U.S. Patent 5,225,900</text></patcit>, <patcit id="pcit0059" dnum="US5301044A"><text>U.S. Patent 5,301,044</text></patcit>, <patcit id="pcit0060" dnum="US5286286A"><text>U.S. Patent 5,286,286</text></patcit>, <patcit id="pcit0061" dnum="US5275647A"><text>U.S. Patent 5,275,647</text></patcit>, <patcit id="pcit0062" dnum="US5208630A"><text>U.S. Patent 5,208,630</text></patcit>, <patcit id="pcit0063" dnum="US5202265A"><text>U.S. Patent 5,202,265</text></patcit>, <patcit id="pcit0064" dnum="US5271764A"><text>U.S. Patent 5,271,764</text></patcit>, <patcit id="pcit0065" dnum="US5256193A"><text>U.S. Patent 5,256,193</text></patcit>, <patcit id="pcit0066" dnum="US5385803A"><text>U.S. Patent 5,385,803</text></patcit>, and <patcit id="pcit0067" dnum="US5554480A"><text>U.S. Patent 5,554,480</text></patcit>.

0037In a specific embodiment, the colorant is an isocyanate-derived colored resin as disclosed in, for example, <patcit id="pcit0068" dnum="US5780528A"><text>U.S. Patent 5,780,528</text></patcit> and <patcit id="pcit0069" dnum="US5919839A"><text>U.S. Patent 5,919,839</text></patcit>. In this embodiment, the colorant is the reaction product of a hydroxyl-substituted or primary or secondary amino-substituted chromophore with an isocyanate. Examples of suitable isocyanates include monoisocyanates, diisocyanates, triisocyanates, copolymers of a diisocyanate, copolymers of a triisocyanate, polyisocyanates (having more than three isocyanate functional groups), and the like, as well as mixtures thereof. Specific examples of suitable isocyanates include those listed hereinabove as being suitable for reaction with the hydroxyl-substituted or amino-substituted antioxidant. Examples of suitable hydroxyl-substituted and primary or secondary amino-substituted chromophores include those disclosed in, for example, <patcit id="pcit0070" dnum="US3157633A"><text>U.S. Patent 3,157,633</text></patcit>, <patcit id="pcit0071" dnum="US3927044A"><text>U.S. Patent 3,927,044</text></patcit>, <patcit id="pcit0072" dnum="US3994835A"><text>U.S. Patent 3,994,835</text></patcit>, <patcit id="pcit0073" dnum="US4102644A"><text>U.S. Patent 4,102,644</text></patcit>, <patcit id="pcit0074" dnum="US4113721A"><text>U.S. Patent 4,113,721</text></patcit>, <patcit id="pcit0075" dnum="US4132840A"><text>U.S. Patent 4,132,840</text></patcit>, <patcit id="pcit0076" dnum="US4137243A"><text>U.S. Patent 4,137,243</text></patcit>, <patcit id="pcit0077" dnum="US4170564A"><text>U.S. Patent 4,170,564</text></patcit>, <patcit id="pcit0078" dnum="US4284729A"><text>U.S. Patent 4,284,729</text></patcit>, <patcit id="pcit0079" dnum="US4507407A"><text>U.S. Patent 4,507,407</text></patcit>, <patcit id="pcit0080" dnum="US4640690A"><text>U.S. Patent 4,640,690</text></patcit>, <patcit id="pcit0081" dnum="US4732570A"><text>U.S. Patent 4,732,570</text></patcit>, <patcit id="pcit0082" dnum="US4751254A"><text>U.S. Patent 4,751,254</text></patcit>, <patcit id="pcit0083" dnum="US4751254A"><text>U.S. Patent 4,751,254</text></patcit>, <patcit id="pcit0084" dnum="US4761502A"><text>U.S. Patent 4,761,502</text></patcit>, <patcit id="pcit0085" dnum="US4775748A"><text>U.S. Patent 4,775,748</text></patcit>, <patcit id="pcit0086" dnum="US4812141A"><text>U.S. Patent 4,812,141</text></patcit>, <patcit id="pcit0087" dnum="US4846846A"><text>U.S. Patent 4,846,846</text></patcit>, <patcit id="pcit0088" dnum="US4871371A"><text>U.S. Patent 4,871,371</text></patcit>, <patcit id="pcit0089" dnum="US4912203A"><text>U.S. Patent 4,912,203</text></patcit>, <patcit id="pcit0090" dnum="US4978362A"><text>U.S. Patent 4,978,362</text></patcit>, <patcit id="pcit0091" dnum="US5043013A"><text>U.S. Patent 5,043,013</text></patcit>, <patcit id="pcit0092" dnum="US5059244A"><text>U.S. Potent 5,059,244</text></patcit>, <patcit id="pcit0093" dnum="US5149800A"><text>U.S. Potent 5,149,800</text></patcit>, <patcit id="pcit0094" dnum="US5177200A"><text>U.S. Patent 5,177,200</text></patcit>, <patcit id="pcit0095" dnum="US5270363A"><text>U.S. Patent 5,270,363</text></patcit>, <patcit id="pcit0096" dnum="US5290921A"><text>U.S. Patent 5,290,921</text></patcit>, and <patcit id="pcit0097" dnum="US5731398A"><text>U.S. Potent 5,731,398</text></patcit> . ydroxyl-containing and primary or secondary amino-containing colorants from the classes of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, Basic Dyes, Sulphur Dyes, Vat Dyes, and the like can also be used.

