U.S. patent application number 10/606631 was filed with the patent office on 2004-12-30 for phase change inks containing colorant compounds.
This patent application is currently assigned to Xerox Corporation. Invention is credited to Banning, Jeffery H., Bridgeman, Randall R., Duff, James M., Thomas, Jule W. JR., Wedler, Wolfgang G., Wu, Bo.
Application Number | 20040261657 10/606631 |
Document ID | / |
Family ID | 33418695 |
Filed Date | 2004-12-30 |
United States Patent
Application |
20040261657 |
Kind Code |
A1 |
Wu, Bo ; et al. |
December 30, 2004 |
PHASE CHANGE INKS CONTAINING COLORANT COMPOUNDS
Abstract
A phase change ink composition comprising a phase change ink
carrier and a colorant compound of the formula 1 wherein M is
either (1) a metal ion having a positive charge of +y wherein y is
an integer which is at least 2, said metal ion being capable of
forming a compound with at least two 2 chromogen moieties, or (2) a
metal-containing moiety capable of forming a compound with at least
two 3 chromogen moieties, z is an integer representing the number
of 4 chromogen moieties associated with the metal and is at least
2, and R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, a, b, c, d, Y, Q.sup.-, A, and CA are as defined
herein.
Inventors: |
Wu, Bo; (Wilsonville,
OR) ; Banning, Jeffery H.; (Hillsboro, OR) ;
Duff, James M.; (Mississauga, CA) ; Wedler, Wolfgang
G.; (Tualatin, OR) ; Thomas, Jule W. JR.;
(West Linn, OR) ; Bridgeman, Randall R.; (Hubbard,
OR) |
Correspondence
Address: |
PATENT DOCUMENTATION CENTER
XEROX CORPORATION
100 CLINTON AVE., SOUTH, XEROX SQUARE, 20TH FLOOR
ROCHESTER
NY
14644
US
|
Assignee: |
Xerox Corporation
|
Family ID: |
33418695 |
Appl. No.: |
10/606631 |
Filed: |
June 26, 2003 |
Current U.S.
Class: |
106/31.29 ;
106/31.43; 106/31.47; 106/31.61; 106/31.75; 106/31.77; 347/100 |
Current CPC
Class: |
C09D 11/34 20130101 |
Class at
Publication: |
106/031.29 ;
106/031.43; 106/031.75; 106/031.47; 106/031.77; 106/031.61;
347/100 |
International
Class: |
C09D 011/00; B41J
002/01 |
Claims
What is claimed is:
1. A phase change ink composition comprising a phase change ink
carrier and a colorant compound of the formula 183wherein M is
either (1) a metal ion having a positive charge of +y wherein y is
an integer which is at least 2, said metal ion being capable of
forming a compound with at least two 184chromogen moieties, or (2)
a metal-containing moiety capable of forming a compound with at
least two 185chromogen moieties, is an integer representing the
number of 186chromogen moieties associated with the metal and is at
least 2, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each, independently
of the others, is (i) a hydrogen atom, (ii) an alkyl group, (iii)
an aryl group, (iv) an arylalkyl group, or (v) an alkylayl group,
wherein R.sub.1 and R.sub.2 can be joined together to form a ring,
wherein R.sub.3 and R.sub.4 can be-joined together to form a ring,
and wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 can each be
joined, to a phenyl ring in the central structure, a and b each,
independently of the others, is an integer which is 0, 1, 2, or 3,
c is an integer which is 0, 1, 2, 3, or 4, each R.sub.5, R.sub.6,
and R.sub.7, independently of the others, is (i) an alkyl group,
(ii) an aryl group, (iii) an arylalkyl group, (iv) on, alkylaryl
group, (v) a, halogen atom, (vi) an ester group, (vii) an amide
group, (viii) a sulfone group, (ix) an amine group or ammonium
group, (x) a nitrile group, (xi) a nitro: group, (xii) a hydroxy
group, (xiii) a cyano group, (xiv) a pyridine or pyridinium group,
(xv) an ether group, (xvi) an aldehyde group, (xvii) a ketone
group, (xviii) a carbonyl group, (xix) a thiocarbonyl group, (xx) a
sulfate group, (xxi) a sulfide group, (xxii) a sulfoxide group,
(xxiii) a phosphine or phosphonium group, (xxiv) a phosphate group,
(xxv) a mercapto group, (xxvi) a nitroso group, (xxvii) an acyl
group, (xxviii) an acid anhydride group, (xxix) an azide group,
(xxx) an azo group, (xxxi) a cyanato group, (xxxii) an isocyanato
group, (xxxiii) a thiocyanato group, (xxxiv) an isothiocyanato
group, (xxxv) a urethane group, or (xxxvi) a urea group, wherein
R.sub.5, R.sub.6, and R.sub.7 can each be joined to a phenyl ring
in the central structure, 187R.sub.8, R.sub.9, and R.sub.10 each,
independently of the others, is (i) a hydrogen atom, (ii) an alkyl
group, (iii) an aryl group, (iv) an arylalkyl group, or (v) an
alkylaryl group, provided that the number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R.sub.7+R-
.sub.8+R.sub.9+R.sub.10 is at least about 16, Q.sup.- is a
COO.sup.- group or a SO.sub.3.sup.- group, d is an integer which is
1, 2, 3, 4, or 5, A is an anion, and CA is either a hydrogen atom
or a cation associated with all but one of the Q-0 groups.
2. A phase change ink composition according to claim 1 wherein the
phase change ink carrier comprises a monoamide, a tetra-amide, or a
mixture thereof.
3. A phase change ink composition according to claim 1 wherein the
phase change ink carrier comprises (a) stearyl stearamide, (b) a
dimer acid based tetra-amide that is the reaction product of dimer
acid, ethylene diamine, and stearic acid, or (c) mixtures
thereof.
4. A phase change ink composition according to claim 1 wherein the
phase change ink carrier comprises (a) stearyl stearamide, (b) a
dimer acid based tetra-amide that is the reaction product of dimer
acid, ethylene diamine, and a carboxylic acid having at least about
36 carbon atoms, or (c) mixtures thereof.
5. A phase change ink composition according to claim 4 wherein the
carboxylic acid has at least about 40 carbon atoms, and wherein the
carboxylic acid has no more than about 200 carbon atoms.
6. A phase change ink composition according to claim 1 wherein the
phase change ink carrier comprises an isocyanate-derived
material.
7. A phase change ink composition according to claim 1 wherein the
phase change ink carrier comprises a urethane isocyanate-derived
material, a urea isocyanate-derived material, a urethane/urea
isocyanate-derived material, or mixtures thereof.
8. A phase change ink composition according to claim 1 wherein the
phase change ink carrier comprises a mixture of one or more amides
and one or more isocyanate-derived materials.
9. A phase change ink composition according to claim 1 wherein the
phase change ink carrier comprises one or more materials selected
from paraffins, microcrystalline waxes, polyethylene waxes, ester
waxes, amide waxes, fatty acids, fatty alcohols, fatty amides,
sulfonamide materials, tall oil rosins, rosin esters,
ethylene/vinyl acetate copolymers, ethylene/acrylic acid
copolymers, ethylene/vinyl acetate/acrylic acid copolymers,
copolymers of acrylic acid with polyamides, ionomers, and mixtures
thereof.
10. A phase change ink composition according to claim 1 wherein the
phase change ink carrier is present in the ink in an amount of at
least about 0.1 percent by weight of the ink and wherein the phase
change ink carrier is present in the ink in an amount of no more
than about 99 percent by weight of the ink.
11. A phase change ink composition according to claim 1 wherein the
phase change ink carrier is present in the ink in an amount of at
least about 50 percent by weight of the ink and wherein the phase
change ink carrier is present in the ink in an amount of no more
than about 98 percent by weight of the ink.
12. A phase change ink composition according to claim 1 wherein the
phase change ink carrier is present in the ink in an amount of at
least about 90 percent by weight of the ink and wherein the phase
change ink carrier is present in the ink in an amount of no more
than about 95 percent by weight of the ink.
13. A phase change ink composition according to claim 1 wherein the
ink further contains an antioxidant.
14. A phase change ink composition according to claim 13 wherein
the antioxidant is present in the ink in an amount of at least
about 0.01 percent by weight of the ink, and wherein the
antioxidant is present in the ink in an amount of no more than
about 20 percent by weight of the ink.
15. A phase change ink composition according to claim 1 wherein the
ink further contains a viscosity modifier.
16. A phase change ink composition according to claim 15 wherein
the viscosity modifier is an aliphatic ketone.
17. A phase change ink composition according to claim wherein the
viscosity modifier is present in the ink in an amount of at least
about 0.1 percent by weight of the ink and wherein the viscosity
modifier is present in the ink in an amount of no more than about
99 percent by weight of the ink.
18. A phase change ink composition according to claim 1 wherein the
ink carrier comprises (a) a polyethylene wax, (b) a stearyl
stearamide wax, (c) a dimer acid based tetra-amide that is the
reaction product of dimer acid, ethylene diamine, and a carboxylic
acid having at least about 36 carbon atoms, (d) a urethane resin
derived from the reaction, of two equivalents of hydroabietyl
alcohol and one equivalent of isophorone diisocyanate, (e) a
urethane resin that is the adduct of three equivalents of stearyl
isocyanate and a glycerol-based alcohol, and (f) an
antioxidant.
19. A phase change ink composition according to claim 1 wherein the
ink carrier comprises (a) a polyethylene wax in an amount of at
least about 25 percent by weight of the ink and in an amount of no
more than about 60 percent by weight of the ink, (b) a stearyl
stearamide wax in an amount of at least about 8 percent by weight
of the ink and in an amount of no more than about 32 percent by
weight of the ink, (c) a dimer acid based tetra-amide that is the
reaction product of dimer acid, ethylene diamine, and a carboxylic
acid having at least about 36 carbon atoms in an amount of at least
about 10 percent by weight of the ink and in an amount of no more
than about 32 percent by weight of the ink, (d) a urethane resin
derived from the reaction of two equivalents of hydroabietyl
alcohol and one equivalent of isophorone diisocyanate in an amount
of at least about 6 percent by weight of the ink and in an amount
of no more than about 16 percent by weight of the ink, (e)
aurethane resin that is the adduct of three equivalents of stearyl
isocyanate and a glycerol-based alcohol in an amount of at least
about 2 percent by weight of the ink and in an amount of no more
than about 13 percent by weight of the ink, and (f) an antioxidant
in an amount of at least about 0.01 percent by weight of the ink
and in an amount of no more than about 1 percent by weight of the
ink.
20. A phase change ink composition according to claim 1 wherein the
colorant is present in the ink in an amount of at least about 0.1
percent by weight of the ink.
21. A phase change ink composition according to claim 1 wherein the
colorant is present in the ink in an amount of at least about 0.5
percent by weight of the ink.
22. A phase change ink composition according to claim 1 wherein the
colorant is present in the ink in an amount of at least about 1
percent by weight of the ink.
23. A phase change ink composition according to claim 1 wherein the
colorant is present in the ink in an amount of no more than about
20 percent by weight of the ink.
24. A phase change ink composition according to claim wherein the
colorant is present in the ink in an amount of no more than about
13 percent by weight of the ink.
25. A phase change ink composition according to claim 1 wherein the
colorant is present in the ink in an amount of no more than about 6
percent by weight of the ink.
26. A phase change ink composition according to, claim 1 wherein
the ink has a melting point of no lower than about 50.degree. C.
and wherein the ink has a melting point of no higher than about
160.degree. C.
27. A phase change ink composition according to claim 1 wherein the
ink has a melting point of no lower than about 70.degree. C. and
wherein the ink has a melting point of no higher than about
140.degree. C.
28. A phase change ink composition according to claim 1 wherein the
ink has a melting point of no lower than about 80.degree. C. and
wherein the ink has a melting point of no higher than about
100.degree. C.
29. A phase change ink composition according to claim 1 wherein the
ink has a melt viscosity at a temperature of about 140.degree. C.
of no more than about 30 centipoise.
30. A phase change ink composition according to claim 1 wherein the
ink has a melt viscosity at a temperature of about 140-C of no more
than about 20 centipoise.
31. A phase change ink composition according to claim 1 wherein the
ink has d melt viscosity at a temperature of about 140.degree. C.
of no more than about 15 centipoise.
32. A phase change ink composition according to claim 1 wherein the
ink has a melt viscosity at a temperature of about 140-C of no less
than about 1 centipoise.
33. A phase change ink composition according to claim 1 wherein the
ink has a melt viscosity at a temperature of about 140.degree. C.
of no less than about 5 centipoise.
34. A phase change ink composition according to claim 1 wherein the
ink has a melt viscosity at a temperature of about 140.degree. C.
of no less than about 7 centipoise.
35. A phase change ink composition according to claim 1 further
containing an anthraquinone colorant.
36. A phase change ink composition according to claim 35 wherein
the anthraquinone colorant is Solvent Red. 72.
37. A phase change ink composition according to claim 35 wherein
the anthraquinone colorant is of the formula 188wherein R.sub.2 is
a linear alkyl group having an average of about 50 carbon
atoms.
38. A phase change ink composition according to claim 1 further
containing an acid having a K.sub.0 value greater than that of the
K.sub.a of the Q and/or Q.sup.- groups on the colorant.
39. A phase change ink composition according to claim 38 wherein
the acid is para-toluene-sulfonic acid, dodecylbenzenesulfonic
acid, hydrochloric acid, trifluoroacetic acid, methylsulfonic acid,
trifluoromethyl sulfonic acid, hydrobromic acid, or a mixture
thereof.
40. A phase change ink composition according to claim 1 wherein M
is a metal ion of a metal selected from magnesium, calcium,
strontium, barium, radium, aluminum, gallium, germanium, indium,
tin, antimony, tellurium, thallium, lead, bismuth, polonium,
scandium, titanium, vanadium, chromium, manganese, iron, cobalt,
nickel, copper, zinc, zirconium, niobium molybdenum, technetium,
ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum,
tungsten, rhenium, osmium, iridium, platinum, gold, mercury, metals
of the lanthamide series, metals of the actinide series, and
mixtures thereof.
41. A phase change ink composition according to claim 1 wherein M
is a metal ion of a metal selected from zinc, calcium, bismuth,
tin, iron, copper, aluminum, nickel, titanium, chromium, or
mixtures thereof.
42. A phase change ink composition according to claim 1 wherein M
is a zinc metal ion.
43. A phase change ink composition according to claim 1 wherein M
is a metal-containing moiety which is a metal ionic moiety.
44. A phase change ink composition according to claim 1 wherein M
is a metal-containing moiety which is a metal coordination
compound.
45. A phase change ink composition according to claim 1 wherein M
is a metal-containing moiety which is a heteropolyacid.
46. A phase change ink composition according to claim 45 wherein
the heteropolyacid is a phosphotungstic acid, a silicotungstic
acid, a phosphomolybdic acid, or a mixture thereof.
47. A phase change ink composition according to claim 45 wherein
the heteropolyacid is a mixture of phosphomolybdic acid and
phosphotungstic acid.
48. A phase change ink, composition according to claim 1 wherein
the compound is of the formula 189wherein M is a metal cation, y is
an integer representing the charge on the metal cation and is at
least 2, A is an anion, and x is an integer representing the charge
on the anion.
49. A phase change ink composition according to claim 1 wherein a,
b, and c are each zero.
50. A phase change ink composition according to claim 1 wherein d
is 1.
51. A phase change ink composition according to claim 1 wherein d
is 2.
52. A phase change ink composition according to claim 1 wherein d
is 1 and Q.sup.- is a COO.sup.- group.
53. A phase change ink composition according to claim 1 wherein d
is 1 and Q.sup.- is a SO.sub.3-- group.
54. A phase change ink composition according to claim 1 wherein
190
55. A phase change ink composition according to claim 1 wherein
191
56. A phase change ink composition according to claim 1 wherein
192
57. A phase change ink composition according to claim 1 wherein
193
58. A phase change ink composition according to claim 1 wherein at
least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is an alkyl
group.
59. A phase change ink composition according to claim 58 wherein
the alkyl group is a linear alkyl group.
60. A phase change ink composition according to claim 58 wherein
the alkyl group is a branched alkyl group.
61. A phase change ink composition according to claim 58 wherein
the alkyl group is a saturated alkyl group.
62. A phase change ink composition according to claim 58 wherein
the alkyl group is an unsaturated alkyl group.
63. A phase change ink composition according to claim 58 wherein
the alkyl group is a cyclic alkyl group.
64. A phase change ink composition according to claim 58 wherein
the alkyl group is a substituted alkyl group.
65. A phase change ink composition according to claim 58 wherein
the alkyl group is an unsubstituted alkyl group.
66. A phase change ink composition according to claim 58 wherein
the alkyl group has at least about 18 carbon atoms.
67. A phase change ink composition according to claim 58 wherein at
least one hetero atom selected from oxygen, nitrogen, sulfur,
silicon; or phosphorus is present in the alkyl group.
68. A phase change ink composition according to claim 58 wherein no
hetero atoms are present in the alkyl group.
69. A phase change ink composition according to claim 1 wherein at
least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is an aryl
group.
70. A phase change ink composition according to claim 69 wherein
the aryl group is a substituted aryl group.
71. A phase change ink composition according to claim 69 wherein
the aryl group is an unsubstituted aryl group.
72. A phase change ink composition according to claim 69 wherein at
least one hetero atom selected from oxygen, nitrogen, sulfur,
silicon, or phosphorus is present in the aryl group.
73. A phase change ink composition according to claim 69 wherein no
hetero atoms are present in the aryl group.
74. A phase change ink composition according to claim 1 wherein at
least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is an arylalkyl
group.
75. A phase change ink composition according to claim 74 wherein
the arylolkyl group is a substituted arylalkyl group.
76. A phase change ink composition according to claim 74 wherein
the arylalkyl group is an unsubstituted arylalkyl group.
77. A phase change ink composition according to claim 74 wherein at
least one hetero atom selected from oxygen, nitrogen, sulfur,
silicon, or phosphorus is present in the arylalkyl group.
78. A phase change ink composition according to claim 74 wherein no
hetero atoms are present in the arylalkyl group.
79. A phase change ink composition according to claim 1 wherein at
least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is an alkylaryl
group.
80. A phase change ink composition according to claim 79 wherein
the alkylaryl group is a substituted alkylaryl group.
81. A phase change ink composition according to claim 79 wherein
the alkylaryl group is an unsubstituted alkylaryl group.
82. A phase change ink composition according to claim 79 wherein at
least one hetero atom selected from oxygen, nitrogen, sulfur,
silicon, or phosphorus is present in the alkylaryl group.
83. A phase change ink composition according to claim 79 wherein no
hetero atoms are present in the alkylaryl group.
84. A phase change ink composition according to claim 1 wherein
R.sub.1 and R.sub.2 are joined together to form d ring.
85. A phase change ink composition according to claim 1 wherein
R.sub.1 and R.sub.2 are joined together to form a ring and wherein
R.sub.3 and R.sub.4 are joined together to form a ring.
86. A phase change ink composition according to claim 1 wherein at
least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is joined to a
phenyl ring in the central structure.
87. A phase change ink composition according to claim 1 wherein the
number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R.sub.-
7+R.sub.8+R.sub.9+R.sub.10 is at least about 32.
88. A phase change ink composition according to claim 1 wherein the
number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R.sub.-
7+R.sub.8+R.sub.9+R.sub.10 is at least about 48.
89. A phase change ink composition according to claim 1 wherein the
number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R.sub.-
7+R.sub.8+R.sub.9+R.sub.10 is at least about 72.
90. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 194
91. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 195
92. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 196
93. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 197wherein n is at least about 11.
94. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 198
95. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 199wherein n is at least about 12.
96. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 200wherein n is at least about 12.
97. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 201wherein n is at least about 12.
98. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 202
99. A phase change ink composition according to claim 1 wherein the
chromogen is of the formula 203wherein n is at least about 12.
100. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 204wherein n is at least about
12.
101. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 205wherein n is at least about
12.
102. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 206
103. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 207wherein n is at least about
12.
104. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 208wherein n is at least about
12.
105. A phase change ink composition according to claim 1 wherein
the chromogen is; of the formula 209wherein n is at least about
12.
106. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 210
107. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 211
108. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 212
109. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 213wherein n is at least about
12.
110. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 214wherein n is at least about
12.
111. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 215wherein n is at least about
12.
112. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 216
113. A phase change ink composition according to claim. 1 wherein
the chromogen is of the formula 217wherein n is at least ab out
12.
114. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 218wherein n is at least about
12.
115. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 219wherein n is at least about
12.
116. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 220wherein n has an average value
of at least about 12.
117. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 221wherein n has an average value
of about 50.
118. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 222
119. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 223
120. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 224
121. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 225
122. A phase change ink composition according to claim 1 wherein
the chromogen is of the formula 226
123. A phase change ink composition according to claim 1 wherein M
is a zinc cation, y is 2, and the chromogen is of the formula
227
124. A phase change ink composition according to claim 123 wherein
z is 2.
125. A phase change ink composition according to claim 1 wherein M
is a calcium cation, y is 2, and the chromogen is of the formula
228
126. A phase change ink composition according to claim 125 wherein
z is 2.
127. A phase change ink composition according to claim 1 wherein M
is a bismuth cation, y is 3, and the chromogen is of the formula
229
128. A phase change ink composition according to claim 127 wherein
z is 3.
129. A phase change ink composition according to claim 1 wherein M
is a tin cation, y is 2, and the chromogen is of the formula
230
130. A phase change ink composition according to claim 129 wherein
z is 2.
131. A phase change ink composition according to claim 1 wherein M
is an iron cation, y is 2, and the chromogen is of the formula
231
132. A phase change ink composition according to claim 131 wherein
z is 2.
133. A phase change ink composition according to claim 1 wherein M
is a copper cation, y is 2, and the chromogen is of the formula
232
134. A phase change ink composition according to claim 133 wherein
z is 2.
135. A phase change ink composition according to claim 1 wherein M
is an aluminum cation, y is 3, and the chromogen is of the formula
233
136. A phase change ink composition according to claim 135 wherein
z is 3.
137. A phase change ink composition according to claim 1 wherein M
is a nickel cation, y is 2, and the chromogen islof the formula
234
138. A phase change ink composition according to claim 137 wherein
z is 2.
139. A phase change ink composition according to claim 1 wherein M
is a titanium cation, y is 4, and the chromogen is of the formula
235
140. A phase change ink composition according to claim 139 wherein
z is 4.
141. A phase change ink composition according to claim 1 wherein M
is a chromium cation, y is 3, and the chromogen is of the formula
236
142. A phase change ink composition according to claim 141 wherein
z is 3.
143. A phase change ink composition comprising a phase change ink
carrier and a colorant which is the reaction product of (a) a
chromogen of the formula 237wherein R.sub.1, R.sub.2, R.sub.3, and
R.sub.4 each, independently of the others, is (i) a hydrogen atom,
(ii) an alkyl group, (iii) an aryl group, (iv) an arylalkyl group,
or (v) an alkylaryl group, wherein R.sub.1 and R.sub.2 can be
joined together to form a ring, wherein R.sub.3 and R.sub.4 can be
joined together to form a ring, and wherein R.sub.1, R.sub.2,
R.sub.3, and R.sub.4 can each be joined to a phenyl ring in the
central structure, a and b each, independently of the others, is an
integer which is 0, 1, 2, or 3, c is an integer which is 0, 1, 2,
3, or 4, each R.sub.5, R.sub.6, and R.sub.7, independently of the
others, is (i) an alkyl group, (ii) an aryl group, (iii) an
arylalkyl group, (iv) an alkylaryl group, (v) a halogen atom, (vi)
an ester group, (vii) an amide group, (viii) a sulfone group, (ix)
an amine group or ammonium group, (x) a nitrite group, (xi) a nitro
group, (xii) a hydroxy group, (xiii) a cyano group, (xiv) a
pyridine or pyridinium group, (xv) an ether group, (xvi) an
aldehyde group, (xvii) a ketone group, (xviii) a carbonyl group,
(xix) a thiocarbonyl group, (xx) a sulfate group, (xxi) a sulfide
group, (xxii) a sulfoxide group, (xxiii) a phosphine or phosphonium
group, (xxiv) a phosphate group, (xxv) a mercapto group, (xxvi) a
nitroso group, (xxvii) an acyl group, (xxviii) an acid anhydride
group, (xxix) an azide group, (xxx) an azo group, (xxxi) a cyanato
group, (xxxii) an isocyanato group, (xxxiii) a thiocyanato group,
(xxxiv) an iso thiocyanato group, (xxxv) a urethane group, or
(xxxvi) a urea group, wherein R.sub.5, R.sub.6, and R.sub.7 can
each be joined to a phenyl ring in the central structure,
238R.sub.8, R.sub.9, and R.sub.10 each, independently of the
others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an aryl
group, (iv) an arylalkyl group, or (v) an alkylaryl group,
provided; that the number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.su-
b.4+R.sub.5+R.sub.6+R.sub.7+R.sub.8+R.sub.9+R.sub.10 is at least
about 16, Q.sup.- is a COO.sup.- group or a SC.sub.3.sup.- group, d
is an integer which is 1, 2, 3, 4, or 5, A is an anion, and CA is
either a hydrogen atom or a cation associated with all but one of
the Q.sup.- groups, and (b) a metal salt of which the metal portion
is either (1) a metal ion having a positive charge of +y wherein y
is an integer which is at least 2, said metal ion being capable of
forming a compound with at least two 239chromogen moieties, or (2)
a metal-containing moiety capable of forming a compound with at
least two 240chromogen moieties.
