U.S. patent application number 10/265547 was filed with the patent office on 2004-04-08 for yellow dyes and ink compositions.
Invention is credited to Feeman, James Frederic, Holloway, Ann P..
Application Number | 20040068102 10/265547 |
Document ID | / |
Family ID | 32042476 |
Filed Date | 2004-04-08 |
United States Patent
Application |
20040068102 |
Kind Code |
A1 |
Holloway, Ann P. ; et
al. |
April 8, 2004 |
Yellow dyes and ink compositions
Abstract
Provided are novel yellow azo dyes which are useful in ink
compositions, especially ink jet ink compositions. The dyes and ink
compositions of the present invention exhibit a good balance of
optical density, print reliability, water fastness and light
fastness and exhibit improved water solubility, thus rendering the
ink compositions to be especially suitable for printheads having
small nozzle openings.
Inventors: |
Holloway, Ann P.;
(Lexington, KY) ; Feeman, James Frederic;
(Wyomissing, PA) |
Correspondence
Address: |
LEXMARK INTERNATIONAL, INC.
INTELLECTUAL PROPERTY LAW DEPARTMENT
740 WEST NEW CIRCLE ROAD
BLDG. 082-1
LEXINGTON
KY
40550-0999
US
|
Family ID: |
32042476 |
Appl. No.: |
10/265547 |
Filed: |
October 7, 2002 |
Current U.S.
Class: |
534/632 |
Current CPC
Class: |
C09D 11/328 20130101;
C09B 43/16 20130101 |
Class at
Publication: |
534/632 |
International
Class: |
C09B 037/00 |
Claims
We claim:
1. A compound of Formula (I): 50wherein R.sup.1 comprises
--SO.sub.3M or --CO.sub.2M; R comprises --H, -lower alkyl, -lower
alkoxy, -halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or
--CO.sub.2M; R.sup.3 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
R.sup.4 comprises --H, -lower alkyl, or -lower alkoxy; R.sup.5
comprises a group of the formula: 51--NH-lower alkylene-SO.sub.3M;
--NH-lower alkylene-(CO.sub.2M).sub.m; --S-lower
alkylene-SO.sub.3M; or --S-lower alkylene-(CO.sub.2M).sub.m;
wherein R.sup.9 and R.sup.13 comprise, independently, --SO.sub.3M
or --CO.sub.2M; R.sup.10 and R.sup.14 comprise, independently, --H,
-lower alkyl, -lower alkoxy, -halogen, --NH--C(O)-lower alkyl,
--SO.sub.3M, or --CO.sub.2M; R.sup.11 comprises --H, -lower alkyl,
-lower alkoxy, --O-lower-alkylene-CO.sub.2M, -lower
alkylene-CO.sub.2M, --NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl,
or --CO.sub.2M; R.sup.12 comprises --H, -lower alkyl, or -lower
alkoxy; R.sup.6 comprises a group of the formula: 52--NH-lower
alkylene-SO.sub.3M; --NH-lower alkylene-(CO.sub.2M).sub.m;
--S-lower alkylene-SO.sub.2M; --S-lower alkylene-(CO.sub.2M).sub.m;
or --NH--R.sup.7, wherein R.sup.15 comprises --SO.sub.3M or
--CO.sub.2M; R.sup.16 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
R.sup.17 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.18--O)--H, R.sup.18 comprises --H, --CH.sub.3,
--CH.sub.2CH.sub.3, or --CH.sub.2OH, m is 1 or 2; M comprises --H,
-Li, -Na, -K, --N(R.sup.19).sub.4, or --HN(R.sup.19).sub.3, wherein
R.sup.19 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.20--O)--H, R.sup.20 comprises --H, --CH.sub.3,
--CH.sub.2CH.sub.3, or --CH.sub.2OH.
2. The compound of claim 1, wherein R.sup.1 comprises
--SO.sub.3M.
3. The compound of claim 1, wherein R.sup.1 comprises
--CO.sub.2M.
4. The compound of claim 1, wherein R.sub.3 and R.sub.4 comprise,
independently, hydrogen or lower alkoxy.
5. The compound of claim 1, wherein R.sub.5 comprises a group of
the formula: --NH-lower alkylene-SO.sub.3M; --NH-lower
alkylene-(CO2M).sub.m; --S-lower alkylene-SO2M; or --S-lower
alkylene-(CO.sub.2M).sub.m.
6. The compound of claim 1, wherein the compound of Formula(I) is
selected from 53
7. A compound of Formula (II): 54wherein: R.sup.3 comprises a lower
alkoxy group; R.sup.5 comprises a group of the formula:
55--NH-lower alkylene-SO.sub.3M; --NH-lower
alkylene-(CO.sub.2M).sub.m; --S-lower alkylene-SO.sub.3M; or
--S-lower alkylene-(CO.sub.2M).sub.m; wherein R.sup.9 and R.sup.13
comprise, independently, --SO.sub.3M or --CO.sub.2M; R.sup.10 and
R.sup.14 comprise, independently, --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
R.sup.11 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
R.sup.12 comprises --H, -lower alkyl, or -lower alkoxy; R.sup.6
comprises a group of the formula: 56--NH-lower alkylene-SO.sub.3M;
--NH-lower alkylene-(CO.sub.2M).sub.m; --S-lower
alkylene-SO.sub.2M; --S-lower alkylene-(CO.sub.2M).sub.m; or
--NH--R.sup.17, wherein R.sup.15 comprises --SO.sub.3M or
--CO.sub.2M; R.sup.16 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
R.sup.17 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.18--O)--H, R.sup.18 comprises --H, --CH.sub.3,
--CH.sub.2CH.sub.3, or --CH.sub.2OH, m is 1 or 2; M comprises --H,
-Li, -Na, -K, --N(R.sup.19).sub.4, or --HN(R.sup.19).sub.3, wherein
R.sup.19 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.20--O)--H, R.sup.20 comprises-H, --CH.sub.3,
--CH.sub.2CH.sub.3, or --CH.sub.2OH.