0038The colorant is present in the phase change ink of the present invention in any desired or effective amount to obtain the desired color or hue, typically at least 0.1 percent by weight of the ink, preferably at least 0.2 percent by weight of the ink, and more preferably at least 0.5 percent by weight of the ink, and typically no more than 50 percent by weight of the ink, preferably no more than 20 percent by weight of the ink, and more preferably no more than 10 percent by weight of the ink, although the amount can be outside of these ranges.

0039The inks of the present invention can also optionally contain an antioxidant. The optional antioxidants of the ink compositions protect the images from oxidation and also protect the ink components from oxidation during the heating portion of the ink preparation process. Specific examples of suitable antioxidants include NAUGUARD® 524. NAUGUARD® 76, and NAUGUARD® 512 IRGANOX® 1010, and the like. When present, the optional antioxidant is present in the ink in any desired or effective amount, in embodiments of at least 0.01, 0.1 or 1 percent by weight of the ink, and in embodiments of no more than 20, 5 or 3 percent by weight of the ink, although the amount can be outside of these ranges.

0040The inks of the present invention can also optionally contain a viscosity modifier. Examples of suitable viscosity modifiers include aliphatic ketones, such as stearone, and the like. When present, the optional viscosity modifier is present in the ink in any desired or effective amount, in embodiments of at least 0.1, 1 or 10 percent by weight of the ink, and in embodiments of no more than 99, 30 or 15 percent by weight of the ink, although the amount can be outside of these ranges.

0041Other optional additives to the inks include clarifiers, such as UNION CAMP® X37-523-235, in an amount in embodiments of at least 0.01, 0.1 or 5 percent by weight of the ink, and in embodiments of no more than 98, 50 or 10 percent by weight of the ink, although the amount can be outside of these ranges, tackifiers, such as FORAL® 85. a glycerol ester of hydrogenated abietic (rosin) acid, FORAL® 105, a pentaerythritol ester of hydroabietic (rosin) acid, CELLOLYN® 21, a hydroobietic (rosin) alcohol ester of phthalic acid, ARAKAWA KE-311 Resin, a triglyceride of hydrogenated abietic (rosin) acid, synthetic polyterpene resins such as NEVTAC® 2300. NEVTAC® 100, and NEVTAC® 80, WINGTACK® 86, a modified synthetic polyterpene resin, and the like, in an amount in embodiments of at least 0.1, 5 or 10 percent by weight of the ink, and in embodiments of no more than 98, 75 or 50 percent by weight of the ink, although the amount can be outside of these range, adhesives, such as VERSAMID® 757, 759, or 744, in an amount in embodiments of at least 0.1, 1 or 5 percent by weight of the ink, and in embodiments of no more than 98, 50 or 10 percent by weight of the ink, although the amount can be outside of these ranges, plasticizers, such as UNIPLEX® 250, the phthalate ester plasticizers commercially available from Monsanto under the trade name SANTICIZER®, such as dioctyl phthalate, diundecyl phthalate, alkylbenzyl phthalate (SANTICIZER® 278), triphenyl phosphate, KP-140®, a tributoxyethyl phosphate, MORFLEX® 150, a dicyclohexyl phthalate, trioctyl trimellitate, and the like, in an amount in embodiments of at least 0.1, 1 or 2 percent by weight of the ink, and in embodiments of no more than 50, 30 or 10 percent by weight of the ink, although the amount can be outside of these ranges, and the like.

0042The inks of the present invention can also optionally contain other materials.