144. A process which comprises (1) incorporating into an ink jet
printing apparatus a phase change ink composition comprising a
phase change ink carrier and a colorant compound of the formula
241wherein M is either (1) a metal ion having a positive charge of
+y wherein y is an integer which is at least 2, said metal ion
being capable 242chromogen moieties, or (2) a metal-containing
moiety capable of forming a compound with at least two 243chromogen
moieties, z is an integer representing the number of 244chromogen
moieties associated with the metal and is at least 2, R.sub.1,
R.sub.2, R.sub.3, and R.sub.4 each, independently of the others, is
(i) a hydrogen atom, (ii) an alkyl group, (iii) an aryl group, (iv)
an arylalkyl group, or (v) an alkylaryl group, wherein R.sub.1 and
R.sub.2 can be joined together to form a ring, wherein R.sub.3 and
R.sub.4 can be joined together to form a ring, and wherein R.sub.1,
R.sub.2, R.sub.3, and R.sub.4 can each be joined to a phenyl ring
in the central structure, a and b each, independently of the
others, is an integer which is 0, 1, 2, or 3, c is an integer which
is 0, 1, 2, 3, or 4, each R.sub.5, R.sub.6, and R.sub.7,
independently of the others, is (i) an alkyl group, (ii) an aryl
group, (iii) an arylalkyl group, (iv) an alkylaryl group, (v) a
halogen atom, (vi) an ester group, (vii) an amide group, (viii) a
sulfone group, (ix) an amine group or ammonium group, (x) a nitrile
group, (xi) a nitro group, (xii) a hydroxy group, (xiii) a cyano
group, (xiv) a pyridine or pyridinium group, (xv) an ether group,
(xvi) an aldehyde group, (xvii) a ketone group, (xviii) a carbonyl
group, (xix) a thiocarbonyl group, (xx) a sulfate group, (xxi) a
sulfide group, (xxii) a sulfoxide group, (xxiii) a phosphine or
phosphonium group, (xxiv) a phosphate group, (xxv) a mercapto
group, (xxvi) a nitroso group, (xxvii) an acyl group, (xxviii) an
acid anhydride group, (xxix) an azide group, (xxx) an azo group,
(xxxi) a cyanato group, (xxxii) an isocyanato group, (xxxiii) a
thiocyanato group, (xxxiv) an isothiocyanato group, (xxxv) a
urethane group, or (xxxvi) a urea group, wherein R.sub.5, R.sub.6,
and R.sub.7 can each be joined to a phenyl ring in the central
structure, 245R.sub.8, R.sub.9, and R.sub.10 each, independently of
the others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an
aryl group, (iv) an arylalkyl group, or (v) an alkylaryl group,
provided that the number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R.sub.7+R-
.sub.8+R.sub.9+R.sub.10 is at least about 16, Q.sup.- is a COO--
group or a SO.sub.3-- group, d is an integer which is 1, 2, 3, 4,
or 5, A is an anion, and CA is either a hydrogen atom or a cation
associated with all but one of the Q groups; (2) melting the ink;
and (3) causing droplets of the melted ink to be ejected in an
imagewise pattern onto a substrate.
145. A process according to claim 144 wherein 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.
146. A process according to claim 144 wherein the substrate is a
final recording sheet and droplets of the melted ink are ejected in
an imagewise pattern directly onto the final recording sheet.
147. A process according to claim 144 wherein the substrate is an
intermediate transfer member and droplets of the melted ink are
ejected in an imagewise pattern onto the intermediate transfer
member followed by transfer of the imagewise pattern from the
intermediate transfer member to a final recording sheet.
148. A process according to claim 147 wherein 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.
Description
[0001] Cross-reference is made to the following copending
applications:
[0002] Copending application U.S. Ser. No. 10/260,146, filed Sep.
27, 2002, entitled "Colorant Compounds," with the named inventors
Jeffery H. Banning and C. Wayne Jaeger, the disclosure of which is
totally incorporated herein by reference, discloses compounds of
the formula 5
[0003] wherein Y is a hydrogen atom or a bromine atom, n is an
integer of 0, 1, 2, 3, or 4, R.sub.1 is an alkylene group or an
arylalkylene group, and X is (a) a hydrogen atom, (b) a group of
the formula 6
[0004] wherein R.sub.2 is an alkyl group, an aryl group, an
arylalkyl group, or an alkylaryl group, (c) an alkyleneoxy,
aryleneoxy, arylalkyleneoxy, or alkylaryleneoxy group, or (d) a
group of the formula 7
[0005] wherein R.sub.4 is an alkyl group, an aryl group, an
arylalkyl group, or an alkylaryl group.
[0006] Copending application U.S. Ser. No. 10/260,376, filed Sep.
27, 2002, entitled "Phase Change Inks," with the named inventors C.
Wayne Jaeger and Jeffery H. Banning, the disclosure of which is
totally incorporated herein by reference, discloses a phase change
ink composition comprising a phase change ink carrier and a
colorant compound of the formula 8
[0007] wherein Y is a hydrogen atom or a bromine atom, n is an
integer of 0, 1, 2, 3, or 4, R.sub.1 is an alkylene group or an
arylalkylene group, and X is (a) a hydrogen atom, (b) a group of
the formula 9
[0008] wherein R.sub.2 is an alkyl group, an aryl group, an
arylalkyl group, or an alkylaryl group, (c) an alkyleneoxy,
aryleneoxy, arylalkyleneoxy, or alkylaryleneoxy group, or (d) a
group of the formula 10
[0009] wherein R.sub.4 is an alkyl group, an aryl group, an
arylalkyl group, or an alkylaryl group.
[0010] Copending application U.S. Ser. No. 10/260,379, filed Sep.
27, 2002, entitled "Methods for Making Colorant Compounds," with
the named inventors C. Wayne Jaeger and Jeffery H. Banning, the
disclosure of which is totally incorporated herein by reference,
discloses a process for preparing a colorant of the formula 11
[0011] wherein Y is a hydrogen atom or a bromine atom, n is an
integer of 0, 1, 2, 3, or 4, R.sub.1 is an alkylene group or an
arylalkylene group, R.sub.2 is an alkyl group, an aryl group, an
arylalkyl group, or an alkylaryl group, and R.sub.4 is an alkyl
group, an aryl group, a n arylalkyl group, or an alkylaryl group,
can be prepared by a process which comprises (a) preparing a first
reaction mixture by admixing (1) leucoquinizarin and, optionally,
quinizarin, (2) an aminobenzene substituted with an alcohol group
of the formula --R.sub.1--OH, (3) boric acid, and (4) an optional
solvent, and heating the first reaction mixture to prepare an
alcohol-substituted colorant of the formula 12
[0012] followed by (b) converting the colorant thus prepared to
either (i) an ester-substituted colorant by reaction with an
esterificdtion compound which is either (A) an anhydride of the
formula 13
[0013] or (B) an acid of the formula R.sub.2COOH in the presence of
an optional esterification catalyst, or (ii) a urethane-substituted
colorant by reaction with an isocyanate compound of the formula
R.sub.4--N.dbd.C.dbd.O
[0014] and (c) brominating the colorant thus prepared, wherein
either conversion to ester or urethane can be performed before
bromination or bromination can be performed before conversion to
ester or urethane.
[0015] Copending application U.S. Ser. No. ______ (not yet
assigned; Attorney Docket Number D/A3152), filed concurrently
herewith, entitled "Colorant Compounds," with the named inventors
Jeffery H. Banning, Bo Wu, James M. Duff, Wolfgang G. Wedler, Jule
W. Thomas, and Randall R. Bridgeman, the disclosure of which is
totally incorporated herein by reference, discloses compounds of
the formula 14
[0016] wherein M is either (1) a metal ion having a positive charge
of +y wherein y is an integer which is at least 2, said metal ion
being capable of forming a compound with at least two 15
[0017] chromogen moieties, or (2) a metal-containing moiety capable
of forming a compound with at least two 16
[0018] chromogen moieties, z is an integer representing the number
of 17
[0019] chrombgen moieties associated with the metal and is at least
2, and R., R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, a,
b, c, d, Y, Q.sup.-, A, and CA are as defined therein.
[0020] Copending application U.S. Ser. No. ______ (not yet
assigned; Attorney Docket Number D/A3153), filed concurrently
herewith, entitled "Colorant Compounds," with the named inventors
Jeffery H. Banning, Bo Wu, James M. Duff, Wolfgang G. Wedler, and
Donald R. Titterington, the disclosure of which is totally
incorporated herein by reference, discloses compounds of the
formulae 18
[0021] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.15,
R.sub.6, R.sub.7, a, b, c, d, Y, Q, Q.sup.-, A, and CA are, as
defined therein.
[0022] Copending application U.S. Ser. No. ______ (not yet
assigned; Attorney Docket Number D/3153Q), filed concurrently
herewith, entitled "Phase Change Inks Containing Colorant
Compounds," with the named inventors Bo Wu, Jeffery H. Banning,
James M. Duff, Wolfgang G. Wedler, and Donald R. Titterington, the
disclosure of which is totally incorporated herein by reference,
discloses phase change inks comprising a carrier and a colorant of
the formula 19
[0023] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.6, R.sub.7, a, b, c, d, Y. Q, Q-, A, and CA are as defined
therein.
BACKGROUND
[0024] The present invention is directed to phase change inks. More
specifically, the present invention is directed to hot melt or
phase change inks containing specific colorant compounds. One
embodiment of the present invention is directed to a phase change
ink carrier and a colorant compound of the formula 20
[0025] wherein M is either (1) a metal ion having a positive charge
of +y wherein y is an integer which is at least 2, said metal ion
being capable of forming a compound with at least two 21
[0026] chromogen moieties, or (2) a metal-containing moiety capable
of forming a compound with at least two 22
[0027] chromogen moieties, z is an integer representing the number
of 23
[0028] chromogen moieties associated with the metal and is at least
2, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each, independently of
the others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an
aryl group; (iv) an arylalkyl group, or (v) an alkylaryl group,
wherein R.sub.1 and R.sub.2 can be joined together to form a ring,
wherein R.sub.3 and R.sub.4 can be joined together to form a ring,
and wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 can each be
joined to a phenyl ring in the central structure, a and b each,
independently of the others, is an integer which is 0, 1, 2, or 3,
c is an integer which is 0, 1, 2, 3, or 4, each R.sub.5, R.sub.6,
and R.sub.7, independently of the others, is (i) an alkyl group,
(ii) an aryl group, (iii) an arylalkyl group, (iv) an alkylaryl
group, (v) a halogen atom, (vi) an ester group, (vii) an amide
group, (viii) a sulfone group, (ix) an amine group or ammonium
group, (x) a nitrile group, (xi) a nitro group, (xii) a hydroxy
group, (xiii) a cyano group, (xiv) a pyridine or pyridinium group,
(xv) an ether group, (xvi) an aldehyde group, (xvii) a ketone
group, (xviii) a carbonyl group, (xix) a thiocarbonyl group, (xx) a
sulfate group, (xxi) a sulfide group, (xxii) a sulfoxide group,
(xxiii) a phosphine or phosphonium group, (xxiv) a phosphate group,
(xxv) a mercapto group, (xxvi) a nitroso group, (xxvii) on acyl
group, (xxviii) an acid anhydride group, (xxix) an azide group,
(xxx) an azo group, (xxxi) a cyanato group, (xxxii) an isocyanato
group, (xxxiii) a thiocyanato group, (xxxiv) an isothiocyanato
group, (xxxv) a urethane group, or (xxxvi) a urea group, wherein
R.sub.5, R.sub.6, and R.sub.7 can each be joined to a phenyl ring
in the central structure, 24
[0029] R.sub.8, R.sub.9, and R.sub.10 each, independently of the
others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an aryl
group, (iv) an arylalkyl group, or (v) an alkylaryl group, provided
that the number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R?+R.sub.-
8+R.sub.9+R.sub.10 is at least about 16, Q.sup.- is a COO.sup.-
group or a SO.sub.3.sup.- group, d is an integer which is 1, 2, 3,
4, or 5, A is an anion, and CA is either a hydrogen atom or a
cation associated with all but one of the Q.sup.- groups.
[0030] In 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
an 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 an 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, U.S. Pat. No. 5,496,879 and German Patent
Publications DE 4205636AL and DE 4205713AL, the disclosures of each
of which are totally incorporated herein by reference.
[0031] Phase 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 black can be obtained by
mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat. No.
4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each of
which are totally incorporated herein by reference, 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, U.S. Pat. No.
5,221,335, the disclosure of which is totally incorporated herein
by reference. U.S. Pat. No. 5,621,022, the disclosure of which is
totally incorporated herein by reference, discloses the use of a
specific class of polymeric dyes in phase change ink
compositions.
[0032] Phase change inks have also been used for applications
such-as postal marking, industrial marking, and labelling.
[0033] Phase 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.
[0034] Compositions suitable for use as phase change ink carrier
compositions are known. Some representative examples of references
disclosing such materials include U.S. Pat. No. 3,653,932, U.S.
Pat. No. 4,390,369, U.S. Pat. No. 4,484,948, U.S. Pat. No.
4,684,956, U.S. Pat. No. 4,851,045, U.S. Pat. No. 4,889,560, U.S.
Pat. No. 5,006,170, U.S. Pat. No. 5,151,120, U.S. Pat. No.
5,372,852, U.S. Pat. No. 5,496,879, European Patent Publication
0187352, European Patent Publication 0206286, German Patent
Publication DE 4205636AL, German Patent Publication DE 4205713AL,
and PCT Patent Application WO 94/04619, the disclosures of each of
which are totally incorporated herein by reference. 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.
[0035] British Patent Publication GB 2 311 075 (Gregory et al.),
the disclosure of which is totally incorporated herein by
reference, discloses a compound of the formula 25
[0036] wherein X.sup.1 is an ester group or an amide group (such as
of a carboxylic or sulfonic acid) or a fatty amine salt of a
sulfonic acid, each X.sub.2 independently is a substituent, m has a
value of from 0 to 2, Y.sub.1 and Y.sub.2 are each independently H,
alkyl, or halo, each Z independently is an ester or amide group,
and A.sup.- is an anion. The compound is useful as a colorant for
toners, D2T2 printing, plastics, polyesters, nylons, and inks,
especially ink jet or hot melt inks.
[0037] "Rhodamine Dyes and Related Compounds. XV. Rhodamine Dyes
with Hydroaromatic and Polymethylene Radicals," I. S. Ioffe et al.,
Zh. Organ. Khim. (1965), 1 (3), 584-6, the disclosure of which is
totally incorporated herein by reference, discloses a process
wherein heating dichlorofluoran with ZnCl.sub.2--ZnO and the
appropriate amine for 3 hours at 220.degree. followed by treatment
with aqueous HCl gave N,N'-dicyclohexylrhodamine-HCl, m.
180-5.degree., N,N'-di(tetramethylene)- rhodamihe-HCl, decompd.
240.degree., N,N'-di(pentdmethylene)rhodamine-HCl, m. 205-100,
N,N'-di(hexamethylene)rhodamine-HCl, decompd. 1750. These dyes gave
yellow or orange fluorescence and their spectra were given.
[0038] "Rhodamine Dyes and Related Compounds. XI. Aryl- and
Alkylrhodamines Containing Carboxyl Groups," I. S. Ioffe et al.,
Zh. Obsch. Khim. (1964), 34(6), 2041-4, the disclosure of which is
totally incorporated herein by reference, discloses a process
wherein heating aminobenzoic acids with 3,6-dichlorofluoran in the
presence of ZnCl.sub.2 for 6 hours at 24-500 gave after an aqueous
treatment: N,N'-bis(o-carboxyphenyl)rhodamine-HCl; m-isomer-HCl;
and p-isomer-HCl. A similar reaction with HCl salts of glycine,
x-alanine, or .beta.-alanine gave:
N,N'-bis(carboxymethyl)rhodamine-HCl;
N,N'-bis(.alpha.-carboxyethyl- )rhodamine-HCl; and
N,N'-bis(.beta.-carboxyethyl)rhodamine-HCl. The latter group showed
yellow-green fluorescence, lacking in the aryl derivatives. Spectra
of the products are shown.
[0039] "Rhodamine Dyes and Related Compounds. X. Fluorescence of
Solutions of Alkyl- and Arylalkylrhodamines," I. S. Ioffe et al.,
Zh. Obsch. Khim. (1964), 34(6), 2039-41, the disclosure of which is
totally incorporated herein by reference, discloses fluorescence
spectra for the following rhodamines: N,N'-diethyl; N,N'-dibenzyl;
N,N'-bis(.beta.-phenylethyl); N,N'-bis(.beta.-phenylisopropyl). In
symmetrical substituted rhodamines, the entry of an alkyl or
arylalkyl group into both amino residues resulted in the
displacement of fluorescence max. toward longer wavelengths, a
similar displacement of absorption and an increase in the quantum
yield of fluorescence. In unsymmetrical derivatives, an aryl group
entering one of the amino groups shifted the spectra to a greater
degree in the same direction and sharply reduced the quantum yield
of fluorescence.
[0040] "Rhodamine Dyes and Related Compounds. IX. Rhodamine B
Sulfonic Acids and their Derivatives," I. S. Ioffe et al., Zh.
Obsch. Khim. (1964), 34(2), 640-44, the disclosure of which is
totally incorporated herein by reference, discloses that heating
m-Et.sub.2NC.sub.6H.sub.4OH and K .beta.-sulfophthalate at
150.degree. while concentrated H.sub.2SO.sub.4 was being added gave
after 3 hours at 150-700, followed by heating with H.sub.2O 15
min., a residue, of crude sulforhodamine, purified by solution in
hot aqueous Na.sub.2CO.sub.3 and precipitation with AcOH. The mixed
isomeric rhodamine sulfonic acids refluxed 3 hours with 30% AcOH,
clarified, and cooled gave a first isomer with R.sub.f 0.74 on
paper in aqueous-solution (pH 9) while the residue was the other
isomer with R.sub.f 0.98. The first isomer and PCl.sub.5 gave the
sulfonyl chloride, isolated as HCl salt, red solid (from
CHCl.sub.3-ligroine), which with NH.sub.3 in CHCl.sub.3 gave the
sulfonamide, a violet powder. The two isomers and Rhodamine B had
similar spectral characteristics. The two isomers probably contain
the SO.sub.3H group in the 4- and 5-positions of the Ph ring of
Rhodamine B. Their absorption and fluorescence spectra are shown.
Their solutions in CHCl.sub.3 gave stronger fluorescence than those
in Me.sub.2CO.
[0041] "Rhodamine Dyes and Related Compounds. VIII. Amides of
Sulforhodamine B Containing .beta.-Hydroxyethyl and
.beta.-Chloroethyl Groups," I. S. Ioffe et al., Zh. Obsch. Khim.
(1963), 33(12), 394376, the disclosure of which is totally
incorporated herein by reference, discloses that sulforhodamine B
chloride heated 10-12 hours with HOCH.sub.2CH.sub.2NH.sub.2 at
170-80.degree., then triturated with saturated NaCl gave, after
solution in CHCl.sub.3 and precipitation with petroleum ether, 80%
red sulforhodamine B N(.beta.-hydroxyethyl)amide; similar reaction
with HN(CH.sub.2CH.sub.2OH).sub.2 gave 70%
N,N-bis(.beta.-hydroxyethyl)amide, a bright red wax. These treated
with SOCl.sub.2 in CHCl.sub.3 gave, respectively,
N--(.beta.-chloroethyl)amide- , a brown powder, and
N,N-bis(.beta.-chloroethyl)amide, a violet powder. Absorption
spectra of the amides are shown. The (hydroxyethyl)amides displayed
strong orange fluorescence in solution.
[0042] "Rhodamine Dyes and Related Compounds. VII.
(.beta.-Phenylethyl)rho- damines," I. S. Ioffe et al., Zh. Obsch.
Khim. (1963), 33(4), 1089-92, the disclosure of which is totally
incorporated herein by reference, discloses a process wherein
heating dichlorofluoran with PhCH.sub.2CH.sub.2NH.sub.2 or
PhCH.sub.2CH(Me)NH.sub.2 in the presence of ZnO and ZnCl.sub.2 for
5-6 hours at 2200 gave, after heating for 2 hours with aqueous HCl,
96-8% crude products which, after crystallization from alc. HCl,
gave red, powdery N,N'-bis(.beta.-phenylethyl)rhodamine-HCl, m.
172-50, or
N,N'-bis(.alpha.-methyl-.beta.-phenylethyl)rhodamine-HCl, m.
1.75-80; N-phenyl-N'-(C-phenylethyl)rhodamine-HCl, m. 162-60, was
prepared from PhCH.sub.2CH.sub.2NH.sub.2 and
3'-chloro-6'-anilinofluoran under the above conditions. Treated
with alc. NaOH and quenched in H.sub.2O, these hydrochlorides gave
the free bases of the dyes as brown-red solids, which tended to
form colloids in aqueous medium. The free bases m. 123-5.degree.,
decompd. 120.degree., and m. 164-8.degree., respectively. The
ultraviolet and visible spectra of the dyes were similar to the
spectra of dibenzylrhodamine, but had deeper color; strong
fluorescence, was shown by these dyes. The spectrum of the
bis(.beta.-phenylethyl)rhodamine was almost identical: with that of
diethylrhodamine.
[0043] "Rhodamine Dyes and Related Compounds. VI. Chloride and
Amides of Sulforhodamine, B," 1. S. Ioffe et al., Zh. Obsch. Khim.
(1962), 32, 1489-92, the disclosure of which is totally
incorporated herein by reference, discloses that sulforhodamine B
(5 g., dried, at 1250) and 3 g. PCl.sub.5 heated in 50 milliliters
CHCl.sub.3 for 4 hours, then extd. with cold H.sub.2O to remove
excess PCl.sub.6, gave, after concentration of the dried organic
layer and treatment of the residue with much cold petroleum ether,
the dark red p-sulfonyl chloride,
C.sub.27H.sub.29O.sub.6N.sub.2S2Cl, which slowly forms the original
compound on contact with H.sub.2O. With NH.sub.3 in CHCl.sub.3 it
gave the corresponding p-sulfonamide, 81%, red-violet powder, sol.
in EtOH or AcOH; similarly was prepared the p-sulfonanilide,
brown-violet solid. These have absorption spectra similar to the
original compound but with less intense absorption. The p-sulfonyl
chloride has a more intense absorption than the amides.
[0044] "Rhodamine Dyes and Related Compounds. V.
.alpha.-Pyridylrhodamine,- " 1. S. Ioffe et al., Zh. Obsch. Khim.
(1962), 32, 1485-9, the disclosure of which is totally incorporated
herein by reference, discloses a process wherein heating
3,6-dichlorofluorane with 2-aminopyridine in the presence of
ZnCl.sub.2 for 3 hours at 160-800 gave, after extraction with hot
H.sub.2O and EtOH and crystallization of the residue from aqueous
Me.sub.2CO, 3-chloro-6-x-pyridylaminofluorane-HCl, m. 280-20; free
base, m. 185-7.degree.. This heated with 2-aminopyridine and
ZnCl.sub.2 at 250-60.degree. for 6 hours, then precipitated from
hot EtOH--HCl with H.sub.2O, gave red
N,N'-bis(.alpha.-pyridyl)rhodamine-HCl, m. 238-400, also formed
directly from dichlorofluorane and excess aminopyridine at
250-60.degree.. Similarly, 3-chloro-6-anilino-fluorane gave
red-violet N-phenyl-N'-.alpha.-pyridylrhodamine-HCl, m. 225-300.
All these were converted to N,N'-diphenylrhodamine by heating with
PhNH.sub.2 and ZnCl.sub.2 for 3 hours at 180-2000. The absorption
spectra of the products are shown; dipyridylrhodamine has a more
intense color than other members of the group.