8. An ink composition comprising: (a) at least 0.1% by weight of a
compound of Formula (I): 57wherein R.sup.1 comprises --SO.sub.3M or
--CO.sub.2M; R.sup.2 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-- ower alkyl, --SO.sub.3M, or --CO.sub.2M;
R.sup.3 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
R.sup.4 comprises --H, -lower alkyl, or -lower alkoxy; R.sup.5
comprises a group of the formula: 58--NH-lower alkylene-SO.sub.3M;
--NH-lower alkylene-(CO.sub.2M).sub.m; --S-lower
alkylene-SO.sub.3M; or --S-lower alkylene-(CO.sub.2M).sub.m;
wherein R.sup.9 and R.sup.13 comprise, independently, --SO.sub.3M
or --CO.sub.2M; R.sup.10 and R.sup.14 comprise, independently, --H,
-lower alkyl, -lower alkoxy, -halogen, --NH--C(O)-lower alkyl,
--SO.sub.3M, or --CO.sub.2M; R.sup.11 comprises --H, -lower alkyl,
-lower alkoxy, --O-lower-alkylene-CO.sub.2M, -lower
alkylene-CO.sub.2M, --NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl,
or --CO.sub.2M; R.sup.12 comprises --H, -lower alkyl, or -lower
alkoxy; R.sup.6 comprises a group of the formula: 59--NH-lower
alkylene-SO.sub.3M; --NH-lower alkylene-(CO.sub.2M).sub.m;
--S-lower alkylene-SO.sub.2M; --S-lower alkylene-(CO.sub.2M).sub.m;
or --NH--R.sup.17, wherein R.sup.1 comprises --SO.sub.3M or
--CO.sub.2M; R.sup.16 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
R.sup.17 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.18--O)--H, R.sup.18 comprises --H, --CH.sub.3,
--CH.sub.2CH.sub.3, or --CH.sub.2OH, m is 1 or 2; M comprises --H,
--Li, --Na, --K, --N(R.sup.19).sub.4, or --HN(R.sup.19).sub.3,
wherein R.sup.19 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.20--O)--H, R.sup.20 comprises --H, --CH.sub.3,
--CH.sub.2CH.sub.3, or --CH.sub.2OH. (b) water, and (c) at least
one co-solvent.
9. The ink composition of claim 8, wherein R.sup.1 comprises
--SO.sub.3M.
10. The composition of claim 8, wherein R.sup.1 comprises
--CO.sub.2M.
11. The composition of claim 8, wherein R.sup.3 and R.sup.4
comprise, independently, hydrogen or lower alkoxy.
12. The composition of claim 8, wherein R.sup.5 comprises a group
of the formula: --NH-lower alkylene-SO.sub.3M; --NH-lower
alkylene-(CO.sub.2M).sub.m; --S-lower alkylene-SO.sub.2M; and
--S-lower alkylene-(CO.sub.2M).sub.m.
13. The composition of claim 8, wherein the compound of Formula (I)
is selected from 60
14. An ink composition comprising: (a) at least 0.1% by weight of a
compound of Formula (II) 61wherein: R.sup.3 comprises a lower
alkoxy group; R.sup.5 comprises a group of the formula:
62--NH-lower alkylene-SO.sub.3M; --NH-lower
alkylene-(CO.sub.2M).sub.1; --S-lower alkylene-SO.sub.3M; or
--S-lower alkylene-(CO.sub.2M).sub.m; wherein R.sup.9 and R.sup.13
comprise, independently, --SO.sub.3M or --CO.sub.2M; R.sup.10 and
R.sup.14 comprise, independently, --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
R.sup.11 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
R.sup.12 comprises --H, -lower alkyl, or -lower alkoxy; R.sup.6
comprises a group of the formula: 63--NH-lower alkylene-SO.sub.3M;
--NH-lower alkylene-(CO.sub.2M).sub.m; --S-lower
alkylene-SO.sub.2M; --S-lower alkylene-(CO.sub.2M).sub.m; or
--NH--R.sup.17, wherein R.sup.15 comprises --SO.sub.3M or
--CO.sub.2M; R.sup.16 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
R.sup.17 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.18--O)--H, R.sup.18 comprises --H, --CH.sub.3,
--CH.sub.2CH.sub.3, or --CH.sub.2OH, m is 1 or 2; M comprises --H,
--Li, --Na, --K, --N(R.sup.19).sub.4, or --HN(R.sup.19).sub.3,
wherein R.sup.19 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.20--O)--H, R.sup.20 comprises --H, --CH.sub.3,
--CH.sub.2CH.sub.3, or --CH.sub.2OH. (b) water, and (c) at least
one co-solvent.
15. A substrate or medium coated with the ink composition of claim
8.
16. A substrate or medium coated with the ink composition of claim
14.
17. The medium of claim 15, wherein said medium is selected from
paper, projector slides and textile materials.
18. The medium of claim 16, wherein said medium is selected from
paper, projector slides and textile materials.
Description
FIELD OF THE INVENTION
[0001] This invention belongs to the field of organic chemistry. In
particular, it relates to certain azo dyes useful in ink jet ink
compositions.
BACKGROUND OF THE INVENTION
[0002] Inks used in ink jet printing systems typically are
comprised of various dyes either dissolved in water or an organic
solvent or mixtures thereof. There is a need for inks having higher
quality images, printing speed, improved water-fastness and
lightfastness.
[0003] In addition, one trend in modem ink jet printing is the use
of printheads with smaller nozzle openings. The use of smaller
nozzle openings thus requires higher solubility in water, so that
the overall dye content in the ink composition can be increased to
provide the same color strength in a smaller droplet, relative to
traditional printheads and nozzle sizes.
SUMMARY OF THE INVENTION
[0004] Provided are novel azo dyes which are useful in ink
compositions, especially ink jet ink compositions. The dyes and ink
compositions of the present invention exhibit a good to excellent
balance of optical density, color value, waterfastness and
lightfastness, while at the same time exhibiting improved
solubility, thus rendering such ink compositions to be especially
suitable for modern printheads.