0043The ink compositions of the present invention typically have melting points no lower than 50°C, preferably no lower than 70°C, and more preferably no lower than 80°C, and typically have melting points no higher than 160°C, preferably no higher than 140°C, and more preferably no higher than 100°C, although the melting point can be outside of these ranges.

0044The ink compositions of the present invention generally have melt viscosities at the jetting temperature (typically no lower than 75°C, preferably no lower than 100°C, and more preferably no lower than 120°C, and typically no higher than 180°C, preferably no higher than 150°C, and more preferably no higher than 130°C, although the jetting temperature can be outside of these ranges) typically of no more than 30·10^-3 Pa·s (30 centipoise), preferably no more than 20 centipoise, and even more preferably no more than 15·10^-3 Pa·s (15 centipoise), and typically of no less than 2 centipoise, preferably no less than 5 centipoise, and even more preferably no less than 7 centipoise, although the melt viscosity can be outside of these ranges. Since image hardness tend to drop with lower viscosities, it is preferred that the viscosity be as low as possible while still retaining the desired degree of image hardness.

0045The ink compositions of the present invention can be prepared by any desired or suitable method. For example, the ink ingredients can be mixed together, followed by heating, typically to a temperature of from 100 to 140°C, although the temperature can be outside of this range, and stirring until a homogeneous ink composition is obtained, followed by cooling the ink to ambient temperature (typically from 20 to 25°C). The inks of the present invention are solid at ambient temperature.

0046The inks of the present invention can be employed in apparatus for direct printing ink jet processes and in indirect (offset) printing ink jet applications. Another embodiment of the present invention is directed to a process which comprises incorporating an ink of the present invention into an ink jet printing apparatus, melting the ink, and causing droplets of the melted ink to be ejected in an imagewise pattern onto a recording substrate. A direct printing process is also disclosed in, for example, <patcit id="pcit0098" dnum="US5195430A"><text>U.S. Patent 5,195,430</text></patcit>. Yet another embodiment of the present invention is directed to a process which comprises incorporating an ink of the present invention into an ink jet printing apparatus, melting the ink, causing droplets of the melted ink to be ejected in an imagewise pattern onto an intermediate transfer member, and transferring the ink in the imagewise pattern from the intermediate transfer member to a final recording substrate. An offset or indirect printing process is also disclosed in, for example, <patcit id="pcit0099" dnum="US5389958A"><text>U.S. Patent 5,389,958</text></patcit>. In one specific embodiment of the offset or indirect printing process, the intermediate transfer member is heated to a temperature above that of the final recording sheet and below that of the melted ink in the printing apparatus. In one specific embodiment, the printing apparatus employs a piezoelectric printing process wherein droplets of the ink are caused to be ejected in imagewise pattern by oscillations of piezoelectric vibrating elements. Inks of the present invention can also be employed in other hot melt printing processes, such as hot melt acoustic ink jet printing, hot melt thermal ink jet printing, hot melt continuous stream or deflection ink jet printing, or the like. Phase change inks of the present invention can also be used in printing processes other than hot melt ink jet printing processes, such as hot melt gravure printing, hot melt medical imaging printing, or the like.

0047Any 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.

0048Specific embodiments of the invention will now be described in detail.

0049All parts and percentages are by weight unless otherwise indicated.