[0045] "Rhodamine Dyes and Related Compounds. IV. Aryl- and
Benzylrhodamines," I. S. Ioffe et al., Zh. Obsch. Khim. (1962), 32,
1480-5, the disclosure of which is totally incorporated herein by
reference, discloses a process wherein heating fluorescein chloride
with ArNH.sub.2 in the presence of ZnCl.sub.2--ZnO for 4 to 5 hours
at 210-20.degree. gave, after leaching with hot dil. HCl, soln. of
the residue in hot PhNH.sub.2, and pptn. with dil. HCl, the
following N,N'-diarylrhodamines which were isolated as HCl salts:
Ph, m. 255-600; o-meC6H.sub.4, m. 205-100; m-meC6H.sub.4, m.
195-2000; p-meC.sub.6H.sub.4, m. 255-60.degree.. PhCH.sub.2NH.sub.2
similarly gave N,N'-dibenzylrhodamine, m. 160-50; HCl salt decomp.
160-50; di-HCl salt decomp. 2100. PhCH.sub.2NH.sub.2 and
3-chloro-6-anilinofluorane gave 90-5% N-phenyl-N'-benzylrhodamine
isolated as the HCl salt, m. 200-100. The absorption spectra of
these rhodamines are shown. Dibenzylrhodamine fluoresces strongly
in solution, while the phenyl benzyl analog has a weak
fluorescence. The benzyl groups cause a bathochromic shift of the
absorption band in the substituted rhodamines; the diarylrhodamines
form blue-violet solutions unlike the orange-yellow produced by
unsubstituted rhodamine. The di-HCl salt of dibenzylrhodamine loses
one HCl in soln as shown by behavior in EtOH.
[0046] "Rhodamine Dyes and Related Compounds. III. Reaction of
m-aminophenol With Phthalic Anhydride in Hot Sulfuric Acid," I. S.
Ioffe et al., Zh. Obsch. Khim. (1962), 32, 1477-80, the disclosure
of which is totally incorporated herein by reference, discloses
that heating 25 g. of m-H.sub.2C.sub.6H.sub.4OH with 20, g.
o-C.sub.6H.sub.4(CO)20 in 100 milliliters concentrated
H.sub.2SO.sub.4 at 160-200.degree. for 2-8 hours was used to
examine the effects of conditions of condensation on the reaction
products. Rhodamine formation began at 170.degree. and reached a
max. (20%) in 2 hours at 190.degree.. Rhodol was a constant
byproduct as a result of partial deamination of rhodamine. The
deamination is promoted by longer reaction time and higher
temperatures. These factors also promoted the formation of a dark,
amorphous material. o-Hydroxysulfanilic acid was formed in the
reaction in up to 32% yield at 160.degree. in 2 hours; more drastic
conditions lowered its yield rapidly. Prior to the appearance of
substantial amounts of rhodamine in the mixture, sulfonation of
m-H.sub.2C.sub.6H.sub.4OH takes place, and the resulting compound
appears to be the intermediate which reacts, with this compound
forming rhodamine by displacement of the sulfonic acid group. This
was confirmed by reaction of o-C.sub.6H.sub.4(CO).sub.2O with
o-hydroxysulfanilic acid under the conditions shown above.
m-Aminosalicylic acid also yields the same products in a mixture
similar to that formed by m-H.sub.2C.sub.6H.sub.4OH.
[0047] "Rhodamine Dyes and Related Compounds. XVIII.
N,N'-Dialkylrhodamines with Long Chain Hydrocarbon Radicals," I. S.
Ioffe et al., Zh. Organ. Khim. (1970), 6(2), 369-71, the disclosure
of which is totally incorporated herein by reference, discloses a
process wherein the condensation of I (X=Cl) with RNH.sub.2
(R.dbd.C.sub.6H.sub.13, C.sub.8H.sub.17, C.sub.16H.sub.33, or
C.sub.18H.sub.37) gave the title dyes. (I, X=NHR) (II). The
presence of alkyl groups in 11 did not change their color in
comparison with II. (R.dbd.H); all II absorbed strongly at 523-6
nm. However, long alkyl chains altered the hydrophobic properties
of II as shown by the change of their partition coefficients in
oil-alc. or kerosine-alc. systems with the length of R chain.
[0048] "Rhodamine Dyes and Related Compounds. XIX. Mutual
Transformations of Colorless and Chlored Forms of N,N'-Substituted
Rhodamine," I. S. Ioffe et al., Zh. Organ. Khim. (1972), 8(8),
1726-9, the disclosure of which is totally incorporated herein by
reference, discloses that substituted rhodamines give colored
solutions in polar and colorless solutions in nonpolar solvents.
The solvent polarity at which the colorless lactone form is
converted to the quinoid, internal salt form depends on the number
and structure of alkyl, aryl, or H substituents. Absorption spectra
of N,N'-diethylrhodamine in water-dioxane mixtures show how the
light absorption increases when the solvent polarity (i.e., water
amount in the mixture) is increased.
[0049] "Synthesis of N-Substituted Flaveosines, Acridine Analogs of
Rhodamine Dyes," I. S. Ioffe et al., Zh. Org. Khim. (1966), 2(9),
1721, the disclosure of which is totally incorporated herein by
reference, discloses that o-(3,6-chloro-9-acridinyl)benzoic acid
heated with BuNH2 or Bu.sub.2NH readily gave the
hydrochlorides.
[0050] "Rhodamine Dyes and Related Compounds. XVII. Acridine
Analogs of Rhodamine and Fluorescein," I. S. Ioffe et al., Zh.
Organ. Khim. (1966), 2(5), 927-31, the disclosure of which is
totally incorporated herein by reference, discloses absorption
spectra for flaveosin, fluorescein, azafluorescein, their Et esters
and diacetyl derivatives. Replacement of the xanthene structure by
the acridine group changed the spectra of such dyes. Azafluorescein
heated with PCl.sub.5 at 95-1000.degree. gave
o-(3,6-dichloro-9-acridinyl)-benzoic acid, decomp. >3000; its uv
spectrum was similar to that of unsubstituted acridinylbenzoic
acid. One of the flavebsin compounds heated with 25%
H.sub.2SO.sub.4 in a sealed tube 10 hours at 200-20.degree. gave
azafluorescein, decomp. >3800; heated with EtOH--H.sub.2SO.sub.4
it gave one of the flaveosins, decomp. >3000
Ac.sub.2O--H.sub.2SO.sub.4 gave in 1 hour one of the flaveosins,
decomp. 2060. The compound formed by treatment of
3,6-dichlorofluorane with NH.sub.3 was prepared. Its uv spectrum is
given.
[0051] "New Lipophilic Rhodamines and Their Application to Optical
Potassium Sensing," T. Werner et al., Journal of Fluorescence, Vol.
2, No. 3, pp. 93798 (1992), the disclosure of which is totally
incorporated herein by reference, discloses' the synthesis of new
lipophilic fluorescent rhodamines directly from
3,6-dichlorofluoresceins and the respective long-chain amines with
excellent solubility in lipids and lipophilic membranes.
Spectrophotomenric and luminescent properties of the dyes are
reported and discussed with respect to their application in new
optical ion sensors. One rhodamine was applied in a polyvinyl
chloride)-based sensor membrane for continuous and sensitive
optical determination of potassium ion, using valinomycin as the
neutral ion carrier.
[0052] U.S. Pat. No. 1,991,482 (Allemann), the disclosure of which
is totally incorporated herein by reference, discloses a process of
producing rhodamine dyes which comprises condensing a halogenated
primary amine of: the benzene series with fluorescein dichloride
and sulfonating the condensed product.
[0053] U.S. Pat. No. 5,847,162 (Lee et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
class of 4,7-dichlororhodamia ne compounds useful as fluorescent
dyes having the structure 26
[0054] wherein R.sub.1-R.sub.6 are hydrogen, fluorine, chlorine,
lower alkyl lower alkene, lower alkyne, sulfonate, sulfone, amino,
amido, nitrile, lower alkoxy, lining group, or combinations thereof
or, when taken together, R.sub.1 and R.sub.6 is benzo, or, when
taken together, R.sub.4 and R.sub.5 is benzo; Y.sub.1-Y.sub.4 are
hydrogen or lower alkyl or, when taken together, Y, and R.sub.2 is
propano and Y.sub.2 and R.sub.1 is propano, or, when taken
together, Y.sub.3 and R.sub.3 is propano and Y.sub.4 and R.sub.4 is
propano; and X.sub.1-X.sub.3 taken separately are selected from the
group consisting of hydrogen, chlorine, fluorine, lower alkyl
carboxylate, sulfonic acid, --CH.sub.2OH, and linking group. In
another aspect, the invention includes reagents labeled with the
4,7-dichlororhodamine dye compounds, including deoxynucleotides,
dideoxynucleotides, and polynucleotides. In an additional aspect,
the invention includes methods utilizing such dye compounds and
reagents including dideoxy polynucleotide sequencing and fragment
analysis methods.
[0055] U.S. Pat. No. 4,935,059 (Mayer et al.), the disclosure of
which is totally incorporated herein by reference, discloses basic
rhodamine dyes suitable for use in recording fluids for the ink jet
process and for coloring paper stock having the formula 27
[0056] where L is C.sub.2-C.sub.10-alkylene, R.sup.1, R.sup.2, and
R.sup.3 are each independently of the others hydrogen, substituted
or unsubstituted C.sub.1-C.sub.10-alkyl or
C.sub.5-C.sub.7-cycloalkyl or R.sup.1 and R.sup.2 together with the
nitrogen atom linking them together are a hetero cyclic radical, An
is one equivalent of an anion and m and n are each independently of
the other 0 or 1.
[0057] U.S. Pat. No. 4,647,675 (Mayer et al.), the disclosure of
which is totally incorporated herein by reference, discloses
compounds of the general formula 28
[0058] where A.sup.- is an anion, R is hydrogen or unsubstituted or
substituted alkyl or cycloalkyl, R.sup.1 and R.sup.2 independently
of one another are each hydrogen or unsubstituted or substituted
alkyl or cycloalkyl, or one of the radicals may furthermore be
aryl, or R.sup.1 and R.sup.2, together with the nitrogen atom, form
a saturated heterocyclic structure, the radicals R.sup.3
independently of one another are each hydrogen or
C.sub.1-C.sub.4-alkyl, R.sub.4 and R.sup.5 independently of one
another are each unsubstituted or substituted alkyl or cycloalkyl,
or one of the radicals may furthermore be hydrogen, aryl or
hetaryl, R.sup.4 and R.sup.5, together with the nitrogen atom, form
a saturated heterocyclic structure, n is 1, 2 or 3, X is hydrogen,
chlorine, bromine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
nitro and Y is hydrogen or chlorine, are particularly useful for
dyeing paper stocks.
[0059] U.S. Pat. No. 1,981,515 (Kyrides), the disclosure of which
is totally incorporated herein by reference, discloses
intermediates for rhodamine dyestuffs.
[0060] U.S. Pat. No. 1,981,516 (Kyrides), the disclosure of which
is totally incorporated herein by reference, discloses
intermediates for secondary alkylated rhodamine dyes.
[0061] British Patent Publication GB 421 737, the disclosure of
which is totally incorporated herein by reference, discloses dyes
of the rhodamine series which are prepared by condensing
naphthalene-2:3-dicarboxylic acid with a m-aminophenol in which the
nitrogen group is substituted by one or two alkyl groups, the
products, if desired, being sulphonated. The unsulphonated products
may be used as lake colouring matters whilst the sulphonated dyes
are acid wool dyes. In examples, (1) naphthalene-2:3-dicarboxylic
acid is condensed with diethyl-m-aminophenol in the presence of
zinc chloride giving a product which dyes tannin-mordanted cotton
in the same shade as Rhodamine B and a sulphonated product which
dyes wool bluish-red shades; (2) monoethyl-m-aminophenol is used
instead of the diethyl-m-aminophenol in example (1), yielding a
dye, which when sulphonated dyes wool red-orange shades; (3)
2-ethylamino-p-cresol replaces the diethyl-m-aminophenol in example
(1), yielding a dye dyeing and printing tannin-mordanted cotton in
shades similar to Rhodamine 69BS and when sulphonated dyeing wool
red.
[0062] Japanese Patent Publication JP 61221265, the disclosure of
which is totally incorporated herein by reference, discloses
rhodamine compounds of formula I 29
[0063] wherein R.sub.1, R.sub.3 are each lower alkyl; R.sub.2 is
lower alkyl, 10C or higher long-chain alkyl; R.sub.4 is 10C or
higher long-chain alkyl; X.sup.- is an anion, or squarylium
compounds of formula II 30
[0064] wherein R.sub.2 is 10C or higher long-chain alkyl. Example:
3,6-(N,N'-diethyl-N,N'-dioctadecyl) diamino-9-(2-carboxyphenyl)
xanthilium perchlorate. Use: materials for molecular electronics,
which are suitable for use as materials for photoelectric
converter, optical memory, etc. Preparation:
2-(4-N,N'-diethylamino-2-hydroxybenzoyl)-benzoi- c acid, which is a
condensate between N-ethyl-N-octadecyl-m-hydroxyaniline and
phthalic anhydride, is reacted with.
N-ethyl-N-octadecyl-m-hydroxyani- line to obtain the compound of
formula I. 3-HOC.sub.6H.sub.4N(Et)(CH.sub.2- ).sub.17Me and
phthalic anhydride were heated at 150.degree. for 4 hours, treated
with aqueous NH.sub.3, and the amorphous intermediate mixed with
aqueous HClO.sub.4 forming a compound of formula I
(R.dbd.R.sub.2=Et; R.sub.1.dbd.R.sub.3.dbd.C.sub.18H.sub.37;
X.dbd.ClO.sub.4), having .lambda..sub.max (MeOH) 550 nm.
[0065] U.S. Pat. No. 5,084,099 (Jaeger et al.), the disclosure of
which is totally incorporated herein by reference, discloses
modified phase change ink compatible colorants which comprise a
phase change ink soluble complex of (a) a tertiary alkyl primary
amine and (b) dye chromophores, i.e., materials that absorb light
in the visible wavelength region to produce color having at least
one pendant acid functional. group in the free acid form (not the
salt of that acid). These modified colorants are extremely useful
in producing phase change inks when combined with a phase change
ink carrier, even though the unmodified dye chromophores have
limited solubility in the phase change ink carrier. Thin films of
uniform thickness of the subject phase change ink compositions
which employ the modified phase change ink colorants exhibit a high
degree of lightness and chroma. The primary amine-dye chromophore
complexes are soluble in the phase change ink carrier and exhibit
excellent thermal stability.
[0066] U.S. Pat. No. 5,507,864 (Jaeger et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
phase change ink composition that includes a combination of
different dye types such as an anthraquinone dye and a xanthene
dye, which is most preferably a rhodamine dye. While each dye type
is insufficiently soluble with respect to favored carrier
compositions to preserve color saturation in reduced ink quantity
prints, the dye type combination permits increased dye loading and
maintains print quality. In a preferred embodiment of the
invention, a favored carrier composition is adjusted to promote the
colored form of a preferred rhodamine dye (C.I. Solvent Red 49) and
mixed with a preferred anthraquinone dye (C.I. Solvent Red. 172)
whose concentration is kept below a critical level to prevent post
printed blooming. The resulting preferred phase change ink
compositions provide a magenta phase change-ink with enhanced light
fastness and color saturation, as well as good compatibility with
preferred existing subtractive primary color phase change inks.
[0067] U.S. Pat. No. 5,621,022 (Jaeger et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
phase change ink composition wherein the ink composition utilizes
polymeric dyes in combination with a selected phase change ink
carrier composition.
[0068] U.S. Pat. No. 5,747,554 (Sacripante et al.), the disclosure
of which is totally incorporated herein by reference, discloses an
ink composition comprising a polyesterified-dye (I) or
polyurethane-dye (II) with a viscosity of from about 3 centipoise
to about 20 centipoise at a temperature of from about 125.degree.
C. to about 165.degree. C. and represented by the formulas 31
[0069] wherein A is an organic chromophore, Y is an oxyalkylene or
poly(oxyalkylene), R is an arylene or alkylene, n represents the
number of repeating segments, and is an integer of from about 2 to
about 50, and p represents the number of chains per chromophore and
is an integer of from about 1 to about 6.
[0070] U.S. Pat. No. 5,902,841 (Jaeger et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
phase change ink composition wherein the ink composition utilizes
colorant in combination with a selected phase change ink carrier
composition containing at least one hydroxy-functional fatty amide
compound.
[0071] European Patent Publication 0565 798 (Shustack), the
disclosure of which is totally incorporated herein by reference,
discloses ultraviolet radiation-curable primary and secondary
coating compositions for optical fibers., The primary coatings
comprise a hydrocarbon polyol-based reactively terminated aliphatic
urethane oligomer; a hydrocarbon-monomer terminated with at least
one end group capable of reacting with the terminus of the
oligomer; and an optional photoinitiator. The secondary coatings
comprise a polyester and/or polyether-based aliphatic urethane
reactively terminated oligomer; a hydrocarbonaceous
viscosity-adjusting component capable of reacting with the reactive
terminus of (I); and an optional photoinitiator. Also disclosed are
optical fibers coated with the secondary coating alone or with the
primary and secondary coatings of the invention.
[0072] While known compositions and processes are-suitable for
their intended purposes, a need remains for new magenta colorant
compositions. In addition, a need remains for magenta colorant
compositions particularly suitable for use in phase change inks.
Further, a need remains for magenta colorants with desirable
thermal stability. Additionally, a need remains for magenta
colorants that exhibit minimal undesirable discoloration when
exposed to elevated temperatures. There is also a need for magenta
colorants that exhibit a desirable brilliance. In addition, there
is a need for magenta colorants that exhibit a desirable hue.
Further, there is a need for magenta colorants that are of
desirable chroma. Additionally, there is a need for magenta
colorants that have desirably high lightfastness characteristics. A
need also remains for magenta colorants that have a desirably
pleasing color. In addition, a need remains for magenta colorants
that exhibit desirable solubility characteristics in phase change
ink carrier compositions. Further, a need remains for magenta
colorants that enable phase change inks to be jetted at
temperatures of over 135.degree. C. while maintaining thermal
stability. Additionally, a need remains for magenta colorants that
enable phase change inks that generate images with low pile height.
There is also a need for magenta colorants that enable phase change
inks that generate images that approach lithographic thin image
quality. In addition, there is a need for magenta colorants that
exhibit oxidative stability. Further, there is a need for magenta
colorants that do not precipitate from phase change ink carriers.
Additionally, there is a need for magenta colorants that do not,
when included in phase change inks, diffuse into adjacently printed
inks of different colors. A need also remains for magenta colorants
that do not leach from media such as phase change ink carriers into
tape adhesives, paper, or the like. In addition, a need remains for
magenta colorants that, when incorporated into phase change inks,
do not lead to clogging of a phase change ink jet printhead.
Further, there is a need for magenta colorants that enable phase
change inks that generate images with sharp edges that remain sharp
over time. Additionally, there is a need for magenta colorants that
enable phase change inks that generate images which retain their
high image quality in warm climates. Further, there is a need for
magenta colorants that enable phase change inks that generate
images of desirably high optical density. Additionally, there is a
need for magenta colorants that, because of their good solubility
in phase change ink carriers, enable the generation of images of
low pile height without the loss of desirably high optical density.
A need also remains for magenta colorants that enable
cost-effective inks. In addition, a need remains for magenta
colorants that are compounds having metal compounds associated with
chromogens, wherein the thermal stability of the metal compound
colorants exceeds that of the chromogens unassociated with a
metal.
SUMMARY
[0073] The present invention is directed to a phase change ink
composition comprising a phase change ink carrier and a colorant
compound of the formula 32
[0074] wherein M is either (1) a metal ion having a positive charge
of +y wherein y is an integer which is at least 2, said metal ion
being capable of forming a compound with at least two 33
[0075] chromogen moieties, or (2) a metal-containing moiety capable
of forming a compound with at least two 34
[0076] chromogen moieties, z is an integer representing the number
of 35
[0077] chromogen moieties associated with the metal and is at least
2, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each, independently of
the others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an
aryl group, (iv) an arylalkyl group, or (v) an alkylaryl group,
wherein R.sub.1 and R.sub.2 can be joined together to form a ring,
wherein R.sub.3 and R.sub.4 can be joined together to form a ring,
and wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 can each be
joined to a phenyl ring in the central structure, a and b each,
independently of the others, is an integer which is 0, 1, 2, or 3,
c is an integer which is 0, 1, 2, 3, or 4, each R.sub.5, R.sub.6,
and R.sub.7, independently of the others, is (i) an alkyl group,
(ii) an aryl group, (iii) an arylalkyl group, (iv), an alkylaryl
group, (v) a halogen atom, (vi) an ester group, (vii) an amide
group, (viii) a sulfone group, (ix) an amine group or ammonium
group, (x) a nitrile group, (xi) a nitro group, (xii) a hydroxy
group, (xiii) a cyano group, (xiv) a pyridine or pyridinium group,
(xv) an ether group, (xvi) an aldehyde group, (xvii) a ketone
group, (xviii) a carbonyl group, (xix) a thiocarbonyl group, (xx) a
sulfate group, (xxi) a sulfide group, (xxii) a sulfoxide group,
(xxiii) a phosphine or phosphonium group, (xxiv) a phosphate group,
(xxv) a mercapto group, (xxvi) a nitroso group, (xxvii) an acyl
group, (xxviii) an acid anhydride group, (xxix) an azide group,
(xxx) an azo group, (xxxi) a cyanato group, (xxxii) an isocyanato
group, (xxxiii) a thiocyanato group, (xxxiv) an isothiocyanato
group, (xxxv) a urethane group, or (xxxvi) a urea group, wherein
R.sub.5, R.sub.6, and R.sub.7 can each be joined to a phenyl ring
in the central structure, 36
[0078] R.sub.8, R.sub.9, and R.sub.10 each, independently of the
others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an aryl
group, (iv) an arylalkyl group, or (v) an alkylaryl group, provided
that the number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R.sub.7+R-
.sub.8+R.sub.9+R.sub.10 is at least about 16, Q.sup.- is a
COO.sup.- group or a SO.sub.3-- group, d is an integer which is 1,
2, 3, 4, or 5, A is an anion, and CA is either a hydrogen atom or a
cation associated with all but one of the Q.sup.- groups.
DETAILED DESCRIPTION
[0079] The present invention is directed to phase change inks
containing colorant compounds of the formula 37
[0080] wherein M is either (1) a metal ion having a positive charge
of +y wherein y is an integer which is at least 2, said metal ion
being capable of forming a compound with at least two 38
[0081] chromogen moieties, or (2) a: metal-containing moiety
capable of forming a compound, with at least two 39
[0082] chromogen moieties, and z is an integer representing the
number of 40
[0083] chromogen moieties associated with the metal and is at least
2. There is no necessary upper limit on the value of z.
[0084] Examples of metal cations having a positive charge of +y
wherein y is an integer which is at least 2 include +2, +3, +4, and
higher cations of magnesium, calcium, strontium, barium, radium,
aluminum, gallium, germanium, indium, tin, antimony, tellurium,
thallium, lead, bismuth, polonium, scandium, titanium, vanadium,
chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium,
niobium molybdenum, technetium, ruthenium, rhodium, palladium,
silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium,
iridium, platinum, gold, mercury, metals of the lanthamide series,
such as europium and the like, metals of the actinide series, and
the like.