[0005] The novel azo dyes of the present invention are of the
following Formula (I): 1
[0006] wherein
[0007] R.sup.1 comprises --SO.sub.3M or --CO.sub.2M;
[0008] R.sup.2 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
[0009] R.sup.3 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
[0010] R.sup.4 comprises --H, -lower alkyl, or -lower alkoxy;
[0011] R.sup.5 comprises a group of the formula: 2
[0012] --NH-lower alkylene-SO.sub.3M;
[0013] --NH-lower alkylene-(CO.sub.2M).sub.m;
[0014] --S-lower alkylene-SO.sub.3M; or
[0015] --S-lower alkylene-(CO.sub.2M).sub.m;
[0016] wherein
[0017] R.sup.9 and R.sup.13 comprise, independently, --SO.sub.3M or
--CO.sub.2M;
[0018] R.sup.10 and R.sup.14 comprise, independently, --H, -lower
alkyl, -lower alkoxy, -halogen, --NH--C(O)-lower alkyl,
--SO.sub.3M, or --CO.sub.2M;
[0019] R.sup.11 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
[0020] R.sup.12 comprises --H, -lower alkyl, or -lower alkoxy;
[0021] R.sup.6 comprises a group of the formula: 3
[0022] --NH-lower alkylene-SO.sub.3M;
[0023] --NH-lower alkylene-(CO.sub.2M).sub.m;
[0024] --S-lower alkylene-SO.sub.2M;
[0025] --S-lower alkylene-(CO.sub.2M).sub.m; or
[0026] --NH--R.sup.17,
[0027] wherein
[0028] R.sup.15 comprises --SO.sub.3M or --CO.sub.2M;
[0029] R.sup.16 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
[0030] R.sup.17 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.18-O)--- H,
[0031] R.sup.18 comprises H, --CH.sub.3, --CH.sub.2CH.sub.3, or
--CH.sub.2OH,
[0032] m is 1 or 2;
[0033] M comprises --H, --Li, -Na, -K, --N(R.sup.19).sub.4, or
--HN(R.sup.19).sub.3,
[0034] wherein
[0035] R.sup.19 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.20--O)-- -H,
[0036] R.sup.20 comprises --H, --CH.sub.3, --CH.sub.2CH.sub.3, or
--CH.sub.2OH.
[0037] The present invention also provides ink compositions
comprising the dye of Formula (I), water, and a co-solvent.
DETAILED DESCRIPTION OF THE INVENTION
[0038] In a first embodiment, the present invention provides a
compound of Formula (I): 4
[0039] wherein
[0040] R.sup.1 comprises --SO.sub.3M or --CO.sub.2M;
[0041] R.sup.2 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
[0042] R.sup.3 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
[0043] R.sup.4 comprises --H, -lower alkyl, or -lower alkoxy;
[0044] R.sup.5 comprises a group of the formula 5
[0045] --NH-lower alkylene-SO.sub.3M;
[0046] --NH-lower alkylene-(CO.sub.2M).sub.m;
[0047] --S-lower alkylene-SO.sub.3M; or
[0048] --S-lower alkylene-(CO.sub.2M).sub.m;
[0049] wherein
[0050] R.sup.9 and R.sup.13 comprise, independently, --SO.sub.3M or
--CO.sub.2M;
[0051] R.sup.10 and R.sup.14 comprise, independently, --H, -lower
alkyl, -lower alkoxy, -halogen, --NH--C(O)-lower alkyl,
--SO.sub.3M, or --CO.sub.2M;
[0052] R.sup.11 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
[0053] R.sup.12 comprises --H, -lower alkyl, or -lower alkoxy;
[0054] R.sup.6 comprises a group of the formula 6
[0055] --NH-lower alkylene-SO.sub.3M;
[0056] --NH-lower alkylene-(CO.sub.2M).sub.m;
[0057] --S-lower alkylene-SO.sub.2M;
[0058] --S-lower alkylene-(CO.sub.2M).sub.m; or
[0059] --NH--R.sup.7,
[0060] wherein
[0061] R.sup.1 comprises --SO.sub.3M or --CO.sub.2M;
[0062] R.sup.16 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
[0063] R.sup.17 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.8--O)--- H,
[0064] R.sup.18 comprises --H, --CH.sub.3, --CH.sub.2CH.sub.3, or
--CH.sub.2OH,
[0065] m is 1 or 2;
[0066] M comprises --H, -Li, -Na, -K, --N(R.sup.19).sub.4, or
--HN(R.sup.19).sub.3,
[0067] wherein
[0068] R.sup.19 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.20--O)-- -H,
[0069] R.sup.20 comprises --H, --CH.sub.3, --CH.sub.2CH.sub.3, or
--CH.sub.2OH.
[0070] In a preferred embodiment, the present invention provides a
compound of Formula (II): 7
[0071] wherein:
[0072] R.sup.3 comprises a lower alkoxy group; and
[0073] R.sup.5 and R.sup.6 are as defined above for Formula
(I).
[0074] M comprises --H, --Li, --Na, --K, --N(R.sup.19).sub.4, or
--HN(R.sup.19).sub.3,
[0075] wherein
[0076] R.sup.19 comprises --H, -lower alkyl, or
(CH.sub.2CHR.sup.20--O)--H- ,
[0077] R.sup.20 comprises --H, --CH.sub.3, --CH.sub.2CH.sub.3, or
--CH.sub.2OH.
[0078] Especially preferred dyes of the present invention include
dyes of the Formula (III), (IV), and (V): 8
[0079] The azo dyes of the present invention are useful as dyes,
especially as dyes in ink jet ink compositions. The azo dyes of the
present invention have improved solubility which results in
improved ink jet printhead reliability, especially when utilized
with smaller diameter nozzles, while maintaining a good to
excellent balance of optical density, color value, waterfastness
and lightfastness. A further aspect of the present invention
provides an ink composition comprising:
[0080] (a) at least 0.1% by weight of a compound of Formula (I):
9
[0081] wherein
[0082] R.sup.1 comprises --SO.sub.3M or --CO.sub.2M;
[0083] R.sup.2 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
[0084] R.sup.3 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
[0085] R.sup.4 comprises --H, -lower alkyl, or -lower alkoxy;
[0086] R.sup.5 comprises a group of the formula 10
[0087] --NH-lower alkylene-SO.sub.3M;
[0088] --NH-lower alkylene-(CO.sub.2M).sub.m;
[0089] --S-lower alkylene-SO.sub.3M; or
[0090] --S-lower alkylene-(CO.sub.2M).sub.m;
[0091] wherein
[0092] R.sup.9 and R.sup.13 comprise, independently, --SO.sub.3M or
--CO.sub.2M;
[0093] R.sup.10 and R.sup.14 comprise, independently, --H, -lower
alkyl, -lower alkoxy, -halogen, --NH--C(O)-lower alkyl,
--SO.sub.3M, or --CO.sub.2M;
[0094] R.sup.11 comprises --H, -lower alkyl, -lower alkoxy,
--O-lower-alkylene-CO.sub.2M, -lower alkylene-CO.sub.2M,
--NH--C(O)--CO.sub.2M, --NH--C(O)-lower alkyl, or --CO.sub.2M;
[0095] R.sup.12 comprises --H, -lower alkyl, or -lower alkoxy;
[0096] R.sup.6 comprises a group of the formula 11
[0097] --NH-lower alkylene-SO.sub.3M;
[0098] --NH-lower alkylene-(CO.sub.2M).sub.m;
[0099] --S-lower alkylene-SO.sub.2M;
[0100] --S-lower alkylene-(CO.sub.2M).sub.m; or
[0101] --NH--R.sup.17,
[0102] wherein
[0103] R.sup.15 comprises --SO.sub.3M or --CO.sub.2M;
[0104] R.sup.16 comprises --H, -lower alkyl, -lower alkoxy,
-halogen, --NH--C(O)-lower alkyl, --SO.sub.3M, or --CO.sub.2M;
[0105] R.sup.17 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.18--O)-- -H,
[0106] R.sup.18 comprises --H, --CH.sub.3, --CH.sub.2CH.sub.3, or
--CH.sub.2OH,
[0107] m is 1 or 2;
[0108] M comprises --H, --Li, --Na, --K, --N(R.sup.19).sub.4, or
--HN(R.sup.19).sub.3,
[0109] wherein
[0110] R.sup.19 comprises --H, -lower alkyl, or
--(CH.sub.2CHR.sup.20--O)-- -H,
[0111] R.sup.20 comprises --H, --CH.sub.3, --CH.sub.2CH.sub.3, or
--CH.sub.2OH.