EXAMPLE <b>I</b>

0050To a 1,000 milliliter four-neck round bottom flask fitted with a Trubore stirrer, N₂ inlet, Dean-Stark trap with condenser and N₂ outlet and thermocouple-temperature controller was added 350.62 grams (0.3675 moles) of UNICID 700 (a mono-acid of the formula CH₃(CH₂)_nCOOH, wherein n has an average value of about 46 and is believed to have a range of from 40 to 52) and 0.79 grams of NAUGARD 524 (antioxidant). The mixture was heated to 115°C to melt and stirred at atmospheric pressure under N₂. 51.33 grams (0.1167 moles) of JEFFAMINE T-403 (mixture of triamines of the formula <chemistry id="chem0027" num="0027"><img file="EP1514912B1_D0027.tif" /></chemistry> wherein x. y, and z are each integers representing the number of repeat propyleneoxy units, wherein x, y, and z may each be zero, and wherein the sum of x+y+z is from 5 to 6) was then added to the reaction mixture, and the reaction temperature was increased to 200°C gradually over 0.5 hour and held at that temperature for another 3 hours. Some water was carried out by slow blowing N₂ and condensed into the trap when the mixture temperature reached about 180°C. The trap and condenser were then removed, and vacuum (about 25 mm Hg) was applied for about 0.5 hour and then released. The liquid product was cooled down to about 150°C and poured onto aluminum to solidify. The resulting product was believed to be of the formula <chemistry id="chem0028" num="0028"><img file="EP1514912B1_D0028.tif" /></chemistry> wherein n, x, y, and z are as defined hereinabove in this Example. This material is an example of one having heteroatoms (i.e., oxygen) in a central R alkylene group. The resulting triamide product was titrated for its acid number and amine value measured in units of mg KOH per gram. Acid and amine values were determined by dissolving the material in a mixture of 50 percent by weight butanol and 50 percent by weight toluene, heating, and titrating the acid number with aqueous potassium hydroxide and titrating the amine number with aqueous hydrogen chloride. The acid and amine numbers indicated the degree of reaction completion, indicating how much amine remained in the molecule; residual amine can in some instances discolor if incorporated into a phase change ink. Its viscosity was measured (in centipoise) on a Ferrani-Shirley cone-plate viscometer at 135°C. Its melting point was measured (in °C) by differential scanning calorimetry using a TA instrument 2920 calorimeter at a scanning rote of 20°C per minute: the DSC scan had two melting peaks, and both numbers are reported. The results were as indicated below in Table 1. Miscibility of this triamide product with POLYWAX PE 655 (polyethylene wax) was tested by melting, shaking the mixture at 135°C, and then checking its clarity visually. The mixtures were melted, shaken, and then checked visually: clear mixtures were considered miscible, and hazy mixtures were considered not miscible. The hazy mixtures eventually become two phase mixtures after standing still in the oven at 135°C. The results were as indicated below in Table 2.

EXAMPLE

<u>II</u>

0051The procedure of Example I was repeated with the same stoichiometry but UNICID 550 (a mono-acid of the formula CH₃(CH₂)_nCOOH, wherein n has an average value of about 37 and is believed to have a range of from 34 to 40). The product was believed to be of the formula <chemistry id="chem0029" num="0029"><img file="EP1514912B1_D0029.tif" /></chemistry> n is as defined hereinabove in this Example and x, y. and z are as defined in Example I. The properties of the resulting triamide product are listed in Tables 1 and 2.

EXAMPLE

<u>III</u>

0052The procedure of Example I was repeated with the same stoichiometry but UNICID 350 (a mono-acid of the formula CH₃(CH₂)_nCOOH, wherein n has an average value of about 23 and is believed to have a range of from 20 to 26) was used instead of UNICID 700. The product was believed to be of the formula <chemistry id="chem0030" num="0030"><img file="EP1514912B1_D0030.tif" /></chemistry> n is as defined hereinabove in this Example and x, y, and z are as defined in Example I. The properties of the resulting triamide product are listed in Tables 1 and 2.

EXAMPLE <b>IV</b>

0053The procedure of Example I was repeated with the some stoichiometry but stearic acid (a mono-acid) of the formula         CH₃(CH₂)₁₆COOH was used instead of UNICID 700. The product was believed to be of the formula <chemistry id="chem0031" num="0031"><img file="EP1514912B1_D0031.tif" /></chemistry> n is 16 and x, y, and z are as defined in Example I. The properties of the resulting triamide product are listed in Tables 1 and 2.

EXAMPLE <b>V</b>

0054The procedure of Example I was repeated with the same stoichiometry but tris(2-aminoethyl)amine (TREN-HP, 98+%, of the formula N(CH₂CH₂NH₂)₃) was used instead of JEFFAMINE T-403. The product was believed to be of the formula N(CH₂CH₂-NH-C(=O)-(CH₂)₄₆CH₃)₃. This material is an example of one having a heteroatom (i.e., nitrogen) in a central R alkylene group The properties of the resulting triamide product are listed in Tables 1 and 2.

EXAMPLE <b>VI</b>

0055The procedure of Example I wos repeated with the same stoichiometry but tris(2-aminoethyl)amine (TREN-HP, 98+%, of the formula N(CH₂CH₂NH₂)₃) was used instead of JEFFAMINE T-403 and UNICID 350 (a mono-acid) of the formula CH₃(CH₂)_nCOOH, wherein n has an average value of about 23 and is believed to have a range of from 20 to 26) was used instead of UNICID 700. The product was believed to be of the formula N(CH₂CH₂-NH-C(=O)-(CH₂)_nCH₃)₃ wherein n is as defined hereinabove in this Example. The properties of the resulting triamide product are listed in Tables 1 and 2.