[0085] Examples of Metal-Containing Moieties Include:
[0086] metal ionic moieties, such as Me.sup.3+X.sup.- wherein Me
represents a trivalent metal atom and X represents a monovalent
anion, such as Cl.sup.-, Br.sup.-, I.sup.-, HSO.sub.4.sup.-,
HSO.sub.3.sup.-, CH.sub.3SO.sub.3.sup.-,
CH.sub.3C.sub.6H.sub.4SO.sub.3.sup.-, NO.sub.3.sup.-, HCOO.sup.-,
CH.sub.3COO.sup.-, H.sub.2PO.sub.4.sup.-, SCN.sup.-,
BF.sub.4.sup.-, ClO.sub.4.sup.-, SSO.sub.3.sup.-, PF.sub.6.sup.-,
SbCl.sub.6.sup.-, or the like, or Me.sup.4+X.sup.- or
Me.sup.4+X.sup.- or Me.sup.4+X.sub.2.sup.- wherein Me represents a
tetravalent metal atom, X represents a monovalent anion, and
X.sub.2 represents 2 monovalent anions, Me.sup.4+X.sup.2.sup.-
wherein Me represents a tetravalent metal atom and X.sub.2.sup.-
represents a divalent anion, and the like;
[0087] metal coordination compounds, wherein metals such as
magnesium, calcium, strontium, barium, radium, aluminum, gallium,
germanium, indium, tin, antimony, tellurium, thallium, lead,
bismuth, polonium, scandium, titanium, vanadium, chromium,
manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium
molybdenum, technetium, ruthenium, rhodium, palladium, silver,
cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium,
platinum, gold, mercury, metals of the lanthamide series, such as
europium and the like, metals of the actinide series, and the like
are associated with one or more ligands, such as carbonyl (carbon
monoxide) ligands, ferrocene ligands, halide ligands, such as
fluoride, chloride, bromide, iodide, or the like, amine ligands of
the formula 41
[0088] wherein R.sub.51, R.sub.52, and R.sub.53 each, independently
of the others, is (i) a hydrogen atom, (ii) a halogen atom, such as
fluorine, chlorine, bromine, iodine, or the like, (iii) 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
one embodiment with at least 1 carbon atom, and in one embodiment
with no more than about 55 carbon atoms, in another embodiment with
no more than about 30 carbon atoms, and in yet another embodiment
with no more than about 20 carbon atoms, although the number of
carbon atoms can be outside of these ranges, (iv) 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 one embodiment with at least about 6 carbon atoms,
and in one embodiment with no more than about 26 carbon atoms, in
another embodiment with no more than about 22 carbon atoms, and in
yet another embodiment with no more than about 18 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
(v) 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 one embodiment with at least about 7 carbon atoms, and
in one embodiment with no more than about 55 carbon atoms, in
another embodiment with no more than about 30 carbon atoms, and in
yet another embodiment with no more than about 20 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as benzyl or the like, or (vi) 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 one embodiment
with at least about 7 carbon atoms, and in one embodiment with no
more than about 55 carbon atoms, in another embodiment with no more
than about 30 carbon atoms, and in yet another embodiment with no
more than about 20 carbon atoms, although the number of carbon
atoms can be outside of these ranges, such as tolyl or the like,
wherein, one or more of R.sub.51, R.sub.52, and R.sub.53 can be
joined together to form a ring, and wherein the substituents on the
substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be
(but are not limited to) hydroxy groups, halogen a atoms, amine
groups, imine groups, ammonium groups, cyano groups, pyridine
groups, pyridinium groups, ether groups, aldehyde groups, ketone
groups, ester groups, amide 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, acyl groups, acid anhydride
groups, azide groups, azo groups, cyanato groups, isocyanato
groups, thiocyanato groups, isothiocyanato groups, carboxylate
groups, carboxylic acid groups, urethane groups, urea groups,
mixtures thereof, and the like, wherein two or more substituents
can be joined together to form a ring, with specific examples of
suitable amine ligands including ammonia, trimethylamine,
ethylenediamine, bipyridine, and the like, phosphine ligands of the
formula 42
[0089] wherein R.sub.61, R.sub.62, and R.sub.63 each, independently
of the others, is (i) a hydrogen atom, (ii)a halogen atom, such as
fluorine, chlorine, bromine, iodine, or the like, (iii) 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
one embodiment with at least 1 carbon atom, and in one embodiment
with no more than about 55 carbon atoms, in another embodiment with
no more than about 30 carbon atoms, and in yet another embodiment
with no more than about 20 carbon atoms, although the number of
carbon atoms can be outside of these ranges, (iv) 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 one embodiment with at least about 6 carbon atoms,
and in one embodiment with no more than about 26 carbon atoms, in
another embodiment with no more than about 22 carbon atoms, and in
yet another embodiment with no more than about 18 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
(v) 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 hot be present in either
or both of the alkyl portion and the aryl portion of the arylalkyl
group), in one embodiment with at least about 7 carbon atoms, and
in one embodiment with no more than about 55 carbon atoms, in
another embodiment with no more than about 30 carbon atoms, and in
yet another embodiment with no more than about 20 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as benzyl or the like, (vi) 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 one embodiment
with at least about 7 carbon atoms, and in one embodiment with no
more than about 55 carbon atoms, in another embodiment with no more
than about 30 carbon atoms, and in yet another embodiment with no
more than about 20 carbon atoms, although the number of carbon
atoms can be outside of these ranges, such as tolyl or the like,
(vii) an alkoxy group (including linear, branched, saturated,
unsaturated, cyclic, substituted, and unsubstituted alkoxy groups,
and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in the alkoxy group), in one embodiment with at least 1 carbon
atom, and in one embodiment with no more than about 55 carbon
atoms, in another embodiment with no more than about 30 carbon
atoms, and in yet another embodiment with no more than about 20
carbon-atoms, although the number of carbon atoms can be outside of
these ranges, (viii) an aryloxy group (including unsubstituted and
substituted aryloxy groups, and wherein hetero atoms, such as
oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either
may or may not be present in the aryloxy group), in one embodiment
with at least about 6 carbon atoms, and in one embodiment with no
more than about 26 carbon atoms, in another embodiment with no more
than about 22 carbon atoms, and in yet another embodiment with no
more than about 18 carbon atoms, although the number of carbon
atoms can be outside of these ranges, (ix) an arylalkyloxy group
(including unsubstituted and substituted arylalkyloxy groups,
wherein the alkyl portion of the arylalkyloxy 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 arylalkyloxy group), in
one embodiment with at least about 7 carbon atoms, and in one
embodiment with no more than about 55 carbon atoms, in another
embodiment with no more than about 30 carbon atoms, and in yet
another embodiment with no more than about 20 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as benzyloxy or the like, or (x) an alkylaryloxy group
(including unsubstituted and substituted alkylaryloxy groups,
wherein the alkyl portion of the alkylaryloxy 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 alkylaryloxy group), in
one embodiment with at least about 7 carbon atoms, and in one
embodiment with no more than about 55 carbon atoms, in another
embodiment with no more than about 30 carbon atoms, and in yet
another embodiment with no more than about 20 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as tolyloxy or the like, wherein one or more of R.sub.61;
R.sub.62, and R.sub.63 can be joined together to form a ring, and
wherein the substituents on the substituted alkyl, alkoxy, cryl,
aryloxy, arylalkyl, arylalkyloxy, alkylaryl, and alkylaryloxy
groups can be (but are not limited to) hydroxy groups, halogen
atoms, amine groups, imine groups, ammonium groups, cyano groups,
pyridine groups, pyridinium groups, ether groups, aldehyde groups,
ketone groups, ester groups, amide groups, carbonyl groups,
thiocarbonyl groups, sulfate groups, sultanate groups, sulfonic
acid groups, sulfide groups, sulfoxide groups, phosphine groups,
phosphonium groups, phosphate, groups, nitrile groups, mercapto
groups, nitro groups, nitroso groups, sulfone groups, acyl groups,
acid anhydride groups, azide groups, azo groups, cyanato groups,
isocyanato groups, thiocyanato groups, isothiocyanato groups,
carboxylate groups, carboxylic acid groups, urethane groups, urea
groups, mixtures thereof, and the like, wherein two or more
substituents can be joined together to form a ring, with specific
examples of suitable phosphine ligands including phosphine,
trifluorophosphine, trichlorophosphine, trimethylphosphine,
triphenylphosphine, trethoxyphosphine, and the like, water ligands,
cyano ligands, isocyano ligands, hydroxide anions, nitro ligands,
nitrito ligands, thiocyanato ligands, nitric oxide ligands, and the
like; including monodentate ligands, bidentate ligands, tridentate
ligands, tetradentate ligands, pentadentate ligands, hexadentate
ligands (such as ethylene diamine tetraacetic acid), bridging
ligands joining two or more metal atoms in a complex, crown ether
ligands, and the like; a wide variety of ligands and metal
complexes are disclosed in, for example, Advanced Inorganic
Chemistry, Fourth Edition, F. A. Cotton and G. Wilkinson, John
Wiley & Sons (1980), the disclosure of which is totally
incorporated herein by reference;
[0090] heteropblyacids, also known as polyoxometalates, which are
acids comprising inorganic metal-oxygen clusters; these materials
are discussed in, for example, "Polyoxometalate Chemistry: An Old
Field with New Dimensions in Several Disciplines," M. T. Pope et
al., Angew. Chem. Int. Ed. Engl., Vol. 30, p. 34 (1991), the
disclosure of which is totally incorporated herein by reference;
examples of heteropolyacids include phosphotungstic acids,
including (but not limited to) those of the general formula
H.sub.3PO.sub.4.12WO.sub.3.XH.sub.2O (wherein X is variable, with
common values including (but not being limited to) 12, 24, or the
like), silicotungstic acids, including (but not limited to) those
of the general formula H.sub.4SiO.sub.2.12WO.sub.3XH.sub.2O
(wherein X is variable, with common values including (but not being
limited to) 12, 24, 26, or the like), phosphomolybdic acids,
including (but not limited to) those of the general formula
12MoO.sub.3H.sub.3PO.sub.4.XH.sub.2O (wherein X is variable, with
common values including (but not being limited to) 12, 24, 26, or
the like) and the like, all commercially available from, for
example, Aldrich Chemical Co., Milwaukee, Wis., as well as mixtures
thereof;
[0091] and any other metal-containing moiety capable of forming a
compound with at least two 43
[0092] moieties.
[0093] By "capable of forming a compound with at least two 44
[0094] chromogen moieties" His meant that the metal cation or
metal-containing moiety can react with two or more 45
[0095] chromogen moieties to form a compound. Any kind of
association between the 46
[0096] chromogen moiety and the metal cation or metal-containing
moiety to form a compound is suitable, including ionic compounds,
covalent compounds, coordination compounds, and the like.
[0097] R.sub.1, R.sub.2, R.sub.3, and R.sub.4 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
one embodiment with at least 1 carbon atom, in another embodiment
with at least about 2 carbon atoms, in yet another embodiment with
at least about 6 carbon atoms, in another embodiment with at least
about 8 carbon atoms, and in yet another embodiment with at least
about 18 carbon atoms, and in one embodiment with no more than
about 55 carbon atoms, in another embodiment with no more than
about 30 carbon atoms, and in yet another embodiment with no more
than about 20 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
one embodiment with at least about 6 carbon atoms, in another
embodiment with at least about 10 carbon atoms, and in yet another
embodiment with at least about 14 carbon atoms, and in one
embodiment with no more than about 26 carbon atoms, in another
embodiment with no more than about 22 carbon atoms, and in yet
another embodiment with no more than about 18 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 one embodiment with at least about 7 carbon atoms, in
another embodiment with at least about 12 carbon atoms, and in yet
another embodiment with at least about 18 carbon atoms, and in one
embodiment with no more than about 55 carbon atoms, in another
embodiment with no more than about 30 carbon atoms, and in yet
another embodiment with no more than about 20 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 one embodiment
with at least about 7 carbon atoms, in another embodiment with at
least about 12 carbon atoms, and in yet another embodiment with at
least about 18 carbon atoms, and in on e embodiment with no more
than about 51 carbon atoms, in another embodiment with no more than
about 30 carbon atoms, and in yet another embodiment with no more
than about 20 carbon atoms, although the number of carbon atoms can
be outside of these ranges, such as tolyl or, the like, wherein
R.sub.1 and R.sub.2 can be joined together to form a ring, wherein
R.sub.3 and R.sub.4 can be joined together to form a ring, and
wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 can each be joined
to a phenyl ring in the central structure, a and b each,
independently of the others, is an integer which is 0, 1, 2, or 3,
c is an integer which is 0, 1, 2, 3, or 4, each R.sub.5, R.sub.6,
and R.sub.7, 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
one embodiment with at least 1 carbon atom, and in one embodiment
with no more than about 50 carbon atoms, in another embodiment with
no more than about 30 carbon atoms, and in yet another embodiment
with no more than about 18 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 one embodiment with at least about 6 carbon atoms,
and in one embodiment with no more than about 0.55 carbon tom, in
another embodiment with no more than about 30 carbon atoms, and in
yet another embodiment with no more than about 18 carbon atoms,
although the number of carbon atoms can 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 one embodiment with at least about 7 carbon atoms, and
in one embodiment with no more than about 55 carbon atoms, in
another embodiment with no more than about 30 carbon atoms, and in
yet another embodiment with no m ore than about 18 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as benzyl or the like, (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 one embodiment
with at least about 7 carbon atoms, and in one embodiment with no
more than about 55 carbon atoms, in another embodiment with no more
than about 30 carbon atoms, and in yet another embodiment with no
more than about 18 carbon atoms, although the number of carbon
atoms can be outside of these ranges, such as tolyl or the like,
(v) a halogen atom, such as fluorine, chlorine, bromine, iodine, or
the like, (vi) an ester group, (vii) an amide group, (viii) a
sulfone group, (ix) an amine group or ammonium group, (xi) a nitro
group, (xii) a hydroxy group, (xiii) a cyano group, (xiv) a
pyridine or pyridinium group, (xv) an ether group, (xvi) an
aldehyde group, (xvii) a ketone group, (xviii) a carbonyl group,
(xix) a thiocarbonyl group, (xx) a sulfate group, (xxi) a sulfide
group, (xxii) a sulfoxide group, (xxiii) a phosphine or phosphonium
group, (xxiv) a phosphate group, (xxv) a mercapto group, (xxvi) a
nitroso group, (xxvii) an acyl group, (xxviii) an acid anhydride
group, (xxix) an azide group, (xxx) an azo group, (xxxi) a cyanato
group, (xxxii) an isocyanato group, (xxxiii) a thiocyanato group,
(xxxiv) an isothiocyanato group, (xxxv) a urethane group, or
(xxxvi) a urea group, wherein R.sub.5, R.sub.6, and R.sub.7 can
each be joined to a phenyl ring in the central structure, 47
[0098] R.sub.8, R.sub.9, and R.sub.10 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 one embodiment
with at least 1 carbon atom, in another embodiment with at least
about 2 carbon atoms, in yet another embodiment with at least about
6 carbon atoms, in another embodiment with at least about 8 carbon
atoms, and in yet another embodiment with at least about 18 carbon
atoms, and in ane embodiment with no more than about 55 carbon
atoms, in another embodiment with no more than about 30 carbon
atoms, and in yet another embodiment with no more than about 20
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 one embodiment with at
least about 6 carbon atoms, in another embodiment with at least
about 10 carbon atoms, and in yet another embodiment with at least
about 14 carbon atoms; and in one embodiment with no more than
about 26 carbon atoms, in another embodiment with no more than
about 22 carbon atoms, and in yet another embodiment with no more
than about 18 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 one embodiment
with at least about 7 carbon atoms, in another embodiment with at
least about 12 carbon atoms, and in yet another embodiment with at
least about 18 carbon atoms, Land in one embodiment with no more
than about 55 carbon atoms, in another embodiment with no more than
about 30 carbon atoms, and in yet another embodiment with no more
than about 20 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 one embodiment with at least about 7 carbon atoms, in
another embodiment with at least about 12 carbon atoms, and in yet
another embodiment with at least about 18 carbon atoms, and in one
embodiment with no more than about 55 carbon atoms, in another
embodiment with no more than about 30 carbon atoms, and in yet
another embodiment with no more than about 20 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as tolyl or the like, provided that the number of carbon atoms
in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R.sub.7+R.sub.8+R.sub.9+R-
.sub.10 is in one embodiment at least about 16, in another
embodiment at least about 18, in yet another embodiment at least
about 20, in still another embodiment at least about 22, in another
embodiment at least about 24, in yet another embodiment at least
about 26, in still another embodiment at least about 28, in another
embodiment at least about 30, in yet another embodiment at least
about 32, in still another embodiment at least about: 34, in
another embodiment at least about 36, in yet another embodiment at
least about 38, in still another embodiment at least about 40, in
another embodiment at least about 42, in yet another embodiment at
least about 44, in still another embodiment at least about 46, in
another embodiment at least about 48, in yet another embodiment at
least about 50, in still another embodiment at least about 52, in
another embodiment at least about 54, in yet another embodiment at
least about 56, in still another embodiment at least; about 58, in
another embodiment at least about 60, in yet another embodiment at
least about 62, in still another embodiment at least about 64, in
another embodiment at least about 66, in yet another embodiment at
least about 68, in still another embodiment at least about 70, and
in another embodiment at least about 72, each Q.sup.-,
independently of the others, is a COO.sup.- group or a
SO.sub.3.sup.- group, d is an integer which is 1, 2, 3, 4, or 5, A
is an anion, with examples of suitable anions including (but not
being limited to) Cl.sup.-, Br.sup.-, I.sup.-, HSO.sub.4.sup.-,
HSO.sub.3.sup.-, 1/2 SO.sub.4.sup.2.sup.-, 1/2 SO.sub.32.sup.-;
CH.sub.3SO.sub.3.sup.-, CH.sub.3C.sub.6H.sub.4SO.sub.3.sup.-,
NO.sub.3.sup.-, HCOO.sup.-, CH.sub.3COO.sup.-,
H.sub.2PO.sub.4.sup.-, 1/2 HPO.sub.42.sup.-, SCN.sup.-,
BF.sub.4.sup.-, ClO.sub.4.sup.-, SSO.sub.3.sup.-, PF.sub.6.sup.-,
SbCl.sub.6.sup.-, or the like, as well as mixtures thereof, and CA
is either a hydrogen atom or a cation associated with all but one
of the Q.sup.- groups, with examples of suitable cations including
(but not being limited to) alkali metal cations, such as Li.sup.+,
Na.sup.+, K.sup.+, Rb.sup.+, and Cs.sup.+, nonpolymeric or
monomeric ammonium and quaternary amine cations, including those of
the general formula 48
[0099] wherein each of R.sub.21, R.sub.22, R.sub.23, and R.sub.24,
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
one embodiment with at least 1 carbon atom, in another embodiment
with at least about 2 carbon atoms, in yet another embodiment with
at least about 6 carbon atoms, in another embodiment with at least
about 8 carbon atoms, and in yet another embodiment with at least
about 18 carbon atoms, and in one embodiment with no more than
about 55 carbon atoms, in another embodiment with no more than
about 30 carbon atoms, and in yet another embodiment with no more
than about 20 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
one embodiment with at least about 6 carbon atoms, in another
embodiment with at least about 10 carbon atoms, and in yet another
embodiment with at least about 14 carbon atoms, and in one
embodiment with no more than about 26 carbon atoms, in another
embodiment with no more than about 22 carbon atoms, and in yet
another embodiment with no more than about 18 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 one embodiment with at least about 7 carbon atoms, in
another embodiment with at least about 12 carbon atoms, and in yet
another embodiment with at least about 18 carbon atoms, and in one
embodiment with no-more than about 55 carbon atoms, in another
embodiment with no more than about 30 carbon atoms, and in yet
another embodiment with no more than about 20 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 one embodiment
with at least about 7 carbon atoms, in another embodiment with at
least about 12 carbon atoms, and in yet another embodiment with at
least about 18 carbon atoms, and in one embodiment with no more
than about 55 carbon atoms, in another embodiment with no more than
about 30 carbon atoms, and in yet another embodiment with no more
than about 20 carbon atoms, although the number of carbon atoms can
be outside of these ranges, such as tolyl or the like, wherein one
or more of R.sub.21, R.sub.22, R.sub.23, and R.sub.24 can be joined
together to form a ring, and wherein the substituents on the
substituted alkyl, aryl arylalkyl, and alkylaryl groups can be (but
are not limited to) hydroxy groups, halogen atoms, amine groups,
imine groups, ammonium groups, cyano groups, pyridine groups,
pyridinium groups, ether groups, aldehyde groups, ketone groups,
ester groups, amide groups, carbonyl groups, thiocarbonyl groups,
sulfate groups, sultfonate groups, sulfonic acid groups, sulfide
groups, sulfoxide groups, phosphine groups, phosphonium groups,
phosphate groups, nitrile groups, mercapto groups, nitro groups,
nitroso groups, sulfone groups, acyl groups, acid anhydride groups,
azide groups, azo groups, cyanato groups, isocyanato groups,
thiocyanato groups, isothiocyanato groups, carboxylate groups,
carboxylic acid groups, urethane groups, urea groups, mixtures
thereof, and the like, wherein two or more substituents can be
joined together to form a ring, oligomeric and polymeric cations,
such as cationic polymers or oligomers, and the like, as well as
mixtures thereof.
[0100] In situations wherein 49
[0101] and either (i) one of the R.sub.7 groups is in the ortho
position and is either an ester based on a carboxylic acid, an
ester based on a sulfonic acid, an amide based on a carboxylic
acid, or an amide based on a sulfonic acid, or (ii) one of the
Q.sup.- groups is a sulfonate salt, i.e., when the chromogen is of
the formula 50
[0102] wherein R.sub.12 R.sub.13, R.sub.14, R.sub.15, R.sub.16, and
R.sub.17 each independently of the other, 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
one embodiment with at least 1 carbon atom, and in one embodiment
with no more than about 50 carbon atoms, in another embodiment with
no more than about 30 carbon atoms, and in yet another embodiment
with no more than about 18 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 one embodiment with at least about 6 carbon atoms,
and in one embodiment with no more than about 55 carbon atoms in
another embodiment with no more than about 30 carbon atoms, and in
yet another embodiment with no more than about 18 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
(iii) an aryldlkyl group (including unsubstituted and substituted
aryllkyl 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 one embodiment with at least about 7 carbon atoms, and
in one embodiment with no more than about 55 carbon atoms, in
another embodiment with no more than about 30 carbon atoms, and in
yet another embodiment with no more than about 18 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 alkylaro 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 one embodiment
with at least about 7 carbon atoms, and in one embodiment with no
more than about 55 carbon atoms, in another embodiment with no more
than about 30 carbon atoms, and in yet another embodiment with no
more than about 18 carbon atoms, although the number of carbon
atoms can be outside of these ranges, such as tolyl or the like,
wherein the substituents on the substituted alkyl, aryl, arylalkyl,
and alkylaryl groups can be (but are not limited to) hydroxy
groups, halogen atoms, amine groups, imine groups, ammonium groups,
cyano groups, pyridine groups, pyridinium groups, ether groups,
aldehyde groups, ketone groups, ester groups, amide 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, acyl groups, acid anhydride groups, azide groups, azo
groups, cyanato groups, isocyanato groups, thiocyanato groups,
isothiocyanato groups, carboxylate groups, carboxylic acid groups,
urethane groups, urea groups, mixtures thereof, and the like,
wherein two or more substituents can be joined together to form a
ring, in one specific embodiment, (I) either (a) c is an integer
which is 0, 1, 2, or 3, or (b) d is an integer which is 1, 2, 3, or
4, and (II) either (a) three of R.sub.1, R.sub.2, R.sub.3, and
R.sub.4 are hydrogen atoms; (b) only one of R.sub.1, R.sub.2,
R.sub.3, and R.sub.4 is a hydrogen atom; (c) R.sub.1 and R.sub.2
are both hydrogen atoms; (d) R.sub.3 and R.sub.4 are both hydrogen
atoms; or (e) R.sub.1 and R.sub.3 are both hydrogen atoms and
R.sub.2 and R.sub.4 are each, independently of the other, either
alkyl groups or arylalkyl groups.
[0103] In one embodiment, the number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4 is at least about 16, in another
embodiment at least about 18, in yet another embodiment at least
about 20, in still another embodiment at least about 22, in another
embodiment at least about 24, in yet another embodiment at least
about 26, in still another embodiment at least about 28, in another
embodiment at least about; 30, in yet another embodiment at least
about 32, in still another embodiment at least about 34, in another
embodiment at least-about 36, in yet another embodiment at least
about 38, in still another embodiment at least about 40, in another
embodiment at least about 42, in yet another embodiment at least
about 44, in still another embodiment at least about 46, in another
embodiment at least about 48, in yet another embodiment at least
about 50, in still another embodiment at least about 52, in another
embodiment at least about 54, in: yet another embodiment at least
about 56, in still another embodiment at least about 58, in another
embodiment at least about 60, in yet another embodiment at least
about 62, in still another embodiment at least about 64, in another
embodiment at least about 66, in yet another embodiment at least
about 68, in still another embodiment at least about 70, and in
another embodiment at least about 72.
[0104] Since hetero atoms can be included in the alkyl, aryl,
arylalkyl, and alkylaryl groups, and since the groups can be
substituted, it is to be understood that R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, and R.sub.10
can also be groups such as alkoxy, polyalkyleneoxy, aryloxy,
polyaryleneoxy, arylalkyloxy, polyarylalkyleneoxy, alkylaryloxy, or
polyalkylaryleneoxy groups, provided that the oxygen atom in such a
group is not directly bonded to a nitrogen, oxygen, or sulfur atom
in the 51
[0105] central structure.