[0112] (b) water, and
[0113] (c) at least one co-solvent.
[0114] In the above formulae, and hereafter the term "lower alkyl"
refers to a straight or branched-chain C.sub.1-C.sub.4 alkyl group.
Examples include methyl, ethyl, propyl, isopropyl, n-butyl,
t-butyl, and isobutyl.
[0115] The term "lower alkoxy" refers to a C.sub.1-C.sub.4 alkoxy
group. Examples include methoxy, ethoxy, propoxy, and butoxy.
[0116] Likewise, the terms "lower hydroxyalkyl" and "lower
cyanoalkyl" preferably refer to C.sub.1-C.sub.4 alkyl groups
substituted by at least one hydroxy or cyano group,
respectively.
[0117] The term "lower alkylene" refers to a divalent group of the
formula --(CH.sub.2)-m wherein m is an integer of from 1 to 4.
Examples include methylene, ethylene, propylene, and butylene.
[0118] The compounds of this invention may be prepared by
diazotizing, for example, an optionally and appropriately
substituted aminobenzene sulfonic acid, aminobenzoic acid, or
aminophthalic acid, coupling with aniline, or an appropriately
substituted aniline such as, for example, ortho- or meta-toluidine,
ortho- or meta-anisidine, ortho- or meta-phenetidine, cresidine,
dimethoxyaniline, diethoxyaniline, an appropriately substituted
3-aminophenoxyacetic acid, propionic, or butyric acid or an
appropriately substituted 3'-aminophenylacetic, propionic or
butyric acid, reacting the resultant aminoazobenzene intermediate
compound in equimolar quantity with cyanuric chloride, then
optionally reacting the product with a second molar equivalent of
the same or a different aminoazobenzene intermediate compound, or
with a suitable aminoalkylenesulfonic acid, an aminoalkylene-mono
or dicarboxylic acid, an aminobenzene mono or di-carboxylic acid,
an aniline-mono- or disulfonic acid, an amino-naphthalene mono- or
di-sulfonic acid, a mercaptoacetic, propionic, or succinic acid, or
a mercaptoalkylenesulfonic acid, and finally reacting this product
with an equimolar quanitity of ammonia, a primary aliphatic or
alkanolamine, an aminoalkylenesulfonic acid, an aminoalkylene
mono-or di-carboxylic acid, an aminobenzene mono-or dicarboxylic
acid, an aminobenzene mono or disulfonic acid, an aminonaphthalene
mono or disulfonic acid, a mercaptoalkylene sulfonic acid or a
mercaptoalkylene mono- or dicarboxylic acid, the final dye
structure containing at least three sulfonic acid groups or an
equally water-solubilizing combination of carboxylic and sulfonic
acid groups, such as two or three carboxylic acid groups with two
sulfonic acid groups, or three to four carboxylic acid groups with
one sulfonic acid group.
[0119] Examples of compounds from which the diazonium component may
be derived include: metanilic acid, sulfanilic acid, anisidine
sulfonic acids, phenetidine sulfonic acids, toluidine sulfonic
acids, 4- or 6-chlorometanilic acid, anthanilic sulfonic acid, 2, 3
or 4-aminobenzoic acid, 3- or 4-aminophthalic acid, 4- or
5-aminoisophthalic acid, 2-amino-3-methoxybenzoic acid,
4-amino-3-methylbenzoic acid.
[0120] Suitable couplers include, for example, aniline, o- or
m-toluidine, o- or m-anisidine, o- or m-phenitidine,
m-aminoacetanilide, m-aminoacetanilide sulfonic acid, an ortho or
meta-amino phenylacetic, -propionic or -butyric acid, an ortho or
meta-aminophenoxyacetic, propionic or -butyric acid,
2,5-dimethoxyaniline, 2,5-diethoxyaniline, cresidine, and
anthranilic acid.
[0121] Examples of intermediates suitable for the second and third
reactions with the cyanuric chloride to produce R.sup.5 and
R.sup.6, in addition to a substituted aminoazobenzene compound for
R.sup.5 include, for example, taurine, 3-aminopropanesulfonic acid,
orthanilic acid, metanilic acid, sulfanilic acid, 2, 3, or
4-aminobenzoic acid, 3 or 4-aminophthalic acid, 4 or
5-aminoisophthalic acid, an anisidinesulfonic acid, a toluidine
sulfonic acid, 4- or 6-chlorometanilic acid,
4-amino-3-methoxybenzoic acid, phenetidine sulfonic acids,
m-aminoacetanilide sulfonic acid, aniline disulfonic acid, Amino G
acid, Amino J acid, Amino R acid, napthionic acid, Broenner's acid,
Laurent's acid, C acid, epsilon acid, Cleve's acid,
2-mercaptoethanesulfonic acid, 3-mercapto-1-propanesulfonic acid,
3-aminoadipic acid, mercaptosuccinic acid, thiolactic acid,
mercaptoacetic acid, 2, 3, or 4-aminobutyric acid,
3-aminoisobutyric acid, 5-aminovaleric acid, ethanolamine, ammonia,
methyl amine, ethyl amine, propyl amine, 3-aminopropanol, and
2-(2'-aminoethoxy)-ethanol.