EXAMPLE <b>VII</b>

0056The procedure of Example I was repeated with the some stoichiometry but stearic amine (AMINE D, of the formula CH₃(CH₂)₁₇-NH₂) was used instead of JEFFAMINE T-403 and EMPOL 1045 (a trimer acid mixture believed to contain various branched isomers which may include unsaturations and cyclic groups and believed to have about 54 carbon atoms, including the three carbon atoms in the three -COOH groups: further information on trimer acids of this type is disclosed in, for example, "<nplcit id="ncit0001" npl-type="b"><text>Dimer Acids." Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 8, 4th Ed. (1992), pp. 223 to 237</text></nplcit>, and in <patcit id="pcit0100" dnum="US2793219A"><text>U.S. Patent 2,793,219</text></patcit> and <patcit id="pcit0101" dnum="US2793220A"><text>U.S. Patent 2.793,220</text></patcit>) was used instead of UNICID 700. The properties of the resulting triamide product are listed in Tables 1 and 2.

COMPARATIVE EXAMPLE A

0057The procedure of Example I was repeated except that a mixture of 162.82 grams (0.283 moles) of dimer acid (EMPOL 1008, a dimer acid), 583.83 grams (0.612 moles) of UNICID 700, and 1.5 grams of NAUGARD 524 were heated to melt before adding 33.06 grams (0.55 moles) of ethylene diamine. The properties of the resultant tetra-amide product are listed in Tables 1 and 2.

COMPARATIVE EXAMPLE B

0058For comparative purposes, the characteristics of UniRez 2970 (a tetra-amide, a dimer acid mixture believed to contain various branched isomers which may include unsaturations and cyclic groups and believed to have about 36 carbon atoms, including the two carbon atoms in the two -COOH groups; further information on dimer acids of this type is disclosed in, for example, "<nplcit id="ncit0002" npl-type="b"><text>Dimer Acids." Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 8, 4th Ed. (1992), pp. 223 to 237</text></nplcit>, and in <patcit id="pcit0102" dnum="US2793219A"><text>U.S. Patent 2,793,219</text></patcit> and <patcit id="pcit0103" dnum="US2793220A"><text>U.S. Patent 2,793,220</text></patcit>, were also measured. <tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="18mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="23mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><colspec colnum="5" colname="col5" colwidth="23mm" /><thead><row><entry align="center" valign="top">Example</entry><entry align="center" valign="top">viscosity</entry><entry align="center" valign="top">Melting point</entry><entry align="center" valign="top">acid number</entry><entry align="center" valign="top">amine value</entry></row></thead><tbody><row><entry align="center">I</entry><entry align="center">27.9</entry><entry align="center">98.3, 104.5</entry><entry align="center">9.6</entry><entry align="center">1.7</entry></row><row><entry align="center">II</entry><entry align="center">22.9</entry><entry align="center">92.3, 100.3</entry><entry align="center">5.6</entry><entry align="center">1</entry></row><row><entry align="center">III</entry><entry align="center">13.4</entry><entry align="center">58.5, 67.9</entry><entry align="center">18</entry><entry align="center">1.5</entry></row><row><entry align="center">IV</entry><entry align="center">14.1</entry><entry align="center">51.4, 60.8</entry><entry align="center">22.3</entry><entry align="center">7</entry></row><row><entry align="center">V</entry><entry align="center">39.0</entry><entry align="center">115.0</entry><entry align="center">4.6</entry><entry align="center">0.1</entry></row><row><entry align="center">VI</entry><entry align="center">18.7</entry><entry align="center">102.9</entry><entry align="center">9.6</entry><entry align="center">0.7</entry></row><row><entry align="center">VII</entry><entry align="center">49.8</entry><entry align="center">56.14</entry><entry align="center">27</entry><entry align="center">---</entry></row><row><entry align="center">A</entry><entry align="center">66 to 69</entry><entry align="center">116 to 119</entry><entry align="center">7.7 to 14</entry><entry align="center">0.4</entry></row><row><entry align="center">B</entry><entry align="center">81</entry><entry align="center">108, 125</entry><entry align="center">---</entry><entry align="center">---</entry></row></tbody></tgroup><tgroup cols="5" rowsep="0"><colspec colnum="1" colname="col1" colwidth="18mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="23mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><colspec colnum="5" colname="col5" colwidth="23mm" /><tbody><row><entry namest="col1" nameend="col5" align="justify">- - - = not measured</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="10"><colspec colnum="1" colname="col1" colwidth="19mm" /><colspec colnum="2" colname="col2" colwidth="12mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="13mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="12mm" /><colspec colnum="10" colname="col10" colwidth="16mm" /><thead><row><entry align="center" valign="top">wt.% in PE</entry><entry namest="col2" nameend="col8" align="center" valign="top">Triamides</entry><entry namest="col9" nameend="col10" align="center" valign="top">Tetra-amides</entry></row><row><entry align="center" valign="top" /><entry align="center" valign="top">I</entry><entry align="center" valign="top">II</entry><entry align="center" valign="top">III</entry><entry align="center" valign="top">IV</entry><entry align="center" valign="top">V</entry><entry align="center" valign="top">VI</entry><entry align="center" valign="top">VII</entry><entry align="center" valign="top">A</entry><entry align="center" valign="top">B</entry></row></thead><tbody><row><entry align="center">10</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">Clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">---</entry><entry align="center">haze</entry><entry align="center">haze</entry></row><row><entry align="center">15</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">haze ---</entry></row><row><entry align="center">20</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">Clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">haze</entry><entry align="center">clear</entry><entry align="center">haze</entry></row><row><entry align="center">25</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">clear</entry><entry align="center">---</entry></row><row><entry align="center">30</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">Clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">---</entry><entry align="center">clear</entry><entry align="center">haze</entry></row><row><entry align="center">35</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">clear</entry><entry align="center">---</entry></row><row><entry align="center">40</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">Clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">haze</entry><entry align="center">clear</entry><entry align="center">---</entry></row><row><entry align="center">50</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">Clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center" /><entry align="center" /><entry align="center">haze</entry></row><row><entry align="center">60</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">haze</entry><entry align="center">clear</entry><entry align="center">---</entry></row><row><entry align="center">70</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">Clear</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">haze</entry></row><row><entry align="center">80</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">---</entry><entry align="center">clear</entry><entry align="center">clear</entry><entry align="center">---</entry></row></tbody></tgroup><tgroup cols="10" rowsep="0"><colspec colnum="1" colname="col1" colwidth="19mm" /><colspec colnum="2" colname="col2" colwidth="12mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="13mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="12mm" /><colspec colnum="10" colname="col10" colwidth="16mm" /><tbody><row><entry namest="col1" nameend="col10" align="justify">--- = not measured</entry></row></tbody></tgroup></table></tables>