[0106] Examples of situations wherein one of the R.sub.1-4 groups
is a cycloalkyl is when 52
[0107] Examples of situations wherein the R.sub.1-4 groups are
joined together to form a ring are when 53
[0108] Examples of situations wherein one of the, R.sub.1-4 groups
is joined to a phenyl ring in the central structure is when 54
[0109] Compounds for the inks of the present invention include
those wherein the chromogen is a monocarboxylic acid or a
monocarboxylate, wherein 55
[0110] a dicarboxylic acid or a dicarboxylate, wherein 56
[0111] tricdrboxylic acids and tricarboxylates, tetracarboxylic
acids and tetracarboxylates, pentacarboxylic acids and
pentacarboxylates, monosulfonic acids and monosulfonates, wherein
57
[0112] disulfonic acids and disulfonates, wherein 58
[0113] SO.sub.3 trisulfonic acids and trisulfonates, fetrasulfonic
acids and tetrasulfonates, pentasulfonic acids and pentasulfonates,
monocarboxylic acid monosulfonic acids and monocarboxylate
monosulfonates, wherein 59
[0114] monocarboxylic acid disulfonic acids and monocarboxylate
disulfonates, monocarboxylic acid trisulfonic acids and
monocarboxylate trisulfonates, monocarboxylic acid tetrasulfonic
acids and monocarboxylate tetrasulfonates, dicarboxylic acid
monosulfonic acids and dicarboxylate monosulfonates, dicarboxylic
acid disulfonic acids and dicarboxylate disulfonates, dicarboxylic
acid trisulfonic acids and dicarboxylate trisulfonates,
tricarboxylic acid monosulfonic acids and tricarboxylate
monosulfonates, tricarboxylic acid disulfonic acids and
tricarboxylate disulfonates, tetracarboxylic acid monosulfonic
acids and tetracarboxylate monosulfonates, and the like. In
addition, it is possible for a compound according to the present
invention to have both one or more acid groups (i.e., COOH or
SO.sub.3H) and one or more anionic salt groups (i.e., COO.sup.- or
SO.sub.3.sup.-) present in the molecule.
[0115] Colorant compounds suitable for inks according to the
present invention include rhodamines, wherein 60
[0116] wherein the chromogen is of the general formula 61
[0117] acridines, wherein 62
[0118] wherein the chromogen is of the general formula 63
[0119] sulforhodamines, wherein 64
[0120] wherein the chromogen is of the general formula 65
[0121] anthracenes, wherein 66
[0122] wherein the chromogen is of the general formula 67
[0123] and the like.
[0124] In a specific embodiment, the anion A can be an organic
dianion of the formula A.sub.1-R.sub.11-A.sub.2 wherein A.sub.1
and, A.sub.2 each, independently of the other, are anionic groups,
such as carboxylate, sulfonate, or the like, and wherein R.sub.11
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 one embodiment with at least 1 carbon
atom, in another embodiment with at least about 2 carbon atoms, in
yet another embodiment with at least about 6 carbon atoms, in
another embodiment with a t least about 8 carbon atoms, and in yet
another embodiment with at least about 18 carbon atoms, and in one
embodiment with no more than about 55 carbon atoms, in another
embodiment with no more than about 30 carbon atoms, and in yet
another embodiment with no more than about 20 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 one embodiment with at least
about 6 carbon atoms, in another embodiment with at least about 10
carbon atoms, and in yet another embodiment with at least about 14
carbon atoms, and in one embodiment with no more than about 26
carbon atoms, in another embodiment with no more than about 22
carbon atoms, and in yet another embodiment with no more than about
18 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 drylalkylene group), in one
embodiment with at least about 7 carbon atoms, in another
embodiment with at least about 12 carbon atoms and in yet another
embodiment with at least about 18 carbon atoms, and in one
embodiment with no more than about 55 carbon atoms, in another
embodiment with no more than about 30 carbon atoms, and in yet
another embodiment with no more than about 20 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as benzyl 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
one embodiment with at least about 7 carbon atoms, in another
embodiment with at least about 12 carbon atoms, and in yet: another
embodiment with at least about 18 carbon atoms, and in one
embodiment with no more than about 55 carbon, atoms, in another
embodiment with no more than about 35 carbon atoms, and in yet
another embodiment with no more than about 20 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as tolyl or the like, and wherein the substituents on the
substituted alkylene, arylene, arylalkylene, and alkylarylene
groups can be (but are not limited to) hydroxy groups, halogen
atoms, amine groups, imine groups, ammonium groups, cyano groups,
pyridine groups, pyridinium groups, ether groups, aldehyde groups,
ketone groups, ester groups, amide 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, acyl groups,
acid anhydride groups, azide groups, azo groups, cyanato groups,
isocyanato groups, thiocyanato groups, isothiocyanato groups,
carboxylate groups, carboxylic acid groups, urethane groups, urea
groups, mixtures thereof, and the like, wherein two or more
substituents can be joined together to form a ring. Examples of
suitable organic dianions include unsubstituted and substituted
naphthalene disulfonates, unsubstituted and substituted benzene
disulfonates, and the like, as well as mixtures thereof.
[0125] In another specific embodiment, the anion A can be an
orgdnic trianion, tetraanion, and higher, an, oligomeric and
polymeric anion, such as a polysulfonate or polycarboxylate, or the
like.
[0126] In one specific embodiment, the chromogen for the colorant
compounds for the inks according to the present invention is of the
formula 68
[0127] It is to be understood that in chromogens of the formula
69
[0128] the positive charge is delocalized, and that other
tautomeric structures can be drawn, including (but not limited to)
70
[0129] and the like. It is to be understood that all possible
tautomeric forms of these colorants are included within the above
formulae.
[0130] In one specific embodiment, the compounds in the inks of the
present invention are of the general formula 71
[0131] wherein M is a metal cation, y is an integer representing
the charge on the metal cation and is at least 2, A is an anion,
and x is an integer representing the charge on the anion.
[0132] Colorant compounds for inks of the present invention can be
prepared by any desired or effective procedure. Preparation of the
chromogen will be discussed first. By "chromogen" is meant the
72
[0133] component of the metal compound which is later reacted with
the metal cation or metal containing moiety to form the colorant of
the present invention. For example, a dihalofluorescein, such as
dichlorofluorescein or the like, can be admixed with one or more
amines having the desired R.sub.1, R.sub.2, R.sub.3, and R.sub.4
groups thereon, an optional zinc halide, such as zinc chloride or
the like, and an optional normucleophilic base, such as calcium
oxide, zinc oxide, or the like, either neat or, optionally, in the
presence of a solvent.
[0134] The amine and the dihalofluorescein are present in any
desired or effective relative amounts, tin one embodiment at least
about 0.9 mole of base per every one mole of dihalofluorescein, in
another embodiment at least about 0.95 mole of base per every one
mole of dihalofluorescein, and in yet another embodiment at least
about 1 mole of base per every one mole of dihalofluorescein, and
in one embodiment no more than about 20 moles of base per every one
mole of dihalofluorescein, in another embodiment no more than about
10 moles of base per every one mole of dihalofluorescein, and in
yet another embodiment no more than about 2 moles of base per every
one mole of dihalofluorescein, although the relative amounts can be
outside of these ranges.
[0135] Dichlorofluorescein is commercially available from, for,
example, Aldrich Chemical Co., Milwaukee, Wis. Dihalofluoresceins
can also be prepared by the reaction of fluorescein with PX.sub.5
wherein X is fluorine, chlorine, bromine, or iodine, or with a
toluenesulfonylhalide, such as toluenesulfonylchloride or the
like.
[0136] When an optional zinc halide is used, the dihalofluorescein
and the zinc halide are present in any desired or effective
relative amounts, in one embodiment at least about 2 moles of zinc
halide per every one mole of dihalofluorescein, in another
embodiment at least about 2.5 moles of zinc halide per every one
mole of dihalofluorescein, and yet in another embodiment at least
about 3 moles of zinc halide per every one mole of
dihalofluorescein, and in one embodiment no more than about 5 moles
of zinc halide per every one mole of dihalofluorescein, in another
embodiment no more than about 4.5 moles of zinc halide per every
one mole of dihaloflubrescein, and in yet another embodiment no
more than about 4 moles of zinc halide per every one mole of
dihalofluorescein, although the relative amounts can be outside of
these ranges.
[0137] When an optional base is used, the base is present in any
desired or effective amount, in one embodiment at least about 2
equivalents of base per every one mole of dihalofluorescein (i.e.,
about 2 moles of monobasic base per every one mole of
dihalofluorescein, about 1 mole of dibasic base, such as calcium
oxide, per every one mole of dihalofluorescein, and the like), in
another embodiment at least about 2.5 equivalents of base per every
one mole of dihalofluorescein, and yet in another embodiment at
least about 3 equivalents of base per every one mole of
dihalofluorescein, and in one embodiment no more than about 10
equivalents of base per every one mole of dihalofluorescein, in
another embodiment no more than about 5 equivalents of base per
every one mole of dihalofluorescein, and in yet another embodiment
no more than about 3.2 equivalents of base per every one mole of
dihalofluorescein, although the relative amounts can be outside of
these ranges.
[0138] If desired, the reaction can be run neat, in the absence of
a solvent. In addition, if desired, the reaction can be run in the
presence of an optional solvent. Examples of suitable solvents
include tetramethylene sulfone (sulfolane), N-methylpyrrolidone,
dimethyl formamide, dimethyl sulfoxide, octanol, or the like, as
well as mixtures thereof. When present, the optional solvent is
present in any desired or effective amount, in one embodiment at
least about 11 liter per every 0.1 mole of dihalofluorescein, in
another embodiment at least about 1 liter per every 0.3 mole of
dihalofluorescein, and in yet another embodiment at least about 1
liter per every 0.35 mole of dihalofluorescein, and in one
embodiment no more than about 1 liter per every 2 moles of
dihalofluorescein, in another embodiment no more than about liter
per every 1.5 moles of dihalofluorescein, and in yet another
embodiment no more than about 1 liter per every 1 mole of
dihalofluorescein, although the relative amounts can be outside of
these ranges.
[0139] The mixture of dihalofluorescein, amine, optional zinc
halide, optional base, and optional solvent is then heated to any
effective temperature, in one embodiment at least about 62.degree.
C., in another embodiment at least about 150.degree. C., and in yet
another embodiment at least about 190.degree. C., and in one
embodiment no more than about 28.degree. C., in another embodiment
no more than about 220.degree. C., and in yet another embodiment no
more than about 200.degree. C., although the temperature can be
outside of these ranges.
[0140] The mixture of dihalofluorescein, amine, optional zinc
halide, optional base, and optional solvent is heated for any
effective period of time, in one embodiment at least about 5
minutes, in another embodiment at least about 2 hours, and in yet
another embodiment at least about 3 hours, and in one embodiment no
more than about 4 days, in another embodiment no more than about 60
hours, and in yet another embodiment no more than about 40 hours,
although the time can be outside of these ranges.
[0141] If desired, the resulting chromogen product can be purified
by pouring the reaction mixture into an organic non-water-soluble
and non-water-miscible solvent in which the product is soluble or
miscible and in which undesirable salt byproducts are not soluble,
such as methyl isobutyl ketone, toluene, hexane, heptane, or the
like, followed by admixing the solvent containing the product with
water in a separatory funnel and separating the aqueous and organic
phases.
[0142] The crude chromogen product can then, if desired, be further
purified by washing it with aqueous EDTA to remove metal salts,
followed by washing with water. If desired, a titration or other
instrumental technique, such as AA (atomic absorption) or ICP
(inductively coupled plasma) can be performed to determine if the
metal salts have been completely removed. The purified product can
be isolated by distilling off any solvents.
[0143] Various substituents<can be placed on the rings of the
chromogens of the present invention by any desired or effective
method, such as, for example, the methods disclosed in U.S. Pat.
No. 5,847,162 and U.S. Pat. No. 1,991,482, the disclosures of each
of which are totally incorporated herein by reference.
[0144] Additional numbers of carbon atoms can be placed on the
central structure by, for example, selecting long chain amines as
reactants. Examples of such compounds include (but are not limited
to) those of the formulae 73
[0145] wherein Y, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 have the
same definitions as given hereinabove, G is either 74
[0146] and (1) R is a linear alkyl group of the formula
--C.sub.nH.sub.2.sub.n+1 wherein n is at least about 12, (2) R is a
branched alkyl group of the formula --C.sub.nH.sub.2n+1 wherein n
is at least about 12, (3) R is an ether group of the formula
--(CH.sub.2).sub.3--O--C.sub.nH.sub.2n+1 wherein n is at least
about 11, and the like, as well as their ring-opened, or
protonated, or free-base forms and their zwitterionic forms.
[0147] Additional numbers of carbon atoms can also be placed on the
central structure by, for example, first preparing the
corresponding alcohols and then reacting these alcohols with, for
example, high-carbon-number acids to prepare esters,
high-carbon-number isocyanates to prepare urethanes, or the like.
Examples of such compounds include (but are not limited to) those
of the formulae 75
[0148] wherein Y, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 have the
same definitions as given hereinabove, G is either 76
[0149] and (1) R is a group of the formula 77
[0150] wherein n is at least about 12, (2) R is a group of the
formula 78
[0151] wherein n is at least about 12, (3) R is a group of the
formula 79
[0152] wherein n is at least about 12, (4) R is a group of the
formula 80
[0153] wherein n is at least about 12, (5) R is a group of the
formula 81
[0154] wherein n is at least about 12, (6) R is a group of the
formula 82
[0155] wherein n is at least about 12, (7) two R groups on the same
nitrogen atom form a group, with the nitrogen atom, of the formula
83
[0156] wherein n is at least about 12, (8) two R groups on the same
nitrogen atom form a group, with the nitrogen atom, of the formula
84
[0157] wherein n is at least about 12, (9) two R groups on the same
nitrogen atom form a group, with the nitrogen atom, of the formula
85
[0158] wherein n is at least about 12, and the like, as well as
their ring-opened, or protonated, or free-base forms and their
zwitterionic forms.
[0159] Some specific examples of such compounds include (a) those
of the formulae 86
[0160] wherein n is at least about 11, (b) those of the formulae
87
[0161] wherein n is at least about 12, (c) those of the formulae
88
[0162] wherein n is at least about 12, (d) those of the formulae
89
[0163] wherein n is at least about 12, (e) those of the formulae
9091
[0164] wherein n is at least about 12, (f) those of the formulae
9293
[0165] wherein n is at least about 12, (g) those of the formulae
9495
[0166] wherein n is at least about 12, (h) those of the formulae
96
[0167] wherein n is at least about 12, (i) those of the formulae
97
[0168] wherein n is at least about 12, (j) those of the formulae
98
[0169] wherein n is at least about 12, (k) those of the formulae
99
[0170] wherein n is at least about 12, (1) those of the formulae
100
[0171] wherein n is at least about 12, (m) those of the formulae
101
[0172] n is at least about 12, (n) those of the formulae 102
[0173] wherein n is at least about 12, (O) those of the formulae
103
[0174] wherein n is at least about 12, (p) those of the formulae
104
[0175] wherein n is at least about 12 and the like.
[0176] The chromogen can then be formed into a metal compound
colorant by admixing it with an appropriate metal salt, optionally
in the presence of a solvent, such as acetone, toluene, methyl
isobutyl ketone, or the like.
[0177] Examples of suitable metals are provided hereinabove.
Examples of suitable salts include those formed from the desired
metal and any desired or effective anions, including (but not
limited to) F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-, SCN.sup.--,
CF.sub.3SO.sub.3.sup.--, [C.sub.10H.sub.8(SO.sub.3).sub.2]2.sup.-,
CH.sub.3.sup.-C.sub.6H.sub.4.su- p.-SO.sub.3.sup.-, PF.sub.6.sup.-,
ClO.sub.4.sup.-, NO.sub.2.sup.-C.sub.6H.sub.4.sup.-SO.sub.3.sup.-,
NH.sub.2.sup.-C.sub.6H.- sub.4.sup.-SO.sub.3.sup.-, SCN.sup.-,
dodecylbenzene sulfonate, or the like.
[0178] The chromogen and the metal salt are present in any desired
or effective relative amounts, generally at least about 2 moles of
chromogen per every one mole of metal salt, and higher when higher
ratios of chromogen to metal or metal containing moiety are
desired, although the relative amounts can be outside of these
ranges.
[0179] When present, the optional solvent is present in any desired
or effective amount, in one embodiment at least about 1 liter per
every 0.01 mole of chromogen, in another embodiment at least about
1 liter per every 0.04 mole of chromogen, and in yet another
embodiment at least about 1 liter per every 0.08 mole of chromogen,
and in one embodiment no more than about 1 liter per every 0.5 mole
of chromogen, in another embodiment no more than about 1 liter per
every 0.1 mole of chromogen, and in yet another embodiment no more
than about 1 liter per every 0.09 mole of chromogen, although the
relative amounts can be outside of these ranges.
[0180] The chromogen and the metal salt are allowed to react for
any desired or effective period of time, in one embodiment at least
about 0.5 hour, in another embodiment at least about 8 hours, and
in yet another embodiment at least about 12 hours, and in one
embodiment no more than about 96 hours, in another embodiment no
more than about 48 hours, and in yet another embodiment no more
than about 24 hours, although the time can be outside of these
ranges.
[0181] The chromogen and the metal salt are allowed to react at any
desired or effective temperature, in one embodiment at least about
25.degree. C., in another embodiment at, least about 55.degree. C.,
and in yet another embodiment at least about 100.degree. C., and in
one embodiment no more than about 190.degree. C., in another
embodiment no more than about 150.degree. C., and in yet another
embodiment no more than about 110.degree. C., although the time can
be outside of these ranges. When an optional solvent is used,
generally lower temperatures can be employed, whereas when the
reaction is run neat, the temperature is sufficiently high to
render the chromogen molten.
[0182] The resulting product can then be isolated by any desired or
effective method, such as by distilling, off the solvent, cooling
the reaction mixture (when the product is soluble in the solvent at
elevated temperatures and insoluble in the solvent at lowered
temperatures), or the like.
[0183] Another embodiment of the present invention is directed to a
compound comprising the reaction product of (a) a chromogen of the
formula 105
[0184] wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each,
independently of the others, is (i) a hydrogen atom, (ii) an alkyl
group, (iii) an aryl group, (iv) an arylalkyl group, or (v) an
alkylaryl group, wherein R.sub.1 and R.sub.2 can be joined together
to form a ring, wherein R.sub.3 and R.sub.4 can be joined together
to form a ring, and wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4
can each be joined to a phenyl ring in the central structure., a
and b each, independently of the others, is an integer which is 0,
1, 2, or 3, c is an integer which is 0, 1, 2, 3, or 4, each
R.sub.5, R.sub.6, and R.sub.7, independently of the others, is (i)
an alkyl group, (ii) an aryl group, (iii) an arylalkyl group, (iv)
an alkylaryl group, (v) a halogen atom, (vi) an ester group, (vii)
an amide group, (viii) a sulfone group, (ix) an amine group or
ammonium group, (x) a nitrite group, (xi) a nitro group, (xii) a
hydroxy group, (xiii) a cyano group, (xiv) a pyridine or pyridinium
group, (xv) an ether group, (xvi) an aldehyde group, (xvii) a
ketone group, (xviii) a carbonyl group, (xix) a thiocarbonyl group,
(xx) a sulfate group, (xxi) a sulfide group, (xxii) a sulfoxide
group, (xxiii) a phosphine or phosphonium group, (xxiv) a phosphate
group, (xxv) a mercapto group, (xxvi) a nitroso group, (xxvii) an
acyl group, (xxviii) an acid anhydride group, (xxix) an azide
group, (xxx) an azo group, (xxxi) a cyanato group, (xxxii) an
isocyanato group, (xxxiii) a thiocyanato group, (xxxiv) an
isothiocyanato group, (xxxv) a urethane group, or (xxxvi) a urea
group, wherein R.sub.5, R.sub.6, and R.sub.7 can each be joined to
a phenyl ring in the central structure, 106
[0185] R.sub.8, R.sub.9, and R.sub.10 each, independently of the
others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an aryl
group, (iv) an arylalkyl group, or (v) an alkylaryl group, provided
that the number of carbon atoms in
R.sub.1+R.sub.2+R.sub.3+R.sub.4+R.sub.5+R.sub.6+R.sub.7+R-
.sub.8+R.sub.9+R.sub.10 is at least about 16, Q.sup.- is a
COO.sup.- group or a SO.sub.3-- group, d is an integer which is 1,
2, 3, 4, or 5, A is an anion, and CA is either a hydrogen atom or a
cation associated with all but one of the Q.sup.- groups, and (b) a
metal salt of which the metal portion is either (1) a metal ion
having a positive charge of +y wherein y is an integer which is at
least 2, said metal ion being capable of forming a compound with at
least two 107
[0186] moieties, or (2) a metal-containing moiety capable of
forming a compound with at least two 108
[0187] moieties.
[0188] While not being limited to any particular theory, it is
believed that in at least some embodiments of the present invention
and with at least some metal cations or metal-containing moieties,
coordination complexes may form. For example, when Q.sup.- is: a
carboxylate anion, d is 1, and the metal is capable of coordinating
to four ligands, a metal colorant compound ac cording to the
present invention may have the formula 109
[0189] wherein the arrowheaded bonds represent coordination bonds
between lone pairs of electrons on a carbonyl group and the metal.
For example, when M is a metal that makes square planar
coordination complexes, the metal colorant compound may have the
structure 110
[0190] When M is a metal that makes tetrahedral coordination
complexes, the metal colorant compound may have the structure
111
[0191] When Q.sup.- is a carboxylate anion, d is 1, and the metal
is capable of coordinating to six ligands, making octahedral
coordination complexes, the metal colorant compound may have the
structure 112
[0192] It is believed that sulfonate anions will form complexes
similar to those formed by carboxylate anions.
[0193] Phase change inks of the present invention contain a phase
change carrier system or composition. The phase change carrier
composition is typically designed for use in either a direct
printing mode or an indirect or offset printing transfer
system.
[0194] In the direct printing mode, the phase change carrier
composition in one embodiment contains one or more materials that
enable the phase change ink (1) to be applied in a thin film of
uniform thickness on the final recording substrate (such as paper,
transparency material, and the like) when cooled to ambient
temperature after printing directly to the recording substrate, (2)
to be ductile while retaining sufficient flexibility so that the
applied image on the substrate will not fracture upon bending, and
(3) to possess a high degree of lightness, chroma; transparency,
and thermal stability.
[0195] In an offset printing transfer or indirect printing mode,
the phase change carrier composition in one embodiment exhibits not
only the characteristics desirable for direct printing mode inks,
but also certain fluidic and mechanical properties desirable for
use in such a system, as described in, for example, U.S. Pat. No.
5,389,958 the disclosure of which is totally incorporated herein by
reference.
[0196] 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.
Specific examples of suitable fatty amide ink carrier materials
include stearyl stearamide, a dimer acid based tetra-amide, that is
the reaction product of dimer acid, ethylene diamine, and stearic
acid, a dimer acid based tetra-amide that is the reaction product
of dimer acid, ethylene diamine, and a carboxylic acid having at
least about 36 carbon atoms, and the like, as well as mixtures
thereof. When the fatty amide ink carrier is a dimer acid based
tetra-amide that is the reaction product of dimer acid, ethylene
diamine, and a carboxylic acid having at least about 36 carbon
atoms, the carboxylic acid is of the general formula 113
[0197] wherein R is an alkyl group, including linear, branched,
saturated, unsaturated, and cyclic alkyl groups, said alkyl group
in one embodiment having at least about 36 carbon atoms, in another
embodiment having at least about 40 carbon atoms, said alkyl group
in one embodiment having no more than about 200 carbon atoms, in
another embodiment having no more than about 150 carbon atoms, and
in yet another embodiment having no more than about 100 carbon
atoms, although the number of carbon atoms can be outside of these
ranges. Carboxylic acids of this formula are commercially available
from, for example, Baker Petrolite, Tulsa, Okla., and can also be
prepared as described in Example 1 of U.S. Pat. No. 6,174,937, the
disclosure of which is totally incorporated herein by reference.
Further information on fatty amide carrier materials is disclosed
in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No. 4,889,761,
U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat. No.
6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, U.S.
Pat. No. 6,174,937, and British Patent GB 2 238 792, the
disclosures of each of which are totally incorporated herein by
reference.
[0198] Also 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, U.S. Pat. No. 5,750,604,
U.S. Pat. No. 5,780,528, U.S. Pat. No. 5,782,966, U.S. Pat. No.