[0122] A salt form of the dyes of the present invention may be
obtained by employing throughout the synthesis the corresponding
hydroxide, carbonate, or bicarbonate of an alkali metal, or by
using throughout the synthesis a non-reactive tertiary amine or
quaternary ammonium hydroxide, such as triethanolamine, trimethyl
amine, triethyl amine or tetramethyl or tetraethyl ammonium
hydroxide. In addition, a salt form may be conveniently converted
to a different salt form, or the free acid, by ion exchange, using
well-known equipment and procedures. Purification to remove
impurities and salts may be accomplished by reverse osmosis, using
readily available equipment following usual procedures. The dye
concentration may be adjusted by either evaporation or dilution to
the desired percentage.
[0123] The present invention relates also to ink compositions, for
example aqueous ink compositions. An aqueous ink composition
according to the present invention comprises a dye of formula (I),
water, and, optionally, at least one co-solvent.
[0124] In Table 1, there are listed representative examples of the
water-soluble dyes having the above formula (I) for use in inks in
the present invention.
[0125] The inks preferably have a total content of dyes of from 0.5
to 30% by weight, preferably from 1 to 30% by weight and more
preferably from 1 to 15% by weight, based on the total weight of
the ink. As a lower limit, a limit of 1% by weight, preferably 2%
by weight and most preferably 3% by weight, is preferred.
[0126] Humectant
[0127] In one embodiment of the present invention, the ink
composition may optionally comprise a humectant acting as a
co-solvent. Selection of a suitable humectant depends on the
requirements of the specific application involved, such as desired
surface tension and viscosity, the desired drying time of the ink,
and the type of paper onto which the ink will be printed.
Representative examples of humectants that may be selected include
(1) alcohols, such as methyl alcohol, ethyl alcohol, n-propyl
alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol,
t-butyl alcohol, iso-butyl alcohol, furfuryl alcohol, and
tetrahydrofurfuryl alcohol; (2) ketones or ketoalcohols, such as
acetone, methyl ethyl ketone and diacetone alcohol; (3) ethers,
such as tetrahydrofuran and dioxane; (4) esters, such as ethyl
acetate, ethyl lactate, ethylene carbonate and propylene carbonate;
(5) polyhydric alcohols, such as ethylene glycol, diethylene
glycol, triethylene glycol, propylene glycol, tetraethylene glycol,
polyethylene glycol, glycerol, 2-methyl-2,4-pentanediol,
1,2,6-hexanetriol and thiodiglycol; (6) lower alkyl mono- or
di-ethers derived from alkylene glycols, such as ethylene glycol
monomethyl (or monoethyl) ether, diethylene glycol monomethyl (or
monoethyl) ether, propylene glycol monomethyl (or monoethyl) ether,
triethylene glycol monomethyl (or monoethyl) ether and diethylene
glycol dimethyl (or diethyl) ether; (7) nitrogen-containing cyclic
compounds, such as pyrrolidone, N-methyl-2-pyrrolidone, and
1,3-dimethyl-2-imidazoli- dinone; and (8) sulfur-containing
compounds, such as dimethyl sulfoxide and tetramethylene sulfone.
Other useful organic solvents include lactones and lactams.
Mixtures of these solvents may be used in the present
invention.
[0128] Of the above mentioned humectants, preferred humectants
include; diethylene glycol, polyethylene glycol (200 to 600),
ethylene glycol, triethylene glycol, tetraethylene glycol, glycerin
and N-methyl-2-pyrrolidone, by which the solubility of the employed
dye in the solvent of the ink composition can be increased and the
evaporation of water from the ink composition can be appropriately
controlled, so that the initial properties of the ink composition
can be maintained even for an extended period of continuous use or
storage, or during the periods when the apparatus is not in use,
whereby reliable ink droplet stability and ink droplet ejection
response of the ink composition, particularly after a prolonged
period of non-use of the apparatus, are obtained. The amount of
humectant is determined by the desired properties of the ink and
may range from about 0.1% to about 30% by weight of the ink
composition.
[0129] Pigments
[0130] The ink composition may also optionally comprise additional
colorants. Additional colorants useful in the present invention
include pigments, self-dispersed pigment, polymeric pigment
dispersions, pigment-dye blends, and combinations thereof. The
pigment can be a polymeric pigment concentrate or self-dispersed
pigment concentrate, or a combination of both.
[0131] As is known in the art, a pigment dispersion is a mixture of
a pigment and a dispersing agent, typically a polymeric dispersant
compound. A wide variety of organic and inorganic pigments, alone
or in combination, may be selected for use in the aqueous inks of
the present invention. The key selection criterion for the pigment
is that they must be dispersible in the aqueous medium. The term
"pigment," as used herein, means an insoluble colorant. The
selected pigment may be used in dry or wet form.
[0132] Suitable pigments include organic pigments, and essentially
any of the classes of pigments heretofore used in this art, of a
particle size sufficient to permit free flow of the ink through the
ink jet printing device, especially at the ejecting nozzles that
usually have a diameter ranging from about 10 microns to about 50
microns. Thus, a suitable pigment particle size ranges from about
0.02 to about 15, preferably from about 0.02 to about 5, and more
preferably from about 0.02 to about 1, micron(s) so that when
jetted, the pigment particle size ranges from about 0.005 to about
0.02 microns. Pigments suitable for use in the present invention
include azo pigments, such as azo lakes, insoluble azo pigments,
condensed azo pigments and chelate azo pigments, polycyclic
pigments, perylene pigments, anthraquinone pigments, quinacridone
pigments, dioxazine pigments, thioindigo pigments, isoindolinone
pigments, quinophthalone pigments, and dry lakes. Suitable organic
pigments include nitro pigments, aniline black and daylight
fluorescent pigments. Preferred pigments include carbon black,
Pigment Red 122, Pigment Red 202, Pigment Yellow 74, Pigment Yellow
128, Pigment Yellow 138, Pigment Yellow 155, Pigment Blue 15:3 and
Pigment Blue 15:4.