EXAMPLE

<u>VIII</u>

0059In a stainless steel beaker were combined 64.78 grams of a triamide prepared as described in Example II. 117.60 grams of POLYWAX PE655 (polyethylene wax), 31.20 grams of a diurethane resin prepared as described in Example I of <patcit id="pcit0104" dnum="US5830942A"><text>U.S. Patent 5,830,942</text></patcit>, 9.60 grams of a urethane resin (adduct of three equivalents of stearyl isocyanate and a glycerol-based alcohol, prepared as described in Example 4 of <patcit id="pcit0105" dnum="US6309453B"><text>U.S. Patent 6,309,453</text></patcit>. ), 21.6 grams of stearyl stearamide (KEMAMIDE S-180), and 0.48 grams of NAUGARD 445 (antioxidant). The materials were melted together at a temperature of about 135°C in an oven, then blended by stirring in a temperature controlled mantle for 0.5 hour at 135°C. To the mixture, was then added 8.60 grams of SAVINYL BLACK NS (solvent soluble black dye). The mixture was stirred for an additional 2 hours, and then 2.30 grams of Hyflo Supercel filter aid was added and stirred for another 30 minutes. The ink was then filtered through a heated (135°C) Mott apparatus using Whatman #3 filter paper at 11·10³ kg/m² (15 pounds per square inch). The filtered ink was poured into molds and allowed to solidify to form ink sticks. This final black ink product exhibited a viscosity of about 11.77·10^-3 Pa.s (1.77 centipoise) at 135°C as measured by a Rheometric Scientific RS-2000 cone-plate viscometer. The spectral strength of the ink was determined by dissolving the ink in butanol and measuring the absorbance using a Perkin-Elmer Lambda 2S UV/VIS spectrophotometer. The spectral strength of the ink was measured as 1193 milliliters•Absorbance unit per gram at λ_max. This ink was printed on papers using a PHASER 840 printer, which uses an indirect printing process.

EXAMPLE

<u>IX</u>

0060The process of Example VIII is repeated except that the triamides from Examples I, III, IV, V, VI, and VII are used instead of the triamide from Example II. It is believed that similar results will be obtained.