5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat. No. 5,830,942, U.S.
Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S. Pat. No.
6,309,453, British Patent GB 2 294 939, British Patent GB 2 305
928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCT
Publication WO 94/14902, PCT Publication WO 97/12003, PCT
Publication WO 97/13816, PCT Publication WO 96/14364, PCT
Publication WO 97/33943, and PCT Publication WO 95/04760, the
disclosures of each of which are totally incorporated herein by
reference.
[0199] Mixtures of fatty amide materials and isocyanate-derived
materials can also be employed as the ink carrier composition for
inks of the present invention.
[0200] Additional 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.
[0201] In one specific embodiment, the phase change ink carrier
comprises (a) a polyethylene wax, present in the ink in an amount
in one embodiment of at least about 25 percent by weight of the
ink, in another embodiment of at least about 30 percent by weight
of the ink, and in yet another embodiment of at least about 37
percent by weight of the ink, and in one embodiment of no more than
about 60 percent by weight of the ink, in another embodiment of no
more than about 53 percent by weight of the ink, and in yet another
embodiment of no more than about 48 percent by weight of the ink,
although the amount can be outside of these ranges; (b) a stearyl
stearamide wax, present in the ink in an amount in one embodiment
of at least about 8 percent by weight of the ink, in another
embodiment of at least about 10 percent by weight of the ink, and
in yet another embodiment of at least about 12 percent by weight of
the ink, and in one embodiment of no more than about 32 percent by
weight of the ink, in another embodiment of no more than about 28
percent by weight of the ink, and in yet another embodiment of no
more than about 25 percent by weight of the ink, although the
amount can be outside of these ranges; (c) a dimer acid based
tetra-amide that is the reaction product of dimer acid, ethylene
diamine, and a long chain hydrocarbon having greater than thirty
six carbon atoms and having a terminal carboxylic acid group,
present in the ink in an amount in one embodiment of at least about
10 percent by weight of the ink, in another embodiment of at least
about 13 percent by weight of the ink, and in yet another
embodiment of at least about 16 percent by weight of the ink, and
in one embodiment of no more than about 32 percent by weight of the
ink, in another embodiment of no more than about 27 percent by
weight of the ink, and in yet another embodiment of no more than
about 22 percent by weight of the ink, although the amount can be
outside of, these ranges; (d) a urethane resin derived from the
reaction of two equivalents of hydroabietyl alcohol and one
equivalent of isophorone diisocyanate, present in the ink in an
amount in one embodiment of at least about 6 percent by weight of
the ink, in another embodiment of at least about 8 percent by
weight of the ink, and in yet another embodiment of at least about
10 percent by weight of the ink, and in one embodiment of no more
than about 16 percent by weight of the ink, in another embodiment
of no more than about 14 percent by weight of the ink, and in yet
another embodiment of no more than about 12 percent by weight of
the ink, although the amount can be outside of these ranges; (e) a
urethane resin that is the adduct of three equivalents of stearyl
isocyanate and a glycerol-based propoxylate alcohol, present in the
ink in an amount in one embodiment of at least about 2 percent by
weight of the ink, in another embodiment of at least about 3
percent by weight of the ink, and in yet another embodiment of at
least about 4.5 percent by weight of the ink, and in one embodiment
of no more than about 13 percent by weight of the ink, in another
embodiment of no more than about 10 percent by weight of the ink,
and in yet another embodiment of no more than about 7.5 percent by
weight of the ink, although the amount can be outside of these
ranges; and (f) an antioxidant, present in the ink in an amount in
one embodiment of at least about 0.01 percent by weight of the ink,
in another embodiment of at least about 0.05 percent by weight of
the ink, and in yet another embodiment of at least about 0.1
percent by weight of the ink, and in 20: one embodiment of no more
than about 1 percent by weight of the ink, in another embodiment of
no more than about 0.5 percent by weight of the ink, and in yet
another embodiment of no more than about 0.3 percent by weight of
the ink, although the amount can be outside: of these ranges.
[0202] The ink carrier is present in the phase change ink of the
present invention in any desired or effective amount, in one
embodiment of at least about 0.1 percent by weight of the ink, in
another embodiment of at least about 50 percent by weight of the
ink, and in yet another embodiment of at least about 90 percent by
weight of the ink, and in one embodiment of no more than about 99
percent by weight of the ink, in another embodiment of no more than
about 98 percent by weight of the ink, and in yet another
embodiment of no more than about 95 percent by weight of the ink,
although the amount can be outside of these ranges.
[0203] The phase change inks of the present invention contain a
colorant compound of the formula 114
[0204] This colorant is present in the ink in any desired or
effective amount to obtain the desired color or hue, in one
embodiment of at least about 0.1 percent by weight of the ink, in
another embodiment of at least about 0.5 percent by weight of the
ink, in yet another embodiment of at least about 1 percent by
weight of the ink, in still another embodiment of at least about 2
percent by weight of the ink, and in another-embodiment of at least
about 3 percent by weight of the ink, and in one embodiment of no
more than about 20 percent by weight of the ink, in another
embodiment of no more than about 13 percent by weight of the ink,
and in yet another embodiment of no more than about 6 percent by
weight of the ink, although the amount can be outside of these
ranges. The colorant according to the present invention can either
be the sole colorant in the ink or can be present in combination
with other colorants, such as dyes, pigments, mixtures thereof, and
the like.
[0205] In a specific embodiment, the inks of the present invention
include an anthraquinone colorant in addition to the colorant
according to the present invention. Examples of suitable
anthraquinone colorants include Solvent Red 172, colorants as
disclosed in U.S. Pat. No. 6,395,078 and U.S. Pat. No. 6,422,695,
the disclosures of each of which are totally incorporated herein by
reference, colorants as disclosed in Copending Application U.S.
Ser. No. 10/260,146, Copending Application U.S. Ser. No.
10/260,376, and Copending Application U.S. Ser. No. 10/260,379, the
disclosures of each of which are totally incorporated herein by
reference, and the like. In a specific embodiment, the
anthraquinone colorant is one prepared as described in Example
XVII, Parts 1 through 5. The anthraquinone colorant can be present
in the inks of the present invention in any desired or effective
amount to achieve the desired color, hue, and other
characteristics, in one embodiment of at least about 1 percent by
weight of the ink, in another embodiment of at least about 2
percent by weight of the ink, and in yet another embodiment of at
least about 3 percent by weight of the ink, and in one embodiment
of no more than about 20 percent by weight of the ink, in another
embodiment of no more than about 13 percent by weight of the ink,
and in yet another embodiment of no more than about 6 percent by
weight of the ink, although the amount can be outside of these
ranges.
[0206] In specific embodiments, the inks of the present invention
further contain an acid having a K.sub.a value greater than that of
the K.sub.a of the carboxylic acid and/or sulfonic acid and/or
carboxylate and/or sulfonate groups on the colorant. Specific
examples of suitable acids include organic sulfonic acids,
including alkyl benzene sulfonic acids such as
para-toluene-sulfonic acid, dodecylbenzenesulfonic acid, and the
like, p-toluene sulfonic acid, hydrochloric acid, trifluoroacetic
acid, methylsulfonic acid, trifluoromethyl sulfonic acid,
hydrobromic acid, and the like, as well as mixtures thereof. The
acid is present in any desired or effective amount, in one
embodiment at least about 2 percent by weight of the amount of
colorant according to the present invention, and in another
embodiment at least about 5 percent by weight of the amount of
colorant according to the present invention, and in one embodiment
no more than about 100 percent by weight of the amount of the
colorant according to the present invention, and in another
embodiment no more than about 30 percent by weight of the colorant
according to the present invention, although the amount of acid can
be outside of these ranges.
[0207] The 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.RTM. 524, NAUGUARD.RTM. 76, and NAUGUARD.RTM. 512
(commercially available from Uniroyal Chemical Company, Oxford,
CT), IRGANOX.RTM. 1010 (commercially available from Ciba Geigy),
and the like. When present, the optional antioxidant is present in
the ink in any desired or effective amount, in one embodiment of at
least about 0.01 percent by weight of the ink, in another
embodiment of at least about 0.1 percent by weight of the ink, and
in yet another embodiment of at least about; percent by weight of
the ink, and in one embodiment of no more than about 20 percent by
weight of the ink, in another embodiment of no more than about 5
percent by weight of the ink, and in yet another embodiment of no
more than about 3 percent by weight of the ink, although the amount
can be outside of these ranges.,
[0208] The 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 one embodiment of at
least about 0.1 percent by weight of the ink, in another embodiment
of at least about 1 percent by weight of the ink, and in yet
another embodiment of at least about 10 percent by weight of the
ink, and in one embodiment of no more than about 99 percent by
weight of the ink, in another embodiment of no more than about 30
percent by weight of the ink, and in yet another embodiment of no
more than about 15 percent by weight of the ink, although the
amount can be outside of these ranges.
[0209] Other optional additives to the inks include clarifiers,
such as UNION CAMP.RTM. X37-523-235 (commercially available from
Union Camp), in an amount in one embodiment of at least about 0.01
percent by weight of the ink, in another embodiment of at least
about 0.1 percent by weight of the ink, and in yet another
embodiment of at least about 5 percent by weight of the ink, and in
one embodiment of no more than about 98 percent by weight of the
ink, in another embodiment of no more than about 50 percent by
weight of the ink, and in yet another embodiment of no more than
about 10 percent by weight of the ink, although the amount can be
outside of these ranges, tackifiers; such as FORAL.RTM. 85, a
glycerol ester of hydrogenated abietic (rosin) acid (commercially
available from Hercules), FORAL.RTM. 105, a pentaerythritol ester
of hydroabietic (rosin) acid (commercially available from
Hercules), CELLOLYN.RTM. 21, a hydroabietic (rosin) alcohol ester
of phthalic acid (commercially available from Hercules), ARAKAWA
KE-311 Resin, a triglyceride of hydrogenated abietic (rosin) acid
(commercially available from Arakawa Chemical Industries, Ltd.),
synthetic polyterpene resins such as NEVTAC.RTM. 2300, NEVTAC.RTM.
100, and NEVTAC.RTM. 80 (commercially available from Neville
Chemical Company), WINGTACK.RTM. 86, a modified synthetic
polyterpene resin (commercially available from Goodyear), and the
like, in an amount in one embodiment of at least about 0.1 percent
by weight of the ink, in another embodiment of at least about 5
percent by weight of the ink, and in yet another embodiment of at
least about 10 percent by weight of the ink, and in one embodiment
of no more than about 98 percent by weight of the ink, in another
embodiment of no more than about 75 percent by weight of the ink,
and in yet another embodiment of no more than about 50 percent by
weight of the ink, although the amount can be outside of these
range, adhesives, such as VERSAMID.RTM. 757, 759, or 744
(commercially available from Henkel), in an amount in one
embodiment of at least about 0.1 percent by weight of the ink, in
another embodiment of at least about 1 percent by weight of the
ink, and in yet another embodiment of at least about 5 percent by
weight of the ink, and in one embodiment of no more than about 98
percent by weight of the ink, in another embodiment of no more than
about 50 percent by weight of the ink, and in yet another
embodiment of no more than about 10 percent by weight of the ink,
although the amount can be outside of these ranges, plasticizers,
such as UNIPLEX.RTM. 250 (commercially available from Uniplex), the
phthalate ester plasticizers commercially available from Monsanto
under the trade name SANTICIZER.RTM., such as dioctyl phthdlate,
diundecyl phthalate, alkylbenzyl phthalate (SANTICIZER.RTM. 278),
triphenyl phosphate (commercially available from Monsanto),
KP-140.RTM., a tributoxyethyl phosphate (commercially available
from FMC Corporation), MORFLEX.RTM. 150, a dicyclohexyl phthdlate
(commercially available from Morflex Chemical Company Inc.),
trioctyl trimellitate (commercially available from Eastman Kodak
Co.), and the like, in an amount in one embodiment of at least
about 0.1 percent by weight of the ink, in another embodiment of at
least about 1 percent by weight of the ink, and in yet another
embodiment of at least about 2 percent by weight of the ink, and in
one embodiment of no more than about 50 percent by weight of the
ink, in another embodiment of no more than about 30 percent by
weight of the ink, and in yet another embodiment of no more than
about 10 percent by weight of the ink, although the amount can be
outside of these ranges, and the like.
[0210] The ink compositions of the present invention in one
embodiment have melting points of no lower than about 50.degree.
C., in another embodiment of no lower than about 70.degree. C., and
in yet another embodiment of no lower than about 80.degree. C., and
have melting points in one embodiment of no higher than about
160.degree. C., in another embodiment of no higher than about
140.degree. C., and in yet another embodiment of no higher than
about 100.degree. C., although the melting point can be outside of
these ranges.
[0211] The ink compositions of the present invention generally have
melt viscosities at the jetting temperature (in one embodiment no
lower than about 75.degree. C., in another embodiment no lower than
about 100.degree. C., and in yet another embodiment no lower than
about 120.degree. C., and in one embodiment no higher than about
180.degree. C., and in another embodiment no higher than about
150.degree. C., although the jetting temperature can be outside of
these ranges) in one embodiment of no more than about 30 centipoise
in another embodiment of no more than about 20 centipoise, and in
yet another embodiment of no more than about 15 centipoise, and in
one embodiment of no less than about 2 centipoise, in another
embodiment of no less than about 5 centipoise, and in yet another
embodiment of no less than about 7 centipoise, although the melt
viscosity can be outside of these ranges.
[0212] The 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, to a
temperature in one embodiment of at least about 100.degree. C., and
in one embodiment of no more than about 140.degree. C., although
the temperature can be outside of these ranges, and stirring until
a homogeneous ink composition is obtained, followed by cooling the
ink to ambient temperature (typically from about 20 to about
25.degree. C.). The inks of the present invention are solid at
ambient temperature. In a specific embodiment, during the formation
process, the inks in their molten state are poured into molds and
then allowed to cool and solidify to form ink sticks.
[0213] The 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, U.S. Pat. No. 5,195,430, the disclosure of which is
totally incorporated herein by reference. 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. In a specific embodiment, 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.
An offset or indirect printing process is also disclosed in, for
example, U.S. Pat. No. 5,389,958, the disclosure of which is
totally incorporated herein by reference. 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, and the like.
Phase change inks of the present invention can also be used in
printing processes other than hot melt ink jet printing
processes.
[0214] Any suitable substrate or recording sheet can be employed,
including plain papers such as XEROX.RTM. 4024 papers, XEROX.RTM.
Image: Series papers, Courtland 4024 DP paper, ruled notebook
paper, bond paper, silica coated papers such as Sharp Company
silica coated paper, JuJo paper, Hammermill Laserprint Paper, and
the like, transparency materials, fabrics, textile products,
plastics, polymeric films, inorganic substrates such as metals and
wood, and the like.
[0215] 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.
EXAMPLE IA
Synthesis of Dichlorofluorescein
[0216] A mixture of fluorescein (100 grams, 0.331 mole; obtained
from Aldrich Chemical Co., Milwaukee, Wis.) and PCl.sub.5 (128.5
grams, 0.62 mole; obtained from Aldrich Chemical Co.) in 650
milliliters of chlorobenzene was stirred and heated to 140.degree.
C. in a 1 liter round bottom flask equipped with a reflux
condenser. After 6 hours of heating, the reflux condenser was
replaced with a distillation setup, and POCl.sub.3 formed during
the reaction as well as the chlorobenzene were distilled off. After
all of the POCl.sub.3 and chlorobenzene were removed, 300 grams of
N-methylpyrrolidinone was added and the resulting mixture was
heated to 100.degree. C. with stirring until all of the crude
dichlorofluorescein dissolved. The solution was then poured into a
4 liter beaker containing 1 liter of deionized water. A tan solid
precipitated out and was collected on a filter and dried in a
vacuum oven. The final tan solid matched the IR, NMR, and TLC of
commercially available dichlorofluorescein.
[0217] Other synthetic processes can also be used. For example, a
one-pot process using DMF solvent can be employed wherein the
POCl.sub.3 intermediate is not distilled off but is removed by
reaction with methanol, which also precipitates the
dichlorofluorescein as a white solid. Methods using
toluenesulfonylchloride, a less reactive and corrosive chlorinating
agent than PCl.sub.5, can also be used.
EXAMPLE IB
Synthesis of Tetrastearyl Colorant
[0218] A mixture of dichlorofluorescein (105 grams, 0.284 mole,
prepared as described above), calcium oxide (24, grams, 0.62 mole;
obtained from Aldrich Chemical Co., Milwaukee, Wis.), ZnCl.sub.2
(116 grams, 0.85 mole; obtained from Aldrich Chemical Co.), and
distearyl amine (288 grams, 0.585 mole; ARMEEN 2HT, obtained from
Akzo-Nobel, McCook, Ill.) in 650 milliliters of tetramethylene
sulfone (obtained from Chevron Phillips Chemical Co., LP, The
Woodlands, Tex.) was stirred and heated to 190.degree. C. in a 1
liter round bottom flask. After 10 hours of heating, the deeply
magenta colored mixture was cooled to 120.degree. C. and poured
into 2.5 liters of methyl isobutyl ketone (MIBK) and stirred until
totally dissolved.
EXAMPLE IC
Purification of Tetrastearyl Colorant
[0219] The solution of crude tetrastearyl colorant in MIBK was then
transferred to a 4 liter separatory funnel. Three aqueous EDTA
washes were then performed (50 grams of the tetrasodium salt of
EDTA in 1,000 milliliters of water for each wash) to remove all of
the zinc and calcium salts in the crude reaction product. The
product, dissolved in MIBK, remained on the top layer with the
water/EDTA chelated metal waste on the bottom layer, which was
discarded. Two washes with deionized water (1 liter each) were then
performed. At this point, the MIBK solution was no longer magenta,
but a faint orangeish-red color. The lack of a brilliant magenta
color at this point indicated a ring-closed, or free base, form of
the colorant, believed to be of the formula 115
EXAMPLE ID
Isolation of Tetrastearyl Colorant
[0220] The solution of the ring-closed, purified tetrdstearyl
colorant in MIBK was then transferred to a 2 liter round bottom
flask with distillation setup. The MIBK and residual water were
distilled off and the product, a slightly viscous wax when hot, was
transferred to a jar and allowed to harden. The wax was a deep red
colored, somewhat hard wax when cooled to room temperature.
EXAMPLE IE
Protonation of Tetrastearyl Colorant
[0221] 250 grams of the solid, ring-closed, purified tetrastearyl
colorant prepared in Example ID was then transferred to a 1 liter
beaker and 500 milliliters of MIBK were added and allowed to
dissolve the solid with stirring. A stoichiometric amount of
dodecyl benzene sulfonic acid was added to this solution and
stirred for 1 hour. A deep magenta hue was observed with the
addition of the acid. The solution was then transferred to a
distillation setup and the MIBK removed. The molten ring-opened
waxy colorant was then transferred to an aluminum tin and allowed
to cool to room temperature. The ring-opened, or protonated, or
free-base form of this colorant is believed to be of the formula
116
[0222] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 117
[0223] The process was repeated a number of times substituting for
dodecyl benzene sulfonic acid the following acids: p-toluene
sulfonic acid; hydrochloric acid; trifluoroacetic acid; methyl
sulfonic acid; trifluoromethyl sulfonic acid; and hydrobromic acid.
Similar results were observed in all cases.
EXAMPLE IF
Preparation of Zinc Tetrastearyl Colorant
[0224] To a 1-liter 3-necked roundbottom flask with TEFLON.RTM.
coated magnet and silicone oil bath was added 229 grams of the
ring-closed purified tetrastearyl chromogen and 200 grams of MIBK.
The mixture was heated to reflux. Thereafter, about 12.2 grams of
ZnCl.sub.2 (obtained from Aldrich Chemical Co., Milwaukee, Wis.)
was added in a stoichiometric amount of 2 moles of zinc chloride
per every one mole of tetrastearyl chromogen. The solution was
stirred for about 18 hours. Thereafter, the MIBK was distilled off.
The product, a slightly viscous wax when warm, was transferred to a
jar and allowed to harden. At room temperature, the product was a
deep magenta/red colored somewhat hard wax, believed to be a
coordination compound of the formula 118
EXAMPLE IIB
[0225] The process of Example IB was repeated except that dioctyl
amine (NH((CH.sub.2).sub.7CH.sub.3).sub.2, obtained from Aldrich
Chemical Co., Milwaukee, Wis.) was used instead of distearyl amine.
The dioctyl amine was present in an amount of 1.95 moles of dioctyl
amine per every one mole of dichlorofluorescein.
EXAMPLE IIC
[0226] The process of Example IC was repeated using the product
obtained in Example IIB. It is believed that the purified product
was of the formula 119
[0227] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 120
[0228] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 121
EXAMPLE IID
[0229] The process of Example ID was repeated using the product
obtained in Example IIC.
EXAMPLE IIIB
[0230] The process of Example IB was repeated except that the
reaction was run with 2.05 moles of stearyl amine per every one
mole of dichlorofluorescein.
EXAMPLE IIIC
[0231] The process of Example IC was repeated using the product
obtained in Example 111B. It is believed that the purified product
was of the formula 122
[0232] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula, 123
[0233] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 124
EXAMPLE IIID
[0234] The process of Example ID was repeated using the product
obtained in Example IIIC.
EXAMPLE IVB
[0235] The process of Example IB was repeated except that PRIMENE
JM-T (obtained from Rohm and Haas Company, Philadelphia, Pa.), of
the formula, 125
[0236] was used instead of distearyl amine. The PRIMENE JM-T was
present in an amount of 2 moles of PRIMENE JM-T per every one mole
of dichlorofluorescein.
EXAMPLE IVC
[0237] The process of Example IC was repeated using the product
obtained in Example IVB. It is believed that the purified product
was of the formula 126
[0238] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 127
[0239] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 128
EXAMPLE IVD
[0240] The process of Example ID was repeated using the product
obtained in Example IVC.
EXAMPLE VB
[0241] The process of Example IB was repeated except that UNILIN
425-PA (obtained from Tomah Products, Milton, Wis., of the formula
CH.sub.3(CH.sub.2).sub.31--O--CH.sub.2CH.sub.2CH.sub.2NH.sub.2) was
used instead of distearyl amine. The UNILIN 425-PA was present in
an amount of 2 moles of UNILIN 425-PA per every one mole of
dichlorofluorescein. It is believed that the product was of the
formula 129
[0242] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 130
[0243] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 131
EXAMPLE VIB
[0244] The process of Example --IB was repeated except that
diethanol amine (obtained from Aldrich Chemical Co., Milwaukee,
Wis., of the formula HN(CH.sub.2CH.sub.2OH).sub.2) was used instead
of distearyl amine. The diethanol amine was present in an amount of
2.5 moles of diethanol amine per every one mole of
dichlorofluorescein. In addition, 2 moles of zinc chloride were
used per every one mole of dichlorofluorescein and 1 mole of
calcium oxide was used per every one mole of dichlorofluorescein,
the solvent was N-methylpyrrolidone instead of tetramethylene
sulfone, and the reaction mixture was heated to 125.degree. C. for
100 hours.
EXAMPLE VIC
[0245] The process of Example IC was repeated using the product
obtained in Example VIB except that the product was poured into
methanol and sufficient EDTA was added to remove all of the
Zn.sup.2+ and Ca.sup.2+ ions. It is believed that the purified
product was of the formula 132
EXAMPLE VIC-1
[0246] About 10 grams of the product obtained in Example VIC is
added to 23.4 grams of octadecylisocyanate (available from Aldrich
Chemical Co., Milwaukee, Wis.) at 120.degree. C., after which 2
drops of dibutyltindilaurate catalyst (available from Aldrich
Chemical Co.) is added and the reaction is stirred and heated until
disappearance of the isocyanate peak in the IR is observed. The
tetraurethane rhodamine is poured into aluminum tins and is
believed to be of the formula 133
[0247] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 134
[0248] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 135
EXAMPLE VIIB
[0249] The process of Example IB was repeated except that
N-methyl-D-glucamine (obtained from Aldrich Chemical Co.,
Milwaukee, Wis.), of the formula 136
[0250] was used instead of distearyl amine. The
N-methyl-D-glucamine was present in an amount of 2.5 moles of
N-methyl-D-glucamine per every one mole of dichlorofluorescein. In
addition, 2 moles of zinc chloride were used per every one mole of
dichlorofluorescein and 1.5 moles of calcium oxide was used per
every one mole of dichlorofluorescein, the solvent was
N-methylpyrrolidone instead of tetramethylene sulfone, and the
reaction mixture was heated to 130.degree. C. for 7 days.