[0133] Dispersant
[0134] Dispersants may optionally be used in the present invention,
for example, when a insoluble pigment is used. Appropriate
dispersants include those known in the art, such as the acrylic
terpolymers taught in commonly-assigned U.S. Pat. No. 5,719,204,
and other commonly known dispersants. Factors to be considered in
selecting an appropriate dispersant include the following: First,
the dispersant must firmly anchor to the pigment particle surface
to withstand shear force and the competition of other chemical
species. To ensure this anchoring, a careful match of the polarity
of the pigment particle surface and the hydrophobic group in the
dispersant is required. Second, the physical dimensions of the
hydrophobic group in the dispersant must be adequate to fully cover
the pigment surface, otherwise, the adsorbed polymer will act as a
flocculent. Third, an electrostatic layer of a requisite thickness
around the particle is needed to prevent aggregation of particles
within the aqueous medium.
[0135] The pigment to dispersant (weight) ratio is preferably from
about 3:1 to about 5:1, but may vary from about 1:1 to about
9:1.
[0136] Binder
[0137] A binder may also optionally be used in the ink composition
of the present invention to bridge the pigment particles within the
ink and aid in their adhesion to the print medium. The use of a
binder allows for greater ink durability and increased image
permanence. High T.sub.G binders are generally preferred for long
term jetting requirements, but low T.sub.G binders are preferable
for smear permanence. Also preferred are unimodal random (not
block) polymer binders. Binder may be present in amounts from 0-100
parts to 100 parts of pigment, preferably 5-30 parts to 100 parts
pigment.
[0138] Preferred binders for use in the present invention comprise
a polymer or copolymer formed from monomer classes, including, but
not limited to: acrylate esters, methacrylate esters, styrenes,
substituted styrenes, vinyl acrylates, vinyl acetates,
fluoromethacrylates, acrylamides, substituted acrylamides,
methacrylamides, substituted methacrylamides, and combinations
thereof. Among the esters of acrylic acid and methacrylic acid,
preferred monomers include methyl acrylate, ethyl acrylate, propyl
acrylate, butyl acrylate, lauryl acrylate, methyl methacrylate,
ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl
methacrylate, and isobutylene methacrylate.
[0139] In one embodiment, the binder may comprise a copolymer of
butyl acrylate and methyl methacrylate. In a further embodiment,
the polymeric binder may comprise a copolymer ranging from about
20% to about 40% by weight of methyl methacrylate and about 60% to
about 80% by weight of butyl acrylate. The polymeric binder may
comprise a copolymer ranging from about 27% to about 33% by weight
of methyl methacrylate and about 66% to 72% by weight of butyl
acrylate. In another embodiment, the polymeric binder comprises 10%
to 50% by weight methyl methacrylate, 50% to 85% by weight butyl
acrylate, and 3% to 10% by weight methacrylic acid, based on the
total weight of the polymeric binder; for example 14.5% by weight
methyl methacrylate, 80.5% by weight butyl acrylate, and 5% by
weight methacrylic acid. The foregoing merely represent example of
suitable polymeric binder compositions.
[0140] The polymeric binder may further comprise an acid component.
The acid component may comprise acrylic acid, methacrylic acid,
itaconic acid, vinyl sulfonic acid, maleic acids or combinations
thereof, or may be derived from salts or anhydrides of such acids,
such as methacrylic or malcic anhydride or sodium vinylsulfonate or
acrylomidopropane sulfonate. In one embodiment the acid component
is methacrylic acid. In another embodiment, the acid component is
methacrylic acid in combination with another acid. The acid
component of the polymeric binder ranges from about 1% to about 10%
by weight of the total weight of the polymeric binder. In one
embodiment, when the acid component is methacrylic acid, the acid
component is about 1.1% to about 1.5% by weight of the total weight
of the polymeric binder. In another embodiment, when the acid
component is methacrylic acid, the acid component is about 1.3% by
weight of the total weight of the polymeric binder.
[0141] It should be noted, however, that the examples of ink
compositions discussed herein do not represent the only possible
formulations encompassed by the present invention, and that the
present invention includes ink compositions when the acid component
of the polymeric binder ranges from about 1% to about 10% by weight
of the total weight of the polymeric binder.
[0142] The most preferred binder in the present invention may
comprise from about 0% to about 5% by weight in the ink composition
a unimodal acrylic emulsion which contains a random copolymer
comprised of buthylmethacrylate and methylmethacrylate mononers as
described in co-pending patent application Ser. No. 09/460,959 of
Beach et al. assigned to Lexmark International, Inc. the same
assignee herein.
[0143] Penetrant
[0144] A penetrant may also optionally be used in the ink
composition of the present invention to improve penetration by the
ink drops into the surface of the printed substrate and to reduce
or eliminate intercolor bleeding (i.e., lateral bleeding of color).
Penetrants (which include surfactants) are preferred for use in the
invention. Preferred penetrants for use in the present invention
include 1,2 alkyl diols containing from about 4 to about 10 carbon
atoms in the alkyl group such as those taught in commonly-assigned
U.S. Pat. No. 5,364,461. Most preferred are 1,2-hexanediol and
hexyl carbitol. In a preferred embodiment, the penetrant is present
in the ink composition in an amount of from between about 0.01% to
about 10% by weight, preferably 0.1% to about 3%.
[0145] Surfactant
[0146] The ink compositions may also optionally comprise
surfactants to modify the surface tension of the ink and to control
the penetration of the ink into the paper. Suitable surfactants
include nonionic, amphoteric, cationic, and anionic surfactants.
Preferred surfactants include alkyl sulfate, nonyl phenyl
polyethylene glycol, the SILWET.RTM. series of surfactants (OSI
Sealants, Inc.), the TERGITOL.RTM. series of surfactants (Union
Carbide) and the SURFYNOL.RTM. series of surfactants (Air Products
and Chemicals, Inc.).
[0147] Biocide
[0148] The ink compositions may also optionally comprise additives
that inhibit the growth of fungi and/or bacteria (biocides). Such
additives are usually used in amounts of from 0.01 to 1.0% by
weight, based on the total weight of the ink. Sodium
dehydroacetate, sodium sorbate, 2-pyridine thiol-1-oxide sodium
salt, sodium benzoate and sodium pentachlorophenol can be employed
as biocides. A preferred biocide is 1,2-Benzisothiazolin-3-one,
commercially available as Proxel.RTM. GXL manufactured by
Zeneca.
[0149] Buffer
[0150] Any known pH adjustment agents may optionally be used in the
present invention, so long as they do not have an adverse effect on
the ink composition and can control the pH of the ink
composition.