EXAMPLE VIIC
[0251] The process of Example IC was repeated using the product
obtained in Example VIIB except that the product was poured into
methanol and sufficient EDTA was added to remove all of the
Zn.sup.2+ and Ca.sup.2+ ions. It is believed that the purified
product was of the formula 137
EXAMPLE VIIC-1
[0252] About 10 grams of the product obtained in Example YIJC is
added to 45 grams of octadecylisocyanate (available from Aldrich
Chemical Co., Milwaukee, Wis.) at 120.degree. C., after which 4
drops of dibutyltindilaurate catalyst (available from Aldrich
Chemical Co.) is added and the reaction is stirred and heated until
disappearance of the isocyanate peak in the IR is observed. The
deca-urethane rhodamine is poured into aluminum tins and is
believed to be of the formula 138
[0253] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 139
[0254] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 140
EXAMPLE VIIIB
[0255] The process of Example IB was repeated except that
2-piperidine ethanol (obtained from Aldrich Chemical Co.,
Milwaukee, Wis.), of the formula 141
[0256] was used instead of distearyl amine. The 2-piperidine
ethanol was present in an amount of 2.5 moles of
2-piperidine-ethanol per every one mole of dichlorofluorescein. In
addition, 2 moles of zinc chloride were used per every one mole of
dichlorofluorescein and 1 mole of calcium oxide was used per every
one mole of dichlorofluorescein, the solvent was
N-methylpyrrolidone instead of tetramethylene sulfone, and the
reaction mixture was heated to 160.degree. C. for 24 hours. The
reaction product was then poured into water and filtered and washed
with water. It is believed that the product was of the formula
142
[0257] About 10 grams of the product obtained in Example VIIIB is
added to 10.7 grams of octadecylisocyanate (available from Aldrich
Chemical Co., Milwaukee, Wis.) at 120.degree. C., after which 1
drop of dibutyltindilaurate catalyst (available from Aldrich
Chemical Co.) is added and the reaction is stirred and heated until
disappearance of the isocyanate peak in the IR is observed. The
di-urethane rhodamine is poured into aluminum tins and is believed
to be of the formula 143
[0258] The ring-opened, or protonated, or free-base form of this
colorant is T 5 believed to be of the formula 144
[0259] wherein A is the anion corresponding to the acid used for
protonaton. The zwifterionic form of this colorant is believed to
be of the formula 145
[0260] The process of Example IB was repeated except that
N,N-dimethyl-1,4-phenylene diamine (obtained from Aldrich Chemical
Co., Milwaukee, Wis.), of the formula 146
[0261] was used instead of distearyl amine. The
N,N-dimethyl-1,4-phenylene diamine was present in an amount of 2.5
moles of N,N-dimethyl-1,4-phenyle- ne diamine per every one mole of
dichlorofluorescein. In addition, 2 moles, of zinc chloride were
used per every one mole of dichlorofluorescein and 1 mole of
calcium oxide was used per every one mole of dichlorofluorescein,
the solvent was N-methylpyrrolidone instead of tetramethylene
sulfone, and the reaction mixture was heated to 140.degree. C. for
48 hours. The reaction product was then poured into water and
filtered and washed with water. It is believed that the product was
of the formula 147
[0262] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 148
[0263] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 149
EXAMPLE XB
[0264] The process of Example IB was repeated except that
N,N-diethyl-1,4-phenylene diamine (obtained from Aldrich Chemical
Co., Milwaukee, Wis.), of the formula 150
[0265] was used instead of distearyl amine. The
N,N-diethyl-1,4-phenylene diamine was present in an amount of 2.5
moles of N,N-diethyl-1,4-phenylen- e diamine per every one mole of
dichlorofluorescein. In addition, 2 moles of zinc chloride were
used per every one mole of dichlorofluorescein and 1 mole of
calcium oxide was used per every one mole of dichlorofluorescein,
the solvent was N-methylpyrrolidone instead of tetramethylene
sulfone, and the reaction mixture was heated to 150.degree. C. for
96 hours. The reaction product was then poured into water and
filtered and washed with water. It is believed that the product was
of the formula 151
[0266] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 152
[0267] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 153
EXAMPLE XIB
[0268] The process of Example IB was repeated except that
N-benzylethanolamine (obtained from Aldrich Chemical Co.,
Milwaukee, Wis., of the formula 154
[0269] was used instead of distearyl amine. The
N-benzylethanolamine was present in an amount of 2.5 moles of
N-benzylethanolamine per every one mole of dichlorofluorescein. In
addition, 2 moles of zinc chloride were used per every one mole of
dichlorofluorescein and 1 mole of calcium oxide was used per every
one mole of dichlorofluorescein, the solvent was dimethyl formamide
instead of tetramethylene sulfone, and the reaction mixture was
heated to 150.degree. C. for 48 hours.
EXAMPLE XIC
[0270] The process of Example IC was repeated using the product
obtained in Example XIB except that the product was poured into
methanol and sufficient EDTA was added to remove all of the
Zn.sup.2+ and Ca.sub.2+ ions. It is believed that the purified
product was of the formula 155
EXAMPLE XIC-1
[0271] About 10 grams of the product obtained in Example XIC is
added to 9.9 grams of octadecylisocyanate (available from Aldrich
Chemical Co., Milwaukee, Wis.) at 120.degree. C., after which 1
drop of dibutyltindilaurate catalyst (available from Aldrich
Chemical Co.) is added and the reaction is stirred and heated until
disappearance of the isocyanate peak in the IR is observed. The
diurethane rhodaminee is poured into aluminum tins and is believed
to be of the formula 156
[0272] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 157
[0273] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 158
EXAMPLE XIIB
[0274] The process of Example IB was repeated except that
N-benzylethanolamine (obtained from Aldrich Chemical Co.,
Milwaukee, Wis.), of the formula 159
[0275] was used instead of distearyl amine. The
N-benzylethanolamine was present in an amount of 10 moles of
N-benzylethanolamine per every one mole of dichlorofluorescein. In
addition, 2 moles of zinc chloride were used per every one mole of
dichlorofluorescein and 1 mole of calcium oxide was used per every
one mole of dichlorofluorescein, the solvent was the excess
N-benzylethanolamine instead of tetramethylene sulfone, and the
reaction mixture was refluxed in an oil bath for 48 hours, followed
by distilling off the excess amine.
EXAMPLE XIIC
[0276] The process of Example IC was repeated using the product
obtained in Example XIIB except that the product was poured into
methanol and sufficient EDTA was added to remove all of the
Zn.sup.2+ and Ca.sup.2+ ions. It is believed that the purified
product was of the formula 160
EXAMPLE XIIC-1
[0277] In a glass reaction flask is combined 10 grams of the
product obtained in Example XIIC, 29.8 grams of UNICID.RTM. 700 (a
material containing carboxylic acid of the formula RCOOH wherein R
is a linear alkyl group having an average of about 50 carbon atoms,
also containing other unfunctionalized wax materials in an amount
of up to about 25 percent by weight; available from Baker
Petrolite, Sugarland, Tex.), 152 grams of xylene (available from
Tarr, Inc., Portland, Oreg.), and 0.6 grams of para-toluenesulfonic
acid (available from Capital Resin Corp., Columbus, Ohio). The
materials are mixed and heated to a reflux temperature of about
143.degree. C. After about 72 hours, the reaction is complete. The
reaction mixture is then cooled to 40.degree. C. and filtered. The
filter cake is reslurried and filtered two more times in methanol
to remove residual xylene. The filter cake is then dried in air at
ambient temperature. It is believed that this filter cake will
contain a colorant of the formula 161
[0278] wherein n has an average value of about 50. The ring-opened,
or protonated, or free-base form of this colorant is believed to be
of the formula 162
[0279] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 163
EXAMPLE XIIIB
[0280] The process of Example IB was repeated except that
2-(ethylamino)ethanol (obtained from Aldrich Chemical Co.,
Milwaukee, Wis.), of the formula 164
[0281] was used instead of distearyl amine. The
2-(ethylamino)ethanol was present in an amount of, 20 moles of
2-(ethylamino)ethanol per every one mole of dichlorofluorescein. In
addition, 2 moles of zinc chloride were used per every one mole of
dichlorofluorescein and 1 mole of calcium oxide was used per every
one mole of dichlorofluorescein, the solvent was the excess
2-(ethylamino)ethanol instead of tetramethylene sulfone, and the
reaction mixture was refluxed in an oil bath for 24 hours, followed
by distilling off the excess amine.
EXAMPLE XIIIC
[0282] The process of Example IC was repeated using the product
obtained in Example XIIIB except that the product was poured into
methanol and sufficient EDTA was added to remove all of the
Zn.sup.2+ and Ca.sup.2+ ions. It is believed that the purified
product was of the formula 165
EXAMPLE XIIIC-1
[0283] About 10 grams of the product obtained in Example XIIIC is
added to 12.5 grams of octadecylisocyanate (available from Aldrich
Chemical Co., Milwaukee, Wis.) at 120.degree. C., after which 1
drop of dibutyltindilaurate catalyst (available from Aldrich
Chemical Co.) is added and the reaction is stirred and heated until
disappearance of the isocyanate peak in the IR is observed. The
diurethane rhodamine is poured into aluminum tins and is believed
to be of the formula 166
[0284] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 167
[0285] wherein A.sup.- is the anion corresponding to the acid used
for protonaton. The zwitterionic form of this colorant is believed
to be of the formula 168
EXAMPLE XIVB
[0286] The process of Example IB was repeated except that
2-aminoanthracene (obtained from Aldrich Chemical Co., Milwaukee,
Wis.), of the formula 169
[0287] was used instead of distearyl amine. The 2-aminoanthracene
was, present in an amount of 2.05 moles of 2-aminoanthracene per
every one mole of dichlorofluorescein. It is believed that the
product was of the formula 170
[0288] The ring-opened, or protonated, or free-base form of this
colorant is believed to be of the formula 171
[0289] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic form of this colorant is believed to
be of the formula 172
EXAMPLE XVB
[0290] The process of Example OB was repeated except that a mixture
of stearyl amine (ARMEEN 0.18D; obtained from Akzo-Nobel, McCook,
Ill.) and distearyl amine was used instead of pure distearyl amine.
The stearyl amine was present in an amount of 1.02 moles of stearyl
amine per every, one mole of dichlorofluorescein, and the distearyl
amine was present in an amount of 1.02 moles of distearyl amine per
every one mole of dichlorofluorescein.
EXAMPLE XVC
[0291] The process of Example IC was, repeated using the product
obtained in Example XVB. It is believed that the: purified product
was a mixture of compounds of the formulae 173
[0292] The ring-opened, or protonated, or free-base forms of these
colorants are believed to be of the formulae, respectively, 174
[0293] wherein A is the anion corresponding to the acid used for
protonaton. The zwitterionic forms of these colorants are believed
to be of the formulae, respectively, 175
EXAMPLE XVD
[0294] The process of Example ID was repeated using the product
obtained in Example XVC.
EXAMPLE XVI
[0295] The processes of Examples IA through IC were repeated.
Thereafter, to the solution of the ring-closed purified
tetrastearyl colorant in MIBK was added a naphthalene disulfonate
adduct of the formula 176
[0296] (dinonylnaphthalene disulfonic acid, 50 wt. % in isobutanol,
NACURE.RTM. 155, obtained from King. Industries, Norwalk, Conn.) in
a stoichiometric amount of 2 moles of naphthalene sulfonate adduct
per every one mole of tetrastearyl colorant. The solution was
stirred until a magenta color developed fully. Thereafter, the
solution was transferred to a 2 liter round bottom flask equipped
with distillation setup, and the MIBK was distilled off. The
product, a slightly viscous wax when warm, was transferred to a jar
and allowed to harden. At room temperature, the product was a deep
magenta/red colored somewhat hard wax, believed to be of the
formula 177
EXAMPLE XVII
Preparation of Calcium Tetrastearyl Colorant
[0297] The process of Example I was repeated except that 80.3 grams
of the ring-closed purified tetrastearyl chromogen, 400 grams of
toluene, and 3.5 grams of CaCl.sub.2 were employed. The product, a
slightly viscous wax when warm, was transferred to a jar and
allowed to harden. At room temperature, the product was a deep
magenta/red colored somewhat hard wax.
EXAMPLE XVIII
Preparation of Bismuth Tetrastearyl Colorant
[0298] The process of Example I was repeated except that 100.2
grams of the ring-closed purified tetrastearyl chromogen, 600 grams
of toluene, and 8.2 grams of BiCl.sub.3 were employed. The product,
a slightly viscous wax when warm, was transferred to a jar and
allowed to harden. At room temperature, the product was a deep
magenta/red colored somewhat hard wax.
EXAMPLE XIX
Preparation of Tin Tetrastearyl Colorant
[0299] The process of Example I was repeated except that 100 grams
of the ring-closed purified tetrastearyl chromogen, 1,000 grams of
MIBK, and 8.8 grams of SnCl.sub.2 in a 2 liter. 3-necked
roundbottom flask were employed. The product, a slightly viscous
wax when warm, was transferred to a jar and allowed to harden. At
room temperature, the product was a deep magenta/red colored
somewhat hard wax.
EXAMPLE XX
Preparation of Iron Tetrastearyl Colorant
[0300] The process of Example I was repeated except that 32.4 grams
of the ring-closed purified tetrostearyl chromogen, about 400 grams
of MIBK, and. 1.6 grams of FeCl.sub.2 were employed. The product, a
slightly viscous wax when warm, was transferred to a jar and
allowed to harden. At room temperature, the product was a deep
magenta/red colored somewhat hard wax.
EXAMPLE XXI
Preparation of Copper Tetrastearyl Colorant
[0301] The process of Example I was repeated except that 35 grams
of the ring-closed purified tetrastearyl chromogen, about 400 grams
of MIBK, and 1.83 grams of CuCl.sub.2 were employed. The product, a
slightly viscous wax when warm, was transferred to a jar and
allowed to harden. At room temperature, the product was a deep
magenta/red colored somewhat hard wax.
EXAMPLE XXII
Preparation of Aluminum Tetrastearyl Colorant
[0302] The process of Example I was repeated except that 32.7 grams
of the ring-closed purified tetrastearyl chromogen, about 400 grams
of MIBK, and 1.13 grams of AlCl.sub.3 were employed. The product, a
slightly viscous wax when warm, was transferred to a jar and
allowed to harden. At room temperature the product was a deep
magenta/red colored somewhat hard wax.
EXAMPLE XXIII
Preparation of Nickel Tetrastearyl Colorant
[0303] The process of Example I was repeated except that 5.5 grams
of the ring-closed purified tetrastearyl chromogen, about 100 grams
of MIBK, and 0.53 grams of nickel II acetate
(Ni(CH.sub.3COO).sub.2) were employed. The product, a slightly
viscous wax when warm, was transferred to a jar and allowed to
harden. At room temperature, the product was a deep magenta/red
colored somewhat hard wax.
EXAMPLE XXIV
Preparation of Phosphotungsticmolybdic "Laked" Tetrastearyl
Colorant
[0304] The process of Example I was repeated except that 34.1 grams
of the ring-closed purified tetrastearyl chromogen, about 400 grams
of MIBK, 13.1 grams of phosphotungstic-acid, and 5.6 grams of
phosphomolybdic acid were employed. The product, a slightly viscous
wax when warm, was transferred to a jar and allowed to harden. At
room temperature, the product was a deep magenta/red colored
somewhat hard wax.
EXAMPLE XXV
Preparation of Titanium Tetrastearyl Colorant
[0305] The process of Example I was repeated except that 24.3 grams
of the ring-closed purified tetrastearyl chromogen, about 250 grams
of toluene, and 0.9 grams of titanium IV chloride were employed.
The product, a slightly viscous wax when warm, was transferred to a
jar and allowed to harden. At room temperature, the product was a
deep magenta/red colored somewhat hard wax.
EXAMPLE XXVI
Preparation of Chromium Tetrastearyl Colorant
[0306] The process of Example I was repeated except that 25.2grams
of the ring-closed purified tetrastearyl chromogen, about 250 grams
of MIBK, and 1.04 grams of chromium III chloride were employed. The
product, a slightly viscous wax when warm, was transferred to a jar
and allowed to harden. At room temperature, the product was a deep
magenta/red colored somewhat hard wax.
[0307] The processes of Examples XVII through XXVI are repeated but
substituting the chromogens prepared in Examples II through XVI for
the chromogen prepared in Example I. It is believed that similar
results will be observed.
Ink Preparation and Testing
EXAMPLE XXVII
Preparation of Secondary Colorant
PART I
[0308] A secondary magenta colorant was prepared as follows.
[0309] In a glass reaction flask were combined 73 grams of sublimed
quinizarin (obtained from Aceto Corp., Lake Success, N.Y.), 49
grams of leucoquinizarin (obtained from Aceto Corp.), 66 grams of
4-aminobenzene-ethanol (obtained from Aceto Corp.), 31 grams of
boric acid (obtained from Aldrich Chemical Co., Milwaukee, Wis.),
and 780 grams of methanol (obtained from JT Baker, Phillipsburg,
N.J.). The materials were mixed and heated until the solvent
refluxed at about 66.degree. C.
[0310] After about 16 hours of reflux the reaction was complete,
having generated an alcohol-substituted colorant of the formula
178
[0311] The reaction mixture was cooled and filtered. The product
filter cake was dried in air at ambient temperature.
[0312] The spectral strength of the alcohol-substituted colorant
was determined using a spectrophotographic procedure based on the
measurement of the colorant in solution by dissolving the colorant
in toluene and measuring the absorbance using a Perkin Elmer Lambda
2S UV/VIS spectrophotometer. The spectral strength of the
alcohol-substituted colorant was measured as about 21,000 mL
Absorbance Units per gram at absorption .lambda..sub.max,
indicating a purity of about 80 percent.
Part 2
[0313] In a glass reaction flask were combined 8 grams of the
alcohol-substituted colorant prepared in Part 1 of this Example, 68
grams of glacial acetic acid (obtained from JT Baker), 13 grams of
propionic acid (obtained from Aldrich Chemical Co.), and 2.3 grams
of acetic anhydride (obtained from Aldrich Chemical Co.). The
materials were mixed and heated to a reflux temperature of about
121.degree. C. After about 4 hours of reflux, the reaction was
complete and the reaction mixture contained an ethyl
acetate-substituted colorant of the formula 179
Part 3
[0314] About 91 grams of the reaction mixture containing the ethyl
acetate-substituted colorant from Part 2 of this Example was
charged into a glass reaction flask. The mixture was cooled to a
minimum of 30.degree. C. While mixing, about 9 grams of bromine
(obtained from Aldrich Chemical Co.) was added to the mixture at a
rate such that the temperature remained below about 40.degree. C.
The mixture was then heated to about 40.degree. C. After about 24
hours of mixing the reaction was complete.
[0315] The reaction mixture was then quenched into 234 grams of
deionized water and allowed to cool to room temperature. The
reaction mixture was then filtered. The filter cake was reslurried
and filtered twice in deionized water to remove most of the
residual acetic acid. The filter cake was then dried in a
60.degree. C. oven. This filter cake contained a mixture of
brominated ethyl acetate-substituted colorants of the formulae
180
[0316] The spectral strength of the brominated ethyl
acetate-substituted colorant was determined using a
spectrophotographic procedure based on the measurement of the
colorant in solution by dissolving the colorant in toluene and
measuring the absorbance using a Perkin Elmer Lambda 2S UV/VIS
spectrophotometer. The spectral strength of the brominated ethyl
acetate-substituted colorant was measured as about 15,000 mL
Absorbance Units per gram at absorption .lambda..sub.max. This
spectral strength indicated a purity of about 60 percent.
Part 4
[0317] In a glass reaction flask were combined 18 grams of the
mixture of the brominated ethyl acetate-substituted colorant and
its salt prepared in Part 3 of this Example, 72 grams of
N-methyl-2-pyrrolidone (obtained from Aldrich Chemical Co.), 4
grams of sodium hydroxide (obtained from Aldrich Chemical Co.), and
4 grams of deionized water. The materials were mixed and heated to
about 60.degree. C. After about 3 hours the reaction was
complete.
[0318] The reaction mixture was then quenched into 234 grams of
deionized water and allowed to cool to room temperature. Glacial
acetic acid was added until the solution reached a pHF of between 6
and 7. The reaction mixture was then filtered. The filter cake was
reslurried and filtered twice in deionized water to remove most of
the residual N-methyl-2-pyrrolidone. The filter cake was then dried
in a 60.degree. C. oven. This filter cake contained a brominated
alcohol-substituted colorant of the formula 181
[0319] The spectral strength of the brominated alcohol-substituted
colorant was determined using a spectrophotographic procedure based
on the measurement of the colorant in solution by dissolving the
colorant in an equal mixture, of toluene and tetrahydrofuran and
measuring the absorbance using a Perkin Elmer Lambda 2S UV/VIS
spectrophotometer. The spectral strength of the brominated
alcohol-substituted colorant was measured as about 16,000 mL
Absorbance Units per gram at absorption .lambda..sub.max. This
spectral strength indicated a purity of about 60 percent.
Part 5
[0320] In a glass reaction flask-were combined 16 grams of the
brominated alcohol-substituted colorant prepared in Part 4 of this,
Example, 31 grams of UNICID.RTM. 700 (a material containing
carboxylic acid of the formula R.sub.2COOH wherein R.sub.2 is a
linear alkyl group having an average of about 50 carbon atoms, also
containing other unfunctionalized wax materials in an amount of up
to about 25 percent by weight; obtained from Baker Petrolite,
Sugarland, Tex.), 152 grams of xylene (obtained from Tarr, Inc.,
Portland, Oreg.), and 0.6 grams of para-toluenesulfonic acid
(obtained from Capital Resin Corp., Columbus, Ohio). The materials
were mixed and heated to a reflux temperature of about 143.degree.
C. After about 7 hours, the reaction was complete.
[0321] The reaction mixture was then cooled to 40.degree. C. and
filtered. The filter cake was reslurried and filtered two more
times in methanol to remove residual xylene. The filter cake was
then dried in air at ambient temperature. This filter cake
contained a colorant of the formula 182
[0322] wherein R.sub.2 is a linear alkyl group having an average of
about 50 carbon atoms.
[0323] The spectral strength of the colorant was determined using a
spectrophotographic procedure based on the measurement of the
colorant in solution by dissolving the colorant in an equal mixture
of toluene and tetrahydrofuran and measuring the absorbance using a
Perkin Elmer Lambda 2S UV/VIS spectrophotometer. The spectral
strength of the colorant was measured as about 5,000 mL Absorbance
Units per gram at absorption .lambda..sub.max. This spectral
strength indicated a purity of about 40 percent.
[0324] Ink compositions containing the colorants of Examples IF and
XVII through XXVI, and, for comparison purposes, commercially
available n-butyl Solvent Red 172 (n-BuSR172; UNIGRAPH Red 1900,
obtained from United Color Manufacturing, Inc., Newtown, Pa.),
commercially available Solvent Red 49 (SR49; a rhodamine colorant
obtained from BASF, Germany), and a colorant comprising the
chromrogen of Example ID (said chromogen not being part of a metal
compound according to the present invention) were prepared as
follows.
[0325] Ink A--1: In a stainless steel beaker were combined 153.22
grams of polyethylene wax (PE655, obtained from Baker Petrolite,
Tulsa, Okla., of the formula CH.sub.3(CH.sub.2).sub.50OH.sub.3),
39.72 grams of stearyl stearamide wax (KEMAMIDE.RTM. S-180,
obtained from Crompton Corporation, Greenwich, Conn.), 62.99 grams
of a tetra-amide resin obtained from the reaction of one equivalent
of dimer diacid with two equivalents of ethylene diamine and
UNICID.RTM. 700 (a carboxylic acid derivative of a long chain
alcohol obtained from Baker Petrolite, Tulsa, Okla.), prepared as
described in Example 1 of U.S. Pat. No. 6,174,937, the disclosure
of which is, totally incorporated herein by reference, 39.76 grams
of a urethane resin obtained from the reaction of two equivalents
of ABITOL.RTM.. E hydroabietyl alcohol (obtained from Hercules
Inc., Wilmington, Del.) and one equivalent of isophorone
diisocyanate, prepared as described in Example 1 of U.S. Pat. No.
5,782,966, the disclosure of which is totally incorporated herein
by reference, 27.02 grams of a urethane resin that was the adduct
of three equivalents of stearyl isocyanate and a glycerol-based
alcohol, prepared as described in Example 4 of U.S. Pat. No.