[0151] Buffering agents, such as borax, borates, phosphates,
polyphosphates or citrates (for example, sodium borate, sodium
tetraborate, sodium phosphate, sodium dihydrogen phosphate,
disodium hydrogen phosphate, sodium tripolyphosphate, sodium
pentapolyphosphate and sodium citrate) may also be added to adjust
or maintain a desired pH for the ink. A preferred buffer arc
potassium hydroxide, sodium phosphate or sodium borate. As will be
appreciated, the amount of buffer will depend on the other
components in the ink. However, it has been found that the addition
of small amounts of buffer to the ink, such as from about 0.01% to
about 0.3% by weight, preferably from 0.1 to 1% by weight, is
usefull.
[0152] Chelating Agent
[0153] The ink compositions may also optionally comprise chelating
agents. Chelating agents, such as for example, ethylene diamine
tetraacetate (EDTA), trisodium nitrilotriacetate, hydroxyethyl
ethylenediamine trisoduim acetate, diethylene triamino pentasodium
acetate and uramil disodium acetate, may be added to prevent any
deleterious effects from metal or alkali metal ion contaminants or
impurities. Typically, a chelating agent may be added to the
composition in an amount of from about 0.1% to about 1.0% by
weight. A preferred chelating agent is EDTA.
[0154] Other additives, for example, ultra-violet-ray-absorbing
agents, infrared-ray-absorbing agents, polymeric compounds, and
solubility increasing agents for increasing the solubility of the
dye dissolved in the solvent of the ink composition can be employed
as thought necessary in specific embodiments of an aqueous ink
composition for ink-jet recording according to the present
invention.
EXAMPLES
[0155] Preferred embodiments of an aqueous ink composition for
ink-jet recording according to the present invention will now be
explained by referring to the following examples.
[0156] The following Examples serve to illustrate the invention.
Unless otherwise indicated, parts are parts by weight and
percentages relate to percent by weight. The relationship between
parts by weight and parts by volume is the same as that between
kilograms and liters.
Example 1
[0157] A dye of Formula (IVa) can be prepared according to the
following procedure. 12
[0158] A solution was prepared of 61.4 g of
4-amino-3-methoxyazobenzene-3'- -sulfonic acid (prepared in
conventional manner) in 300 mL of water containing 8 g of sodium
hydroxide. When the solution was complete, it was diluted to 400 mL
with water.
[0159] A 2 liter beaker containing 200 mL water and 200% ice was
placed in an ice/water bath. 18.4 g of finely ground cyanuric
chloride was added to the beaker. With vigorous agitation, half of
the amino-azobenzene derivative solution was added dropwise over 25
minutes. The temperature of the reaction was held at 0.degree. C.
by further addition of ice as required. When all of the solution
was in, the pH of the mixture was slowly raised to about 6.2 by
sifting in 8.4 g of sodium bicarbonate slowly over 15 minutes.
After stirring further for about 15 minutes the red-brown slurry
had changed to bright yellow and a thin-layer chromatogram showed
completion of the reaction. The pH was also stable at 6.2.
[0160] The second half of the amino-azobenzene derivative solution
was then dropped in over 30 minutes. The ice/water bath was removed
and the reaction temperature was allowed to rise to ambient, about
20.degree. C. After stirring for 15 minutes more an additional 8.4
g of sodium bicarbonate was sifted into the reaction slurry over 15
minutes. The pH rose to 7.5 and the reaction was a clear yellow
solution at 1100 mL volume. The reaction was stirred for an
additional 16 hours at about 20.degree. C.
[0161] Next, 25 g Taurine (2-aminoethanesulfonic acid) was added.
The pH was raised to 9 by addition of sodium hydroxide solution.
The solution was heated to 80-85.degree. C. and held at this
temperature and at pH 8.5 to 9 for at least four hours. The
resultant bright yellow dye was highly soluble in water over a wide
pH range and had very good lightfastness when used for ink jet
printing on plain and special papers.
[0162] The dye solution was subjected to reverse osmosis to remove
excess taurine, impurities and salts. Conversion to other salt
forms was accomplished by means of ion exchange according to
well-known procedures.
Example 2
[0163] A dye of Formula (IIIa) can be prepared according to the
following procedure. 13
[0164] The general method of Example I was repeated except that the
second half of the aminoazobenzene derivative solution was replaced
by an equimolar amount of Amino G acid
(2-naphthylamine-6,8-disulfonic acid) in solution, and the taurine
was Replaced by 12.2 g of ethanolamine as the third reactant. A
highly water-soluble Yellow dye of Formula (IIIa) was obtained.
This dye also exhibited very good lightfastness when used in inks
for ink jet printing on plain and special papers.
Example 3
[0165] A dye of Formula (Va) can be prepared according to the
following procedure. 14
[0166] The general method of Example 1 was repeated except that the
second half of the aminoazobenzene derivative solution was replaced
with 12.5 g taurine. The product was a solution of a highly
water-soluble bright yellow dye, having very good lightfastness on
plain or special papers when applied in inks by ink jet
printing.