6,309,453, the disclosure of which is totally incorporated herein
by reference, and, 0.65 gram of NAUGUARD.RTM. 445 antioxidant
(obtained from Uniroyal Chemical Co., Middlebury, Conn.). The
materials were melted together at a temperature of 135.degree. C.
in an oven, and then blended by stirring in a
temperature-controlled mantle at 135.degree. C. for 0.2 hour. To
this mixture was then added 12.31 grams of the colorant prepared as
described in Example IF and 6.70 grams of a secondary magenta
colorant (prepared as described in Parts 1 through 5 of this
Example). After stirring for 2 additional hours, the magenta ink
thus formed was filtered through a heated MOTT.RTM. apparatus
(obtained from Mott Metallurgical) using Whatman #3 filter paper
under a pressure of 15 pounds per square inch. The filtered phase
change ink was poured into molds and allowed to solidify to form
ink sticks. The magenta phase change ink thus prepared exhibited a
viscosity of 10.80 centipoise as measured by a
Rheometrics-cone-plate viscometer at about 140.degree. C., and a
spectral strength of 1,279 milliliters absorbance per gram at 550
nanometers, determined by using a spectrophotographic procedure
based on the measurement of the colorant in solution by dissolving
the solid, ink in n-butanol and measuring the absorbance using a
Perkin Elmer Lambda 2S UV/VIS spectrophotometer.
[0326] Ink A-2: Ink A-2 was prepared in a similar manner to that
used to prepare Ink A-1 but using a different formulation for the
ink composition as described in the table below. The properties of
Ink A-2 were, obtained using the same methods as those used for Ink
A-1. The melting points of 84.degree. C. and 105.degree. C. were
measured by differential scanning calorimetry using a DuPont 2100
calorimeter. Ink A-2 had a glass transition temperature (Tg) of
19.degree. C. As shown in the table, the predominant difference
between Ink A-1 and Ink A-2 is the relative concentration of the
colorant in the ink.
[0327] Ink A-3: Ink A-3 was prepared in a similar manner to that
used to prepare Ink A-1 but using a different formulation for the
ink composition as described in the table below. The properties of
Ink A-3 were obtained using the same methods as those used for Ink
A-1 and Ink A-2. As shown in the table, the predominant difference
between Ink A-3 and Inks A-1 and A-2 is the relative higher
concentration of the colorant in the ink. As a result, the spectral
strength of Ink A-3 is also higher than those of Inks A-1 and A-2,
suggesting very good solubility of the colorant described in
Example IF in the ink carrier.
[0328] Inks B-1 and B-2: Inks B-1 and B-2 were prepared in a
similar manner to that used to prepare Ink A-1 but using the
colorant of Example XVII instead of the colorant of Example IF.
Their formulations are described in the table below. The properties
of Ink B-1 and Ink B-2 were obtained using the same methods as
those used for Inks A-1 and A-2. As shown in the table, the
predominant difference between Ink B-1 and Ink B-2 is the relative
concentration of the colorant in the ink.
[0329] Ink C: Ink C was prepared by the process described for Ink
A-1 except that the colorant from Example XVIII was used in place
of the colorant from Example IF. The properties of Ink C were
obtained using the same methods as those used for Ink A-1.
[0330] Inks D-1 and D-2: Inks D-1 and D-2 were prepared by the
process described for Ink A-1 except that the colorant from Example
XIX was used in place of the colorant from Example IF. The
properties of Ink D-1 and Ink D-2 were obtained using the same
methods as those used for Ink A-1.
[0331] Ink E: Ink E was prepared by the process described for Ink
A-1 except that the colorant from Example XX was used in place of
the dye from Example IF. The properties of Ink E were obtained
using the same methods as those used for Ink A-1'.
[0332] Ink F: Ink F was prepared by the process described for Ink
A-1 except that the colorant from Example XXI was used in place of
the dye from Example IF. The properties of Ink F were obtained
using the same methods as those used for Ink A-1.
[0333] Ink G: Ink G was prepared by the process described for Ink
A-1 except that the colorant from Example XXII was used in place of
the dye from Example IF. The properties of Ink G were obtained
using the same methods as those used for Ink A-1.
[0334] Ink H: Ink H was prepared by the process described for Ink
A-1 except that the colorant from Example XXIII was used in place
of the dye from Example IF. The properties of Ink H were obtained
using the same methods as those used for Ink A-1.
[0335] Ink 1: Ink I was prepared by the process described for Ink
A-1 except that the colorant from Example XXIV was used in place of
the dye from Example IF. The properties of Ink I were obtained
using the same methods as those used for Ink A-1.
[0336] Ink J: Ink J was prepared by the process described for Ink
A-1 except that the colorant from Example XXV was used in place of
the dye from Example IF. The properties of Ink J were obtained
using the same methods as those used for Ink A-1.
[0337] Ink K: Ink K was prepared by the process described for Ink
A-1 except that the colorant from Example XXVI was used in place of
the dye from Example IF. The properties of Ink K were obtained
using the same methods as those used for Ink A-1.
[0338] Comparative Ink II: An ink was prepared by the process
described for Ink A-1 except that instead of the colorant from
Example IF, the commercially available SR 49 and dodecyl benzene
sulfuric acid (DDBSA, Bio-soft S-100, obtained from Stepan Company,
Elwood, Ill.) were used. The properties of Comparative Ink 1 were
obtained using the same methods as those used for Ink A-1.
[0339] Comparative Ink 2: An ink was prepared by the process
described for Ink A-1 except that instead of the colorant from
Example IF, a colorant comprising the chromogen of Example ID (said
chromogen not being part of a metal compound according to the,
present invention) and dodecyl benzene sulfuric acid (DDBSA,
Bio-soft S-100, obtained from Stepan Company, Elwood, Ill.) were
used. The properties of Comparative Ink 2 were obtained using the,
same methods as those used for Ink A-1.
[0340] Comparative Ink 3: An ink was prepared by the process
described for Ink A-1 including the colorant preparation from
Example IF, except that instead of using the chromogen from Example
ID, commercially available Solvent Red 49 was used as the chromogen
to prepare the resulting zinc colorant. The properties of
Comparative Ink 3 were obtained using the same methods as those
used for Ink A-1. Since it was found that the spectral strength of
the unfiltered ink was higher than that of the filtered ink, the
actual relative colorant amount of the colorant is in fact less
than that listed in the following formulation table. Therefore, the
colorant described in Comparative Example 3 has much lower
solubility than that of the colorant described in Example A; it is
believed that the better solubility of the colorant in Inks A-1
through A-3 can be attributed to the long alkyl groups on the
chromogen compared to those of commercially available Solvent Red
49.
[0341] The following tables summarize the compositions of the
various inks and the amounts of ingredients (weight percentage
numbers given in the tables) therein:
1 A-1 A-2 A-3 B-1 B-2 C Example IF colorant 3.56 5.04 6.28 -- -- --
Example XVII colorant -- -- -- 3.98 3.55 -- Example XVIII colorant
-- -- -- -- -- 3.55 POLYWAX 44.36 44.15 43.41 44.06 45.38 45.38
Tetra-amide 19.10 17.81 17.56 18.91 18.47 18.47 S-180 11.51 13.76
13.42 12.55 11.78 11.78 Urethane Resin 1* 11.51 9.75 9.84 10.53
11.13 11.13 Urethane Resin 2** 7.82 7.45 7.41 7.86 7.56 7.56
2.degree. magenta colorant 1.94 1.83 1.87 1.92 1.94 1.94 NAUGUARD
445 0.19 0.19 0.20 0.19 0.19 0.19 Total 100.0 100.0 100.0 100.0
100.0 100.0 D-1 D-2 E F G H Example XIX colorant 3.51 3.55 -- -- --
-- Example XX colorant -- -- 3.55 -- -- -- Example XXI colorant --
-- -- 3.55 -- -- Example XXII colorant -- -- -- -- 3.54 -- Example
XXIII colorant -- -- -- -- -- 3.55 POLYWAX 43.30 45.38 45.89 45.58
46.89 45.38 Tetra-amide 19.96 18.47 18.15 18.34 17.54 18.47 S-180
13.02 11.78 11.91 11.83 12.17 11.78 Urethane Resin 1* 10.30 11.13
10.94 11.05 10.57 11.13 Urethane Resin 2** 7.81 7.56 7.43 7.51 7.18
7.56 2.degree. magenta colorant 1.91 1.94 1.94 1.94 1.93 1.94
NAUGUARD 445 0.20 0.19 0.19 0.20 0.18 0.19 Total 100.0 100.0 100.0
100.0 100.0 100.0 I J K 1 2 3 Example XXIV colorant 3.55 -- -- --
-- -- Example XXV colorant -- 3.55 -- -- -- -- Example XXVI
colorant -- -- 3.54 -- -- -- SR 49 colorant -- -- -- 0.46 -- --
Example ID colorant -- -- -- -- 2.61 -- Zn-SR 49 colorant -- -- --
-- -- 0.75 POLYWAX 45.38 45.38 46.26 45.67 40.16 45.58 Tetra-amide
18.47 18.47 17.93 19.04 17.82 21.35 S-180 11.78 11.78 12.01 13.17
19.38 13.20 Urethane Resin 1* 11.13 11.13 10.80 10.68 12.47 9.00
Urethane Resin 2** 7.56 7.56 7.34 8.09 4.26 8.00 2.degree. magenta
colorant 1.94 1.94 1.94 1.91 2.03 1.92 DDABS -- -- -- 0.80 1.10 --
NAUGUARD 445 0.19 0.19 0.18 0.20 0.18 0.20 Total 100.0 100.0 100.0
100.0 100.0 100.0 *ABITOL E based urethane resin **Glycerol alcohol
based urethane resin
[0342] The magenta inks thus prepared were successfully printed on
HAMMERMILL LASERPRINT.RTM. paper (obtained from International
Paper, Memphis, Tenn.) with a XEROX.RTM. PHASER 860 printer, which
uses a printing process wherein the ink is first jetted in an
imagewise pattern onto an intermediate transfer member followed by
transfer of the imagewise pattern from the intermediate transfer
member to a final recording substrate. The solid field images with
a resolution of 450 dpi.times.600 dpi were generated from the
printer, and their color space data were obtained on an ACS.RTM.
Spectro Sensor.RTM. II Colorimeter (obtained from Applied Color
Systems Inc.) in accordance with the measuring methods stipulated
in ASTM IE805 (Standard Practice of Instrumental Methods of Color
or Color Difference Measurements of Materials) using the
appropriate calibration standards supplied by the instrument
manufacturer. For purposes of verifying and quantifying the overall
calorimetric performance of the inks, measurement data were
reduced, via tristimulus integration, following ASTM E308 (Standard
Method for Computing the Colors of Objects using the CIE System) in
order to calculate the 1976 CIE L* (Lightness), Q*
(redness-greenness), and b* (yellowness-blueness) CIELAB values for
each phase change ink sample.
[0343] Another type of printed sample was generated on HAMMERMILL
LASERPRINT.RTM. paper using a K Printing Proofer (manufactured by
RK Print Coat Instrument Ltd., Litlington, Royston, Heris, SG8 0OZ,
U.K.). In this method, the tested inks were melted onto a printing
plate set at 150.degree. C. temperature. A roller bar fitted with
the paper was then rolled over the plate containing the melted ink
on its surface. The ink on the paper was cooled, resulting in three
separated images of rectangular blocks. The most intensely colored
block contained the most ink deposited on the paper, and was
therefore used to obtain the color value measurements.
[0344] Printed samples of the magenta inks both from the XEROX
PHASER.RTM. printer and from the K-Proofer were evaluated for color
characteristics, which are reported in the tables below. As is
apparent, the CIE L*a*b* values for inks made with colorants
according to the present invention represent a good magenta shade
printed ink. The tables below list the viscosity (.zeta.
centipoise) of the inks at 140.degree. C., the spectral strength in
n-butanol (SS, mL*g.sup.-1cm.sup.-1) and absorbance maximum (Lambda
max, X.sub.max, nm) of the inks, the glass transition point (Tg,
.degree. C.), the melting points (mp, .degree. C., as measured by
DSC), and the CIE L*a*b color coordinates of the prints made either
using the XEROX PHASER.RTM. 860 printer or the K-proofer:
2 A-1 A-2 A-3 B-1 B-2 C .eta. 10.80 10.62 10.79 10.62 10.76 10.65
SS 1279 1619 2095 1187 1102 1151 .lambda..sub.max 550 550 550 549
552 558 T.sub.g -- 18.4 17.7 -- -- -- mp -- 84.3, 83.9, -- -- --
104.6 104.8 L* (860) 55.0 48.4 49.1 71.46 -- 63.07 a* (860) 75.1
80.2 83.7 48.88 -- 60.10 b* (860) -39.1 -34.6 -40.9 -31.03 --
-33.04 L* (K-P) 60.9 -- 52.06 -- 68.49 64.95 a* (K-P) 59.6 -- 74.14
-- 44.62 48.47 b* (K-P) -31.3 -- -40.93 -- -22.36 -27.18 D-1 D-2 E
F G H .eta. 10.75 10.44 10.67 10.67 10.58 10.65 SS 1203 1262 1418
1255 1291 810 .lambda..sub.max 558 556 558 549 556 548 T.sub.g --
-- -- -- -- -- mp -- -- -- -- -- -- L* (860) 61.14 -- -- -- -- --
a* (860) 64.00 -- -- -- -- -- b* (860) -34.56 -- -- -- -- -- L*
(K-P) -- 64.11 55.76 59.42 56.09 63.56 a* (K-P) -- 50.15 51.16
51.41 57.85 45.14 b* (K-P) -- -27.29 -30.26 -32.17 -31.78 -28.69 I
J K 1 2 3 .eta. 10.77 10.60 10.75 10.77 10.54 10.36 SS 887 1082
1115 1279 1328 909 .lambda..sub.max 553 554 552 555 552 543 T.sub.g
-- -- -- 21.2 -- -- mp -- -- -- 82.7, -- -- 103.6 L* (860) -- -- --
54.0 50.1 -- a* (860) -- -- -- 76.8 69.1 -- b* (860) -- -- -- -41.3
-37.2 -- L* (K-P) 56.64 67.58 63.14 60.9 56.3 -- a* (K-P) 57.97
35.64 43.36 68.0 59.3 -- b* (K-P) -33.52 -21.41 -28.36 -42.7 -32.5
-- -- = not measured
[0345] The color values in the above tables indicate that the
colorants' of Inks A through K can be used in hot melt inks with
good magenta color as evidenced by the a* and, b* values of the
prints. As evidenced in the tables, Ink A can exhibit magenta color
with a chroma larger than that of Comparative Ink 1., which was
made from commercially available SR 49, which has been considered
to be a bright magenta dye. In contrast to commercial SR 49 dye,
which normally needs a relatively strong acid such as DDBSA to
develop its color in an ink base, the colorants in Inks A through K
of this invention show reasonably strong magenta color without an
acid developer. Although not being limited to any particular
theory, it is believed that the color development role in the inks
of this invention was played by the metal ion in the colorants.
Good dye solubilities of the colorants in Inks A through C and J
through K of this invention in tested ink bases are demonstrated by
the very high dye loads and corresponding very high spectral
strength of the inks.
EXAMPLE XXVIII
Thermal Stability-Testing
[0346] Colorant degradation can lead to an undesirable color shift
or fade as d result of the colorant decomposition reaction in an
ink. This phenomenon can adversely affect the color quality or
consistency of prints from the inks if the colorant is not
thermally stable. Thermal stability of the colorants in Inks A
through K according to this invention was compared to SR 0.49 dye
in Comparative Ink I by monitoring color changes of the prints from
their cooked inks.
[0347] In one method, the inks were heated in glass jars
continuously in an oven at 140.degree. C., followed by sampling and
printing the inks on HAMMERMILL Laserprint papers using a
K-Proofer, and finally measuring the color changes of the prints of
the sampled inks as a function of time. The color changes of the
resultant prints were monitored by CIELAB values and expressed by
Delta E relative to the initial CIELAB values. The color change of
each sample was determined according to the methods described
hereinabove for obtaining CIELAB values. Color changes were
determined following ASTM D2244-89 (Standard Test Method for
Calculation of Color Differences From instrumentally Measured Color
Coordinates) (delta
E=[(L*.sub.1-L*2).sup.2+(a*.sub.1-a*2).sup.2+(b*.sub.1-b*.sub.2).sup.2].s-
up.1/2). The results for these Inks are shown in the tables below.
As the data in the tables indicate, Inks A-1 through C-1 and Ink K
containing the colorants according to the present invention
demonstrated better color stability than Comparative Ink 1
containing commercial SR 49.
3 Ink 0 1 3 5 10 18 A-1 0.0 1.8 4.0 6.1 14.6 -- B-2 0.0 0.7 1.4 2.5
4.4 -- C 0.0 0.5 2.0 2.6 -- 11.6 D-2 0.0 0.9 2.9 5.5 9.1 -- E 0.0
3.1 13.0 19.5 25.6 -- F 0.0 6.3 14.0 21.5 39.4 -- G 0.0 3.2 6.9 8.3
16.0 -- H 0.0 2.7 6.2 11.4 23.8 -- I 0.0 1.6 3.9 7.6 16.6 -- J 0.0
5.2 10.7 15.6 26.6 -- K 0.0 1.7 3.7 8.0 11.6 -- 1 0.0 2.2 3.7 6.4
10.7 -- .DELTA.E values for various inks heated at 140.degree. C.
for the indicated number of days -- = not measured
[0348] In another method a thermal stability test was performed by
continuously heating the test inks in a printer at 136.degree. C.
and measuring the color change of the prints as a function of time
(referred to as the "No-standby" test). The color changes of the
resultant prints were monitored by CIELAB values and expressed by
Delta E relative to the initial CIELAB values. The color change of
each sample was, determined according to the methods described
hereinabove for obtaining CIELAB values. Color changes were
determined following ASTM D2244-89 (Standard Test Method for
Calculation of Color Differences From instrumentally Measured Color
Coordinates) (delta E=[(L*.sub.1-L*.sub.2).sup.2+(a*.sub.1-
-a*.sub.2).sup.2+(b*.sub.1-b*.sub.2).sup.2].sup.1/2). The results
for tested Inks were as follows:
4 aging time (days) A-1 A-2 B-1 C D-1 1 0 0 0 0 0 0 0 0.3 0.8 0.4 1
1.8 0.6 2.2 0.5 1.6 0.5 1.4 1.7 1 3.7 1 2 0.7 1.5 3.5 3.7 6 2 2.2
1.5 3.4 5.7 7.9 8.4 3 3.8 1.7 3.2 6.3 12 11 4 4.4 2.5 4.1 -- -- 14
5 5.1 2.9 4 -- -- 16 6 6.3 3.7 5.2 -- -- 17 7 7 4 4.4 -- -- 18 8
8.6 4.7 5.1 11 34 20 9 8.1 5.4 5.9 14 38 21 10 8.4 6.2 6.6 16 40 21
11 8.5 6.7 6.7 15 40 22 12 8.6 7.4 7.5 -- -- 24 13 8.2 7.7 8.3 19
44 25 14 8.5 8.1 9 20 45 26 .DELTA.E values for various inks heated
at 140.degree. C. for the indicated number of days -- = not
measured
EXAMPLE XXIX
Qualitative Assessment of Fingerprint Performance on Magenta Ink
Print
[0349] All tested inks were subjected to a qualitative test for
fingerprint resistance at room temperature. This test proceeded in
three steps: printing of the inks, exposure of the prints to a
mixture of finger oils and hand lotion ingredients, and finally a
comparison of the various inks against a reference after a 5-day
period.
[0350] The study was performed by initially printing the inks on
A-size Hammermill Paper, including 20, 30, 40, 50, 60, 70, 80, and
90% ink coverage per sheet. Each sheet was dedicated to one ink
only. For this purpose, the ink had been printed in portrait
orientation in eight rectangular areas, measuring approximately
8".times.1.25"with, each stripe representing one type of coverage.
Three identical prints were generated per ink at a particular
resolution, and two resolutions--355.times.464 dpi, and
600.times.600 dpi--were compared for each ink. The sets of prints
included a reference ink, against which the experimental inks were
compared at the two resolutions.
[0351] After the printing had been completed, the inks were exposed
to a mixture of finger oil and hand lotion. For this purpose, a
test person applied in two subsequent steps a hand lotion to
his/her hands, and dried off excess lotion with a towel. Then, the
person gently touched the printed inks at the right side of a
particular print, starting at 90% coverage strip and proceeded in a
downward motion to the 20% coverage strip. Afterwards, the
procedure was repeated on the same print with the other hand,
starting on the left side with the 20% coverage strip, and moving
upward towards higher coverages. Without renewal of hand lotion,
this was repeated with the next print. After the second print had
been exposed to the finger oils, the person was instructed to
re-apply lotion to the hands in the described manner, and proceed
with the next two prints. When all prints had been exposed to the
finger oils, the prints were deposited into manila folders, whereby
each print was separated from the next by a blank sheet of paper.
The folder then was stored at ambient temperature for 5 days.
[0352] At the end of this time period, the prints were removed from
the manila folders and laid out in a systematic pattern on a
sufficiently large table in a sufficiently bright and evenly lit
room One test person--in some cases several test persons--then
compared visually the finger marks on the prints with those seen on
the prints of the reference ink. Observers were instructed to grade
fingerprint performance qualitatively on a scale from -3 to +3,
with -3 indicating worst behavior, and +3 indicating no finger
marks observed. In this system of grades, the value .+-.0 would
then indicate no difference of performance as compared to the print
of the reference ink.
[0353] The prints were; also aged at elevated temperatures of
45.degree. C. and 60.degree. C. in addition to aging at room
temperature. The tested ink according to the present invention was
Ink A-1 and the reference ink was Comparative Ink 1. The evaluation
scores were as follows:
5 Ink room temp. 45.degree. C. 60.degree. C. A-1 0.7 1.1 1.5 1 0 0
0
[0354] The results in the above table show that the images of the
Ink A-1 prints were less affected by hand oils than those of
Comparative Ink 1, suggesting better image stability.
EXAMPLE XXX
Diffusion Testing
[0355] Ink A-2 and Comparative Ink 1 were tested for diffusion
tendency of their colorants. A clear ink was also prepared in the
same manner as for Ink A-2 but without any colorants. This
diffusion evaluation method used printed images to test for the
ability of the colorant from a magenta ink pixel to diffuse into
neighboring colorless ink pixels that surrounded the magenta ink
pixel. The test prints were generated to contain about 20 percent
individual magenta pixels surrounded by 80 percent clear ink
pixels. The prints were analyzed at room temperature over a number
of days for overall color change detected using a color image
analyzer, and the response was measured as change in delta E
(.DELTA.E) over time and shown in the table below. The color
difference of each sample was determined according to the methods
described hereinabove for obtaining CIELAB values. Color
differences were determined following ASTM D2244-89 (Standard Test
Method for Calculation of Color Differences From instrumentally
Measured Color Coordinates) (delta E
[(L*.sub.1-L*.sub.2).sub.2+(a*.sub.1-a*.sub.2).sup.2+(b*.sub.1-b*.sub.2).-
sup.2]).sup.1/2). Both HAMMERMILL LASERPRINT.RTM. paper and
XEROX.RTM. 4024 paper were used, and the color change results in
terms of .DELTA.E over time were as follows:
6 HAMMERMILL LASERPRINT .RTM. XEROX .RTM. 4024 Comp. Comp. Aging
Time (days) Ink A-2 Ink 1 Ink A-2 Ink 1 0 0 0 0 0 0.75 0.1 0.8 0.5
1.2 1.75 0.5 1.4 0.8 1.8 3 0.3 1.5 0.7 2.0 5.1 0.5 1.7 0.9 2.5 6.95
0.6 2.1 0.8 3.0 22 1.4 3.4 1.3 4.3
[0356] As the data indicate, the colorants examined had all
diffused into surrounding clear base pixels, as evident by the
color change and measured as a change in delta E (.DELTA.E). The
colorant in Ink A-2, however, underwent diffusion to a
significantly lesser degree than the comparative colorant SR49 in
Comparative Ink 1. These results indicate that the colorant in Ink
A-2 is superior to the comparative commercial colorant SR49 in its
ability for minimal dye diffusion. While not being limited to any
particular theory, it is believed that the long alkyl groups of the
colorant prepared in Example IF of this invention hindered the
mobility of the colorant molecule.
[0357] Other embodiments and modifications of the present invention
may occur to those of ordinary skill in the art subsequent to a
review of the information presented herein; these embodiments and
modifications, as well as equivalents thereof, are also included
within the scope of this invention.
[0358] The recited order of processing elements or sequences, or
the use of numbers, letters, or other designations therefor, is not
intended to limit a claimed process to any order except as
specified in the claim itself.
* * * * *