[0167] Further examples of especially preferred embodiments of the
present invention include the following wherein R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6 and M of Formula (1) are as set
forth below in Table 1:
1TABLE 1 Ex. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 M 4
3-SO.sub.3M H 2-OCH.sub.3 H 15 --S--CH.sub.2CH.sub.2--SO.sub.3M Na
5 3-SO.sub.3M H 2-OCH.sub.3 H 16
--S--CH.sub.2CH.sub.2CH.sub.2SO.sub.3M Na 6 3-SO.sub.3M H
3-CH.sub.3 H 17 --NHCH.sub.2CH.sub.2SO.su- b.3M Na 7 3-SO.sub.3M H
2-OCH.sub.3 H 18 --NHCH.sub.2CH.sub.2SO.sub.3M Li 8 3-SO.sub.3M H
2-OCH.sub.3 H 19 --NHCH.sub.2CH.sub.2SO.sub.3M K 9 4-SO.sub.3M H
3-CH.sub.3 H 20 --S--CH.sub.2CH.sub.2--SO.sub.3M Na 10 4-SO.sub.3M
H H H 21 --NH--CH.sub.2CH.sub.2--SO.sub.3M Na 11 4-SO.sub.3M H
2-CH.sub.3 H 22 --NH--CH.sub.2CH.sub.2--SO.su- b.3M Na 12
4-SO.sub.3M H 3-CH.sub.3 H 23 --NH--CH.sub.2CH.sub.2--SO.sub.3M Na
13 5-SO.sub.3M 2-Cl 2-OCH.sub.3 H 24
--NH--CH.sub.2CH.sub.2--SO.sub.3M Na 14 5-SO.sub.3M 2-OCH.sub.3
3-CH.sub.3 H 25 --NH--CH.sub.2CH.sub.2--SO.sub.3M
HN(CH.sub.2CH.sub.2OH).sub.3 15 3-SO.sub.3M H 2-OCH.sub.3 H 26
--NH.sub.2 Na 16 3-SO.sub.3M H 2-OCH.sub.3 H 27
--NH--CH.sub.2--CH.sub.2--OH Na 17 3-SO.sub.3M H 2-OCH.sub.3 H 28
--NH--CH.sub.2CH.sub.2--SO.sub.3M Na 18 3-SO.sub.3M H 2-OCH.sub.3 H
29 --NH--CH.sub.2CH.sub.2--SO.sub.3M Li 19 3-SO.sub.3M H
2-OCH.sub.3 H 30 --NH--CH.sub.2CH.sub.2--SO.su- b.3M Na 20
3-SO.sub.3M H 2-OCH.sub.3 H 31 --NH--CH.sub.3 Na 21 3-SO.sub.3M H
2-OCH.sub.3 H 32 --S--CH.sub.2CH.sub.2CH.sub.2SO.sub.3M Li 22
3-SO.sub.3M H 2-OCH.sub.3 H 33 --S--CH.sub.2CH.sub.2SO.sub.3M Li 23
3-SO.sub.3M H 2-OCH.sub.3 H 34 --NH--CH.sub.2CH.sub.2SO.sub.3M Na
24 3-SO.sub.3M H 2-OCH.sub.3 H 35 --S--CH(CH.sub.3)--CO.sub.2M Na
25 4-SO.sub.3M H 3-CH.sub.3 H 36 37 Li 26 4-SO.sub.3M H 2-CH.sub.3
H 38 39 HN(CH.sub.2CH.sub.2OH).sub.3 27 5-SO.sub.3M 2-CH.sub.3
2-OCH.sub.3 5-CH.sub.3 40 41 Na 28 3-SO.sub.3M H
2-OCH.sub.2CH.sub.3 H 42 43 Li 29 4-SO.sub.3M H 2-OCH.sub.3
5-OCH.sub.3 44 45 Na 30 3-CO.sub.2M 5-CO.sub.2M 2-OCH.sub.3 H 46 47
Na 31 3-SO.sub.3M H 3-CH.sub.3 H 48 49 Li
[0168] In addition to the dyes described herein, the present
invention comprises ink formulations which employ the novel dyes.
Ink formulations generally comprise a colorant and a carrier as
well as optional additives as enumerated above. Some examples of
ink formulations are shown below, as well as test results for the
specified inks.
[0169] The inks of the present invention can be prepared in
customary manner by mixing the individual constituents together,
for example, in the desired amount of water. These inks are
especially suitable as the yellow component for multicolor
printing.
Example 32
[0170] To a sample of the dye of Formula (III) (5% based on total
weight), 0.1% sodium EDTA was added, followed by stirring for 10
minutes. Tetraethylene glycol (8% based on total weight) was then
added and stirring continued for 20 minutes. 1,2-Hexanediol (7%
based on total weight) was added followed by stirring for 20
minutes. Proxel.RTM. GXL biocide (0.2% based on total weight) was
then added and stirring continued for an additional 20 minutes.
Sodium phosphate (0.5% based on total weight) and sodium borate
(0.5% based on total weight) were added and stirring continued for
40 minutes. The pH was adjusted to 8.5 with either acetic acid or
sodium hydroxide and filtered through a 0.22.mu. filter unit. The
balance of the formulation was deionized water. The ink was filled
in heads and tested on ExecJet Ic machines (idle test after 5, 10,
15 and 20 minutes) as described below.
Example 33
[0171] To a sample of the dye of Formula (IV) (5% based on total
weight), 0.1% sodium EDTA was added, followed by stirring for 10
minutes. Tetraethylene glycol (8% based on total weight) was then
added and stirring continued for 20 minutes. 1,2-Hexanediol (7%
based on total weight) was added followed by stirring for 20
minutes. Proxel.RTM. GXL biocide (0.2% based on total weight) was
then added and stirring continued for an additional 20 minutes.
Sodium phosphate (0.5% based on total weight) and sodium borate
(0.5% based on total weight) was added and stirring continued for
40 minutes. The pH was adjusted to 8.5 with either acetic acid or
sodium hydroxide and filtered through a 0.22.mu. filter unit. The
balance of the formulation was deionized water. The ink was filled
in heads and tested on ExecJet IIc machines (idle test after 5, 10,
15 and 20 minutes) as described below.
Example 34
[0172] To a sample of the dye of Formula (V) (5% based on total
weight), 0.1% sodium EDTA was added, followed by stirring for 10
minutes. Tetraethylene glycol (8% based on total weight) was then
added and stirring continued for 20 minutes. 1,2-Hexanediol (7%
based on total weight) was added followed by stirring for 20
minutes. Proxel.RTM. GXL biocide (0.2% based on total weight) was
then added and stirring continued for an additional 20 minutes.
Sodium phosphate (0.5% based on total weight) and sodium borate
(0.5% based on total weight) was added and stirring continued for
40 minutes. The pH was adjusted to 8.5 with either acetic acid or
sodium hydroxide and filtered through a 0.22.mu. filter unit. The
balance of the formulation was deionized water. The ink was filled
in heads and tested on ExecJet IIc machines (idle test after 5, 10,
15 and 20 minutes) as described below.
Test Results For Examples 32-34
[0173] The idle test results are summarized below, showing the %
probability that the head would fail with the following dyes:
2 Idle Time Pro-Jet Yellow (minutes) 1G* Example 32 Example 33
Example 34 5 83% 11% 44% 55% 10 88% 11% 56% 8% 15 88% 22% 78% 0% 20
88% 33% 78% 8% Average 87% 19% 64% 18% No. of Heads 8 3 3 4 Tested
*Pro-Jet Yellow 1G is a commercially available yellow dye used as a
standard for the purposes of this test.
[0174] The foregoing is considered as illustrative only of the
principles of the present invention. Since numerous modifications
and changes will readily occur to those skilled in the art, the
foregoing is not intended to limit the invention to the exact
construction and operation shown and described, and all suitable
modifications and equivalents falling within the scope of the
appended claims are deemed within the present inventive
concept.
[0175] The features of the present invention, together with the
other objectives of the invention, and along with the various
features of novelty which characterize the invention, are pointed
out with particularity in the claims annexed to and forming a part
of this disclosure.
* * * * *